Scientific Output

Over 10.000 scientific papers have been published by members of the Materials Chain since the foundation of the University Alliance Ruhr in 2010. This tremendous output is proof of the excellent environment the Ruhr Area provides for research in the field of materials science and technology.

Below, you can either scroll through the complete list of our annually published material, or search for a specific author or term via the free text search to get to know our research strengths. You can also review the publication record of every Materials Chain member via his or her personal member’s page.

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  • 2022 • 425 A sustainable ultra-high strength Fe18Mn3Ti maraging steel through controlled solute segregation and α-Mn nanoprecipitation
    Kwiatkowski da Silva, A. and Souza Filho, I.R. and Lu, W. and Zilnyk, K.D. and Hupalo, M.F. and Alves, L.M. and Ponge, D. and Gault, B. and Raabe, D.
    Nature Communications 13 (2022)
    The enormous magnitude of 2 billion tons of alloys produced per year demands a change in design philosophy to make materials environmentally, economically, and socially more sustainable. This disqualifies the use of critical elements that are rare or have questionable origin. Amongst the major alloy strengthening mechanisms, a high-dispersion of second-phase precipitates with sizes in the nanometre range is particularly effective for achieving ultra-high strength. Here, we propose an alternative segregation-based strategy for sustainable steels, free of critical elements, which are rendered ultrastrong by second-phase nano-precipitation. We increase the Mn-content in a supersaturated, metastable Fe-Mn solid solution to trigger compositional fluctuations and nano-segregation in the bulk. These fluctuations act as precursors for the nucleation of an unexpected α-Mn phase, which impedes dislocation motion, thus enabling precipitation strengthening. Our steel outperforms most common commercial alloys, yet it is free of critical elements, making it a new platform for sustainable alloy design. © 2022, The Author(s).
    view abstractdoi: 10.1038/s41467-022-30019-x
  • 2022 • 424 Bisstibane-distibane conversion via consecutive single-electron oxidation and reduction reaction
    Gehlhaar, A. and Weinert, H.M. and Wölper, C. and Semleit, N. and Haberhauer, G. and Schulz, S.
    Chemical Communications 58 6682-6685 (2022)
    peri-Substituted naphthalene complexes (Trip2Pn)2Naph (Pn = Sb 1, Bi 2) were synthesised and their redox behaviour investigated. Oxidation of 1 with [Fc][BArF] (BArF = B(C6F5)4) yielded [(Trip2Sb)(TripSb)Naph][BArF] (3) containing the stibane-coordinated stibenium cation [(Trip2Sb)(TripSb)Naph]+. Subsequent reduction of 3 with KC8 yielded distibane (TripSb)2Naph (4). 1-4 were characterised by NMR (1H, 13C) and IR spectroscopy as well as single-crystal X-ray diffraction (sc-XRD), while their electronic structures were analysed by quantum chemical computations. © 2022 The Royal Society of Chemistry
    view abstractdoi: 10.1039/d2cc01986h
  • 2022 • 423 Comparing London dispersion pnictogen-π interactions in naphthyl-substituted dipnictanes
    Gehlhaar, A. and Schiavo, E. and Wölper, C. and Schulte, Y. and Auer, A.A. and Schulz, S.
    Dalton Transactions 51 5016-5023 (2022)
    Using a combination of NMR, single crystal X-ray diffraction (sc-XRD) and quantum chemistry, the structure-directing role of London Dispersion (LD) is demonstrated for dibismuthane Bi2Naph2 (1). 1 shows intermolecular Bi⋯π contacts in the solid-state, while π⋯π interactions as observed in the lighter homologues are missing. Comparison of the whole series of dipnictanes revealed the influence of the pnictogen atom on the strength of London dispersion and highlights its importance in heavy main group element chemistry. © 2022 The Royal Society of Chemistry
    view abstractdoi: 10.1039/d2dt00477a
  • 2022 • 422 Determining the sintering kinetics of Fe and FexOy-Nanoparticles in a well-defined model flow reactor
    Rosenberger, T. and Skenderović, I. and Sellmann, J. and Wollny, P. and Levish, A. and Wlokas, I. and Kempf, A. and Winterer, M. and Kruis, F.E.
    Aerosol Science and Technology 56 833-846 (2022)
    A model flow reactor provides a narrow particle temperature-residence time distribution with well-defined conditions and is mandatory to measure changes of the particle structure precisely. The experimental data of iron and iron oxide agglomerates are used to determine the sintering kinetics considering the temperature-time history of the particles. Thousand particle trajectories are tracked in a validated CFD model at three different furnace temperatures each. Strongly agglomerated particles with a small primary particle size (∼4 nm) are synthesized by spark discharge and are size-selected (25–250 nm) before sintering. The structure development is measured simultaneously with different online instrumentations and the structure calculated by means of structure models. A simple sintering model, based on the reduction of surface energy, is numerically quantified with the experimental results. The surface of the particles is strongly dependent on the primary particle size and the agglomerate structure. The chemical phase is analyzed using the offline techniques XANES, XRD, and EELS. It is observed that the addition of hydrogen led to a reduction of iron oxide to iron nanoparticles and to changes of the sintering kinetics. The sintering exponent (Formula presented.) = 1 was found to be optimal. For Fe, an activation energy (Formula presented.) of 59.15 kJ/mol and a pre-exponential factor (Formula presented.) of 1.57 104 s/m were found, for Fe3O4 an activation energy (Formula presented.) of 55.22 kJ/mol and a pre-exponential factor (Formula presented.) of 2.54 104 s/m. Copyright © 2022 American Association for Aerosol Research. © 2022 American Association for Aerosol Research.
    view abstractdoi: 10.1080/02786826.2022.2089011
  • 2022 • 421 Geminal C-Cl and Si-Cl bond activation of chloromethanes and chlorosilanes by gallanediyl LGa
    Helling, C. and Ganesamoorthy, C. and Wölper, C. and Schulz, S.
    Dalton Transactions 51 2050-2058 (2022)
    The activation of relatively inert E-X σ-bonds by low-valent main group metal complexes is receiving increasing interest. We here confirm the promising potential of gallanediyl LGa (L = HC[C(Me)N(Dip)]2, Dip = 2,6-i-Pr2C6H3) to activate E-Cl (E = C, Si) σ-bonds of group 14 element compounds. Equimolar reactions of LGa with chloromethanes and chlorosilanes EHxCl4-x (E = C, x = 0-2; E = Si, x = 0, 1) occurred with E-Cl bond insertion and formation of gallylmethanes and -silanes L(Cl)GaEHxCl3-x (E = C, x = 2 (1), 1 (2), 0 (3); E = Si, x = 1 (4)). In contrast, consecutive insertion into a geminal E-Cl bond was observed with two equivalents of LGa, yielding digallyl complexes [L(Cl)Ga]2EHxCl2-x (E = C, x = 2 (5); E = Si, x = 1 (6), 0 (7)). Compounds 1-7 were characterized by heteronuclear NMR (1H, 13C, 29Si (4, 6)), IR spectroscopy and elemental analysis, and their solid-state structures were determined by single-crystal X-ray diffraction (sc-XRD). © 2022 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/d1dt04192d
  • 2022 • 420 Heat Treatments of Metastable β Titanium Alloy Ti-24Nb-4Zr-8Sn Processed by Laser Powder Bed Fusion
    Hein, M. and Lopes Dias, N.F. and Pramanik, S. and Stangier, D. and Hoyer, K.-P. and Tillmann, W. and Schaper, M.
    Materials 15 (2022)
    Titanium alloys, especially β alloys, are favorable as implant materials due to their promising combination of low Young’s modulus, high strength, corrosion resistance, and biocompatibility. In particular, the low Young’s moduli reduce the risk of stress shielding and implant loosening. The processing of Ti-24Nb-4Zr-8Sn through laser powder bed fusion is presented. The specimens were heat-treated, and the microstructure was investigated using X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The mechanical properties were determined by hardness and tensile tests. The microstructures reveal a mainly β microstructure with α” formation for high cooling rates and α precipitates after moderate cooling rates or aging. The as-built and α” phase containing conditions exhibit a hardness around 225 HV5, yield strengths (YS) from 340 to 490 MPa, ultimate tensile strengths (UTS) around 706 MPa, fracture elongations around 20%, and Young’s moduli about 50 GPa. The α precipitates containing conditions reveal a hardness around 297 HV5, YS around 812 MPa, UTS from 871 to 931 MPa, fracture elongations around 12%, and Young’s moduli about 75 GPa. Ti-24Nb-4Zr-8Sn exhibits, depending on the heat treatment, promising properties regarding the material behavior and the opportunity to tailor the mechanical performance as a low modulus, high strength implant material. © 2022 by the authors. Licensee MDPI, Basel, Switzerland.
    view abstractdoi: 10.3390/ma15113774
  • 2022 • 419 Microstructure and residual stress evolution in nanocrystalline Cu-Zr thin films
    Chakraborty, J. and Oellers, T. and Raghavan, R. and Ludwig, A. and Dehm, G.
    Journal of Alloys and Compounds 896 (2022)
    Grazing incidence X-ray diffraction (GIXRD) and scanning transmission electron microscopy (STEM) combined with energy dispersive X-ray spectroscopy (EDS) were employed to study the microstructure evolution and stress development in the nanocrystalline Cu100−X-ZrX (2.5 at% ≤ x ≤ 5.5 at%) alloy thin films. Small Zr additions to Cu led to significant lattice parameter anisotropy in the as-deposited Cu-Zr thin films both due to macroscopic lattice strain and stacking faults in the Cu matrix. Strain free lattice parameters obtained after the XRD stress analysis of Cu-Zr thin films confirmed formation of a supersaturated substitutional Cu-Zr solid solution. For the first time, the study of film microstructure by XRD line profile analysis (XLPA) confirmed progressive generation of dislocations and planar faults with increasing Zr composition in Cu-Zr alloy films. These microstructural changes led to the generation of tensile stresses in the thin films along with considerable stress gradients across the films thicknesses which are quantified by the traditional dψhkl−Sin2ψ and GIXRD stress measurement methods. The origin of tensile stresses and stress gradients in the Cu-Zr film are discussed on the basis of film growth and heterogeneous microstructure with changing Zr composition. © 2021
    view abstractdoi: 10.1016/j.jallcom.2021.162799
  • 2022 • 418 Scaling and Confinement in Ultrathin Chalcogenide Films as Exemplified by GeTe
    Kerres, P. and Zhou, Y. and Vaishnav, H. and Raghuwanshi, M. and Wang, J. and Häser, M. and Pohlmann, M. and Cheng, Y. and Schön, C.-F. and Jansen, T. and Bellin, C. and Bürgler, D.E. and Jalil, A.R. and Ringkamp, C. and Kowalc...
    Small 18 (2022)
    Chalcogenides such as GeTe, PbTe, Sb2Te3, and Bi2Se3 are characterized by an unconventional combination of properties enabling a plethora of applications ranging from thermo-electrics to phase change materials, topological insulators, and photonic switches. Chalcogenides possess pronounced optical absorption, relatively low effective masses, reasonably high electron mobilities, soft bonds, large bond polarizabilities, and low thermal conductivities. These remarkable characteristics are linked to an unconventional bonding mechanism characterized by a competition between electron delocalization and electron localization. Confinement, that is, the reduction of the sample dimension as realized in thin films should alter this competition and modify chemical bonds and the resulting properties. Here, pronounced changes of optical and vibrational properties are demonstrated for crystalline films of GeTe, while amorphous films of GeTe show no similar thickness dependence. For crystalline films, this thickness dependence persists up to remarkably large thicknesses above 15 nm. X-ray diffraction and accompanying simulations employing density functional theory relate these changes to thickness dependent structural (Peierls) distortions, due to an increased electron localization between adjacent atoms upon reducing the film thickness. A thickness dependence and hence potential to modify film properties for all chalcogenide films with a similar bonding mechanism is expected. © 2022 The Authors. Small published by Wiley-VCH GmbH.
    view abstractdoi: 10.1002/smll.202201753
  • 2022 • 417 Selective 1,2 addition of polar X–H bonds to the Ga–P double bond of gallaphosphene L(Cl)GaPGaL
    Sharma, M.K. and Wölper, C. and Schulz, S.
    Dalton Transactions 51 1612-1616 (2022)
    Gallaphosphene L(Cl)GaPGaL 1 (L = HC[C(Me)N(2,6-i-Pr2-C6H3)]2) reacts at ambient temperature with a series of polar X–H bonds, i.e. ammonia, primary amines, water, phenol, thiophenol, and selenophenol, selectively with 1,2 addition at the polar Ga–P double bond. The gallium atom serves as electrophile and the phosphorous atom is protonated in all reactions. The resulting complexes L(Cl)GaP(H)Ga(X)L (X = NH22, NHi-Pr 3, NHPh 4, OH 5, OXyl 6, SPh 7, SePh 8) were characterized by IR and heteronuclear (1H, 13C{1H}, 31P{1H}) NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction. This journal is © The Royal Society of Chemistry
    view abstractdoi: 10.1039/d1dt04299h
  • 2022 • 416 Structurally characterised intermediate of the oxidative addition of a heteroleptic germylene to gallanediyle
    Bücker, A. and Wölper, C. and Haberhauer, G. and Schulz, S.
    Chemical Communications 58 9758-9761 (2022)
    Bond activation reactions using main group metal complexes are gaining increasing interest. We report on reactions of LGa (L = HC[C(Me)N(Ar)]2, Ar = Dipp = 2,6-i-Pr2C6H3,) with heteroleptic tetrylenes L′ECl (E = Ge, Sn; L′ = N(SiMe3)Ar), yielding the donor-acceptor complex LGa-Sn(Cl)L′ (1) or the oxidative addition product L(Cl)GaGeL′ (3). The reaction with DMPGeCl (DMP = 2,6-Mes2C6H3, Mes = 2,4,6-Me3C6H2) yielded LGa(μ-Cl)GeDMP (2), which represents an intermediate of the oxidative addition reaction. 1-3 were characterized by NMR and IR spectroscopy as well as by single crystal X-ray diffraction (sc-XRD), while their electronic nature was analyzed by quantum chemical calculations. © 2022 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/d2cc03561h
  • 2022 • 415 Synthesis and redox activity of carbene-coordinated group 13 metal radicals
    Li, B. and Geoghegan, B.L. and Weinert, H.M. and Wölper, C. and Cutsail, G.E. and Schulz, S.
    Chemical Communications 58 4372-4375 (2022)
    Carbenes are known to stabilize main group element compounds with unusual electronic properties. Herein, we report the synthesis of carbene-stabilized group 13 metal radicals (cAAC)MX2(IPr) (M = Al, X = Br 3; M = Ga, X = Cl 4) and the corresponding cations [(cAAC)MX2(IPr)][B(C6F5)4] (M = Al, X = Br 5; M = Ga, X = Cl 6), which were characterized spectroscopically and by sc-XRD. Quantum chemical calculation gave insights into their electronic structures. © 2022 The Royal Society of Chemistry
    view abstractdoi: 10.1039/d2cc00216g
  • 2022 • 414 Thermodynamics-guided alloy and process design for additive manufacturing
    Sun, Z. and Ma, Y. and Ponge, D. and Zaefferer, S. and Jägle, E.A. and Gault, B. and Rollett, A.D. and Raabe, D.
    Nature Communications 13 (2022)
    In conventional processing, metals go through multiple manufacturing steps including casting, plastic deformation, and heat treatment to achieve the desired property. In additive manufacturing (AM) the same target must be reached in one fabrication process, involving solidification and cyclic remelting. The thermodynamic and kinetic differences between the solid and liquid phases lead to constitutional undercooling, local variations in the solidification interval, and unexpected precipitation of secondary phases. These features may cause many undesired defects, one of which is the so-called hot cracking. The response of the thermodynamic and kinetic nature of these phenomena to high cooling rates provides access to the knowledge-based and tailored design of alloys for AM. Here, we illustrate such an approach by solving the hot cracking problem, using the commercially important IN738LC superalloy as a model material. The same approach could also be applied to adapt other hot-cracking susceptible alloy systems for AM. © 2022, The Author(s).
    view abstractdoi: 10.1038/s41467-022-31969-y
  • 2021 • 413 A bioinspired oxoiron(iv) motif supported on a N2S2macrocyclic ligand
    Deutscher, J. and Gerschel, P. and Warm, K. and Kuhlmann, U. and Mebs, S. and Haumann, M. and Dau, H. and Hildebrandt, P. and Apfel, U.-P. and Ray, K.
    Chemical Communications 57 2947-2950 (2021)
    A mononuclear oxoiron(iv) complex1-transbearing two equatorial sulfur ligations is synthesized and characterized as an active-site model of the elusive sulfur-ligated FeIVO intermediates in non-heme iron oxygenases. The introduction of sulfur ligands weakens the Fe-O bond and enhances the oxidative reactivity of the FeIVO unit with a diminished deuterium kinetic isotope effect, thereby providing a compelling rationale for nature's use of thecis-thiolate ligated oxoiron(iv) motif in key metabolic transformations. © The Royal Society of Chemistry 2021.
    view abstractdoi: 10.1039/d1cc00250c
  • 2021 • 412 Devitrification of thin film Cu–Zr metallic glass via ultrashort pulsed laser annealing
    Antonowicz, J. and Zalden, P. and Sokolowski-Tinten, K. and Georgarakis, K. and Minikayev, R. and Pietnoczka, A. and Bertram, F. and Chaika, M. and Chojnacki, M. and Dłużewski, P. and Fronc, K. and Greer, A.L. and Jastrzębski, ...
    Journal of Alloys and Compounds 887 (2021)
    In this work we report on an ultrashort pulsed laser annealing-driven devitrification of thin film Cu67Zr33 metallic glass characterized by micro-beam X-ray diffraction and electron microscopy techniques. The essential feature of ultrashort pulsed laser annealing is ultrafast heating (1014 K/s) by femtosecond optical excitation followed by extremely rapid cooling (1010–12 K/s) due to heat dissipation into the film substrate. During repetitive optical excitation, we take X-ray diffraction snapshots of the intermediate, frozen-in stages of the glass-crystal transformation to study its kinetics. A quantitative analysis of the diffraction patterns supported by electron microscopy result shows that the glass-crystal transformation proceeds by a rapid formation of an energetically favourable layer of crystalline ZrO2 on the free surface of the glassy film accompanied by nucleation and growth of fcc-Cu in the residual amorphous matrix. We demonstrate that at low effective annealing temperatures the devitrification kinetics of both products is correlated, while at high temperatures they decouple and ZrO2 forms an order of magnitude faster than Cu. © 2021 The Authors
    view abstractdoi: 10.1016/j.jallcom.2021.161437
  • 2021 • 411 In situ correlation between metastable phase-transformation mechanism and kinetics in a metallic glass
    Orava, J. and Balachandran, S. and Han, X. and Shuleshova, O. and Nurouzi, E. and Soldatov, I. and Oswald, S. and Gutowski, O. and Ivashko, O. and Dippel, A.-C. and Zimmermann, M. and Ivanov, Y.P. and Greer, A.L. and Raabe, D. and...
    Nature Communications 12 (2021)
    A combination of complementary high-energy X-ray diffraction, containerless solidification during electromagnetic levitation and transmission electron microscopy is used to map in situ the phase evolution in a prototype Cu-Zr-Al glass during flash-annealing imposed at a rate ranging from 102 to 103 K s−1 and during cooling from the liquid state. Such a combination of experimental techniques provides hitherto inaccessible insight into the phase-transformation mechanism and its kinetics with high temporal resolution over the entire temperature range of the existence of the supercooled liquid. On flash-annealing, most of the formed phases represent transient (metastable) states – they crystallographically conform to their equilibrium phases but the compositions, revealed by atom probe tomography, are different. It is only the B2 CuZr phase which is represented by its equilibrium composition, and its growth is facilitated by a kinetic mechanism of Al partitioning; Al-rich precipitates of less than 10 nm in a diameter are revealed. In this work, the kinetic and chemical conditions of the high propensity of the glass for the B2 phase formation are formulated, and the multi-technique approach can be applied to map phase transformations in other metallic-glass-forming systems. © 2021, The Author(s).
    view abstractdoi: 10.1038/s41467-021-23028-9
  • 2021 • 410 Unravelling the Zn-Cu Interaction during Activation of a Zn-promoted Cu/MgO Model Methanol Catalyst
    Pandit, L. and Boubnov, A. and Behrendt, G. and Mockenhaupt, B. and Chowdhury, C. and Jelic, J. and Hansen, A.-L. and Saraçi, E. and Ras, E.-J. and Behrens, M. and Studt, F. and Grunwaldt, J.-D.
    ChemCatChem 13 4120-4132 (2021)
    We report on an inverse model Cu/MgO methanol catalyst modified with 5 % zinc oxide at the Cu surface to element-specifically probe the interplay of metallic copper and zinc oxide during reductive activation. The structure of copper and zinc was unraveled by in situ X-ray diffraction (XRD) and in situ X-ray absorption spectroscopy (XAS) supported by theoretical modelling of the extended X-ray absorption fine structure and X-ray absorption near-edge structure spectra. Temperature-programmed reduction in H2 during in situ XAS showed that copper was reduced starting at 145 °C. With increasing reduction temperature, zinc underwent first a geometrical change in its structure, followed by reduction. The reduced zinc species were identified as surface alloy sites, which coexisted from 200 °C to 340 °C with ZnO species at the copper surface. At 400 °C Zn−Cu bulk-alloyed particles were formed. According to in situ XRD and in situ XAS, about half of the ZnO was not fully reduced, which can be explained by a lack of contact with copper. Our experimental results were further substantiated by density functional theory calculations, which verified that ZnO with neighboring Cu atoms reduced more easily. By combining these results, the distribution, phase and oxidation state of Zn species on Cu were estimated for the activated state of this model catalyst. This insight into the interplay of Cu and Zn forms the basis for deeper understanding the active sites during methanol synthesis. © 2021 The Authors. ChemCatChem published by Wiley-VCH GmbH
    view abstractdoi: 10.1002/cctc.202100692
  • 2020 • 409 Additive-free spin coating of tin oxide thin films: Synthesis, characterization and evaluation of tin β-ketoiminates as a new precursor class for solution deposition processes
    Huster, N. and Zanders, D. and Karle, S. and Rogalla, D. and Devi, A.
    Dalton Transactions 49 10755-10764 (2020)
    The fabrication of SnOx in thin film form via chemical solution deposition (CSD) processes is favored over vacuum based techniques as it is cost effective and simpler. The precursor employed plays a central role in defining the process conditions for CSD. Particularly for processing SnO2 layers that are appealing for sensor or electronic applications, there are limited precursors available for CSD. Thus the focus of this work was to develop metalorganic precursors for tin, based on the ketoiminate ligand class. By systematic molecular engineering of the ligand periphery, a series of new homoleptic Sn(ii) β-ketoiminate complexes was synthesized, namely bis[4-(2-methoxyethylimino)-3-pentanonato] tin, [Sn(MEKI)2] (1), bis[4-(2-ethoxyethylimino)-2-pentanonato] tin, [Sn(EEKI)2] (2), bis[4-(3-methoxypropylimino)-2-pentanonato] tin, [Sn(MPKI)2] (3), bis[4-(3-ethoxypropylimino)-2-pentanonato] tin, [Sn(EPKI)2] (4) and bis[4-(3-isopropoxypropylimino)-2-pentanonato] tin, [Sn(iPPKI)2] (5). All these N-side-chain ether functionalized compounds were analyzed by nuclear magnetic resonance (NMR) spectroscopy, electron impact mass spectrometry (EI-MS), elemental analysis (EA) and thermogravimetric analysis (TGA). The solid state molecular structure of [Sn(MPKI)2] (3) was eludicated by means of single crystal X-ray diffraction (SCXRD). Interestingly, this class of compounds features excellent solubility and stability in common organic solvents alongside good reactivity towards H2O and low decomposition temperatures, thus fulfilling the desired requirements for CSD of tin oxides. With compound 3 as a representative example, we have demonstrated the possibility to directly deposit SnOx layers via hydrolysis upon exposure to air followed by heat treatment under oxygen at moderate temperatures and most importantly without the need for any additive that is generally used in CSD. A range of complementary analytical methods were employed, namely X-ray diffraction (XRD), Rutherford backscattering spectrometry (RBS), nuclear reaction analysis (NRA), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) to analyse the structure, morphology and composition of the SnOx layers. This journal is © The Royal Society of Chemistry.
    view abstractdoi: 10.1039/d0dt01463j
  • 2020 • 408 An aminotetracyanocyclopentadienide system: Light-induced formation of a thermally stable cyclopentadienyl radical
    Nimax, P.R. and Zoller, F. and Blockhaus, T. and Küblböck, T. and Fattakhova-Rohlfing, D. and Sünkel, K.
    New Journal of Chemistry 44 72-78 (2020)
    Crystals of the aminotetracyanocyclopentadienyl radical were obtained from the reaction of CaCl2 with Ag[C5(CN)4(NH2)] and recrystallization in MeOH, performed in sunlight. The radical was characterized by X-ray diffraction, EPR and UV Vis spectroscopy as well as by cyclovoltammetry and DFT calculations. © 2019 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
    view abstractdoi: 10.1039/c9nj04354c
  • 2020 • 407 Identifying the nature of the active sites in methanol synthesis over Cu/ZnO/Al2O3 catalysts
    Laudenschleger, D. and Ruland, H. and Muhler, M.
    Nature Communications 11 (2020)
    The heterogeneously catalysed reaction of hydrogen with carbon monoxide and carbon dioxide (syngas) to methanol is nearly 100 years old, and the standard methanol catalyst Cu/ZnO/Al2O3 has been applied for more than 50 years. Still, the nature of the Zn species on the metallic Cu0 particles (interface sites) is heavily debated. Here, we show that these Zn species are not metallic, but have a positively charged nature under industrial methanol synthesis conditions. Our kinetic results are based on a self-built high-pressure pulse unit, which allows us to inject selective reversible poisons into the syngas feed passing through a fixed-bed reactor containing an industrial Cu/ZnO/Al2O3 catalyst under high-pressure conditions. This method allows us to perform surface-sensitive operando investigations as a function of the reaction conditions, demonstrating that the rate of methanol formation is only decreased in CO2-containing syngas mixtures when pulsing NH3 or methylamines as basic probe molecules. © 2020, The Author(s).
    view abstractdoi: 10.1038/s41467-020-17631-5
  • 2020 • 406 Influences of Cr Content on the Phase Transformation Properties and Stress Change in V-Cr-O Thin-Film Libraries
    Wang, X. and Suhr, E. and Banko, L. and Salomon, S. and Ludwig, Al.
    ACS Applied Electronic Materials 2 1176-1183 (2020)
    VO2-based thin-film libraries with a continuous composition spread of Cr were obtained by reactive cosputtering. Gradual changes in the crystalline structures of VO2 were observed in the thin-film libraries at room temperature as the M1 phase exists for Cr < 1.2 at. %, the M2 phase for Cr > 4.2 at. %, and the T phase in between. Although X-ray diffraction indicates that only VO2 phases exist in the library, X-ray photoelectron spectroscopy reveals an increased V5+/V4+ ratio with increasing Cr content along the V-Cr-O library. A V-Cr-O phase diagram was assessed based on the results of temperature-dependent X-ray diffraction of the libraries. Microstructures of the V-Cr-O libraries were studied by scanning electron microscopy and atomic force microscopy. High-throughput temperature-dependent electrical resistance [R(T)] and stress [σ(T)] measurements were performed on the V-Cr-O libraries to systematically study the influence of Cr on the transformation properties. The transformation temperature Tc was increased by 4.9 K/at. % in the composition range 2.8 at. % < Cr < 7.3 at. % and by 1.2 K/at. % for Cr > 7.3 at. %. The resistance change across the phase transformation was decreased from 3 to 1 order of magnitude with Cr content increasing from 1.1 at. % up to 12.6 at. %, and the R(T) curves became less abrupt. The addition of Cr increased the stress change across the phase transformation up to 1.3 GPa for a Cr content of 3.3 at. %. However, for increased Cr contents from 3.3 to 9 at. %, the stress change decreased to 380 MPa. This could be because of the increased fraction of an O-rich VOx phase in the films and a changed crystallographic orientation for Cr-rich V-Cr-O. Copyright © 2020 American Chemical Society.
    view abstractdoi: 10.1021/acsaelm.0c00256
  • 2020 • 405 Photo-switching and -cyclisation of hydrogen bonded liquid crystals based on resveratrol
    Blanke, M. and Balszuweit, J. and Saccone, M. and Wölper, C. and Doblas Jiménez, D. and Mezger, M. and Voskuhl, J. and Giese, M.
    Chemical Communications 56 1105-1108 (2020)
    A series of hydrogen-bonded liquid crystals based on resveratrol and resveratrone is reported and investigated with respect to their photo-switchability (at 405 nm) and photo-cyclisation (at 300 nm). © 2020 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c9cc07721a
  • 2020 • 404 Sintering and biocompatibility of blended elemental Ti-xNb alloys
    Chen, Y. and Han, P. and Dehghan-Manshadi, A. and Kent, D. and Ehtemam-Haghighi, S. and Jowers, C. and Bermingham, M. and Li, T. and Cooper-White, J. and Dargusch, M.S.
    Journal of the Mechanical Behavior of Biomedical Materials 104 (2020)
    Titanium-niobium (Ti–Nb) alloys have great potential for biomedical applications due to their superior biocompatibility and mechanical properties that match closely to human bone. Powder metallurgy is an ideal technology for efficient manufacture of titanium alloys to generate net-shape, intricately featured and porous components. This work reports on the effects of Nb concentrations on sintered Ti-xNb alloys with the aim to establish an optimal composition in respect to mechanical and biological performances. Ti-xNb alloys with 33, 40, 56 and 66 wt% Nb were fabricated from elemental powders and the sintering response, mechanical properties, microstructures and biocompatibility assessed and compared to conventional commercial purity titanium (CPTi). The sintered densities for all Ti-xNb compositions were around 95%, reducing slightly with increasing Nb due to increasing open porosity. Higher Nb levels retarded sintering leading to more inhomogeneous phase and pore distributions. The compressive strength decreased with increasing Nb, while all Ti-xNb alloys displayed higher strengths than CPTi except the Ti–66Nb alloy. The Young's moduli of the Ti-xNb alloys with ≥40 wt% Nb were substantially lower (30–50%) than CPTi. In-vitro cell culture testing revealed excellent biocompatibility for all Ti-xNb alloys comparable or better than tissue culture plate and CPTi controls, with the Ti–40Nb alloy exhibiting superior cell-material interactions. In view of its mechanical and biological performance, the Ti–40Nb composition is most promising for hard tissue engineering applications. © 2020
    view abstractdoi: 10.1016/j.jmbbm.2020.103691
  • 2020 • 403 Soft X-ray diffraction patterns measured by a LiF detector with sub-micrometre resolution and an ultimate dynamic range
    Makarov, S. and Pikuz, S. and Ryazantsev, S. and Pikuz, T. and Buzmakov, A. and Rose, M. and Lazarev, S. and Senkbeil, T. and Von Gundlach, A. and Stuhr, S. and Rumancev, C. and Dzhigaev, D. and Skopintsev, P. and Zaluzhnyy, I. an...
    Journal of Synchrotron Radiation 27 625-632 (2020)
    The unique diagnostic possibilities of X-ray diffraction, small X-ray scattering and phase-contrast imaging techniques applied with high-intensity coherent X-ray synchrotron and X-ray free-electron laser radiation can only be fully realized if a sufficient dynamic range and/or spatial resolution of the detector is available. In this work, it is demonstrated that the use of lithium fluoride (LiF) as a photoluminescence (PL) imaging detector allows measuring of an X-ray diffraction image with a dynamic range of ∼107 within the sub-micrometre spatial resolution. At the PETRA III facility, the diffraction pattern created behind a circular aperture with a diameter of 5μm irradiated by a beam with a photon energy of 500eV was recorded on a LiF crystal. In the diffraction pattern, the accumulated dose was varied from 1.7 × 105Jcm-3 in the central maximum to 2 × 10-2Jcm-3 in the 16th maximum of diffraction fringes. The period of the last fringe was measured with 0.8μm width. The PL response of the LiF crystal being used as a detector on the irradiation dose of 500eV photons was evaluated. For the particular model of laser-scanning confocal microscope Carl Zeiss LSM700, used for the readout of the PL signal, the calibration dependencies on the intensity of photopumping (excitation) radiation (λ = 488nm) and the gain have been obtained. © 2020. J. Synchrotron Rad.
    view abstractdoi: 10.1107/S1600577520002192
  • 2020 • 402 Synthesis of Bis-BINOL Derivatives: Linking via the 3-, 4-, or 5-Position by Generation of Suitable C 1 -Symmetric Precursors
    Kohlhaas, M. and Lutz, F. and Paransothy, N. and Octa-Smolin, F. and Wölper, C. and Niemeyer, J.
    Synthesis (Germany) 52 853-860 (2020)
    Bis-BINOL derivatives have proven highly useful in applications such as chemosensing or organocatalysis. In this account, we describe strategies for the linking of BINOL units via the 3-, 4-, or 5-positions, showing that unique synthetic strategies are necessary to address each position. We report the synthesis of suitable C 1 -symmetric precursors, which are generated either by monohalogenation or by monodeprotection of C 2 -symmetric starting materials, and their subsequent coupling to give linked bis-BINOL derivatives. © 2020 American Institute of Physics Inc.. All rights reserved.
    view abstractdoi: 10.1055/s-0039-1690763
  • 2019 • 401 Ag-Functionalized CuWO4/WO3 nanocomposites for solar water splitting
    Salimi, R. and Sabbagh Alvani, A.A. and Mei, B.T. and Naseri, N. and Du, S.F. and Mul, G.
    New Journal of Chemistry 43 2196-2203 (2019)
    Ag-Functionalized CuWO4/WO3 heterostructures were successfully prepared via a polyvinyl pyrrolidone (PVP)-assisted sol-gel (PSG) route. Thin films prepared via electrophoretic deposition were used as photoanodes for photoelectrochemical (PEC) water splitting. Compared to pristine CuWO4 and WO3 films, a significant enhancement of the photocurrent (3-4 times) at the thermodynamic potential for oxygen evolution (0.62 V vs. Ag/AgCl, pH 7) was obtained for the Ag-functionalized CuWO4/WO3 photoanodes. The obtained enhancement is shown to be derived from a synergic contribution of heterostructure formation (CuWO4/WO3) and improvements of light utilization by Ag-induced surface plasmon resonance (SPR) effects. Accordingly, a photocurrent of 0.205 mA cm-2 at 0.62 V vs. Ag/AgCl under neutral conditions (without hole scavengers) under front-side simulated AM1.5G illumination was achieved. A detailed analysis of the obtained PEC data alongside performed impedance measurements suggests that charge seperation is significantly improved for the prepared Ag-functionalized CuWO4/WO3 photoanodes. Our work offers beneficial insights to design new plasmonic metal/heterostructured nanocomposites for energy conversion applications. © 2019 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
    view abstractdoi: 10.1039/c8nj05625k
  • 2019 • 400 Alkyloxy modified pyrene fluorophores with tunable photophysical and crystalline properties
    Kapf, A. and Eslahi, H. and Blanke, M. and Saccone, M. and Giese, M. and Albrecht, M.
    New Journal of Chemistry 43 6361-6371 (2019)
    Novel alkyloxy modified 2,7-di-tert-butyl-4,5,9,10-tetra(arylethynyl)pyrenes were prepared through a straightforward Sonogashira coupling approach. Optical properties such as quantum yields and absorption/emission spectra of the fluorophores were investigated by UV/Vis and fluorescence measurements. Aggregation induced excimer formation of the chromophores in polar solvents and in the solid state was proved by the presence of a characteristic bathochromically shifted emission band and a decrease of the emission capability. These results strongly indicate the unexpected observation that the excimer formation of adjacent pyrene rings is not prevented by the introduction of bulky tert-butyl substituents. Single-crystal X-ray and computational analyses reveal the co-planar alignment of adjacent molecules and the presence of π-π-stacking in the molecular packing of the pyrene polyaromatics. Furthermore, fluorescence, DSC and POM measurements indicate that the aggregation behaviour, the thermal characteristics and the crystalline properties are significantly influenced by changing structural features of the attached functional groups at the periphery of the pyrene core. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
    view abstractdoi: 10.1039/c9nj00652d
  • 2019 • 399 Cold spray deposition of Cr2AlC MAX phase for coatings and bond-coat layers
    Go, T. and Sohn, Y.J. and Mauer, G. and Vaßen, R. and Gonzalez-Julian, J.
    Journal of the European Ceramic Society 39 860-867 (2019)
    Highly pure Cr2AlC powders were synthesized and deposited for the first time by cold spray technology on stainless steel substrates. The Cr2AlC coatings were relative dense, up to 91%, and present high purity (&gt; 98%) since only small traces of Cr2Al, Al2O3 and Cr2O3 were detected by XRD, SEM and EDX. The microstructure of the coatings is homogeneous, although some preferential orientation in the basal plane was observed by XRD pole figures. The adhesion between the coating and the substrate is strong, and compressive residual stresses up to 300 MPa in the coating were determined by XRD. Furthermore, a conventional YSZ Thermal Barrier Coating (TBCs) was deposited by Atmospheric Plasma Spray (APS) on top of the cold sprayed Cr2AlC coating in order to demonstrate the processing feasibility of Cr2AlC MAX phases as a bond-coat layer. © 2018 Elsevier Ltd
    view abstractdoi: 10.1016/j.jeurceramsoc.2018.11.035
  • 2019 • 398 Dual-source evaporation of silver bismuth iodide films for planar junction solar cells
    Khazaee, M. and Sardashti, K. and Chung, C.-C. and Sun, J.-P. and Zhou, H. and Bergmann, E. and Dunlap-Shohl, W.A. and Han, Q. and Hill, I.G. and Jones, J.L. and Lupascu, D.C. and Mitzi, D.B.
    Journal of Materials Chemistry A 7 2095-2105 (2019)
    Non-toxic and air-stable silver bismuth iodide semiconductors are promising light absorber candidates for photovoltaic applications owing to a suitable band gap for multi- or single-junction solar cells. Recently, solution-based film fabrication approaches for several silver bismuth iodide stoichiometries have been investigated. The current work reports on a facile and reproducible two-step coevaporation/annealing approach to deposit compact and pinhole-free films of AgBi 2 I 7 , AgBiI 4 and Ag 2 BiI 5 . X-ray diffraction (XRD) in combination with scanning electron microscopy (SEM)/energy-dispersive X-ray spectroscopy (EDX) analysis reveals formation of pure cubic (Fd3m) phase AgBi 2 I 7 , cubic (Fd3m) or rhombohedra (R3m) phase AgBiI 4 , each with &gt;3 μm average grain size, or the rhombohedral phase (R3m) Ag 2 BiI 5 with &gt;200 nm average grain size. A phase transition from rhombohedral to cubic structure is investigated via temperature-dependent X-ray diffraction (TD-XRD). Planar-junction photovoltaic (PV) devices are prepared based on the coevaporated rhombohedral AgBiI 4 films, with titanium dioxide (TiO 2 ) and poly(3-hexylthiophene) (P3HT) as electron- and hole-transport layers, respectively. The best-performing device exhibited a power conversion efficiency (PCE) of as high as 0.9% with open-circuit voltage (V OC ) &gt; 0.8 V in the reverse scan direction (with significant hysteresis). © 2019 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c8ta08679f
  • 2019 • 397 Engineering atomic-level complexity in high-entropy and complex concentrated alloys
    Oh, H.S. and Kim, S.J. and Odbadrakh, K. and Ryu, W.H. and Yoon, K.N. and Mu, S. and Körmann, F. and Ikeda, Y. and Tasan, C.C. and Raabe, D. and Egami, T. and Park, E.S.
    Nature Communications 10 (2019)
    Quantitative and well-targeted design of modern alloys is extremely challenging due to their immense compositional space. When considering only 50 elements for compositional blending the number of possible alloys is practically infinite, as is the associated unexplored property realm. In this paper, we present a simple property-targeted quantitative design approach for atomic-level complexity in complex concentrated and high-entropy alloys, based on quantum-mechanically derived atomic-level pressure approximation. It allows identification of the best suited element mix for high solid-solution strengthening using the simple electronegativity difference among the constituent elements. This approach can be used for designing alloys with customized properties, such as a simple binary NiV solid solution whose yield strength exceeds that of the Cantor high-entropy alloy by nearly a factor of two. This study provides general design rules that enable effective utilization of atomic level information to reduce the immense degrees of freedom in compositional space without sacrificing physics-related plausibility. © 2019, The Author(s).
    view abstractdoi: 10.1038/s41467-019-10012-7
  • 2019 • 396 Femtosecond x-ray diffraction reveals a liquid–liquid phase transition in phase-change materials
    Zalden, P. and Quirin, F. and Schumacher, M. and Siegel, J. and Wei, S. and Koc, A. and Nicoul, M. and Trigo, M. and Andreasson, P. and Enquist, H. and Shu, M.J. and Pardini, T. and Chollet, M. and Zhu, D. and Lemke, H. and Ronneb...
    Science 364 1062-1067 (2019)
    In phase-change memory devices, a material is cycled between glassy and crystalline states. The highly temperature-dependent kinetics of its crystallization process enables application in memory technology, but the transition has not been resolved on an atomic scale. Using femtosecond x-ray diffraction and ab initio computer simulations, we determined the time-dependent pair-correlation function of phase-change materials throughout the melt-quenching and crystallization process. We found a liquid–liquid phase transition in the phase-change materials Ag4In3Sb67Te26 and Ge15Sb85 at 660 and 610 kelvin, respectively. The transition is predominantly caused by the onset of Peierls distortions, the amplitude of which correlates with an increase of the apparent activation energy of diffusivity. This reveals a relationship between atomic structure and kinetics, enabling a systematic optimization of the memory-switching kinetics. 2017 © The Authors, some rights reserved
    view abstractdoi: 10.1126/science.aaw1773
  • 2019 • 395 Hydroxyapatite nanowires rich in [Ca-O-P] sites for ethanol direct coupling showing high C6-12 alcohol yield
    Wang, Q.-N. and Zhou, B.-C. and Weng, X.-F. and Lv, S.-P. and Schüth, F. and Lu, A.-H.
    Chemical Communications 55 10420-10423 (2019)
    Herein, we have shown that the [Ca-O-P] sites exposed on hydroxyapatite are clearly responsible for C-C formation in ethanol direct-coupling, and their high density accelerates the C-C coupling rate and boosts C6-12 alcohol production. Notably, nanowire-like hydroxyapatite exhibited 30.4% selectivity to n-butanol and 63.9% selectivity to C6-12OH at a conversion of 45.7% at 325 °C, and thereby close to 30% yield of C6-12OH, which is greatly higher than that using the state-of-the-art catalysts (6%). © 2019 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c9cc05454e
  • 2019 • 394 Phase Formation during Heat Treatment of Zn- and ZnAlMg-Coated Steels at 400 and 750 °C
    Windmann, M. and Barthen, M. and Opitz, T. and Hahn, I. and Röttger, A. and Theisen, W.
    Steel Research International (2019)
    In contrast to a cold-forming process, a tempered forming process is able to deform high-strength steel used for manufacturing automotive bodyworks in a more economic manner. Cold-formed steel sheets are commonly coated with a Zn or ZnAlMg layer for cathodic corrosion protection. The tempering process would lead to diffusion processes at the steel/coating interface, which is accompanied by the formation of new phases in the coatings. This publication focuses on phase formation in Zn and ZnAlMg coatings on steel sheets, which are heat-treated at 400 and 750 °C. the authors find that the pure Zn coating remains in the solid state and transforms into the intermetallic δ phase (FeZn 10 ) during heat treatment at 400 °C. The coating melts during heating to 750 °C, but remains in the solid state after transformation into the Γ phase (Fe 4 Zn 9 ) and α-Fe. In the ZnAlMg coating, minor iron diffusion occurs at a temperature of 400 °C. Within a dwell time of 600 s, intermetallic Fe–Zn phases are not formed. During heat treatment at 750 °C, phase formation in the ZnAlMg coating is very similar to that in the pure Zn coating, during which Γ (Fe 4 Zn 9 ) and α-Fe are formed. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/srin.201800588
  • 2019 • 393 Retrofitting metal-organic frameworks
    Schneider, C. and Bodesheim, D. and Keupp, J. and Schmid, R. and Kieslich, G.
    Nature Communications 10 (2019)
    The post-synthetic installation of linker molecules between open-metal sites (OMSs) and undercoordinated metal-nodes in a metal-organic framework (MOF) — retrofitting — has recently been discovered as a powerful tool to manipulate macroscopic properties such as the mechanical robustness and the thermal expansion behavior. So far, the choice of cross linkers (CLs) that are used in retrofitting experiments is based on qualitative considerations. Here, we present a low-cost computational framework that provides experimentalists with a tool for evaluating various CLs for retrofitting a given MOF system with OMSs. After applying our approach to the prototypical system CL@Cu3BTC2 (BTC = 1,3,5-benzentricarboxylate) the methodology was expanded to NOTT-100 and NOTT-101 MOFs, identifying several promising CLs for future CL@NOTT-100 and CL@NOTT-101 retrofitting experiments. The developed model is easily adaptable to other MOFs with OMSs and is set-up to be used by experimentalists, providing a guideline for the synthesis of new retrofitted MOFs with modified physicochemical properties. © 2019, The Author(s).
    view abstractdoi: 10.1038/s41467-019-12876-1
  • 2019 • 392 Tailored microstructures of gadolinium zirconate/YSZ multi-layered thermal barrier coatings produced by suspension plasma spray: Durability and erosion testing
    Mahade, S. and Zhou, D. and Curry, N. and Markocsan, N. and Nylén, P. and Vaßen, R.
    Journal of Materials Processing Technology 264 283-294 (2019)
    This work employed an axial suspension plasma spray (SPS) process to deposit two different gadolinium zirconate (GZ) based triple layered thermal barrier coatings (TBCs). The first was a ‘layered’ TBC (GZ dense/GZ/YSZ) where the base layer was YSZ, intermediate layer was a relatively porous GZ and the top layer was a relatively dense GZ. The second triple layered TBC was a ‘composite’ TBC (GZ dense/GZ + YSZ/YSZ) comprising of an YSZ base layer, a GZ + YSZ intermediate layer and a dense GZ top layer. The as sprayed TBCs (layered and composite) were characterized using SEM/EDS and XRD. Two different methods (water intrusion and image analysis) were used to measure the porosity content of the as sprayed TBCs. Fracture toughness measurements were made on the intermediate layers (GZ + YSZ layer of the composite TBC and porous GZ layer of the layered TBC respectively) using micro indentation tests. The GZ + YSZ layer in the composite TBC was shown to have a slightly higher fracture toughness than the relatively porous GZ layer in the layered TBC. Erosion performance of the as sprayed TBCs was evaluated at room temperature where the composite TBC showed higher erosion resistance than the layered TBC. However, in the burner rig test conducted at 1400 °C, the layered TBC showed higher thermal cyclic lifetime than the composite TBC. Failure analysis of the thermally cycled and eroded TBCs was performed using SEM and XRD. © 2018 Elsevier B.V.
    view abstractdoi: 10.1016/j.jmatprotec.2018.09.016
  • 2019 • 391 Tuning the charge flow between Marcus regimes in an organic thin-film device
    Atxabal, A. and Arnold, T. and Parui, S. and Hutsch, S. and Zuccatti, E. and Llopis, R. and Cinchetti, M. and Casanova, F. and Ortmann, F. and Hueso, L.E.
    Nature Communications 10 (2019)
    Marcus’s theory of electron transfer, initially formulated six decades ago for redox reactions in solution, is now of great importance for very diverse scientific communities. The molecular scale tunability of electronic properties renders organic semiconductor materials in principle an ideal platform to test this theory. However, the demonstration of charge transfer in different Marcus regions requires a precise control over the driving force acting on the charge carriers. Here, we make use of a three-terminal hot-electron molecular transistor, which lets us access unconventional transport regimes. Thanks to the control of the injection energy of hot carriers in the molecular thin film we induce an effective negative differential resistance state that is a direct consequence of the Marcus Inverted Region. © 2019, The Author(s).
    view abstractdoi: 10.1038/s41467-019-10114-2
  • 2018 • 390 From Quasicrystals to Crystals with Interpenetrating Icosahedra in Ca-Au-Al: In Situ Variable-Temperature Transformation
    Pham, J. and Meng, F. and Lynn, M.J. and Ma, T. and Kreyssig, A. and Kramer, M.J. and Goldman, A.I. and Miller, G.J.
    Journal of the American Chemical Society 140 1337-1347 (2018)
    The irreversible transformation from an icosahedral quasicrystal (i-QC) CaAu4.39Al1.61 to its cubic 2/1 crystalline approximant (CA) Ca13Au56.31(3)Al21.69 (CaAu4.33(1)Al1.67, Pa3 (No. 205); Pearson symbol: cP728; a = 23.8934(4)), starting at ∼570 °C and complete by ∼650 °C, is discovered from in situ, high-energy, variable-temperature powder X-ray diffraction (PXRD), thereby providing direct experimental evidence for the relationship between QCs and their associated CAs. The new cubic phase crystallizes in a Tsai-type approximant structure under the broader classification of polar intermetallic compounds, in which atoms of different electronegativities, viz., electronegative Au + Al vs electropositive Ca, are arranged in concentric shells. From a structural chemical perspective, the outermost shell of this cubic approximant may be described as interpenetrating and edge-sharing icosahedra, a perspective that is obtained by splitting the traditional structural description of this shell as a 92-atom rhombic triacontahedron into an 80-vertex cage of primarily Au [Au59.86(2)Al17.14□3.00] and an icosahedral shell of only Al [Al10.5□1.5]. Following the proposal that the cubic 2/1 CA approximates the structure of the i-QC and on the basis of the observed transformation, an atomic site analysis of the 2/1 CA, which shows a preference to maximize the number of heteroatomic Au-Al nearest neighbor contacts over homoatomic Al-Al contacts, implies a similar outcome for the i-QC structure. Analysis of the most intense reflections in the diffraction pattern of the cubic 2/1 CA that changed during the phase transformation shows correlations with icosahedral symmetry, and the stability of this cubic phase is assessed using valence electron counts. According to electronic structure calculations, a cubic 1/1 CA, "Ca24Au88Al64" (CaAu3.67Al2.67) is proposed. © 2017 American Chemical Society.
    view abstractdoi: 10.1021/jacs.7b10358
  • 2018 • 389 From stable Sb- and Bi-centered radicals to a compound with a Ga=Sb double bond
    Ganesamoorthy, C. and Helling, C. and Wölper, C. and Frank, W. and Bill, E. and Cutsail, G.E. and Schulz, S.
    Nature Communications 9 (2018)
    Neutral stibinyl and bismuthinyl radicals are typically short-lived, reactive species. Here we show the synthesis and solid-state structures of two stable stibinyl [L(Cl)Ga]2Sb· 1 and bismuthinyl radicals [L(I)Ga]2Bi· 4, which are stabilized by electropositive metal centers. Their description as predominantly metal-centered radicals is consistent with the results of NMR, EPR, SQUID, and DFT studies. The Lewis-acidic character of the Ga ligands allow for significant electron delocalization of the Sb- and Bi- unpaired radical onto the ligand. Single-electron reduction of [L(Cl)Ga]2Sb· gave LGaSbGa(Cl)L 5, the first compound containing a Ga=Sb double bond. The π-bonding contribution is estimated to 9.56 kcal mol-1 by NMR spectroscopy. The bonding situation and electronic structure is analyzed by quantum mechanical computations, revealing significant π backdonation from the Sb to the Ga atom. The formation of 5 illustrates the high-synthetic potential of 1 for the formation of new compounds with unusual electronic structures. © 2017 The Author(s).
    view abstractdoi: 10.1038/s41467-017-02581-2
  • 2018 • 388 Hardness and modulus of Fe2B, Fe3(C,B), and Fe23(C,B)6 borides and carboborides in the Fe-C-B system
    Lentz, J. and Röttger, A. and Theisen, W.
    Materials Characterization 135 192-202 (2018)
    This work provides a comparative and comprehensive study of the indentation hardness and indentation modulus of iron-rich borides and carboborides of types Fe2B, Fe3(C,B), and Fe23(C,B)6. In addition, the hardness and elastic modulus of Cr-rich M7C are investigated for comparative purposes. We investigated the impact of increasing B content and indentation size effect (ISE). The phases of interest were stabilized in cast Fe-C-B alloys that varied with respect to the B / (B + C) ratio and heat treatment. The resulting microstructures were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), and wavelength X-ray spectroscopy (WDS). Dynamic in-situ nanoindentation experiments based on the method of continuous stiffness measurement (CSM) were coupled to SEM and EBSD investigations to determine the mechanical properties of the individual borides and carboborides as a function of the indentation depth. The results were compared to values obtained for the Cr-rich M7C3 carbide. It was found that the hardness of the B-rich Fe3(C,B) phase is considerably higher than pure Fe3C and increases with increasing B content. The ISE was present in all investigated phases, and the hardness decreased as a function of indentation depth. The hardness at infinite indentation depth H0 was estimated according to the model of Nix and Gao. The Fe2B phase was found to be the hardest phase (H0 = 19.04 GPa), followed by M7C3 (H0 = 16.43 GPa), Fe3(C,B) (H0 = 11.18 to 12.24 GPa), and Fe23(C,B)6 (H0 = 10.39 GPa). © 2017 Elsevier Inc.
    view abstractdoi: 10.1016/j.matchar.2017.11.012
  • 2018 • 387 In situ atomic-scale observation of oxidation and decomposition processes in nanocrystalline alloys
    Guo, J. and Haberfehlner, G. and Rosalie, J. and Li, L. and Duarte, M.J. and Kothleitner, G. and Dehm, G. and He, Y. and Pippan, R. and Zhang, Z.
    Nature Communications 9 (2018)
    Oxygen contamination is a problem which inevitably occurs during severe plastic deformation of metallic powders by exposure to air. Although this contamination can change the morphology and properties of the consolidated materials, there is a lack of detailed information about the behavior of oxygen in nanocrystalline alloys. In this study, aberration-corrected high-resolution transmission electron microscopy and associated techniques are used to investigate the behavior of oxygen during in situ heating of highly strained Cu-Fe alloys. Contrary to expectations, oxide formation occurs prior to the decomposition of the metastable Cu-Fe solid solution. This oxide formation commences at relatively low temperatures, generating nanosized clusters of firstly CuO and later Fe2O3. The orientation relationship between these clusters and the matrix differs from that observed in conventional steels. These findings provide a direct observation of oxide formation in single-phase Cu-Fe composites and offer a pathway for the design of nanocrystalline materials strengthened by oxide dispersions. © 2018 The Author(s).
    view abstractdoi: 10.1038/s41467-018-03288-8
  • 2018 • 386 Low-temperature MOCVD deposition of Bi2Te3 thin films using Et2BiTeEt as single source precursor
    Bendt, G. and Gassa, S. and Rieger, F. and Jooss, C. and Schulz, S.
    Journal of Crystal Growth 490 77-83 (2018)
    Et2BiTeEt was used as single source precursor for the deposition of Bi2Te3 thin films on Si(1 0 0) substrates by metal organic chemical vapor deposition (MOCVD) at very low substrate temperatures. Stoichiometric and crystalline Bi2Te3 films were grown at 230 °C, which is approximately 100 °C lower compared to conventional MOCVD processes using one metal organic precursors for each element. The Bi2Te3 films were characterized using scanning electron microscopy, high-resolution transmission electron microscopy and X-ray diffraction. The elemental composition of the films, which was determined by energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy, was found to be strongly dependent of the substrate temperature. © 2018 Elsevier B.V.
    view abstractdoi: 10.1016/j.jcrysgro.2018.03.021
  • 2018 • 385 Microstructure and mechanical properties in the thin film system Cu-Zr
    Oellers, T. and Raghavan, R. and Chakraborty, J. and Kirchlechner, C. and Kostka, A. and Liebscher, C.H. and Dehm, G. and Ludwig, Al.
    Thin Solid Films 645 193-202 (2018)
    A composition-spread Cu-Zr thin film library with Zr contents from 2.5 up to 6.5 at.% was synthesized by magnetron sputtering on a thermally oxidized Si wafer. The compositional and microstructural variations of the Cu-Zr thin film across the composition gradient were examined using energy dispersive X-ray spectroscopy, X-ray diffraction, and high-resolution scanning and transmission electron microscopy of cross-sections fabricated by focused ion beam milling. Composition-dependent hardness and elastic modulus values were obtained by nanoindentation for measurement areas with discrete Zr contents along the composition gradient. Similarly, the electrical resistivity was investigated by 4-point resistivity measurements to study the influence of Zr composition and microstructural changes in the thin film. Both, the mechanical and electrical properties reveal a significant increase in hardness and resistivity with increasing Zr content. The trends of the mechanical and functional properties are discussed with respect to the local microstructure and composition of the thin film library. © 2017
    view abstractdoi: 10.1016/j.tsf.2017.10.030
  • 2018 • 384 Molecular engineering of Ga-ketoiminates: Synthesis, structure and evaluation as precursors for the additive-free spin-coated deposition of gallium oxide thin films
    O'Donoghue, R. and Rahman, S. and Mallick, B. and Winter, M. and Rogalla, D. and Becker, H.-W. and Devi, A.
    New Journal of Chemistry 42 3196-3210 (2018)
    A series of new homo- and heteroleptic gallium ketoiminate compounds, namely, tris[4-[2-(ethoxyethyl)imino]-2-pentanone] gallium(iii) [Ga(eeki)3] [1], tris[4-[3-(methoxypropyl)imino]-2-pentanone] gallium(iii), [Ga(mpki)3] [2], tris[4-[3-(methoxyethyl)imino]-2-pentanone] gallium(iii), [Ga(meki)3] [3], dichloro[4-[(isopropyl)imino]-2-pentanone] gallium(iii) [Ga(ipki)Cl2] [4], bisdimethylamido[4-[(isopropyl)imino]-2-pentanone] gallium(iii) [Ga(ipki)(NMe2)2] [5] and chloro-(bis[4-[3-(ethoxypropyl)imino]-2-pentanone]) gallium(iii) [Ga(epki)2Cl] [6], was synthesised through molecular engineering. The literature known compound chloro-(bis[4-[(isopropyl)imino]-2-pentanone]) gallium(iii) [Ga(ipki)2Cl] [7] was synthesised for comparison. Confirmation of the successful formation and spectroscopic purity of the compounds was determined using nuclear magnetic resonance (NMR) spectroscopy, single crystal X-ray diffraction (XRD), electron ionisation mass spectrometry (EI-MS), and elemental analysis (EA). The thermal properties of the compounds were assessed with thermogravimetric (TG) analysis and revealed compound [4] was suitable for vapour phase deposition processes while the others displayed a decompositional behaviour favourable for solution based thin film deposition processes. The EI-MS fragmentation behaviour of compound [1], with its thermal properties, and excellent solubility in a wide variety of organic solvents, suggested that it was highly eligible to be applied for chemical solution deposition (CSD). Thus, compound [1] was applied for the spin-coating of Ga2O3 thin films without the need for additives or aging to stabilise the solution prior to processing. The as-deposited thin films were amorphous, while annealing under ambient conditions at higher temperatures (850-1000 °C) yielded β-gallium oxide as indicated by XRD. The morphology and composition were analysed by scanning electron microscopy (SEM) and Rutherford backscattering spectrometry (RBS) respectively, while the optical properties were determined using UV-vis spectroscopy and illustrated that films grown with a spin-cycle number &lt;5 were highly transparent (&gt;80%) in the visible range. © 2018 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
    view abstractdoi: 10.1039/c7nj04334a
  • 2018 • 383 Operando Raman spectroscopy on CO2 methanation over alumina-supported Ni, Ni3Fe and NiRh0.1 catalysts: Role of carbon formation as possible deactivation pathway
    Mutz, B. and Sprenger, P. and Wang, W. and Wang, D. and Kleist, W. and Grunwaldt, J.-D.
    Applied Catalysis A: General 556 160-171 (2018)
    The methanation of CO2, as a part of the power-to-gas concept, was studied under various industrially relevant feed compositions with a focus on the formation and influence of carbonaceous species. For this purpose, 5 wt.% Ni/Al2O3, 5 wt.% Ni3Fe/Al2O3 and 3.4 wt.% NiRh0.1/Al2O3 catalysts were prepared and characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), scanning transmission electron microscopy (STEM) combined with energy-dispersive X-ray spectroscopy (EDX) and electron energy loss spectroscopy (EELS). During the methanation of CO2, the Ni3Fe catalyst emerged as the most active and selective catalyst in the mid-temperature regime (300–350 °C). At 400 °C, all three tested catalysts showed high conversion of CO2 (67–75%; Ni &gt; Ni3Fe &gt; NiRh0.1) and selectivity towards CH4 (95–98%). Operando Raman spectroscopy was applied to elucidate the possible influence of carbonaceous species on the performance of the catalysts. Notably, no carbon deposition was observed under various feed compositions, even in CO2 or CO2/CH4 mixtures, e.g. as provided by biogas plants. Only in pure CH4 atmosphere an intensive carbon deposition with graphitic structure occurred as uncovered by operando Raman spectroscopy. Experiments in the lab-scale reactor and a spectroscopic microreactor could be correlated and revealed a strong catalytic deactivation of the carbon covered catalysts including a pronounced shift of the selectivity towards CO. The initial activity could be recovered after reactivation in H2 at elevated temperatures, which led to a removal of the deposits especially from the metal particles. Raman spectroscopy, supported by the results from high-resolution transmission electron microscopy (HRTEM) and EELS, revealed that carbon remained on the support material. The latter did not have any significant influence on the catalytic activity and could be removed in an oxidizing atmosphere. © 2018
    view abstractdoi: 10.1016/j.apcata.2018.01.026
  • 2018 • 382 Synthesis of a gallaarsene {HC[C(Me)N-2,6- i -Pr2-C6H3]2}GaAsCp∗ Containing a Ga=As double bond
    Helling, C. and Wölper, C. and Schulz, S.
    Journal of the American Chemical Society 140 5053-5056 (2018)
    Cp∗AsCl2 (Cp∗ = C5Me5) reacts with one equivalent of LGa (L = HC[C(Me)N(2,6-i-Pr2C6H3)]2) with formation of L(Cl)GaAs(Cl)Cp∗ 1, whereas the reaction with two equivalents of LGa yielded gallaarsene LGaAsCp∗ 2 containing a Ga=As double bond and (η1-Ga(Cp∗)L(η2-GaL)(μ-As3) 3. Compounds 2 and 3 were structurally characterized by single crystal X-ray diffraction, and the π-bonding contribution in 2 was analyzed by temperature-dependent 1H NMR spectroscopy (9.65 kcal mol-1) and by quantum mechanical computation. © 2018 American Chemical Society.
    view abstractdoi: 10.1021/jacs.8b02447
  • 2017 • 381 A novel type of Co–Ti–Cr-base γ/γ′ superalloys with low mass density
    Zenk, C.H. and Povstugar, I. and Li, R. and Rinaldi, F. and Neumeier, S. and Raabe, D. and Göken, M.
    Acta Materialia 135 244-251 (2017)
    A γ′ strengthened Co–Ti–Cr superalloy is presented with a mass density ∼14 % below that of typical Co–Al–W-based alloys. The lattice misfit is sufficiently low to form coherent cuboidal γ′ precipitates. Atom probe tomography shows that Cr partitions to the γ phase, but increases the γ′ volume fraction compared to a binary Co-Ti alloy to more than 60 %. The solubility of Cr in the γ′ phase is significantly higher than expected from previously published values. The γ′ solvus temperature is above 1100 °C. The yield strength shows a distinct increase above 600 °C surpassing that of Co–9Al–8W (at.%) and conventional Co-base superalloys, even more so when it is normalized by the mass density. © 2017 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.actamat.2017.06.024
  • 2017 • 380 A Study on the Tribological Behavior of Vanadium-Doped Arc Sprayed Coatings
    Tillmann, W. and Hagen, L. and Kokalj, D. and Paulus, M. and Tolan, M.
    Journal of Thermal Spray Technology 26 503-516 (2017)
    The formation of thin reactive films in sliding contacts under elevated temperature provides enhanced tribological properties since the formation of Magnéli phases leads to the ability of self-lubricating behavior. This phenomenon was studied for vanadium-doped coating systems which were produced using CVD and PVD technology. Vanadium-containing arc sprayed coatings were not widely examined so far. The aim of this study was to characterize Fe-V coatings deposited by the Twin Wire Arc Spraying process with respect to their oxidation behavior at elevated temperatures and to correlate the formation of oxides to the tribological properties. Dry sliding experiments were performed in the temperature range between 25 and 750 °C. The Fe-V coating possesses a reduced coefficient of friction and wear coefficient (k) at 650 and 750 °C, which were significant lower when compared to conventional Fe-based coatings. The evolution of oxide phases was identified in situ by x-ray diffraction for the investigated temperature range. Further oxidation of (pre-oxidized) arc sprayed Fe-V coatings, as verified by differential thermal analysis and thermo-gravimetric analysis, starts at about 500 °C. © 2017 ASM International
    view abstractdoi: 10.1007/s11666-017-0524-y
  • 2017 • 379 Chemical and structural analysis of gallstones from the Indian subcontinent
    Ramana Ramya, J. and Thanigai Arul, K. and Epple, M. and Giebel, U. and Guendel-Graber, J. and Jayanthi, V. and Sharma, M. and Rela, M. and Narayana Kalkura, S.
    Materials Science and Engineering C 78 878-885 (2017)
    Representative gallstones from north and southern parts of India were analyzed by a combination of physicochemical methods: X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), CHNS analysis, thermal analysis and Nuclear Magnetic Resonance (NMR) spectroscopy (1H and 13C). The stones from north Indian were predominantly consisting of cholesterol monohydrate and anhydrous cholesterol which was confirmed by XRD analysis. FTIR spectroscopy confirmed the presence of cholesterol and calcium bilirubinate in the south Indian gallstones. EDX spectroscopy revealed the presence of carbon, nitrogen, oxygen, calcium, sulfur, sodium and magnesium and chloride in both south Indian and north Indian gallstones. FTIR and NMR spectroscopy confirmed the occurrence of cholesterol in north Indian gallstones. The respective colour of the north Indian and south Indian gallstones was yellowish and black. The morphology of the constituent crystals of the north Indian and south Indian gallstones were platy and globular respectively. The appreciable variation in colour, morphology and composition of south and north Indian gallstones may be due to different food habit and habitat. © 2017 Elsevier B.V.
    view abstractdoi: 10.1016/j.msec.2017.04.004
  • 2017 • 378 Combinatorial study of Fe-Co-V hard magnetic thin films
    Fackler, S.W. and Alexandrakis, V. and König, D. and Kusne, A.G. and Gao, T. and Kramer, M.J. and Stasak, D. and Lopez, K. and Zayac, B. and Mehta, A. and Ludwig, Al. and Takeuchi, I.
    Science and Technology of Advanced Materials 18 231-238 (2017)
    Thin film libraries of Fe-Co-V were fabricated by combinatorial sputtering to study magnetic and structural properties over wide ranges of composition and thickness by high-throughput methods: synchrotron X-ray diffraction, magnetometry, composition, and thickness were measured across the Fe-Co-V libraries. In-plane magnetic hysteresis loops were shown to have a coercive field of 23.9 kA m–1 (300 G) and magnetization of 1000 kA m–1. The out-of-plane direction revealed enhanced coercive fields of 207 kA m–1 (2.6 kG) which was attributed to the shape anisotropy of column grains observed with electron microscopy. Angular dependence of the switching field showed that the magnetization reversal mechanism is governed by 180° domain wall pinning. In the thickness-dependent combinatorial study, co-sputtered composition spreads had a thickness ranging from 50 to 500 nm and (Fe70Co30)100-xVx compositions of x = 2–80. Comparison of high-throughput magneto-optical Kerr effect and traditional vibrating sample magnetometer measurements show agreement of trends in coercive fields across large composition and thickness regions. © 2017 The Author(s). Published by National Institute for Materials Science in partnership with Taylor & Francis.
    view abstractdoi: 10.1080/14686996.2017.1287520
  • 2017 • 377 Complexion-mediated martensitic phase transformation in Titanium
    Zhang, J. and Tasan, C.C. and Lai, M.J. and Dippel, A.-C. and Raabe, D.
    Nature Communications 8 (2017)
    The most efficient way to tune microstructures and mechanical properties of metallic alloys lies in designing and using athermal phase transformations. Examples are shape memory alloys and high strength steels, which together stand for 1,500 million tons annual production. In these materials, martensite formation and mechanical twinning are tuned via composition adjustment for realizing complex microstructures and beneficial mechanical properties. Here we report a new phase transformation that has the potential to widen the application window of Ti alloys, the most important structural material in aerospace design, by nanostructuring them via complexion-mediated transformation. This is a reversible martensitic transformation mechanism that leads to a final nanolaminate structure of α″ (orthorhombic) martensite bounded with planar complexions of athermal ω (a-ω hexagonal). Both phases are crystallographically related to the parent β (BCC) matrix. As expected from a planar complexion, the a-ω is stable only at the hetero-interface. © The Author(s) 2017.
    view abstractdoi: 10.1038/ncomms14210
  • 2017 • 376 Elastically confined martensitic transformation at the nano-scale in a multifunctional titanium alloy
    Wang, H.L. and Hao, Y.L. and He, S.Y. and Li, T. and Cairney, J.M. and Wang, Y.D. and Wang, Y. and Obbard, E.G. and Prima, F. and Du, K. and Li, S.J. and Yang, R.
    Acta Materialia 135 330-339 (2017)
    A martensitic transformation (MT) is a typical first-order diffusionless crystal structural change with strong autocatalysis like avalanche at a speed of sound propagation. This unique characteristic, however, is undetectable in some multifunctional titanium alloys. Recently, a nano-scale elastically confined MT mechanism was proposed because a nano-scale Nb modulation in a Ti-Nb based alloy was observed. Here we analyze the elastic confinement in details and its induced novel properties in a wide temperature range. The statistical analyses of atom probe tomography (APT) data confirm the existence of the nano-scale Nb concentration modulation. The synchrotron X-ray diffraction (SXRD) profiles demonstrate that the nano-scale Nb modulation causes weak diffuse scattering, as evidenced by the extreme broad diffraction bands. The tensile tests find a critical temperature of ∼150 K, where the critical stress to induce the MT and Young's modulus reach the minimum and the superelastic strain reaches the maximum (∼4.5%) and keeps constant as the temperature decreases further to <4.2 K. To reveal these abnormal behaviors of the MT, the Born criterion governing the elastic stability of cubic crystal is modified by introducing an elastic confinement term and a new Clausius-Clapeyron relationship is established to evaluate the elastically confined MT. The results are consistent with the experimental findings, including the solely stress-induced (no thermally induced) reversibility. © 2017 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.actamat.2017.06.040
  • 2017 • 375 Embedment of eutectic tungsten carbides in arc sprayed steel coatings
    Tillmann, W. and Hagen, L. and Kokalj, D.
    Surface and Coatings Technology 331 153-162 (2017)
    Tungsten carbide reinforced deposits have already evolved into a predominant coating system in order to protect stressed surfaces against wear. Among thermal spraying processes, due to a high deposition rate, arc spraying is a promising process to manufacture cost-saving, wear resistant coatings. However, inherent process characteristics prevailing in arc spraying as well as the utilization of tungsten carbides, as a filling for cored wires, could lead to undesirable phase evolutions, which in turn provoke the degradation of the mechanical properties. The embedment of tungsten carbides into the surrounding metallic matrix is affected by metallurgical interactions with molten spray particles. Within the scope of this study, an external injection of tungsten carbides was applied in order to analyze the embedment of tungsten carbides in arc sprayed low alloyed steel. Accordingly, metallographic investigations were carried out, which address the reactive layer at the interface of embedded tungsten carbides to the surrounded iron-based matrix. Microstructural characteristics such as mechanical properties and phase composition were scrutinized by means of nanoindentation, energy dispersive X-ray spectroscopy, and X-ray diffraction, respectively. It was found that the embedment of tungsten carbides, which have been externally injected into the arc burning zone, differs from that obtained from deposits produced with the use of cored wire with tungsten carbide as filling. Thus, externally injected tungsten carbides are less inclined to form eta carbides due to dissolution, which again results in differences in the mechanical properties across the reactive layer. © 2017 Elsevier B.V.
    view abstractdoi: 10.1016/j.surfcoat.2017.10.044
  • 2017 • 374 Erosion Performance of Gadolinium Zirconate-Based Thermal Barrier Coatings Processed by Suspension Plasma Spray
    Mahade, S. and Curry, N. and Björklund, S. and Markocsan, N. and Nylén, P. and Vaßen, R.
    Journal of Thermal Spray Technology 26 108-115 (2017)
    7-8 wt.% Yttria-stabilized zirconia (YSZ) is the standard thermal barrier coating (TBC) material used by the gas turbines industry due to its excellent thermal and thermo-mechanical properties up to 1200 °C. The need for improvement in gas turbine efficiency has led to an increase in the turbine inlet gas temperature. However, above 1200 °C, YSZ has issues such as poor sintering resistance, poor phase stability and susceptibility to calcium magnesium alumino silicates (CMAS) degradation. Gadolinium zirconate (GZ) is considered as one of the promising top coat candidates for TBC applications at high temperatures (>1200 °C) due to its low thermal conductivity, good sintering resistance and CMAS attack resistance. Single-layer 8YSZ, double-layer GZ/YSZ and triple-layer GZdense/GZ/YSZ TBCs were deposited by suspension plasma spray (SPS) process. Microstructural analysis was carried out by scanning electron microscopy (SEM). A columnar microstructure was observed in the single-, double- and triple-layer TBCs. Phase analysis of the as-sprayed TBCs was carried out using XRD (x-ray diffraction) where a tetragonal prime phase of zirconia in the single-layer YSZ TBC and a cubic defect fluorite phase of GZ in the double and triple-layer TBCs was observed. Porosity measurements of the as-sprayed TBCs were made by water intrusion method and image analysis method. The as-sprayed GZ-based multi-layered TBCs were subjected to erosion test at room temperature, and their erosion resistance was compared with single-layer 8YSZ. It was shown that the erosion resistance of 8YSZ single-layer TBC was higher than GZ-based multi-layered TBCs. Among the multi-layered TBCs, triple-layer TBC was slightly better than double layer in terms of erosion resistance. The eroded TBCs were cold-mounted and analyzed by SEM. © 2016, ASM International.
    view abstractdoi: 10.1007/s11666-016-0479-4
  • 2017 • 373 Experimental and Theoretical Understanding of Nitrogen-Doping-Induced Strong Metal-Support Interactions in Pd/TiO2 Catalysts for Nitrobenzene Hydrogenation
    Chen, P. and Khetan, A. and Yang, F. and Migunov, V. and Weide, P. and Stürmer, S.P. and Guo, P. and Kähler, K. and Xia, W. and Mayer, J. and Pitsch, H. and Simon, U. and Muhler, M.
    ACS Catalysis 7 1197-1206 (2017)
    By doping the TiO2 support with nitrogen, strong metal-support interactions (SMSI) in Pd/TiO2 catalysts can be tailored to obtain high-performance supported Pd nanoparticles (NPs) in nitrobenzene (NB) hydrogenation catalysis. According to the comparative studies by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), and diffuse reflectance CO FTIR (CO-DRIFTS), N-doping induced a structural promoting effect, which is beneficial for the dispersion of Pd species on TiO2. High-angle annular dark-field scanning transmission electron microscopy study of Pd on N-doped TiO2 confirmed a predominant presence of sub-2 nm Pd NPs, which are stable under the applied hydrogenation conditions. XPS and CO-DRIFTS revealed the formation of strongly coupled Pd-N species in Pd/TiO2 with N-doped TiO2 as support. Density functional theory (DFT) calculations over model systems with Pdn (n = 1, 5, or 10) clusters deposited on TiO2(101) surface were performed to verify and supplement the experimental observations. In hydrogenation catalysis using NB as a model molecule, Pd NPs on N-doped TiO2 outperformed those on N-free TiO2 in terms of both catalytic activity and stability, which can be attributed to the presence of highly dispersed Pd NPs providing more active sites, and to the formation of Pd-N species favoring the dissociative adsorption of the reactant NB and the easier desorption of the product aniline. (Figure Presented). © 2016 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.6b02963
  • 2017 • 372 Fundamental study of an industrial reactive HPPMS (Cr,Al)N process
    Bobzin, K. and Brögelmann, T. and Kruppe, N.C. and Engels, M. and Von Keudell, A. and Hecimovic, A. and Ludwig, Al. and Grochla, D. and Banko, L.
    Journal of Applied Physics 122 (2017)
    In this work, a fundamental investigation of an industrial (Cr,Al)N reactive high power pulsed magnetron sputtering (HPPMS) process is presented. The results will be used to improve the coating development for the addressed application, which is the tool coating for plastics processing industry. Substrate-oriented plasma diagnostics and deposition of the (Cr,Al)N coatings were performed for a variation of the HPPMS pulse frequency with values from f = 300 Hz to f = 2000 Hz at constant average power P = 2.5 kW and pulse length ton = 40 μs. The plasma was investigated using an oscilloscope, an intensified charge coupled device camera, phase-resolved optical emission spectroscopy, and an energy-dispersive mass spectrometer. The coating properties were determined by means of scanning electron microscopy, glow discharge optical emission spectroscopy, cantilever stress sensors, nanoindentation, and synchrotron X-ray diffraction. Regarding the plasma properties, it was found that the average energy within the plasma is nearly constant for the frequency variation. In contrast, the metal to gas ion flux ratio is changed from JM/JG = 0.51 to JM/JG = 0.10 for increasing frequency. Regarding the coating properties, a structure refinement as well as lower residual stresses, higher universal hardness, and a changing crystal orientation from (111) to (200) were observed at higher frequencies. By correlating the plasma and coating properties, it can be concluded that the change in the gas ion to metal ion flux ratio results in a competitive crystal growth of the film, which results in changing coating properties. © 2017 Author(s).
    view abstractdoi: 10.1063/1.4990997
  • 2017 • 371 Hybrid biocomposites based on titania nanotubes and a hydroxyapatite coating deposited by RF-magnetron sputtering: Surface topography, structure, and mechanical properties
    Chernozem, R.V. and Surmeneva, M.A. and Krause, B. and Baumbach, T. and Ignatov, V.P. and Tyurin, A.I. and Loza, K. and Epple, M. and Surmenev, R.A.
    Applied Surface Science 426 229-237 (2017)
    In this study, biocomposites based on porous titanium oxide structures and a calcium phosphate (CaP) or hydroxyapatite (HA) coating are described and prepared. Nanotubes (NTs) with different pore dimensions were processed using anodic oxidation of Ti substrates in a NH4F-containing electrolyte solution at anodization voltages of 30 and 60 V with a DC power supply. The external diameters of the nanotubes prepared at 30 V and 60 V were 53 ± 10 and 98 ± 16 nm, respectively. RF-magnetron sputtering of the HA target in a single deposition run was performed to prepare a coating on the surface of TiO2 NTs prepared at 30 and 60 V. The thickness of the CaP coating deposited on the mirror-polished Si substrate in the same deposition run with TiO2 NTs was determined by optical ellipsometry (SE) 95 ± 5 nm. Uncoated and CaP-coated NTs were annealed at 500 °C in air. Afterwards, the presence of TiO2 (anatase) was observed. The scanning electron microscopy (SEM), X-ray diffraction (XRD), photoelectron spectroscopy (XPS) and nanoindentation results revealed the influence that the NT dimensions had on the CaP coating deposition process. The tubular surfaces of the NTs were completely coated with the HA coating when prepared at 30 V, and no homogeneous CaP coating was observed when prepared at 60 V. The XRD patterns show peaks assigned to crystalline HA only for the coated TiO2 NTs prepared at 30 V. High-resolution XPS spectra show binding energies (BE) of Ca 2p, P 2p and O 1s core-levels corresponding to HA and amorphous calcium phosphate on TiO2 NTs prepared at 30 V and 60 V, respectively. Fabrication of TiO2 NTs results in a significant decrease to the elastic modulus and nanohardness compared to the Ti substrate. The porous structure of the NTs causes an increase in the elastic strain to failure of the coating (H/E) and the parameter used to describe the resistance of the material to plastic deformation (H3/E2) at the nanoscale level compared to the Ti substrate. Furthermore, only the HA coating on the NTs exhibits a significantly increased H/E ratio and H3/E2 factor compared to the NTs and Ti substrate. Increases in resistance to penetration for the indenter were also observed for HA-coated TiO2 NTs prepared at 30 V compared to uncoated and CaP-coated NTs prepared at 60 V. © 2017 Elsevier B.V.
    view abstractdoi: 10.1016/j.apsusc.2017.07.199
  • 2017 • 370 Identification of a ternary μ-phase in the Co-Ti-W system – An advanced correlative thin-film and bulk combinatorial materials investigation
    Naujoks, D. and Eggeler, Y.M. and Hallensleben, P. and Frenzel, J. and Fries, S.G. and Palumbo, M. and Koßmann, J. and Hammerschmidt, T. and Pfetzing-Micklich, J. and Eggeler, G. and Spiecker, E. and Drautz, R. and Ludwig, Al.
    Acta Materialia 138 100-110 (2017)
    The formation of a ternary μ-phase is documented for the system Co-Ti-W. The relevant compositional stability range is identified by high-throughput energy dispersive X-ray spectroscopy, electrical resistance and X-ray diffraction maps from a thin-film materials library (1 μm thickness). Bulk samples of the identified compositions were fabricated to allow for correlative film and bulk studies. Using analytical scanning and transmission electron microscopy, we demonstrate that in both, thin film and bulk samples, the D85 phase (μ-phase) coexists with the C36-phase and the A2-phase at comparable average chemical compositions. Young's moduli and hardness values of the μ-phase and the C36-phase were determined by nanoindentation. The trends of experimentally obtained elastic moduli are consistent with density functional theory (DFT) calculations. DFT analysis also supports the experimental findings, that the μ-phase can solve up to 18 at.% Ti. Based on the experimental and DFT results it is shown that CALPHAD modeling can be modified to account for the new findings. © 2017 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.actamat.2017.07.037
  • 2017 • 369 Improving the zT value of thermoelectrics by nanostructuring: tuning the nanoparticle morphology of Sb2Te3 by using ionic liquids
    Schaumann, J. and Loor, M. and Ünal, D. and Mudring, A. and Heimann, S. and Hagemann, U. and Schulz, S. and Maculewicz, F. and Schierning, G.
    Dalton Transactions 46 656-668 (2017)
    A systematic study on the microwave-assisted thermolysis of the single source precursor (Et2Sb)2Te (1) in different asymmetric 1-alkyl-3-methylimidazolium- and symmetric 1,3-dialkylimidazolium-based ionic liquids (ILs) reveals the distinctive role of both the anion and the cation in tuning the morphology and microstructure of the resulting Sb2Te3 nanoparticles as evidenced by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), and X-ray photoelectron spectroscopy (XPS). A comparison of the electrical and thermal conductivities as well as the Seebeck coefficient of the Sb2Te3 nanoparticles obtained from different ILs reveals the strong influence of the specific IL, from which C4mimI was identified as the best solvent, on the thermoelectric properties of as-prepared nanosized Sb2Te3. This work provides design guidelines for ILs, which allow the synthesis of nanostructured thermoelectrics with improved performances. © The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c6dt04323b
  • 2017 • 368 Influence of Ni to Co ratio in mixed Co and Ni phosphides on their electrocatalytic oxygen evolution activity
    Barwe, S. and Andronescu, C. and Vasile, E. and Masa, J. and Schuhmann, W.
    Electrochemistry Communications 79 41-45 (2017)
    Prompted by the impact of Ni-based support materials on the intrinsic activity of electrocatalysts, we investigated the influence of partial Co substitution by Ni during the reductive thermal synthesis of cobalt-cobalt phosphide nanoparticles from triphenylphosphine complexes. The obtained catalysts were characterised by X-ray diffraction and electrochemistry. Increasing the amount of Ni in the precursor complexes leads to materials with lower overpotential for the OER at low current densities, and lower Tafel slopes. Co nanoparticles, which are only formed in materials with low Ni content, increase the intrinsic material conductivity and reduce the OER overpotential at high current densities. © 2017
    view abstractdoi: 10.1016/j.elecom.2017.04.014
  • 2017 • 367 Influence of pH Value and Ionic Liquids on the Solubility of L-Alanine and L-Glutamic Acid in Aqueous Solutions at 30 °C
    Voges, M. and Prikhodko, I. V. and Prill, S. and Hubner, M. and Sadowski, G. and Held, C.
    Journal of Chemical and Engineering Data 62 52--61 (2017)
    The solubility of the amino acids L-alanine and L-glutamic acid and its sodium salt (sodium L-glutamate monohydrate) in aqueous solutions at 30 degrees C and atmospheric pressure was investigated in the pH range between 3 and 9 and in the presence of the ionic liquids (ILs) 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim][OTf]) and choline dihydrogencitrate ([ch] [dhcit]) at pH 7. The solubility of L-alanine and L-glutamic acid in the solutions without IL was measured by UV spectroscopy and with a gravimetrical method. In the presence of an IL HPLC-analysis was applied. The solid phases were characterized using Raman spectroscopy and powder X-ray diffraction to distinguish the amino acids from their salts. While the solubility of L-alanine did not depend on pH within the considered pH range, the solubility of L-glutamic acid strongly increased with increasing pH. Below pH 6.2 the solid phase was characterized to be L-glutamic acid, while sodium L-glutamate monohydrate was found to be the solid at pH higher than 6.2. It could be observed that the solubility of sodium L-glutamate monohydrate was comparatively high, and increased with increasing pH. Upon addition of the ILs under investigation ([bmim][OTf]) and [ch] [dhcit]) the solubility of L-alanine and L-glutamic acid was decreased. Original PC-SAFT was applied to predict the solubility of L-alanine and L-glutamic acid (and its sodium salt) in water, with and without the ILs under consideration, at the experimental conditions with quantitative agreement to the experimental data.
    view abstractdoi: 10.1021/acs.jced.6b00367
  • 2017 • 366 Influence of Si content on mechanical and tribological properties of TiAlSiN PVD coatings at elevated temperatures
    Tillmann, W. and Dildrop, M.
    Surface and Coatings Technology 321 448-454 (2017)
    TiN- and CrN-based binary or ternary coatings have been used for many years in order to extend the service life of machining tools. The increasing demands in the metalworking industry require more efficient coating systems. According to recent studies, silicon offers promising opportunities to positively influence the characteristics of thin titanium or chromium-based coatings. The nanocomposite TiAlSiN presents a high hardness and a fine grain structure. Furthermore, by adding silicon, the oxidation resistance as well as the tribological properties can be increased and improved. In this study, TiAlSiN coatings with different Si contents (0–10.9 at%) were produced by means of magnetron sputtering. In order to test the possibility to sputter pure, low conductive silicon targets, different sputter and bias modes were tested. The ratios of the other coating elements were kept constant while varying the silicon content inside the PVD coatings. Nitrided steel samples (AISI H11) were used as substrate materials. The influence of the Si content on the tribomechanical properties of TiAlSiN were analyzed. The analyses focused on the coatings with a silicon content of 5–10 at% due to the change of the coating morphology within this range. The coating morphology and different chemical compositions of the silicon-doped coatings were investigated by means of scanning electron microscopy and EDX analyses. Phase analyses were conducted and residual stresses were measured by means of X-ray diffraction. The hardness and Young's modulus of the PVD coatings were investigated using nanoindentation. Furthermore, scratch tests were performed in order to characterize the adhesion between the substrate and the coating. Finally, high temperature tribometer tests were executed to determine the wear resistance of the TiAlSiN coatings at room temperature as well as at elevated temperatures (500 °C, 800 °C). © 2017 Elsevier B.V.
    view abstractdoi: 10.1016/j.surfcoat.2017.05.014
  • 2017 • 365 Kinetics and crystallization path of a Fe-based metallic glass alloy
    Duarte, M.J. and Kostka, A. and Crespo, D. and Jimenez, J.A. and Dippel, A.-C. and Renner, F.U. and Dehm, G.
    Acta Materialia 127 341-350 (2017)
    The thermal stability and the quantification of the different transformation processes involved in the overall crystallization of the Fe50Cr15Mo14C15B6 amorphous alloy were investigated by several characterization techniques. Formation of various metastable and stable phases during the devitrification process in the sequence α-Fe, χ-Cr6Fe18Mo5, M23(C,B)6, M7C3, η-Fe3Mo3C and FeMo2B2 (with M = Fe, Cr, Mo), was observed by in-situ synchrotron high energy X-ray diffraction and in-situ transmission electron microscopy. By combining these techniques with differential scanning calorimetry data, the crystallization states and their temperature range of stability under continuous heating were related with the evolution of the crystallized fraction and the phase sequence as a function of temperature, revealing structural and chemical details of the different transformation mechanisms. © 2017 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.actamat.2017.01.031
  • 2017 • 364 Laser synthesis, structure and chemical properties of colloidal nickel-molybdenum nanoparticles for the substitution of noble metals in heterogeneous catalysis
    Marzun, G. and Levish, A. and Mackert, V. and Kallio, T. and Barcikowski, S. and Wagener, P.
    Journal of Colloid and Interface Science 489 57-67 (2017)
    Platinum and iridium are rare and expensive noble metals that are used as catalysts for different sectors including in heterogeneous chemical automotive emission catalysis and electrochemical energy conversion. Nickel and its alloys are promising materials to substitute noble metals. Nickel based materials are cost-effective with good availability and show comparable catalytic performances. The nickel-molybdenum system is a very interesting alternative to platinum in water electrolysis. We produced ligand-free nickel-molybdenum nanoparticles by laser ablation in water and acetone. Our results show that segregated particles were formed in water due to the oxidation of the metals. X-ray diffraction shows a significant change in the lattice parameter due to a diffusion of molybdenum atoms into the nickel lattice with increasing activity in the electrochemical oxygen evolution reaction. Even though the solubility of molecular oxygen in acetone is higher than in water, there were no oxides and a more homogeneous metal distribution in the particles in acetone as seen by TEM-EDX. This showed that dissolved molecular oxygen does not control oxide formation. Overall, the laser ablation of pressed micro particulate mixtures in liquids offers a combinational synthesis approach that allows the screening of alloy nanoparticles for catalytic testing and can convert micro-mixtures into nano-alloys. © 2016 Elsevier Inc.
    view abstractdoi: 10.1016/j.jcis.2016.09.014
  • 2017 • 363 Low temperature growth of gallium oxide thin films via plasma enhanced atomic layer deposition
    O'Donoghue, R. and Rechmann, J. and Aghaee, M. and Rogalla, D. and Becker, H.-W. and Creatore, M. and Wieck, A.D. and Devi, A.
    Dalton Transactions 46 16551-16561 (2017)
    Herein we describe an efficient low temperature (60-160 °C) plasma enhanced atomic layer deposition (PEALD) process for gallium oxide (Ga2O3) thin films using hexakis(dimethylamido)digallium [Ga(NMe2)3]2 with oxygen (O2) plasma on Si(100). The use of O2 plasma was found to have a significant improvement on the growth rate and deposition temperature when compared to former Ga2O3 processes. The process yielded the second highest growth rates (1.5 Å per cycle) in terms of Ga2O3 ALD and the lowest temperature to date for the ALD growth of Ga2O3 and typical ALD characteristics were determined. From in situ quartz crystal microbalance (QCM) studies and ex situ ellipsometry measurements, it was deduced that the process is initially substrate-inhibited. Complementary analytical techniques were employed to investigate the crystallinity (grazing-incidence X-ray diffraction), composition (Rutherford backscattering analysis/nuclear reaction analysis/X-ray photoelectron spectroscopy), morphology (X-ray reflectivity/atomic force microscopy) which revealed the formation of amorphous, homogeneous and nearly stoichiometric Ga2O3 thin films of high purity (carbon and nitrogen &lt;2 at.%) under optimised process conditions. Tauc plots obtained via UV-Vis spectroscopy yielded a band gap of 4.9 eV and the transmittance values were more than 80%. Upon annealing at 1000 °C, the transformation to oxygen rich polycrystalline β-gallium oxide took place, which also resulted in the densification and roughening of the layer, accompanied by a slight reduction in the band gap. This work outlines a fast and efficient method for the low temperature ALD growth of Ga2O3 thin films and provides the means to deposit Ga2O3 upon thermally sensitive polymers like polyethylene terephthalate. © 2017 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c7dt03427j
  • 2017 • 362 Low-Temperature Atomic Layer Deposition of Cobalt Oxide as an Effective Catalyst for Photoelectrochemical Water-Splitting Devices
    Kim, J. and Iivonen, T. and Hämäläinen, J. and Kemell, M. and Meinander, K. and Mizohata, K. and Wang, L. and Räisänen, J. and Beranek, R. and Leskelä, M. and Devi, A.
    Chemistry of Materials 29 5796-5805 (2017)
    We have developed a low-temperature atomic layer deposition (ALD) process for depositing crystalline and phase pure spinel cobalt oxide (Co3O4) films at 120 °C using [Co(tBu2DAD)2] and ozone as coreagent. X-ray diffraction, UV-vis spectroscopy, atomic force microscopy, field emission scanning electron microscopy, X-ray photoelectron spectroscopy, and time-of-flight elastic recoil detection analysis were performed to characterize the structure and properties of the films. The as-deposited Co3O4 films are crystalline with a low amount of impurities (&lt;2% C and &lt;5% H) despite low deposition temperatures. Deposition of Co3O4 onto thin TiO2 photoanodes (100 nm) for water oxidation resulted in 30% improvement of photocurrent (after 10 ALD cycles yielding small Co3O4 particles) as compared to pristine TiO2 films), and exhibited no detrimental effects on photocurrent response up to 300 deposition cycles (approximately 35 nm thick films), demonstrating the applicability of the developed ALD process for deposition of effective catalyst particles and layers in photoelectrochemical water-splitting devices. © 2017 American Chemical Society.
    view abstractdoi: 10.1021/acs.chemmater.6b05346
  • 2017 • 361 Massive nanoprecipitation in an Fe-19Ni-xAl maraging steel triggered by the intrinsic heat treatment during laser metal deposition
    Kürnsteiner, P. and Wilms, M.B. and Weisheit, A. and Barriobero-Vila, P. and Jägle, E.A. and Raabe, D.
    Acta Materialia 129 52-60 (2017)
    Due to the layer-by-layer build-up of additively manufactured parts, the deposited material experiences a cyclic re-heating in the form of a sequence of temperature pulses. In the current work, this “intrinsic heat treatment (IHT)” was exploited to induce the precipitation of NiAl nanoparticles in an Fe-19Ni-xAl (at%) model maraging steel, a system known for rapid clustering. We used Laser Metal Deposition (LMD) to synthesize compositionally graded specimens. This allowed for the efficient screening of effects associated with varying Al contents ranging from 0 to 25 at% and for identifying promising concentrations for further studies. Based on the existence of the desired martensitic matrix, an upper bound for the Al concentration of 15 at% was defined. Owing to the presence of NiAl precipitates as observed by Atom Probe Tomography (APT), a lower bound of 3–5 at% Al was established. Within this concentration window, increasing the Al concentration gave rise to an increase in hardness by 225 HV due to an exceptionally high number density of 1025 NiAl precipitates per m3, as measured by APT. This work demonstrates the possibility of exploiting the IHT of the LMD process for the production of samples that are precipitation strengthened during the additive manufacturing process without need for any further heat treatment. © 2017
    view abstractdoi: 10.1016/j.actamat.2017.02.069
  • 2017 • 360 Microstructure and texture evolution during severe plastic deformation of CrMnFeCoNi high-entropy alloy
    Skrotzki, W. and Pukenas, A. and Joni, B. and Odor, E. and Ungar, T. and Hohenwarter, A. and Pippan, R. and George, E.P.
    IOP Conference Series: Materials Science and Engineering 194 (2017)
    An equiatomic high-entropy alloy CrMnFeCoNi was severely deformed at room temperature by high pressure torsion up to shear strains of about 170. Its microstructure and texture were analyzed by X-ray diffraction (X-ray line profile analysis and X-ray microdiffraction, respectively). It is shown that at a shear strain of about 20 a steady state domain/grain size of 24 nm and a dislocation density of 3 × 1016 m-2 is reached, while the twin density goes over a maximum of 2% at this strain. The texture developed is typical for sheared face-centred cubic metals, but it is extremely weak. The results are discussed in terms of the mechanisms of deformation, including dislocation slip, twinning and grain boundary sliding. © Published under licence by IOP Publishing Ltd.
    view abstractdoi: 10.1088/1757-899X/194/1/012028
  • 2017 • 359 New amidinate complexes of indium(III): Promising CVD precursors for transparent and conductive In2O3 thin films
    Gebhard, M. and Hellwig, M. and Kroll, A. and Rogalla, D. and Winter, M. and Mallick, B. and Ludwig, Ar. and Wiesing, M. and Wieck, A.D. and Grundmeier, G. and Devi, A.
    Dalton Transactions 46 10220-10231 (2017)
    For the first time, synthesis of two new amidinate-ligand comprising heteroleptic indium complexes, namely [InCl(amd)2] (1) and [InMe(amd)2] (2), via salt-metathesis and their detailed characterization is reported. For comparison, the earlier reported homoleptic tris-amidinate [In(amd)3] (3) was also synthesized and analyzed in detail especially with respect to the thermal properties and molecular crystal structure analysis which are reported here for the first time. From nuclear magnetic resonance spectroscopy (NMR) and single-crystal X-ray diffraction (XRD), all three compounds were found to be monomeric with C2 (compound 1 and 2) and C3 symmetry (compound 3). Both halide-free compounds 2 and 3 were evaluated regarding their thermal properties using temperature-dependent 1H-NMR, thermogravimetric analysis (TGA) and iso-TGA, revealing suitable volatility and thermal stability for their application as potential precursors for chemical vapor phase thin film deposition methods. Indeed, metalorganic chemical vapor deposition (MOCVD) experiments over a broad temperature range (400 °C-700 °C) revealed the suitability of these two compounds to fabricate In2O3 thin films in the presence of oxygen on Si, thermally grown SiO2 and fused silica substrates. The as-deposited thin films were characterized in terms of their crystallinity via X-ray diffraction (XRD), morphology by scanning electron microscopy (SEM) and composition through complementary techniques such as Rutherford-backscattering spectrometry (RBS) in combination with nuclear reaction analysis (NRA) and X-ray photoelectron spectroscopy (XPS). From UV/Vis spectroscopy, the deposited In2O3 thin films on fused silica substrates were found to be highly transparent (T &gt; 95% at 560 nm, compound 3). In addition, Hall measurements revealed high charge carrier densities of 1.8 × 1020 cm-3 (2) and 6.5 × 1019 cm-3 (3) with a Hall-mobility of 48 cm2 V-1 s-1 (2) and 74 cm2 V-1 s-1 (3) for the respective thin films, rendering the obtained thin films applicable as a transparent conducting oxide that could be suitable for optoelectronic applications. © 2017 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c7dt01280b
  • 2017 • 358 Peculiarities in thermal evolution of precipitated amorphous calcium phosphates with an initial Ca/P ratio of 1:1
    Zyman, Z. and Epple, M. and Goncharenko, A. and Rokhmistrov, D. and Prymak, O. and Loza, K.
    Journal of Materials Science: Materials in Medicine 28 (2017)
    Thermal evolution of amorphous calcium phosphate (ACP) powder from a fast nitrate synthesis with a Ca/P ratio of 1:1 were studied in the range of 20–980 °C. The powder consisted of amorphous dicalcium phosphate anhydrate (CaHPO4) after heating to 200 °C. CaHPO4 gradually condensed to amorphous calcium pyrophosphate Ca2P2O7 (CPP) between 200 to 620 °C. Amorphous CPP crystallized at 620–740 °C to a metastable polymorph α′-CPP of the high-temperature phase α-CPP and β-CPP. The α′-CPP/ β-CPP phase ratio reached a maximum at 800 °C (60 wt% α′-CPP/40 wt% β-CPP), and α′-CPP gradually transformed to β-CPP at a higher temperature. Some β-TCP occurred at 900 °C, so that a three-phasic mixture was obtained in the powder heated to 980 °C. The occurrence of metastable α′-CPP is attributed to Ostwald’s step rule, and a mechanism for β-TCP formation is proposed. The advantages of prospective biomaterials from these powders are discussed. © 2017, Springer Science+Business Media New York.
    view abstractdoi: 10.1007/s10856-016-5820-4
  • 2017 • 357 Photocatalytic Polymerization of 3,4-Ethylenedioxythiophene over Cesium Lead Iodide Perovskite Quantum Dots
    Chen, K. and Deng, X. and Dodekatos, G. and Tüysüz, H.
    Journal of the American Chemical Society 139 12267-12273 (2017)
    The outstanding performance of halide perovskites in optoelectronic applications can be partly attributed to their high absorption coefficient and long carrier lifetime, which are also desirable for photocatalysts. Herein, we report that cesium lead iodide perovskite quantum dots (CsPbI3 QDs) can be used as catalysts to promote the polymerization of 2,2′,5′,2″-ter-3,4-ethylenedioxythiophene under visible light illumination while preserving the quantum dot in the desirable cubic crystal phase. Simultaneously, the generated conducting poly(3,4-ethylenedioxythiophene), PEDOT, encapsulates and stabilizes the morphology of the CsPbI3 QDs. The photocatalytic polymerization clearly depends on the concentration of the CsPbI3 QDs, and the CsPbI3 QDs maintain the desirable perovskite phase when the concentration of the QD increases. Molecular oxygen and 1,4-benzoquinone can serve as electron acceptors during the photocatalytic polymerization reaction. When molecular oxygen is used, the structure of the CsPbI3 QD transforms from cubic to orthorhombic, while usage of 1,4-benzoquinone preserves the cubic phase of CsPbI3 QD. This novel approach enables the one-step formation of CsPbI3/PEDOT composite, which could be promising for the preparation of novel optoelectronic materials and high performance devices. © 2017 American Chemical Society.
    view abstractdoi: 10.1021/jacs.7b06413
  • 2017 • 356 Reduction of [Cp*Sb]4 with Subvalent Main-Group Metal Reductants: Syntheses and Structures of [(L1Mg)4(Sb4)] and [(L2Ga)2(Sb4)] Containing Edge-Missing Sb4 Units
    Ganesamoorthy, C. and Krüger, J. and Wölper, C. and Nizovtsev, A.S. and Schulz, S.
    Chemistry - A European Journal 23 2461-2468 (2017)
    [Cp*Sb]4 (Cp*=C5Me5) reacts with [L1Mg]2 and L2Ga with formation of [(L1Mg)4(μ4,η1:2:2:2-Sb4)] (L1=iPr2NC[N(2,6-iPr2C6H3)]2, 1) and [(L2Ga)2(μ,η2:2-Sb4)] (L2=HC[C(Me)N(2,6-iPr2C6H3)]2, 2). The cleavage of the Sb−Sb and Sb−C bonds in [Cp*Sb]4 are the crucial steps in both reactions. The formation of 1 occurred by elimination of the Cp* anion and formation of Cp*MgL1, while 2 was formed by reductive elimination of Cp*2 and oxidative addition of L2Ga to the Sb4 unit. 1 and 2 were characterized by heteronuclear NMR spectroscopy and single-crystal X-ray diffraction, and their bonding situation was studied by quantum chemical calculations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/chem.201605547
  • 2017 • 355 Relaxation dynamics and transformation kinetics of deeply supercooled water: Temperature, pressure, doping, and proton/deuteron isotope effects
    Lemke, S. and Handle, P.H. and Plaga, L.J. and Stern, J.N. and Seidl, M. and Fuentes-Landete, V. and Amann-Winkel, K. and Köster, K.W. and Gainaru, C. and Loerting, T. and Böhmer, R.
    Journal of Chemical Physics 147 (2017)
    Above its glass transition, the equilibrated high-density amorphous ice (HDA) transforms to the low-density pendant (LDA). The temperature dependence of the transformation is monitored at ambient pressure using dielectric spectroscopy and at elevated pressures using dilatometry. It is found that near the glass transition temperature of deuterated samples, the transformation kinetics is 300 times slower than the structural relaxation, while for protonated samples, the time scale separation is at least 30 000 and insensitive to doping. The kinetics of the HDA to LDA transformation lacks a proton/deuteron isotope effect, revealing that this process is dominated by the restructuring of the oxygen network. The x-ray diffraction experiments performed on samples at intermediate transition stages reflect a linear combination of the LDA and HDA patterns implying a macroscopic phase separation, instead of a local intermixing of the two amorphous states. © 2017 Author(s).
    view abstractdoi: 10.1063/1.4993790
  • 2017 • 354 Spinel-Structured ZnCr2O4 with Excess Zn Is the Active ZnO/Cr2O3 Catalyst for High-Temperature Methanol Synthesis
    Song, H. and Laudenschleger, D. and Carey, J.J. and Ruland, H. and Nolan, M. and Muhler, M.
    ACS Catalysis 7 7610-7622 (2017)
    A series of ZnO/Cr2O3 catalysts with different Zn:Cr ratios was prepared by coprecipitation at a constant pH of 7 and applied in methanol synthesis at 260-300 °C and 60 bar. The X-ray diffraction (XRD) results showed that the calcined catalysts with ratios from 65:35 to 55:45 consist of ZnCr2O4 spinel with a low degree of crystallinity. For catalysts with Zn:Cr ratios smaller than 1, the formation of chromates was observed in agreement with temperature-programmed reduction results. Raman and XRD results did not provide evidence for the presence of segregated ZnO, indicating the existence of Zn-rich nonstoichiometric Zn-Cr spinel in the calcined catalyst. The catalyst with Zn:Cr = 65:35 exhibits the best performance in methanol synthesis. The Zn:Cr ratio of this catalyst corresponds to that of the Zn4Cr2(OH)12CO3 precursor with hydrotalcite-like structure obtained by coprecipitation, which is converted during calcination into a nonstoichiometric Zn-Cr spinel with an optimum amount of oxygen vacancies resulting in high activity in methanol synthesis. Density functional theory calculations are used to examine the formation of oxygen vacancies and to measure the reducibility of the methanol synthesis catalysts. Doping Cr into bulk and the (10-10) surface of ZnO does not enhance the reducibility of ZnO, confirming that Cr:ZnO cannot be the active phase. The (100) surface of the ZnCr2O4 spinel has a favorable oxygen vacancy formation energy of 1.58 eV. Doping this surface with excess Zn charge-balanced by oxygen vacancies to give a 60% Zn content yields a catalyst composed of an amorphous ZnO layer supported on the spinel with high reducibility, confirming this as the active phase for the methanol synthesis catalyst. © 2017 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.7b01822
  • 2017 • 353 Stability, phase separation and oxidation of a supersaturated nanocrystalline Cu-33 at.% Cr thin film alloy
    Harzer, T.P. and Dehm, G.
    Thin Solid Films 623 48-58 (2017)
    A binary nanocrystalline Cu67Cr33 thin film alloy consisting of columnar grains was synthesized via co-evaporation of the constituent elements under non-equilibrium ultra-high vacuum conditions using molecular beam epitaxy. In the as-deposited state, the alloy film is a supersaturated solid solution with a single-phase body-centered cubic structure. In order to study the thermal stability of the microstructure and phase separation behavior towards the two phase equilibrium structure, isothermal annealing experiments in a temperature range of 150 °C – 500 °C were conducted inside a transmission electron microscope and compared to data obtained by X-ray diffraction under protective N2 atmosphere. It is shown that the single-phase nature of the alloy film is maintained for annealing temperatures of ≤ 300 °C, whereas heat treatment at temperatures of ≥ 400 °C results in the formation of a second phase, i.e. the equilibrium face-centered cubic phase of Cu. Phase separation proceeds predominantly by a spinodal-type decomposition process but a simultaneous diffusion of Cr along the columnar grain boundaries to the surface of the alloy film is observed as well. Temperature dependent diffusion coefficients for volume and grain boundary diffusion along with the activation energy for volume diffusion of Cr within the crystal lattice of the alloy film in a temperature range between 400 °C – 500 °C are determined from analytical in situ transmission electron microscopy experiments. Moreover, grain boundary diffusion of Cr leads to the growth of an external Cr-rich oxide scale. It is found that the growth kinetics of this oxide scale exhibits a transition from a linear to a nearly parabolic growth rate. © 2016 Elsevier B.V.
    view abstractdoi: 10.1016/j.tsf.2016.12.048
  • 2017 • 352 Syntheses and structures of N,C,N-stabilized antimony chalcogenides
    Ganesamoorthy, C. and Wölper, C. and Dostál, L. and Schulz, S.
    Journal of Organometallic Chemistry 845 38-43 (2017)
    The oxidation reactions of ArSb [Ar = 2,6-(HC=N-t-Bu)2C6H3] with S8, grey Se and Te as well as E2Ph2 (E = S, Se, Te) are demonstrated. The reactions of ArSb with elemental sulfur and selenium occurred at elevated temperatures and yielded ArSbE (E = S, 1; Se 2), whereas the reactions with E2Ph2 proceeded at room temperature with subsequent formation of the corresponding insertion complexes ArSb(EPh)2 (E = S 3; Se 4). In addition, ArSb(TePh)2 (5) was formed at very low temperature and showed a temperature-dependent reversible equilibrium with ArSb and Te2Ph2 between -80 °C and 20 °C. The formation and structure of compounds 1-4, which were isolated in good yields, are assigned through multinuclear NMR (1H, 13C, 77Se), IR spectroscopy and microanalyses data. In addition, the molecular structures of 2-4 are further confirmed by single crystal X-ray diffraction studies. © 2017.
    view abstractdoi: 10.1016/j.jorganchem.2017.01.007
  • 2017 • 351 Synthesis and evaluation of new copper ketoiminate precursors for a facile and additive-free solution-based approach to nanoscale copper oxide thin films
    Karle, Sarah and Rogalla, Detlef and Ludwig, Arne and Becker, Hans-Werner and Wieck, Andreas Dirk and Grafen, Markus and Ostendorf, Andreas and Devi, Anjana
    Dalton Transactions 46 2670--2679 (2017)
    Novel copper ketoiminate compounds were synthesized and for the first time applied for additive-free solution-based deposition of nanoscale copper oxide thin films. The two closely related compounds, namely the bis[4-(2-ethoxyethyl-imino)-3-pentanonato] copper, [Cu(EEKI)(2)], and bis[4-(3-methoxypropylimino)- 3-pentanonato] copper, [Cu(MPKI)(2)], were characterized by means of elemental and thermogravimetric analysis (TGA), as well as electron impact mass spectrometry (EI-MS). The advantages of these compounds are that they are liquid and possess excellent solubility in common organic solvents in addition to an optimum reactivity towards ambient moisture that enables a facile solution-based approach to nanoscale copper oxide thin films. Moreover, no additives or aging is needed to stabilize the solution processing of the copper oxide layers. [Cu(MPKI)(2)] was tested in detail for the deposition of copper oxide thin films by spin coating. Upon one-step annealing, high-quality, uniform, crystalline copper oxide thin films were deposited on Si, SiO2, as well as on quartz substrates. Structural, morphological and compositional characteristics of the copper oxide nanostructures were investigated in detail by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and a combined analysis using Rutherford backscattering spectroscopy (RBS) and nuclear reaction analysis (NRA). It was possible to control the copper oxide phases (CuO and Cu2O) by systematic tuning of the post-deposition annealing conditions. The functional properties in terms of optical band gap were investigated using UV/Vis spectroscopy, while the transport properties, such as resistivity, mobility and carrier concentration were analyzed employing Hall measurements, which confirmed the p-type conductivity of the copper oxide layers.
    view abstractdoi: 10.1039/c6dt04399b
  • 2017 • 350 Tailoring microstructure, mechanical and tribological properties of NiTi thin films by controlling in-situ annealing temperature
    Momeni, S. and Biskupek, J. and Tillmann, W.
    Thin Solid Films 628 13-21 (2017)
    Magnetron sputtered near equiatomic NiTi thin films were deposited on Si (100) and hot work tool steel substrates. The deposited thin films were in-situ annealed at four different temperatures viz., 80 °C, 305 °C, 425 °C, and 525 °C. The effect of the in-situ annealing temperature on the microstructure of the film, the morphology, as well as mechanical and tribological properties was studied using X-ray diffraction, synchrotron diffraction, transmission electron microscopy, energy dispersive X-ray spectroscopy, ball-on-disc, scratch test, and three dimensional optical microscopy. The obtained results revealed how the variation of in-situ annealing temperature affects the crystallization, microstructure evolution, as well as mechanical and tribological properties of NiTi thin films. © 2017
    view abstractdoi: 10.1016/j.tsf.2017.02.052
  • 2017 • 349 Ultra-stiff metallic glasses through bond energy density design
    Schnabel, V. and Köhler, M. and Music, D. and Bednarcik, J. and Clegg, W.J. and Raabe, D. and Schneider, J.M.
    Journal of Physics Condensed Matter 29 (2017)
    The elastic properties of crystalline metals scale with their valence electron density. Similar observations have been made for metallic glasses. However, for metallic glasses where covalent bonding predominates, such as metalloid metallic glasses, this relationship appears to break down. At present, the reasons for this are not understood. Using high energy x-ray diffraction analysis of melt spun and thin film metallic glasses combined with density functional theory based molecular dynamics simulations, we show that the physical origin of the ultrahigh stiffness in both metalloid and non-metalloid metallic glasses is best understood in terms of the bond energy density. Using the bond energy density as novel materials design criterion for ultra-stiff metallic glasses, we are able to predict a Co33.0Ta3.5B63.5 short range ordered material by density functional theory based molecular dynamics simulations with a high bond energy density of 0.94 eV Å-3 and a bulk modulus of 263 GPa, which is 17% greater than the stiffest Co-B based metallic glasses reported in literature. © 2017 IOP Publishing Ltd.
    view abstractdoi: 10.1088/1361-648X/aa72cb
  • 2016 • 348 (MeZn)2(μ-η2:η2-N6Ph2): A Powerful Starting Reagent for the Synthesis of Metal Hexazene Complexes
    Stienen, C. and Gondzik, S. and Gehlhaar, A. and Haack, R. and Wölper, C. and Jansen, G. and Schulz, S.
    Organometallics 35 1022-1029 (2016)
    [(MeLDippZn)2(μ-η2:η2-PhN6Ph)] (3), which was synthesized by reaction of MeLDipp 2Zn2 with PhN3, reacts with two equivalents of Me2Zn to give [(MeZn)2(μ-η2:η2-PhN6Ph)] (2). The reaction of 2 with pyridine gave [(MeZn)2(μ-η2:η2-PhN6Ph)(Py)2] (4), while reactions with H-acidic ligands (MeLMesH, MeLPhH) occurred with elimination of methane and formation of [(MeLMesZn)2(μ-η2:η2-PhN6Ph)] (1) and [(MeLPhZn)2(μ-η2:η2-PhN6Ph)] (5). The reaction of 1 with two equivalents of MeLi yielded the heterobimetallic hexazene complex [(MeZn)(μ-η2:η2-PhN6Ph)(Li)], which was found to undergo stepwise reaction with Me2AlCl to give [MeZn(μ-η2:η2-PhN6Ph)AlMe2] and finally [(Me2Al)2(μ-η2:η2-PhN6Ph)(thf)2] (6). Compounds 3-6 were characterized by elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction. Quantum chemical calculations were performed in order to investigate the electronic structure of 4′ and 6′ in more detail and to identify the absorption bands of the hexazene unit. © 2016 American Chemical Society.
    view abstractdoi: 10.1021/acs.organomet.6b00116
  • 2016 • 347 Ab initio Prediction of Martensitic and Intermartensitic Phase Boundaries in Ni-Mn-Ga
    Dutta, B. and Çaklr, A. and Giacobbe, C. and Al-Zubi, A. and Hickel, T. and Acet, M. and Neugebauer, J.
    Physical Review Letters 116 (2016)
    Despite the importance of martensitic transformations of Ni-Mn-Ga Heusler alloys for their magnetocaloric and shape-memory properties, the martensitic part of their phase diagrams is not well determined. Using an ab initio approach that includes the interplay of lattice and vibrational degrees of freedom we identify an intermartensitic transformation between a modulated and a nonmodulated phase as a function of excess Ni and Mn content. Based on an evaluation of the theoretical findings and experimental x-ray diffraction data for Mn-rich alloys, we are able to predict the phase diagram for Ni-rich alloys. In contrast to other mechanisms discussed for various material systems in the literature, we herewith show that the intermartensitic transformation can be understood solely using thermodynamic concepts. © 2016 American Physical Society.
    view abstractdoi: 10.1103/PhysRevLett.116.025503
  • 2016 • 346 Are Mo2BC nanocrystalline coatings damage resistant? Insights from comparative tension experiments
    Djaziri, S. and Gleich, S. and Bolvardi, H. and Kirchlechner, C. and Hans, M. and Scheu, C. and Schneider, J.M. and Dehm, G.
    Surface and Coatings Technology 289 213-218 (2016)
    Mo2BC nanocrystalline coatings were deposited on Cu substrates to compare their mechanical performance with bench-mark TiAlN, and pure Mo, Al and Al2O3 reference coatings. The Mo2BC coatings were characterized by X-ray diffraction and transmission electron microscopy to analyze the microstructure. In order to study the damage behavior, the coatings were subjected to uniaxial tensile loading and the crack spacing with increasing strain was monitored using optical and scanning electron microscopy. Based on crack density measurements, the Mo2BC coatings were found to be significantly less prone to cracking than the bench-mark TiAlN coatings. The higher resistance to cracking arises from the electronic structure of the Mo2BC nanolaminates, which imparts moderate ductility to the deformation behavior. © 2016 Elsevier B.V.
    view abstractdoi: 10.1016/j.surfcoat.2016.02.010
  • 2016 • 345 Atomic displacement in the CrMnFeCoNi high-entropy alloy - A scaling factor to predict solid solution strengthening
    Okamoto, N.L. and Yuge, K. and Tanaka, K. and Inui, H. and George, E.P.
    AIP Advances 6 (2016)
    Although metals strengthened by alloying have been used for millennia, models to quantify solid solution strengthening (SSS) were first proposed scarcely seventy years ago. Early models could predict the strengths of only simple alloys such as dilute binaries and not those of compositionally complex alloys because of the difficulty of calculating dislocation-solute interaction energies. Recently, models and theories of SSS have been proposed to tackle complex high-entropy alloys (HEAs). Here we show that the strength at 0 K of a prototypical HEA, CrMnFeCoNi, can be scaled and predicted using the root-mean-square atomic displacement, which can be deduced from X-ray diffraction and first-principles calculations as the isotropic atomic displacement parameter, that is, the average displacements of the constituent atoms from regular lattice positions. We show that our approach can be applied successfully to rationalize SSS in FeCoNi, MnFeCoNi, MnCoNi, MnFeNi, CrCoNi, CrFeCoNi, and CrMnCoNi, which are all medium-entropy subsets of the CrMnFeCoNi HEA. © 2016 Author(s).
    view abstractdoi: 10.1063/1.4971371
  • 2016 • 344 Composite cavitation resistant PVD coatings based on NiTi thin films
    Momeni, S. and Tillmann, W. and Pohl, M.
    Materials and Design 110 830-838 (2016)
    As a protective coating, TiCN hard PVD coating was deposited on magnetron sputtered NiTi thin films under various coating architectures. The microstructure, composition, mechanical properties, tribological performance as well as the cavitation resistance of deposited coatings were analyzed by using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), nanoindentation, ball–on-disc, scratch test, three dimensional (3D) optical microscopy, and the standard ultrasonic cavitation test (ASTM G 32). The obtained results revealed that under a specific coating architecture, the superelasticity of NiTi can be combined with high hardness and wear resistance of TiCN coatings. As a consequence of the combination of these properties, the composite NiTi based coatings are capable of presenting remarkable cavitation resistance and tribological performance. © 2016 Elsevier Ltd
    view abstractdoi: 10.1016/j.matdes.2016.08.054
  • 2016 • 343 Copper(II), zinc(II) and copper(II)/zinc(II)-containing carbonate-substituted hydroxyapatite: Synthesis, characterization and thermal behaviour
    Livitska, O. and Strutynska, N. and Zatovsky, I. and Nikolenko, I. and Slobodyanik, N. and Prylutskyy, Y. and Epple, M. and Prymak, O. and Byeda, A.
    Materialwissenschaft und Werkstofftechnik 47 85-91 (2016)
    A new approach for the preparation of nanoscale copper- and zinc-containing sodium- and carbonate-substituted apatites is presented. The thermal transformations of the samples in the temperature range 80-1000 °C were determined by temperature-programmed desorption mass spectroscopy and thermogravimetry. The chemical and phase compositions of the copper- and zinc-containing sodium- and carbonate-substituted apatites were studied by atomic absorption spectroscopy and X-ray diffraction, respectively. The degree and nature of the carbonate substitution were determined by elemental analysis (C, H, N) and infrared spectroscopy, respectively. In addition, scanning electron microscopy (SEM) showed nanoparticles (about 10-20 nm in diameter) with a stability to aggregation under processes by microwave radiation. Samples annealed at 700 °C were crystalline and had an apatite structure. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/mawe.201600460
  • 2016 • 342 Defect Recovery in Severely Deformed Ferrite Lamellae During Annealing and Its Impact on the Softening of Cold-Drawn Pearlitic Steel Wires
    Chen, Y.Z. and Csiszár, G. and Cizek, J. and Shi, X.H. and Borchers, C. and Li, Y.J. and Liu, F. and Kirchheim, R.
    Metallurgical and Materials Transactions A: Physical Metallurgy and Materials Science 47 726-738 (2016)
    Cold-drawn pearlitic steel wires with a drawing true strain of 3 were annealed at temperatures (Tann) ranging from 423 K to 723 K (150 °C to 450 °C) with an interval of 50 K. Recovery of the lattice defects in the severely deformed ferrite lamellae were characterized by means of high-energy X-ray diffraction and positron annihilation techniques (including positron annihilation spectroscopy and coincidence Doppler broadening spectroscopy). Accordingly, the impact of defect recovery on the softening of the annealed wires was investigated. It is found that at low temperatures [Tann ≤ 523 K (250 °C)], the recovery of the lattice defects in ferrite lamellae is dominated by the agglomeration and annihilation of vacancy clusters, while at Tann &gt; 523 K (250 °C), the recovery process is controlled by the annihilation of dislocations. Further analyses on the softening of the annealed wires indicate that the evolutions of dislocation density and concentration of vacancy clusters, and the strain age hardening in ferrite lamellae play important roles in changing the strength of the wires. The strain aging hardening leads to a maximum strength at 473 K (150 °C). Above 523 K (250 °C), the annihilations of vacancy clusters and dislocations in ferrite lamellae cause a continuous softening of the wires, where the decrease in dislocation density plays a major role. © 2015, The Minerals, Metals & Materials Society and ASM International.
    view abstractdoi: 10.1007/s11661-015-3263-z
  • 2016 • 341 Determination of the young modulus of Ti-TiAl3 metallic intermetallic laminate composites by nano-indentation
    Yener, T. and Güler, S. and Siddique, S. and Walther, F. and Zeytin, S.
    Acta Physica Polonica A 129 604-606 (2016)
    Nano-indentation is an important technique to determine the Young modulus of multiphase materials where normal tensile tests are not appropriate. In this work, Ti-TiAl3 metallic-intermetallic laminate composites have been fabricated successfully in open atmosphere using commercial purity Al and Ti foils with 250 μm and 500 μm initial thicknesses, respectively. Sintering process was performed at 700 °C under 2 MPa pressure for 7.5 h. Mechanical properties including the Young modulus were determined after manufacturing. The Young moduli of metallic and intermetallic phases were determined as 89 GPa and 140 GPa, respectively. Microstructure analyses showed that aluminum foil was almost consumed by forming a titanium aluminide intermetallic compound. Titanium aluminides grow up through spherical shaped islands and metallic-intermetallic interface is a wavy form in Ti-Al system. Thus, the final microstructure consists of alternating layers of intermetallic compound and unreacted Ti metal. Microstructure and phase characterizations were performed by scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction. Hardness of test samples was determined as 600 HV for intermetallic zone and 130 HV for metallic zone by the Vickers indentation method.
    view abstractdoi: 10.12693/APhysPolA.129.604
  • 2016 • 340 Effect of pH on the spontaneous synthesis of palladium nanoparticles on reduced graphene oxide
    Zhang, X. and Ooki, W. and Kosaka, Y.R. and Okonogi, A. and Marzun, G. and Wagener, P. and Barcikowski, S. and Kondo, T. and Nakamura, J.
    Applied Surface Science 389 911-915 (2016)
    Palladium (Pd) nanoparticles were spontaneously deposited on reduced graphene oxide (rGO) without any external reducing agents. The prepared Pd/rGO composites were then characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Spontaneous deposition occurred because of a redox reaction between the Pd precursor and rGO, which involved reduction of bivalent Pd to metallic Pd0 and oxidation of the sp2 carbon of rGO to oxygen-containing functional groups. The amount of Pd deposited on rGO varied with pH, and this was attributed to electrostatic interactions between the Pd precursor and rGO based on the results of zeta potential measurements. The importance of the redox reaction in the spontaneous deposition was demonstrated in the experiment with Zn, Ni, Cu, Ag, Pt, Pd, and Au. © 2016 Elsevier B.V.
    view abstractdoi: 10.1016/j.apsusc.2016.08.014
  • 2016 • 339 Effect of Plasma Enthalpy on the Structure of La2Zr2O7 Coatings Prepared by Suspension Plasma Spraying
    Zotov, N. and Guignard, A. and Mauer, G. and Vaßen, R.
    Journal of the American Ceramic Society 99 1086-1091 (2016)
    La2Zr2O7 coatings, prepared by suspension plasma spraying, have been studied by X-ray diffraction (XRD) as a function of torch power. Rietveld refinements of high-resolution XRD data show that with increasing plasma temperature (as a result of the increasing torch power), the La2Zr2O7 coatings remain cation ordered but progressively anion disordered. © 2015 The American Ceramic Society.
    view abstractdoi: 10.1111/jace.14058
  • 2016 • 338 Effect of Residual Stress on the Wear Resistance of Thermal Spray Coatings
    Luo, W. and Selvadurai, U. and Tillmann, W.
    Journal of Thermal Spray Technology 25 321-330 (2016)
    The wear resistance of thermal spray coatings mainly depends on coating properties such as the microstructure, hardness, and porosity, as well as on the residual stress in the coating. The residual stress is induced by a variety of influences e.g., temperature gradients, difference of the thermal expansion coefficient of the coating/substrate materials, and the geometry of the components. To investigate the residual stress, the impulse excitation technique was employed to measure the Young’s and shear moduli. The residual stress was determined by the hole-drilling method and x-ray diffraction. Pin-on-Disk and Pin-on-Tube tests were used to investigate the wear behavior. After the wear tests, the wear volume was measured by means of a 3D-profilometer. The results show that the value of the residual stress can be modified by varying the coating thickness and the substrate geometry. The compressive stress in the HVOF-sprayed WC-Co coatings has a significant positive influence on the wear resistance whereas the tensile stress has a negative effect. © 2015, ASM International.
    view abstractdoi: 10.1007/s11666-015-0309-0
  • 2016 • 337 Effects of CO2 on submicronic carbon particulate (soot) formed during coal pyrolysis in a drop tube reactor
    Senneca, O. and Apicella, B. and Heuer, S. and Schiemann, M. and Scherer, V. and Stanzione, F. and Ciajolo, A. and Russo, C.
    Combustion and Flame 172 302-308 (2016)
    In oxycombustion and gasification processes coal pyrolysis occurs in CO2-rich atmospheres. The present work investigates the effect of such conditions on the quantity and quality of the submicronic carbon particulate produced. Pyrolysis experiments were carried out in either N2 or CO2 atmospheres in a laminar drop tube reactor, with wall temperatures of 1573 K, heating rates of 104–105 K/s and residence times below 130 ms, so as to reproduce pyrolysis conditions comparable to those of pulverized coal-fired boilers. The carbon particulate sampled in the reactor was found to have bimodal distribution in the micronic and submicronic ranges. A method based on solvent extraction was applied to carbon particulate for separating the two modes and determining the relative mass contribution of micronic and submicronic fractions. In CO2 atmosphere the amount of submicronic fraction of carbon particulate, referred to as soot, was found to be up to four times as much as upon N2 experiments. Beside the larger formation of soot, relevant differences in terms of combustion reactivity, size distribution and chemical structure of the residual carbon particulate produced in CO2 environment in respect to N2 environment were observed by means of a large array of techniques including thermogravimetry, microscopy (SEM+EDX), FT-IR, UV–visible and Raman spectroscopy along with XRD and XPS techniques. © 2016 The Combustion Institute
    view abstractdoi: 10.1016/j.combustflame.2016.07.023
  • 2016 • 336 Exceptional damage-tolerance of a medium-entropy alloy CrCoNi at cryogenic temperatures
    Gludovatz, B. and Hohenwarter, A. and Thurston, K.V.S. and Bei, H. and Wu, Z. and George, E.P. and Ritchie, R.O.
    Nature Communications 7 (2016)
    High-entropy alloys are an intriguing new class of metallic materials that derive their properties from being multi-element systems that can crystallize as a single phase, despite containing high concentrations of five or more elements with different crystal structures. Here we examine an equiatomic medium-entropy alloy containing only three elements, CrCoNi, as a single-phase face-centred cubic solid solution, which displays strength-toughness properties that exceed those of all high-entropy alloys and most multi-phase alloys. At room temperature, the alloy shows tensile strengths of almost 1 GPa, failure strains of ∼70% and KJIc fracture-toughness values above 200 MPa m1/2; at cryogenic temperatures strength, ductility and toughness of the CrCoNi alloy improve to strength levels above 1.3 GPa, failure strains up to 90% and KJIc values of 275 MPa m1/2. Such properties appear to result from continuous steady strain hardening, which acts to suppress plastic instability, resulting from pronounced dislocation activity and deformation-induced nano-twinning. © 2016, Nature Publishing Group. All rights reserved.
    view abstractdoi: 10.1038/ncomms10602
  • 2016 • 335 Growth, characterization, and transport properties of ternary (Bi1-xSbx)2Te3 topological insulator layers
    Weyrich, C. and Drögeler, M. and Kampmeier, J. and Eschbach, M. and Mussler, G. and Merzenich, T. and Stoica, T. and Batov, I.E. and Schubert, J. and Plucinski, L. and Beschoten, B. and Schneider, C.M. and Stampfer, C. and Grütz...
    Journal of Physics Condensed Matter 28 (2016)
    Ternary (Bi1-xSbx)2Te3 films with an Sb content between 0 and 100% were deposited on a Si(1 1 1) substrate by means of molecular beam epitaxy. X-ray diffraction measurements confirm single crystal growth in all cases. The Sb content is determined by x-ray photoelectron spectroscopy. Consistent values of the Sb content are obtained from Raman spectroscopy. Scanning Raman spectroscopy reveals that the (Bi1-xSbx)2Te3 layers with an intermediate Sb content show spatial composition inhomogeneities. The observed spectra broadening in angular-resolved photoemission spectroscopy (ARPES) is also attributed to this phenomena. Upon increasing the Sb content from x = 0 to 1 the ARPES measurements show a shift of the Fermi level from the conduction band to the valence band. This shift is also confirmed by corresponding magnetotransport measurements where the conductance changes from n- to p-type. In this transition region, an increase of the resistivity is found, indicating a location of the Fermi level within the band gap region. More detailed measurements in the transition region reveals that the transport takes place in two independent channels. By means of a gate electrode the transport can be changed from n- to p-type, thus allowing a tuning of the Fermi level within the topologically protected surface states. © 2016 IOP Publishing Ltd.
    view abstractdoi: 10.1088/0953-8984/28/49/495501
  • 2016 • 334 Growth, nanostructure, and optical properties of epitaxial VNX/MgO(001) (0.80 ≤ x ≤ 1.00) layers deposited by reactive magnetron sputtering
    Mei, A.B. and Tuteja, M. and Sangiovanni, D.G. and Haasch, R.T. and Rockett, A. and Hultman, L. and Petrov, I. and Greene, J.E.
    Journal of Materials Chemistry C 4 7924-7938 (2016)
    VNx/MgO(001) films, ∼300 nm thick, with x ranging from 1.00 (stoichiometric) to 0.80 are grown by magnetically-unbalanced reactive magnetron sputter deposition in mixed N2/Ar atmospheres. The combination of lattice-resolution cross-sectional electron microscopy with X-ray diffraction ω - 2θ, φ-scans, pole figures, and high resolution reciprocal space maps show that VNx layers are epitaxial single crystals which grow cube-on-cube with respect to their substrates: (001) VNx ∥(001)MgO and [100] VNx∥[100]MgO. VNx(001) relaxed lattice parameters a0(x) decrease linearly from 0.4134 (x = 1.00) to 0.4098 nm (x = 0.80), in agreement with density functional theory (DFT) calculations. Near-stoichiometric VNx layers (0.95 ≲ x ≤ 1.0) are fully relaxed during growth, while films with lower x values are partially strained as a result of increased anion vacancies impeding dislocation glide. VNx complex dielectric functions ϵ(ω) are determined between 0.7 and 4.5 eV using variable-angle spectroscopic ellipsometry and valence states are probed via ultraviolet photoelectron spectroscopy (UPS) in concert with DFT calculations. VN(001) UPS spectra exhibit a feature at binding energies ranging from the Fermi level to 3 eV, together with two peaks deeper in the valence band. These results are consistent with electronic densities of states computed by scaling Kohn-Sham electronic eigenvalues to account for many-body interactions. Imaginary VN(001) dielectric functions ϵ(ω) determined by ellipsometry also agree with theoretical values obtained within the random-phase approximation using scaled eigenvalues. Analyses of optical matrix element calculations reveal that VNx dielectric responses are controlled by the phase space for interband transitions; band-structure analyses indicate that ϵ2(ω) spectral features in the infrared-visible range arise primarily from the combination of intraband and d-d transitions, while features at higher energies result primarily from p-d interband transitions. The combined nanostructural and spectroscopic analyses establish that, surprisingly, N vacancies are essentially non-interacting in high-quality epitaxial VNx containing vacancy concentrations up to ∼1022 cm-3 (x = 0.80). © 2016 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c6tc02289h
  • 2016 • 333 In Situ EPR Study of the Redox Properties of CuO-CeO2 Catalysts for Preferential CO Oxidation (PROX)
    Wang, F. and Büchel, R. and Savitsky, A. and Zalibera, M. and Widmann, D. and Pratsinis, S.E. and Lubitz, W. and Schüth, F.
    ACS Catalysis 6 3520-3530 (2016)
    Understanding the redox properties of metal oxide based catalysts is a major task in catalysis research. In situ electron paramagnetic resonance (EPR) spectroscopy is capable of monitoring the change of metal ion valences and formation of active sites during redox reactions, allowing for the identification of ongoing redox pathways. Here in situ EPR spectroscopy combined with online gas analysis, supported by ex situ X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), X-ray absorption near edge structure (XANES), temporal analysis of product (TAP), and mass spectrometry (MS) studies, was utilized to study the redox behavior of CuO-CeO2 catalysts under PROX conditions (preferential oxidation of carbon monoxide in hydrogen). Two redox mechanisms are revealed: (i) a synergetic mechanism that involves the redox pair Ce4+/Ce3+ during oxidation of Cu0/Cu+ species to Cu2+ and (ii) a direct mechanism that bypasses the redox pair Ce4+/Ce3+. In addition, EPR experiments with isotopically enriched 17O2 established the synergetic mechanism as the major redox reaction pathway. The results emphasize the importance of the interactions between Cu and Ce atoms for catalyst performance. With the guidance of these results, an optimized CuO-CeO2 catalyst could be designed. A rather wide temperature operation window of 11 K (from 377 to 388 K), with 99% conversion efficiency and 99% selectivity, was achieved for the preferential oxidation of CO in a H2 feed. © 2016 American Chemical Society.
    view abstractdoi: 10.1021/acscatal.6b00589
  • 2016 • 332 In-situ observation of successive crystallizations and metastable intermediates in the formation of metal-organic frameworks
    Yeung, H.H.-M. and Wu, Y. and Henke, S. and Cheetham, A.K. and O'Hare, D. and Walton, R.I.
    Angewandte Chemie - International Edition 55 2012-2016 (2016)
    Understanding the driving forces controlling crystallization is essential for the efficient synthesis and design of new materials, particularly metal-organic frameworks (MOFs), where mild solvothermal synthesis often allows access to various phases from the same reagents. Using high-energy in situ synchrotron X-ray powder diffraction, we monitor the crystallization of lithium tartrate MOFs, observing the successive crystallization and dissolution of three competing phases in one reaction. By determining rate constants and activation energies, we fully quantify the reaction energy landscape, gaining important predictive power for the choice of reaction conditions. Different reaction rates are explained by the structural relationships between the products and the reactants; larger changes in conformation result in higher activation energies. The methods we demonstrate can easily be applied to other materials, opening the door to a greater understanding of crystallization in general. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201508763
  • 2016 • 331 Influence of Machine Hammer Peening on the Tribological Behavior and the Residual Stresses of Wear Resistant Thermally Sprayed Coatings
    Rausch, S. and Wiederkehr, P. and Biermann, D. and Zabel, A. and Selvadurai, U. and Hagen, L. and Tillmann, W.
    Procedia CIRP 45 275-278 (2016)
    WC-W2C iron based cermet coatings are widely used in the field of wear protection. In surface engineering, machine hammer peening (MHP) is a novel surface treatment technology, which enhances the surface properties, especially for surfaces in tribological contact. In this study, the wear behavior of peened WC-W2C FeCrCMnSi arc sprayed coatings is characterized and compared to conventional coatings under as-sprayed conditions. The resulting strain hardening effects were measured by mechanical response using nanoindentation. In addition, residual stresses at the surfaces were determined using X-ray diffraction and the sin2ψ method. © 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license.
    view abstractdoi: 10.1016/j.procir.2016.02.059
  • 2016 • 330 Investigation of the self-healing sliding wear characteristics of NiTi-based PVD coatings on tool steel
    Momeni, S. and Tillmann, W.
    Wear 368-369 53-59 (2016)
    Excellent damping capacity and superelasticity of the bulk NiTi shape memory alloy (SMA) makes it a suitable material of choice for tools in machining process as well as tribological systems. Although thin film of NiTi SMA has a same damping capacity as NiTi bulk alloys, it has a poor mechanical properties and undesirable tribological performance. This study aims at eliminating these application limitations for NiTi thin films. In order to achieve this goal, NiTi thin films were magnetron sputtered as an interlayer between reactively sputtered hard TiCN coatings and hot work tool steel substrates. The microstructure, composition, crystallographic phases, mechanical and tribological properties of the deposited thin films were analyzed by using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), nanoindentation, ball-on-disc, scratch test, and three dimensional (3D) optical microscopy. It was found that under a specific coating architecture, the superelasticity of NiTi inter-layer can be combined with high hardness and wear resistance of TiCN protective layers. The obtained results revealed that the thickness of NiTi interlayers is an important factor controlling mechanical and tribological performance of bilayer composite coating systems. © 2016 Elsevier B.V.
    view abstractdoi: 10.1016/j.wear.2016.08.004
  • 2016 • 329 Investigation on femto-second laser irradiation assisted shock peening of medium carbon (0.4% C) steel
    Majumdar, J.D. and Gurevich, E.L. and Kumari, R. and Ostendorf, A.
    Applied Surface Science 364 133-140 (2016)
    In the present study, the effect of femtosecond laser irradiation on the peening behavior of 0.4% C steel has been evaluated. Laser irradiation has been conducted with a 100 μJ and 300 fs laser with multiple pulses under varied energy. Followed by laser irradiation, a detailed characterization of the processed zone was undertaken by scanning electron microscopy, and X-ray diffraction technique. Finally, the residual stress distribution, microhardness and wear resistance properties of the processed zone were also evaluated. Laser processing leads to shock peening associated with plasma formation and its expansion, formation of martensite and ferrito-pearlitic phase in the microstructure. Due to laser processing, there is introduction of residual stress on the surface which varies from high tensile (140 MPa) to compressive (-335 MPa) as compared to 152 MPa of the substrate. There is a significant increase in microhardness to 350-500 VHN as compared to 250 VHN of substrate. The fretting wear behavior against hardened steel ball shows a significant reduction in wear depth due to laser processing. Finally, a conclusion of the mechanism of wear has been established. © 2015 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.apsusc.2015.12.058
  • 2016 • 328 Investigations on the Initial Stress Evolution During Atmospheric Plasma Spraying of YSZ by In Situ Curvature Measurement
    Mutter, M. and Mauer, G. and Mücke, R. and Vaßen, R. and Back, H.C. and Gibmeier, J.
    Journal of Thermal Spray Technology 25 672-683 (2016)
    The residual stresses within plasma-sprayed coatings are an important factor that can influence the lifetime as well as the performance in operation. The investigation of stresses evolving during deposition and post-deposition cooling for atmospheric plasma spraying of yttria-stabilized zirconia coatings using in situ measurement of the samples curvature is a powerful tool for identifying the factors that contribute to stress generation. Under various spray conditions, the first deposition pass leads to a significantly larger increase in samples curvature than the subsequent passes. It is shown in this work that the amount of curvature change at the onset of spraying is significantly influenced by the spray conditions, as well as by the substrate material. More information on the origin of this steep curvature increase at the onset of spraying was obtained by single splat experiments, which yielded information on the splat bonding behavior under various conditions. A comparison of the compressive yield strength for different substrate materials indicated the influence of substrate residual stress relaxation. Residual stress measurements using the incremental hole-drilling method and x-ray diffraction confirmed that the coating deposition affects the substrate residual stress level. The yield strength data were combined with the substrate near-surface temperature during deposition, obtained by finite element simulations, and with the measured residual stress-profile. This revealed that residual stress relaxation is the key factor for the initial curvature increase. © 2016, ASM International.
    view abstractdoi: 10.1007/s11666-016-0398-4
  • 2016 • 327 Lewis acid-base adducts of group 13 elements: Synthesis, structure and reactivity toward benzaldehyde
    Ganesamoorthy, C. and Matthias, M. and Bläser, D. and Wölper, C. and Schulz, S.
    Dalton Transactions 45 11437-11444 (2016)
    Lewis acid-base adducts [LGa-M(C6F5)3] (M = B 1, Al 2, Ga 3) were prepared by the reaction of gallanediyl LGa {L = HC[C(Me)N(2,6-i-Pr2C6H3)]2} with the Lewis acids M(C6F5)3 (M = B, Al, Ga). Benzaldehyde reacts with [LGa-M(C6F5)3] (M = B 1, Al 2) at room temperature with the insertion and formation of [LGa(C6F5){CH(Ph)(OB(C6F5)2)}] (4) and the zwitterionic species [LGa(C6F5){CH(Ph)(OAl(C6F5)2)}] (5), respectively, which was found to decompose at 80 °C with the formation of {(C6F5)2Al(OCH2Ph)}2 (6). Any attempts to isolate the insertion complex of [LGa-Ga(C6F5)3] with benzaldehyde failed and only {(C6F5)2Ga(OCH2Ph)}2 (7) was isolated at elevated temperatures. 2-5 and 7 were structurally characterized by heteronuclear NMR spectroscopy and single crystal X-ray diffraction. © The Royal Society of Chemistry 2016.
    view abstractdoi: 10.1039/c6dt01688j
  • 2016 • 326 Magnetization and transport properties of single crystalline RPd2P2 (R=Y, La–Nd, Sm–Ho, Yb)
    Drachuck, G. and Böhmer, A.E. and Bud'ko, S.L. and Canfield, P.C.
    Journal of Magnetism and Magnetic Materials 417 420-433 (2016)
    Single crystals of RPd2P2 (R=Y, La–Nd, Sm–Ho, Yb) were grown out of a high temperature solution rich in Pd and P and characterized by room-temperature powder X-ray diffraction, anisotropic temperature- and field-dependent magnetization and temperature-dependent in-plane resistivity measurements. In this series, YPd2P2 and LaPd2P2 YbPd2P2 (with Yb2+) are non-local-moment bearing. Furthermore, YPd2P2 and LaPd2P2 are found to be superconducting with Tc≃0.75 and 0.96 K respectively. CePd2P2 and PrPd2P2 magnetically order at low temperature with a ferromagnetic component along the crystallographic c-axis. The rest of the series manifest low temperature antiferromagnetic ordering. EuPd2P2 has Eu2+ ions and both EuPd2P2 and GdPd2P2 have isotropic paramagnetic susceptibilities consistent with L=0 and [formula presented] and exhibit multiple magnetic transitions. For R=Eu–Dy, there are multiple, T&gt;1.8K transitions in zero applied magnetic field and for R=Nd, Eu, Gd, Tb, and Dy there are clear metamagnetic transitions at T=2.0 K for H&lt;55kOe. Strong anisotropies arising mostly from crystal electric field (CEF) effects were observed for most magnetic rare earths with L≠0. The experimentally estimated CEF parameters B20 were calculated from the anisotropic paramagnetic θab and θc values and compared to theoretical trends across the rare earth series. The ordering temperatures as well as the polycrystalline averaged paramagnetic Curie–Weiss temperature, θave, were extracted from magnetization and resistivity measurements, and compared to the de-Gennes factor. © 2016 Elsevier B.V.
    view abstractdoi: 10.1016/j.jmmm.2016.05.089
  • 2016 • 325 Mechanism of the Fe3(B,C) and Fe23(C,B)6 solid-state transformation in the hypoeutectic region of the Fe-C-B system
    Lentz, J. and Röttger, A. and Theisen, W.
    Acta Materialia 119 80-91 (2016)
    This study investigates the microstructural mechanisms involved in the solid-state transformation of the Fe3(B,C) → Fe23(C,B)6 phases in the hypoeutectic region of the iron-carbon-boron (Fe-C-B) system. We analyzed the influence of different initial microstructural characteristics on the Fe3(B,C) → Fe23(C,B)6 transformation with regards to the matrix phase, matrix C content, B/(C + B) ratio, and agglomeration of the parental Fe3(B,C) phase. We performed thermodynamic calculations using the CALPHAD method, validated by laboratory melts with varying B/(B + C) ratios. These laboratory melts were then microstructurally characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), and wavelength-dispersive X-ray spectroscopy (WDS). We particularly focused on solid-state transformation of borides and carboborides of type M3(C,B) and M23(C,B)6 in the hypoeutectic region of the ternary system Fe-C-B, investigated via both in situ and ex situ XRD measurements. It was found that the solid-state transformations are influenced by enriched B inside the eutectic structure, a result of solidification. This increased B content is not reduced in solid state due to the kinetic limitations of B and C inside the hard-phase structure. Thus phase stability is subject to local equilibria depending on the local C and B concentration of the hard-phase structure. In this process the Fe23(C,B)6 phase also forms a shell-like structure surrounding the Fe3(B,C) and Fe2B phases. © 2016 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.actamat.2016.08.009
  • 2016 • 324 Mixed-linker solid solutions of functionalized pillared-layer MOFs - Adjusting structural flexibility, gas sorption, and thermal responsiveness
    Schwedler, I. and Henke, S. and Wharmby, M.T. and Bajpe, S.R. and Cheetham, A.K. and Fischer, R.A.
    Dalton Transactions 45 4230-4241 (2016)
    Flexible metal-organic frameworks (MOFs) can undergo fascinating structural transitions triggered by external stimuli, such as adsorption/desorption of specific guest molecules or temperature changes. In this detailed study we investigate the potentials and limitations of tuning framework flexibility systematically by exploiting the powerful concept of mixed-linker solid solutions. We chose the prototypical family of functionalized pillared-layer MOFs of the general type Zn2(fu1-bdc)2x(fu2-bdc)2-2xdabco (with x = 1.00, 0.75, 0.50, 0.25 and 0.00; fu-bdc = 2,5-dialkoxy-1,4-benzenedicarboxylate with varying alkoxy chain length, dabco = 1,4-diazabicyclo[2.2.2]octane) and examined their guest responsive, as well as intrinsic temperature dependent structural flexibility by X-ray diffraction, gas physisorption and calorimetric measurements. The ratio of the different fu-bdc linkers can be adjusted freely, offering opportunity for a targeted design of these functional materials by modulating their key features, such as magnitude of framework contraction upon guest removal, breathing behaviour upon CO2 adsorption/desorption, thermoresponsive phase behaviour, and their general thermal expansivity, by the careful choice of fu-bdc linkers and their combination. © The Royal Society of Chemistry 2016.
    view abstractdoi: 10.1039/c5dt03825a
  • 2016 • 323 Multiple mechanisms of lath martensite plasticity
    Morsdorf, L. and Jeannin, O. and Barbier, D. and Mitsuhara, M. and Raabe, D. and Tasan, C.C.
    Acta Materialia 121 202-214 (2016)
    The multi-scale complexity of lath martensitic microstructures requires scale-bridging analyses to better understand the deformation mechanisms activated therein. In this study, plasticity in lath martensite is investigated by multi-field mapping of deformation-induced microstructure, topography, and strain evolution at different spatial resolution vs. field-of-view combinations. These investigations reveal site-specific initiation of dislocation activity within laths, as well as significant plastic accommodation in the vicinity of high angle block and packet boundaries. The observation of interface plasticity raises several questions regarding the role of thin inter-lath austenite films. Thus, accompanying transmission electron microscopy and synchrotron x-ray diffraction experiments are carried out to investigate the stability of these films to mechanical loading, and to discuss alternative boundary sliding mechanisms to explain the observed interface strain localization. © 2016 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.actamat.2016.09.006
  • 2016 • 322 On the role of the stability of functional groups in multi-walled carbon nanotubes applied as support in iron-based high-temperature Fischer-Tropsch synthesis
    Chew, L.M. and Xia, W. and Düdder, H. and Weide, P. and Ruland, H. and Muhler, M.
    Catalysis Today 270 85-92 (2016)
    The role of the stability of surface functional groups in oxygen- and nitrogen-functionalized multi-walled carbon nanotubes (CNTs) applied as support for iron catalysts in high-temperature Fischer-Tropsch synthesis was studied in a fixed-bed U-tube reactor at 340°C and 25 bar with a H2:CO ratio of 1. Iron oxide nanoparticles supported on untreated oxygen-functionalized CNTs (OCNTs) and nitrogen-functionalized CNTs (NCNTs) as well as thermally treated OCNTs were synthesized by the dry impregnation method using ammonium ferric citrate as iron precursor. The properties of all catalysts were examined using X-ray diffraction, temperature-programmed reduction in H2, X-ray photoelectron spectroscopy and temperature-programmed oxidation in O2. The activity loss for iron nanoparticles supported on untreated OCNTs was found to originate from severe sintering and carbon encapsulation of the iron carbide nanoparticles under reaction conditions. Conversely, the sintering of the iron carbide nanoparticles on thermally treated OCNTs and untreated NCNTs during reaction was far less pronounced. The presence of more stable surface functional groups in both thermally treated OCNTs and untreated NCNTs is assumed to be responsible for the less severe sintering of the iron carbide nanoparticles during reaction. As a result, no activity loss for iron nanoparticles supported on thermally treated OCNTs and untreated NCNTs was observed, which even became gradually more active under reaction conditions. © 2015 Published by Elsevier B.V.
    view abstractdoi: 10.1016/j.cattod.2015.09.023
  • 2016 • 321 Phase selection and nanocrystallization in Cu-free soft magnetic FeSiNbB amorphous alloy upon rapid annealing
    Morsdorf, L. and Pradeep, K.G. and Herzer, G. and Kovács, A. and Dunin-Borkowski, R.E. and Povstugar, I. and Konygin, G. and Choi, P. and Raabe, D.
    Journal of Applied Physics 119 (2016)
    Nucleation of soft magnetic Fe3Si nanocrystals in Cu-free Fe74.5Si15.5Nb3B7 alloy, upon rapid (10 s) and conventional (30 min) annealing, was investigated using x-ray diffraction, transmission electron microscopy, Mössbauer spectroscopy, and atom probe tomography. By employing rapid annealing, preferential nucleation of Fe3Si nanocrystals was achieved, whereas otherwise there is simultaneous nucleation of both Fe3Si and undesired Fe-B compound phases. Analysis revealed that the enhanced Nb diffusivity, achieved during rapid annealing, facilitates homogeneous nucleation of Fe3Si nanocrystals while shifting the secondary Fe-B crystallization to higher temperatures resulting in pure soft magnetic nanocrystallization with very low coercivities of ∼10 A/m. © 2016 AIP Publishing LLC.
    view abstractdoi: 10.1063/1.4944595
  • 2016 • 320 PKU-20: A new silicogermanate constructed from sti and asv layers
    Chen, Y. and Su, J. and Huang, S. and Liang, J. and Lin, X. and Liao, F. and Sun, J. and Wang, Y. and Lin, J. and Gies, H.
    Microporous and Mesoporous Materials 224 384-391 (2016)
    A new silicogermanate (PKU-20) was hydrothermally synthesized using triethylisopropylammonium cation as the structure directing agent in the presence of fluoride. Its structure was determined from a combination of synchrotron single crystal X-ray diffraction and powder X-ray diffraction data. PKU-20 crystallizes in the monoclinic space group C2/m, with the lattice parameters of a = 18.5901(6) Å, b = 13.9118 (4) Å, c = 22.2614 (7) Å and β = 100.1514 (12)°. The framework of PKU-20 is constructed from an alternate stacking of sti and asv layers. The sti layer is exactly the same as that in the STI framework,while the asv layer is a new layer sliced off from the ASV framework parallel to the (112) plane. The take-out scheme of the layer is discussed on the basis of a composite building unit "D4R-lau-D4R". PKU-20 possesses a two-dimensional channel system, where the 10-ring channels parallel to the [010] direction are intercrossed by 12-ring pockets along the [101] direction. © 2016 Elsevier Inc. All rights reserved.
    view abstractdoi: 10.1016/j.micromeso.2015.12.052
  • 2016 • 319 Plasmonic Au/TiO2 nanostructures for glycerol oxidation
    Dodekatos, G. and Tüysüz, H.
    Catalysis Science and Technology 6 7307-7315 (2016)
    Au nanoparticles supported on P25 TiO2 (Au/TiO2) were prepared by a facile deposition-precipitation method with urea and investigated for surface plasmon-assisted glycerol oxidation under base-free conditions. Au/TiO2 samples were characterized in detail by X-ray diffraction, UV-vis spectroscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy. The adopted synthetic methodology permits deposition of Au nanoparticles with similar mean particle sizes up to 12.5 wt% loading that allows for the evaluation of the influence of the Au amount (without changing the particle size) on its photocatalytic performance for glycerol oxidation. The reaction conditions were optimized by carrying out a systematic study with different Au loadings on TiO2, reaction times, temperatures, catalyst amounts, O2 pressures and Au particle sizes for photocatalytic reactions as well as traditional heterogeneous catalysis. It has been shown that visible light irradiation during the reaction has a beneficial effect on the conversion of glycerol where the best catalytic results were observed for 7.5 wt% Au loading with an average particle size of around 3 nm. The main product observed, with selectivities up to 63%, was high-value dihydroxyacetone that has important industrial applications, particularly in the cosmetic industry. © 2016 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c6cy01192f
  • 2016 • 318 Polaron-induced lattice distortion of (In,Ga)As/GaAs quantum dots by optically excited carriers
    Tiemeyer, S. and Bombeck, M. and Göhring, H. and Paulus, M. and Sternemann, C. and Nase, J. and Wirkert, F.J. and Möller, J. and Büning, T. and Seeck, O.H. and Reuter, D. and Wieck, A.D. and Bayer, M. and Tolan, M.
    Nanotechnology 27 (2016)
    We report on a high resolution x-ray diffraction study unveiling the effect of carriers optically injected into (In,Ga)As quantum dots on the surrounding GaAs crystal matrix. We find a tetragonal lattice expansion with enhanced elongation along the [001] crystal axis that is superimposed on an isotropic lattice extension. The isotropic contribution arises from excitation induced lattice heating as confirmed by temperature dependent reference studies. The tetragonal expansion on the femtometer scale is tentatively attributed to polaron formation by carriers trapped in the quantum dots. © 2016 IOP Publishing Ltd.
    view abstractdoi: 10.1088/0957-4484/27/42/425702
  • 2016 • 317 Predicting the solubility of pharmaceutical cocrystals in solvent/anti-solvent mixtures
    Lange, L. and Heisel, S. and Sadowski, G.
    Molecules 21 (2016)
    In this work, the solubilities of pharmaceutical cocrystals in solvent/anti-solvent systems were predicted using PC-SAFT in order to increase the efficiency of cocrystal formation processes. Modeling results and experimental data were compared for the cocrystal system nicotinamide/succinic acid (2:1) in the solvent/anti-solvent mixtures ethanol/water, ethanol/acetonitrile and ethanol/ethyl acetate at 298.15 K and in the ethanol/ethyl acetate mixture also at 310.15 K. The solubility of the investigated cocrystal slightly increased when adding small amounts of anti-solvent to the solvent, but drastically decreased for high anti-solvent amounts. Furthermore, the solubilities of nicotinamide, succinic acid and the cocrystal in the considered solvent/anti-solvent mixtures showed strong deviations from ideal-solution behavior. However, by accounting for the thermodynamic non-ideality of the components, PC-SAFT is able to predict the solubilities in all above-mentioned solvent/anti-solvent systems in good agreement with the experimental data. © 2016 by the authors; licensee MDPI.
    view abstractdoi: 10.3390/molecules21050593
  • 2016 • 316 Pseudomorphic Transformation of Organometal Halide Perovskite Using the Gaseous Hydrogen Halide Reaction
    Chen, K. and Deng, X. and Goddard, R. and Tüysüz, H.
    Chemistry of Materials 28 5530-5537 (2016)
    Halide exchange is a facile method of adjusting the band gap and optimizing the performance of organometal halide perovskite. During the halide exchange processes, preserving the crystallinity and morphology of highly crystalline materials will be desirable for preparing novel materials with outstanding performance. In this study, the gasous hydrogen halides were used as reactants for halide exchange processes. The mutual conversions among three halides for condense films were realized. Moreover, perovskite inverse opals and perovskite single crystals were also adopted as substrates to illustrate the morphology preservation and crystallinity preservation, respectively. Powder X-ray diffraction and UV-vis diffuse reflectance spectra demonstrated the segregation when smaller ions were substituted by larger ions. Scanning electron microscopy displayed the direct evidence for morphology preservation during the transformation. For the first time, single crystal X-ray diffraction confirmed the single-crystal-to-single-crystal transformation from bromide to chloride analogy, which demonstrated that the presented method can preserve the crystalline framework of large-sized perovskite during the halide exchange. © 2016 American Chemical Society.
    view abstractdoi: 10.1021/acs.chemmater.6b02233
  • 2016 • 315 Revealing the relationships between chemistry, topology and stiffness of ultrastrong Co-based metallic glass thin films: A combinatorial approach
    Schnabel, V. and Köhler, M. and Evertz, S. and Gamcova, J. and Bednarcik, J. and Music, D. and Raabe, D. and Schneider, J.M.
    Acta Materialia 107 213-219 (2016)
    An efficient way to study the relationship between chemical composition and mechanical properties of thin films is to utilize the combinatorial approach, where spatially resolved mechanical property measurements are conducted along a concentration gradient. However, for thin film glasses many properties including the mechanical response are affected by chemical topology. Here a novel method is introduced which enables spatially resolved short range order analysis along concentration gradients of combinatorially synthesized metallic glass thin films. For this purpose a CoZrTaB metallic glass film of 3 μm thickness is deposited on a polyimide foil, which is investigated by high energy X-ray diffraction in transmission mode. Through the correlative chemistry-topology-stiffness investigation, we observe that an increase in metalloid concentration from 26.4 to 32.7 at% and the associated formation of localized (hybridized) metal - metalloid bonds induce a 10% increase in stiffness. Concomitantly, along the same composition gradient, a metalloid-concentration-induced increase in first order metal - metal bond distances of 1% is observed, which infers itinerant (metallic) bond weakening. Hence, the metalloid concentration induced increase in hybridized bonding dominates the corresponding weakening of metallic bonds. © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2016.01.060
  • 2016 • 314 Reverse water-gas shift reaction at the Cu/ZnO interface: Influence of the Cu/Zn ratio on structure-activity correlations
    Álvarez Galván, C. and Schumann, J. and Behrens, M. and Fierro, J.L.G. and Schlögl, R. and Frei, E.
    Applied Catalysis B: Environmental 195 104-111 (2016)
    The physicochemical properties of hydroxycarbonate-based precipitates [zincian malachite (ZM) and aurichalcite precursors], calcined CuO/ZnO precatalysts and finally reduced Cu/ZnO catalysts, with several Cu-Zn ratios, have been investigated by different characterization techniques. Results from isothermal physisorption of N2 (BET), X-ray Diffraction (XRD), Temperature Programmed Reduction (TPR), N2O Reactive Frontal Chromatography (N2O-RFC), X-ray Photoelectron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM) have been correlated with the catalytic activity for the reverse water-gas shift (rWGS) reaction in order to provide insight into the controversial nature of active species in carbon dioxide activation, respectively the role of Cu and ZnO. Average crystalline domain size of CuO and ZnO show a relationship with the amount of each phase in the calcined sample. This is in agreement with the TPR profiles, which indicate a better dispersion of Cu for the ZnO-rich samples and a shift for the first reduction step to higher temperatures (Tonset for CuII to CuI). XPS measurements point out the surface enrichment of ZnO is less pronounced with higher ZnO/(ZnO + Cu) ratios. Activity results show that catalysts derived from high surface area ex-aurichalcite (Zn content, 50-70% atom) catalysts are more active in rWGS with lower apparent activation energies than ex-ZM catalysts (Zn content, 15-30% atom) with comparable apparent Cu surface area/N2O capacity. Thus, the CO formation rate as function of the apparent Cu surface area indicates that the reaction rate is not dependent on the exposed apparent Cu surface, but from an adjusted interface composition predetermined by the precursor structure and its thermal post-treatment. © 2016 Elsevier B.V.
    view abstractdoi: 10.1016/j.apcatb.2016.05.007
  • 2016 • 313 Setting mechanical properties of high strength steels for rapid hot forming processes
    Löbbe, C. and Hering, O. and Hiegemann, L. and Tekkaya, A.E.
    Materials 9 (2016)
    Hot stamping of sheet metal is an established method for the manufacturing of light weight products with tailored properties. However, the generally-applied continuous roller furnace manifests two crucial disadvantages: The overall process time is long and a local setting of mechanical properties is only feasible through special cooling techniques. Hot forming with rapid heating directly before shaping is a new approach, which not only reduces the thermal intervention in the zones of critical formability and requested properties, but also allows the processing of an advantageous microstructure characterized by less grain growth, additional fractions (e.g., retained austenite), and undissolved carbides. Since the austenitization and homogenization process is strongly dependent on the microstructure constitution, the general applicability for the process relevant parameters is unknown. Thus, different austenitization parameters are analyzed for the conventional high strength steels 22MnB5, Docol 1400M, and DP1000 in respect of the mechanical properties. In order to characterize the resulting microstructure, the light optical and scanning electron microscopy, micro and macro hardness measurements, and the X-ray diffraction are conducted subsequent to tensile tests. The investigation proves not only the feasibility to adjust the strength and ductility flexibly, unique microstructures are also observed and the governing mechanisms are clarified. © 2016 by the authors.
    view abstractdoi: 10.3390/ma9040229
  • 2016 • 312 Spent Tea Leaf Templating of Cobalt-Based Mixed Oxide Nanocrystals for Water Oxidation
    Deng, X. and Chan, C.K. and Tüysüz, H.
    ACS Applied Materials and Interfaces 8 32488-32495 (2016)
    The facile synthesis of nanostructured cobalt oxides using spent tea leaves as a hard template is reported. Following an impregnation-calcination and template removal pathway, sheetlike structures containing nanosized crystallites of Co3O4 are obtained. Co3O4 incorporated with Cu, Ni, Fe, and Mn (M/Co = 1/8 atomic ratio) are also prepared, and the materials are thoroughly characterized using X-ray diffraction, electron microscopy, and N2 sorption. The method is applicable to several commercial tea leaves and is successfully scaled up to prepare over 7 g of Co3O4 with the same nanostructure. The oxides are then tested for electrochemical water oxidation, and Cu, Ni, and Fe incorporations show beneficial effect on the catalytic activity of Co3O4, achieving performance comparable to levels from benchmark electrocatalysts. These data suggest that tea leaf templating can be utilized as a facile and promising approach to prepare nanostructured functional catalyst. © 2016 American Chemical Society.
    view abstractdoi: 10.1021/acsami.6b12005
  • 2016 • 311 Spray Deposition of Titania Films with Incorporated Crystalline Nanoparticles for All-Solid-State Dye-Sensitized Solar Cells Using P3HT
    Song, L. and Wang, W. and Körstgens, V. and Moseguí González, D. and Yao, Y. and Minar, N.K. and Feckl, J.M. and Peters, K. and Bein, T. and Fattakhova-Rohlfing, D. and Santoro, G. and Roth, S.V. and Müller-Buschbaum, P.
    Advanced Functional Materials 26 1498-1506 (2016)
    Spray coating, a simple and low-cost technique for large-scale film deposition, is employed to fabricate mesoporous titania films, which are electron-transporting layers in all-solid-state dye-sensitized solar cells (DSSCs). To optimize solar cell performance, presynthesized crystalline titania nanoparticles are introduced into the mesoporous titania films. The composite film morphology is examined with scanning electron microscopy, grazing incidence small-angle X-ray scattering, and nitrogen adsorption-desorption isotherms. The crystal phase and crystallite sizes are verified by X-ray diffraction measurements. The photovoltaic performance of all-solid-state DSSCs is investigated. The findings reveal that an optimal active layer of the all-solid-state DSSC is obtained by including 50 wt% titania nanoparticles, showing a foam-like morphology with an average pore size of 20 nm, featuring an anatase phase, and presenting a surface area of 225.2 m2 g-1. The optimized morphology obtained by adding 50 wt% presynthesized crystalline titania nanoparticles yields, correspondingly, the best solar cell efficiency of 2.7 ± 0.1%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/adfm.201504498
  • 2016 • 310 Strain-induced phase transformation of a thin Co film on flexible substrates
    Marx, V.M. and Kirchlechner, C. and Breitbach, B. and Cordill, M.J. and Többens, D.M. and Waitz, T. and Dehm, G.
    Acta Materialia 121 227-233 (2016)
    The strain-induced FCC to HCP phase transformation of a two phase Co film on polyimide was investigated by performing a tensile test in an X-ray diffractometer. During straining of the 2 μm thick film, the intensity of the (002)FCC peak continuously decreases at engineering strains between 2 and 8% and remains constant at higher strains. Complementary in situ tensile tests under an optical light microscope showed crack formation at 6.7% and crack saturation at around 10% engineering strain. The strain-induced phase transformation starts before the first cracks form leading to a maximum lattice strain of approximately 0.9% as initiation strain measured from the (101¯1)HCP peak with the sin2ψ method which converts to a film stress of approximately 1270 ± 150 MPa. It could be revealed that a strain-induced phase transformation can enhance the ductility and therefore delay the crack onset of a thin cobalt film. © 2016 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.actamat.2016.09.015
  • 2016 • 309 Strong cooperative coupling of pressure-induced magnetic order and nematicity in FeSe
    Kothapalli, K. and Böhmer, A.E. and Jayasekara, W.T. and Ueland, B.G. and Das, P. and Sapkota, A. and Taufour, V. and Xiao, Y. and Alp, E. and Bud'ko, S.L. and Canfield, P.C. and Kreyssig, A. and Goldman, A.I.
    Nature Communications 7 (2016)
    A hallmark of the iron-based superconductors is the strong coupling between magnetic, structural and electronic degrees of freedom. However, a universal picture of the normal state properties of these compounds has been confounded by recent investigations of FeSe where the nematic (structural) and magnetic transitions appear to be decoupled. Here, using synchrotron-based high-energy x-ray diffraction and time-domain Mössbauer spectroscopy, we show that nematicity and magnetism in FeSe under applied pressure are indeed strongly coupled. Distinct structural and magnetic transitions are observed for pressures between 1.0 and 1.7 GPa and merge into a single first-order transition for pressures ≥31.7 GPa, reminiscent of what has been found for the evolution of these transitions in the prototypical system Ba(Fe1-xCox)2As2. Our results are consistent with a spin-driven mechanism for nematic order in FeSe and provide an important step towards a universal description of the normal state properties of the iron-based superconductors.
    view abstractdoi: 10.1038/ncomms12728
  • 2016 • 308 Strong metal-support interaction and alloying in Pd/ZnO catalysts for CO oxidation
    Kast, P. and Friedrich, M. and Girgsdies, F. and Kröhnert, J. and Teschner, D. and Lunkenbein, T. and Behrens, M. and Schlögl, R.
    Catalysis Today 260 21-31 (2016)
    Pd/ZnO catalysts with different Pd content have been synthesized, thoroughly characterized and investigated with regard to their reduction behavior in hydrogen or carbon monoxide containing atmospheres, by applying CO-chemisorption, photoelectron spectroscopy, X-ray diffraction, electron microscopy, TPR and DRIFTS techniques. As a catalytic test reaction, CO-oxidation has been applied. The interaction of the noble metal with the support has been revealed in a way that can distinguish between alloying and other surface spreading/wetting phenomena, induced by strong metal-support interaction (SMSI). It was found that while alloy formation promoted CO-oxidation activity additional ZnOx formation by SMSI had the opposite effect. Zinc enrichment at the surface was detected during reduction of the catalysts, depending on the reducing agent and the Pd particle size. © 2015 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.cattod.2015.05.021
  • 2016 • 307 Synthesis and Structure of Bis(diphenylphosphinimino)methanide and Bis(diphenylphosphinimino)methanediide Beryllium Complexes
    Bayram, M. and Naglav, D. and Wölper, C. and Schulz, S.
    Organometallics 35 2378-2383 (2016)
    Reactions of BeEt2 with bis(diphenylphosphinimino)methanes H2C[PPh2NR]2 yielded the first bis(diphenylphosphinimino)methanide and bis(diphenylphosphinimino)methanediide beryllium complexes [CH(PPh2N-2,6-i-Pr2C6H3)2]BeEt (1), [C(PPh2NSiMe3)2](BeEt)2 (2), and [C(PPh2NPh)2](BeEt)2 (3), respectively. 1-3 were characterized by multinuclear NMR and IR spectroscopy as well as single-crystal X-ray diffraction. © 2016 American Chemical Society.
    view abstractdoi: 10.1021/acs.organomet.6b00380
  • 2016 • 306 Synthesis and structure of strontium ferrite nanowires and nanotubes of high aspect ratio
    Ebrahimi, F. and Ashrafizadeh, F. and Bakhshi, S.R. and Farle, M.
    Journal of Sol-Gel Science and Technology 77 708-717 (2016)
    Abstract: Strontium hexaferrite nanowires and nanotubes were synthesized in porous anodic aluminum oxide templates. Different solution-based synthesis techniques (spin coating, vacuum suction, and dip coating) were investigated. Strontium ferrite nanopowders were also synthesized by a similar sol–gel process. The morphology, structure, and composition of the embedded hexaferrite nanostructures were examined by field emission scanning electron microscope, X-ray diffraction, and transmission electron microscopy. Strontium ferrite wires with Fe/Sr ratios from 10 to 12 under different annealing temperatures of 500–700 °C were studied. The results showed that dip coating could produce fine and uniform strontium ferrite nanowires. The ratio of Fe/Sr of 11 and a calcination temperature of 650 °C were found to be optimum conditions. The produced material may be of importance for novel microwave-frequency nanoscale devices. Graphical Abstract: [Figure not available: see fulltext.] © 2015, Springer Science+Business Media New York.
    view abstractdoi: 10.1007/s10971-015-3902-2
  • 2016 • 305 Synthesis of Bi2Te3 and (Bi: XSb1- x)2Te3 nanoparticles using the novel IL [C4mim]3[Bi3I12]
    Loor, M. and Bendt, G. and Hagemann, U. and Wölper, C. and Assenmacher, W. and Schulz, S.
    Dalton Transactions 45 15326-15335 (2016)
    The novel Bi-containing reactive ionic liquid [C4mim]3[Bi3I12], which was synthesized in quantitative yield by equimolar reaction of BiI3 and [C4mim]I, was used as a novel Bi-source for the ionothermal synthesis of Bi2Te3 nanoparticles by reaction with (Et3Si)2Te in the ionic liquid [C4mim]I. The solid state structure of [C4mim]3[Bi3I12] was determined by single crystal X-ray diffraction. In addition, the ionothermal synthesis of the single source precursor (Et2Sb)2Te and [C4mim]3[Bi3I12] yielded the ternary (BixSb1-x)2Te3 (x = 0.25, 0.5, 0.75) nanoparticles. The chemical composition and phase purity of the tetradymite-type materials were determined by EDX and XRD and the surface composition of the nanoparticles was further investigated by IR and XPS. In addition, the morphology of the nanoparticles was investigated by SEM and TEM. © 2016 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c6dt02361d
  • 2016 • 304 The effect of silicon-substrate orientation on the local piezoelectric characteristics of LiNbO3 films
    Kiselev, D.A. and Zhukov, R.N. and Ksenich, S.V. and Kubasov, I.V. and Temirov, A.A. and Timushkin, N.G. and Bykov, A.S. and Malinkovich, M.D. and Shvartsman, V.V. and Lupascu, D.C. and Parkhomenko, Y.N.
    Journal of Surface Investigation 10 742-747 (2016)
    The domain structure of lithium-niobate thin films grown on Si(111) and Si(100) substrates coated with a native oxide layer with a thickness of no less than 2 nm is investigated by X-ray diffraction, scanning electron microscopy and piezoresponse force microscopy. The films are synthesized by the rf magnetron sputtering of a single-crystal lithium-niobate target. A high degree of grain orientation in the polycrystalline films is demonstrated. The piezoelectric coefficients dzz of the lithium-niobate films on Si(111) and Si(100) substrates are calculated from the measured dependences of the amplitude of the piezoresponse signal on the ac voltage applied between the cantilever tip and the substrate. Piezoelectric hysteresis loops are obtained in the remanent piezoelectric response regime © 2016, Pleiades Publishing, Ltd.
    view abstractdoi: 10.1134/S1027451016040091
  • 2016 • 303 The effect of sodium on the structure-activity relationships of cobalt-modified Cu/ZnO/Al2O3 catalysts applied in the hydrogenation of carbon monoxide to higher alcohols
    Anton, J. and Nebel, J. and Song, H. and Froese, C. and Weide, P. and Ruland, H. and Muhler, M. and Kaluza, S.
    Journal of Catalysis 335 175-186 (2016)
    A series of Co-modified Cu/ZnO/Al2O3 methanol synthesis catalysts with different Na loadings was prepared and applied in higher alcohol synthesis (HAS) at 280 °C, 60 bar and a ratio of H2/CO = 1. The bulk and surface properties of the catalysts were characterized after reduction and after 40 h time on stream (TOS) without exposing the catalysts to air during the transfer and the measurements. Increased presence of metallic Co0 after reduction at 350 °C was confirmed by X-ray photoelectron spectroscopy indicating metallic Cu0 to act as a reduction promoter. Catalysts with low Na loadings (≤0.6 wt%) showed strong initial deactivation presumably due to coking of isolated Co0 surface sites favoring hydrocarbon formation. The selectivity to higher alcohols gradually increased during the first 10 h TOS indicating enhanced Cu-Co surface alloy formation considered as active sites for HAS. In contrast, with high Na loadings (≥0.8 wt%) deactivation did not occur and stable performance with constant CO conversion and product distribution was observed indicating significantly altered structural properties. High Na loadings caused the stabilizing amorphous oxide matrix to collapse resulting in strong sintering of the metallic Cu particles, and an increased carbidization of metallic Co0 forming bulk Co2C was observed by X-ray diffraction. Close contact between metallic Co0 and Co2C, which is known to facilitate molecular CO adsorption, is assumed to generate additional active sites for HAS. © 2016 Elsevier Inc. All rights reserved.
    view abstractdoi: 10.1016/j.jcat.2015.12.016
  • 2016 • 302 The interaction between stearic acid monolayers and butane under elevated pressures
    Giebel, F. and Paulus, M. and Nase, J. and Kiesel, I. and Bieder, S. and Tolan, M.
    Colloids and Surfaces A: Physicochemical and Engineering Aspects 504 126-130 (2016)
    A study on the interaction between butane and lipid membranes is presented. Monomolecular films of stearic acid were prepared on a water surface and were exposed to dense gas phases of n-butane and isobutane. From X-ray reflectivity measurements and grazing incidence X-ray diffraction, the accumulation of gas molecules at the liquid-gas interface was analyzed. We show that the gas molecules penetrate into the lipid membrane and accumulate between the head group and tail group of the lipids. This process goes in hand with an increase of the long-range lateral crystallographic order within the lipid film. This and the formation of multilayer islands points to an expulsion of lipids by the gas molecules. At higher pressures close to the condensation pressure of the studied gases, the vertical and lateral order is lost, indicating an adsorbed liquid film in which the lipids are dissolved. © 2016 Elsevier B.V.
    view abstractdoi: 10.1016/j.colsurfa.2016.05.067
  • 2016 • 301 Time-Resolved InSitu X-ray Diffraction Reveals Metal-Dependent Metal-Organic Framework Formation
    Wu, Y. and Henke, S. and Kieslich, G. and Schwedler, I. and Yang, M. S. and Fraser, D. A. X. and O'Hare, D.
    Angewandte Chemie-international Edition 55 14081--14084 (2016)
    Versatility in metal substitution is one of the key aspects of metal-organic framework (MOF) chemistry, allowing properties to be tuned in a rational way. As a result, it important to understand why MOF syntheses involving different metals arrive at or fail to produce the same topological outcome. Frequently, conditions are tuned by trial-and-error to make MOFs with different metal species. We ask: is it possible to adjust synthetic conditions in a systematic way in order to design routes to desired phases? We have used insitu X-ray powder diffraction to study the solvothermal formation of isostructural M-2(bdc)(2)dabco (M=Zn, Co, Ni) pillared-paddlewheel MOFs in real time. The metal ion strongly influences both kinetics and intermediates observed, leading in some cases to multiphase reaction profiles of unprecedented complexity. The standard models used for MOF crystallization break down in these cases; we show that a simple kinetic model describes the data and provides important chemical insights on phase selection.
    view abstractdoi: 10.1002/anie.201608463
  • 2016 • 300 Tribological development of TiCN coatings by adjusting the flowing rate of reactive gases
    Tillmann, W. and Momeni, S.
    Journal of Physics and Chemistry of Solids 90 45-53 (2016)
    TiCN coatings were deposited by means of direct current magnetron sputtering of Ti targets in presence of N2 and C2H2 reactive gases. The microstructure, composition, mechanical and tribological properties of the deposited thin films were analyzed by using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), nanoindentation, ball-on-disc, scratch test, and three dimensional (3D) optical microscopy. The obtained results presents a reproducible processing route for tailoring microstructure, mechanical and tribological behavior of TiCN coatings by controlling flowing rate of the reactive gases. © 2015 Elsevier Ltd.
    view abstractdoi: 10.1016/j.jpcs.2015.11.009
  • 2016 • 299 X-ray diffraction (XRD)-studies on the temperature dependent interface reactions on hafnium, zirconium, and nickel coated monocrystalline diamonds used in grinding segments for stone and concrete machining
    Tillmann, W. and Tolan, M. and Pinho Ferreira, M. and Paulus, M. and Becke, M. and Stangier, D.
    Materialwissenschaft und Werkstofftechnik 47 1193-1201 (2016)
    Diamond impregnated metal matrix composites are the state of the art solution for the machining of mineral materials. The type of interface reactions between the metal matrix and diamond surface has an essential influence on the tool performance and durability. To improve the diamond retention, the diamonds can be coated by physical vapour deposition with metallic materials, which enforce interface reactions. Hence, this paper focuses on the investigation of the interfacial area on metal-coated monocrystalline diamonds. Hafnium and zirconium, both known as carbide forming elements, are used as coating materials. The third coating, which is used to determine its catalytic influences when applied as a physical vapour deposition (PVD)-layer, is nickel. Additionally, the coated diamond samples were heat-treated to investigate the starting point of the formation of new phases. X-ray diffraction-analyses revealed the assumed carbide formation on hafnium and zirconium coated samples. The formation temperature was identified between 800 °C and 1000 °C for hafnium and zirconium coatings. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/mawe.201600713
  • 2016 • 298 Zeolite Beta Formation from Clear Sols: Silicate Speciation, Particle Formation and Crystallization Monitored by Complementary Analysis Methods
    Castro, M. and Haouas, M. and Lim, I. and Bongard, H.J. and Schüth, F. and Taulelle, F. and Karlsson, G. and Alfredsson, V. and Breyneart, E. and Kirschhock, C.E.A. and Schmidt, W.
    Chemistry - A European Journal 22 15307-15319 (2016)
    The formation of silicate nanoaggregates (NAs) at the very early stages of precursor sols and zeolite beta crystallization from silicate nanoparticles (NPs) are investigated in detail using a combination of different analysis methods, including liquid-state29Si,27Al,14N, and1H NMR spectroscopy, mass spectrometry (MS), small-angle X-ray scattering (SAXS), X-ray diffraction (XRD), and transmission electron microscopy at cryogenic temperatures (cryo-TEM). Prior to hydrothermal treatment, silicate NAs are observed if the Si/OH ratio in the reaction mixture is greater than 1. Condensation of oligomers within the NAs then generates NPs. Aluminum doped into the synthesis mixtures is located exclusively in the NPs, and is found exclusively in a state that is fourfold connected to silicate, favoring their condensation and aggregation. These results are in agreement with general trends observed for other systems. Silicate NAs are essential intermediates for zeolite formation and are generated by the aggregation of hydrated oligomers, aluminate, and templating cations. Subsequent further intra-nanoaggregate silicate condensation results in the formation of NPs.1H and14N liquid NMR as well as diffusion ordered spectroscopy (DOSY) experiments provide evidence for weakly restricted rotational and translational mobility of the organic template within NAs as a consequence of specific silicate–template interactions. NAs thus appear as key species in clear sols, and their presence in the precursor sol favors silicate condensation and further crystallization, promoted either by increasing the Si/OH ratio or by heating. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
    view abstractdoi: 10.1002/chem.201600511
  • 2015 • 297 A new zeolite formed from interlayer expansion of the precursor COK-5
    Bian, C. and Wu, Q. and Zhang, J. and Chen, F. and Pan, S. and Wang, L. and Meng, X. and Müller, U. and Feyen, M. and Yilmaz, B. and Gies, H. and Zhang, W. and Bao, X. and De Vos, D. and Yokoi, T. and Tatsumi, T. and Xiao, F.-S.
    Microporous and Mesoporous Materials 214 204-209 (2015)
    The layered silicate COK-5 has been used for an interlayer expansion reaction with dichlorodimethylsilane (DCDMS) at 180 °C to interconnect neighboring layers, yielding a new and crystalline microporous framework. The samples containing the methyl functional groups in the as-made form and having OH groups in the calcined form were designed as COE-5 and calcined COE-5. These samples were characterized with X-ray diffraction (XRD), N<inf>2</inf> sorption isotherms, inductively coupled plasma optical emission spectrometry (ICP-OES), infrared spectroscopy (IR), high-resolution transmission electron micrograph (HRTEM), thermogravimetry-differential thermal analysis (TG-DTA), and 29Si and 13C solid-state magic-angle spinning nuclear magnetic resonance (MAS NMR), as well as the contact angle techniques. XRD patterns and HRTEM images suggest that the sample interlayer spacing has been expanded by nearly 0.5 Å. The N<inf>2</inf> sorption isotherms of the materials show the BET surface areas are 165 m2/g for COE-5 and 340 m2/g for calcined COE-5. 29Si and 13C MAS NMR as well as IR spectroscopy confirm the insertion of the linker group -Si(CH<inf>3</inf>)<inf>2</inf>- connecting neighboring layers. Interestingly, calcined COE-5 shows enhanced catalytic performance in the acetalisation of glycerol with acetone to produce solketal, compared with COK-5. © 2015 Elsevier Inc.
    view abstractdoi: 10.1016/j.micromeso.2015.04.017
  • 2015 • 296 A novel approach for analyzing the dissolution mechanism of solid dispersions
    Ji, Y. and Paus, R. and Prudic, A. and Lübbert, C. and Sadowski, G.
    Pharmaceutical Research 32 2559-2578 (2015)
    Purpose To analyze the dissolution mechanism of solid dispersions of poorly water-soluble active pharmaceutical ingredients (APIs), to predict the dissolution profiles of the APIs and to find appropriate ways to improve their dissolution rate. Methods The dissolution profiles of indomethacin and naproxen from solid dispersions in PVP K25 were measured in vitro using a rotating-disk system (USP II). A chemical-potential-gradient model combined with the thermodynamic model PC-SAFT was developed to investigate the dissolution mechanism of indomethacin and naproxen from their solid dispersions at different conditions and to predict the dissolution profiles of these APIs. Results The results show that the dissolution of the investigated solid dispersions is controlled by dissolution of both, API and PVP K25 as they codissolve according to the initial API loading. Moreover, the dissolution of indomethacin and naproxen was improved by decreasing the API loading in polymer (leading to amorphous solid dispersions) and increasing stirring speed, temperature and pH of the dissolution medium. The dissolution of indomethacin and naproxen from their amorphous solid dispersions is mainly controlled by the surface reaction, which implies that indomethacin and naproxen dissolution can be effectively improved by formulation design and by improving their solvation performance. Conclusions The chemical-potential-gradient model combined with PC-SAFTcan be used to analyze the dissolution mechanism of solid dispersions and to describe and predict the dissolution profiles of API as function of stirring speed, temperature and pH value of the medium. This work helps to find appropriate ways to improve the dissolution rate of poorly-soluble APIs. © Springer Science+Business Media New York 2015.
    view abstractdoi: 10.1007/s11095-015-1644-z
  • 2015 • 295 Amorphous and Crystalline Sodium Tantalate Composites for Photocatalytic Water Splitting
    Grewe, T. and Tüysüz, H.
    ACS Applied Materials and Interfaces 7 23153-23162 (2015)
    A facile hydrothermal synthesis protocol for the fabrication of sodium tantalates for photocatalytic water splitting is presented. Mixtures of tantalum and sodium ethoxide precursors were dispersed in ethanol, and ammonium hydroxide solution was used as mineralizer. By adjusting the amount of mineralizer, a variety of sodium tantalates with various morphologies, textural parameters, band gaps, crystal phases, and degrees of crystallinity were fabricated. The reaction was carefully monitored with a pressure sensor inside the autoclave reactor, and the obtained samples were characterized using X-ray diffraction, transmission electron microscopy, N2-physisorption, and ultraviolet-visible light spectroscopy. Among the series, the amorphous sample and the composite sample that consists of amorphous and crystalline phases showed superior activity toward photocatalytic hydrogen production than highly crystalline samples. Particularly, an amorphous sodium tantalate with a small fraction of crystalline nanoparticles with perovskite structure was found to be the most active sample, reaching a hydrogen rate of 3.6 mmol h-1 from water/methanol without the use of any cocatalyst. Despite its amorphous nature, this photocatalyst gave an apparent photocatalyst activity of 1200 μmol g-1 L-1 h-1 W1-, which is 4.5-fold higher than highly crystalline NaTaO3. In addition, the most active sample gave promising activity for overall water splitting with a hydrogen production rate of 94 μmol h-1, which is superior to highly crystalline NaTaO3 prepared by conventional solid-solid state route. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/acsami.5b06965
  • 2015 • 294 An in situ powder diffraction cell for high-pressure hydrogenation experiments using laboratory X-ray diffractometers
    Moury, R. and Hauschild, K. and Kersten, W. and Ternieden, J. and Felderhoff, M. and Weidenthaler, C.
    Journal of Applied Crystallography 48 79-84 (2015)
    An in situ diffraction cell is presented which has been designed and constructed for in-house powder diffraction experiments under high gas pressures up to 30MPa. For a proof of principle, the in situ cell has been tested for several hydrogenation experiments under elevated pressures and temperatures. LaNi5 was chosen as an example for hydrogenation, applying simultaneously 5.5MPaH2 pressure at a temperature of 423K. For testing the high-pressure-temperature suitability of the in situ cell, pressure-temperature experiments up to 14MPa at 373K were performed, studying the rehydrogenation of NaH and Al to NaAlH4. The experimental setup enables recording of in situ X-ray diffraction data on laboratory instruments with short data acquisition times at elevated hydrogen pressures and temperatures. © 2015 International Union of Crystallography.
    view abstractdoi: 10.1107/S1600576714025692
  • 2015 • 293 Atomic scale study of CU clustering and pseudo-homogeneous Fe-Si nanocrystallization in soft magnetic FeSiNbB(CU) alloys
    Pradeep, K.G. and Herzer, G. and Raabe, D.
    Ultramicroscopy 159 285-291 (2015)
    A local electrode atom probe has been employed to trace the onset of Cu clustering followed by their coarsening and subsequent growth upon rapid (10s) annealing of an amorphous Fe73.5Si15.5Cu1Nb3B7 alloy. It has been found that the clustering of Cu atoms introduces heterogeneities in the amorphous matrix, leading to the formation of Fe rich regions which crystallizes pseudo-homogeneously into Fe-Si nanocrystals upon annealing. In this paper, we present the data treatment method that allows for the visualization of these different phases and to understand their morphology while still quantifying them in terms of their size, number density and volume fraction. The crystallite size of Fe-Si nanocrystals as estimated from the atom probe data are found to be in good agreement with other complementary techniques like XRD and TEM, emphasizing the importance of this approach towards accurate structural analysis. In addition, a composition driven data segmentation approach has been attempted to determine and distinguish nanocrystalline regions from the remaining amorphous matrix. Such an analysis introduces the possibility of retrieving crystallographic information from extremely fine (2-4nm sized) nanocrystalline regions of very low volume fraction (< 5Vol%) thereby providing crucial in-sights into the chemical heterogeneity induced crystallization process of amorphous materials. © 2015 Elsevier B.V.
    view abstractdoi: 10.1016/j.ultramic.2015.04.006
  • 2015 • 292 Boron-alloyed Fe-Cr-C-B tool steels - Thermodynamic calculations and experimental validation
    Röttger, A. and Lentz, J. and Theisen, W.
    Materials and Design 88 420-429 (2015)
    This study focuses on the development of boron-alloyed tool steels. The influence of Cr additions from 0 to 10mass% on microstructural changes were investigated for a constant metalloid content (C+B=2.4mass%). In the first step, thermodynamic calculations were performed to map the quaternary Fe-Cr-C-B system. In the second step, thermodynamic calculations were validated with laboratory melts that were investigated with respect to the microstructure and phase composition. The results of thermodynamic calculations correspond to real material behavior of Fe-Cr-C-B alloys. Furthermore, the influence of chromium on hard phase formation was investigated by means of phase analysis methods, X-ray diffraction (XRD), and energy dispersive spectrometry (EDS). Nanoindentation was used to determine hard phase properties (hardness, Young's modulus). It was shown that chromium promotes the formation of M2B-type borides. An increase in the Cr content within the M2B phase led to a transformation from the tetragonal structure into an orthorhombic structure. This transformation is accompanied by an increase in hardness and in the Young's modulus. In contrast, Cr also promotes the formation of Cr-rich carboborides of type M23(C,B)6. However, an increased Cr content within the M23(C,B)6 phase is not associated with an increase in hardness or elastic modulus. © 2015 Published by Elsevier Ltd.
    view abstractdoi: 10.1016/j.matdes.2015.08.157
  • 2015 • 291 Characteristics of flexibility in metal-organic framework solid solutions of composition [Zn2(BME-bdc)x(DB-bdc)2-xdabco]n: In situ powder X-ray diffraction, in situ NMR spectroscopy, and molecular dynamics simulations
    Bon, V. and Pallmann, J. and Eisbein, E. and Hoffmann, H.C. and Senkovska, I. and Schwedler, I. and Schneemann, A. and Henke, S. and Wallacher, D. and Fischer, R.A. and Seifert, G. and Brunner, E. and Kaskel, S.
    Microporous and Mesoporous Materials 216 64-74 (2015)
    Porosity switching in the crystalline solid state is a unique phenomenon observed only in a limited number of materials. The switching behavior of two metal-organic frameworks as well as their respective solid solutions of composition [Zn2(BME-bdc)x(DB-bdc)2-xdabco]n (x = 2; 1.5; 1.0; 0.5; 0) is studied in situ during the adsorption of CO2 and Xe using X-ray diffraction and NMR techniques. The diffraction data, measured during the adsorption suggest a direct one-step phase transition (switching) from the narrow pore phase to the large pore phase beyond the transition pressure. An intermediate phase was found only in one compound within a narrow pressure range around the phase transition pressure region. In situ high-pressure 13C NMR spectroscopy of adsorbed CO2 also allowed following the gating behavior of the studied materials by monitoring the signal of adsorbed CO2. The 13C NMR spectra exhibit a pronounced broadening indicating a certain degree of order for the adsorbed molecules inside the pores. This ordering effect and the resulting line broadening depend on the linker functionalization as could be confirmed by corresponding molecular dynamics (MD) simulations. © 2015 Elsevier Inc.
    view abstractdoi: 10.1016/j.micromeso.2015.02.042
  • 2015 • 290 Chemical vapor deposition of Si/SiC nano-multilayer thin films
    Weber, A. and Remfort, R. and Wöhrl, N. and Assenmacher, W. and Schulz, S.
    Thin Solid Films 593 44-52 (2015)
    Stoichiometric SiC films were deposited with the commercially available single source precursor Et3SiH by classical thermal chemical vapor deposition (CVD) as well as plasma-enhanced CVD at low temperatures in the absence of any other reactive gases. Temperature-variable deposition studies revealed that polycrystalline films containing different SiC polytypes with a Si to carbon ratio of close to 1:1 are formed at 1000°C in thermal CVD process and below 100°C in the plasma-enhanced CVD process. The plasma enhanced CVD process enables the reduction of residual stress in the deposited films and offers the deposition on temperature sensitive substrates in the future. In both deposition processes the film thickness can be controlled by variation of the process parameters such as the substrate temperature and the deposition time. The resulting material films were characterized with respect to their chemical composition and their crystallinity using scanning electron microscope, energy dispersive X-ray spectroscopy (XRD), atomic force microscopy, X-ray diffraction, grazing incidence X-ray diffraction, secondary ion mass spectrometry and Raman spectroscopy. Finally, Si/SiC multilayers of up to 10 individual layers of equal thickness (about 450 nm) were deposited at 1000°C using Et3SiH and SiH4. The resulting multilayers features amorphous SiC films alternating with Si films, which feature larger crystals up to 300 nm size as measured by transmission electron microscopy as well as by XRD. XRD features three distinct peaks for Si(111), Si(220) and Si(311). © 2015 Published by Elsevier B.V.
    view abstractdoi: 10.1016/j.tsf.2015.08.042
  • 2015 • 289 Combinatorial synthesis and high-throughput characterization of the thin film materials system Co-Mn-Ge: Composition, structure, and magnetic properties
    Salomon, S. and Hamann, S. and Decker, P. and Savan, A. and Meshi, L. and Ludwig, Al.
    Physica Status Solidi (A) Applications and Materials Science 212 1969-1974 (2015)
    Co-Mn-Ge is a system of interest for magnetocaloric applications as a solid state magnetic refrigerant. A thin film materials library covering a large fraction of the Co-Mn-Ge ternary composition space was fabricated by sputter deposition. After deposition, it was annealed at 600°C for 3 h and quenched subsequently. An energy-dispersive X-ray spectroscopy and X-ray diffraction-based cluster analysis revealed the regions of existence for the CoMnGe and the Co<inf>2</inf>MnGe single phase areas. Furthermore, high intensity diffraction peaks revealed the presence of the hexagonal (Co, Mn)<inf>7</inf>Ge<inf>6</inf> phase in a region that also featured the CoMnGe phase. In this region, a non-linear, symmetric, and hysteretic shift of the (200) diffraction peak of the (Co, Mn)<inf>7</inf>Ge<inf>6</inf> phase was observed by temperature-dependent X-ray diffraction for Co<inf>23</inf>Mn<inf>33</inf>Ge<inf>44</inf>, indicating a structural phase transition taking place between 350 and 375 K upon heating and 325 and 300 K upon cooling. This coincides with a magnetic transition near 325 K from the ferromagnetic to the paramagnetic state. However, no magnetostructural coupling was identified in the temperature range from 330 to 300 K upon cooling. Magnetostriction and an undetected structural transition of the CoMnGe phase were ruled out as probable causes for the non-linear shifts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/pssa.201532075
  • 2015 • 288 Comparison of NiTi thin films sputtered from separate elemental targets and Ti-rich alloy targets
    Tillmann, W. and Momeni, S.
    Journal of Materials Processing Technology 220 184-190 (2015)
    The kind of sputtering targets can adversely affect the microstructure, phase transformation behavior, mechanical and tribological properties of near equi-atomic NiTi thin films. This new finding was systematically investigated by employing comprehensive characterization and analysis techniques, including X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), differential scanning calorimetry (DSC), nanoindentation, ball-on-disc, and three dimensional (3D) optical microscopy. © 2015 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.jmatprotec.2015.01.014
  • 2015 • 287 Comprehensive investigation of phase transformation during diffusion alloying of Nb-rich powder metallurgical tool steels
    Weddeling, A. and Krell, J. and Huth, S. and Theisen, W.
    Powder Metallurgy 58 142-151 (2015)
    Stainless tool steels highly alloyed in niobium can be produced by powder metallurgy using diffusion alloying. Steel powder atomised without carbon is subsequently mixed with graphite and hot isostatically pressed. The atomised powder contains the intermetallic Laves phase NbFe<inf>2</inf>that transforms into MC-type carbides during HIP when graphite has been added. The obtained structure features a fine distribution of carbides to increase wear resistance and chromium fully dissolved in the matrix to provide corrosion resistance. X-ray diffraction (XRD) measurements and reflection position analysis with additional scanning electron microscopy (SEM) have been conducted to study the phase transition of NbFe<inf>2</inf>Laves phase into NbC carbides in two high Nb alloyed stainless tool steels. The results show that carburisation starts at 1000-1050°C and also confirm the correlation between oxide reduction and carburisation. The formed carbides are distinctly understoichiometric, which leads to an overestimation of the suitable quantitiy of added carbon in the thermodynamic calculations. © 2015 Institute of Materials, Minerals and Mining Published by Maney on behalf of the Institute.
    view abstractdoi: 10.1179/1743290115Y.0000000001
  • 2015 • 286 Correlation between surface properties and wettability of multi-scale structured biocompatible surfaces
    Gorodzha, S.N. and Surmeneva, M.A. and Prymak, O. and Wittmar, A. and Ulbricht, M. and Epple, M. and Teresov, A. and Koval, N. and Surmenev, R.A.
    IOP Conference Series: Materials Science and Engineering 98 (2015)
    The influence of surface properties of radio-frequency (RF) magnetron deposited hydroxyapatite (HA) and Si-containing HA coatings on wettability was studied. The composition and morphology of the coatings fabricated on titanium (Ti) were characterized using atomic force microscopy (AFM) and X-ray diffraction (XRD). The surface wettability was studied using contact angle analysis. Different geometric parameters of acid-etched (AE) and pulse electron beam (PEB)-treated Ti substrates and silicate content in the HA films resulted in the different morphology of the coatings at micro- and nano- length scales. Water contact angles for the HA coated Ti samples were evaluated as a combined effect of micro roughness of the substrate and nano-roughness of the HA films resulting in higher water contact angles compared with acid-etched (AE) or pulse electron beam (PEB) treated Ti substrates. © Published under licence by IOP Publishing Ltd.
    view abstractdoi: 10.1088/1757-899X/98/1/012026
  • 2015 • 285 Deformation mechanism of ω-enriched Ti-Nb-based gum metal: Dislocation channeling and deformation induced ω-β transformation
    Lai, M.J. and Tasan, C.C. and Raabe, D.
    Acta Materialia 100 290-300 (2015)
    Gum metal, a class of multifunctional β titanium alloys, has attracted much attention in the past decade due to its initially-proposed dislocation-free deformation mechanism based on giant faults, i.e., macroscopic planar defects carrying significant plastic strain. Special deformation features were observed in these alloys, such as plastic flow localization, pronounced surface steps, low work hardening, and large elongation. These were all proposed to arise from the special giant fault mechanism activated in the β-Ti matrix, while the initial presence or mechanically-induced formation of other phases was debated in several follow-up studies. Here, we set off with Ti-Nb-based gum metal samples with confirmed presence of large amounts of nanometer-sized hexagonal ω particles. Deformation experiments demonstrate all the features observed in the original reports, mentioned above. However, careful characterization reveals that the deformation bands (similar to giant faults) where plastic flow localized are "dislocation channels" that are depleted of ω phase. These channels are proposed to form by a {1 1 2}<1 1 1> dislocation dissociation mechanism, promoting reverse transformation of the ω phase into the β phase. The deformation induced ω-β transformation and the associated dislocation channeling process can explain the presence of the aforementioned special deformation features in the current gum metal. © 2015 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.actamat.2015.08.047
  • 2015 • 284 Deposition and characterization of single magnetron deposited Fe:SnOx coatings
    Kormunda, M. and Fischer, D. and Hertwig, A. and Beck, U. and Sebik, M. and Pavlik, J. and Esser, N.
    Thin Solid Films 595 200-208 (2015)
    Coatings deposited bymagnetron co-sputtering froma single RF magnetronwith a ceramic SnO2 target with iron inset in argon plasma were studied. Themass spectra of the process identified Sn+ and SnO+ species as the dominant species sputtered fromthe target, but no SnO2 + specieswere detected. The dominant positive ions in argon plasma are Ar+ species. The only detected negative ions were O-. Sputtered neutral tin related species were not detected. Iron related species were also not detected because their concentration is below the detection limit. The concentration of iron dopant in the tin oxide coatings was controlled by the RF bias applied on the substrate holder while the discharge pressure also has some influence. The iron concentration was in the range from 0.9 at.% up to 19 at.% increasing with the substrate bias while the sheet resistivity decreases. The stoichiometry ratio of O/(Sn+Fe) in the coatings increased from 1.7 up to 2 in dependence on the substrate bias from floating bias (-5 V) up to-120 V of RF self-bias, respectively. The tin in the coatings was mainly bonded in Sn4+ state and iron was mainly in Fe2+ state when other tin bonding states were detected only in a small amounts. Iron bonding states in contrary to elemental compositions of the coatings were not influenced by the RF bias applied on the substrate. The coatings showed high transparency in the visible spectral range. However, an increased metallic behavior could be detected by using a higher RF bias for the deposition. The X-ray diffraction patterns and electron microscopy pictures made on the coatings confirmed the presence of an amorphous phase. © 2015 Published by Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.tsf.2015.11.009
  • 2015 • 283 Detoxification of hexavalent chromium in wastewater containing organic substances using simonkolleite-TiO2 photocatalyst
    Abdel Moniem, S.M. and Ali, M.E.M. and Gad-Allah, T.A. and Khalil, A.S.G. and Ulbricht, M. and El-Shahat, M.F. and Ashmawy, A.M. and Ibrahim, H.S.
    Process Safety and Environmental Protection 95 247-254 (2015)
    Innovative simple method for the preparation of simonkolleite-TiO<inf>2</inf> photocatalyst with different Zn contents was achieved. The prepared photocatalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), FT-IR, Raman and diffuse reflectance spectroscopy techniques. The photocatalytic activities of the materials were evaluated for the simultaneous detoxification of hexavalent chromium (Cr(VI)) and oxidation of organic compounds commonly present in wastewater under simulated solar light. The best photoreduction efficiency of Cr(VI) has been achieved at 1000 ppm simonkolleite-TiO<inf>2</inf> photocatalyst of 5% Zn/TiO<inf>2</inf> weight ratio, and pH value of 2.5 to enhance the adsorption onto catalyst surface. Photoreduction was significantly improved by using formic acid as holes scavenger owing to its chemical adsorption on the catalyst surface. Finally, 100% photoreduction of Cr(VI) could be achieved using formic/simonkolleite-TiO<inf>2</inf> systems under sunlight.
    view abstractdoi: 10.1016/j.psep.2015.03.010
  • 2015 • 282 From layered zeolite precursors to zeolites with a three-dimensional porosity: Textural and structural modifications through alkaline treatment
    De Baerdemaeker, T. and Feyen, M. and Vanbergen, T. and Müller, U. and Yilmaz, B. and Xiao, F.-S. and Zhang, W. and Yokoi, T. and Bao, X. and De Vos, D.E. and Gies, H.
    Chemistry of Materials 27 316-326 (2015)
    The layered zeolite precursor RUB-36, consisting of ferrierite-type layers, can be transformed into a three-dimensional framework through various methods such as topotactic condensation into the CDO topology, or interlayer expansion either in the presence or absence of a silylating agent. However, the plate-like morphology of the micrometer sized crystals hampers the accessibility of the 2D micropore system, in which the channels run parallel to the plates. With the aim of introducing mesoporosity, alkaline treatments were performed on different RUB-36 derived expanded materials, and on RUB-36 itself. The effect on the physicochemical properties was examined using N2 physisorption, powder X-ray diffraction, scanning electron microscopy and 27Al MAS NMR whereas the influence on the catalytic activity was evaluated using esterification and alkylation reactions. After calcination, the purely inorganic, interlayer expanded material could be transformed into a mesopore containing FER-type material by selective removal of the interlayer T atom followed by the recombination of the layers. In the precalcination state, organic moieties, originating from the silylating agent or from the organic structure directing agent (OSDA), increase the hydrophobicity of the interlayer expanded structure and its stability against the alkaline treatment. In RUB-36, the high OSDA content limited the amount of mesopore formation through alkaline treatment. However, using the appropriate conditions, the subsequent interlayer expansion of alkaline treated RUB-36 also resulted in a mesopore containing interlayer expanded structure. © 2014 American Chemical Society.
    view abstractdoi: 10.1021/cm504014d
  • 2015 • 281 Impact of ambient pressure on titania nanoparticle formation during spray-flame synthesis
    Hardt, S. and Wlokas, I. and Schulz, C. and Wiggers, H.
    Journal of Nanoscience and Nanotechnology 15 9449-9456 (2015)
    Nanocrystalline titania was synthesized via liquid-fed spray-flame synthesis in a hermetically closed system at various pressures. Titanium tetraisopropoxide dissolved in isopropanol was used as precursor. The size, crystal structure, degree of agglomeration, morphology and the band gap of the as-prepared particles were investigated ex situ by nitrogen adsorption, transmission electron microscopy, X-ray diffraction, and UV-VIS absorption spectroscopy. In comparison to synthesis at atmospheric pressure it was found that decreasing pressure has a significant influence on the particle size distribution leading to smaller particles with reduced geometric standard deviation while particle morphology and crystal structure are not affected. Computational fluid dynamics simulations support the experimental findings also indicating a significant decrease in particle size at reduced pressure. Although it is well known that decreasing pressure leads to smaller particle sizes, it is (to our knowledge) the first time that this relation was investigated for spray-flame synthesis. Copyright © 2015 American Scientific Publishers All rights reserved.
    view abstractdoi: 10.1166/jnn.2015.10607
  • 2015 • 280 In Situ X-ray Diffraction Study of Co-Al Nanocomposites as Catalysts for Ammonia Decomposition
    Gu, Y.-Q. and Fu, X.-P. and Du, P.-P. and Gu, D. and Jin, Z. and Huang, Y.-Y. and Si, R. and Zheng, L.-Q. and Song, Q.-S. and Jia, C.-J. and Weidenthaler, C.
    Journal of Physical Chemistry C 119 17102-17110 (2015)
    Co-Al nanocomposite materials as active and stable catalysts for ammonia decomposition have been synthesized by a one-pot evaporation-induced self-assembly method. The catalysts were characterized by various techniques including powder X-ray diffraction (XRD), X-ray absorption fine structure (XAFS), X-ray photoelectron spectroscopy (XPS), N<inf>2</inf> adsorption/desorption, and transmission/scanning electron microscopy (TEM/SEM). Especially, in situ XRD under catalytic reaction conditions was performed, and metallic Co with a cubic structure was identified to be most probably the active crystalline phase for the decomposition of ammonia; also, contribution of CoO to the catalytic activity cannot be excluded. Most importantly, the introduction of alumina can significantly suppress the agglomeration of the active metallic Co phase and thus maintain the high activity of the cobalt catalyst. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/acs.jpcc.5b02932
  • 2015 • 279 In-situ annealing of NiTi thin films at different temperatures
    Tillmann, W. and Momeni, S.
    Sensors and Actuators, A: Physical 221 9-14 (2015)
    Magnetron sputtered NiTi thin films are usually sputtered at ambient temperature and need a post-annealing treatment to promote crystallization and obtain shape memory effect. However, this treatment could adversely affect the microstructure as well as the morphology of the film. Within this study, NiTi thin films were generated by annealing during the sputtering process. The effect of the sputtering temperature on the morphology of the film, the composition, and shape memory behavior was studied using X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), field emission scanning electron microscopy (FESEM), and differential scanning calorimetry (DSC). © 2014 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.sna.2014.10.034
  • 2015 • 278 Influence of carbon content, particle size, and partial manganese substitution on the electrochemical performance of LiFexMn1-xPO4/carbon composites
    Hamid, N.A. and Wennig, S. and Heinzel, A. and Schulz, C. and Wiggers, H.
    Ionics 21 1857-1866 (2015)
    LiFePO<inf>4</inf>/C and LiFe<inf>x</inf>Mn<inf>1-x</inf>PO<inf>4</inf>/C (x = 0.7) nanocomposites were successfully synthesized via scalable spray-flame synthesis followed by solid-state reaction. A solution of iron (III) acetylacetonate and tributyl phosphate in toluene was used to produce amorphous, nanosized FePO<inf>4</inf>⋅H<inf>2</inf>O in a spray-flame reactor which was then milled with Li<inf>2</inf>CO<inf>3</inf> and glucose to produce a LiFePO<inf>4</inf>/C composite material in a solid-state reaction. The influence of calcination temperature and carbon content on the properties of the resulting material was investigated using specific surface area measurements (BET), X-ray diffraction (XRD), electron microscopy, and electrochemical characterization. The impact of manganese addition on the electrochemical behavior was analyzed using cyclic voltammetry (CV) and constant-current (CC) measurements. XRD shows that the combination of gas-phase synthesis and subsequent solid-state reaction yields highly pure LiFePO<inf>4</inf>/C. BET measurement revealed that the particle size of LiFePO<inf>4</inf> in the composite depends on the amount of glucose. A discharge capacity of more than 140 mAh/g at C/20 is achieved for LiFePO<inf>4</inf>/C with a carbon content of 6 wt%. This material supports high charge as well as discharge rates delivering more than 60 mAh/g at 16 C and sustains good cycle stability providing 115 mAh/g at 1 C. The energy density of the olivine increases about 10 % by substituting 30 mol% of iron by manganese while preserving the electrochemical performance of pure LiFePO<inf>4</inf>/C. © 2015, Springer-Verlag Berlin Heidelberg.
    view abstractdoi: 10.1007/s11581-015-1366-6
  • 2015 • 277 Influence of film thickness and composition on the martensitic transformation in epitaxial Ni-Mn-Sn thin films
    Teichert, N. and Auge, A. and Yüzüak, E. and Dincer, I. and Elerman, Y. and Krumme, B. and Wende, H. and Yildirim, O. and Potzger, K. and Hütten, A.
    Acta Materialia 86 279-285 (2015)
    Two series of epitaxial Ni-Mn-Sn thin films of different thickness are investigated for the thickness and composition dependence of the martensitic transformation. Thin films ranging in thickness from 20 to 200 nm (series A) and 10 to 100 nm (series B) were prepared by magnetron co-sputtering and deposited on heated MgO(0 0 1) substrates. The structural characterization was done by temperature-dependent X-ray diffraction measurements. Magnetization and resistivity measurements were performed to investigate the transformation characteristics. We find a strong influence of the film thickness on the relative amount of material undergoing the martensitic transformation, the temperature range of the transformation, and the transformation temperatures. The main contribution originates from the rigid substrate which delays the transformation of the Ni-Mn-Sn near the interface and even leads to a layer of residual austenite at low temperatures. Another issue are size effects which presumably broaden the martensitic transformation and decrease the transformation temperatures. By variation of the thin film composition we find changes of the substrate influence due to a different mismatch between the lattice of MgO and austenite. A better phase compatibility between martensite and austenite, denoted by λ2, not only results in a smaller hysteresis but is also beneficial for the transformation of material close to the substrate. © 2014 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.actamat.2014.12.019
  • 2015 • 276 Influence of humidity on the phase behavior of API/polymer formulations
    Prudic, A. and Ji, Y. and Luebbert, C. and Sadowski, G.
    European Journal of Pharmaceutics and Biopharmaceutics 94 352-362 (2015)
    Amorphous formulations of APIs in polymers tend to absorb water from the atmosphere. This absorption of water can induce API recrystallization, leading to reduced long-term stability during storage. In this work, the phase behavior of different formulations was investigated as a function of relative humidity. Indomethacin and naproxen were chosen as model APIs and poly(vinyl pyrrolidone) (PVP) and poly(vinyl pyrrolidone-co-vinyl acetate) (PVPVA64) as excipients. The formulations were prepared by spray drying. The water sorption in pure polymers and in formulations was measured at 25 °C and at different values of relative humidity (RH = 25%, 50% and 75%). Most water was absorbed in PVP-containing systems, and water sorption was decreasing with increasing API content. These trends could also be predicted in good agreement with the experimental data using the thermodynamic model PC-SAFT. Furthermore, the effect of absorbed water on API solubility in the polymer and on the glass-transition temperature of the formulations was predicted with PC-SAFT and the Gordon-Taylor equation, respectively. The absorbed water was found to significantly decrease the API solubility in the polymer as well as the glass-transition temperature of the formulation. Based on a quantitative modeling of the API/polymer phase diagrams as a function of relative humidity, appropriate API/polymer compositions can now be selected to ensure long-term stable amorphous formulations at given storage conditions. © 2015 Published by Elsevier B.V.
    view abstractdoi: 10.1016/j.ejpb.2015.06.009
  • 2015 • 275 Influence of in-situ and postannealing technique on tribological performance of NiTi SMA thin films
    Tillmann, W. and Momeni, S.
    Surface and Coatings Technology 276 286-295 (2015)
    Magnetron sputtered NiTi thin films were crystallized through two convenient techniques: (i) postannealing and (ii) in-situ annealing during the deposition. The annealing parameters (temperature and time) were kept constant by employing each technique. The microstructure, morphology, phase transformation behavior, mechanical and tribological properties of these thin films were investigated using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), 4-point probe resistivity measurement, nanoindentation test, pin-on-disc, scratch test and three dimensional (3D) optical microscopy. The results show how postannealing and in-situ annealing techniques can differently affect properties of NiTi thin films in spite of employing similar annealing temperature and time. © 2015 Elsevier B.V..
    view abstractdoi: 10.1016/j.surfcoat.2015.07.012
  • 2015 • 274 Insights into the structural, electronic, and magnetic properties of Fe2−xTixO3/Fe2O3 thin films with x = 0.44 grown on Al2O3 (0001)
    Dennenwaldt, T. and Lübbe, M. and Winklhofer, M. and Müller, A. and Döblinger, M. and Nabi, H.S. and Gandman, M. and Cohen-Hyams, T. and Kaplan, W.D. and Moritz, W. and Pentcheva, R. and Scheu, C.
    Journal of Materials Science 50 122-137 (2015)
    The interface between hematite (α-Fe2 IIIO3) and ilmenite (FeIITiO3), a weak ferrimagnet and an antiferromagnet, respectively, has been suggested to be strongly ferrimagnetic due to the formation of a mixed valence layer of Fe2+/Fe3+ (1:1 ratio) caused by compensation of charge mismatch at the chemically abrupt boundary. Here, we report for the first time direct experimental evidence for a chemically distinct layer emerging at heterointerfaces in the hematite—Ti-doped-hematite system. Using molecular beam epitaxy, we have grown thin films (~25 nm thickness) of α-Fe2O3 on α-Al2O3 (0001) substrates, which were capped with a ~25 nm thick Fe2−xTixO3 layer (x = 0.44). An additional 3 nm cap of α-Fe2O3 was deposited on top. The films were structurally characterized in situ with surface X-ray diffraction, which showed a partial low index orientation relationship between film and substrate in terms of the [0001] axis and revealed two predominant domains with (Formula presented.) one with (Formula presented.) and a twin domain with (Formula presented.). Electron energy loss spectroscopy profiles across the Fe2−xTixO3/Fe2O3 interface show that Fe2+/Fe3+ ratios peak right at the interface. This strongly suggests the formation of a chemically distinct interface layer, which might also be magnetically distinct as indicated by the observed magnetic enhancement in the Fe2−xTixO3/α-Fe2O3/Al2O3 system compared to the pure α-Fe2O3/Al2O3 system. © 2014, Springer Science+Business Media New York.
    view abstractdoi: 10.1007/s10853-014-8572-x
  • 2015 • 273 Intermartensitic transitions and phase stability in Ni50Mn50-xSnx Heusler alloys
    Çakir, A. and Righi, L. and Albertini, F. and Acet, M. and Farle, M.
    Acta Materialia 99 140-149 (2015)
    Ni-Mn based Heusler alloys are of considerable interest due to their multifunctional properties such as magnetic shape memory, magnetocaloric effect and spintronics. The reason for these multifunctional properties is the presence of a first order martensitic transition and its strong coupling to the magnetization. In this work, one of the outstanding class of martensitic Heuslers, Ni-Mn-Sn, is investigated in relation to magneto-structural phase transitions and the stability of the various crystallographic structures under varying temperature. Temperature-dependent X-ray diffraction, resistance and magnetization measurements on Ni<inf>50</inf>Mn<inf>50-x</inf>Sn<inf>x</inf> alloys are performed in a broad valence electron concentration range 7.91 ≤ (e/a) ≤ 8.34 (5.1 ≤ x ≤ 20.3at.%). The results reveal that in addition to the austenite-martensite transition, further intermartensitic transitions take place with decreasing temperature. Depending on the composition, we observe that the parent martensite phase tends to transform to L1<inf>0</inf> martensite as the ground state phase when the temperature is lowered. A phase diagram of Ni<inf>50</inf>Mn<inf>50-x</inf>Sn<inf>x</inf> is constructed to include intermartensitic phase transition boundaries. © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2015.07.072
  • 2015 • 272 Interplay of strain and interdiffusion in Heusler alloy bilayers
    Dutta, B. and Hickel, T. and Neugebauer, J. and Behler, C. and Fähler, S. and Behler, A. and Waske, A. and Teichert, N. and Schmalhorst, J.-M. and Hütten, A.
    Physica Status Solidi - Rapid Research Letters 9 321-325 (2015)
    Combining conventional and inverse magnetocaloric materials promises to enhance solid state refrigeration. As a first step here we present epitaxial Ni-Mn-Ga/Ni-Mn-Sn bilayer films. We examine the dependence of the lateral and normal lattice constants on the deposition sequence by combining experimental and ab initio techniques. Structural properties are determined with X-ray diffraction as well as highresolution transmission electron microscopy, while ab initio calculations explain the interplay of strain, local relaxations and the interdiffusion of atoms. The latter is confirmed by Auger electron spectroscopy and is expected to have a noticeable impact on the functional properties of the Heusler materials. ( © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/pssr.201510070
  • 2015 • 271 Local electronic and magnetic properties of pure and Mn-containing magnetocaloric LaFe13-xSix compounds inferred from Mössbauer spectroscopy and magnetometry
    Makarov, S.I. and Krautz, M. and Salamon, S. and Skokov, K. and Teixeira, C.S. and Gutfleisch, O. and Wende, H. and Keune, W.
    Journal of Physics D: Applied Physics 48 (2015)
    Manganese containing La-Fe-Si alloys are important magnetocaloric compounds, since Mn atoms prevent segregation of hydrogen in partially hydrogenated La-Fe-Mn-Si alloys when their Curie temperature is tuned to room temperature by hydrogen. The effect of Mn alloying on the Fe atomic magnetic moment μ<inf>Fe</inf> is still rather unexplored. Therefore, we investigated the (local) magnetic and electric hyperfine interactions in the strongly magnetocaloric compound LaFe<inf>11.3</inf>Mn<inf>0.3</inf>Si<inf>1.4</inf> and, for comparison, LaFe<inf>11.6</inf>Si<inf>1.4</inf> by 57Fe Mössbauer spectroscopy, and the global magnetic properties by vibrating sample magnetometry. The NaZn<inf>13</inf> structure was confirmed by x-ray diffraction. Two non-equivalent Fe lattice sites are known to exist in this material: the (96i) sites (Fe<inf>II</inf>) of low local symmetry, and the highly symmetrical (8b) sites (Fe<inf>I</inf>). At room temperature in the paramagnetic state, the electric hyperfine parameters of Fe atoms on both sites were obtained. At low temperatures (4.8 K), the observed magnetically split nuclear Zeeman sextets with broad apparent lines were analyzed in terms of a distribution P(B<inf>hf</inf>) of hyperfine magnetic fields B<inf>hf</inf>. The average hyperfine field 〈B<inf>hf</inf>〉, originating predominantly from Fe<inf>II</inf> sites, was found to be rather high (30.7(1) T at 4.8 K) for LaFe<inf>11.6</inf>Si<inf>1.4</inf>, and the approximate relation 〈B<inf>hf</inf>〉 = Aμ<inf>Fe</inf> is confirmed for Fe<inf>II</inf> sites, with A = 14.2 T/μ<inf>B</inf>. 〈B<inf>hf</inf>〉 is significantly reduced (to 27.7(1) T at 4.8 K) for the Mn-containing sample LaFe<inf>11.3</inf>Mn<inf>0.3</inf>Si<inf>1.4</inf>, providing evidence for a reduction by 9.7% of the average Fe atomic moment μ<inf>Fe</inf> from ∼2.16 μ<inf>B</inf> to a value of ∼1.95 μ<inf>B</inf> by Mn substitution of Fe. Our Mössbauer results are in good agreement with magnetometry, which reveals a reduction of the saturation magnetization of M<inf>s</inf> = 163.1(1) Am2 kg-1 of LaFe<inf>11.6</inf>Si<inf>1.4</inf> by 10.5% due to Mn substitution. © 2015 IOP Publishing Ltd.
    view abstractdoi: 10.1088/0022-3727/48/30/305006
  • 2015 • 270 Magnetodielectric effect in relaxor/ferrimagnetic composites
    Naveed Ul-Haq, M. and Yunus, T. and Mumtaz, A. and Shvartsman, V.V. and Lupascu, D.C.
    Journal of Alloys and Compounds 640 462-467 (2015)
    Abstract We report on the effect of an applied static magnetic field on the dielectric properties of ferroelectric relaxor/ferrimagnetic composites consisting of [Ba(Sn<inf>0.3</inf>Ti<inf>0.7</inf>)O<inf>3</inf>]<inf>0.8</inf>-[CoFe<inf>2</inf>O<inf>4</inf>]<inf>0.2</inf> (BST<inf>0.8</inf>-CFO<inf>0.2</inf>). The pure Ba(Sn<inf>0.3</inf>Ti<inf>0.7</inf>)O<inf>3</inf> (BST30) as well as the composites, were synthesized by solid state reaction method. The X-ray diffraction analysis confirmed that BST30 and CFO coexist in the composite without any secondary phase. The real and the imaginary part of the dielectric permittivity were studied as a function of temperature, with and without static magnetic field, respectively. Relaxor characteristics such as dielectric permittivity and its peak temperature are observed to vary with the magnetic field. This is explained in the context that the applied magnetic field creates magnetostriction in the ferrite phase which is transferred to the relaxor phase via the interface coupling. The strain in the relaxor phase results in the reorientation of local polarization entities, polar nano regions (PNRs), which alters the dielectric characteristics of the sample. This effect is explained in relation to local order parameter q(T) which is found to increase in a certain temperature range above the typical ferroelectric temperature regime with the application of magnetic field. © 2015 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.jallcom.2015.03.215
  • 2015 • 269 Manganese tetraboride, MnB4: High-temperature crystal structure, p-n transition, 55Mn NMR spectroscopy, solid solutions, and mechanical properties
    Knappschneider, A. and Litterscheid, C. and Brgoch, J. and George, N.C. and Henke, S.c and Cheetham, A.K. and Hu, J.G. and Seshadri, R. and Albert, B.
    Chemistry - A European Journal 21 8177-8181 (2015)
    The structural and electronic properties of MnB<inf>4</inf> were studied by high-temperature powder X-ray diffraction and measurements of the conductivity and Seebeck coefficient on spark-plasma-sintered samples. A transition from the room-temperature monoclinic structure (space group P2<inf>1</inf>/c) to a high-temperature orthorhombic structure (space group Pnnm) was observed at about 650K. The material remained semiconducting after the transition, but its behavior changed from p-type to n-type. 55Mn NMR measurements revealed an isotropic chemical shift of -1315ppm, confirming an oxidation state of Mn close to I. Solid solutions of Cr<inf>1-x</inf>Mn<inf>x</inf>B<inf>4</inf> (two phases in space groups Pnnm and P2<inf>1</inf>/c) were synthesized for the first time. In addition, nanoindentation studies yielded values of (496±26) and (25.3±1.7)GPa for the Young's modulus and hardness, respectively, compared to values of 530 and 37GPa obtained by DFT calculations. Phase transition: Monoclinic manganese tetraboride can be transformed into an orthorhombic phase thermally or by forming solid solutions with chromium tetraboride. The structural phase transition of semiconducting MnB<inf>4</inf> is accompanied by a p-n transition. 55Mn NMR spectroscopy confirmed the oxidation state I of the metal atom, and nanoindentation experiments resulted in hardness values that are in accordance with DFT calculations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201406631
  • 2015 • 268 Martensitic transformation in Eurofer-97 and ODS-Eurofer steels: A comparative study
    Zilnyk, K.D. and Oliveira, V.B. and Sandim, H.R.Z. and Möslang, A. and Raabe, D.
    Journal of Nuclear Materials 462 360-367 (2015)
    (Figure Presented). Reduced-activation ferritic-martensitic Eurofer-97 and ODS-Eurofer steels are potential candidates for structural applications in advanced nuclear reactors. Samples of both steel grades in the as-tempered condition were austenitized in vacuum for 1 h from 900 °C to 1300 °C followed by air cooling to room temperature. The microstructure was characterized by dilatometry, electron backscatter diffraction (EBSD), and X-ray diffraction (XRD). Thermodynamic calculations provided by Thermo-Calc software were used to determine their transformation temperatures. Even having similar chemical composition, important changes were observed after martensitic transformation in these steels. Significant austenitic grain growth was observed in Eurofer-97 steel leading to the development of coarser martensitic packets. Contrastingly, austenitic grain growth was prevented in ODS-Eurofer steel due to fine and stable dispersion of Y-based particles. © 2014 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.jnucmat.2014.12.112
  • 2015 • 267 MeL2Zn2(μ-1,6-Ph2-N6)-a building block for new hexazene complexes
    Gondzik, S. and Wölper, C. and Haack, R. and Jansen, G. and Schulz, S.
    Dalton Transactions 44 15703-15711 (2015)
    The zinc hexazene complex MeL<inf>2</inf>Zn<inf>2</inf>(μ-1,6-Ph<inf>2</inf>-N<inf>6</inf>) 1 (MeL = HC[C(Me)N(2,4,6-Me<inf>3</inf>C<inf>6</inf>H<inf>2</inf>)]<inf>2</inf>) is a suitable hexazene transfer reagent in reactions with main group metal and transition metal complexes containing M-Me units. The reactions proceed with elimination of MeLZnMe and the resulting complexes were characterized by NMR and IR spectroscopy and single crystal X-ray diffraction (5, 8). Quantum chemical calculations were performed to investigate the electronic structure of 5′ and 8′ in more detail and to identify the absorption bands of the hexazene unit. © 2015 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c5dt02423d
  • 2015 • 266 MOCVD of TiO2 thin films from a modified titanium alkoxide precursor
    Kim, S.J. and Dang, V.-S. and Xu, K. and Barreca, D. and Maccato, C. and Carraro, G. and Bhakta, R.K. and Winter, M. and Becker, H.-W. and Rogalla, D. and Sada, C. and Fischer, R.A. and Devi, A.
    Physica Status Solidi (A) Applications and Materials Science 212 1563-1570 (2015)
    A new titanium precursor, [Ti(OPri)<inf>2</inf>(deacam)<inf>2</inf>] (deacam = N,N-diethylacetoacetamide), was developed by the reaction of the parent Ti alkoxide with the β-ketoamide. The compound, obtained as a monomeric six-coordinated complex, was used in metal organic chemical vapor deposition (MOCVD) of TiO<inf>2</inf> both as a single source precursor (SSP) and in the presence of oxygen. The high thermal stability of [Ti(OPri)<inf>2</inf>(deacam)<inf>2</inf>] enabled the fabrication of TiO<inf>2</inf> films over a wide temperature range, with steady growth rates between 500 and 800 °C. The microstructure of the obtained systems was analyzed by X-ray diffraction (XRD) and Raman spectroscopy, whereas atomic force microscopy (AFM) and field emission-scanning electron microscopy (FE-SEM) measurements were performed to investigate the surface morphology and nanoorganization. Film composition was investigated by complementary techniques like Rutherford backscattering spectrometry (RBS), nuclear reaction analysis (NRA), X-ray photoelectron spectroscopy (XPS), and secondary ion mass spectrometry (SIMS). The electrical properties of the layers were investigated by performing capacitance voltage (C-V) and leakage current measurements. © 2015 Wiley-VCH Verlag GmbH & Co. KGaA.
    view abstractdoi: 10.1002/pssa.201532271
  • 2015 • 265 Non-equiatomic high entropy alloys: Approach towards rapid alloy screening and property-oriented design
    Pradeep, K.G. and Tasan, C.C. and Yao, M.J. and Deng, Y. and Springer, H. and Raabe, D.
    Materials Science and Engineering A 648 183-192 (2015)
    The high entropy alloy (HEA) concept has triggered a renewed interest in alloy design, even though some aspects of the underlying thermodynamic concepts are still under debate. This study addresses the short-comings of this alloy design strategy with the aim to open up new directions of HEA research targeting specifically non-equiatomic yet massively alloyed compositions. We propose that a wide range of massive single phase solid solutions could be designed by including non-equiatomic variants. It is demonstrated by introducing a set of novel non-equiatomic multi-component CoCrFeMnNi alloys produced by metallurgical rapid alloy prototyping. Despite the reduced configurational entropy, detailed characterization of these materials reveals a strong resemblance to the well-studied equiatomic single phase HEA: The microstructure of these novel alloys exhibits a random distribution of alloying elements (confirmed by Energy-Dispersive Spectroscopy and Atom Probe Tomography) in a single face-centered-cubic phase (confirmed by X-ray Diffraction and Electron Backscatter Diffraction), which deforms through planar slip (confirmed by Electron-Channeling Contrast Imaging) and leads to excellent ductility (confirmed by uniaxial tensile tests). This approach widens the field of HEAs to non-equiatomic multi-component alloys since the concept enables to tailor the stacking fault energy and associated transformation phenomena which act as main mechanisms to design useful strain hardening behavior. © 2015 Elsevier B.V.
    view abstractdoi: 10.1016/j.msea.2015.09.010
  • 2015 • 264 Non-innocence of β-diketiminato ligands
    Gondzik, S. and Bläser, D. and Wölper, C. and Schulz, S.
    Journal of Organometallic Chemistry 783 92-95 (2015)
    The homoleptic thio-β-ketiminate zinc complex [MesNC(Me)CH{C(Me)NMes}S]2Zn (1) was obtained from reactions of elemental sulfur with the β-diketiminato zinc complexes [CH{C(Me)NMes}2]ZnMe, [CH{C(Me)NMes}2]2Zn2 and [[CH{C(Me)NMes}2]Zn-TePh]2. 1 and the byproducts were characterized by multinuclear NMR (1H, 13C, 125Te) and IR spectroscopy, elemental analyses as well as by single crystal X-ray diffraction. © 2015 Published by Elsevier B.V.
    view abstractdoi: 10.1016/j.jorganchem.2015.02.028
  • 2015 • 263 Quantitative phase separation in multiferroic Bi0.88Sm0.12FeO3 ceramics via piezoresponse force microscopy
    Alikin, D.O. and Turygin, A.P. and Walker, J. and Rojac, T. and Shvartsman, V.V. and Shur, V.Y. and Kholkin, A.L.
    Journal of Applied Physics 118 (2015)
    BiFeO<inf>3</inf> (BFO) is a classical multiferroic material with both ferroelectric and magnetic ordering at room temperature. Doping of this material with rare-earth oxides was found to be an efficient way to enhance the otherwise low piezoelectric response of unmodified BFO ceramics. In this work, we studied two types of bulk Sm-modified BFO ceramics with compositions close to the morphotropic phase boundary (MPB) prepared by different solid-state processing methods. In both samples, coexistence of polar R3c and antipolar P<inf>bam</inf> phases was detected by conventional X-ray diffraction (XRD); the non-polar P<inf>nma</inf> or P<inf>bnm</inf> phase also has potential to be present due to the compositional proximity to the polar-to-non-polar phase boundary. Two approaches to separate the phases based on the piezoresponse force microscopy measurements have been proposed. The obtained fractions of the polar and non-polar/anti-polar phases were close to those determined by quantitative XRD analysis. The results thus reveal a useful method for quantitative determination of the phase composition in multi-phase ceramic systems, including the technologically most important MPB systems. © 2015 AIP Publishing LLC.
    view abstractdoi: 10.1063/1.4927812
  • 2015 • 262 Routes towards catalytically active TiO2 doped porous cellulose
    Wittmar, A. and Thierfeld, H. and Köcher, S. and Ulbricht, M.
    RSC Advances 5 35866-35873 (2015)
    Cellulose-TiO<inf>2</inf> nanocomposites have been successfully prepared by non-solvent induced phase separation, either from cellulose solutions in ionic liquids or from cellulose acetate solutions in classical organic solvents followed by deacetylation ("regeneration"). Commercially available titania nanoparticles from gas phase synthesis processes have been used and processed as dispersions in the respective polymer solution. The used TiO<inf>2</inf> nanoparticles have been characterized by means of transmission electron microscopy (TEM) and X-ray diffraction (XRD), and their dispersions in ionic liquids and organic solvents have been evaluated by dynamic light scattering (DLS) and advanced rheology. The intermediate polymer solutions used in the phase separation process have been studied by advanced rheology. The resulting nanocomposites have been characterized by means of scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). Special attention has been given to the complex relationship between the characteristics of the phase separation process and the porous structure of the formed nanocomposites. Two catalytic tests, based on the photocatalytic degradation of model organic dyes under UV irradiation, have been used for the characterization of the TiO<inf>2</inf> doped nanocomposites. The proof-of-concept experiments demonstrated the feasibility of photocatalyst immobilization in porous cellulose via phase separation of nanoparticle dispersions in polymer solutions, as indicated by UV-activated dye degradation in aqueous solution. © The Royal Society of Chemistry.2015.
    view abstractdoi: 10.1039/c5ra03707g
  • 2015 • 261 Superconductivity-induced re-entrance of the orthorhombic distortion in Ba1-xKxFe2As2
    Böhmer, A.E. and Hardy, F. and Wang, L. and Wolf, T. and Schweiss, P. and Meingast, C.
    Nature Communications 6 (2015)
    Detailed knowledge of the phase diagram and the nature of the competing magnetic and superconducting phases is imperative for a deeper understanding of the physics of iron-based superconductivity. Magnetism in the iron-based superconductors is usually a stripe-type spin-density-wave, which breaks the tetragonal symmetry of the lattice, and is known to compete strongly with superconductivity. Recently, it was found that in some systems an additional spin-density-wave transition occurs, which restores this tetragonal symmetry, however, its interaction with superconductivity remains unclear. Here, using thermodynamic measurements on Ba1-xKxFe2As2 single crystals, we show that the spin-density-wave phase of tetragonal symmetry competes much stronger with superconductivity than the stripe-type spin-density-wave phase, which results in a novel re-entrance of the latter at or slightly below the superconducting transition. © 2015 Macmillan Publishers Limited. All rights reserved.
    view abstractdoi: 10.1038/ncomms8911
  • 2015 • 260 Synthesis and characterization of antimicrobial textile finishing based on Ag:ZnO nanoparticles/chitosan biocomposites
    Buşilə, M. and Muşat, V. and Textor, T. and Mahltig, B.
    RSC Advances 5 21562-21571 (2015)
    ZnO and Ag:ZnO nanoparticles were prepared by hydrolysis of zinc acetate in the presence of lithium hydroxide (LiOH). In combination with binders based on hybrid polymer sols, these metal oxide materials were applied for textile treatment. Hybrid coatings based on ZnO, Ag:ZnO/CS, chitosan (CS), 3-glycidyloxypropyltrimethoxysilane (GPTMS) and tetraethoxysilane (TEOS) prepared by sol-gel method were applied on cotton 100% and cotton/polyester (50/50%) textiles using "pad-dry-cure" technique. The obtained nanoparticles incorporated within chitosan matrix were characterised by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), UV-Vis spectroscopy and field emission scanning electron microscopy (FE-SEM). The antimicrobial activity of Ag/CS, ZnO/CS and Ag:ZnO/CS composite coatings was investigated in comparison to that of the pure chitosan using the paper disc method on Mueller-Hinton agar, against the Gram-negative E. coli and the Gram-positive S. aureus bacteria. For the same composite coatings applied on textile, the antimicrobial activity was investigated by UV-Vis absorption spectroscopy using TTC method, against the bacteria E. coli and M. luteus. The investigated nanocomposite materials showed good antimicrobial activity and are promising materials for use as medical applications. This journal is © The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c4ra13918f
  • 2015 • 259 Synthesis and X-ray Crystal Structure of Diimidosulfinate Transition Metal Complexes
    Bayram, M. and Bläser, D. and Wölper, C. and Schulz, S.
    Organometallics 34 3421-3427 (2015)
    Bis(trimethylsilyl)sulfurdiimide S(NSiMe3)2 reacts with equimolar amounts of Me2Zn and Cp∗2Zn either with insertion into the metal-carbon bond and formation of the expected S-methyl diimidosulfinate complex [MeZnN(SiMe3)S(Me)NSiMe3]2 1 or the unexpected complex {Me3SiNS[N(SiMe3)SNSiMe3]N(SiMe3)Zn}2 2. Insertion reactions were also observed with Cp∗MMe3 (M = Ti, Zr, Hf), yielding Cp∗(Me)2M[Me3SiNS(Me)NSiMe3] (M = Ti 3, Zr 4, Hf 5), whereas the corresponding Cl-substituted derivatives Cp∗(Cl)2M[(Me3SiNS(Me)NSiMe3] (M = Ti 6, Zr 7, Hf 8) were obtained from salt elimination reactions of Li S-methyl diimidosulfinate (Me3SiN)2S(Me)Li(thf)]2 9 with Cp∗MCl3. Compounds 1-8 were characterized by heteronuclear NMR (1H and 13C) and IR spectroscopy, and the solid state structures of 1-5 and 9 were determined by single crystal X-ray diffraction. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/acs.organomet.5b00407
  • 2015 • 258 The crystallographic template effect assisting the formation of stable α-Al2O3 during low temperature oxidation of Fe-Al alloys
    Brito, P. and Pinto, H. and Kostka, A.
    Corrosion Science (2015)
    The role of thermally grown α-Fe2O3 on the nucleation of α-Al2O3 during oxidation of binary Fe-Al alloys with 15 and 26 at.%Al at 700°C was investigated. Surface morphology of the oxide scales indicated direct nucleation of α-Al2O3 preferentially instead of conversion from metastable Al2O3 polymorphs. Oxide scale development over time was also monitored by use of synchrotron X-ray diffraction and Raman spectroscopy. The results showed that the α-Fe2O3 crystal lattice decreases in volume as oxidation progresses, which was found to be consistent with an Al3+ enrichment of α-Fe2O3 as confirmed by the change in relative intensity of α-Fe2O3 Raman peaks. © 2016 Elsevier Ltd.
    view abstractdoi: 10.1016/j.corsci.2016.01.007
  • 2015 • 257 Three-Dimensional, Fibrous Lithium Iron Phosphate Structures Deposited by Magnetron Sputtering
    Bünting, A. and Uhlenbruck, S. and Sebold, D. and Buchkremer, H.P. and Vaßen, R.
    ACS Applied Materials and Interfaces 7 22594-22600 (2015)
    Crystalline, three-dimensional (3D) structured lithium iron phosphate (LiFePO4) thin films with additional carbon are fabricated by a radio frequency (RF) magnetron-sputtering process in a single step. The 3D structured thin films are obtained at deposition temperatures of 600 °C and deposition times longer than 60 min by using a conventional sputtering setup. In contrast to glancing angle deposition (GLAD) techniques, no tilting of the substrate is required. Thin films are characterized by X-ray diffraction (XRD), Raman spectrospcopy, scanning electron microscopy (SEM), cyclic voltammetry (CV), and galvanostatic charging and discharging. The structured LiFePO4 + C thin films consist of fibers that grow perpendicular to the substrate surface. The fibers have diameters up to 500 nm and crystallize in the desired olivine structure. The 3D structured thin films have superior electrochemical properties compared with dense two-dimensional (2D) LiFePO4 thin films and are, hence, very promising for application in 3D microbatteries. © 2015 American Chemical Society.
    view abstractdoi: 10.1021/acsami.5b07090
  • 2015 • 256 Time-resolved X-ray diffraction reveals the hidden mechanism of high piezoelectric activity in a uniaxial ferroelectric
    Gorfman, S. and Choe, H. and Shvartsman, V.V. and Ziolkowski, M. and Vogt, M. and Strempfer, J. and Łukasiewicz, T. and Pietsch, U. and Dec, J.
    Physical Review Letters 114 (2015)
    High piezoelectric activity of many ferroelectrics has been the focus of numerous recent studies. The structural origin of this activity remains poorly understood due to a lack of appropriate experimental techniques and mixing of different mechanisms related to ferroelectricity and ferroelasticity. Our work reports on the study of a uniaxial Sr0.5Ba0.5Nb2O6 ferroelectric where the formation of regions with different spontaneous strains is ruled out by the symmetry and where the interrelation between piezoelectricity and ferroelectricity can be inspected in an isolated fashion. We performed x-ray diffraction experiments on a single crystalline sample under alternating electric field and observed an unknown hidden-in-the-bulk mechanism, which suggests that the highest piezoelectric activity is realized in the volumes where nucleation of small ferroelectric domains takes place. This new mechanism creates a novel roadmap for designing materials with enhanced piezoelectric properties. © 2015 American Physical Society.
    view abstractdoi: 10.1103/PhysRevLett.114.097601
  • 2015 • 255 Tribological performance of near equiatomic and Ti-rich NiTi shape memory alloy thin films
    Tillmann, W. and Momeni, S.
    Acta Materialia 92 189-196 (2015)
    Near equiatomic and Ti-rich NiTi shape memory alloy thin films were magnetron sputtered with the same processing parameters and thickness of 3 μm. The microstructure, composition, shape memory behavior, mechanical and tribological properties of the deposited thin films were analyzed by using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), differential scanning calorimetry (DSC), nanoindentation, ball-on-disc, scratch test, and three dimensional (3D) optical microscopy. The obtained results clearly show how the crystallization evolution and precipitation formation of these two sets of thin films can drastically influence their mechanical and tribological performances. © 2015 Acta Materialia Inc. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2015.04.006
  • 2015 • 254 Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: Structure-activity relationship
    Guo, Y. and Gu, D. and Jin, Z. and Du, P.-P. and Si, R. and Tao, J. and Xu, W.-Q. and Huang, Y.-Y. and Senanayake, S. and Song, Q.-S. and Jia, C.-J. and Schüth, F.
    Nanoscale 7 4920-4928 (2015)
    Uniform Au nanoparticles (∼2 nm) with narrow size-distribution (standard deviation: 0.5-0.6 nm) supported on both hydroxylated (Fe-OH) and dehydrated iron oxide (Fe-O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) showed high homogeneity in the supported Au nanoparticles. The ex situ and in situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reduction by hydrogen (H<inf>2</inf>-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe-OH < Au/Fe-O) and CD (Au/Fe-OH > Au/Fe-O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe-OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeO<inf>x</inf> catalysts with very similar structural characteristics in CO oxidation. © The Royal Society of Chemistry 2015.
    view abstractdoi: 10.1039/c4nr06967f
  • 2015 • 253 [001] Preferentially-oriented 2D tungsten disulfide nanosheets as anode materials for superior lithium storage
    Yang, W. and Wang, J. and Si, C. and Peng, Z. and Frenzel, J. and Eggeler, G. and Zhang, Z.
    Journal of Materials Chemistry A 3 17811-17819 (2015)
    Rechargeable lithium ion batteries (LIBs) have transformed portable electronics and will play a crucial role in transportation, such as electric vehicles. For higher energy storage in LIBs, two issues should be addressed, that is, the fundamental understanding of the chemistry taking place in LIBs and the discovery of new materials. Here we design and fabricate two-dimensional (2D) WS<inf>2</inf> nanosheets with preferential [001] orientation and perfect single crystalline structures. Being used as an anode for LIBs, the WS<inf>2</inf>-nanosheet electrode exhibits a high specific capacity, good cycling performance and excellent rate capability. Considering the controversy in the lithium storage mechanism of WS<inf>2</inf>, ex-situ X-ray diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS) analyses clearly verify that the recharge product (3.0 V vs. Li+/Li) of the WS<inf>2</inf> electrode after fully discharging to 0.01 V (vs. Li+/Li) tends to reverse to WS<inf>2</inf>. More remarkably, the [001] preferentially-oriented 2D WS<inf>2</inf> nanosheets are also promising candidates for applications in photocatalysis, water splitting, and so forth. © The Royal Society of Chemistry 2015.
    view abstractdoi: 10.1039/c5ta04176g
  • 2014 • 252 A facile solution-doping method to improve a low-temperature zinc oxide precursor: Towards low-cost electronics on plastic foil
    Weber, D. and Botnaraş, S. and Pham, D.V. and Merkulov, A. and Steiger, J. and Schmechel, R. and De Cola, L.
    Advanced Functional Materials 24 2537-2543 (2014)
    Optimization of thin-film transistors performance is usually accompanied by an increase of the process temperature. This work presents a method to raise the field effect mobility by a factor of 3 without a change of the process parameters. The modification involves a solution doping process where an ammine zinc complex is formed in the presence of metal ions of the 13th group, namely gallium and indium. Morphological studies, including scanning electron microscopy and atomic force microscopy, reveal the difference among the resulting films. Moreover, X-ray diffraction results show that the doping affects the preferred orientation of the zinc oxide crystals in the resulting film. The electrical properties vary distinctly and are best for a solution doped with both gallium and indium. With a double-layer system the performance of this new precursor exceeds field effect mobility values of 1 cm2 V-1 s-1 after a maximum process temperature of 160 °C. The performance of ZnO-based field-effect transistors is improved by a simple solution-doping procedure using ions of the 13th group. The method has a strong influence on the film morphology and orientation of the crystallites. This leads to field effect mobility values comparable to amorphous silicon. The low conversion temperature allows the fabrication on flexible substrates. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/adfm.201303461
  • 2014 • 251 Ab initio structure determination of interlayer expanded zeolites by single crystal rotation electron diffraction
    Guo, P. and Liu, L. and Yun, Y. and Su, J. and Wan, W. and Gies, H. and Zhang, H. and Xiao, F.-S. and Zou, X.
    Dalton Transactions 43 10593-10601 (2014)
    Layered solids often form thin plate-like crystals that are too small to be studied by single-crystal X-ray diffraction. Although powder X-ray diffraction (PXRD) is the conventional method for studying such solids, it has limitations because of peak broadening and peak overlapping. We have recently developed a software-based rotation electron diffraction (RED) method for automated collection and processing of 3D electron diffraction data. Here we demonstrate the ab initio structure determination of two interlayer expanded zeolites, the microporous silicates COE-3 and COE-4 (COE-n stands for International Network of Centers of Excellence-n), from submicron-sized crystals by the RED method. COE-3 and COE-4 are built of ferrierite-type layers pillared by (-O-Si(CH 3)2-O-) and (-O-Si(OH)2-O-) linker groups, respectively. The structures contain 2D intersecting 10-ring channels running parallel to the ferrierite layers. Because both COE-3 and COE-4 are electron-beam sensitive, a combination of RED datasets from 2 to 3 different crystals was needed for the structure solution and subsequent structure refinement. The structures were further refined by Rietveld refinement against the PXRD data. The structure models obtained from RED and PXRD were compared. This journal is © the Partner Organisations 2014.
    view abstractdoi: 10.1039/c4dt00458b
  • 2014 • 250 Aluminum-doped ZnO nanoparticles: Gas-phase synthesis and dopant location
    Schilling, C. and Zähres, M. and Mayer, C. and Winterer, M.
    Journal of Nanoparticle Research 16 (2014)
    Aluminum-doped ZnO (AZO) nanoparticles are studied widely as transparent conducting alternatives for indium tin oxide. However, the properties of AZO vary in different investigations not only with the amount of dopant and the particle size, but also with other parameters such as synthesis method and conditions. Hence, AZO nanoparticles, synthesized in the gas phase, were investigated to study the influence of the synthesis parameters dopant level, reactor temperature and residence time in the reaction zone on the particle characteristics. The local structure of the dopant in semiconductors determines whether the doping is functional, i.e., whether mobile charge carriers are generated. Therefore, information obtained from 27Al solid-state NMR spectroscopy, X-ray diffraction, photoluminescence and UV-Vis spectroscopy was used to understand how the local structure influences particles characteristics and how the local structure itself can be influenced by the synthesis parameters. In addition to AZO particles of different Al content, pure ZnO, Al2O3, ZnAl2O4 and core-shell particles of ZnO and Al2O3 were synthesized for comparison and aid to a deeper understanding of the formation of AZO nanoparticles in the gas phase. © 2014 Springer Science+Business Media.
    view abstractdoi: 10.1007/s11051-014-2506-z
  • 2014 • 249 Amine-based solvents for exfoliating graphite to graphene outperform the dispersing capacity of N-methyl-pyrrolidone and surfactants
    Sun, Z. and Huang, X. and Liu, F. and Yang, X. and Rösler, C. and Fischer, R.A. and Muhler, M. and Schuhmann, W.
    Chemical Communications 50 10382-10385 (2014)
    Four organic amine-based solvents were discovered which enable direct exfoliation of graphite to produce high-quality and oxygen-free graphene nanosheets. These solvents outperform previously used solvents and additives such as N-methyl-pyrrolidone and surfactants in terms of their dispersing capacity. The resulting dispersions allow the facile fabrication of zeolitic imidazolate framework (ZIF)-graphene nanocomposites with remarkable CO 2 storage capability. This journal is © the Partner Organisations 2014.
    view abstractdoi: 10.1039/c4cc03923h
  • 2014 • 248 Analysis of stress gradients in physical vapour deposition multilayers by X-ray diffraction at fixed depth intervals
    Fischer, G. and Selvadurai, U. and Nellesen, J. and Sprute, T. and Tillmann, W.
    Journal of Applied Crystallography 47 335-345 (2014)
    The objective of this article is to develop and apply a model for the design and evaluation of X-ray diffraction experiments to measure phase-specific residual stress profiles in multilayer systems. Using synchrotron radiation and angle-dispersive diffraction, the stress measurements are performed on the basis of the sin2ψ method. Instead of the traditional Ω or χ mode, the experiments are carried out by a simultaneous variation of the goniometer angles χ, Ω and φG to ensure that the penetration and information depth and the measuring direction φ remain unchanged when the polar angle ψ is varied. The applicability of this measuring and evaluation strategy is demonstrated by the example of a multilayer system consisting of Ti and TiAlN layers, alternately deposited on a steel substrate by means of physical vapour deposition. © 2014 International Union of Crystallography.
    view abstractdoi: 10.1107/S1600576713030951
  • 2014 • 247 Atomic-scale analysis of carbon partitioning between martensite and austenite by atom probe tomography and correlative transmission electron microscopy
    Toji, Y. and Matsuda, H. and Herbig, M. and Choi, P.-P. and Raabe, D.
    Acta Materialia 65 215-228 (2014)
    Carbon partitioning between ferritic and austenitic phases is essential for austenite stabilization in the most advanced steels such as those produced by the quenching and partitioning (Q&P) process. The atomistic analysis of the carbon partitioning in Q&P alloys is, however, difficult owing to the simultaneous occurrence of bainite transformation, which can also contribute to carbon enrichment into remaining austenite and hence overlap with the carbon partitioning from martensite into austenite. Therefore, we provide here a direct atomic-scale evidence of carbon partitioning from martensite into austenite without the presence of bainite transformation. Carbon partitioning is investigated by means of atom probe tomography and correlative transmission electron microscopy. A model steel (Fe-0.59 wt.% C (2.7 at.% C)-2.0 wt.% Si-2.9 wt.% Mn) with martensite finish temperature below room temperature was designed and used in order to clearly separate the carbon partitioning between martensite and austenite from the bainite transformation. The steel was austenitized at 900°C, then water-quenched and tempered at 400°C. Approximately 8 vol.% retained austenite existed in the asquenched state. We confirmed by X-ray diffraction and dilatometry that austenite decomposition via bainite transformation did not occur during tempering. No carbon enrichment in austenite was observed in the as-quenched specimen. On the other hand, clear carbon enrichment in austenite was observed in the 400°C tempered specimens with a carbon concentration inside the austenite of 5-8 at.%. The results hence quantitatively revealed carbon partitioning from martensite to austenite, excluding bainite transformation during the Q&P heat treatment. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2013.10.064
  • 2014 • 246 Composition-structure-function diagrams of Ti-Ni-Au thin film shape memory alloys
    Buenconsejo, P.J.S. and Ludwig, Al.
    ACS Combinatorial Science 16 678-685 (2014)
    Ti-Ni-Au thin film materials libraries were prepared from multilayer precursors by combinatorial sputtering. The materials libraries were annealed at 500, 600, and 700 °C for 1 h and then characterized by high-throughput methods to investigate the relations between composition, structure and functional properties. The identified relations were visualized in functional phase diagrams. The goal is to identify composition regions that are suitable as high temperature shape memory alloys. Phase transforming compositions were identified by electrical resistance measured during thermal cycles in the range of -20 and 250 °C. Three phase transformation paths were confirmed: (1) B2-R, (2) B2-R-B19', and (3) B2-B19. For the materials library annealed at 500 °C only the B2-R transformation was observed. For the materials libraries annealed at 600 and 700 °C, all transformation paths were observed. High transformation temperatures (Ms ≈100 °C) were only obtained by annealing at 600 or 700 °C, and with compositions of Ti ≈ 50 at. % and Au &gt; 20 at. %. This is the composition range that undergoes B2-B19 transformation. The phase transformation behaviors were explained according to the compositional and annealing temperature dependence of phase/structure formation, as revealed by X-ray diffraction analysis of the materials libraries. © 2014 American Chemical Society.
    view abstractdoi: 10.1021/co5000745
  • 2014 • 245 CrN/AlN nanolaminate coatings deposited via high power pulsed and middle frequency pulsed magnetron sputtering
    Bagcivan, N. and Bobzin, K. and Ludwig, Al. and Grochla, D. and Brugnara, R.H.
    Thin Solid Films 572 153-160 (2014)
    Nanolaminate coatings based on transition metal nitrides such as CrN, AlN and TiN deposited via physical vapor deposition (PVD) have shown great advantage as protective coatings on tools and components subject to high loads in tribological applications. By varying the individual layer materials and their thicknesses it is possible to optimize the coating properties, e.g. hardness, Young's modulus and thermal stability. One way for further improvement of coating properties is the use of advanced PVD technologies. High power pulsed magnetron sputtering (HPPMS) is an advancement of pulsed magnetron sputtering (MS). The use of HPPMS allows a better control of the energetic bombardment of the substrate due to the higher ionization degree of metallic species. It provides an opportunity to influence chemical and mechanical properties by varying the process parameters. The present work deals with the development of CrN/AlN nanolaminate coatings in an industrial scale unit by using two different PVD technologies. Therefore, HPPMS and mfMS (middle frequency magnetron sputtering) technologies were used. The bilayer period Λ, i.e. the thickness of a CrN/AlN double layer, was varied between 6.2nm and 47.8 nm by varying the rotational speed of the substrate holders. In a second step the highest rotational speed was chosen and further HPPMS CrN/AlN coatings were deposited applying different HPPMS pulse lengths (40, 80, 200 μs) at the same mean cathode power and frequency. Thickness, morphology, roughness and phase composition of the coatings were analyzed by means of scanning electron microscopy (SEM), confocal laser microscopy, and X-ray diffraction (XRD), respectively. The chemical composition was determined using glow discharge optical emission spectroscopy (GDOES). Detailed characterization of the nanolaminate was conducted by transmission electron microscopy (TEM). The hardness and the Young's modulus were analyzed by nanoindentation measurements. The residual stress was determined via Si microcantilever curvature measurements. The phase analysis revealed the formation of h-Cr2N, c-CrN and c-AlN mixed phases for the mfMS CrN/AlN coatings, whereas the HPPMS coatings exhibited only cubic phases (c-CrN, c-AlN). A hardness of 31.0 GPa was measured for the HPPMS coating with a bilayer period of 6.2 nm. The decrease of the HPPMS pulse length at constant mean power leads to a considerable increase of the cathode current on the Cr and Al target associated with an increased ion flux towards the substrate. Furthermore, it was observed that the deposition rate of HPPMS CrN/AlN decreases with shorter pulse lengths, so that a CrN/AlN coating with a bilayer period of 2.9 nm, a high hardness of 40.8 GPa and a high compressive stress (- 4.37 GPa) was achieved using a short pulse length of 40 μs. © 2014 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.tsf.2014.06.058
  • 2014 • 244 Crystallization, phase evolution and corrosion of Fe-based metallic glasses: An atomic-scale structural and chemical characterization study
    Duarte, M.J. and Kostka, A. and Jimenez, J.A. and Choi, P. and Klemm, J. and Crespo, D. and Raabe, D. and Renner, F.U.
    Acta Materialia 71 20-30 (2014)
    Understanding phase changes, including their formation and evolution, is critical for the performance of functional as well as structural materials. We analyze in detail microstructural and chemical transformations of the amorphous steel Fe50Cr15Mo14C15B6 during isothermal treatments at temperatures ranging from 550 to 800 °C. By combining high-resolution transmission electron microscopy and Rietveld analyses of X-ray diffraction patterns together with the local chemical data obtained by atom probe tomography, this research provides relevant information at the atomic scale about the mechanisms of crystallization and the subsequent phases evolution. During the initial stages of crystallization a stable (Fe,Cr) 23(C,B)6 precipitates as well as two metastable intermediates of M3(C,B) and the intermetallic χ-phase. When full crystallization is reached, only a percolated nano-scale Cr-rich (Fe,Cr) 23(C,B)6 and Mo-rich η-Fe3Mo3C structure is detected, with no evidence to suggest that other phases appear at any subsequent time. Finally, the corrosion behavior of the developed phases is discussed from considerations of the obtained atomic information. © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2014.02.027
  • 2014 • 243 Deposition of superelastic composite NiTi based films
    Tillmann, W. and Momeni, S.
    Vacuum 104 41-46 (2014)
    In recent years, NiTi shape memory alloys (SMA) thin films have been widely used as promising high-performance materials in the field of biomedical and microelectromechanical (MEMS) systems. However, there are still important problems such as their unsatisfactory mechanical and tribological properties including a limited hardness and wear resistance. This study aimed at deposition of layered composite thin films made of NiTi and TiCN thin films on Si (100) substrate by means of DC magnetron sputtering. Subsequently, microstructures, mechanical properties and shape memory behavior of these bilayers were investigated using Nanoindentation, X-ray diffraction (XRD), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The results of this study confirmed that the presence of TiCN layer on NiTi thin film modifies its mechanical properties while maintaining the shape memory effects. The initial findings of this research work are suggestive of the potential for fabrication of self-healed composite NiTi based films. © 2014 Published by Elsevier Ltd.
    view abstractdoi: 10.1016/j.vacuum.2013.12.010
  • 2014 • 242 Effect of a side reaction involving structural changes of the surfactants on the shape control of cobalt nanoparticles
    Comesaña-Hermo, M. and Estivill, R. and Ciuculescu, D. and Li, Z.-A. and Spasova, M. and Farle, M. and Amiens, C.
    Langmuir 30 4474-4482 (2014)
    Cobalt nanoparticles with different sizes and morphologies including spheres, rods, disks, and hexagonal prisms have been synthesized through the decomposition of the olefinic precursor [Co(η3-C 8H13)(η4-C8H12)] under dihydrogen, in the presence of hexadecylamine and different rhodamine derivatives, or aromatic carboxylic acids. UV-vis spectroscopy, X-ray diffraction, low and high resolution transmission electron microscopy, and electron tomography have been used to characterize the nanomaterials. Especially, the Co nanodisks formed present characteristics that make them ideal nanocrystals for applications such as magnetic data storage. Focusing on their growth process, we have evidenced that a reaction between hexadecylamine and rhodamine B occurs during the formation of these Co nanodisks. This reaction limits the amount of free acid and amine, usually at the origin of the formation of single crystal Co rods and wires, in the growth medium of the nanocrystals. As a consequence, a growth mechanism based on the structure of the preformed seeds rather than oriented attachment or template assisted growth is postulated to explain the formation of the nanodisks. © 2014 American Chemical Society.
    view abstractdoi: 10.1021/la5005165
  • 2014 • 241 Enhanced superplasticity in an Al-alloyed multicomponent Mn-Si-Cr-C steel
    Zhang, H. and Pradeep, K.G. and Mandal, S. and Ponge, D. and Choi, P. and Tasan, C.C. and Raabe, D.
    Acta Materialia 63 232-244 (2014)
    Excellent superplasticity (elongation ∼720%) is observed in a novel multi-component (Mn-S-Cr-Al alloyed) ultrahigh carbon steel during tensile testing at a strain rate of 2 × 10-3 s-1 and a temperature of 1053 K (just above the equilibrium austenite-pearlite transformation temperature). In order to understand superplasticity in this material and its strong Al dependence, the deformation-induced microstructure evolution is characterized at various length scales down to atomic resolution, using X-ray diffraction, scanning electron microscopy, electron backscatter diffraction, energy-dispersive X-ray spectroscopy and atom probe tomography. The results reveal that 1 wt.% Al addition influences various microprocesses during deformation, e.g. it impedes Ostwald ripening of carbides, carbide dissolution, austenite nucleation and growth and void growth. As a result, the size of the austenite grains and voids remains relatively fine (< 10 μm) during superplastic deformation, and fine-grained superplasticity is enabled without premature failure. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2013.10.034
  • 2014 • 240 Epitaxial Cu(001) films grown on a Cr/Ag/Fe/GaAs(001) buffer system
    Gottlob, D.M. and Jansen, T. and Hoppe, M. and Bürgler, D.E. and Schneider, C.M.
    Thin Solid Films 562 250-253 (2014)
    We present a procedure to prepare single-crystalline, high-purity Cu(001) films (templates) suitable as substrates for subsequent epitaxial thin-film growth. The template films were grown in a dedicated molecular-beam epitaxy system on a Cr/Ag/Fe/GaAs(001) buffer layer system. Low-energy electron diffraction and X-ray diffraction were applied to determine the surface orientation and the epitaxial relationship between all layers of the stack. Post-annealing at moderate temperatures enhances the quality of the film as shown by low-energy electron diffraction and atomic force microscopy. X-ray photoemission and Auger electron spectroscopy confirm that no atoms of the buffer layers diffuse into the Cu film during the initial preparation and the post-annealing treatment. The completed Cu(001) template system can be exposed to air and afterwards refurbished by Ar+-ion bombardment and annealing, enabling the transfer between vacuum systems. The procedure provides suitable conductive thin film templates for studies of epitaxial thin films, e.g. on the magnetic and magnetotransport properties of Co and Ni based films and multilayers. © 2014 Elsevier B.V.
    view abstractdoi: 10.1016/j.tsf.2014.04.078
  • 2014 • 239 Evidences of defect contribution in magnetically ordered Sm-implanted GaN
    Lo, F.-Y. and Guo, J.-Y. and Huang, C.-D. and Chou, K.-C. and Liu, H.-L. and Ney, V. and Ney, A. and Chern, M.-Y. and Shvarkov, S. and Reuter, D. and Wieck, A.D. and Pezzagna, S. and Massies, J.
    Current Applied Physics 14 S7-S11 (2014)
    Samarium (Sm) ions of 200 keV in energy were implanted into highly-resistive molecular-beam-epitaxy grown GaN thin films with a focused-ion-beam implanter at room temperature. The implantation doses range between 1014 and 1016 cm-2. X-ray diffraction revealed Sm incorporation into GaN matrix without secondary phase. Raman-scattering spectroscopy identified impurity-independent defect-related oscillation modes. Slight decrease in band gap and significant reduction in transmittance were observed by optical transmission spectroscopy. Photoluminescence spectra showed emission peaks related to background p-type impurity. Ferromagnetic hysteresis loops were recorded from GaN implanted with highest Sm dose, and magnetic ordering was observed from Sm-implanted GaN with dose of and above 1015 cm-2. The long-range magnetic ordering can be attributed to interaction of Sm ions through the implantation-induced Ga vacancy. © 2013 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.cap.2013.11.051
  • 2014 • 238 Fabrication of a Ni-Cu thin film material library using pulsed electrodeposition
    Srinivas, P. and Hamann, S. and Wambach, M. and Ludwig, Al. and Dey, S.R.
    Journal of the Electrochemical Society 161 D504-D509 (2014)
    A thin film composition gradient library of the Ni-Cu alloy system is generated through an electrodeposition technique using a complexing citrate electrolyte bath in a modified Hull cell. Energy dispersive X-ray spectroscopy, scanning electron microscopy and automated X-ray diffraction are performed to assess composition, surface morphology, and crystallographic structure of the deposited film as a function of the lateral position on the materials library. The results confirmed deposition of single phase polycrystalline f.c.c. Ni-Cu alloy system with varied lateral composition and lattice parameter, afcc as well. © 2014 The Electrochemical Society. All rights reserved.
    view abstractdoi: 10.1149/2.0451410jes
  • 2014 • 237 Fabrication of Ag/TiO2 photocatalyst for the treatment of simulated hospital wastewater under sunlight
    Badawy, M.I. and Souaya, E.M.R. and Gad-Allah, T.A. and Abdel-Wahed, M.S. and Ulbricht, M.
    Environmental Progress and Sustainable Energy 33 886-894 (2014)
    In this study, photocatalytic activity of titanium dioxide was modified by doping with silver metal. This was done by simple preparation procedure at room temperature. Different preparation conditions were studied and their effects on photocatalytic activity were investigated. The obtained nanopowders were characterized using X-ray diffraction (XRD), X-ray fluorescence (XRF), specific surface area measurement, UV-Visible absorption, and transmission electron microscope (TEM). Photocatalytic activities of the prepared samples under simulated sunlight were evaluated with respect to their efficiencies for the degradation of five pharmaceutical compounds commonly present in hospital wastewater. Prepared samples showed very high efficiency for photodegradation of the studied pharmaceutical compounds. Maximum photodegradation rate of the simulated hospital wastewater was obtained using 1000 ppm of the material with 0.1% Ag/TiO2 (weight ratio) calcined at 300°C and pH 5. However, the best pH of the degradation of each pharmaceutical compound varies according to the pKa. © 2013 American Institute of Chemical Engineers.
    view abstractdoi: 10.1002/ep.11869
  • 2014 • 236 Femtospex: A versatile optical pump-soft x-ray probe facility with 100fs x-ray pulses of variable polarization
    Holldack, K. and Bahrdt, J. and Balzer, A. and Bovensiepen, U. and Brzhezinskaya, M. and Erko, A. and Eschenlohr, A. and Follath, R. and Firsov, A. and Frentrup, W. and Le Guyader, L. and Kachel, T. and Kuske, P. and Mitzner, R. a...
    Journal of Synchrotron Radiation 21 1090-1104 (2014)
    Here the major upgrades of the femtoslicing facility at BESSYII (Khan et al., 2006) are reviewed, giving a tutorial on how elliptical-polarized ultrashort soft X-ray pulses from electron storage rings are generated at high repetition rates. Employing a 6kHz femtosecond-laser system consisting of two amplifiers that are seeded by one Ti:Sa oscillator, the total average flux of photons of 100fs duration (FWHM) has been increased by a factor of 120 to up to 10 6 photons s -1 (0.1% bandwidth) -1 on the sample in the range from 250 to 1400eV. Thanks to a new beamline design, a factor of 20 enhanced flux and improvements of the stability together with the top-up mode of the accelerator have been achieved. The previously unavoidable problem of increased picosecond-background at higher repetition rates, caused by 'halo' photons, has also been solved by hopping between different 'camshaft' bunches in a dedicated fill pattern ('3+1 camshaft fill') of the storage ring. In addition to an increased X-ray performance at variable (linear and elliptical) polarization, the sample excitation in pump-probe experiments has been considerably extended using an optical parametric amplifier that supports the range from the near-UV to the far-IR regime. Dedicated endstations covering ultrafast magnetism experiments based on time-resolved X-ray circular dichroism have been either upgraded or, in the case of time-resolved resonant soft X-ray diffraction and reflection, newly constructed and adapted to femtoslicing requirements. Experiments at low temperatures down to 6K and magnetic fields up to 0.5T are supported. The FemtoSpeX facility is now operated as a 24h user facility enabling a new class of experiments in ultrafast magnetism and in the field of transient phenomena and phase transitions in solids. © 2014 International Union of Crystallography.
    view abstractdoi: 10.1107/S1600577514012247
  • 2014 • 235 Formation of intermetallic phases in Al-coated hot-stamped 22MnB5 sheets in terms of coating thickness and Si content
    Windmann, M. and Röttger, A. and Theisen, W.
    Surface and Coatings Technology 246 17-25 (2014)
    AlSiFe coatings with differing thicknesses and Si contents were applied to steel sheets by hot dipping. The steel sheets were austenitized at TAUS=920°C for different dwell times and then quenched in water. Phase formation as a function of coating thickness and Si content at the steel substrate/coating interface was investigated by ex-situ phase analysis with synchrotron radiation and by electron backscatter diffraction (EBSD). X-ray diffraction (XRD) and EBSD investigations confirmed the formation of AlFe-rich intermetallics at the steel/coating interface as a result of a strong diffusion of the elements Al and Fe. Within the first minute, Fe diffusion into the partially melted Al-base coatings promotes the formation of intermetallics of type Al8Fe2Si, Al13Fe4, and Al5Fe2. After the coating has transformed completely into Al-Fe intermetallics, Al diffusion into the steel substrate becomes more pronounced, thus reducing the Al content in the Al-Fe intermetallics and promoting formation of the phases of type Al2Fe and AlFe in the coating and formation of an Al-rich bcc layer in the steel substrate. The transformation kinetics of the resulting Al-, Fe-rich intermetallics are influenced by the coating thickness and the chemical composition of the Al-base coating. On the one hand, faster saturation of Fe in the Al-base coating is promoted by a shorter diffusion path and therefore by a thinner coating thickness. Otherwise, Si influences the diffusivity of the elements Al and Fe in the Al-, Fe-rich intermetallics and promotes the formation of Si-richer intermetallics, which then act as nuclei for Fe-richer intermetallics. © 2014 Elsevier B.V.
    view abstractdoi: 10.1016/j.surfcoat.2014.02.056
  • 2014 • 234 High-concentration graphene dispersions with minimal stabilizer: a scaffold for enzyme immobilization for glucose oxidation
    Sun, Z. and Vivekananthan, J. and Guschin, D.A. and Huang, X. and Kuznetsov, V. and Ebbinghaus, P. and Sarfraz, A. and Muhler, M. and Schuhmann, W.
    Chemistry (Weinheim an der Bergstrasse, Germany) 20 5752-5761 (2014)
    Modified acrylate polymers are able to effectively exfoliate and stabilize pristine graphene nanosheets in aqueous media. Starting with pre-exfoliated graphite greatly promotes the exfoliation level. The graphene concentration is significantly increased up to 11 mg mL(-1) by vacuum evaporation of the solvent from the dispersions under ambient temperature. TEM shows that 75 % of the flakes have fewer than five layers with about 18 % of the flakes consisting of monolayers. Importantly, a successive centrifugation and redispersion strategy is developed to enable the formation of dispersions with exceptionally high graphene-to-stabilizer ratio. Characterization by high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and Raman spectroscopy shows the flakes to be of high quality with very low levels of defects. These dispersions can act as a scaffold for the immobilization of enzymes applied, for example, in glucose oxidation. The electrochemical current density was significantly enhanced to be approximately six times higher than an electrode in the absence of graphene, thus showing potential applications in enzymatic biofuel cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201400098
  • 2014 • 233 High-throughput fabrication of Au-Cu nanoparticle libraries by combinatorial sputtering in ionic liquids
    König, D. and Richter, K. and Siegel, A. and Mudring, A.-V. and Ludwig, Al.
    Advanced Functional Materials 24 2049-2056 (2014)
    Materials libraries of binary alloy nanoparticles (NPs) are synthesized by combinatorial co-sputter deposition of Cu and Au into the ionic liquid (IL) 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C 1C4im][Tf2N]), which is contained in a micromachined cavity array substrate. The resulting NPs and NP-suspensions are investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), UV-Vis measurements (UV-Vis), and attenuated total reflection Fourier transformed infrared (ATR-FTIR) spectroscopy. Whereas the NPs can be directly observed in the IL using TEM, for XRD measurements the NP concentration is too low to lead to satisfactory results. Thus, a new NP isolation process involving capping agents is developed which enables separation of NPs from the IL without changing their size, morphology, composition, and state of aggregation. The results of the NP characterization show that next to the unary Cu and Au NPs, both stoichiometric and non-stoichiometric Cu-Au NPs smaller than 7 nm can be readily obtained. Whereas the size and shape of the alloy NPs change with alloy composition, for a fixed composition the NPs have a small size distribution. The measured lattice constants of all capped NPs show unexpected increased values, which could be related to the NP/surfactant interactions. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/adfm.201303140
  • 2014 • 232 In-situ measurement of loading stresses with X-ray diffraction for yield locus determination
    Güner, A. and Zillmann, B. and Lampke, T. and Tekkaya, A.E.
    International Journal of Automotive Technology 15 303-316 (2014)
    The application of the X-ray diffraction method is introduced to solve the problem of inhomogeneous deformation fields in the specimens used for sheet metal characterization. In this method, strains are measured on one side of a specimen with optical measurement systems. On the other side, loading stresses on a specimen are captured with an X-ray diffractometer mounted on a universal testing machine. By this way, the whole stress-strain history of a material point is tracked during testing. The method was first applied to uniaxial tension tests, whereby the applicability of the theory of stress factors and effective X-ray elastic constants were tested. The relaxation behavior of a sheet material which shows itself as stress drops during in-situ experimentation was characterized and compensated by a visco-plastic material model for different stress states. The proposed method was applied to characterize aluminum alloy AA5182 under plane strain tension and shear conditions and the results were compared with the conventionally obtained yield locus. Numerical analyses of a workpiece with the Vegter and Yld2000-2D material models show that the enriched yield locus definition with accurate plane strain tension and shear stresses captures the experimentally obtained surface strains more precisely. © 2014 The Korean Society of Automotive Engineers and Springer-Verlag Berlin Heidelberg.
    view abstractdoi: 10.1007/s12239-014-0031-9
  • 2014 • 231 Influence of substrate pre-treatments on residual stresses and tribo-mechanical properties of TiAlN-based PVD coatings
    Sprute, T. and Tillmann, W. and Grisales, D. and Selvadurai, U. and Fischer, G.
    Surface and Coatings Technology 260 369-379 (2014)
    Residual stresses in the substrate and in the PVD coating have a significant influence on the coating adhesion and lifespan of machining as well as forming tools. Therefore, the understanding and control of the system's residual stresses will lead to a better performance of the coated components. Moreover, although investigations were conducted in the field of stress analysis of PVD coatings, they do not focus on interdependencies of residual stresses in the substrate and in the coating. In this investigation, three different metallographically prepared substrates were used. SiC grinding, diamond grinding, and SiC grinding and plasma nitriding preparations were selected, due to the substantial differences in their final residual stress states. Additionally, a Ti/TiAlN multilayer coating and a reference TiAlN monolayer were deposited on each pre-treated substrate. Their initial and final residual stress states were measured by means of X-ray diffraction. In addition to the residual stress analyses, tribo-mechanical tests, such as nano-indentation, ball-on-disc, and scratch tests were performed in order to correlate the results with these residual stress states. © 2014 Elsevier B.V.
    view abstractdoi: 10.1016/j.surfcoat.2014.08.075
  • 2014 • 230 Influence of the PM-Processing Route and Nitrogen Content on the Properties of Ni-Free Austenitic Stainless Steel
    Lefor, K. and Walter, M. and Weddeling, A. and Hryha, E. and Huth, S. and Weber, S. and Nyborg, L. and Theisen, W.
    Metallurgical and Materials Transactions A: Physical Metallurgy and Materials Science 46 1154-1167 (2014)
    Ni-free austenitic steels alloyed with Cr and Mn are an alternative to conventional Ni-containing steels. Nitrogen alloying of these steel grades is beneficial for several reasons such as increased strength and corrosion resistance. Low solubility in liquid and δ-ferrite restricts the maximal N-content that can be achieved via conventional metallurgy. Higher contents can be alloyed by powder-metallurgical (PM) production via gas–solid interaction. The performance of sintered parts is determined by appropriate sintering parameters. Three major PM-processing routes, hot isostatic pressing, supersolidus liquid phase sintering (SLPS), and solid-state sintering, were performed to study the influence of PM-processing route and N-content on densification, fracture, and mechanical properties. Sintering routes are designed with the assistance of thermodynamic calculations, differential thermal analysis, and residual gas analysis. Fracture surfaces were studied by X-ray photoelectron spectroscopy, secondary electron microscopy, and energy dispersive X-ray spectroscopy. Tensile tests and X-ray diffraction were performed to study mechanical properties and austenite stability. This study demonstrates that SLPS process reaches high densification of the high-Mn-containing powder material while the desired N-contents were successfully alloyed via gas–solid interaction. Produced specimens show tensile strengths >1000 MPa combined with strain to fracture of 60 pct and thus overcome the other tested production routes as well as conventional stainless austenitic or martensitic grades. © 2014, The Author(s).
    view abstractdoi: 10.1007/s11661-014-2701-7
  • 2014 • 229 Interface reactions of Ag@TiO2 nanocomposite films
    Zuo, J. and Rao, J. and Eggeler, G.
    Materials Chemistry and Physics 145 90-98 (2014)
    TiO2 films were sputtered on 100-nm-thick Ag layers at various O2 partial pressures to study forming processes at the interface. The interfacial reactions during the deposition process were investigated by means of transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, atomic force microscopy and UV-vis reflection spectra. The sputtering process led to formation of Ag nanoparticles surrounded by Ag 2O and TiO2 in the TiO2 film matrix as well as on the surface. The presence of oxygen in the plasma resulted in enrichment of silver oxides on the surface and an intermixing of Ag in the TiO2 matrix. The film structures could be explained based on the interplay among the formation of silver oxide, the nucleation and growth of TiO2, as well as the mobility of silver and silver oxides within the growing TiO2 films. © 2014 Elsevier B.V.
    view abstractdoi: 10.1016/j.matchemphys.2014.01.041
  • 2014 • 228 Intermolecular interactions in highly concentrated protein solutions upon compression and the role of the solvent
    Grobelny, S. and Erlkamp, M. and Möller, J. and Tolan, M. and Winter, R.
    Journal of Chemical Physics 141 (2014)
    The influence of high hydrostatic pressure on the structure and protein-protein interaction potential of highly concentrated lysozyme solutions up to about 370 mg ml1was studied and analyzed using small-angle X-ray scattering in combination with a liquid-state theoretical approach. In the concentration region below 200 mg ml1, the interaction parameters of lysozyme solutions are affected by pressure in a nonlinear way, which is probably due to significant changes in the structural properties of bulk water, i.e., due to a solvent-mediated effect. Conversely, for higher concentrated protein solutions, where hydration layers below ∼4 water molecules are reached, the interaction potential turns rather insensitive to compression. The onset of transient (dynamic) clustering is envisaged in this concentration range. Our results also show that pressure suppresses protein nucleation, aggregation and finally crystallization in supersaturated condensed protein solutions. These findings are of importance for controlling and fine-tuning protein crystallization. Moreover, these results are also important for understanding the high stability of highly concentrated protein solutions (as they occur intracellularly) in organisms thriving under hydrostatic pressure conditions such as in the deep sea, where pressures up to the kbar-level are reached. © 2014 AIP Publishing LLC.
    view abstractdoi: 10.1063/1.4895542
  • 2014 • 227 Investigation into mixing capability and solid dispersion preparation using the DSM Xplore Pharma Micro Extruder
    Sakai, T. and Thommes, M.
    Journal of Pharmacy and Pharmacology 66 218-231 (2014)
    Objectives The goal of this investigation was to qualify the DSM Xplore Pharma Micro Extruder as a formulation screening tool for early-stage hot-melt extrusion. Methods Dispersive and distributive mixing was investigated using soluplus, copovidone or basic butylated methacrylate copolymer with sodium chloride (NaCl) in a batch size of 5 g. Eleven types of solid dispersions were prepared using various drugs and carriers in batches of 5 g in accordance with the literature. Key findings The dispersive mixing was a function of screw speed and recirculation time and the particle size was remarkably reduced after 1 min of processing, regardless of the polymers. An inverse relationship between the particle size and specific mechanical energy (SME) was also found. The SME values were higher than those in large-scale extruders. After 1 min recirculation at 200 rpm, the uniformity of NaCl content met the criteria of the European Pharmacopoeia, indicating that distributive mixing was achieved in this time. For the solid dispersions preparations, the results from different scanning calorimetry, powder X-ray diffractometry and in-vitro dissolution tests confirmed that all solid-dispersion systems were successfully prepared. Conclusions These findings demonstrated that the extruder is a useful tool to screen solid-dispersion formulations and their material properties on a small scale. © 2013 Royal Pharmaceutical Society.
    view abstractdoi: 10.1111/jphp.12085
  • 2014 • 226 Large recovery strain in Fe-Mn-Si-based shape memory steels obtained by engineering annealing twin boundaries
    Wen, Y.H. and Peng, H.B. and Raabe, D. and Gutierrez-Urrutia, I. and Chen, J. and Du, Y.Y.
    Nature Communications 5 (2014)
    Shape memory alloys are a unique class of materials that can recover their original shape upon heating after a large deformation. Ti-Ni alloys with a large recovery strain are expensive, while low-cost conventional processed Fe-Mn-Si-based steels suffer from a low recovery strain (<3%). Here we show that the low recovery strain results from interactions between stress-induced martensite and a high density of annealing twin boundaries. Reducing the density of twin boundaries is thus a critical factor for obtaining a large recovery strain in these steels. By significantly suppressing the formation of twin boundaries, we attain a tensile recovery strain of 7.6% in an annealed cast polycrystalline Fe-20.2Mn-5.6Si-8.9Cr-5.0Ni steel (weight%). Further attractiveness of this material lies in its low-cost alloying components and simple synthesis-processing cycle consisting only of casting plus annealing. This enables these steels to be used at a large scale as structural materials with advanced functional properties © 2014 Macmillan Publishers Limited. All rights reserved.
    view abstractdoi: 10.1038/ncomms5964
  • 2014 • 225 Large-scale synthesis and catalytic activity of nanoporous Cu-O system towards CO oxidation
    Kou, T. and Si, C. and Gao, Y. and Frenzel, J. and Wang, H. and Yan, X. and Bai, Q. and Eggeler, G. and Zhang, Z.
    RSC Advances 4 65004-65011 (2014)
    Nanoporous Cu-O system catalysts with different oxidation states of Cu have been fabricated through a combination of dealloying as-milled Al66.7Cu33.3 alloy powders and subsequent thermal annealing. X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) have been used to characterize the microstructure and surface chemical states of Cu-O catalysts. The peculiar nanoporous structure can be retained in Cu-O catalysts after thermal treatment. Catalytic experiments reveal that all the Cu-O samples exhibit complete CO conversion below 170 °C. The optimal catalytic performance could be achieved through the combination of annealing in air with hydrogen treatment for the Cu-O catalyst, which shows a near complete conversion temperature (T90%) of 132 °C and an activation energy of 91.3 KJ mol-1. In addition, the present strategy (ball milling, dealloying and subsequent thermal treatment) could be scaled up to fabricate high-performance Cu-O catalysts towards CO oxidation. This journal is © The Royal Society of Chemistry 2014.
    view abstractdoi: 10.1039/c4ra12227e
  • 2014 • 224 Magnetically driven suppression of nematic order in an iron-based superconductor
    Avci, S. and Chmaissem, O. and Allred, J.M. and Rosenkranz, S. and Eremin, I. and Chubukov, A.V. and Bugaris, D.E. and Chung, D.Y. and Kanatzidis, M.G. and Castellan, J.-P. and Schlueter, J.A. and Claus, H. and Khalyavin, D.D. and...
    Nature Communications 5 (2014)
    A theory of superconductivity in the iron-based materials requires an understanding of the phase diagram of the normal state. In these compounds, superconductivity emerges when stripe spin density wave (SDW) order is suppressed by doping, pressure or atomic disorder. This magnetic order is often pre-empted by nematic order, whose origin is yet to be resolved. One scenario is that nematic order is driven by orbital ordering of the iron 3d electrons that triggers stripe SDW order. Another is that magnetic interactions produce a spin-nematic phase, which then induces orbital order. Here we report the observation by neutron powder diffraction of an additional fourfold-symmetric phase in Ba 1 ̂'x Na x Fe 2 As 2 close to the suppression of SDW order, which is consistent with the predictions of magnetically driven models of nematic order.
    view abstractdoi: 10.1038/ncomms4845
  • 2014 • 223 Methanetrisamidines in coordination chemistry-syntheses, structures and CH-NH tautomerism
    Gutschank, B. and Schulz, S. and Bläser, D. and Wölper, C.
    Dalton Transactions 43 2907-2914 (2014)
    Methanetrisamidines {HC[C(NR)NHR]3} (R = i-Pr 1a; Ph 1b) were reacted with different metal complexes. Reaction of 1a with NiCl 2(H2O)6 occurred with protonation of 1a and formation of {[C(C(NHi-Pr)2)3]2+[NiCl 4]2-} 2, whereas the reaction with CuCl gave [C(C(N(i-Pr)CuCl)NHi-Pr)2(C(NHi-Pr)2)] 3. The formation of 2 and 3, which contain the N-H tautomeric form of 1a, occurred with H-migration from carbon to nitrogen. In contrast, reactions of 1b with [M(NCMe) 3(CO)3] (M = Cr, Mo, W) yielded octahedral complexes fac-[M(CO)3CH(C(NHPh)NPh)3] (M = Cr 4a, Mo 4b, W 4c), in which the C-H tautomeric form is preserved. 1b is a rather strong σ-donor ligand as was shown by IR spectroscopy. The structures of 2, 3 and 4a were determined by single crystal X-ray diffraction. © 2014 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c3dt53261e
  • 2014 • 222 Nanocrystalline barium strontium titanate ceramics synthesized via the "organosol" route and spark plasma sintering
    Gao, Y. and Shvartsman, V.V. and Gautam, D. and Winterer, M. and Lupascu, D.C.
    Journal of the American Ceramic Society 97 2139-2146 (2014)
    Dense nanocrystalline barium strontium titanate Ba0.6Sr 0.4TiO3 (BST) ceramics with an average grain size around 40 nm and very small dispersion were obtained by spark plasma sintering at 950°C and 1050°C starting from nonagglomerated nanopowders (~20 nm). The powders were synthesized by a modified "Organosol" process. X-ray diffraction (XRD) and dielectric measurements in the temperature range 173-313 K were used to investigate the evolution of crystal structure and the ferroelectric to paraelectric phase transformation behavior for the sintered BST ceramics with different grain sizes. The Curie temperature TC decreases, whereas the phase transition becomes diffuse for the particle size decreasing from about 190 to 40 nm with matching XRD and permittivity data. Even the ceramics with an average grain size as small as 40 nm show the transition into the ferroelectric state. The dielectric permittivity ε shows relatively good thermal stability over a wide temperature range. The dielectric losses are smaller than 2%-4% in the frequency range of 100 Hz-1 MHz and temperature interval 160-320 K. A decrease in the dielectric permittivity in nanocrystalline ceramics was observed compared to submicrometer-sized ceramics. © 2014 The American Ceramic Society.
    view abstractdoi: 10.1111/jace.12933
  • 2014 • 221 Nanostructured Er2O3 thin films grown by metalorganic chemical vapour deposition
    Xu, K. and Dang, V.-S. and Ney, A. and De Los Arcos, T. and Devi, A.
    Journal of Nanoscience and Nanotechnology 14 5095-5102 (2014)
    Metalorganic chemical vapor deposition (MOCVD) of nanostructured Er 2O3 thin films was performed using the Er-tris-guanidinate precursor [Er(DPDMG)3] (DPDMG = diisopropyl-2- dimethylamidoguanidinato) as the Er source and oxygen. Film deposition was carried out on Si(100) and quartz glass substrates and the process parameters namely temperature, pressure and oxygen flow rate were varied. The resulting thin films were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM) for investigating the crystallinity and morphology, respectively. The chemical composition of the film was investigated by X-ray photoelectron spectroscopy (XPS) measurements. Transmittance and absorption spectra of the 600 °C film grown on glass substrates were performed by UV-vis measurements revealing more than 80% transmittance. The potential of Er2O3 thin films as gate dielectrics was verified by carrying out capacitance-voltage (C-V ) and current-voltage (I-V ) measurements. Dielectric constants estimated from the accumulation capacitance were found to be in the range of 10-12 in AC frequencies of 1 MHz down to 10 kHz and the leakage current of the order of 2×10-8 A/cm2 at the applied field of 1 MV cm-1 was measured for films deposited under optimised process conditions. The low leakage current and high dielectric constant implies good quality of the Er2O3 layers relevant for high-k applications. These layers were found to be paramagnetic with a slightly reduced magnetic moment of the Er3+ ions. Copyright © 2014 American Scientific Publishers All rights reserved.
    view abstractdoi: 10.1166/jnn.2014.8848
  • 2014 • 220 Novel β-ketoiminato complexes of zirconium: Synthesis, characterization and evaluation for solution based processing of ZrO2 thin films
    Banerjee, M. and Seidel, R.W. and Winter, M. and Becker, H.-W. and Rogalla, D. and Devi, A.
    Dalton Transactions 43 2384-2396 (2014)
    Treatment of tetrakis(diethylamido)zirconium(iv); [Zr(NEt2) 4] with a series of β-ketoimines ({[RHN]C(CH3)C(H) C(CH3)O} where R is a functionalized side-chain; 4-(2- methoxyethylamino)pent-3-en-2-one, Hmeap; 4-(3-methoxypropylamino)pent-3-en-2- one, Hmpap; 4-(2-(dimethylamino)ethylamino)pent-3-en-2-one, Hdeap; 4-(3-(dimethylamino)propylamino)pent-3-en-2-one, Hdpap) leads to an amine substitution reaction that yielded novel monomeric heteroleptic mixed amido-ketoiminato complexes of the type bis(4-(2-methoxyethylamino)pent-3-en-2- onato)bis(diethylamido)zirconium(iv) (1), bis(4-(3-methoxypropylamino)pent-3-en- 2-onato)bis(diethylamido)zirconium(iv) (2), and bis(4-(3-(dimethylamino) propylamino)pent-3-en-2-onato)bis(diethylamido)zirconium(iv) (3), and eight-coordinated homoleptic complexes tetrakis(4-(2-methoxyethylamino)pent-3- en-2-onato)zirconium(iv) (4) and tetrakis(4-(2-(dimethylamino)ethylamino)pent-3- en-2-onato)zirconium(iv) (5), depending on the ratio of the ligand to zirconium. Adopting a similar strategy with zirconium alkoxide, namely [Zr(O iPr)4·iPrOH], with β-ketoimine Hmeap, leads to the formation of a dimer, bis(μ2-isopropoxo)bis(4- (2-methoxyethylamino)pent-3-en-2-onato)tetrakis(isopropoxo)dizirconium(iv) (6). The newly synthesised complexes were characterized by NMR spectroscopy, mass spectrometry, single crystal X-ray diffraction, elemental analysis and thermal analysis. The low decomposition temperature facilitated by the stepwise elimination of the ketominate ligand from the complex and the stability of the complexes obtained in air as well as in solution makes them highly suitable for solution based processing of ZrO2 thin films, which is demonstrated using compound 5 on Si(100) substrates. High quality ZrO2 films were obtained and were investigated for their structure, morphology, composition and optical properties. Low temperature crystallisation of ZrO2 is achieved by a simple chemical deposition process using the new class of Zr precursors and the films exhibit an optical transmittance above 90%. © 2014 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c3dt52335g
  • 2014 • 219 One-step synthesis of bismuth molybdate catalysts via flame spray pyrolysis for the selective oxidation of propylene to acrolein
    Schuh, K. and Kleist, W. and Høj, M. and Trouillet, V. and Jensen, A.D. and Grunwaldt, J.-D.
    Chemical Communications 50 15404-15406 (2014)
    Flame spray pyrolysis (FSP) of Bi(iii)- and Mo(vi)-2-ethylhexanoate dissolved in xylene resulted in various nanocrystalline bismuth molybdate phases depending on the Bi/Mo ratio. Besides α-Bi2Mo3O12 and γ-Bi2MoO6, FSP gave direct access to the metastable β-Bi2Mo2O9 phase with high surface area (19 m2 g-1). This phase is normally only obtained at high calcination temperatures (&gt;560 °C) resulting in lower surface areas. The β-phase was stable up to 400 °C and showed superior catalytic performance compared to α- and γ-phases in selective oxidation of propylene to acrolein at temperatures relevant for industrial applications (360 °C). This journal is © The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c4cc07527g
  • 2014 • 218 Oxygen-deficient titania as alternative support for Pt catalysts for the oxygen reduction reaction
    Zhao, A. and Masa, J. and Xia, W.
    Journal of Energy Chemistry 23 701-707 (2014)
    Insufficient electrochemical stability is a major challenge for carbon materials in oxygen reduction reaction (ORR) due to carbon corrosion and insufficient metal-support interactions. In this work, titania is explored as an alternative support for Pt catalysts. Oxygen deficient titania samples including TiO<inf>2-x</inf> and TiO<inf>2-x</inf>N<inf>y</inf> were obtained by thermal treatment of anatase TiO<inf>2</inf> under flowing H<inf>2</inf> and NH<inf>3</inf>, respectively. Pt nanoparticles were deposited on the titania by a modified ethylene glycol method. The samples were characterized by N<inf>2</inf>-physisorption, X-ray diffraction and X-ray photoelectron spectroscopy. The ORR activity and long-term stability of supported Pt catalysts were evaluated using linear sweep voltammetry and chronoamperometry in 0.1 mol/L HClO<inf>4</inf>. Pt/TiO<inf>2-x</inf> and Pt/TiO<inf>2-x</inf>N<inf>y</inf> showed higher ORR activities than Pt/TiO<inf>2</inf> as indicated by higher onset potentials. Oxygen deficiency in TiO<inf>2-x</inf> and TiO<inf>2-x</inf>N<inf>y</inf> contributed to the high ORR activity due to enhanced charge transfer, as disclosed by electrochemical impedance spectroscopy studies. Electrochemical stability studies revealed that Pt/TiO<inf>2-x</inf> exhibited a higher stability with a lower current decay rate than commercial Pt/C, which can be attributed to the stable oxide support and strong interaction between Pt nanoparticles and the oxygen-deficient TiO<inf>2-x</inf> support. © 2014 Dalian Institute of Chemical Physics, the Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/S2095-4956(14)60202-3
  • 2014 • 217 Photocatalytic and antimicrobial Ag/ZnO nanocomposites for functionalization of textile fabrics
    Ibǎnescu, M. and Muşat, V. and Textor, T. and Badilita, V. and Mahltig, B.
    Journal of Alloys and Compounds 610 244-249 (2014)
    The utilization of ZnO nanoparticles with photocatalytic and antimicrobial activity for textile treatment has received much attention in recent years. Since silver is a well-known but more expensive antibacterial material, it is of interest to study the extent to which a small amount of silver increases the photocatalytic and antimicrobial activity of the less expensive zinc oxide nanoparticles. This paper reports on the preparation of Ag/ZnO composite nanoparticles by reducing silver on the surface of commercial ZnO nanoparticles dispersed in isopropanol. Crystalline structure, particle size and band gap energy of as-prepared composite nanoparticles were investigated by X-ray diffraction and UV-Vis absorption measurements. Long term stable sols of ZnO and Ag/ZnO nanoparticles were prepared and applied as liquid coating agent for textile treatment, in combination with inorganic-organic hybrid polymer binder sols prepared from the precursors 3-glycidyloxypropyltrimethoxysilane (GPTMS) and tetraethoxysilane (TEOS). The coating process was carried out on cotton fabrics and cotton/polyester blended fabrics using the pad-dry-cure method. The photocatalytic activity of the nanoparticles, as prepared or applied on textile fabrics, was studied through the degradation of the dye methylene blue (MB) in water under the UV irradiation. The antimicrobial activity of the nanoparticles applied on textile fabrics, was tested against the Gram-negative bacterium Escherichia coli and Gram-positive Micrococcus luteus. © 2014 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.jallcom.2014.04.138
  • 2014 • 216 Platinum-cobalt bimetallic nanoparticles in hollow carbon nanospheres for hydrogenolysis of 5-hydroxymethylfurfural
    Wang, G.-H. and Hilgert, J. and Richter, F.H. and Wang, F. and Bongard, H.-J. and Spliethoff, B. and Weidenthaler, C. and Schüth, F.
    Nature Materials 13 293-300 (2014)
    The synthesis of 2,5-dimethylfuran (DMF) from 5-hydroxymethylfurfural (HMF) is a highly attractive route to a renewable fuel. However, achieving high yields in this reaction is a substantial challenge. Here it is described how PtCo bimetallic nanoparticles with diameters of 3.6 ± 0.7 nm can solve this problem. Over PtCo catalysts the conversion of HMF was 100% within 10 min and the yield to DMF reached 98% after 2 h, which substantially exceeds the best results reported in the literature. Moreover, the synthetic method can be generalized to other bimetallic nanoparticles encapsulated in hollow carbon spheres. © 2014 Macmillan Publishers Limited.
    view abstractdoi: 10.1038/nmat3872
  • 2014 • 215 Pressure-induced changes on the electronic structure and electron topology in the direct FCC → SH transformation of silicon
    Tse, J.S. and Hanfland, M. and Flacau, R. and Desgreniers, S. and Li, Z. and Mende, K. and Gilmore, K. and Nyrow, A. and Moretti Sala, M. and Sternemann, C.
    Journal of Physical Chemistry C 118 1161-1166 (2014)
    X-ray diffraction experiments at 80 K show that when silicon is compressed under hydrostatic conditions the intermediate high-pressure phases are bypassed leading to a direct transformation to the simple hexagonal structure at 17 GPa. A maximum entropy analysis of the diffraction patterns reveals dramatic alterations in the valence electron distribution from tetrahedral covalent bonding to localization in the interstitial sites and along the one-dimensional silicon atom chain running along adjacent hexagonal layers. Changes in the orbital character of the unoccupied states are confirmed using X-ray Raman scattering spectroscopy and theoretical Bethe-Salpeter equation calculations. This is the first direct observation indicating that the silicon valence electrons in 3s and 3p orbitals are transferred to the 3d orbitals at high density which proves that electrons of compressed elemental solids migrate from their native bonding configuration to interstitial regions. © 2013 American Chemical Society.
    view abstractdoi: 10.1021/jp408666q
  • 2014 • 214 Rapid identification of areas of interest in thin film materials libraries by combining electrical, optical, X-ray diffraction, and mechanical high-throughput measurements: A case study for the system ni-al
    Thienhaus, S. and Naujoks, D. and Pfetzing-Micklich, J. and König, D. and Ludwig, Al.
    ACS Combinatorial Science 16 686-694 (2014)
    The efficient identification of compositional areas of interest in thin film materials systems fabricated by combinatorial deposition methods is essential in combinatorial materials science. We use a combination of compositional screening by EDX together with high-throughput measurements of electrical and optical properties of thin film libraries to determine efficiently the areas of interest in a materials system. Areas of interest are compositions which show distinctive properties. The crystallinity of the thus determined areas is identified by X-ray diffraction. Additionally, by using automated nanoindentation across the materials library, mechanical data of the thin films can be obtained which complements the identification of areas of interest. The feasibility of this approach is demonstrated by using a Ni-Al thin film library as a reference system. The obtained results promise that this approach can be used for the case of ternary and higher order systems. © 2014 American Chemical Society.
    view abstractdoi: 10.1021/co5000757
  • 2014 • 213 Reaction of L2Zn2 with Ph2E 2-synthesis of LZnEPh and reactions with oxygen and H-acidic substrates
    Gondzik, S. and Schulz, S. and Bläser, D. and Wölper, C.
    Chemical Communications 50 1189-1191 (2014)
    L<inf>2</inf>Zn<inf>2</inf> (L = HC[C(Me)N(2,4,6-Me<inf>3</inf>C <inf>6</inf>H<inf>2</inf>)]<inf>2</inf>) and Ph<inf>2</inf>E<inf>2</inf> (E = Se, Te) react to form LZnSePh (1) and LZnTePh (2). 1 and 2 further react with H<inf>2</inf>O and EtOH to form LZnOH (3) and LZnOEt (4), respectively, whereas the reaction of 2 with oxygen yielded [LZnOTe(O)Ph]<inf>2</inf> (5). 1, 4 and 5 were characterized by single crystal X-ray diffraction. © 2014 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c3cc48677j
  • 2014 • 212 Real-time visualization of nanocrystal solid-solid transformation pathways
    Wittenberg, J.S. and Miller, T.A. and Szilagyi, E. and Lutker, K. and Quirin, F. and Lu, W. and Lemke, H. and Zhu, D. and Chollet, M. and Robinson, J. and Wen, H. and Sokolowski-Tinten, K. and Alivisatos, A.P. and Lindenberg, A.M.
    Nano Letters 14 1995-1999 (2014)
    Measurement and understanding of the microscopic pathways materials follow as they transform is crucial for the design and synthesis of new metastable phases of matter. Here we employ femtosecond single-shot X-ray diffraction techniques to measure the pathways underlying solid-solid phase transitions in cadmium sulfide nanorods, a model system for a general class of martensitic transformations. Using picosecond rise-time laser-generated shocks to trigger the transformation, we directly observe the transition state dynamics associated with the wurtzite-to-rocksalt structural phase transformation in cadmium sulfide with atomic-scale resolution. A stress-dependent transition path is observed. At high peak stresses, the majority of the sample is converted directly into the rocksalt phase with no evidence of an intermediate prior to rocksalt formation. At lower peak stresses, a transient five-coordinated intermediate structure is observed consistent with previous first principles modeling. © 2014 American Chemical Society.
    view abstractdoi: 10.1021/nl500043c
  • 2014 • 211 Recovery, recrystallization, grain growth and phase stability of a family of FCC-structured multi-component equiatomic solid solution alloys
    Wu, Z. and Bei, H. and Otto, F. and Pharr, G.M. and George, E.P.
    Intermetallics 46 131-140 (2014)
    The equiatomic high-entropy alloy FeNiCoCrMn is known to crystallize as a single phase with the face-centered cubic (FCC) crystal structure. To better understand this quinary solid solution alloy, we investigate various binary, ternary and quaternary alloys made from its constituent elements. Our goals are twofold: (i) to investigate which of these lower order systems also form solid solution alloys consisting of a single FCC phase, and (ii) to characterize their phase stability and recovery, recrystallization, and grain growth behaviors. X-ray diffraction (XRD) and scanning electron microscopy with backscattered electron images showed that three of the five possible quaternaries (FeNiCoCr, FeNiCoMn and NiCoCrMn), five of the ten possible ternaries (FeNiCo, FeNiCr, FeNiMn, NiCoCr, and NiCoMn), and two of the ten possible binaries (FeNi and NiCo) were single-phase FCC solid solutions in the cast and homogenized condition, whereas the others either had different crystal structures or were multi-phase. The single-phase FCC quaternary, FeNiCoCr, along with its equiatomic ternary and binary subsidiaries, were selected for further investigations of phase stability and the thermomechanical processing needed to obtain equiaxed grain structures. Only four of these subsidiary alloys - two binaries (FeNi and NiCo) and two ternaries (FeNiCo and NiCoCr) - were found to be single-phase FCC after rolling at room temperature followed by annealing for 1 h at temperatures of 300-1100 C. Pure Ni, which is FCC and one of the constituents of the quinary high-entropy alloy (FeNiCoCrMn), was also investigated for comparison with the higher order alloys. Among the materials investigated after thermomechanical processing (FeNiCoCr, FeNiCo, NiCoCr, FeNi, NiCo, and Ni), FeNiCo and Ni showed abnormal grain growth at relatively low annealing temperatures, while the other four showed normal grain growth behavior. The grain growth exponents for all five of the equiatomic alloys were found to be ∼0.25 (compared to ∼0.5 for unalloyed Ni), suggesting that solute drag may control grain growth in the alloys. For all five alloys, as well as for pure Ni, microhardness increases as the grain size decreases in a Hall-Petch type way. The ternary alloy NiCoCr was the hardest of the alloys investigated in this study, even when compared to the quaternary FeNiCoCr alloy. This suggests that solute hardening in equiatomic alloys depends not just on the number of alloying elements but also their type. © 2013 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.intermet.2013.10.024
  • 2014 • 210 Solid-state structures of bis(diethylbismuthanyl)sulfane, -selenane, and -tellurane
    Heimann, S. and Bläser, D. and Wölper, C. and Schulz, S.
    Organometallics 33 2295-2300 (2014)
    Tetraethyldibismuthine (Bi2Et4) reacts with elemental chalcogens with insertion into the Bi-Bi bond and formation of bis(diethylbismuthanyl)chalcogenanes ((Et2Bi)2E; E = S (1), Se (2), Te (3)). The structures of 1-3 were determined by single crystal X-ray diffraction. The complexes exclusively adopt syn-anti conformations in the solid state. The molecules show weak intermolecular Bi··· chalcogen contacts, resulting in the formation of a three-dimensional network of corner-shared Bi4E tetrahedra (E = S, Se, Te). © 2014 American Chemical Society.
    view abstractdoi: 10.1021/om500208c
  • 2014 • 209 Spinel Mn-Co oxide in N-doped carbon nanotubes as a bifunctional electrocatalyst synthesized by oxidative cutting
    Zhao, A. and Masa, J. and Xia, W. and Maljusch, A. and Willinger, M.-G. and Clavel, G. and Xie, K. and Schlögl, R. and Schuhmann, W. and Muhler, M.
    Journal of the American Chemical Society 136 7551-7554 (2014)
    The notorious instability of non-precious-metal catalysts for oxygen reduction and evolution is by far the single unresolved impediment for their practical applications. We have designed highly stable and active bifunctional catalysts for reversible oxygen electrodes by oxidative thermal scission, where we concurrently rupture nitrogen-doped carbon nanotubes and oxidize Co and Mn nanoparticles buried inside them to form spinel Mn-Co oxide nanoparticles partially embedded in the nanotubes. Impressively high dual activity for oxygen reduction and evolution is achieved using these catalysts, surpassing those of Pt/C, RuO2, and IrO2 and thus raising the prospect of functional low-cost, non-precious-metal bifunctional catalysts in metal-air batteries and reversible fuel cells, among others, for a sustainable and green energy future. © 2014 American Chemical Society.
    view abstractdoi: 10.1021/ja502532y
  • 2014 • 208 Stable zinc oxide nanoparticle dispersions in ionic liquids
    Wittmar, A. and Gautam, D. and Schilling, C. and Dörfler, U. and Mayer-Zaika, W. and Winterer, M. and Ulbricht, M.
    Journal of Nanoparticle Research 16 (2014)
    The influence of the hydrophilicity and length of the cation alkyl chain in imidazolium-based ionic liquids on the dispersability of ZnO nanoparticles by ultrasound treatment was studied by dynamic light scattering and advanced rheology. ZnO nano-powder synthesized by chemical vapor synthesis was used in parallel with one commercially available material. Before preparation of the dispersion, the nanoparticles characteristics were determined by transmission electron microscopy, X-ray diffraction, nitrogen adsorption with BET analysis, and FT-IR spectroscopy. Hydrophilic ionic liquids dispersed all studied nanopowders better and in the series of hydrophilic ionic liquids, an improvement of the dispersion quality with increasing length of the alkyl chain of the cation was observed. Especially, for ionic liquids with short alkyl chain, additional factors like nanoparticle concentration in the dispersion and the period of the ultrasonic treatment had significant influence on the dispersion quality. Additionally, nanopowder characteristics (crystallite shape and size as well as the agglomeration level) influenced the dispersion quality. The results indicate that the studied ionic liquids are promising candidates for absorber media at the end of the gas phase synthesis reactor allowing the direct preparation of non-agglomerated nanoparticle dispersions without supplementary addition of dispersants and stabilizers. © Springer Science+Business Media 2014.
    view abstractdoi: 10.1007/s11051-014-2341-2
  • 2014 • 207 Strain response of thermal barrier coatings captured under extreme engine environments through synchrotron X-ray diffraction
    Knipe, K. and Manero II, A. and Siddiqui, S.F. and Meid, C. and Wischek, J. and Okasinski, J. and Almer, J. and Karlsson, A.M. and Bartsch, M. and Raghavan, S.
    Nature Communications 5 (2014)
    The mechanical behaviour of thermal barrier coatings in operation holds the key to understanding durability of jet engine turbine blades. Here we report the results from experiments that monitor strains in the layers of a coating subjected to thermal gradients and mechanical loads representing extreme engine environments. Hollow cylindrical specimens, with electron beam physical vapour deposited coatings, were tested with internal cooling and external heating under various controlled conditions. High-energy synchrotron X-ray measurements captured the in situ strain response through the depth of each layer, revealing the link between these conditions and the evolution of local strains. Results of this study demonstrate that variations in these conditions create corresponding trends in depth-resolved strains with the largest effects displayed at or near the interface with the bond coat. With larger temperature drops across the coating, significant strain gradients are seen, which can contribute to failure modes occurring within the layer adjacent to the interface. © 2014 Macmillan Publishers Limited. All rights reserved.
    view abstractdoi: 10.1038/ncomms5559
  • 2014 • 206 Strain state, film and surface morphology of epitaxial topological insulator Bi2Se3 films on Si(111)
    Klein, C. and Vyshnepolsky, M. and Kompch, A. and Klasing, F. and Hanisch-Blicharski, A. and Winterer, M. and Horn-von Hoegen, M.
    Thin Solid Films 564 241-245 (2014)
    Epitaxial Bi2Se3 films were grown by molecular beam epitaxy on Si(111)-Bi(3×3)R30° at temperatures between 200 and 250 °C. The surface and bulk morphology was characterized by high resolution low energy electron diffraction, X-ray diffraction, and atomic force microscopy for various film thicknesses between 6 and 90 nm. The films are atomically smooth without small angle mosaics or small angle rotational domains. The precise determination of lattice parameter reveals that films grown at higher temperature exhibit a smaller value for the vertical lattice parameter. The presence of random stacking faults in the film is reflected by a parabolic increase of the width of the diffraction peaks in X-ray diffraction. © 2014 Elsevier B.V.
    view abstractdoi: 10.1016/j.tsf.2014.04.024
  • 2014 • 205 Structural and functional characterization of enamel pigmentation in shrews
    Dumont, M. and Tütken, T. and Kostka, A. and Duarte, M.J. and Borodin, S.
    Journal of Structural Biology 186 38-48 (2014)
    Pigmented tooth enamel occurs in several vertebrate clades, ranging from mammals to fish. Although an iron compound is associated with this orange to red colored pigmentation, its chemical and structural organization within the enamel is unknown. To determine the nature of the iron compound, we investigated heavily pigmented teeth of the northern short-tailed shrew Blarina brevicauda using combined characterization techniques such as scanning and transmission electron microscopy and synchrotron X-ray diffraction. We found that the pigmentation of the enamel with an iron content of around 8. wt% results from a close to amorphous magnetite phase deposited around the nm-sized enamel crystals. Furthermore, the influence of the pigmentation on the enamel hardness was determined by nanoindentation measurements. Finally, the biomechanical function and biological context are discussed in light of the obtained results. © 2014 Elsevier Inc.
    view abstractdoi: 10.1016/j.jsb.2014.02.006
  • 2014 • 204 Structural, optical, and magnetic properties of highly-resistive Sm-implanted GaN thin films
    Lo, F.-Y. and Huang, C.-D. and Chou, K.-C. and Guo, J.-Y. and Liu, H.-L. and Ney, V. and Ney, A. and Shvarkov, S. and Pezzagna, S. and Reuter, D. and Chia, C.-T. and Chern, M.-Y. and Wieck, A.D. and Massies, J.
    Journal of Applied Physics 116 (2014)
    Samarium ions of 200 keV in energy were implanted into highly-resistive molecular-beam-epitaxy grown GaN thin films with a focused-ion-beam implanter at room temperature. The implantation doses range from 1 × 1014 to 1 × 1016cm-2. Structural properties studied by x-ray diffraction and Raman-scattering spectroscopy revealed Sm incorporation into GaN matrix without secondary phase. The optical measurements showed that the band gap and optical constants changed very slightly by the implantation. Photoluminescence measurements showed emission spectra similar to p-type GaN for all samples. Magnetic investigations with a superconducting quantum interference device identified magnetic ordering for Sm dose of and above 1 × 1015cm-2 before thermal annealing, while ferromagnetism was only observed after thermal annealing from the sample with highest Sm dose. The long-range magnetic ordering can be attributed to interaction of Sm ions through the implantation-induced Ga vacancy. © 2014 AIP Publishing LLC.
    view abstractdoi: 10.1063/1.4891226
  • 2014 • 203 Syntheses and structures of bis-amidinate-alane complexes
    Bayram, M. and Bläser, D. and Wölper, C. and Schulz, S.
    Organometallics 33 2080-2087 (2014)
    Insertion reactions of α,ω-bis-carbodiimides (RNCN) 2X (1-5: R = Et, t-Bu, Ph; X = C3H6, C 4H8) with 2 equiv of AlMe3 yielded the dinuclear tethered bis-amidinate-alane complexes [RNC(Me)NAlMe2] 2X (R = Et, X = C4H8 (6); R = t-Bu, X = C 3H6 (7), C4H8 (8)). Analogous reactions with 4 equiv of AlMe3 resulted in the coordination of two additional AlMe3 molecules, yielding the tetranuclear bis-amidinate complexes [EtN(AlMe3)C(Me)NAlMe2]2X (X = C 3H6 (9), C4H8 (10)) and [t-BuNC(Me)N(AlMe3)AlMe2]2X (X = C 3H6 (11), C4H8 (12)). In addition, equimolar reactions between (RNCN)2X (R = Et, X = C3H 6, C4H8; R = Ph, X = C4H 8) and 2 equiv of AlMe3 at elevated temperatures occurred with intramolecular cyclization and formation of [EtNC(Me)NC3H 6N(AlMe3)CNEt]AlMe2 (13) and [RNC(Me)NC 4H8N(AlMe3)CNR]AlMe2 (R = Et (14), Ph (15)). Hydrolysis of 11 gave the protonated free ligand PhNC(Me)NC 4H8N(H)CNPh (16) in high yield. 6-16 were characterized by elemental analyses, multinuclear NMR (1H, 13C) and IR spectroscopy, and single-crystal X-ray diffraction (7, 10-14, 16). © 2014 American Chemical Society.
    view abstractdoi: 10.1021/om5002217
  • 2014 • 202 The influence of multilayer design on residual stress gradients in Ti/TiAlN systems
    Selvadurai, U. and Tillmann, W. and Fischer, G. and Sprute, T.
    Materials Science Forum 768-769 264-271 (2014)
    In this research work, Ti/TiAlN multilayers of various designs were deposited on substrates pretreated by nitriding and etching procedures. The influence of the multilayer design on residual stress depth profiles was systematically analyzed for multilayers with different Titanium interlayer thicknesses. The depth-dependency of stress was measured by a modified sin2ψ method, using various defined gracing incident angles and measuring angles that ensure constant penetration depths. The residual stresses were investigated by synchrotron X-ray diffraction (SXRD) at the HASYLAB at DESY in Hamburg, Germany. SXRD allows a phase specific stress evaluation of the ceramic and metallic layers of the multilayer systems and the adjacent substrate region. This investigation reveals an influence of the Ti layer thickness on the values and the slope of the residual stress profile in ceramic TiAlN layers. © (2014) Trans Tech Publications, Switzerland.
    view abstractdoi: 10.4028/
  • 2014 • 201 Tribological and mechanical properties of Ti/TiAlN/TiAlCN nanoscale multilayer PVD coatings deposited on AISI H11 hot work tool steel
    Al-Bukhaiti, M.A. and Al-Hatab, K.A. and Tillmann, W. and Hoffmann, F. and Sprute, T.
    Applied Surface Science 318 180-190 (2014)
    A new [Ti/TiAlN/TiAlCN]5 multilayer coatings were deposited onto polished substrate AISI H11 (DIN 1.2343) steel by an industrial magnetron sputtering device. The tribological performance of the coated system was investigated by a ball-on-disk tribometer against 100Cr6 steel and Al2O3 balls. The friction coefficients and specific wear rates were measured at various normal loads (2, 5, 8, and 10 N) and sliding velocities (0.2, 0.4, and 0.8 m/s) in ambient air and dry conditions. The phase structure, composition, wear tracks morphologies, hardness, and film/substrate adhesion of the coatings were characterized by light-microscopy, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), 3D-surface analyzer, nanoindentation, and scratch tests. Results showed that the deposited coatings showed low wear rates in the scale of 10-15 m3/N m, low friction coefficients against 100Cr6 and Al2O3 balls in the range of 0.25-0.37, and good hardness in the range of 17-20 GPa. Results also revealed that the friction coefficients and disc wear rates decrease and increase, respectively with the increase in normal load and sliding velocity for both coating/Al2O3 and coating/100Cr6 sliding system. Compared with the uncoated-H11 substrate, the deposited coating exhibited superior tribological and mechanical properties. The dominant wear mechanism was abrasive wear for coating/Al2O3 pair, while for coating/100Cr6 pair, a combination of mild adhesive wear, severe adhesive wear, and abrasive wear (extensive plowing) were the dominant wear mechanisms at different applied normal loads. © 2014 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.apsusc.2014.03.026
  • 2013 • 200 A new route for the preparation of mesoporous carbon materials with high performance in lithium–sulphur battery cathodes
    Oschatz, M. and Thieme, S. and Borchardt, L. and Lohe, M.R. and Biemelt, T. and Brückner, J. and Althues, H. and Kaskel, S.
    Chemical Communications 49 5832-5834 (2013)
    A novel method for the preparation of highly mesoporous carbon materials (Kroll-Carbons; KCs) is described based on reactive carbochlorination etching of titania nanoparticles inside a dense carbon matrix leading to mesoporous carbons with precisely controllable porosity and high performance as cathode materials for lithium–sulphur (Li–S) batteries. © 2013 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c3cc42841a
  • 2013 • 199 A Z′ = 6 crystal structure of (E)-N,N′-dicyclohexylacetamidine
    Krasnopolski, M. and Seidel, R.W. and Goddard, R. and Breidung, J. and Winter, M.V. and Devi, A. and Fischer, R.A.
    Journal of Molecular Structure 1031 239-245 (2013)
    The crystal and molecular structure of (E)-N,N′- dicyclohexylacetamidine (1) is described. Crystalline material of 1 was obtained by sublimation. Single-crystal X-ray analysis revealed a centrosymmetric triclinic structure (space group P1̄) with six molecules in the asymmetric unit (Z′ = 6). The six crystallographically distinct molecules all exhibit an E-syn structure, but differ in the orientation of the cyclohexyl groups about the central acetamidine moiety. In the crystal, the molecules form polymeric helices via NH⋯N hydrogen bonds. The crystal structure comprises two crystallographically distinct helices of opposite handedness (P and M form). The characterisation of 1 in the solid-state is augmented by powder X-ray diffraction, infrared spectroscopy and thermal analysis. Density functional theory (DFT) structure optimisation and frequency calculation were performed at the B3LYP/cc-pVTZ level. The DFT results for the isolated molecule are compared with the experimental results for the solid-state. © 2012 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.molstruc.2012.10.003
  • 2013 • 198 Atomic-scale compositional characterization of a nanocrystalline AlCrCuFeNiZn high-entropy alloy using atom probe tomography
    Pradeep, K.G. and Wanderka, N. and Choi, P. and Banhart, J. and Murty, B.S. and Raabe, D.
    Acta Materialia 61 4696-4706 (2013)
    We have studied a nanocrystalline AlCrCuFeNiZn high-entropy alloy synthesized by ball milling followed by hot compaction at 600 C for 15 min at 650 MPa. X-ray diffraction reveals that the mechanically alloyed powder consists of a solid-solution body-centered cubic (bcc) matrix containing 12 vol.% face-centered cubic (fcc) phase. After hot compaction, it consists of 60 vol.% bcc and 40 vol.% fcc. Composition analysis by atom probe tomography shows that the material is not a homogeneous fcc-bcc solid solution but instead a composite of bcc structured Ni-Al-, Cr-Fe- and Fe-Cr-based regions and of fcc Cu-Zn-based regions. The Cu-Zn-rich phase has 30 at.% Zn α-brass composition. It segregates predominantly along grain boundaries thereby stabilizing the nanocrystalline microstructure and preventing grain growth. The Cr- and Fe-rich bcc regions were presumably formed by spinodal decomposition of a Cr-Fe phase that was inherited from the hot compacted state. The Ni-Al phase remains stable even after hot compaction and forms the dominant bcc matrix phase. The crystallite sizes are in the range of 20-30 nm as determined by transmission electron microscopy. The hot compacted alloy exhibited very high hardness of 870 ± 10 HV. The results reveal that phase decomposition rather than homogeneous mixing is prevalent in this alloy. Hence, our current observations fail to justify the present high-entropy alloy design concept. Therefore, a strategy guided more by structure and thermodynamics for designing high-entropy alloys is encouraged as a pathway towards exploiting the solid-solution and stability idea inherent in this concept. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2013.04.059
  • 2013 • 197 Bimodal substrate biasing to control gamma-Al2O3 deposition during reactive magnetron sputtering
    Prenzel, M. and Kortmann, A. and Stein, A. and von Keudell, A. and Nahif, F. and Schneider, J. M.
    Journal of Applied Physics 114 113301 (2013)
    Al2O3 thin films have been deposited at substrate temperatures between 500 degrees C and 600 degrees C by reactive magnetron sputtering using an additional arbitrary substrate bias to tailor the energy distribution of the incident ions. The films were characterized by X-ray diffraction and Fourier transform infrared spectroscopy. The film structure being amorphous, nanocrystalline, or crystalline was correlated with characteristic ion energy distributions. The evolving crystalline structure is connected with different levels of displacements per atom (dpa) in the growing film as being derived from TRIM simulations. The boundary between the formation of crystalline films and amorphous or nanocrystalline films was at 0.8 dpa for a substrate temperature of 500 degrees C. This threshold shifts to 0.6 dpa for films grown at 550 degrees C. (C) 2013 AIP Publishing LLC.
    view abstractdoi: 10.1063/1.4819227
  • 2013 • 196 Carbon reactivity of binder metals in diamond-metal composites - Characterization by scanning electron microscopy and X-ray diffraction
    Tillmann, W. and Ferreira, M. and Steffen, A. and Rüster, K. and Möller, J. and Bieder, S. and Paulus, M. and Tolan, M.
    Diamond and Related Materials 38 118-123 (2013)
    Diamond tooling is a successfully used technique in machining of very hard materials such as minerals and concrete. The type and strength of bonding between the diamond grains, that are mainly responsible for the machining process (e.g. cutting or grinding), and the metallic binder phase is directly linked to the tools quality. Therefore it is of interest to investigate the carbon reactivity of commonly used binder materials. This paper reports about the investigation of the interfacial area between diamonds and one-component metallic binder matrices. As matrix material pure chromium, cobalt, copper, iron, and nickel was used. After the sintering process the diamonds were extracted from the metallic matrix and analyzed by scanning electron microscopy and X-ray diffraction. The morphology of the diamond surface was investigated and a phase analysis was done. These experimental studies support the hypothesis that the carbon reactivity of transition metals is linked to their d-orbital electron configuration. © 2013 Elsevier B.V.
    view abstractdoi: 10.1016/j.diamond.2013.07.002
  • 2013 • 195 Catalytic reduction of nitrogen oxides via nanoscopic oxide catalysts within activated carbons at room temperature
    Sager, U. and Schmidt, W. and Schmidt, F. and Suhartiningsih
    Adsorption 19 1027-1033 (2013)
    Cabin air filters consisting of activated carbon infiltrated with nanoscopic metal oxide particles as catalysts have been investigated for the reduction of nitrogen oxides within motor-car cabins. In that concept, nitrogen dioxide is adsorbed on the activated carbon during operation conditions of the car and then reduced by the catalysts within the pores. The conversion has to take place at ambient temperature during the relatively long standstill periods of motor-cars. In this article we are going to discuss the manufacturing of the adsorbents by "liquid phase infiltration" and their characterization by techniques, such as nitrogen sorption analysis, X-ray diffraction, thermogravimetry, energy dispersive X-ray spectroscopy, and electron microscopy. The new adsorbents were evaluated in repeated breakthrough tests using NO 2 (4 ppmV as feed concentration) in humid air as the adsorptive. In the intermittent rest periods of varying duration the volume flow through the fixed bed of adsorbent was stopped. The measured breakthrough curves indicate a catalytic conversion of the nitrogen dioxide in the filter beds. © 2013 Springer Science+Business Media New York.
    view abstractdoi: 10.1007/s10450-013-9521-8
  • 2013 • 194 Characterization of crocodile teeth: Correlation of composition, microstructure, and hardness
    Enax, J. and Fabritius, H.-O. and Rack, A. and Prymak, O. and Raabe, D. and Epple, M.
    Journal of Structural Biology 184 155-163 (2013)
    Structure and composition of teeth of the saltwater crocodile Crocodylus porosus were characterized by several high-resolution analytical techniques. X-ray diffraction in combination with elemental analysis and infrared spectroscopy showed that the mineral phase of the teeth is a carbonated calcium-deficient nanocrystalline hydroxyapatite in all three tooth-constituting tissues: Dentin, enamel, and cementum. The fluoride content in the three tissues is very low (<0.1. wt.%) and comparable to that in human teeth. The mineral content of dentin, enamel, and cementum as determined by thermogravimetry is 71.3, 80.5, and 66.8. wt.%, respectively. Synchrotron X-ray microtomography showed the internal structure and allowed to visualize the degree of mineralization in dentin, enamel, and cementum. Virtual sections through the tooth and scanning electron micrographs showed that the enamel layer is comparably thin (100-200 μm). The crystallites in the enamel are oriented perpendicularly to the tooth surface. At the dentin-enamel-junction, the packing density of crystallites decreases, and the crystallites do not display an ordered structure as in the enamel. The microhardness was 0.60 ± 0.05. GPa for dentin, 3.15 ± 0.15. GPa for enamel, 0.26 ± 0.08. GPa for cementum close to the crown, and 0.31 ± 0.04. GPa for cementum close to the root margin. This can be explained with the different degree of mineralization of the different tissue types and is comparable with human teeth. © 2013 Elsevier Inc.
    view abstractdoi: 10.1016/j.jsb.2013.09.018
  • 2013 • 193 Composition-dependent crystal structure and martensitic transformation in Heusler Ni-Mn-Sn alloys
    Zheng, H. and Wang, W. and Xue, S. and Zhai, Q. and Frenzel, J. and Luo, Z.
    Acta Materialia 61 4648-4656 (2013)
    In the present work, modulated four- and five-layered orthorhombic, seven-layered monoclinic (4O, 10M and 14M) and unmodulated double tetragonal (L10) martensites are characterized in Heusler Ni-Mn-Sn alloys using X-ray diffraction, high-resolution transmission electron microscopy, electron diffraction techniques and thermal analysis. All modulated layered martensites exhibit twins and stacking faults, while the L10 martensite shows fewer structural defects. The substitution of Sn with Mn in Ni 50Mn37+xSn13-x (x = 0, 2, 4) enhances the martensitic transition temperatures, while the transition temperatures decrease with increasing Mn content for constant Sn levels in Ni50-yMn37+ySn13 (y = 0, 2, 4). The compositional dependence of the martensitic transition temperatures is mainly attributed to the valence electron concentration (e/a) and the unit-cell volume of the high-temperature phase. With increasing transition temperatures (or e/a), the resultant martensitic crystal structure evolves in a sequence of 4O → 10M → 14M → L10 in bulk Ni-Mn-Sn alloys. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2013.04.035
  • 2013 • 192 Cu2MnAl thin films grown onto sapphire and MgO substrates: Exchange stiffness and magnetic anisotropy
    Belmeguenai, M. and Tuzcuoglu, H. and Chérif, S.M. and Westerholt, K. and Chauveau, T. and Mazaleyrat, F. and Moch, P.
    Physica Status Solidi (A) Applications and Materials Science 210 553-558 (2013)
    Cu2MnAl films of different thicknesses (50, 70, and 100 nm) were grown by UHV RF-sputtering on a-plane sapphire or on MgO (100) substrates. Their structural and static magnetic properties have been studied by X-rays diffraction (XRD) and by vibrating sample magnetometry (VSM), respectively. The Cu2MnAl films exhibit a (100) and (110)-texture when grown on MgO and sapphire substrates, respectively. The best growth quality and the higher magnetization at saturation were obtained for the films grown on MgO. Dynamic magnetic properties were investigated using micro-strip line ferromagnetic resonance (MS-FMR). From the resonance measurements varying the direction and the amplitude of the in-plane and out-of-plane applied magnetic fields we derive the effective magnetization, the Landé g-factor (g = 2.11), the exchange constant (Aex = 0.34 μerg cm-1) and the magnetic anisotropy terms. The in-plane anisotropy can be described as a superposition of two terms showing a small twofold and a dominant fourfold symmetry. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/pssa.201228187
  • 2013 • 191 Development of a stable high-aluminum austenitic stainless steel for hydrogen applications
    Martin, M. and Weber, S. and Theisen, W. and Michler, T. and Naumann, J.
    International Journal of Hydrogen Energy 38 5989-6001 (2013)
    A novel high-aluminum austenitic stainless steel has been produced in the laboratory with the aim of developing a lean-alloyed material with a high resistance to hydrogen environment embrittlement. The susceptibility to hydrogen environment embrittlement was evaluated by means of tensile tests at a slow strain rate in pure hydrogen gas at a pressure of 40 MPa and a temperature of -50 C. Under these conditions, the yield strength, tensile strength and elongation to rupture are not affected by hydrogen in comparison to companion tests carried out in air. Moreover, a very high ductility in hydrogen is evidenced by a reduction of area of 70% in the high-pressure and low-temperature hydrogen environment. The lean degree of alloying is reflected in the molybdenum-free character of the material and a nickel content of 8.0 wt.%. With regard to the alloy concept, a combination of high-carbon, high-manganese, and high-aluminum contents confer an extremely high stability against the formation of strain-induced martensite. This aspect was investigated by means of in-situ magnetic measurements and ex-situ X-ray diffraction. The overall performance of the novel alloy was compared with two reference materials, 304L and 316L austenitic stainless steels, both industrially produced. Its capability of maintaining a fully austenitic structure during tensile testing has been identified as a key aspect to avoid hydrogen environment embrittlement. Copyright © 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.ijhydene.2013.02.127
  • 2013 • 190 Direct gas-phase synthesis of single-phase β-FeSi2 nanoparticles
    Bywalez, R. and Orthner, H. and Mehmedovic, E. and Imlau, R. and Kovacs, A. and Luysberg, M. and Wiggers, H.
    Journal of Nanoparticle Research 15 (2013)
    For the first time, phase-pure β-FeSi2 nanoparticles were successfully produced by gas-phase synthesis. We present a method to fabricate larger quantities of semiconducting β-FeSi2 nanoparticles, with crystallite sizes between 10 and 30 nm, for solar and thermoelectric applications utilizing a hot-wall reactor. A general outline for the production of those particles by thermal decomposition of silane and iron pentacarbonyl is provided based on kinetic data. The synthesized particles are investigated by X-ray diffraction and transmission electron microscopy, providing evidence that the as-prepared materials are indeed β-FeSi2, while revealing morphological characteristics inherent to the nanoparticles created. © 2013 Springer Science+Business Media.
    view abstractdoi: 10.1007/s11051-013-1878-9
  • 2013 • 189 Effect of carrier gas composition on transferred arc metal nanoparticle synthesis
    Stein, M. and Kiesler, D. and Kruis, F.E.
    Journal of Nanoparticle Research 15 (2013)
    Metal nanoparticles are used in a great number of applications; an effective and economical production scaling-up is hence desirable. A simple and cost-effective transferred arc process is developed, which produces pure metal (Zn, Cu, and Ag) nanoparticles with high production rates, while allowing fast optimization based on energy efficiency. Different carrier gas compositions, as well as the electrode arrangements and the power input are investigated to improve the production and its efficiency and to understand the arc production behavior. The production rates are determined by a novel process monitoring method, which combines an online microbalance method with a scanning mobility particle sizer for fast production rate and size distribution measurement. Particle characterization is performed via scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction measurements. It is found that the carrier gas composition has the largest impact on the particle production rate and can increase it with orders of magnitude. This appears to be not only a result of the increased heat flux and melt temperature but also of the formation of tiny nitrogen (hydrogen) bubbles in the molten feedstock, which impacts feedstock evaporation significantly in bi-atomic gases. A production rate of sub 200 nm particles from 20 up to 2,500 mg/h has been realized for the different metals. In this production range, specific power consumptions as low as 0.08 kWh/g have been reached. © 2013 Springer Science+Business Media Dordrecht.
    view abstractdoi: 10.1007/s11051-012-1400-9
  • 2013 • 188 Effect of jute as fiber reinforcement controlling the hydration characteristics of cement matrix
    Chakraborty, S. and Kundu, S.P. and Roy, A. and Adhikari, B. and Majumder, S.B.
    Industrial and Engineering Chemistry Research 52 1252-1260 (2013)
    The present investigation deals with the effect of jute as a natural fiber reinforcement on the setting and hydration behavior of cement. The addition of jute fiber in cement matrix increases the setting time and standard water consistency value. The hydration characteristics of fiber reinforced cement were investigated using a variety of analytical techniques including thermal, infrared spectroscopy, X-ray diffraction, and free lime estimation by titration. Through these analyses it was demonstrated that the hydration kinetics of cement is retarded with the increase in jute contents in cement matrix. A model has been proposed to explain the retarded hydration kinetics of jute fiber reinforced cement composites. The prolonged setting of these fiber reinforced cement composites would be beneficial for applications where the premixed cement aggregates are required to be transported from a distant place to the construction site. © 2012 American Chemical Society.
    view abstractdoi: 10.1021/ie300607r
  • 2013 • 187 Electric in-plane polarization in multiferroic CoFe2O 4/BaTiO3 nanocomposite tuned by magnetic fields
    Schmitz-Antoniak, C. and Schmitz, D. and Borisov, P. and De Groot, F.M.F. and Stienen, S. and Warland, A. and Krumme, B. and Feyerherm, R. and Dudzik, E. and Kleemann, W. and Wende, H.
    Nature Communications 4 (2013)
    Ferrimagnetic CoFe2O4 nanopillars embedded in a ferroelectric BaTiO3 matrix are an example for a two-phase magnetoelectrically coupled system. They operate at room temperature and are free of any resource-critical rare-earth element, which makes them interesting for potential applications. Prior studies succeeded in showing strain-mediated coupling between the two subsystems. In particular, the electric properties can be tuned by magnetic fields and the magnetic properties by electric fields. Here we take the analysis of the coupling to a new level utilizing soft X-ray absorption spectroscopy and its associated linear dichroism. We demonstrate that an in-plane magnetic field breaks the tetragonal symmetry of the (1,3)-type CoFe2O4/BaTiO3 structures and discuss it in terms of off-diagonal magnetostrictive-piezoelectric coupling. This coupling creates staggered in-plane components of the electric polarization, which are stable even at magnetic remanence due to hysteretic behaviour of structural changes in the BaTiO3 matrix. The competing mechanisms of clamping and relaxation effects are discussed in detail. © 2013 Macmillan Publishers Limited. All rights reserved.
    view abstractdoi: 10.1038/ncomms3051
  • 2013 • 186 Eu-doped ZnO nanowire arrays grown by electrodeposition
    Lupan, O. and Pauporté, T. and Viana, B. and Aschehoug, P. and Ahmadi, M. and Cuenya, B.R. and Rudzevich, Y. and Lin, Y. and Chow, L.
    Applied Surface Science 282 782-788 (2013)
    The preparation of efficient light emitting diodes requires active optical layers working at low voltage for light emission. Trivalent lanthanide doped wide-bandgap semiconducting oxide nanostructures are promising active materials in opto-electronic devices. In this work we report on the electrochemical deposition (ECD) of Eu-doped ZnO (ZnO:Eu) nanowire arrays on glass substrates coated with F-doped polycrystalline SnO2. The structural, chemical and optical properties of ZnO:Eu nanowires have been systematically characterized by X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, secondary ion mass spectrometry, and photoluminescence. XRD results suggest the substitution of Zn2+ by Eu ions in the crystalline lattice. High-resolution TEM and associated electron diffraction studies indicate an interplanar spacing of 0.52 nm which corresponds to the (0 0 0 1) crystal plane of the hexagonal ZnO, and a growth along the c-direction. The ZnO:Eu nanowires have a single crystal structure, without noticeable defects. According to EDX, SIMS and XPS studies, cationic Eu species are detected in these samples showing the incorporation of Eu into the ZnO matrix. The oxidation states of europium ions in the nanowires are determined as +3 (74%) and +2 (26%). Photoluminescence studies demonstrated red emission from the Eu-doped ZnO nanowire arrays. When Eu was incorporated during the nanowire growth, the sharp 5D0-7F 2 transition of the Eu3+ ion at around 612 nm was observed. These results suggest that Eu doped ZnO nanowires could pave the way for efficient, multispectral LEDs and optical devices. © 2013 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.apsusc.2013.06.053
  • 2013 • 185 Experimental and theoretical investigation of molybdenum carbide and nitride as catalysts for ammonia decomposition
    Zheng, W. and Cotter, T.P. and Kaghazchi, P. and Jacob, T. and Frank, B. and Schlichte, K. and Zhang, W. and Su, D.S. and Schüth, F. and Schlögl, R.
    Journal of the American Chemical Society 135 3458-3464 (2013)
    Constant COx-free H2 production from the catalytic decomposition of ammonia could be achieved over a high-surface-area molybdenum carbide catalyst prepared by a temperature-programmed reduction-carburization method. The fresh and used catalyst was characterized by N2 adsorption/desorption, powder X-ray diffraction, scanning and transmission electron microscopy, and electron energy-loss spectroscopy at different stages. Observed deactivation (in the first 15 h) of the high-surface-area carbide during the reaction was ascribed to considerable reduction of the specific surface area due to nitridation of the carbide under the reaction conditions. Theoretical calculations confirm that the N atoms tend to occupy subsurface sites, leading to the formation of nitride under an NH3 atmosphere. The relatively high rate of reaction (30 mmol/((g of cat.) min)) observed for the catalytic decomposition of NH3 is ascribed to highly energetic sites (twin boundaries, stacking faults, steps, and defects) which are observed in both the molybdenum carbide and nitride samples. The prevalence of such sites in the as-synthesized material results in a much higher H2 production rate in comparison with that for previously reported Mo-based catalysts. © 2013 American Chemical Society.
    view abstractdoi: 10.1021/ja309734u
  • 2013 • 184 Extended investigation of intermartensitic transitions in Ni-Mn-Ga magnetic shape memory alloys: A detailed phase diagram determination
    Çakir, A. and Righi, L. and Albertini, F. and Acet, M. and Farle, M. and Aktürk, S.
    Journal of Applied Physics 114 (2013)
    Martensitic transitions in shape memory Ni-Mn-Ga Heusler alloys take place between a high temperature austenite and a low temperature martensite phase. However, intermartensitic transformations have also been encountered that occur from one martensite phase to another. To examine intermartensitic transitions in magnetic shape memory alloys in detail, we carried out temperature dependent magnetization, resistivity, and x-ray diffraction measurements to investigate the intermartensitic transition in Ni50Mn50- xGax in the composition range 12 ≤ x ≤ 25 at. %. Rietveld refined x-ray diffraction results are found to be consistent with magnetization and resistivity data. Depending on composition, we observe that intermartensitic transitions occur in the sequences 7 M → L 1 0, 5 M → 7 M, and 5 M → 7 M → L 1 0 with decreasing temperature. The L1 0 non-modulated structure is most stable at low temperature. © 2013 AIP Publishing LLC.
    view abstractdoi: 10.1063/1.4831667
  • 2013 • 183 Functionally graded vacuum plasma sprayed and magnetron sputtered tungsten/EUROFER97 interlayers for joints in helium-cooled divertor components
    Weber, T. and Stüber, M. and Ulrich, S. and Vaßen, R. and Basuki, W.W. and Lohmiller, J. and Sittel, W. and Aktaa, J.
    Journal of Nuclear Materials 436 29-39 (2013)
    Two coating technologies, magnetron sputtering and vacuum plasma spraying, have been investigated for their capability in producing functionally graded tungsten/EUROFER97 layers. In a first step, non-graded layers with different mixing ratios were deposited on tungsten substrates and characterized by nanoindentation, macroindentation, X-ray diffraction, transmission, Auger and scanning electron microscopy. The thermal stability of the sprayed layers against heat treatments at 800-1100 °C for 60 min was further analyzed. In a second step, the produced functionally graded layers deposited on tungsten substrates were joined to EUROFER97 bulk-material by diffusion bonding. The bonding and the graded joints were microscopically characterized and exposed to thermal cycles between 20 °C and 650 °C. Results from this study show that both coating technologies are ideal for the synthesis of functionally graded tungsten/EUROFER97 coatings. This is important in providing insights for fture development of joints with functionally graded interlayers. © 2013 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.jnucmat.2013.01.286
  • 2013 • 182 Grafting of titanium dioxide microspheres with a temperature-responsive polymer via surface-initiated atom transfer radical polymerization without the use of silane coupling agents
    Smirnov, E.A. and Meledina, M.A. and Garshev, A.V. and Chelpanov, V.I. and Frost, S. and Wieneke, J.U. and Ulbricht, M.
    Polymer International 62 836-841 (2013)
    Titania microspheres with narrow size distribution and diameters of about 1 μm were prepared and subsequently functionalized using surface-initiated atom transfer radical polymerization (ATRP) of N-isopropylacrylamide. The ATRP initiator was immobilized on the particle surface via acylation of surface hydroxyl groups with α-bromoisobutyryl bromide. Subsequently, an established ATRP reaction system was used for the preparation of titania surface-grafted poly(N-isopropylacrylamide) (PNiPAAm). Characterization was performed with electron microscopies, X-ray diffraction, infrared spectroscopy and dynamic light scattering. It was found that the particle size in aqueous dispersions changed reversibly with temperature as expected for a shell of PNiPAAm, a polymer with a lower critical solution temperature at 32 °C. This confirmed the successful preparation of functional, stimuli-responsive TiO2 microparticles via a straightforward controlled surface-initiated polymerization method. © 2012 Society of Chemical Industry.
    view abstractdoi: 10.1002/pi.4377
  • 2013 • 181 Grazing-incidence X-ray diffraction of single GaAs nanowires at locations defined by focused ion beams
    Bussone, G. and Schott, R. and Biermanns, A. and Davydok, A. and Reuter, D. and Carbone, G. and Schülli, T.U. and Wieck, A.D. and Pietsch, U.
    Journal of Applied Crystallography 46 887-892 (2013)
    Grazing-incidence X-ray diffraction measurements on single GaAs nanowires (NWs) grown on a (111)-oriented GaAs substrate by molecular beam epitaxy are reported. The positions of the NWs are intentionally determined by a direct implantation of Au with focused ion beams. This controlled arrangement in combination with a nanofocused X-ray beam allows the in-plane lattice parameter of single NWs to be probed, which is not possible for randomly grown NWs. Reciprocal space maps were collected at different heights along the NW to investigate the crystal structure. Simultaneously, substrate areas with different distances from the Au-implantation spots below the NWs were probed. Around the NWs, the data revealed a 0.4% decrease in the lattice spacing in the substrate compared with the expected unstrained value. This suggests the presence of a compressed region due to Au implantation. © 2013 International Union of Crystallography Printed in Singapore - all rights reserved.
    view abstractdoi: 10.1107/S0021889813004226
  • 2013 • 180 High-throughput compositional and structural evaluation of a Li a(NixMnyCoz)Or thin film battery materials library
    Borhani-Haghighi, S. and Kieschnick, M. and Motemani, Y. and Savan, A. and Rogalla, D. and Becker, H.-W. and Meijer, J. and Ludwig, Al.
    ACS Combinatorial Science 15 401-409 (2013)
    A Lia(NixMnyCoz)Or cathode materials library was fabricated by combinatorial magnetron sputtering. The compositional analysis of the library was performed by a new high-throughput approach for Li-content measurement in thin films, which combines automated energy-dispersive X-ray spectroscopy, Deuteron-induced gamma emission, and Rutherford backscattering measurements. Furthermore, combining this approach with thickness measurements allows the mapping of density values of samples from the materials library. By correlating the obtained compositional data with structural data from high-throughput X-ray diffraction measurements, those compositions which show a layered (R3Ì...m) structure and are therefore most interesting for Li-battery applications (for cathode (positive) electrodes) can be rapidly identified. This structure was identified as being most pronounced in the compositions Li0.6(Ni0.16Mn 0.35Co0.48)O2, Li0.7(Ni 0.10Mn0.37Co0.51)O2, Li 0.6(Ni0.23Mn0.33Co0.43)O 2, Li0.3(Ni0.65Mn0.08Co 0.26)O2, Li0.3(Ni0.63Mn 0.08Co0.29)O2, Li0.4(Ni 0.56Mn0.09Co0.34)O2, Li 0.5(Ni0.45Mn0.13Co0.42)O 2, and Li0.6(Ni0.34Mn0.14Co 0.52)O2. © 2013 American Chemical Society.
    view abstractdoi: 10.1021/co4000166
  • 2013 • 179 Influence of the cation alkyl chain length of imidazolium-based room temperature ionic liquids on the dispersibility of TiO2 nanopowders
    Wittmar, A. and Gajda, M. and Gautam, D. and Dörfler, U. and Winterer, M. and Ulbricht, M.
    Journal of Nanoparticle Research 15 (2013)
    The influence of the length of the cation alkyl chain on the dispersibility by ultrasonic treatment of TiO2 nanopowders in hydrophilic imidazolium-based room temperature ionic liquids was studied for the first time by dynamic light scattering and advanced rheology. TiO2 nanopowders had been synthesized by chemical vapor synthesis (CVS) under varied conditions leading to two different materials. A commercial nanopowder had been used for comparison. Characterizations had been done using transmission electron microscopy, X-ray diffraction, nitrogen adsorption with BET analysis, and FT-IR spectroscopy. Primary particle sizes were about 6 and 8 nm for the CVS-based and 26 nm for the commercial materials. The particle size distribution in the dispersion was strongly influenced by the length of the cation alkyl chain for all the investigated powders with different structural characteristics and concentrations in the dispersion. It was found that an increase of the alkyl chain length was beneficial, leading to a narrowing of the particle size distribution and a decrease of the agglomerate size in dispersion. The smallest average nanoparticle sizes in dispersion were around 30 nm. Additionally, the surface functionality of the nanoparticles, the concentration of the solid material in the liquid, and the period of ultrasonic treatment control the dispersion quality, especially in the case of the ionic liquids with the shorter alkyl chain. The influence of the nanopowders characteristics on their dispersibility decreases considerably with increasing cation alkyl chain length. The results indicate that ionic liquids with adapted structure are candidates as absorber media for nanoparticles synthesized in gas phase processes to obtain liquid dispersions directly without redispergation. © 2013 Springer Science+Business Media Dordrecht.
    view abstractdoi: 10.1007/s11051-013-1463-2
  • 2013 • 178 Influence of the precipitation method on acid-base-catalyzed reactions over Mg-Zr mixed oxides
    Kozlowski, J.T. and Behrens, M. and Schlögl, R. and Davis, R.J.
    ChemCatChem 5 1989-1997 (2013)
    To examine the promotional effect that zirconia has on magnesia in catalysis, mixed oxides were prepared by coprecipitation under controlled-pH conditions or rising-pH conditions. The resulting mixed oxides were characterized by using NH3 and CO2 adsorption microcalorimetry, X-ray diffraction, and scanning electron microscopy. The samples were also tested as catalysts for transesterification of tributyrin with methanol, coupling of acetone, and conversion of ethanol to ethene, ethanal, and butanol. Zirconia promoted the activity of MgO for both transesterification and acetone coupling reactions, presumably by exposing new acid-base pairs at the surface. During ethanol conversion, however, zirconia promoted the dehydration reactions. Characterization and reactivity results suggest that a Mg-Zr sample prepared by controlled-pH precipitation exposes more ZrO2 than a sample prepared by the rising-pH method. © 2013 WILEY-VCH Verlag GmbH & Co.
    view abstractdoi: 10.1002/cctc.201200833
  • 2013 • 177 Insights into the topotactic conversion process from layered silicate RUB-36 to FER-type zeolite by layer reassembly
    Zhao, Z. and Zhang, W. and Ren, P. and Han, X. and Müller, U. and Yilmaz, B. and Feyen, M. and Gies, H. and Xiao, F.-S. and De Vos, D. and Tatsumi, T. and Bao, X.
    Chemistry of Materials 25 840-847 (2013)
    Layered RUB-36 and PREFER (lamellar precursor of ferrierite) are the precursors of CDO and FER-type zeolites, respectively. Both are composed of the same ferrierite (FER) layer building blocks. Topotactic conversion from RUB-36 to pure silica zeolite ZSM-35 has been demonstrated in the presence of a surfactant cetyltrimethylammonium hydroxide (CTAOH). The transformation mechanism of this process was revealed, for the first time, by the detailed investigations of powder X-ray diffraction (XRD), scanning electron microscopy (SEM), thermal analysis, and one-and two-dimensional (2-D) solid-state magic-angle spinning nuclear magnetic resonance (MAS NMR) as well as theoretical simulations. During swelling at room temperature, cetyltrimethylammonium cations (CTA+) replacing the original template were intercalated into FER layers to expand the interlayer distance remarkably and consequently to destroy the strong hydrogen-bonding interactions between the layers. 2-D 1H-29Si heteronuclear correlation (HETCOR) NMR indicates that the surfactant polar heads approximate the FER layers in swollen RUB-36. After deswelling, only a small amount of CTA+ cations with long tails lay in the void space between the FER layers. The Monte Carlo simulations on the deswollen RUB-36 further elucidate the occlusion of CTA+ cations in the pre-10 member ring of the layered ferrierite precursor, which may act as the structure-directing agent for the formation of FER-structured zeolite. The FER layer reassembly from the alteration of CTA+ conformation at the interlayers is of key importance to the topotactic transformation of RUB-36 to FER-type zeolite by the dehydration-condensation reaction. This may open up more applications in the lamellar zeolite system by the layer restacking approach. © 2013 American Chemical Society.
    view abstractdoi: 10.1021/cm303131c
  • 2013 • 176 Interface-directed spinodal decomposition in TiAlN/CrN multilayer hard coatings studied by atom probe tomography
    Povstugar, I. and Choi, P.-P. and Tytko, D. and Ahn, J.-P. and Raabe, D.
    Acta Materialia 61 7534-7542 (2013)
    Microstructural and compositional changes in TiAlN/CrN multilayered films occurring at temperatures up to 1000 C were studied at different length scales by a combination of atom probe tomography, transmission electron microscopy and X-ray diffraction. We observe the onset of decomposition of the multilayer structure at 700 C via the mechanism of interface-directed spinodal decomposition of TiAlN layers, where Al atoms preferentially move toward the nearest interface and segregate there. The interface-directed mechanism later transforms into isotropic spinodal decomposition and is accompanied by intense interdiffusion between the constituting layers. Distinct compositional gradients across columnar grain boundaries (extending perpendicular to the multilayers) are detected at this stage of decomposition. Drastic differences in decomposition behavior across the film depth were observed at elevated temperatures (800-1000 C): the layered structure completely dissolves in the near-surface part but persists in the regions distant from the surface. The influence of residual stresses caused by the sputter deposition process on the thermally induced evolution of the multilayer thin films is discussed. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2013.08.028
  • 2013 • 175 Intrinsic nitrogen-doped CVD-grown TiO2 thin films from all-N-coordinated Ti precursors for photoelectrochemical applications
    Kim, S.J. and Xu, K. and Parala, H. and Beranek, R. and Bledowski, M. and Sliozberg, K. and Becker, H.-W. and Rogalla, D. and Barreca, D. and Maccato, C. and Sada, C. and Schuhmann, W. and Fischer, R.A. and Devi, A.
    Chemical Vapor Deposition 19 45-52 (2013)
    N-doped titanium dioxide (TiO2) thin films are grown on Si(100) and indium tin oxide (ITO)-coated borosilicate glass substrates by metal-organic (MO)CVD. The intrinsic doping of TiO2 thin films is achieved using all-nitrogen-coordinated Ti precursors in the presence of oxygen. The titanium amide-guanidinate complex, [Ti(NMe2)3(guan)] (guan = N,N′-diisopropyl-2-dimethylamidoguanidinato) has been developed to compensate for the thermal instability of the parent alkylamide [Ti(NMe 2)4]. Both of these amide-based compounds are tested and compared as precursors for intrinsically N-doped TiO2 at various deposition temperatures in the absence of additional N sources. The structure and morphology of TiO2 thin films are characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). Rutherford back scattering (RBS), nuclear reaction analysis (NRA), and secondary ion mass spectrometry (SIMS) analyses are performed to determine N content and distribution in the films. The optical and photoelectrochemical properties of TiO2 thin films on ITO substrates are also examined. N-doped TiO2 thin films, grown from [Ti(NMe 2)3(guan)] at 600 °C, exhibit the lowest optical absorption edge (3.0 eV) and the highest visible light photocurrent response. When compared to undoped TiO2, while in UV light photoconversion efficiency decreases significantly, the intrinsically N-doped TiO2 shows enhanced photocurrents under visible light irradiation. The intrinsic doping of TiO2 thin films with nitrogen by MOCVD and the investigation of the photo-electrochemical properties of the films are reported. N-doped anatase phase TiO2 thin films are grown on Si(100) and ITO substrates under specific processing conditions, using [Ti(NMe2) 4] (1) and [Ti(NMe2)3(guan)] (2) (guan = N,N′-diisopropyl-2-dimethylamidoguanidinato) as precursors. The films grown from [Ti(NMe2)3(guan)] at 600 °C show relatively large surface roughness and lower bandgap related with high N content. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cvde.201206996
  • 2013 • 174 Lipid-based intravesical drug delivery systems with controlled release of trospium chloride for the urinary bladder
    Haupt, M. and Thommes, M. and Heidenreich, A. and Breitkreutz, J.
    Journal of Controlled Release 170 161-166 (2013)
    The overactive bladder (OAB) is a common disease with an overactivity of the detrusor muscle in the bladder wall. Besides peroral administration of anticholinergic drugs and bladder irrigations, there is a need for a sustained release formulation in the urinary bladder. In order to realise a local long-term treatment of the overactive urinary bladder, lipidic drug delivery systems were prepared. Requirements for an intravesical application are a long-term controlled release of trospium chloride, a high drug loading and small sized drug carriers to permit an insertion through the urethra into the urinary bladder. The drug delivery systems were manufactured by using compression (mini-tablets), solid lipid extrusion (extrudates) and a melting and casting technique (mini-moulds) with different amounts of trospium chloride and glyceryl tristearate as matrix former. Drug release depended on the drug loading and the preparation method. Mini-tablets and lipidic extrudates showed a drug release over five days, whereas that from mini-moulds was negligibly small. The appearance of polymorphic transformations during processing and storage was investigated by using differential scanning calorimetry and X-ray diffraction. In contrast to mini-tablets and mini-moulds, lipidic extrudates showed no polymorphic transformations. In summary, lipids are suitable matrix formers for a highly water-soluble drug, like trospium chloride. Despite a drug loading of up to 30%, it was feasible to achieve a drug release ranging from several days up to weeks. In addition, small dosage forms with a size of only a few millimetres were realised. Therefore, an insertion and excretion through the urethra is possible and the requirements for an intravesical application are fulfilled. © 2013 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.jconrel.2013.05.018
  • 2013 • 173 Low-temperature martensitic transformation in tool steels in relation to their deep cryogenic treatment
    Gavriljuk, V.G. and Theisen, W. and Sirosh, V.V. and Polshin, E.V. and Kortmann, A. and Mogilny, G.S. and Petrov, Yu.N. and Tarusin, Ye.V.
    Acta Materialia 61 1705-1715 (2013)
    The low-temperature martensitic transformation in steel X153CrMoV12 containing (mass%) 1.55C, 11.90Cr, 0.70V, 0.86Mo is studied using dilatometry, Mössbauer spectroscopy, X-ray diffraction, mechanical spectroscopy and transmission electron microscopy. Some additional measurements were carried out on steel X220CrMoV13-4. It is shown that, in contrast to the widely known absence of martensitic transformation during deep cryogenic treatment, this transformation occurs with isothermal kinetics within the temperature range of -100 down to -170 °C with its largest intensity near -150 °C. No transformation is observed at -196 °C. The remarkable features of the isothermal martensitic transformation are: (i) the plastic deformation, which is explained by the absence of ageing of martensite at low temperatures; and (ii) the abnormally low tetragonality of martensite. In contrast to existing interpretations, the abnormally low c/a ratio is interpreted in terms of the capture of immobile carbon atoms by gliding dislocations during plastic deformation at low temperatures. A recommendation is proposed for optimizing the deep cryogenic treatment of tool steels. © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2012.11.045
  • 2013 • 172 Magnetization dynamics in Co2MnGe/Al2O3/Co tunnel junctions grown on different substrates
    Belmeguenai, M. and Tuzcuoglu, H. and Zighem, F. and Chérif, S.-M. and Roussigné, Y. and Westerholt, K. and Moch, P. and El Bahoui, A. and Genevois, C. and Fnidiki, A.
    Sensor Letters 11 2043-2048 (2013)
    We study static and dynamic magnetic properties of Co2MnGe (13 nm)/Al2O3 (3 nm)/Co (13 nm) tunnel magnetic junctions, deposited on various single crystalline substrates (a-plane sapphire, MgO(100), Si(111)). The results are compared to the magnetic properties of Co and of Co2MnGe single films lying on sapphire substrates. X-rays diffraction always shows (110) orientation of the Co2MnGe films. Structural observations obtained by high resolution transmission electron microscopy confirmed the high quality of the tunnel magnetic junction grown on sapphire. Our vibrating sample magnetometry measurements reveal in-plane anisotropy only in samples grown on a sapphire substrate. Depending on the substrate, the ferromagnetic resonance spectra of the tunnel magnetic junctions, studied by the microstrip technique, show one or two pseudo-uniform modes. In the case of MgO and of Si substrates only one mode is observed: it is described by magnetic parameters (g-factor, effective magnetization, in-plane magnetic anisotropy) derived in the frame of a simple expression of the magnetic energy density; these parameters are practically identical to those obtained for the Co single film. With a sapphire substrate two modes are present: one of them does not appreciably differ from the observed mode in the Co single film while the other one is similar to the mode appearing in the Co2MnGe single film: their magnetic parameters can thus be determined independently, using a classical model for the energy density in the absence of interlayer exchange coupling. Copyright © 2013 American Scientific Publishers.
    view abstractdoi: 10.1166/sl.2013.3064
  • 2013 • 171 Molybdenum-based catalysts for the decomposition of ammonia: In situ X-ray diffraction studies, microstructure, and catalytic properties
    Tagliazucca, V. and Schlichte, K. and Schüth, F. and Weidenthaler, C.
    Journal of Catalysis 305 277-289 (2013)
    The ammonia decomposition reaction over molybdenum-based catalysts is an example for the complex influence of different factors, such as phase composition, size of crystalline domains, or defect concentration, on the catalytic behavior of a material. In situ powder diffraction allows the direct analysis of how catalysts change during a reaction with respect to the atomic structure or microstructure in terms of defects or size changes. In this article, the influence of catalyst treatment such as pre-reduction or ball milling on the catalytic properties is discussed in detail. © 2013 Elsevier Inc. All rights reserved.
    view abstractdoi: 10.1016/j.jcat.2013.05.011
  • 2013 • 170 Morphology control of thin P3HT-Si-NCs composite films for hybrid photovoltaic cells
    Cunha, M. and Bernardo, G. and Hilliou, L. and Wiggers, H. and Pereira, R.N.
    Materials Science Forum 730-732 227-231 (2013)
    This work deals with an experimental investigation of the microstructure/morphology of spin-casted composite thin films of poly(3-hexylthiophene) (P3HT) and silicon nanocrystals (Si- NCs), in the weight proportion 1:1, which develop under different deposition conditions. The experimental parameters considered were the following: i) solvent quality; ii) spinning rate; iii) spinning time and iv) solution concentration. The developed morphologies were characterized by means of optical microscopy and X-ray diffraction (XRD) measurements. The present work aims at a) establishing the relationship between processing conditions and resultant morphology and b) defining the most relevant processing parameters that govern and are of significance for the induced morphology. © (2013) Trans Tech Publications, Switzerland.
    view abstractdoi: 10.4028/
  • 2013 • 169 Nanocrystalline Fe-C alloys produced by ball milling of iron and graphite
    Chen, Y.Z. and Herz, A. and Li, Y.J. and Borchers, C. and Choi, P. and Raabe, D. and Kirchheim, R.
    Acta Materialia 61 3172-3185 (2013)
    A series of nanocrystalline Fe-C alloys with different carbon concentrations (xtot) up to 19.4 at.% (4.90 wt.%) are prepared by ball milling. The microstructures of these alloys are characterized by transmission electron microscopy and X-ray diffraction, and partitioning of carbon between grain boundaries and grain interiors is determined by atom probe tomography. It is found that the segregation of carbon to grain boundaries of α-ferrite can significantly reduce its grain size to a few nanometers. When the grain boundaries of ferrite are saturated with carbon, a metastable thermodynamic equilibrium between the matrix and the grain boundaries is approached, inducing a decreasing grain size with increasing xtot. Eventually the size reaches a lower limit of about 6 nm in alloys with x tot &gt; 6.19 at.% (1.40 wt.%); a further increase in xtot leads to the precipitation of carbon as Fe3C. The observed presence of an amorphous structure in 19.4 at.% C (4.90 wt.%) alloy is ascribed to a deformation-driven amorphization of Fe3C by severe plastic deformation. By measuring the temperature dependence of the grain size for an alloy with 1.77 at.% C additional evidence is provided for a metastable equilibrium reached in the nanocrystalline alloy. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2013.02.006
  • 2013 • 168 Physical, chemical and biological properties of micro-arc deposited calcium phosphate coatings on titanium and zirconium-niobium alloy
    Legostaeva, E.V. and Kulyashova, K.S. and Komarova, E.G. and Epple, M. and Sharkeev, Y.P. and Khlusov, I.A.
    Materialwissenschaft und Werkstofftechnik 44 188-197 (2013)
    A comparative investigation of the physical, chemical and biological properties of micro-arc deposited calcium phosphate coatings on titanium and zirconium-niobium substrates was performed. Calcium phosphate coatings on titanium have a higher surface density, porosity and pore size, and a more homogeneous surface topography. Under the same conditions, calcium phosphate coatings on zirconium-niobium have a relief topography, but their surface density, porosity and pore size were all smaller. X-ray diffraction of the coatings showed that the coatings on titanium were X-ray amorphous whereas the coatings on zirconium-niobium consisted of a mixture of crystalline CaZr 4(PO4)6, ZrP2O7, and ZrO2. These differences are due to different electrical and thermophysical characteristics of substrates and passivating films on their surfaces. The coatings were shown to be biocompatible by in-vitro cell culture experiments. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/mawe.201300107
  • 2013 • 167 Polymer modified jute fibre as reinforcing agent controlling the physical and mechanical characteristics of cement mortar
    Chakraborty, S. and Kundu, S.P. and Roy, A. and Adhikari, B. and Majumder, S.B.
    Construction and Building Materials 49 214-222 (2013)
    Polymer modified alkali treated jute fibre as a reinforcing agent, substantially improves the physical and mechanical properties of cement mortar with a mix design cement:sand:fibre:water::1:3:0.01:0.6. The workability of the mortar is found to increase systematically from 155 ± 5 mm (control mortar) to 167 ± 8 mm (0.2050% polymer modified mortar). The density of the mortar is increased from 2092 kg/m3 to 2136 kg/m3 with a concomitant reduction of both water absorption and apparent porosity. Optimal polymer content in emulsion (0.0513%) is found to increase the compressive strength, modulus of rupture and flexural toughness 25%, 28%, 387% respectively as compared to control mortar. Based on the X-ray diffraction and infra-red spectroscopy analyses of the mortar samples a plausible mechanism of the effect of modified jute fibre controlling the physical and mechanical properties of cement mortar has been proposed. © 2013 Elsevier Inc. All rights reserved.
    view abstractdoi: 10.1016/j.conbuildmat.2013.08.025
  • 2013 • 166 Preparation of a silicate-containing hydroxyapatite-based coating by magnetron sputtering: Structure and osteoblast-like MG63 cells in vitro study
    Surmeneva, M.A. and Kovtun, A. and Peetsch, A. and Goroja, S.N. and Sharonova, A.A. and Pichugin, V.F. and Grubova, I.Y. and Ivanova, A.A. and Teresov, A.D. and Koval, N.N. and Buck, V. and Wittmar, A. and Ulbricht, M. and Prymak,...
    RSC Advances 3 11240-11246 (2013)
    Silicate-containing hydroxyapatite-based coatings with different structure and calcium/phosphate ratios were prepared by radio-frequency magnetron sputtering on silicon and titanium substrates, respectively. Scanning electron microscopy, X-ray diffraction and IR spectroscopy were used to investigate the effect of the substrate bias on the properties of the silicate-containing hydroxyapatite-based coatings. The deposition rate, composition, and microstructure of the deposited coatings were all controlled by changing the bias voltage from grounded (0 V) to -50 and -100 V. The biocompatibility was assessed by cell culture with human osteoblast-like cells (MG-63 cell line), showing a good biocompatibility and cell growth on the substrates. © 2013 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c3ra40446c
  • 2013 • 165 Preparation of amorphous and nanocrystalline sodium tantalum oxide photocatalysts with porous matrix structure for overall water splitting
    Tüysüz, H. and Chan, C.K.
    Nano Energy 2 116-123 (2013)
    Herein, we report the preparation of a series of surfactant-free nanostructured sodium tantalum oxide using NaTa(OC3H7)6 as a single precursor. The reaction conditions for the novel synthetic method were optimized and the morphology and crystal structure of the prepared materials were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Condensation and polymerization of NaTa(OC3H7)6 under atmospheric pressure gave a porous amorphous structure that could be converted to crystalline NaTaO3 while crystalline Na2Ta2O6 nanocrystals with a 25nm average particle size could be obtained from a hydrothermal method using NH3 as a base catalyst. In addition, the photocatalytic behaviors of the prepared materials were investigated for overall water splitting into hydrogen and oxygen. Unexpectedly, porous amorphous sodium tantalum oxide showed much better catalytic activity over the crystalline one. The synthesized Na2Ta2O6 nanocrystals also indicated promising activity for overall water splitting without any co-catalyst in comparison to bulk NaTaO3. © 2012 Elsevier Ltd.
    view abstractdoi: 10.1016/j.nanoen.2012.08.003
  • 2013 • 164 Rational synthesis of Beta zeolite with improved quality by decreasing crystallization temperature in organotemplate-free route
    Zhang, H. and Xie, B. and Meng, X. and Müller, U. and Yilmaz, B. and Feyen, M. and Maurer, S. and Gies, H. and Tatsumi, T. and Bao, X. and Zhang, W. and De Vos, D. and Xiao, F.-S.
    Microporous and Mesoporous Materials 180 123-129 (2013)
    Beta zeolite as efficient catalyst has been widely used in industrial processes, and its synthesis is normally performed in the presence of tetraethylammonium hydroxide as organic template. Recent works show successful organotemplate-free and seed-directed synthesis of Beta zeolite (Beta-SDS) in the presence of Beta seeds at 140 C, providing a novel route for synthesizing low-cost zeolite catalysts. Notably, in the case for synthesizing Beta-SDS at 140 C (Beta-SDS140), the use of seeds is still very high (8-10% in silica source) and impurity of MOR zeolite easily appears due to the fast crystallization rate. We demonstrate here a rational synthesis of Beta-SDS at 120 C (Beta-SDS120) with pure BEA structure and improved zeolite quality in the presence of a very small amount of Beta seeds (as low as 1.4%) by decreasing zeolite crystallization rate. X-ray diffraction patterns show that calcination at 550 C for 4 h results in the loss of crystallinity at 8.0% and 15.8% for Beta-SDS120 and Beta-SDS140, respectively, suggesting that Beta-SDS120 has higher thermal stability than Beta-SDS140. N2 adsorption isotherms show that Beta-SDS120 has much higher surface area (655 m2/g) and micropore volume (0.25 cm3/g) than Beta-SDS140 (450 m 2/g, 0.18 cm3/g). These phenomena are reasonably assigned to that Beta-SDS120 samples have much less framework defects such as terminal Si-OH groups than Beta-SDS140. The Beta-SDS120 samples with good crystallinity, high thermal stability, large surface area and pore volume offer a good opportunity for their industrial applications as efficient and low-cost catalytic and adsorptive materials.© 2013 Elsevier Inc. All rights reserved.
    view abstractdoi: 10.1016/j.micromeso.2013.06.031
  • 2013 • 163 Simple synthesis of superparamagnetic magnetite nanoparticles as highly efficient contrast agent
    Jha, D.K. and Shameem, M. and Patel, A.B. and Kostka, A. and Schneider, P. and Erbe, A. and Deb, P.
    Materials Letters 95 186-189 (2013)
    Magnetite nanoparticles have been prepared by one-pot thermal decomposition process using iron (III) acetylacetonate in stearic acid in ambient environment. In this process, stearic acid acts as solvent as well as capping agent for the particles. These as-prepared hydrophobic magnetite nanoparticles have been converted into a hydrophilic form using tetramethylammonium hydroxide. This controlled surface functionalization approach limits microstructural and phase alteration due to the ligand exchange. A detailed investigation was carried out on the microstructural characteristics of these nanoparticles with the aid of X-ray diffraction, infrared spectroscopy, XPS and transmission electron microscopy. The hydrophilic superparamagnetic magnetite particles posses extraordinary transverse relaxivity and contrast property, making them potential T2 contrast agent in clinical magnetic resonance imaging. © 2013 Elsevier B.V.
    view abstractdoi: 10.1016/j.matlet.2012.12.096
  • 2013 • 162 Solid dispersions prepared by continuous cogrinding in an air jet mill
    Muehlenfeld, C. and Kann, B. and Windbergs, M. and Thommes, M.
    Journal of Pharmaceutical Sciences 102 4132-4139 (2013)
    Embedding a poorly water-soluble drug as a solid dispersion in a hydrophilic carrier by cogrinding is a possible strategy for enhancing the drug dissolution rate. Although general interest in continuous processes for manufacturing drug formulations has increased, many publications still focus on batch processes. The jet mill used in this study is a promising tool for continuous cogrinding. Investigation of different drug-to-carrier ratios (griseofulvin/mannitol) demonstrated that a drug load of 10% is best suited to investigate the enhanced dissolution behavior. To gain deeper insight into the underlying mechanisms, the coground dispersion is compared with different physical mixtures in terms of physicochemical properties and dissolution behavior. Differential scanning calorimetry and X-ray powder diffraction were used to verify the crystalline structure of the coground formulation. On the basis of the Hixson-Crowell model, particle size reduction was ruled out as the main reason for dissolution enhancement. An increase of surface free energies because of grinding is shown with contact angle measurements. Confocal Raman microscopy investigations revealed the drug's bulk dispersity in the coground formulation as an additional factor for the increased dissolution rate. In conclusion, the continuous cogrinding approach is a promising technique to prepare the drug in a rapidly dissolving, yet crystalline, form. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association.
    view abstractdoi: 10.1002/jps.23731
  • 2013 • 161 Solid-State structures of trialkylbismuthines BiR3 (R = Me, i -Pr)
    Schulz, S. and Kuczkowski, A. and Bläser, D. and Wölper, C. and Jansen, G. and Haack, R.
    Organometallics 32 5445-5450 (2013)
    Two trialkylbismuthines BiR3 (R = Me (1), i-Pr (2)) were structurally characterized by single-crystal X-ray diffraction. Single crystals were grown using an IR-laser-assisted technique. 1 forms short intermolecular Bi···Bi interactions in the solid state, which were further investigated through quantum chemical computations with ab initio coupled cluster and dispersion-corrected density functional methods. © 2013 American Chemical Society.
    view abstractdoi: 10.1021/om400730r
  • 2013 • 160 Strain mapping of crack extension in pseudoelastic NiTi shape memory alloys during static loading
    Young, M.L. and Gollerthan, S. and Baruj, A. and Frenzel, J. and Schmahl, W.W. and Eggeler, G.
    Acta Materialia 61 5800-5806 (2013)
    Crack extension in pseudoelastic binary NiTi shape memory alloy (SMA) compact tension (CT) specimens was examined during static loading. The material composition of 50.7 at.% Ni (austenitic, pseudoelastic) was investigated using high-energy synchrotron X-ray diffraction. A miniature CT specimen was developed, which is small enough to allow in situ testing in a synchrotron beam line to identify phases, textures and lattice strains in front of a crack tip. Stress-induced martensite in pseudoelastic NiTi SMAs was mapped in front of the crack of a CT specimen during static loading using synchrotron radiation. The phase volume fraction and lattice microstrain results are discussed and compared with results from thermographic measurements. The Poisson effect is observed by comparing the lattice strains in the loading direction and transverse to the loading direction. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2013.06.024
  • 2013 • 159 Stress-induced stabilization of crystals in shape memory natural rubber
    Heuwers, B. and Quitmann, D. and Hoeher, R. and Reinders, F.M. and Tiemeyer, S. and Sternemann, C. and Tolan, M. and Katzenberg, F. and Tiller, J.C.
    Macromolecular Rapid Communications 34 180-184 (2013)
    In contrast to all known shape memory polymers, the melting temperature of crystals in shape memory natural rubber (SMNR) can be greatly manipulated by the application of external mechanical stress. As shown previously, stress perpendicular to the prior programming direction decreases the melting temperature by up to 40 K. In this study, we investigated the influence of mechanical stress parallel to prior stretching direction during programming on the stability of the elongation-stabilizing crystals. It was found that parallel stress stabilizes the crystals, which is indicated by linear increase of the trigger temperature by up to 17 K. The crystal melting temperature can be increased up to 126.5 °C under constrained conditions as shown by X-ray diffraction measurements. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/marc.201200594
  • 2013 • 158 Structure and magnetization in CoPd thin films and nanocontacts
    Morgan, C. and Schmalbuch, K. and García-Sánchez, F. and Schneider, C.M. and Meyer, C.
    Journal of Magnetism and Magnetic Materials 325 112-116 (2013)
    We present results showing the structural and magnetic properties of MBE-grown extended films and nanostructured elements of various CoPd alloys. X-ray diffraction studies show that the thin films are polycrystalline, yet exhibit a strong preferential growth orientation along the (111) direction. Magnetic force microscopy and SQUID are used to gain an understanding of the magnetic behavior of the CoPd system with respect to competing anisotropy contributions, based on temperature-dependent SQUID data, collected between 4 and 300 K. The idea and potential implications of using CoPd as a contact material to achieve spin injection in carbon nanotube-based devices is discussed. © 2012 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.jmmm.2012.07.052
  • 2013 • 157 Study of time and pressure dependent phenomena at the hard X-ray beamline BL9 of DELTA
    Wirkert, F.J. and Paulus, M. and Sternemann, C. and Nase, J. and Schroer, M.A. and Wieland, D.C.F. and Bieder, S. and Degen, P. and Rehage, H. and Tolan, M.
    Journal of Physics: Conference Series 425 (2013)
    The beamline BL9 of DELTA (Dortmund ELecTron Accelerator) is a multi-purpose beamline operating in an energy range between 4 and 27 keV. A short overview of the beamline and the experimental endstation is given. Exemplarily three typical applications, namely X-ray diffraction from interfaces, small angle X-ray scattering under high hydrostatic pressure and fast X-ray reflectivity measurements, are discussed in some detail in order to demonstrate the capabilities of the beamline.
    view abstractdoi: 10.1088/1742-6596/425/20/202006
  • 2013 • 156 Surface grafting of Corchorus olitorius fibre: A green approach for the development of activated bioadsorbent
    Roy, A. and Chakraborty, S. and Kundu, S.P. and Majumder, S.B. and Adhikari, B.
    Carbohydrate Polymers 92 2118-2127 (2013)
    The present work is an endeavor to prepare lignocellulosic biomass based adsorbent, suitable for removal of organic and inorganic pollutants from industrial effluents. Lignocellulosic Corchorus olitorius fibre (jute fibre) surface was grafted with naturally available polyphenol, tannin, preceded by the epoxy-activation of fibre surface with epichlorohydrin under mild condition in an aqueous suspension. The reaction parameters for the modification, viz., concentration of epichlorohydrin and tannin, time, and temperature were optimized. The successful occurrence of surface modification of jute fibre (JF) was characterized and estimated from weight gain percent, elemental analysis, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction, scanning electron and atomic force microscopy, and thermogravimetric analysis. An extensive analysis of deconvoluted FTIR spectra using the Voigt model was utilized to ensure the surface grafting. The microbiological susceptibility study revealed high persistency of JF towards biodegradation after efficient grafting with tannin. © 2012 Elsevier Ltd.
    view abstractdoi: 10.1016/j.carbpol.2012.11.039
  • 2013 • 155 Symmetrization driven spin transition in ε-FeOOH at high pressure
    Gleason, A.E. and Quiroga, C.E. and Suzuki, A. and Pentcheva, R. and Mao, W.L.
    Earth and Planetary Science Letters 379 49-55 (2013)
    Structural and electronic spin transitions in high-pressure ε-FeOOH are studied using a combination of high pressure X-ray emission spectroscopy (XES), X-ray diffraction (XRD) and density functional theory (DFT) calculations. Using XES, a high- to low-spin transition in trivalent iron is found in ε-FeOOH on compression between 40 and 60 GPa. This is accompanied by a sudden discontinuity in unit cell volume at 53( ± 2) GPa, obtained from XRD data collected over the same compression range. These results are consistent with DFT calculations using an on-site Coulomb repulsion term (GGA+U), which predict a spin transition in ε-FeOOH at 64.8 GPa. A second order phase transition from P21nm to Pnnm is predicted from DFT at ~43 GPa and evidenced in the XRD data from the anisotropic stiffening of the lattice parameters around the spin transition. In addition, the DFT results give evidence that the spin collapse is assisted by symmetrization of hydrogen bonds during the transition from P21nm to Pnnm. As the presence of hydrogen, even in small quantities, can affect phase relations, melting temperature, rheology, and other key properties of the Earth's mantle, our study unveils a connection between water (hydroxyl) content and the spin-transition pressure of Fe3+ in the Earth's mantle. © 2013 Elsevier B.V.
    view abstractdoi: 10.1016/j.epsl.2013.08.012
  • 2013 • 154 Synchrotron X-ray measurement techniques for thermal barrier coated cylindrical samples under thermal gradients
    Siddiqui, S.F. and Knipe, K. and Manero, A. and Meid, C. and Wischek, J. and Okasinski, J. and Almer, J. and Karlsson, A.M. and Bartsch, M. and Raghavan, S.
    Review of Scientific Instruments 84 (2013)
    Measurement techniques to obtain accurate in situ synchrotron strain measurements of thermal barrier coating systems (TBCs) applied to hollow cylindrical specimens are presented in this work. The Electron Beam Physical Vapor Deposition coated specimens with internal cooling were designed to achieve realistic temperature gradients over the TBC coated material such as that occurring in the turbine blades of aeroengines. Effects of the circular cross section on the x-ray diffraction (XRD) measurements in the various layers, including the thermally grown oxide, are investigated using high-energy synchrotron x-rays. Multiple approaches for beam penetration including collection, tangential, and normal to the layers, along with variations in collection parameters are compared for their ability to attain high-resolution XRD data from the internal layers. This study displays the ability to monitor in situ, the response of the internal layers within the TBC, while implementing a thermal gradient across the thickness of the coated sample. The thermal setup maintained coating surface temperatures in the range of operating conditions, while monitoring the substrate cooling, for a controlled thermal gradient. Through variation in measurement location and beam parameters, sufficient intensities are obtained from the internal layers which can be used for depth resolved strain measurements. Results are used to establish the various techniques for obtaining XRD measurements through multi-layered coating systems and their outcomes will pave the way towards goals in achieving realistic in situ testing of these coatings. © 2013 AIP Publishing LLC.
    view abstractdoi: 10.1063/1.4817543
  • 2013 • 153 Synthesis and characterization of Cu-doped ZnO one-dimensional structures for miniaturized sensor applications with faster response
    Chow, L. and Lupan, O. and Chai, G. and Khallaf, H. and Ono, L.K. and Roldan Cuenya, B. and Tiginyanu, I.M. and Ursaki, V.V. and Sontea, V. and Schulte, A.
    Sensors and Actuators, A: Physical 189 399-408 (2013)
    Detection of chemicals and biological species is an important issue to human health and safety. In this paper, we report the hydrothermal synthesis at 95 °C of Cu-doped ZnO low-dimensional rods for room-temperature (RT) sensing applications and enhanced sensor performances. X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Raman and photoluminescence are used to characterize the material properties. To demonstrate the suitability of the Cu-doped ZnO rods for gas sensor applications and for comparison with pure ZnO, we fabricated a double rod device using Focused Ion Beam. The responses of pure-ZnO and Cu-doped ZnO rods studied in exactly the same condition are reported. We found that Cu-ZnO sensors have enhanced RT sensitivity, faster response time, and good selectivity. Miniaturized Cu-ZnO rod-based sensors can serve as a good candidate for effective H2 detectors with low power consumption. © 2012 Elsevier B.V.
    view abstractdoi: 10.1016/j.sna.2012.09.006
  • 2013 • 152 The structural and electronic promoting effect of nitrogen-doped carbon nanotubes on supported Pd nanoparticles for selective olefin hydrogenation
    Chen, P. and Chew, L.M. and Kostka, A. and Muhler, M. and Xia, W.
    Catalysis Science and Technology 3 1964-1971 (2013)
    A high-performance Pd catalyst for selective olefin hydrogenation was synthesized by supporting Pd nanoparticles on nitrogen-doped carbon nanotubes (NCNTs). X-ray diffraction, hydrogen chemisorption, transmission electron microscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize Pd supported on NCNTs and nitrogen-free oxygen-functionalized CNTs (OCNTs). The Pd nanoparticles were stabilized on NCNTs with narrower size distribution compared with OCNTs. The XPS analysis revealed that the nitrogen functional groups favor the reduction of Pd on CNTs suggesting an electronic promoter effect. The Pd/NCNT catalyst showed extraordinary catalytic performance in terms of activity, selectivity and stability in the selective hydrogenation of cyclooctadiene, which is related to the structural and electronic promoting effect of the NCNT support. © 2013 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c3cy00097d
  • 2013 • 151 Time- and space-resolved high-throughput characterization of stresses during sputtering and thermal processing of Al-Cr-N thin films
    Grochla, D. and Siegel, A. and Hamann, S. and Buenconsejo, P.J.S. and Kieschnick, M. and Brunken, H. and König, D. and Ludwig, Al.
    Journal of Physics D: Applied Physics 46 (2013)
    (Al100-xCrx)N thin-film materials libraries (x = 31-79 at%) were fabricated on micro-machined cantilever arrays, in order to simultaneously investigate the evolution of stresses during film growth as well as during thermal processing by analysing the changes in cantilever curvature. The issue of the dependence of stress in the growing films on composition, at comparable film thicknesses, was investigated. Among the various experimental parameters studied, it was found that the applied substrate bias has the strongest influence on stress evolution and microstructure formation. The compositions of the films, as well as the applied substrate bias, have a pronounced effect on the lattice parameter and the coherence length. For example, applying a substrate bias in general leads to compressive residual stress, increases the lattice parameter and decreases the coherence length. Moreover, bias can change the film texture from [1 1 1] orientation to [2 0 0]. Further detailed analysis using x-ray diffraction and transmission electron microscopy clearly revealed the presence of a [1 1 1] highly textured face centred cubic (B1 type) Al-Cr-N phase in the as-deposited state as well as the coexistence of the hexagonal [1 1 0] textured Cr2N phase, which forms in the Cr-rich region. These results show that the combinatorial approach provides insight into how stresses and compositions are related to phases and microstructures of different Al-Cr-N compositions fabricated in the form of materials libraries. © 2013 IOP Publishing Ltd.
    view abstractdoi: 10.1088/0022-3727/46/8/084011
  • 2013 • 150 Zr(NEtMe)2(guan-NEtMe2)2] as a novel atomic layer deposition precursor: ZrO2 film growth and mechanistic studies
    Blanquart, T. and Niinistö, J. and Aslam, N. and Banerjee, M. and Tomczak, Y. and Gavagnin, M. and Longo, V. and Puukilainen, E. and Wanzenboeck, H.D. and Kessels, W.M.M. and Devi, A. and Hoffmann-Eifert, S. and Ritala, M. and Leskelä, M.
    Chemistry of Materials 25 3088-3095 (2013)
    [Zr(NEtMe)2(guan-NEtMe2)2], a recently developed compound, was investigated as a novel precursor for the atomic layer deposition (ALD) of ZrO2. With water as the oxygen source, the growth rate remained constant over a wide temperature range, whereas with ozone the growth rate increased steadily with deposition temperature. Both ALD processes were successfully developed: the characteristic self-limiting ALD growth mode was confirmed at 300 C. The growth rates were exceptionally high, 0.9 and 1.15 Å/cycle with water and ozone, respectively. X-ray diffraction (XRD) indicated that the films were deposited in the high-permittivity cubic phase, even when grown at temperatures as low as 250 C. Compositional analysis performed by means of X-ray photoelectron spectroscopy (XPS) demonstrated low carbon and nitrogen contamination (< 2 at. % when deposited with ozone). The films presented low root-mean-square (rms) roughness, below 5% of the film thickness, as well as excellent step coverage and conformality on 30:1 aspect ratio trench structures. Dielectric characterization was performed on ZrO 2 metal-insulator-metal (MIM) capacitors and demonstrated high permittivity and low leakage current, as well as good stability of the capacitance. The ALD reaction mechanism was studied in situ: adsorption of the precursor through reaction of the two guan-NEtMe2 ligands with the surface-OD groups was confirmed by the quartz crystal microbalance (QCM) and quadrupole mass spectrometric (QMS) results. © 2013 American Chemical Society.
    view abstractdoi: 10.1021/cm401279v
  • 2012 • 149 A comparison of the solid-state structures of halogen azides XN3 (X=Cl, Br, I)
    Lyhs, B. and Bläser, D. and Wölper, C. and Schulz, S. and Jansen, G.
    Angewandte Chemie - International Edition 51 12859-12863 (2012)
    Delicate crystals: ClN3 adopts a polymeric structure in the solid state (see picture; N blue, Cl green) with short intermolecular Cl×××Cl distances, as was observed for the elemental halogen. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201206028
  • 2012 • 148 A facile route to reassemble titania nanoparticles into ordered chain-like networks on substrate
    Cheng, Y.-J. and Wolkenhauer, M. and Bumbu, G.-G. and Gutmann, J.S.
    Macromolecular Rapid Communications 33 218-224 (2012)
    A facile route to reassemble titania nanoparticles within the titania-block copolymer composite films has been developed. The titania nanoparticles templated by the amphiphilic block copolymer of poly(styrene)-block-poly (ethylene oxide) (PS-b-PEO) were frozen in the continuous PS matrix. Upon UV exposure, the PS matrix was partially degraded, allowing the titania nanoparticles to rearrange into chain-like networks exhibiting a closer packing. The local structures of the Titania chain-like networks were investigated by both AFM and SEM; the lateral structures and vertical structures of the films were studied by GISAXS and X-ray reflectivity respectively. Both the image analysis and X-ray scattering characterization prove the reassembly of the titania nanoparticles after UV exposure. The mechanism of the nanoparticle assembly is discussed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/marc.201100638
  • 2012 • 147 Ag/ZnO nanomaterials as high performance sensors for flammable and toxic gases
    Simon, Q. and Barreca, D. and Gasparotto, A. and MacCato, C. and Tondello, E. and Sada, C. and Comini, E. and Devi, A. and Fischer, R.A.
    Nanotechnology 23 (2012)
    Ag/ZnO nanocomposites supported on polycrystalline Al 2O 3 were synthesized by an unprecedented approach combining plasma enhanced chemical vapor deposition (PE-CVD) of ZnO matrices and the subsequent deposition of Ag nanoparticles (NPs) by radio frequency (RF) sputtering. The system structure, composition and morphology were investigated by glancing incidence x-ray diffraction (GIXRD), secondary ion mass spectrometry (SIMS), field emission scanning electron microscopy (FE-SEM) and energy dispersive x-ray spectroscopy (EDXS). A tailored dispersion and distribution of silver particles could be obtained under mild conditions by the sole variation of the sputtering time. Gas sensing properties toward flammable and toxic gases, both reducing (CH 3CH 2OH, CH 3COCH 3) and oxidizing (O 3), were investigated in the temperature range 100400°C. Beside the high sensitivity, the developed sensors exhibited a response proportional to Ag content, thanks to catalytic and electronic effects promoted by silver NPs. In addition, discrimination between oxidizing and reducing analytes was enabled by a suitable choice of the adopted working temperature.
    view abstractdoi: 10.1088/0957-4484/23/2/025502
  • 2012 • 146 Annealing effect on structural and magnetic properties of Cu 2MnAL heusler alloy films
    Topkaya, R. and Yilgin, R. and Kazan, S. and Akdoǧan, N. and Obaida., M. and Inam, H. and Westerholt, K.
    Journal of Superconductivity and Novel Magnetism 25 2605-2609 (2012)
    Cu2MnAl Heusler alloy films were grown on MgO (001) substrates by using the ion beam sputtering technique. The films were post-annealed at varying temperatures in order to investigate the influence of annealing on crystal structure and magnetic properties. The structural properties of Cu 2MnAl films have been investigated by using x-ray diffraction (XRD) and magnetic properties have been investigated by both vibrating sample magnetometer (VSM) and ferromagnetic resonance (FMR) techniques. The experimental data indicates that the crystal structure of the films strongly depends on the annealing temperature. When the films were annealed at 200 °C, the saturation magnetization (Ms = 250 emu/cm3) achieved its maximum and the coercive field (Hc 7 Oe) reached its minimum with B2 ordered structure. In addition, FMR results have revealed that the Cu2MnAl film annealed 200 °C has the highest effective magnetization. The combination of structural and magnetic characterization indicates that the optimum growth temperature is 200 °C for the Cu2MnAl Heusler alloy films on MgO substrates. © Springer Science+Business Media, LLC 2011.
    view abstractdoi: 10.1007/s10948-011-1228-z
  • 2012 • 145 Atomic layer deposition of Gd 2O 3 and Dy 2O 3: A study of the ALD characteristics and structural and electrical properties
    Xu, K. and Ranjith, R. and Laha, A. and Parala, H. and Milanov, A.P. and Fischer, R.A. and Bugiel, E. and Feydt, J. and Irsen, S. and Toader, T. and Bock, C. and Rogalla, D. and Osten, H.-J. and Kunze, U. and Devi, A.
    Chemistry of Materials 24 651-658 (2012)
    Gd 2O 3 and Dy 2O 3 thin films were grown by atomic layer deposition (ALD) on Si(100) substrates using the homoleptic rare earth guanidinate based precursors, namely, tris(N,N′- diisopropyl-2-dimethylamido-guanidinato)gadolinium(III) [Gd(DPDMG) 3] (1) and tris(N,N′-diisopropyl-2-dimethylamido-guanidinato)dysprosium(III) [Dy(DPDMG) 3] (2), respectively. Both complexes are volatile and exhibit high reactivity and good thermal stability, which are ideal characteristics of a good ALD precursor. Thin Gd 2O 3 and Dy 2O 3 layers were grown by ALD, where the precursors were used in combination with water as a reactant at reduced pressure at the substrate temperature ranging from 150 °C to 350 °C. A constant growth per cycle (GPC) of 1.1 Å was obtained at deposition temperatures between 175 and 275 °C for Gd 2O 3, and in the case of Dy 2O 3, a GPC of 1.0 Å was obtained at 200-275 °C. The self-limiting ALD growth characteristics and the saturation behavior of the precursors were confirmed at substrate temperatures of 225 and 250 °C within the ALD window for both Gd 2O 3 and Dy 2O 3. Thin films were structurally characterized by grazing incidence X-ray diffraction (GI-XRD), atomic force microscopy (AFM), and transmission electron microscopy (TEM) analyses for crystallinity and morphology. The chemical composition of the layer was examined by Rutherford backscattering (RBS) analysis and Auger electron spectroscopy (AES) depth profile measurements. The electrical properties of the ALD grown layers were analyzed by capacitance-voltage (C-V) and current-voltage (I-V) measurements. Upon subjection to a forming gas treatment, the ALD grown layers show promising dielectric behavior, with no hysteresis and reduced interface trap densities, thus revealing the potential of these layers as high-k oxide for application in complementary metal oxide semiconductor based devices. © 2012 American Chemical Society.
    view abstractdoi: 10.1021/cm2020862
  • 2012 • 144 Chemical vapor functionalization: A continuous production process for functionalized ZnO nanoparticles
    Ali, M. and Donakowski, M.D. and Mayer, C. and Winterer, M.
    Journal of Nanoparticle Research 14 (2012)
    The continuous functionalization of nanoparticles in the gas-phase directly after their generation, chemical vapor functionalization, is studied with ZnO and 1-hexanol as a model system using two reactors in series. In the first reactor ZnO nanoparticles are synthesized in the gas-phase from diethylzinc and oxygen at 1,073 K with grain sizes of 13 nm as determined by Rietveld refinement of X-ray diffractograms. The second reactor, connected at the exit of the first reactor and kept at lower temperatures (573, 673, and 773 K), is used as a functionalization chamber. At the connection point of the two reactors, the vapor of 1-hexanol is injected to react with the surface of ZnO nanoparticles in the gas phase. The process has been analyzed by quadrupole mass spectrometry to obtain information about optimal conditions for functionalization. Dynamic light scattering data show that the functionalized particles have substantially improved colloidal dispersibility with hydrodynamic diameters of 60 nm. Diffuse reflectance fourier transform infrared spectra and 1H nuclear magnetic resonance spectra are consistent with 1-hexanol adsorbed at the particle surface acting as a functionalizing agent. The agglomerate size is substantially reduced owing to chemical vapor functionalization. © Springer Science+Business Media B.V. 2012.
    view abstractdoi: 10.1007/s11051-011-0689-0
  • 2012 • 143 Co-templating ionothermal synthesis and structure characterization of two new 2D layered aluminophosphates
    Wei, Y. and Marler, B. and Zhang, L. and Tian, Z. and Graetsch, H. and Gies, H.
    Dalton Transactions 41 12408-12415 (2012)
    For the first time, the co-templating ionothermal methodology was used in the preparation of layered aluminophosphate materials. With the addition of either 1,2-ethylenediamine or 1,6-hexanediamine to the ionic liquid 1-ethyl-3-methyl imidazolium chloride, two new 2D layered aluminophosphates RUB-A1 [Al 3P 4O 16][NH 3CH 2CH 2NH 3] 0.5[C 6N 2H 11] 2 and RUB-A2 [Al 3P 4O 16][NH 3(CH 2) 6NH 3][NH 3(CH 2) 6NH 2] 0.5[C 6N 2H 11] 0.5[H 2O] have been synthesized ionothermally by co-templating. The structure of RUB-A1 has been determined from single-crystal X-ray diffraction data using direct methods, while the structure of RUB-A2 has been solved ab initio from powder X-ray diffraction data with limited resolution using direct-space methods. Both of these two compounds have a 2D layered structure consisting of macroanionic sheets of composition [Al 3P 4O 16] 3- stacked in an AAAA sequence. The inorganic layers are built up from alternatively vertex-sharing [AlO 4]- and [PO 3(O)]-tetrahedral units forming a 4.6.8 and a 4.6.12 network for RUB-A1 and RUB-A2, respectively. The layer topology of RUB-A1 is closely related to the previously known 4.6.8-layer topology but with a different sequence of phosphoryl group orientation. Combining the results of structure analysis with the NMR, chemical analysis and TG-DTA experiments, we show that both the ionic liquid cation and the protonated diamines are located in the interlayer space and together direct the formation of these two structures. © 2012 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c2dt31150j
  • 2012 • 142 Cross-amyloid interaction of Aβ and IAPP at lipid membranes
    Seeliger, J. and Evers, F. and Jeworrek, C. and Kapoor, S. and Weise, K. and Andreetto, E. and Tolan, M. and Kapurniotu, A. and Winter, R.
    Angewandte Chemie - International Edition 51 679-683 (2012)
    Membrane controlled protein assembly: A study of the amyloid interaction of the islet amyloid polypeptide (IAPP), β-amyloid (Aβ), and a mixture of both with an anionic model raft membrane showed the dominant effect of IAPP on the aggregation process and on the hydrogen-bonding pattern of the assemblies present in the mixture (see picture). The analysis of the interaction of Aβ with IAPP-GI-a non-amyloidogenic IAPP mimic-confirmed these findings. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201105877
  • 2012 • 141 Deposition of La 1-xSr xFe 1-yCo yO 3-δ coatings with different phase compositions and microstructures by low-pressure plasma spraying-thin film (LPPS-TF) processes
    Zotov, N. and Hospach A. and Mauer G. and Sebold D. and Vaßen, R.
    Journal of Thermal Spray Technology 21 441-447 (2012)
    Perovskite-type materials with the general chemical formula A 1-xÁ xB́ 1-yB́ yO 3δ have received considerable attention as candidates for oxygen separation membranes. Preparation of La 1-xSr xFe 1-yCo yO 3-δ (LSFC) coatings by low-pressure plasma spraying-thin film processes using different plasma spray parameters is reported and discussed. Deposition with Ar-He plasma leads to formation of coatings containing a mixture of cubic LSFC perovskite, SrLaFeO4, FeCo, and metal oxides. Coatings deposited at higher oxygen partial pressures by pumping oxygen into the vacuum chamber contain more than 85% perovskite and only a few percent Fe32xCoxO4, and/or CoO. The microstructures of the investigated LSFC coatings depend sensitively on the oxygen partial pressure, the substrate temperature, the plasma jet velocities, and the deposition rate. Coatings deposited with Ar-rich plasma, relatively low net torch power, and with higher plasma jet velocities are most promising for applications as oxygen permeation membranes. © ASM International.
    view abstractdoi: 10.1007/s11666-012-9768-8
  • 2012 • 140 Embedded argon as a tool for sampling local structure in thin plasma deposited aluminum oxide films
    Prenzel, M. and de los Arcos, T. and Kortmann, A. and Winter, J. and von Keudell, A.
    Journal of Applied Physics 112 103306 (2012)
    Al2O3 thin films, either amorphous or of varying degrees of crystallinity, were deposited by two-frequency radio-frequency magnetron sputtering. Film crystallinity was investigated by Fourier transform infrared spectroscopy and X-ray diffraction (XRD). X-ray photoelectron spectroscopy (XPS) was employed to determine the amount of Ar naturally trapped within the films during the deposition process. A clear correlation was found between the existence of crystalline phases, as determined by XRD, and a shift towards lower binding energy positions of the Ar2p core levels of embedded gas. The shift is due to differences in the local Al2O3 matrix (amorphous or crystalline) of the embedded gas, thus, providing an XPS fingerprint that can be used to qualitatively determine the presence or absence of crystalline phases in very thin films. (C) 2012 American Institute of Physics. []
    view abstractdoi: 10.1063/1.4767383
  • 2012 • 139 Gas-solid interactions during nonisothermal heat treatment of a high-strength CrMnCN austenitic steel powder: Influence of atmospheric conditions and heating rate on the densification behavior
    Krasokha, N. and Weber, S. and Huth, S. and Zumsande, K. and Theisen, W.
    Metallurgical and Materials Transactions A: Physical Metallurgy and Materials Science 43 4237-4246 (2012)
    This work deals with gas-solid interactions between a high-alloyed steel powder and the surrounding atmosphere during continuous heating. It is motivated by the recently developed corrosion-resistant CrMnCN austenitic cast steels. Here, powder metallurgical processing would be desirable to manufacture highly homogeneous parts and/or novel corrosion-resistant metal-matrix composites. However, the successful use of this new production route calls for a comprehensive investigation of interactions between the sintering atmosphere and the metallic powder to prevent undesirable changes to the chemical composition, e.g., degassing of nitrogen or evaporation of manganese. In this study, dilatometric measurements combined with residual gas analysis, high-temperature X-ray diffraction (XRD) measurements, and thermodynamic equilibrium calculations provided detailed information about the influence of different atmospheric conditions on the microstructure, constitution, and densification behavior of a gasatomized CrMnCN steel powder during continuous heating. Intensive desorption of nitrogen led to the conclusion that a vacuum atmosphere is not suitable for powder metallurgical (PM) processing. Exposure to an N2-containing atmosphere resulted in the formation of nitrides and lattice expansion. Experimental findings have shown that the N content can be controlled by the nitrogen partial pressure. Furthermore, the reduction of surface oxides because of a carbothermal reaction at elevated temperatures and the resulting enhancement of the powder's densification behavior are discussed in this work. © The Minerals, Metals & Materials Society and ASM International 2012.
    view abstractdoi: 10.1007/s11661-012-1234-1
  • 2012 • 138 Growth optimization and characterization of lattice-matched Al 0.82In 0.18N optical confinement layer for edge emitting nitride laser diodes
    Kim-Chauveau, H. and Frayssinet, E. and Damilano, B. and De Mierry, P. and Bodiou, L. and Nguyen, L. and Vennéguès, P. and Chauveau, J.-M. and Cordier, Y. and Duboz, J.Y. and Charash, R. and Vajpeyi, A. and Lamy, J.-M. and Akhte...
    Journal of Crystal Growth 338 20-29 (2012)
    We present the growth optimization and the doping by the metal organic chemical vapor deposition of lattice-matched Al 0.82In 0.18N bottom optical confinement layers for edge emitting laser diodes. Due to the increasing size and density of V-shaped defects in Al 1-xIn xN with increasing thickness, we have designed an Al 1-xIn xN/GaN multilayer structure by optimizing the growth and thickness of the GaN interlayer. The Al 1-xIn xN and GaN interlayers in the multilayer structure were both doped using the same SiH 4 flow, while the Si levels in both layers were found to be significantly different by SIMS. The optimized 8×(Al 0.82In 0.18N/GaN=54/6 nm) multilayer structures grown on free-standing GaN substrates were characterized by high resolution X-ray diffraction, atomic force microscopy and transmission electron microscopy, along with the in-situ measurements of stress evolution during growth. Finally, lasing was obtained from the UV (394 nm) to blue (436 nm) wavelengths, in electrically injected, edge-emitting, cleaved-facet laser diodes with 480 nm thick Si-doped Al 1-xIn xN/GaN multilayers as bottom waveguide claddings. © 2011 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.jcrysgro.2011.10.016
  • 2012 • 137 High-capacity cathodes for lithium-ion batteries from nanostructured LiFePO 4 synthesized by highly-flexible and scalable flame spray pyrolysis
    Hamid, N.A. and Wennig, S. and Hardt, S. and Heinzel, A. and Schulz, C. and Wiggers, H.
    Journal of Power Sources 216 76-83 (2012)
    Olivine, LiFePO 4 is a promising cathode material for lithium-ion batteries due to its low cost, environmental acceptability and high stability. Its low electric conductivity prevented it for a long time from being used in large-scale applications. Decreasing its particle size along with carbon coating significantly improves electronic conductivity and lithium diffusion. With respect to the controlled formation of very small particles with large specific surface, gas-phase synthesis opens an economic and flexible route towards high-quality battery materials. Amorphous FePO 4 was synthesized as precursor material for LiFePO 4 by flame spray pyrolysis of a solution of iron acetylacetonate and tributyl phosphate in toluene. The pristine FePO 4 with a specific surface from 126-218 m 2 g -1 was post-processed to LiFePO 4/C composite material via a solid-state reaction using Li 2CO 3 and glucose. The final olivine LiFePO 4/C particles still showed a large specific surface of 24 m 2 g -1 and were characterized using X-ray diffraction (XRD), electron microscopy, X-ray photoelectron spectrocopy (XPS) and elemental analysis. Electrochemical investigations of the final LiFePO 4/C composites show reversible capacities of more than 145 mAh g -1 (about 115 mAh g -1 with respect to the total coating mass). The material supports high drain rates at 16 C while delivering 40 mAh g -1 and causes excellent cycle stability. © 2012 Elsevier B.V.
    view abstractdoi: 10.1016/j.jpowsour.2012.05.047
  • 2012 • 136 Improvement in mechanical properties of jute fibres through mild alkali treatment as demonstrated by utilisation of the Weibull distribution model
    Roy, A. and Chakraborty, S. and Kundu, S.P. and Basak, R.K. and Basu Majumder, S. and Adhikari, B.
    Bioresource Technology 107 222-228 (2012)
    Chemically modified jute fibres are potentially useful as natural reinforcement in composite materials. Jute fibres were treated with 0.25%-1.0% sodium hydroxide (NaOH) solution for 0.5-48. h. The hydrophilicity, surface morphology, crystallinity index, thermal and mechanical characteristics of untreated and alkali treated fibres were studied.The two-parameter Weibull distribution model was applied to deal with the variation in mechanical properties of the natural fibres. Alkali treatment enhanced the tensile strength and elongation at break by 82% and 45%, respectively but decreased the hydrophilicity by 50.5% and the diameter of the fibres by 37%. © 2011 Elsevier Ltd.
    view abstractdoi: 10.1016/j.biortech.2011.11.073
  • 2012 • 135 In situ study of γ-TiAl lamellae formation in supersaturated α 2-Ti 3Al grains
    Cha, L. and Schmoelzer, T. and Zhang, Z. and Mayer, S. and Clemens, H. and Staron, P. and Dehm, G.
    Advanced Engineering Materials 14 299-303 (2012)
    In situ heating transmission electron microscopy (TEM) was used to investigate the initial stage of γ-TiAl lamellae formation in an intermetallic Ti-45Al-7.5Nb alloy (in at.%). The material was heat treated and quenched in a non-equilibrium state to consist mainly of supersaturated, ordered α 2-Ti 3Al grains. Subsequently, specimens were annealed inside a TEM up to 750 °C. The in situ TEM study revealed that ultra-fine γ-TiAl laths precipitate in the α 2-matrix at ≈730 °C which exhibit the classical Blackburn orientation relationship, i.e. (0001)α 2//(111)γ and [$112̄0] α 2//< 110]γ. The microstructural development observed in the in situ TEM experiment is compared to results from conventional ex situ TEM studies. In order to investigate the precipitation behavior of the γ-phase with a complementary method, in situ high energy X-ray diffraction experiments were performed which confirmed the finding that γ-laths start to precipitate at ≈730 °C from the supersaturated α 2- matrix. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/adem.201100272
  • 2012 • 134 Influence of process parameters on the crystallinity, morphology and composition of tungsten oxide-based thin films grown by metalorganic chemical vapor deposition
    De Los Arcos, T. and Cwik, S. and Milanov, A.P. and Gwildies, V. and Parala, H. and Wagner, T. and Birkner, A. and Rogalla, D. and Becker, H.-W. and Winter, J. and Ludwig, Al. and Fischer, R.A. and Devi, A.
    Thin Solid Films 522 11-16 (2012)
    The growth of tungsten oxide (WO 3) based thin films was achieved via metalorganic chemical vapor deposition using an all-nitrogen coordinated tungsten precursor in combination with oxygen. Film growth was performed on Si(100) substrates in the temperature range of 400-800 °C. Employing multi-technique approaches like X-ray diffraction, scanning electron microscopy, atomic force microscopy, Rutherford back scattering, nuclear reaction analysis and X-ray photoelectron spectroscopy, the variation of the growth characteristics and film properties with deposition temperature were studied in terms of crystallinity, structure, surface roughness and composition. Special attention was devoted to the investigation of variations in the film composition for the as-deposited and annealed films. © 2011 Elsevier B.V.
    view abstractdoi: 10.1016/j.tsf.2011.12.007
  • 2012 • 133 Influence of Tb doping on the luminescence characteristics of ZnO nanoparticles
    Sharma, A. and Dhar, S. and Singh, B.P. and Kundu, T. and Spasova, M. and Farle, M.
    Journal of Nanoparticle Research 14 (2012)
    Structural and optical properties of the Tb-doped ZnO nanoparticles with average diameter ≈4 nm have been systematically investigated. Our X-ray diffraction studies show a contraction of the ZnO lattice with the increase of the Tb mole-fraction x for x ≤ 0.02 and an expansion beyond x ≈ 0.02. The photoluminescence spectra are found to be comprised of a near band edge ultra violet luminescence (UVL) and a broad green luminescence (GL) band. Under the atmospheric condition, the intensity of the GL band is found to increase with the Tb molefraction over the entire doping range. On the other hand, under the vacuum condition, it has been observed that the GL intensity decreases with the increase of x up to x ≈ 0.02 but further increase of x leads to a gradual revival of the GL emission. Our study suggests that for x ≤ 0.02, GL results due to the physisorption of certain groups on the surface of the nanoparticles (GL-groups). It is also found that in this Tb mole-fraction regime, Tb incorporates mostly on the surface of the nanoparticles and affects the UVL to GL intensity ratio by influencing the attachment of the GL-groups. However, for x > 0.02, GL originates not only from the GL-groups but also from certain point defects, which are likely to be generated due to the incorporation of Tb in the core of the nanoparticles. A simple rate equation model is introduced to get a quantitative understanding about the variation of the density of the centers responsible for the GL emission as a function of x under the atmospheric and the vacuum conditions. © Springer Science+Business Media B.V. 2012.
    view abstractdoi: 10.1007/s11051-011-0676-5
  • 2012 • 132 Interfacial interaction driven CO oxidation: Nanostructured Ce 1-xLa xO 2-δ/TiO 2 solid solutions
    Katta, L. and Reddy, B.M. and Muhler, M. and Grünert, W.
    Catalysis Science and Technology 2 745-753 (2012)
    Titania supported ceria-lanthana solid solutions (Ce xLa 1-xO 2-δ/TiO 2; CLT) have been synthesized by a facile and economical route. Existence of synergism between ceria-lanthana (CL) solid solutions and titania-anatase phase, which leads to decrease in the crystallite size, retarded titania phase transformation, and improved redox properties, has been thoroughly investigated by various techniques, namely, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), UV-visible diffuse reflectance spectroscopy (UV-vis DRS), Raman spectroscopy (UV-RS and Vis-RS), BET surface area analysis, and temperature programmed reduction (TPR). Two key observations made from the whole exercise were (i) mutual interaction of Ce and Ti ions could impose typical Ce-O-Ti modes at the interfacial region and (ii) the La 3+ ion as a dopant provokes a large number of oxygen vacancies via a charge compensation mechanism. The promising role of these factors in the CO oxidation (one of the most formidable challenges) has been comprehensively described. The observed enhanced activity for the CLT sample is primarily attributed to an apparent specific orientation of the active component over the support, which is endorsed by the interfacial interaction. This specific mode could facilitate the CO adsorption with simultaneous bulk oxygen diffusion for more consumption and in turn better activity. © 2012 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c2cy00449f
  • 2012 • 131 Low-temperature synthesis of crystalline BaTiO 3 nanoparticles by one-step "organosol"-precipitation
    Gao, Y. and Shvartsman, V.V. and Elsukova, A. and Lupascu, D.C.
    Journal of Materials Chemistry 22 17573-17583 (2012)
    The "organosol" precipitation method is proposed to produce nanosized particles of barium titanate (BaTiO 3) at temperatures as low as room temperature. The advantages of this method are a high yield, a simple but precise control of the size of the particles, low process temperature, short reaction time, as well as low cost of reagents. The particles were systematically characterized by powder X-ray diffraction (XRD), Raman scattering, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), thermogravimetric thermal analysis (TGA/DSC), infrared spectroscopy (IR), and impedance analysis. The as-prepared BaTiO 3 nanocrystals exhibit a granular shape of around 15 nm in diameter. Oleic acid retards crystallization and thus allows generation of a uniformly small grain size and excellent dispersibility in organic solvents. The surface energy of the particles is modified and crystallization in cubes also arises. The mechanism of powder formation is discussed. The method offers an alternate low-cost route to perovskite nanopowders easily dispersed in organic media. © 2012 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c2jm33373b
  • 2012 • 130 Modification of pineapple leaf fibers and graft copolymerization of acrylonitrile onto modified fibers
    Maniruzzaman, M. and Rahman, M.A. and Gafur, M.A. and Fabritius, H. and Raabe, D.
    Journal of Composite Materials 46 79-90 (2012)
    Raw pineapple leaf fibers (PALFs) were chemically modified by scouring, NaOH treatment, and bleaching (NaClO2). The graft copolymerization of synthetic acrylonitrile monomer onto bleached PALFs was carried out in aqueous medium using potassium persulfate (K2S2O8/FeSO4) as a redox initiator. The maximum grafting level at optimum conditions, namely, monomer concentration, initiator concentration, catalyst concentration, reaction time, and temperature have been determined. The main objective of this study is to decrease the amorphous region of lignocellulose in PALFs and improve its hydrophobic nature by incorporation of synthetic polymer of polyacrylonitrile and mechanical properties. The modified and grafted fibers were characterized by Fourier transform infrared spectroscopy, scanning electron microscope, thermogravimetric analysis, and X-ray diffraction study techniques. The moisture content and tensile strength properties were also evaluated for their environmental and mechanical performances. © The Author(s) 2011.
    view abstractdoi: 10.1177/0021998311410486
  • 2012 • 129 Nanoscale austenite reversion through partitioning, segregation and kinetic freezing: Example of a ductile 2 GPa Fe-Cr-C steel
    Yuan, L. and Ponge, D. and Wittig, J. and Choi, P. and Jiménez, J.A. and Raabe, D.
    Acta Materialia 60 2790-2804 (2012)
    Austenite reversion during tempering of a Fe-13.6 Cr-0.44 C (wt.%) martensite results in an ultra-high-strength ferritic stainless steel with excellent ductility. The austenite reversion mechanism is coupled to the kinetic freezing of carbon during low-temperature partitioning at the interfaces between martensite and retained austenite and to carbon segregation at martensite-martensite grain boundaries. An advantage of austenite reversion is its scalability, i.e. changing tempering time and temperature tailors the desired strength-ductility profiles (e.g. tempering at 400 °C for 1 min produces a 2 GPa ultimate tensile strength (UTS) and 14% elongation while 30 min at 400 °C results in a UTS of ∼1.75 GPa with an elongation of 23%). The austenite reversion process, carbide precipitation and carbon segregation have been characterized by X-ray diffraction, electron back-scatter diffraction, transmission electron microscopy and atom probe tomography in order to develop the structure-property relationships that control the material's strength and ductility. © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2012.01.045
  • 2012 • 128 Nanoscale size effect on surface spin canting in iron oxide nanoparticles synthesized by the microemulsion method
    Darbandi, M. and Stromberg, F. and Landers, J. and Reckers, N. and Sanyal, B. and Keune, W. and Wende, H.
    Journal of Physics D: Applied Physics 45 (2012)
    Uniformly sized and crystalline iron oxide nanoparticles (IONPs) with spinel structure and mean diameters of about 3, 6 and 9nm were synthesized in high yield using the microemulsion route at room temperature. The nanoparticles (NPs) were stabilized in situ by organic surfactant molecules which acted both as a stabilizer of the microemulsion system and as a capping layer of the NP surface. NP size control was attained by careful adjustment of the preparation conditions. The structure, morphology and NP size distribution were investigated by x-ray diffraction, transmission electron microscopy and scanning electron microscopy. A particular effort was devoted in this work to study the effect of size and capping of these NPs on their magnetic structure by in-field Mössbauer spectroscopy at 4.2K. The mean canting angle (relative to the applied field direction) of the Fe spins was observed to increase with decreasing NP size due to the enhanced surface-to-volume ratio. Comparing bare and capped NPs of the same diameter, we verified that the spin canting was not affected by the organic capping. This implied almost identical magnetic orientations of bare and capped NPs. Simultaneously, the capping material was capable of preventing agglomeration effects which can occur in case of direct particle contact. Using a core/shell model, we showed that spin canting originated from the surface shell of the NPs. Furthermore, the Mössbauer spectral parameters provided evidence for the existence of a high fraction of Fe 3O 4 (magnetite) in the IONP. © 2012 IOP Publishing Ltd.
    view abstractdoi: 10.1088/0022-3727/45/19/195001
  • 2012 • 127 New insights into hard phases of CoCrMo metal-on-metal hip replacements
    Liao, Y. and Pourzal, R. and Stemmer, P. and Wimmer, M.A. and Jacobs, J.J. and Fischer, A. and Marks, L.D.
    Journal of the Mechanical Behavior of Biomedical Materials 12 39-49 (2012)
    The microstructural and mechanical properties of the hard phases in CoCrMo prosthetic alloys in both cast and wrought conditions were examined using transmission electron microscopy and nanoindentation. Besides the known carbides of M23C6-type (M=Cr, Mo, Co) and M6C-type which are formed by either eutectic solidification or precipitation, a new mixed-phase hard constituent has been found in the cast alloys, which is composed of ~100nm fine grains. The nanosized grains were identified to be mostly of M23C6 type using nano-beam precession electron diffraction, and the chemical composition varied from grain to grain being either Cr- or Co-rich. In contrast, the carbides within the wrought alloy having the same M23C6 structure were homogeneous, which can be attributed to the repeated heating and deformation steps. Nanoindentation measurements showed that the hardness of the hard phase mixture in the cast specimen was ~15.7GPa, while the M23C6 carbides in the wrought alloy were twice as hard (~30.7GPa). The origin of the nanostructured hard phase mixture was found to be related to slow cooling during casting. Mixed hard phases were produced at a cooling rate of 0.2°C/s, whereas single phase carbides were formed at a cooling rate of 50°C/s. This is consistent with sluggish kinetics and rationalizes different and partly conflicting microstructural results in the literature, and could be a source of variations in the performance of prosthetic devices in-vivo. © 2012 Elsevier Ltd.
    view abstractdoi: 10.1016/j.jmbbm.2012.03.013
  • 2012 • 126 Performance of fluorene and terthiophene copolymer in bilayer photovoltaic devices: The role of the polymer conformations
    Marchiori, C.F.N. and Yamamoto, N.A.D. and Grova, I.R. and MacEdo, A.G. and Paulus, M. and Sternemann, C. and Huotari, S. and Akcelrud, L. and Roman, L.S. and Koehler, M.
    Organic Electronics: physics, materials, applications 13 2716-2726 (2012)
    We report experiments using fluorene and terthiophene copolymer as the active layer in bilayer devices with C 60. The highest short circuit current, open circuit voltage and power conversion efficiency upon AM1.5 illumination were 6.8 mA/cm 2, 0.68 V and 2.33%, respectively. Density functional theory analysis was used to identify the most stable configurations of the terthiophene moieties in the polymer: the most stable form has the thiophene rings in the alternate configuration (anti) and the second conformation has the thiophene rings pointing to the same direction (syn). Comparing theoretical results with measurements of absorbance, X-ray diffraction, and X-ray reflectometry experiments, we conclude that the annealing treatment produces conformational anti to syn transition along the backbone of poly[9,9′-n-dihexyl-2,7-fluorene-alt-2,5-terthiophene] (LaPPS45). The syn segments of the chain condensed then in a lamellar ordered structure which increases the degree of crystallinity of the annealed samples and improve the light harvest at long wavelengths. From absorption measurements of films submitted to different annealing temperatures and with the help of theoretical calculations we propose a "wave-like" aggregation pattern to the syn segments in those lamellas. © 2012 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.orgel.2012.08.002
  • 2012 • 125 Rare-earth substituted HfO2 thin films grown by metalorganic chemical vapor deposition
    Devi, A. and Cwik, S. and Xu, K. and Milanov, A.P. and Noei, H. and Wang, Y. and Barreca, D. and Meijer, J. and Rogalla, D. and Kahn, D. and Cross, R. and Parala, H. and Paul, S.
    Thin Solid Films 520 4512-4517 (2012)
    Thin films of HfGdOx and HfDyOx were deposited by metalorganic chemical vapor deposition (MOCVD) utilizing guanidinate precursors for Hf, Gd and Dy. The close match in the thermal properties of the precursors enabled the MOCVD of rare-earth (RE) substituted HfO2 over a wide temperature window. Film deposition was carried out in the temperature range 300-700 °C in the presence of oxygen on Si(100) substrates. HfGdO x films were analyzed in detail for their structure, composition and morphology using X-ray diffraction, Rutherford backscattering spectrometry, proton induced X-ray emission, X-ray photoelectron spectroscopy and scanning electron microscopy. The electrical properties of HfGdOx in terms of capacitance-voltage and current-voltage characteristics of metal-insulator- semiconductor device structures were evaluated. © 2011 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.tsf.2011.10.141
  • 2012 • 124 Spray roasting of iron chloride FeCl 2: Laboratory scale experiments and a model for numerical simulation
    Schiemann, M. and Wirtz, S. and Scherer, V. and Bärhold, F.
    Powder Technology 228 301-308 (2012)
    Iron chloride solutions are a waste product in steel pickling plants. A technique to recover the spent solutions is the so-called spray roasting process, where the spent solution is sprayed into a hot reaction atmosphere and solid iron oxide particles are formed. The particle formation in spray roasting reactors has important influence on the efficiency of the recovery process and on the quality of the desired by-product Fe 2O 3. A laboratory reactor was designed to investigate the particle formation. Experiments were carried out covering the predominant conditions in spray roasting reactors. The results offer valuable insight into the particle formation process, providing data on the surface structure of the Fe 2O 3 particles formed and on the progress of chemical conversion. Based on these results, a simplified model applicable to CFD-modelling of spray roasting reactors has been developed. Simulations of particle trajectories in the laboratory reactor are presented to show the capabilities of the model. © 2012 Elsevier B.V.
    view abstractdoi: 10.1016/j.powtec.2012.05.037
  • 2012 • 123 Strain-induced phase transitions in epitaxial NaNbO3 thin films grown by metal-organic chemical vapour deposition
    Schwarzkopf, J. and Schmidbauer, M. and Remmele, T. and Duk, A. and Kwasniewski, A. and Bin Anooz, S. and Devi, A. and Fornari, R.
    Journal of Applied Crystallography 45 1015-1023 (2012)
    Epitaxially strained NaNbO3 films were grown by liquid-delivery spin metal-organic chemical vapour deposition on several oxide substrates, inducing tensile and compressive lattice strain. High-resolution X-ray diffraction measurements reveal that coherently grown compressively strained NaNbO3 films on NdGaO3 exhibit the orthorhombic c phase. With increasing in-plane strain a first structural phase transition to the monoclinic r phase and, further on, for films grown under tensile strain on rare earth scandates, a second phase transition to the aa phase, are observed. Our results are in good agreement with the pathway of phase transitions predicted by Diéguez, Rabe & Vanderbilt [Phys. Rev. B, (2005), 72, 144101] for NaNbO3 films.
    view abstractdoi: 10.1107/S0021889812035911
  • 2012 • 122 Strontium doping in mullite-type bismuth aluminate: A vacancy investigation using neutrons, photons and electrons
    Gesing, T.M. and Schowalter, M. and Weidenthaler, C. and Murshed, M.M. and Nénert, G. and Mendive, C.B. and Curti, M. and Rosenauer, A. and Buhl, J.-C. and Schneider, H. and Fischer, R.X.
    Journal of Materials Chemistry 22 18814-18823 (2012)
    We report on strontium doped dibismuth-nonaoxoaluminate(iii) produced at 1023 K. Partial substitution of bismuth by strontium in the structure yields oxygen vacancies for charge balance. Introducing oxygen vacancies rearranged the associated Al<inf>2</inf>O<inf>7</inf> double-tetrahedra forming "Al <inf>3</inf>O<inf>10</inf>" tri-clusters which were identified by multi-quantum 27Al MAS NMR. Both STEM-EDX and XPS showed homogeneous distribution of strontium in the bulk and on the surface, respectively. Moreover, XPS confirms the valence state of bismuth after doping. The orientations of bismuth 6s2 lone electron pairs were calculated using DFT methods. The amount of strontium in the crystal structure was further confirmed from the decomposition product SrAl<inf>12</inf>O<inf>19</inf> formed during the temperature-dependent X-ray powder diffraction. The structural proof was carried out by refining the structure of (Bi<inf>0.94</inf>Sr <inf>0.06</inf>)<inf>2</inf>Al<inf>4</inf>O<inf>8.94</inf> from powder neutron and X-ray diffraction data. Rietveld refinements clearly showed the under occupation of one oxygen site and the shift of two aluminum atoms from the double-tetrahedra to two tri-cluster sites. © The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c2jm33208f
  • 2012 • 121 Structural and magnetic properties of Co 2MnSi thin films
    Belmeguenai, M. and Zighem, F. and Faurie, D. and Tuzcuoglu, H. and Chérif, S.-M. and Moch, P. and Westerholt, K. and Seiler, W.
    Physica Status Solidi (A) Applications and Materials Science 209 1328-1333 (2012)
    Co 2MnSi (CMS) films of different thicknesses (20, 50, and 100 nm) were grown by radio frequency (RF) sputtering on a-plane sapphire substrates. Our X-rays diffraction (XRD) study shows that, in all the samples, the cubic 〈110〉 CMS axis is normal to the substrate and that six well defined preferential in-plane orientations are present. Static and dynamic magnetic properties were investigated using vibrating sample magnetometry (VSM) and microstrip line ferromagnetic resonance (MS-FMR), respectively. From the resonance measurements versus the direction and the amplitude of an applied magnetic field, most of the magnetic parameters are derived, i.e.: the magnetization, the gyromagnetic factor, the exchange stiffness coefficient, and the magnetic anisotropy terms. The in-plane anisotropy results from the superposition of two terms showing a twofold and a fourfold symmetry, respectively. The observed behavior of the hysteresis loops is in agreement with this complex form of the in-plane anisotropy. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/pssa.201228039
  • 2012 • 120 Structural properties of amorphous metal carbides: Theory and experiment
    Kádas, K. and Andersson, M. and Holmström, E. and Wende, H. and Karis, O. and Urbonaite, S. and Butorin, S.M. and Nikitenko, S. and Kvashnina, K.O. and Jansson, U. and Eriksson, O.
    Acta Materialia 60 4720-4728 (2012)
    By means of theoretical modeling and experimental synthesis and characterization, we investigate the structural properties of amorphous Zr-Si-C. Two chemical compositions are selected: Zr0.31Si0.29 C0.40 and Zr0.60Si0.33C0.07. Amorphous structures are generated in the theoretical part of our work by the stochastic quenching (SQ) method, and detailed comparison is made regarding the structure and density of the experimentally synthesized films. These films are analyzed experimentally using X-ray absorption spectroscopy, transmission electron microscopy and X-ray diffraction. Our results demonstrate a remarkable agreement between theory and experiment concerning bond distances and atomic coordination of this complex amorphous metal carbide. The demonstrated power of the SQ method opens up avenues for theoretical predictions of amorphous materials in general. © 2012 Acta Materialia Inc. Published by Elsevier Ltd.
    view abstractdoi: 10.1016/j.actamat.2012.04.044
  • 2012 • 119 Subsurface influence on the structure of protein adsorbates as revealed by in situ X-ray reflectivity
    Hähl, H. and Evers, F. and Grandthyll, S. and Paulus, M. and Sternemann, C. and Loskill, P. and Lessel, M. and Hüsecken, A.K. and Brenner, T. and Tolan, M. and Jacobs, K.
    Langmuir 28 7747-7756 (2012)
    The adsorption process of proteins to surfaces is governed by the mutual interactions among proteins, the solution, and the substrate. Interactions arising from the substrate are usually attributed to the uppermost atomic layer. This actual surface defines the surface chemistry and hence steric and electrostatic interactions. For a comprehensive understanding, however, the interactions arising from the bulk material also have to be considered. Our protein adsorption experiments with globular proteins (α-amylase, bovine serum albumin, and lysozyme) clearly reveal the influence of the subsurface material via van der Waals forces. Here, a set of functionalized silicon wafers enables a distinction between the effects of surface chemistry and the subsurface composition of the substrate. Whereas the surface chemistry controls whether the individual proteins are denatured, the strength of the van der Waals forces affects the final layer density and hence the adsorbed amount of proteins. The results imply that van der Waals forces mainly influence surface processes, which govern the structure formation of the protein adsorbates, such as surface diffusion and spreading. © 2012 American Chemical Society.
    view abstractdoi: 10.1021/la300850g
  • 2012 • 118 Surfactant-induced nonhydrolytic synthesis of phase-pure ZrO2 nanoparticles from metal-organic and oxocluster precursors
    Sliem, M.A. and Schmidt, D.A. and Bétard, A. and Kalidindi, S.B. and Gross, S. and Havenith, M. and Devi, A. and Fischer, R.A.
    Chemistry of Materials 24 4274-4282 (2012)
    Nonhydrolytic/non-sol-gel pyrolytic synthesis technique, as a convenient method, was applied to synthesize zirconium oxide nanoparticles (ZrO2 NPs). Pyrolysis of either the mononuclear keto ester/alkoxide complex zirconium bis(isopropoxide)bis(tert-butylacetoacetate) [Zr(OiPr) 2(tbaoac)2] (I) or the oligonuclear oxocluster compound [Zr6(OH)4O4(OMc)12] (II, Mc = methacrylate) generated ZrO2 NPs at moderate conditions of 300-400 °C. Trioctylamine, stearic acid, and/or oleic acid, which act as both solvents and stabilizing agents, were used. Under the adopted process conditions, the stabilizing agent oleic acid plays a vital role in determining the phase of as-synthesized colloidal ZrO2 nanoparticles, which yield the high-temperature tetragonal phase at moderate conditions of 335 °C. Those as-synthesized samples that contained both monoclinic and tetragonal ZrO2 phases (depending on the choice of the surfactant) were transformed into pure tetragonal phase at 1000 °C. An unambiguous phase determination of ZrO2 nanoparticles was carried out by the combination of powder X-ray diffraction (XRD) and Raman spectroscopy. Furthermore, the samples were analyzed by transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) and photoluminescence (PL) spectroscopy, dynamic light scattering (DLS), and Fourier transform infrared (FT-IR) spectroscopy to elucidate the structure, chemical composition, and morphology of the obtained nanoparticles. Also, the phase transformations of the as-synthesized ZrO2 nanoparticles upon annealing were followed via Raman spectroscopy. © 2012 American Chemical Society.
    view abstractdoi: 10.1021/cm301128a
  • 2012 • 117 Synthesis and characterization of α-, β-, and γ-Ga 2o 3 prepared from aqueous solutions by controlled precipitation
    Li, L. and Wei, W. and Behrens, M.
    Solid State Sciences 14 971-981 (2012)
    α, β and γ-Ga 2O 3 have been successfully obtained in an easily scalable synthesis using aqueous solution of gallium nitrate and sodium carbonate as starting materials without any surfactant and additive. α and β-Ga 2O 3 were obtained by calcination at 350 and 700 °, respectively, of α-GaOOH, prepared by controlled precipitation at constant pH 6 and T = 55 °, with 24 h of aging. Aging was necessary to fully convert the initially preciptated gel into a well-crystalline and phase-pure material. γ-Ga 2O 3 was obtained after calcination at 500 ° of gallia gel, synthesized at constant pH 4 and T = 25 °, without aging. These three polymorphs have a for gallia relatively high surface area: 55 m 2/g (α-Ga 2O 3), 23 m 2/g (β-Ga 2O 3) and 116 m 2/g (γ-Ga 2O 3). The combination of X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), nitrogen physisorption and thermogravimetry (TG) was employed to characterize the samples and their formation. © 2012 Elsevier Masson SAS. All rights reserved.
    view abstractdoi: 10.1016/j.solidstatesciences.2012.04.037
  • 2012 • 116 Synthesis of high surface area ZnO powder by continuous precipitation
    Boz, I. and Kaluza, S. and Boroǧlu, M.S. and Muhler, M.
    Materials Research Bulletin 47 1185-1190 (2012)
    Synthesis of high surface area ZnO powder was achieved by continuous precipitation using zinc ions and urea at low temperature of 90 °C. The powder precipitated resulted in high-purity single-phase ZnO powder when calcined at 280 °C for 3 h in air. The solution pH and the precipitation duration strongly affected the surface area of the calcined ZnO powder. Detailed structural characterizations demonstrated that the synthesized ZnO powder were single crystalline with wurtzite hexagonal phase. The powdered samples precipitated by homogeneous precipitation crystallized directly to hydrozincite without any intermediate phase formation. The phase structures, morphologies and properties of the final ZnO powders were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), dynamic light scattering particle size analysis (DLS), and nitrogen physisorption in order to determine the specific surface area (BET) and the pore size distribution (BJH). © 2012 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.materresbull.2012.02.005
  • 2012 • 115 Synthesis, structure, tautomerism, and reactivity of methanetrisamidines
    Gutschank, B. and Schulz, S. and Marcinkowski, M. and Jansen, G. and Bandmann, H. and Bläser, D. and Wölper, C.
    Angewandte Chemie - International Edition 51 10893-10897 (2012)
    Tout au contraire: Both tautomeric forms of a methanetrisamidine were structurally characterized for the first time by X-ray diffraction and by ab initio calculations (see structures; gray C, red H, blue N). Their reactivity as proton acceptors and multianionic ligands was demonstrated. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201205030
  • 2012 • 114 The effect of ionic strength, temperature, and pressure on the interaction potential of dense protein solutions: From nonlinear pressure response to protein crystallization
    Möller, J. and Schroer, M.A. and Erlkamp, M. and Grobelny, S. and Paulus, M. and Tiemeyer, S. and Wirkert, F.J. and Tolan, M. and Winter, R.
    Biophysical Journal 102 2641-2648 (2012)
    Understanding the intermolecular interaction potential, V(r), of proteins under the influence of temperature, pressure, and salt concentration is essential for understanding protein aggregation, crystallization, and protein phase behavior in general. Here, we report small-angle x-ray scattering studies on dense lysozyme solutions of high ionic strength as a function of temperature and pressure. We show that the interaction potential changes in a nonlinear fashion over a wide range of temperatures, salt, and protein concentrations. Neither temperature nor protein and salt concentration lead to marked changes in the pressure dependence of V(r), indicating that changes of the water structure dominate the pressure dependence of the intermolecular forces. Furthermore, by analysis of the temperature, pressure, and ionic strength dependence of the normalized second virial coefficient, b2, we show that the interaction can be fine-tuned by pressure, which can be used to optimize b 2 values for controlled protein crystallization. © 2012 Biophysical Society.
    view abstractdoi: 10.1016/j.bpj.2012.04.043
  • 2012 • 113 The Role of Oxygen- and Nitrogen-containing Surface Groups on the Sintering of Iron Nanoparticles on Carbon Nanotubes in Different Atmospheres
    Sánchez, M.D. and Chen, P. and Reinecke, T. and Muhler, M. and Xia, W.
    ChemCatChem 4 1997-2004 (2012)
    The sintering of iron nanoparticles on carbon nanotubes (CNTs) under different atmospheres was investigated. CNTs were first treated with HNO3 vapor at 200°C to obtain O-functionalized CNTs (OCNTs). The OCNTs were treated in ammonia at 400°C to obtain N-doped CNTs (NCNTs). Highly dispersed FeOx nanoparticles were subsequently deposited by chemical vapor deposition from ferrocene under oxidizing conditions. The obtained FeOx/OCNT and FeOx/NCNT samples were allowed to sinter at 500°C under flowing helium, hydrogen, or ammonia. The samples were studied by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. A significant increase in particle size and a decrease in Fe surface atomic concentration were observed in all the sintered samples. The sintering on OCNTs was more severe than on NCNTs, which can be attributed to stronger metal-substrate interactions and a higher amount of surface defects on NCNTs. The applied gas atmosphere had a substantial influence on the sintering behavior of the nanoparticles: treatment in helium led to the growth of particles and a significant widening of particle size distributions, whereas treatment in hydrogen or ammonia resulted in the growth of particles, but not in the widening of particle size distributions. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cctc.201200286
  • 2012 • 112 Toward highly stable electrocatalysts via nanoparticle pore confinement
    Galeano, C. and Meier, J.C. and Peinecke, V. and Bongard, H. and Katsounaros, I. and Topalov, A.A. and Lu, A. and Mayrhofer, K.J.J. and Schüth, F.
    Journal of the American Chemical Society 134 20457-20465 (2012)
    The durability of electrode materials is a limiting parameter for many electrochemical energy conversion systems. In particular, electrocatalysts for the essential oxygen reduction reaction (ORR) present some of the most challenging instability issues shortening their practical lifetime. Here, we report a mesostructured graphitic carbon support, Hollow Graphitic Spheres (HGS) with a specific surface area exceeding 1000 m2 g-1 and precisely controlled pore structure, that was specifically developed to overcome the long-term catalyst degradation, while still sustaining high activity. The synthetic pathway leads to platinum nanoparticles of approximately 3 to 4 nm size encapsulated in the HGS pore structure that are stable at 850 C and, more importantly, during simulated accelerated electrochemical aging. Moreover, the high stability of the cathode electrocatalyst is also retained in a fully assembled polymer electrolyte membrane fuel cell (PEMFC). Identical location scanning and scanning transmission electron microscopy (IL-SEM and IL-STEM) conclusively proved that during electrochemical cycling the encapsulation significantly suppresses detachment and agglomeration of Pt nanoparticles, two of the major degradation mechanisms in fuel cell catalysts of this particle size. Thus, beyond providing an improved electrocatalyst, this study describes the blueprint for targeted improvement of fuel cell catalysts by design of the carbon support. © 2012 American Chemical Society.
    view abstractdoi: 10.1021/ja308570c
  • 2011 • 111 A facile synthesis of shape- and size-controlled α-Fe 2O3 nanoparticles through hydrothermal method
    Wang, G.-H. and Li, W.-C. and Jia, K.-M. and Lu, A.-H. and Feyen, M. and Spliethoff, B. and SchÜth, F.
    Nano 6 469-479 (2011)
    α-Fe2O3 nanoparticles have wide-ranging applications such as in catalysis, sensoring, painting, etc. This is the reason to study their controlled synthesis. Here we have investigated the synthesis of uniform α-Fe2O3 nanoparticles using amino acids as morphology control agents. The products were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetry (TG) and differential thermal analysis (DTA). It was found that the type and the amount of amino acids as well as the reaction temperatures have significant influence on the shape and size of the obtained α-Fe2O3 nanoparticles. The use of acidic amino acids (always contain C=O in the side chain) typically leads to the formation of α-Fe2O3 nanoparticles with spindle shape. However, rhombohedrally shaped α-Fe 2O3 nanoparticles were formed in presence of basic amino acids (always contain -NH2 in the side chain). Increasing the amount of amino acid generally results in α-Fe2O3 nanoparticles with decreasing particle sizes. © 2011 World Scientific Publishing Company.
    view abstractdoi: 10.1142/S1793292011002846
  • 2011 • 110 Aminotroponiminatozinc(I) complexes: Syntheses and spectroscopic analyses
    Nayek, H.P. and Lühl, A. and Schulz, S. and Köppe, R. and Roesky, P.W.
    Chemistry - A European Journal 17 1773-1777 (2011)
    Aminotroponiminates-very effective ligands for the stabilization of low-valent ZnI-ZnI bonded compounds (see scheme). For the first time a stretching motion of the Zn-Zn bond, which is almost uncoupled to other vibrations, was found in the Raman spectrum. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201002443
  • 2011 • 109 Atomic vapor deposition approach to In 2O 3 thin films
    Hellwig, M. and Parala, H. and Cybinksa, J. and Barreca, D. and Gasparotto, A. and Niermann, B. and Becker, H.-W. and Rogalla, D. and Feydt, J. and Irsen, S. and Mudring, A.-V. and Winter, J. and Fischer, R.A. and Devi, A.
    Journal of Nanoscience and Nanotechnology 11 8094-8100 (2011)
    In 2O 3 thin films were grown by atomic vapor deposition (AVD) on Si(100) and glass substrates from a tris-guanidinate complex of indium [In(NiPr 2guanid) 3] under an oxygen atmosphere. The effects of the growth temperature on the structure, morphology and composition of In 2O 3 films were investigated. X-ray diffraction (XRD) measurements revealed that In 2O 3 films deposited in the temperature range 450-700°C crystallised in the cubic phase. The film morphology, studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM), was strongly dependent on the substrate temperature. Stoichiometric In 2O 3 films were formed under optimised processing conditions as was confirmed by X-ray photoelectron and X-ray excited Auger electron spectroscopies (XPS, XE-AES), as well as by Rutherford backscattering spectrometry (RBS). Finally, optical properties were investigated by photoluminescence (PL) measurements, spectroscopic ellipsometry (SE) and optical absorption. In 2O 3 films grown on glass exhibited excellent transparency (≈90%) in the Visible (Vis) spectral region. Copyright © 2011 American Scientific Publishers All rights reserved.
    view abstractdoi: 10.1166/jnn.2011.5024
  • 2011 • 108 Composition and orientation effects on the final recrystallization texture of coarse-grained Nb-containing AISI 430 ferritic stainless steels
    Siqueira, R.P. and Sandim, H.R.Z. and Oliveira, T.R. and Raabe, D.
    Materials Science and Engineering A 528 3513-3519 (2011)
    Composition and orientation effects on the final recrystallization texture of three coarse-grained Nb-containing AISI 430 ferritic stainless steels (FSSs) were investigated. Hot-bands of steels containing distinct amounts of niobium, carbon and nitrogen were annealed at 1250 °C for 2. h to promote grain growth. In particular, the amounts of Nb in solid solution vary from one grade to another. For purposes of comparison, the texture evolution of a hot-band sheet annealed at 1030 °C for 1. min (finer grain structure) was also investigated. Subsequently, the four sheets were cold rolled up to 80% reduction and then annealed at 800 °C for 15. min. Texture was determined using X-ray diffraction and electron backscatter diffraction (EBSD). Noticeable differences regarding the final recrystallization texture and microstructure were observed in the four investigated grades. Results suggest that distinct nucleation mechanisms take place within these large grains leading to the development of different final recrystallization textures. © 2011 Elsevier B.V.
    view abstractdoi: 10.1016/j.msea.2011.01.007
  • 2011 • 107 Dislocation storage in single slip-oriented Cu micro-tensile samples: New insights via X-ray microdiffraction
    Kirchlechner, C. and Kiener, D. and Motz, C. and Labat, S. and Vaxelaire, N. and Perroud, O. and Micha, J.-S. and Ulrich, O. and Thomas, O. and Dehm, G. and Keckes, J.
    Philosophical Magazine 91 1256-1264 (2011)
    Synchrotron X-ray microdiffraction was used to characterize the deformation structure of single crystalline Cu micro-tensile specimens which were oriented for single slip. The 3-m thick samples were strained in situ in a scanning electron microscope (SEM). Electron microscopy observations revealed glide steps at the surface indicating single slip. While the slip steps at the surface must have formed by the predominant activation of the primary glide system, analysis of Laue peak streaking directions revealed that, even at low strains, dislocations had been activated and stored on an unpredicted slip system. Furthermore, the Laue scans showed that multiple slip takes over at a later state of deformation. © 2011 Taylor & Francis.
    view abstractdoi: 10.1080/14786431003785639
  • 2011 • 106 Dissolution of iron oxide nanoparticles inside polymer nanocapsules
    Möller, J. and Cebi, M. and Schroer, M.A. and Paulus, M. and Degen, P. and Sahle, C.J. and Wieland, D.C.F. and Leick, S. and Nyrow, A. and Rehage, H. and Tolan, M.
    Physical Chemistry Chemical Physics 13 20354-20360 (2011)
    The structure of poly(organosiloxane) nanocapsules partially filled with iron oxide cores of different sizes was revealed by small angle X-ray scattering and X-ray diffraction. The nanocapsules are synthesized by the formation of a poly(organosiloxane) shell around iron oxide nanoparticles and the simultaneous partial dissolution of these cores. Due to the high scattering contrast of the iron oxide cores compared to the polymer shell, the particle size distribution of the cores inside the capsules can be measured by small angle X-ray scattering. Additional information can be revealed by X-ray diffraction, which gives insights into the formation of the polymer network and the structure of the iron oxide cores. The study shows how the crystallinity and size of the nanoparticles as well as the shape and width of the size distribution can be altered by the synthesis parameters. © 2011 the Owner Societies.
    view abstractdoi: 10.1039/c1cp22161b
  • 2011 • 105 Effect of heat-treatment on grain growth of nanocrystalline tricalcium phosphate powder synthesized via the precipitation method
    Mobasherpour, I. and Salahi, E. and Manafi, S.A. and Kamachali, R.D.
    Materials Science- Poland 29 203-208 (2011)
    Nanocrystalline tricalcium phosphate powder was synthesized via the solution- precipitation method followed by heat treatment in order to achieve phase evolution, which was then studied by XRD and TEM techniques. The crystallites sizes were estimated by the Scherrer method and results were confirmed by TEM micrographs. The experimental observations showed that nanocrystalline tricalcium phosphate can be successfully prepared from raw materials by the precipitation technique. This technique is a competitive method for nanocrystalline tricalcium phosphate synthesis compared to other techniques. Moreover, a simple kinetic growth investigation was performed on the nanocrystalline growth process during heat treatment. Results have shown growth rate to increase exponentially with temperature and the growth rate constants to increase with time. The average activation energies of tricalcium phosphate grain growth obtained by this method were 84.78 and 134.38 KJ/mol. © Wroclaw University of Technology.
    view abstractdoi: 10.2478/s13536-011-0032-6
  • 2011 • 104 Effect of welding parameters on residual stresses in dissimilar joint of stainless steel to carbon steel
    Ranjbarnodeh, E. and Serajzadeh, S. and Kokabi, A.H. and Fischer, A.
    Journal of Materials Science 46 3225-3232 (2011)
    In this study, a thermo-mechanical model was utilized to investigate the effects of welding parameters on the distribution of residual stresses in dissimilar TIG welds of low carbon and ferritic stainless steels. To solve the governing thermal and mechanical problems, a finite element program, ANSYS, was employed while the different aspects such as welding sequence and dilution were considered in the numerical solution. To validate the predictions, the model results were compared with the residual stresses measured by X-ray diffraction technique and a reasonable agreement was found. The results show that the magnitude of tensile residual stresses decrease as the welding current increases while lower residual stresses are produced in the longer samples. In addition, the magnitudes of residual stresses significantly decrease when a symmetric welding sequence is employed especially for the carbon steel part with the higher yield strength. © 2010 Springer Science+Business Media, LLC.
    view abstractdoi: 10.1007/s10853-010-5207-8
  • 2011 • 103 Effects of specific versus nonspecific ionic interactions on the structure and lateral organization of lipopolysaccharides
    Jeworrek, C. and Evers, F. and Howe, J. and Brandenburg, K. and Tolan, M. and Winter, R.
    Biophysical Journal 100 2169-2177 (2011)
    We report x-ray reflectivity and grazing incidence x-ray diffraction measurements of lipopolysaccharide (LPS) monolayers at the water-air interface. Our investigations reveal that the structure and lateral ordering of the LPS molecules is very different from phospholipid systems and can be modulated by the ionic strength of the aqueous subphase in an ion-dependent manner. Our findings also indicate differential effects of monovalent and divalent ions on the two-dimensional ordering of lipid domains. Na+ ions interact unspecifically with LPS molecules based on their ability to efficiently screen the negative charges of the LPS molecules, whereas Ca2+ ions interact specifically by cross-linking adjacent molecules in the monolayer. At low lateral pressures, Na+ ions present in the subphase lead to a LPS monolayer structure ordered over large areas with high compressibility, nearly hexagonal packing of the hydrocarbon chains, and high density in the LPS headgroup region. At higher film pressures, the LPS monolayer becomes more rigid and results in a less perfect, oblique packing of the LPS hydrocarbon chains as well as a smaller lateral size of highly ordered domains on the monolayer. Furthermore, associated with the increased surface pressure, a conformational change of the sugar headgroups occurs, leading to a thickening of the entire LPS monolayer structure. The effect of Ca2+ ions in the subphase is to increase the rigidity of the LPS monolayer, leading to an oblique packing of the hydrocarbon chains already at low film pressures, an upright orientation of the sugar moieties, and much smaller sizes of ordered domains in the plane of the monolayer. In the presence of both Na+-and Ca2+ ions in the subphase, the screening effect of Na+ is predominant at low film pressures, whereas, at higher film pressures, the structure and lateral organization of LPS molecules is governed by the influence of Ca2+ ions. The unspecific charge-screening effect of the Na+ ions on the conformation of the sugar moiety becomes less dominant at biologically relevant lateral pressures. © 2011 by the Biophysical Society.
    view abstractdoi: 10.1016/j.bpj.2011.03.019
  • 2011 • 102 Evaluation of homoleptic guanidinate and amidinate complexes of gadolinium and dysprosium for MOCVD of rare-earth nitride thin films
    Thiede, T.B. and Krasnopolski, M. and Milanov, A.P. and De Los Arcos, T. and Ney, A. and Becker, H.-W. and Rogalla, D. and Winter, J. and Devi, A. and Fischer, R.A.
    Chemistry of Materials 23 1430-1440 (2011)
    Metal-organic chemical vapor deposition (MOCVD) of thin films of two representative rare-earth nitrides is reported here for the first time. Four homoleptic, all-nitrogen-coordinated, rare-earth (RE) complexes were evaluated as precursors for the respective nitride thin film materials. Two guanidinato complexes [RE{(iPrN)2C(NMe2)}3] [RE = Gd (1), Dy (2)] and two amidinato complexes [RE{(iPrN) 2CMe}3] [RE = Gd (3), Dy (4)] were compared and used either as single source precursors or together with ammonia for MOCVD of gadolinium nitride (GdN) and dysprosium nitride (DyN), respectively. The thermal properties of the precursors were studied and the fragmentation patterns were characterized by high-resolution electron impact-mass spectrometry (HR EI-MS). The obtained nitride films were investigated using a series of techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), nuclear reaction analysis (NRA), Rutherford backscattering (RBS), and X-ray photoelectron spectroscopy (XPS). The films contain preferentially oriented grains of fcc-GdN and DyN and are contaminated with small amounts of carbon and oxygen (significantly below 10 at.-% in the best cases). The temperature-dependent magnetic properties of the films, as measured using a superconducting quantum interference device (SQUID), suggest the existence of small ferromagnetic grains of the rare-earth nitrides that exhibit superparamagnetism. Despite the chemical and structural similarity of the guanidinato and amidinato complexes (1-4), a distinctly different behavior as MOCVD precursors was found for 1 and 2, compared with that for 3 and 4. While the guanidinates operate well as single-source precursors (SSPs), the amidinates are not suited at all as SSPs, but give very good nitride films when used in the presence of ammonia. This characteristic behavior was correlated with the different fragmentation mechanisms, as revealed by EI-MS. © 2011 American Chemical Society.
    view abstractdoi: 10.1021/cm102840v
  • 2011 • 101 Exploring the piezophilic behavior of natural cosolvent mixtures
    Schroer, M.A. and Zhai, Y. and Wieland, D.C.F. and Sahle, C.J. and Nase, J. and Paulus, M. and Tolan, M. and Winter, R.
    Angewandte Chemie - International Edition 50 11413-11416 (2011)
    Marine organisms have evolved a surprising mechanism to counteract the deleterious effects of urea by trimethylammonium N-oxide (TMAO). The effect of pressure on the structure and intermolecular interactions of lysozyme in urea and TMAO solutions was studied (see picture). These findings help to understand the compensatory effect of urea-TMAO mixtures in deep-sea organisms. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/anie.201104380
  • 2011 • 100 Finite element modeling of the effect of heat input on residual stresses in dissimilar joints
    Ranjbarnodeh, E. and Serajzadeh, S. and Hosein Kokabi, A. and Hanke, S. and Fischer, A.
    International Journal of Advanced Manufacturing Technology 55 649-656 (2011)
    In the present study, a thermo-elastic-plastic model was developed in order to evaluate the residual stresses in dissimilar automatic tungsten inert gas (TIG) welds between plain carbon steel CK4 and a ferritic stainless steel AISI409. The effect of welding heat input on the magnitude and the distribution of residual stresses was investigated and the results of simulation were validated by X-ray diffraction measurements. It is shown that the calculated residual stresses are in good agreement with the residual stresses determined experimentally. It was found that the magnitudes of stresses at the weld center line increases with increasing the welding speed. © 2010 Springer-Verlag London Limited.
    view abstractdoi: 10.1007/s00170-010-3095-3
  • 2011 • 99 Ge-Si-O phase separation and Ge nanocrystal growth in Ge:SiO x/SiO2 multilayers - A new dc magnetron approach
    Zschintzsch, M. and Sahle, C.J. and Borany, J.V. and Sternemann, C. and Mücklich, A. and Nyrow, A. and Schwamberger, A. and Tolan, M.
    Nanotechnology 22 (2011)
    Ge:SiOx/SiO2 multilayers are fabricated using a new reactive dc magnetron sputtering approach. The influence of the multilayer stoichiometry on the ternary Ge-Si-O phase separation and the subsequent size-controlled Ge nanocrystal formation is explored by means of x-ray absorption spectroscopy, x-ray diffraction, electron microscopy and Raman spectroscopy. The ternary system Ge-Si-O reveals complete Ge-O phase separation at 400 °C which does not differ significantly to the binary Ge-O system. Ge nanocrystals of < 5nm size are generated after subsequent annealing below 700°C. It is shown that Ge oxides contained in the as-deposited multilayers are reduced by a surrounding unsaturated silica matrix. A stoichiometric regime was found where almost no GeO2 is present after annealing. Thus, the Ge nanocrystals become completely embedded in a stoichiometric silica matrix favouring the use for photovoltaic applications. © IOP Publishing Ltd.
    view abstractdoi: 10.1088/0957-4484/22/48/485303
  • 2011 • 98 Growth of epitaxial sodium-bismuth-titanate films by metal-organic chemical vapor phase deposition
    Schwarzkopf, J. and Schmidbauer, M. and Duk, A. and Kwasniewski, A. and Anooz, S.B. and Wagner, G. and Devi, A. and Fornari, R.
    Thin Solid Films 520 239-244 (2011)
    The liquid-delivery spin metal-organic chemical vapor phase deposition method was used to grow epitaxial sodium-bismuth-titanate films of the system Bi4Ti3O12 + xNa0.5Bi 0.5TiO3 on SrTiO3(001) substrates. Na(thd), Ti(OiPr)2(thd)2 and Bi(thd)3, solved in toluene, were applied as source materials. Depending on the substrate temperature and the Na/Bi ratio in the gas phase several structural phases of sodium-bismuth-titanate were detected. With increasing temperature and/or Na/Bi ratio, phase transitions from an Aurivillius phase with m = 3 to m = 4 via an interleaved state with m = 3.5, and, finally, to Na0.5Bi 0.5TiO3 with perovskite structure (m = ∞) were established. These phase transitions proceed at remarkably lower temperatures than in ceramics or bulk crystals for which they had been exclusively observed so far. © 2011 Elsevier B.V.
    view abstractdoi: 10.1016/j.tsf.2011.07.050
  • 2011 • 97 High-energy X-ray diffraction studies of i-Sc12Zn88
    Goldman, A.I. and Kreyssig, A. and Nandi, S. and Kim, M.G. and Caudle, M.L. and Canfield, P.C.
    Philosophical Magazine 91 2427-2433 (2011)
    Although quasicrystals form in a wide variety of ternary and quaternary metallic alloys, examples of stable binary icosahedral quasicrystals are quite rare. Indeed, it has been a decade since the discovery of icosahedral phases in Yb-Cd and Ca-Cd. We have discovered millimeter-sized facetted grains of i- Sc12Zn88 with icosahedral (pentagonal dodecahedral and rhombic triacontahedral) morphologies in solution-grown samples. Structural characterization of the bulk icosahedral phase was accomplished through single-grain high-energy X-ray diffraction. For both growth morphologies, all diffraction peaks could be indexed by a primitive (P-type) icosahedral phase. The two types of morphology do, however, present interesting differences in their respective degrees of quasicrystalline order. © 2011 Taylor &amp; Francis.
    view abstractdoi: 10.1080/14786435.2010.511599
  • 2011 • 96 High-temperature stable, iron-based core-shell catalysts for ammonia decomposition
    Feyen, M. and Weidenthaler, C. and Güttel, R. and Schlichte, K. and Holle, U. and Lu, A.-H. and Schüth, F.
    Chemistry - A European Journal 17 598-605 (2011)
    High-temperature, stable core-shell catalysts for ammonia decomposition have been synthesized. The highly active catalysts, which were found to be also excellent model systems for fundamental studies, are based on α-Fe 2O 3 nanoparticles coated by porous silica shells. In a bottom-up approach, hematite nanoparticles were firstly obtained from the hydrothermal reaction of ferric chlorides, L-lysine, and water with adjustable average sizes of 35, 47, and 75nm. Secondly, particles of each size could be coated by a porous silica shell by means of the base-catalyzed hydrolysis of tetraethylorthosilicate (TEOS) with cetyltetramethylammonium bromide (CTABr) as porogen. After calcination, TEM, high-resolution scanning electron microscopy (HR-SEM), energy-dispersive X-ray (EDX), XRD, and nitrogen sorption studies confirmed the successful encapsulation of hematite nanoparticles inside porous silica shells with a thickness of 20nm, thereby leading to composites with surface areas of approximately 380 m 2g -1 and iron contents between 10.5 and 12.2wt%. The obtained catalysts were tested in ammonia decomposition. The influence of temperature, iron oxide core size, possible diffusion limitations, and dilution effects of the reagent gas stream with noble gases were studied. The catalysts are highly stable at 750°C with a space velocity of 120000 cm 3 g cat -1h -1 and maintained conversions of around 80% for the testing period time of 33 h. On the basis of the excellent stability under reaction conditions up to 800°C, the system was investigated by in situ XRD, in which body-centered iron was determined, in addition to FeN x, as the crystalline phase under reaction conditions above 650deg;C. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201001827
  • 2011 • 95 Highly active metal-free nitrogen-containing carbon catalysts for oxygen reduction synthesized by thermal treatment of polypyridine-carbon black mixtures
    Xia, W. and Masa, J. and Bron, M. and Schuhmann, W. and Muhler, M.
    Electrochemistry Communications 13 593-596 (2011)
    A straight-forward method for the synthesis of metal-free catalysts for oxygen reduction by thermal treatment of a mixture of poly(3,5-pyridine) with carbon black in helium is reported. The catalyst was characterized by X-ray diffraction and photoelectron spectroscopy, cyclic voltammetry and rotating disk electrode measurements. The new catalyst exhibited remarkable activity similar to Pt-based catalysts in alkaline media. © 2011 Elsevier B.V. All Rights Reserved.
    view abstractdoi: 10.1016/j.elecom.2011.03.018
  • 2011 • 94 Highly dispersed MoO 3/Al 2O 3 shell-core composites synthesized by CVD of Mo(CO) 6 under atmospheric pressure
    Shi, G. and Franzke, T. and Xia, W. and Sanchez, M.D. and Muhler, M.
    Chemical Vapor Deposition 17 162-169 (2011)
    MoO 3/γ-Al 2O 3 composites are synthesized by CVD under atmospheric pressure using Mo(CO) 6 as the precursor and porous γ-Al 2O 3 particles in a horizontal, rotating, hot-wall reactor, which is also used for calcination in air. The composites are characterized by N 2 physisorption, atomic absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmission electron microscopy (TEM), and laser Raman spectroscopy (LRS). The synthesized samples exhibit excellent porosity, even at high Mo loadings. A much higher Mo yield is achieved when applying sublimation-adsorption in static air instead of using flowing N 2. A high degree of Mo dispersion on alumina is confirmed by XRD, LRS, and TEM; with a Mo surface density as high as 5.2 atoms nm -2, the sample is X-ray amorphous, there are no polymeric molybdate species detectable by LRS, and the island size of the molybdate species is about 1 nm according to TEM. The XPS analysis shows that exclusively Mo VI species are present on all synthesized samples. Thus, the applied rotating, hot-wall reactor achieves efficient mixing and homogeneous deposition. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cvde.201106909
  • 2011 • 93 Hydrothermally highly stable acidic mesoporous aluminosilicate spheres with radial channels
    Gu, X. and Jiang, T. and Tao, H. and Zhou, S. and Liu, X. and Ren, J. and Wang, Y. and Lu, G. and Schmidt, W.
    Journal of Materials Chemistry 21 880-886 (2011)
    Hydrothermally highly stable mesoporous aluminosilicate spheres with radial channels were synthesized in the CTAB-NaF-TPAOH system through a one-step procedure at high aging temperature. The characterization by transmission electron microscopy (TEM), X-ray diffraction (XRD), nitrogen adsorption/desorption analysis, 27Al MAS solid state NMR spectroscopy, pyridine adsorption FT-IR combined with the typical hydrothermal treatments showed that this kind of material exhibited large surface area, specific pore arrangement, strong acidity and high hydrothermal stability. Detailed studies suggest that F- ions direct the perpendicular arrangement of aluminosilicate clusters during the hydrothermal treatment at 160°C, while TPA+ stabilized the structure. Both F- and TPA+ ions are considered to improve the acidity and hydrothermal stability of this material through coordination of framework atoms, thus, enhancing the condensation of Si-O-Si bonds in the amorphous pore walls. Due to the accessible radial pore arrangement and high acidity, the catalytic activity for Friedel-Crafts alkylation of toluene with benzyl alcohol was excellent with 100% conversion of benzyl alcohol.
    view abstractdoi: 10.1039/c0jm01973a
  • 2011 • 92 Improvement of the dissolution rate of poorly soluble drugs by solid crystal suspensions
    Thommes, M. and Ely, D.R. and Carvajal, M.T. and Pinal, R.
    Molecular Pharmaceutics 8 727-735 (2011)
    We present a novel extrusion based approach where the dissolution rate of poorly soluble drugs (griseofulvin, phenytoin and spironolactone) is significantly accelerated. The drug and highly soluble mannitol are coprocessed in a hot melt extrusion operation. The obtained product is an intimate mixture of the crystalline drug and crystalline excipient, with up to 50% (w/w) drug load. The in vitro drug release from the obtained solid crystalline suspensions is over 2 orders of magnitude faster than that of the pure drug. Since the resulting product is crystalline, the accelerated dissolution rate does not bear the physical stability concerns inherent to amorphous formulations. This approach is useful in situations where the drug is not a good glass former or in cases where it is difficult to stabilize the amorphous drug. Being thermodynamically stable, the dissolution profile and the solid state properties of the product are maintained after storage at 40 °C, 75% RH for at least 90 days. © 2011 American Chemical Society.
    view abstractdoi: 10.1021/mp1003493
  • 2011 • 91 In-vitro investigation of magnetron-sputtered coatings based on silicon-substituted hydroxyapatite
    Surmeneva, M.A. and Surmenev, R.A. and Pichugin, V.F. and Chernousova, S.S. and Epple, M.
    Journal of Surface Investigation 5 1202-1207 (2011)
    Silicon-containing calcium phosphate (Si-CaP) coatings on titanium and austenite steel substrates have been prepared by method of high-frequency magnetron sputtering. The powder of silicon-containing hydroxyapatite Ca 10(PO 4) 6 - x(SiO 4) x(HO) 2 - x (Si-HA), where x = 0. 5 obtained using a mechanochemical technique, was used as a target material. The obtained coatings were X-ray amorphous; the elemental composition of the coatings depended on the composition of the target to be sputtered. The coatings were heated in air for 3 hours to the temperature 700°C with the aim of changing their structure. The bioactivity of the coatings was studied using in-vitro tests. The solution of the simulated body fluid (SBF) oversaturated with respect to HA was used as a model medium. The phase elemental composition and morphology of the deposited and annealed Si-CaP coatings before and after submersion into the solution were controlled using the methods of X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDAX), and scanning electron microscopy (SEM). According to the XFA and IR-spectroscopy data, heat treatment in the air yields the formation of an apatite-like phase in the coating. Thermostating of "metal + coating" specimens in the solution of simulated body fluid revealed that all obtained coatings were biologically active, and a calcium phosphate layer was formed on the coating surface during mineralization. The annealed coatings show a higher chemical stability under physiological conditions as compared to amorphous coatings. © 2011 Pleiades Publishing, Ltd.
    view abstractdoi: 10.1134/S1027451011120135
  • 2011 • 90 Influence of Na on the structure of Bi4Ti3O 12 films deposited by liquid-delivery spin MOCVD
    Schwarzkopf, J. and Dirsyte, R. and Devi, A. and Kwasniewski, A. and Schmidbauer, M. and Wagner, G. and Michling, M. and Schmeisser, D. and Fornari, R.
    Thin Solid Films 519 5754-5759 (2011)
    Thin Na-substituted Bi4Ti3O12 films were grown by the liquid-delivery spin metal-organic chemical vapor deposition (MOCVD) method with different concentrations of sodium bis(trimethylsilyl)amide [Na(TMSA)] as Na precursor. At a substrate temperature of 600 °C the original Aurivillius structure was preserved, however high resolution x-ray diffraction (HRXRD) studies indicate that the Na-substituted phase exhibits a slightly smaller lattice parameter compared to the pure Bi4Ti 3O12 phase. From additional x-ray photoemission spectroscopy (XPS) results, we have concluded that monovalent Na+ ions have been incorporated on Bi3+ sites in the perovskite units. The proposed charge compensation for this aliovalent substitution is explained by a shift of the valence state of Bi3+ ions in the vicinity of the incorporated Na+ ions from 3+ to 5+. Due to the small ionic radius of the Bi5+ ions, the incorporation efficiency amounts to a few atomic percent only. © 2010 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.tsf.2010.12.206
  • 2011 • 89 Influence of Ti/TiAlN-multilayer designs on their residual stresses and mechanical properties
    Vogli, E. and Tillmann, W. and Selvadurai-Lassl, U. and Fischer, G. and Herper, J.
    Applied Surface Science 257 8550-8557 (2011)
    In this research work, Ti/TiAlN multilayers of various designs were deposited onto substrates pretreated by different etching procedures. The influence of multilayer design and substrate pretreatment on multilayers adhesion, hardness, wear and friction coefficients was systematically analyzed and correlated with residual stresses of these multilayers as well as with residual stresses on the coating-near substrate region, which were analyzed by synchrotron X-ray diffraction at HZB-BESSYII. These investigations show that the adhesion can be improved by a specific etching procedure, which cause increased compressive stress in the coating-near the substrate region. Additionally, it was found, that the multilayer with the thickest ceramic layers has the highest hardness and the lowest wear coefficients as well as the lowest compressive residual stress within studied multilayers. © 2011 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.apsusc.2011.05.013
  • 2011 • 88 Insertion reactions of heterocumulenes into Zn-C bonds: Synthesis and structural characterization of multinuclear zinc amidate complexes
    Schmidt, S. and Schäper, R. and Schulz, S. and Bläser, D. and Wölper, C.
    Organometallics 30 1073-1078 (2011)
    Reactions of ZnMe2 with isocyanates RNCO proceeded with insertion of the isocyanate into the Zn-Me bond, giving the corresponding heteroleptic amidate complexes [MeZnOC(Me)NR]x (R = i-Pr (1), t-Bu (2)) and [{MeZn}4Zn{OC(Me)NC6F5}6] (3) in high yields. In contrast, ZnCp*2 reacts with isocyanates and isothiocyanates with formation of homoleptic complexes of the type [Zn{OC(Cp*)NR}2]2 (R = Et (4), i-Pr (5)) and [Zn{SC(Cp*)N-i-Pr}2]2 (6). 1-6 were characterized by elemental analyses, multinuclear NMR (1H, 13C, 19F) and IR spectroscopy, and single-crystal X-ray diffraction (1, 2, 5). © 2011 American Chemical Society.
    view abstractdoi: 10.1021/om101107e
  • 2011 • 87 Intercalation in layered metal-organic frameworks: Reversible inclusion of an extended π-system
    Arslan, H.K. and Shekhah, O. and Wieland, D.C.F. and Paulus, M. and Sternemann, C. and Schroer, M.A. and Tiemeyer, S. and Tolan, M. and Fischer, R.A. and Wöll, C.
    Journal of the American Chemical Society 133 8158-8161 (2011)
    We report the synthesis of layered [Zn 2(bdc) 2(H 2O) 2] and [Cu 2(bdc) 2(H 2O) 2] (bdc = benzdicarboxylate) metal-organic frameworks (MOF) carried out using the liquid-phase epitaxy approach employing self-assembled monolayer (SAM) modified Au-substrates. We obtain Cu and Zn MOF-2 structures, which have not yet been obtained using conventional, solvothermal synthesis methods. The 2D Cu 2+ dimer paddle wheel planes characteristic for the MOF are found to be strictly planar, with the planes oriented perpendicular to the substrate. Intercalation of an organic dye, DXP, leads to a reversible tilting of the planes, demonstrating the huge potential of these surface-anchored MOFs for the intercalation of large, planar molecules. © 2011 American Chemical Society.
    view abstractdoi: 10.1021/ja2037996
  • 2011 • 86 Knowledge-based development of a nitrate-free synthesis route for Cu/ZnO methanol synthesis catalysts via formate precursors
    Behrens, M. and Kißner, S. and Girsgdies, F. and Kasatkin, I. and Hermerschmidt, F. and Mette, K. and Ruland, H. and Muhler, M. and Schlögl, R.
    Chemical Communications 47 1701-1703 (2011)
    High-performance Cu/ZnO/(Al2O3) methanol synthesis catalysts are conventionally prepared by co-precipitation from nitrate solutions and subsequent thermal treatment. A new synthesis route is presented, which is based on similar preparation steps and leads to active catalysts, but avoids nitrate contaminated waste water. © 2011 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c0cc04933f
  • 2011 • 85 Malonate complexes of dysprosium: Synthesis, characterization and application for LI-MOCVD of dysprosium containing thin films
    Milanov, A.P. and Seidel, R.W. and Barreca, D. and Gasparotto, A. and Winter, M. and Feydt, J. and Irsen, S. and Becker, H.-W. and Devi, A.
    Dalton Transactions 40 62-78 (2011)
    A series of malonate complexes of dysprosium were synthesized as potential metalorganic precursors for Dy containing oxide thin films using chemical vapor deposition (CVD) related techniques. The steric bulkiness of the dialkylmalonato ligand employed was systematically varied and its influence on the resulting structural and physico-chemical properties that is relevant for MOCVD was studied. Single crystal X-ray diffraction analysis revealed that the five homoleptic tris-malonato Dy complexes (1-5) are dimers with distorted square-face bicapped trigonal-prismatic geometry and a coordination number of eight. In an attempt to decrease the nuclearity and increase the solubility of the complexes in various solvents, the focus was to react these dimeric complexes with Lewis bases such as 2,2′-biypridyl and pyridine (6-9). This resulted in monomeric tris-malonato mono Lewis base adduct complexes with improved thermal properties. Finally considering the ease of synthesis, the monomeric nature and promising thermal characteristics, the silymalonate adduct complex [Dy(dsml)3bipy] (8) was selected as single source precursor for growing DySixOy thin films by liquid injection metalorganic chemical vapor deposition (LI-MOCVD) process. The as-deposited films were analyzed for their morphology and composition by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, Rutherford backscattering (RBS) analysis and X-ray photoelectron spectroscopy. © 2011 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/c0dt00455c
  • 2011 • 84 Martensitic transformation in rapidly solidified Heusler Ni 49Mn39Sn12 ribbons
    Zheng, H. and Wu, D. and Xue, S. and Frenzel, J. and Eggeler, G. and Zhai, Q.
    Acta Materialia 59 5692-5699 (2011)
    In the present work, the microstructure evolution and kinetics of the martensitic transformation are investigated in as-spun and annealed ribbons of Heusler Ni49Mn39Sn12 using electron microscopy, X-ray diffraction and differential scanning calorimetry. Both ribbons undergo a reversible martensitic transformation during thermal cycling and the low-temperature martensite is confirmed to be a modulated four-layered orthorhombic (4O) structure through in situ cooling transmission electronic microscopy investigation. The annealing effect on the martensitic transformation behavior is discussed from the viewpoints of electron concentration, Mn-Mn interatomic distance, atomic order degree and grain size. A strong cooling-rate dependence of phase transition kinetics is found and the mechanism is analyzed. The satisfactory reproducibility obtained during thermal cycling test of this alloy ribbons offers great potential for practical applications. © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2011.05.044
  • 2011 • 83 MBE growth optimization of topological insulator Bi2Te 3 films
    Krumrain, J. and Mussler, G. and Borisova, S. and Stoica, T. and Plucinski, L. and Schneider, C.M. and Grützmacher, D.
    Journal of Crystal Growth 324 115-118 (2011)
    We investigated the growth of the topological insulator Bi 2Te3 on Si(1 1 1) substrates by means of molecular-beam epitaxy (MBE). The substrate temperature as well as the Bi and Te beam-equivalent pressure (BEP) was varied in a large range. The structure and morphology of the layers were studied using X-ray diffraction (XRD), X-ray reflectivity (XRR) and atomic force microscopy (AFM). The layer-by-layer growth mode with quintuple layer (QL) as an unit is accomplished on large plateaus if the MBE growth takes place in a Te overpressure. At carefully optimized MBE growth parameters, we obtained atomically smooth, single-crystal Bi 2Te3 with large area single QL covering about 75% of the layer surface. Angular-resolved photoelectron spectroscopy reveals a linear energy dispersion of charge carriers at the surface, evidencing topologically insulating properties of the Bi2Te3 epilayers. © 2011 Elsevier B.V.
    view abstractdoi: 10.1016/j.jcrysgro.2011.03.008
  • 2011 • 82 Methylated [(arene)(1,3-cyclohexadiene)Ru(0)] complexes as low-melting MOCVD precursor complexes with a controlled follow-up chemistry of the ligands
    Jipa, I. and Danova, K. and Popovska, N. and Siddiqi, M.A. and Siddiqui, R.A. and Atakan, B. and Cremer, T. and Maier, F. and Marbach, H. and Steinrück, H.-P. and Heinemann, F.W. and Zenneck, U.
    Journal of Materials Chemistry 21 3014-3024 (2011)
    [(Benzene)(2-methyl-1,3-cyclohexadiene)Ru(0)] (1), [(1,3-cyclohexadiene) (toluene)Ru(0)] (2), and [(methyl-cyclohexadiene)(toluene)Ru(0)] (3, mixture of isomers) have been prepared and tested as new metal organic ruthenium precursor complexes for chemical vapor deposition (MOCVD) with favorable properties. 1 is a low-melting precursor complex (mp = 29 °C) and the isomeric mixture 3 forms a liquid at room temperature. X-ray diffraction studies of single crystals of complexes 1 and 2 are characteristic for true Ru(0) π-complexes without molecular structure peculiarities or significant intermolecular interactions in the solid state, which could hinder undecomposed evaporation. Differential thermal analysis (DTA), differential scanning calorimetry (DSC) and vapor pressure data qualify the compounds as almost ideal MOCVD precursors. Thin ruthenium films have been deposited successfully on silicon wafers and substrate temperatures between 200 and 450 °C in inert gas atmospheres. Film growth and properties were evaluated by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and four-point probe conductivity measurements. All films consist of polycrystalline metallic ruthenium with a low surface roughness. © The Royal Society of Chemistry 2011.
    view abstractdoi: 10.1039/c0jm02652b
  • 2011 • 81 Methylated [(benzene)(1,3-butadiene)Ru0] derivatives as novel MOCVD precursors with favorable properties
    Jipa, I. and Siddiqi, M.A. and Siddiqui, R.A. and Atakan, B. and Marbach, H. and Cremer, T. and Maier, F. and Steinrück, H.-P. and Danova, K. and Popovska, N. and Heinemann, F.W. and Zenneck, U.
    Chemical Vapor Deposition 17 15-21 (2011)
    [(Benzene)(2-methyl-1,3-butadiene)Ru0] (1), [(benzene)(2,3- dimethyl-1,3-butadiene)Ru0] (2), and [(2,3-dimethyl-1,3-butadiene) (toluene)Ru0] (3) are prepared and tested as new metal-organic (MO) ruthenium precursor complexes with favorable deposition properties for the CVD of thin ruthenium films. X-ray diffraction (XRD) studies of single crystals of the complexes are characteristic for true Ru0 π-complexes without molecular structure peculiarities or significant intermolecular interactions in the solid state, which can hinder undecomposed evaporation. Differential thermal analysis (DTA) and vapor pressure data qualify the compounds as almost ideal MOCVD precursors. Thin ruthenium films are deposited successfully on silicon wafers at substrate temperatures between 200 and 400°C in a nitrogen gas atmosphere. X-ray photoelectron spectroscopy (XPS), four-point probe conductivity measurements, and atomic force microscopy (AFM) are used to characterize the films. All films consist of polycrystalline metallic ruthenium with a low surface roughness. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cvde.201006853
  • 2011 • 80 MOCVD of ZnO films from bis(ketoiminato)Zn(II) precursors: Structure, morphology and optical properties
    Bekermann, D. and Ludwig, Ar. and Toader, T. and MacCato, C. and Barreca, D. and Gasparotto, A. and Bock, C. and Wieck, A.D. and Kunze, U. and Tondello, E. and Fischer, R.A. and Devi, A.
    Chemical Vapor Deposition 17 155-161 (2011)
    Two closely related bis(ketoiminato) zinc precursors, which are air stable and possess favorable properties for metal-organic (MO)CVD, are successfully employed for the growth of ZnO films on silicon and borosilicate glass substrates at temperatures between 400 and 700 °C. The as-deposited films are investigated by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), nuclear reaction analysis (NRA), as well as by UV-vis absorption spectroscopy and photoluminescence (PL) measurements. The structure, morphology, and composition of the as-grown films show a strong dependence on the substrate temperature. The formation of pure and (001)-oriented wurtzite-type stoichiometric ZnO is observed. PL measurements are performed both at room temperature and 77 K, revealing a defect-free emission of ZnO films. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cvde.201006898
  • 2011 • 79 p-Co3O4/n-ZnO, Obtained by PECVD, Analyzed by X-ray Photoelectron Spectroscopy
    Bekermann, D. and Gasparotto, A. and Barreca, D. and Devi, A. and Fischer, R.A.
    Surface Science Spectra 18 36-45 (2011)
    The present work focuses on the X-ray Photoelectron Spectroscopy (XPS) and X-ray Excited Auger Electron Spectroscopy (XE-AES) of a Co3O4/ZnO nanosystem. The composite material was obtained via a two-step Plasma Enhanced-Chemical Vapor Deposition (PECVD) process in Ar/O2 mixtures, consisting in the initial deposition of ZnO and the subsequent growth of Co3O4 onto the pristine matrices. Zn(ketoimi)2 (ketoimi = [CH3O(CH2)3NC(CH3)=C(H)C(CH3)=O]) and Co(dpm)2 (dpm = 2,2,6,6-tetramethyl-3,5-heptanedionate) were used as zinc and cobalt precursors, respectively. In particular, strongly 〈001〉 oriented ZnO was grown at 300 °C, followed by the deposition of Co3O4 at 200 °C, applying a radio-frequency (RF) power of 20 W. Structural, morphological and compositional investigations were performed by Glancing Incidence X-ray Diffraction (GIXRD), Field Emission-Scanning Electron Microscopy (FE-SEM) and Energy Dispersive X-ray Spectroscopy (EDXS). Surface XPS and XE-AES analyses were carried out to study in detail the system O 1s, Zn 2p3/2, Zn 3p and Co 2p core levels, as well as the Zn and Co Auger peaks. The obtained results evidenced the formation of a composite material, in which ZnO and Co3O4 preserved their chemical identity. © 2011 American Vacuum Society.
    view abstractdoi: 10.1116/11.20111003
  • 2011 • 78 Phase transformation, structural and functional fatigue properties of Ti-Ni-Hf shape memory thin films
    König, D. and Zarnetta, R. and Savan, A. and Brunken, H. and Ludwig, Al.
    Acta Materialia 59 3267-3275 (2011)
    The shape memory thin film system Ti-Ni-Hf was investigated with regard to its structural, phase transformation and functional fatigue properties by means of combinatorial and high-throughput methods. Temperature-dependent resistance measurements revealed a broad compositional region showing a reversible phase transformation. A ternary Laves phase was identified using X-ray diffraction as a precipitate phase within the transforming composition region. With increasing Ti content, the amount of the Laves phase increases, which results in an increase in the thermal hysteresis and a simultaneous decrease in the transformation temperatures. Shape memory properties were characterized by temperature-dependent stress change measurements using micromachined Si cantilever array wafers coated with Ti-Ni-Hf. The recovery stress was found to increase for small amounts of Laves phase precipitates. Strengthening of the matrix due to the Laves phase precipitates is concluded to be responsible for the observed increase in recovery stress and improved functional fatigue properties for (Ti,Hf)-rich alloy compositions (Ti 40.0Ni 47.5Hf 12.5). © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2011.01.066
  • 2011 • 77 Photoluminescent zinc oxide polymer nanocomposites fabricated using picosecond laser ablation in an organic solvent
    Wagener, P. and Faramarzi, S. and Schwenke, A. and Rosenfeld, R. and Barcikowski, S.
    Applied Surface Science 257 7231-7237 (2011)
    Nanocomposites made of ZnO nanoparticles dispersed in thermoplastic polyurethane were synthesized using picosecond laser ablation of zinc in a polymer-doped solution of tetrahydrofuran. The pre-added polymer stabilizes the ZnO nanoparticles in situ during laser ablation by forming a polymer shell around the nanoparticles. This close-contact polymer shell has a layer thickness up to 30 nm. Analysis of ZnO polyurethane nanocomposites using optical spectroscopy, high resolution transmission electron microscopy and X-ray diffraction revealed that oxidized and crystalline ZnO nanoparticles were produced. Those nanocomposites showed a green photoluminescence emission centred at 538 nm after excitation at 350 nm, which should be attributed to oxygen defects generated during the laser formation mechanism of the monocrystalline nanoparticles. Further, the influence of pulse energy and polymer concentration on the production rate, laser fluence and energy-specific mass productivity was investigated. © 2011 Elsevier B.V.
    view abstractdoi: 10.1016/j.apsusc.2011.03.097
  • 2011 • 76 Physical metallurgy and properties of β-solidifying TiAl based alloys
    Clemens, H. and Schmoelzer, T. and Schloffer, M. and Schwaighofer, E. and Mayer, S. and Dehm, G.
    Materials Research Society Symposium Proceedings 1295 95-100 (2011)
    In this paper, the physical metallurgy and properties of a novel family of high-strength γ-TiAl-based alloys is reviewed succinctly. These so-called TNM™ alloys contain Nb and Mo additions in the range of 3-7 atomic percent as well as small additions of B and C. For the definition of the alloy composition thermodynamic calculations using the CALPHAD method were conducted. The predicted phase transformation and ordering temperatures were verified by differential scanning calorimetry and in situ high-energy X-ray diffraction. TNM alloys solidify via the β-phase and exhibit an adjustable β-phase volume fraction at temperatures, where hot-working processes are performed. Due to the high volume fraction of β-phase these alloys can be processed isothermally as well as under near conventional conditions. In order to study the occurring deformation and recrystallization processes during hot-working, in situ diffraction experiments were conducted during compression tests at elevated temperatures. With subsequent heat-treatments a significant reduction of the β-phase is achieved. These outstanding features of TNM alloys distinguish them from other TiAl alloys which must exclusively be processed under isothermal conditions and/or which always exhibit a high fraction of β-phase at service temperature. After hot-working and multi-step heat-treatments, these alloys show yield strength levels > 800 MPa at room temperature and also good creep resistance at elevated temperatures. © 2011 Materials Research Society.
    view abstractdoi: 10.1557/opl.2011.29
  • 2011 • 75 Picosecond acoustic response of a laser-heated gold-film studied with time-resolved x-ray diffraction
    Nicoul, M. and Shymanovich, U. and Tarasevitch, A. and Von Der Linde, D. and Sokolowski-Tinten, K.
    Applied Physics Letters 98 (2011)
    We apply time-resolved x-ray diffraction using ultrashort x-ray pulses from a laser-produced plasma to probe the picosecond acoustic response of a thin laser-heated gold film. Measurements of the temporal changes in the angular distribution of diffracted x-rays provide direct quantitative information on the transient evolution of lattice strain. This allows to disentangle electronic and thermal pressure contributions driving lattice expansion after impulsive laser excitation. The electron-lattice energy equilibration time τE = (5±0.3) ps as well as the electronic Grüneisen parameter γe = (1.48±0.3) have been determined. © 2011 American Institute of Physics.
    view abstractdoi: 10.1063/1.3584864
  • 2011 • 74 Plasma enhanced-CVD of undoped and fluorine-doped Co3O 4 nanosystems for novel gas sensors
    Barreca, D. and Bekermann, D. and Comini, E. and Devi, A. and Fischer, R.A. and Gasparotto, A. and Gavagnin, M. and MacCato, C. and Sada, C. and Sberveglieri, G. and Tondello, E.
    Sensors and Actuators, B: Chemical 160 79-86 (2011)
    Co3O4-based nanosystems were prepared on polycrystalline Al2O3 by plasma enhanced-chemical vapor deposition (PE-CVD), at temperatures ranging between 200 and 400 °C. The use of two different precursors, Co(dpm)2 (dpm = 2,2,6,6-tetramethyl-3, 5-heptanedionate) and Co(hfa)2·TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N′,N′- tetramethylethylenediamine) enabled the synthesis of undoped and fluorine-doped Co3O4 specimens, respectively. A thorough characterization of their properties was performed by glancing incidence X-ray diffraction (GIXRD), atomic force microscopy (AFM), field emission-scanning electron microscopy (FE-SEM), secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS). For the first time, the gas sensing properties of such PE-CVD nanosystems were investigated in the detection of ethanol and acetone. The results show an appreciable response improvement upon doping and functional performances directly dependent on the fluorine content in the Co3O4 system. © 2011 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.snb.2011.07.016
  • 2011 • 73 Prevention of catalyst deactivation in the hydrogenolysis of glycerol by Ga 2O 3-modified copper/zinc oxide catalysts
    Bienholz, A. and Blume, R. and Knop-Gericke, A. and Girgsdies, F. and Behrens, M. and Claus, P.
    Journal of Physical Chemistry C 115 999-1005 (2011)
    Copper/zinc oxide catalysts prepared by coprecipitation were proved to be highly active and selective in the hydrogenolysis of glycerol. However, they suffer from strong deactivation in the course of reaction. Modifying the CuO/ZnO catalyst with Ga 2O 3 extremely enhances the stability of the catalyst as even after four consecutive experiments over a Cu/ZnO/Ga 2O 3 catalyst no deactivation is observed. The catalysts were characterized by temperature-programmed reduction, powder X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy coupled with energy-dispersive X-ray analysis, and inductively coupled plasma optical emission spectrometry. As the Cu/ZnO/Ga 2O 3 catalyst is stable even under harsh reaction conditions of 220 °C and in the presence of water, a space-time-yield as high as 22.1 g propylene glycol/(g Cu h) can be obtained. © 2010 American Chemical Society.
    view abstractdoi: 10.1021/jp104925k
  • 2011 • 72 Reversible fcc ↔ bcc transformation in freestanding epitaxially grown Fe-Pd ferromagnetic shape memory films
    Edler, T. and Hamann, S. and Ludwig, Al. and Mayr, S.G.
    Scripta Materialia 64 89-92 (2011)
    Using temperature-dependent X-ray diffraction and magnetization measurements, a reversible face-centered cubic (fcc) to body-centered cubic (bcc) structural transformation was confirmed in freestanding epitaxially grown Fe70Pd30 films after lift-off from their MgO (1 0 0) substrates - a transformation generally considered irreversible in bulk samples. The latter is accompanied by a distinct change of the sample magnetization. In contrast, substrate constraints were found to suppress the thermoelastic fcc to bcc transformation in substrate-attached films. © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.scriptamat.2010.09.013
  • 2011 • 71 Structural and magnetic characterization of self-assembled iron oxide nanoparticle arrays
    Benitez, M.J. and Mishra, D. and Szary, P. and Badini Confalonieri, G.A. and Feyen, M. and Lu, A.H. and Agudo, L. and Eggeler, G. and Petracic, O. and Zabel, H.
    Journal of Physics Condensed Matter 23 (2011)
    We report about a combined structural and magnetometric characterization of self-assembled magnetic nanoparticle arrays. Monodisperse iron oxide nanoparticles with a diameter of 20nm were synthesized by thermal decomposition. The nanoparticle suspension was spin-coated on Si substrates to achieve self-organized arrays of particles and subsequently annealed at various conditions. The samples were characterized by x-ray diffraction, and bright and dark field high resolution transmission electron microscopy. The structural analysis is compared to magnetization measurements obtained by superconducting quantum interference device magnetometry. We can identify either multi-phase FexO/γ-Fe2O3 or multi-phase Fe xO/Fe3O4 nanoparticles. The Fe xO/γ-Fe2O3 system shows a pronounced exchange bias effect which explains the peculiar magnetization data found for this system. © 2011 IOP Publishing Ltd.
    view abstractdoi: 10.1088/0953-8984/23/12/126003
  • 2011 • 70 Structural characteristics and catalytic performance of alumina-supported nanosized ceria-lanthana solid solutions
    Katta, L. and Thrimurthulu, G. and Reddy, B.M. and Muhler, M. and Grünert, W.
    Catalysis Science and Technology 1 1645-1652 (2011)
    Alumina-supported nanosized ceria-lanthana solid solutions (CeO <inf>2</inf>-La<inf>2</inf>O<inf>3</inf>/Al<inf>2</inf>O<inf>3</inf> (CLA) = 80:20:100 mol% based on oxides) were synthesized by a modified deposition coprecipitation method from ultra-high dilute aqueous solutions. The synthesized materials were subjected to various calcination temperatures from 773 to 1073 K to understand the surface structure and the thermal stability. Structural and redox properties were deeply investigated by different characterization techniques, namely, X-ray diffraction (XRD), Raman spectroscopy (RS), transmission electron microscopy (TEM), UV-visible diffuse reflectance spectroscopy (UV-vis DRS), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction (H<inf>2</inf>-TPR), and Brunauer-Emmett-Teller (BET) surface area. The catalytic efficiency was evaluated for CO oxidation at normal atmospheric pressure. BET surface area measurements revealed that synthesized samples exhibit reasonably high specific surface area. As revealed by XRD measurements, samples maintain structural integrity up to 1073 K without any disproportionation of phases. XPS results suggested that there is no significant change in the Ce3+ amount during thermal treatments due to the absence of undesirable cerium aluminate formation. A significant number of oxygen vacancies were confirmed from Raman and UV-vis DRS measurements. The CLA 773 sample exhibited superior CO oxidation activity. The better activity of the catalyst was proved to be due to a high dispersion in the form of nanosized ceria-lanthana solid solutions over the alumina support, facile reduction, and a high oxygen storage capacity. © The Royal Society of Chemistry 2011.
    view abstractdoi: 10.1039/c1cy00312g
  • 2011 • 69 Structural characterization of Et4Sb2 and Et 4Bi2
    Kuczkowski, A. and Heimann, S. and Weber, A. and Schulz, S. and Bläser, D. and Wölper, C.
    Organometallics 30 4730-4735 (2011)
    The solid-state structures of Et4Sb2 (1) and Et 4Bi2 (2) were determined by single-crystal X-ray diffraction. Single crystals of 1 and 2 were grown in a closed quartz glass capillary under an inert argon atmosphere on the diffractometer using a specific IR-laser-assisted technique. 1 shows short intermolecular Sb••• Sb interactions, whereas the closest Bi•••Bi distances are longer than the sum of the van der Waals radii. © 2011 American Chemical Society.
    view abstractdoi: 10.1021/om2005723
  • 2011 • 68 Structural, ferroelectric and magnetic properties of Bi 0.85Sm0.15FeO3 perovskite
    Khomchenko, V.A. and Paixão, J.A. and Costa, B.F.O. and Karpinsky, D.V. and Kholkin, A.L. and Troyanchuk, I.O. and Shvartsman, V.V. and Borisov, P. and Kleemann, W.
    Crystal Research and Technology 46 238-242 (2011)
    Room temperature crystal structure, ferroelectric and magnetic properties of polycrystalline Bi0.85Sm0.15FeO3 samples were investigated. X-ray diffraction study shows that the compound possesses a dominant PbZrO3-like orthorhombic structure with √2a× 2√2a × √2a superlattice (a is the parameter of the cubic perovskite subcell). In contrast to piezoresponse force microscopy data demonstrating some features characteristic of ferroelectrics, polarization vs. electric field measurements reveal the behavior expected for nonpolar materials. Investigation of magnetic properties confirms that 15% samarium substitution suppresses the spin modulation typical of BiFeO3 and induces the appearance of spontaneous magnetization. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/crat.201100040
  • 2011 • 67 Structural, optical, and magnetic properties of Ho-implanted GaN thin films
    Lo, F.-Y. and Guo, J.-Y. and Ney, V. and Ney, A. and Chern, M.-Y. and Melnikov, A. and Pezzagna, S. and Reuter, D. and Wieck, A.D. and Massies, J.
    Journal of Physics: Conference Series 266 (2011)
    Ho ions were implanted into highly-resistive molecular-beam-epitaxy grown GaN thin films with a 100kV focused-ion-beam implanter at room temperature (RT). The implantation doses of Ho ions ranges from 1014 to 10 16 cm-2. Without thermal annealing, the structural, optical, and magnetic properties of the Ho-implanted thin films were investigated. Structural properties studied by x-ray diffraction revealed Ho incorporation into GaN matrix without secondary phase. The overall photoluminescence of any implanted sample is weaker than that of the non-implanted one. The spectra show neutral-donor-bound exciton emission and defect-related blue luminescence. Blocked superparamagnetic behavior was identified from Ho-implanted samples at temperatures below RT by measurements with a superconducting quantum interference device. The highest ordering temperature is 100 K. © Published under licence by IOP Publishing Ltd.
    view abstractdoi: 10.1088/1742-6596/266/1/012097
  • 2011 • 66 Structure and phase behavior of archaeal lipid monolayers
    Jeworrek, C. and Evers, F. and Erlkamp, M. and Grobelny, S. and Tolan, M. and Chong, P.L.-G. and Winter, R.
    Langmuir 27 13113-13121 (2011)
    We report X-ray reflectivity (XRR) and grazing incidence X-ray diffraction (GIXD) measurements of archaeal bipolar tetraether lipid monolayers at the air-water interface. Specifically, Langmuir films made of the polar lipid fraction E (PLFE) isolated from the thermoacidophilic archaeon Sulfolobus acidocaldarius grown at three different temperatures, i.e., 68, 76, and 81 °C, were examined. The dependence of the structure and packing properties of PLFE monolayers on surface pressure were analyzed in a temperature range between 10 and 50 °C at different pH values. Additionally, the interaction of PLFE monolayers (using lipids derived from cells grown at 76 °C) with the ion channel peptide gramicidin was investigated as a function of surface pressure. A total monolayer thickness of approximately 30 Å was found for all monolayers, hinting at a U-shaped conformation of the molecules with both head groups in contact with the interface. The monolayer thickness increased with rising film pressure and decreased with increasing temperature. At 10 and 20 °C, large, highly crystalline domains were observed by GIXD, whereas at higher temperatures no distinct crystallinity could be observed. For lipids derived from cells grown at higher temperatures, a slightly more rigid structure in the lipid dibiphytanyl chains was observed. A change in the pH of the subphase had an influence only on the structure of the lipid head groups. The addition of gramicidin to an PLFE monolayer led to a more disordered state as observed by XRR. In GIXD measurements, no major changes in lateral organization could be observed, except for a decrease of the size of crystalline domains, indicating that gramicidin resides mainly in the disordered areas of the monolayer and causes local membrane perturbation, only. © 2011 American Chemical Society.
    view abstractdoi: 10.1021/la202027s
  • 2011 • 65 Studies on synthesis and characterization of mo based in situ composite by silicothermy co-reduction process
    Paul, B. and Chakraborty, S.P. and Kishor, J. and Sharma, I.G. and Suri, A.K.
    Metallurgical and Materials Transactions B: Process Metallurgy and Materials Processing Science 42 700-710 (2011)
    The results of an in situ synthesis of refractory metal-intermetallic composite (RMIC), Mo-16Cr-4Si (wt pct) multiphase alloy and its characterization, are presented in this study. The alloy was prepared from the oxides of molybdenum and chromium by their co-reduction with Si metal powder as a reductant. The exothermic nature of these reactions resulted in the formation of consolidated composite as a product in a single step. The thermodynamic aspects of exothermic reactions were studied by thermogravimetry/differential thermal analyzer. As-reduced alloys were remelted by arc melting and heat treated to obtain a homogenous microstructure. The evolution of phases and microstructures qA studied by X-ray diffraction, scanning electron microscopy, and energy-dispersive spectrum analysis. The multiphase alloy consisted of Mo3Si and discontinuous (Mo, Cr) (ss) phase with a volume percentage of 28 pct. The synthesized alloys were characterized with respect to composition, phases, microstructure, hardness, and oxidation behavior. © The Minerals Metals & Materials Society and ASM International 2011.
    view abstractdoi: 10.1007/s11663-011-9513-6
  • 2011 • 64 Syntheses and X-ray crystal structures of organoantimony diazides
    Lyhs, B. and Bläser, D. and Wölper, C. and Schulz, S.
    Chemistry - A European Journal 17 4914-4920 (2011)
    Antimony(III) complexes of the general type LSbF2 (3: L 1=[tBuC(NiPr)2]; 4: L2=[tBuC(NDipp) 2], Dipp=2,6-iPr2C6H3) and LSb(N3)2 (6: L1; 7: L2) were prepared in high yields and characterized by elemental analyses, NMR and IR spectroscopy and single-crystal X-ray diffraction. Moreover, the solid-state structures of [L2SbF2][L2Li] (5), [L 2AlH2] (1), and [L′H][L′K(thf)3] (2; L′=HC(NDipp)2) are described, in which the Li (5) and K atoms (2) adopt rather unusual coordination modes. Upping the anti(mony): Antimony(III)bisazides LSb(N3)2 (L=amidinate; see figure) were synthesized by treating the corresponding fluorides LSbF2 with Me3SiN3. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201002730
  • 2011 • 63 Synthesis and magnetic properties of cobalt ferrite nanoparticles
    Etier, M.F. and Shvartsman, V.V. and Stromberg, F. and Landers, J. and Wende, H. and Lupascu, D.C.
    Materials Research Society Symposium Proceedings 1398 12-19 (2011)
    Nanopowders of cobalt iron oxide (CoFe2O4) were successfully fabricated by the co-precipitation method followed by a technique to prevent particle agglomeration. Particle sizes were in the range of 24 to 44 nm. The size of cobalt iron oxide particles decreases with increasing the concentration of the precipitation agent. The crystal structure was confirmed by X-ray diffraction (XRD), the chemical composition by energy dispersive spectroscopy (EDS), and phase changes by thermogravimetric differential thermal analysis (TGA-TDA). The particle morphology was analyzed by scanning electron microscopy (SEM). Magnetic properties were investigated by SQUID magnetometry and Mössbauer spectroscopy. Being nearly monodisperse and non-agglomerated the prepared cobalt iron oxide powders are the base for synthesizing magnetoelectric composites embedded in a ferroelectric BaTiO3 matrix. © 2012 Materials Research Society.
    view abstractdoi: 10.1557/opl.2012.699
  • 2011 • 62 Synthesis and structural characterization of antimony polyazides
    Lyhs, B. and Jansen, G. and Bläser, D. and Wölper, C. and Schulz, S.
    Chemistry - A European Journal 17 11394-11398 (2011)
    The synthesis of antimony polyazides and structural characterization of the pentaazidoantimonite [Sb(N3)5]2- dianion, which is without precedent in Group 15 polyazide chemistry, is reported (see scheme). © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201102224
  • 2011 • 61 Synthesis of active carbon-based catalysts by chemical vapor infiltration for nitrogen oxide conversion
    Busch, M. and Bergmann, U. and Sager, U. and Schmidt, W. and Schmidt, F. and Notthoff, C. and Atakan, B. and Winterer, M.
    Journal of Nanoscience and Nanotechnology 11 7956-7961 (2011)
    Direct reduction of nitrogen oxides is still a challenge. Strong efforts have been made in developing noble and transition metal catalysts on microporous support materials such as active carbons or zeolites. However, the required activation energy and low conversion rates still limit its break-through. Furthermore, infiltration of such microporous matrix materials is commonly performed by wet chemistry routes. Deep infiltration and homogeneous precursor distribution are often challenging due to precursor viscosity or electrostatic shielding and may be inhibited by pore clogging. Gas phase infiltration, as an alternative, can resolve viscosity issues and may contribute to homogeneous infiltration of precursors. In the present work new catalysts based on active carbon substrates were synthesized via chemical vapor infiltration. Iron oxide nano clusters were deposited in the microporous matrix material. Detailed investigation of produced catalysts included nitrogen oxide adsorption, X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Catalytic activity was studied in a recycle flow reactor by time-resolved mass spectrometry at a temperature of 423 K. The infiltrated active carbons showed very homogeneous deposition of iron oxide nano clusters in the range of below 12 to 19 nm, depending on the amount of infiltrated precursor. The specific surface area was not excessively reduced, nor was the pore size distribution changed compared to the original substrate. Catalytic nitrogen oxides conversion was detected at temperatures as low as 423 K. Copyright © 2011 American Scientific Publishers. All rights reserved.
    view abstractdoi: 10.1166/jnn.2011.5074
  • 2011 • 60 Synthesis of tailored WO3 and WOx (2.9 \< x \< 3) nanoparticles by adjusting the combustion conditions in a H2/O 2/Ar premixed flame reactor
    Gupta, A. and Ifeacho, P. and Schulz, C. and Wiggers, H.
    Proceedings of the Combustion Institute 33 1883-1890 (2011)
    Flame synthesis of WO3 and WOx (2.9 < x < 3) nanoparticles is carried out by adding a dilute concentration of WF6 as precursor in a low-pressure H2/O2/Ar premixed flame reactor. The reactor is equipped with molecular-beam sampling and particle mass spectroscopy (PMS) to determine particle composition and sizes as a function of height above burner. Varying the H2/O2 ratio allowed us to tune the stoichiometry of the product. With a H2/O2 ratio of 0.67 white colored stoichiometric WO3 is formed, whereas the H2/O2 ratio &gt;0.8 yields blue colored non-stoichiometric WOx (2.9 < x < 3) nanoparticles. The size of nanoparticles can be controlled by varying the residence time in the high-temperature zone of the reactor as observed by molecular-beam sampling with subsequent analysis using PMS. Transmission electron microscopy (TEM) images of as-synthesized nanoparticles show that particles are non-agglomerated and have an almost spherical morphology. The X-ray diffraction (XRD) pattern of the as-synthesized material indicates that the powders exhibit poor crystallinity, however, subsequent thermal annealing of the sample in air changes its structure from amorphous to crystalline phase. It is observed that particles with sub-stoichiometric composition (WOx) show higher conductivity compared to the stoichiometric WO3 sample. © 2010 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
    view abstractdoi: 10.1016/j.proci.2010.06.162
  • 2011 • 59 The effects of grain size on the phase transformation properties of annealed (Ti/Ni/W) shape memory alloy multilayers
    Buenconsejo, P.J.S. and Zarnetta, R. and Ludwig, Al.
    Scripta Materialia 64 1047-1050 (2011)
    (Ti/Ni/W) n multilayer films were annealed to form a two-phase (B2-TiNi and β-W) system. Grain sizes extracted from X-ray diffraction profiles of annealed films revealed that B2-TiNi decreases with increasing W, due to the immiscible W layers obstructing its grain growth. With decreasing B2-TiNi grain size the R s (B2-R) transformation temperature is not affected but the M s (R-B19′) transformation temperature decreases significantly. Thus the addition of W to Ti-Ni is effective to induce the B2-R single-step transformation due to grain size effects. © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.scriptamat.2011.02.021
  • 2011 • 58 The synthesis of Nb-doped TiO2 nanoparticles by spray drying: An efficient and scalable method
    Mei, B. and Sánchez, M.D. and Reinecke, T. and Kaluza, S. and Xia, W. and Muhler, M.
    Journal of Materials Chemistry 21 11781-11790 (2011)
    Nb-doped TiO2 nanoparticles were prepared by a continuous spray drying process using ammonium niobate (V) oxalate and titanium oxysulfate as water-soluble precursors. The structural and electronic properties were investigated using thermogravimetric analysis, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy. Nb was found to be mainly incorporated as Nb5+ into the TiO2 lattice resulting in a charge compensation by Ti vacancies. The characterization results indicate that Nb was homogeneously distributed within the titania lattice, and that the surface segregation of Nb, which is commonly observed for Nb-doped TiO 2, was significantly less pronounced. The high homogeneity and the lower extent of surface segregation originate from the efficient atomization of homogeneous precursor solutions and the fast evaporation of the solvent in the spray drying process. As a result, the ion mobility is diminished and spheres of well-mixed precursor materials are formed. Using the continuous spray drying process followed by a controlled heat treatment, the phase composition, the crystal size and the surface area of the Nb-doped TiO2 nanoparticles are easily adjustable. © The Royal Society of Chemistry 2011.
    view abstractdoi: 10.1039/c1jm11431j
  • 2011 • 57 Thermal stability of TiAIN/CrN multilayer coatings studied by atom probe tomography
    Choi, P.-P. and Povstugar, I. and Ahn, J.-P. and Kostka, A. and Raabe, D.
    Ultramicroscopy 111 518-523 (2011)
    This study is about the microstructural evolution of TiAlN/CrN multilayers (with a Ti:Al ratio of 0.75:0.25 and average bilayer period of 9 nm) upon thermal treatment. Pulsed laser atom probe analyses were performed in conjunction with transmission electron microscopy and X-ray diffraction. The layers are found to be thermally stable up to 600 °C. At 700 °C TiAlN layers begin to decompose into Ti- and Al-rich nitride layers in the out-of-plane direction. Further increase in temperature to 1000 °C leads to a strong decomposition of the multilayer structure as well as grain coarsening. Layer dissolution and grain coarsening appear to begin at the surface. Domains of AlN and TiCrN larger than 100 nm are found, together with smaller nano-sized AlN precipitates within the TiCrN matrix. Fe and V impurities are detected in the multilayers as well, which diffuse from the steel substrate into the coating along columnar grain boundaries. © 2010 Elsevier B.V.
    view abstractdoi: 10.1016/j.ultramic.2010.11.012
  • 2011 • 56 Thermally driven solid-phase epitaxy of laser-ablated amorphous AlFe films on (0001)-oriented sapphire single crystals
    Trautvetter, M. and Wiedwald, U. and Paul, H. and Minkow, A. and Ziemann, P.
    Applied Physics A: Materials Science and Processing 102 725-730 (2011)
    Solid-phase epitaxy is demonstrated for the metallic binary alloy AlFe. Stoichiometric thin films are deposited at ambient temperature onto c-cut sapphire by pulsed laser deposition (PLD), resulting in smooth amorphous films as revealed by X-ray diffraction (XRD) and atomic force microscopy (AFM). By annealing at 600°C, still smooth epitaxial AlFe films are obtained exhibiting the B2 phase with the (110) direction parallel to the substrate normal and an in-plane orientation as given by AlFe[001]||Al2O 3[112̄0]. While ferromagnetism is observed for the amorphous phase, the formation of the B2 structure is accompanied by paramagnetic behavior, confirming the high structural quality. © Springer-Verlag 2010.
    view abstractdoi: 10.1007/s00339-010-5972-x
  • 2011 • 55 Thin tantalum films on crystalline silicon - a metallic glass
    Stella, K. and Bürstel, D. and Hasselbrink, E. and Diesing, D.
    Physica Status Solidi - Rapid Research Letters 5 68-70 (2011)
    Thin amorphous tantalum films are prepared on Si(111) substrates in a metallic glassy state. The amorphous monoatomic state of the film is characterized by X-ray diffraction studies. The glassy state leads to a negative temperature coefficient of the resistivity (TCR) for low sample temperatures < 200 K which is attributed to incipient localization. Above 200 K a positive TCR is observed as expected for a normal Boltzmann transport regime. Upon heating the Si substrate to 1200 K TaSi2 is formed out of the amorphous tantalum film and the silicon substrate. The TaSi2 layer is crystalline as evident from X-ray diffraction data. Schematic drawing of the evaporation setup on either glass or silicon samples. Scheme of annealing effects. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/pssr.201004510
  • 2011 • 54 TiO 2 coating of high surface area silica gel by chemical vapor deposition of TiCl 4 in a fluidized-bed reactor
    Xia, W. and Mei, B. and Sánchez, M.D. and Strunk, J. and Muhler, M.
    Journal of Nanoscience and Nanotechnology 11 8152-8157 (2011)
    TiO 2 was deposited on high surface area porous silica gel (400 m 2g -1) in a fluidized bed reactor. Chemical vapor deposition was employed for the coating under vacuum conditions with TiCl 4 as precursor. Nitrogen physisorption, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and UV-vis spectroscopy were applied to characterize the obtained TiO 2-SiO 2 composites with different Ti loadings up to 5 wt%. Only a slight decrease in the specific surface area was detected at low Ti loadings. At a Ti loading of 2 wt%, TiO 2 was found to be highly dispersed on the SiO 2 surface likely in form of a thin film. At higher Ti loadings, two weak reflections corresponding to anatase TiO 2 were observed in the diffraction patterns indicating the presence of crystalline bulk TiO 2. High resolution XPS clearly distinguished two types of Ti species, i.e., Ti-O-Si at the interface and Ti-O-Ti in bulk TiO 2. The presence of polymeric TiOx species at low Ti loadings was confirmed by a blue shift in the UV-vis spectra as compared to bulk TiO 2. All these results point to a strong interaction between the TiO 2 deposit and the porous SiO 2 substrate especially at low Ti loadings. Copyright © 2011 American Scientific Publishers All rights reserved.
    view abstractdoi: 10.1166/jnn.2011.5107
  • 2010 • 53 A review of crystallographic textures in chemical vapor-deposited diamond films
    Liu, T. and Raabe, D. and Mao, W.-M.
    Signal, Image and Video Processing 4 1-16 (2010)
    Diamond is one of the most important functional materials for film applications due to its extreme physical and mechanical properties, many of which depend on the crystallographic texture. The influence of various deposition parameters matters to the texture formation and evolution during chemical vapor deposition (CVD) of diamond films. In this overview, the texture evolutions are presented in terms of both simulations and experimental observations. The crystallographic textures in diamond are simulated based on the van der Drift growth selection mechanism. The film morphology and textures associated with the growth parameters α (proportional to the ratio of the growth rate along the 〈100〉 direction to that along the 〈111〉 direction) are presented and determined by applying the fastest growth directions. Thick films with variations in substrate temperature, methane concentration, film thickness, and nitrogen addition were analyzed using high-resolution electron back-scattering diffraction (HR-EBSD) as well as X-ray diffraction (XRD), and the fraction variations of fiber textures with these deposition parameters were explained. In conjunction with the focused ion beam (FIB) technique for specimen preparation, the grain orientations in the beginning nucleation zones were studied using HR-EBSD (50 nm step size) in another two sets of thin films deposited with variations in methane concentration and substrate material. The microstructures, textures, and grain boundary character were characterized. Based on the combination of an FIB unit for serial sectioning and HR-EBSD, diamond growth dynamics was observed using a 3D EBSD technique, with which individual diamond grains were investigated in 3D. Microscopic defects were observed in the vicinity of the high-angle grain boundaries by using the transmission electron microscopy (TEM) technique, and the advances of TEM orientation microscopy make it possible to identify the grain orientations in nano-crystalline diamond. © 2010 Higher Education Press and Springer Berlin Heidelberg.
    view abstractdoi: 10.1007/s11760-008-0099-7
  • 2010 • 52 Alkene epoxidation with mesoporous materials assembled from TS-1 seeds - Is there a hierarchical pore system?
    Reichinger, M. and Schmidt, W. and Berg, M.W.E.v.d. and Aerts, A. and Martens, J.A. and Kirschhock, C.E.A. and Gies, H. and Grünert, W.
    Journal of Catalysis 269 367-375 (2010)
    Hexagonal mesoporous solids were synthesized from solutions containing TS-1 seeds. The products were characterized by XRD, nitrogen and argon physisorption, TEM, TG/DTA of template decomposition (also after extraction of the mesopore template), UV-Vis and IR spectroscopy, and XANES at the TiK edge. Their catalytic activities were assessed for cyclohexene epoxidation in hydrophilic and hydrophobic environment (CH3OH/water, with H2O2 oxidant, and decane, with tert-butyl hydro-peroxide oxidant, respectively) and for n-hexene epoxidation in hydrophilic environment. The mesopore system was clearly documented by XRD, physisorption measurements, and TEM, whereas evidence for micropores by physisorption proved elusive. However, the micropore template was detected in the solids by TG/DTA even after extraction of the mesopore template, and among the Ti sites, which were confirmed to be tetrahedrally coordinated by UV-Vis and XANES, a clear majority was able to coordinate two water molecules. It was concluded that the pore walls had been built up from nanoparticulate TS-1 precursors resulting in walls of ca. 1.5 nm thickness, which resemble rather the exterior layers of a TS-1 crystallite than its (hydrophobic) interior. In cyclohexene epoxidation, the micro-mesophases were by 1-2 orders of magnitude more active than TS-1 and outperformed also Ti-MCM-41, at similar selectivity in hydrophobic medium. With 1-hexene in hydrophilic medium, however, the micro-mesophases failed completely whereas TS-1 exhibited high activity. © 2009 Elsevier Inc. All rights reserved.
    view abstractdoi: 10.1016/j.jcat.2009.11.023
  • 2010 • 51 Artificial single variant martensite in freestanding Fe70Pd 30 films obtained by coherent epitaxial growth
    Bechtold, C. and Buschbeck, J. and Lotnyk, A. and Erkartal, B. and Hamann, S. and Zamponi, C. and Schultz, L. and Ludwig, Al. and Kienle, L. and Fähler, S. and Quandt, E.
    Advanced Materials 22 2668-2671 (2010)
    (Figure Presented) The mechanically soft behavior of the magnetic shape-memory material Fe70Pd30 allows huge tetragonal distortions to be stabilized in sputtered thin films by coherent epitaxial growth on various metallic buffers. Furthermore, it is demonstrated that epitaxial films more than 1 μm thick can be grown, which makes possible freestanding films in an artificial single variant state suitable for microactuators and sensors. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA.
    view abstractdoi: 10.1002/adma.201000599
  • 2010 • 50 Biomimetic formation of thin, coherent iron oxide films under Langmuir monolayers
    Maas, M. and Degen, P. and Rehage, H. and Nebel, H. and Epple, M.
    Colloids and Surfaces A: Physicochemical and Engineering Aspects 354 149-155 (2010)
    This study focuses on the biomimetic formation and growth of thin iron oxide films under Langmuir monolayers. These coherent film structures were formed in the presence of different iron chloride solutions during the addition of an ammonia atmosphere. Stearic acid, stearyl amine and stearyl alcohol were used as film forming surfactants while the subphase contained FeCl2, FeCl3 or a mixture of both salts. The thin, coherent films consisted of X-ray amorphous iron oxide, hydroxide or oxyhydroxide. The films were studied by scanning electron microscopy, atomic force microscopy, X-ray diffraction, dynamic light scattering and surface potential measurements. Based on the experimental results we propose a growth mechanism that is guided by the formation of nanoparticles in the subphase and their assembly and aggregation underneath the Langmuir films. © 2009 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.colsurfa.2009.04.049
  • 2010 • 49 Correlation of phase transformations and magnetic properties in annealed epitaxial Fe-Pd magnetic shape memory alloy films
    Buschbeck, J. and Hamann, S. and Ludwig, Al. and Holzapfel, B. and Schultz, L. and Fähler, S.
    Journal of Applied Physics 107 (2010)
    Single-crystal-like films are promising candidates for magnetic shape memory (MSM) applications on the microscale. For defect reduction and stress relaxation, we apply a heat treatment to pulsed laser deposited, partial epitaxial Fe-Pd films with different compositions. By recrystallization starting from the epitaxial interface, single-crystal-like films are obtained. Deformation twins being present in the as-deposited state are completely eliminated. The epitaxial (100) orientation allows clear monitoring of the transformation from face centered cubic (fcc) austenite to face centered tetragonal (fct) martensite by x-ray diffraction experiments. Transformation from fcc austenite to fct martensite is hindered by constraints from the substrate. At temperatures down to 125 K residual fcc austenite is present. Magnetic measurements performed down to 50 K indicate that during further cooling the phase transformation to body centered tetragonal martensite occurs. The results show that annealing of laser deposited films is a promising route to obtain epitaxial Fe-Pd MSM films that are suitable for applications. © 2010 American Institute of Physics.
    view abstractdoi: 10.1063/1.3383055
  • 2010 • 48 Development and characterization of Fe70Pd30 ferromagnetic shape memory splats
    Kock, I. and Hamann, S. and Brunken, H. and Edler, T. and Mayr, S.G. and Ludwig, Al.
    Intermetallics 18 877-882 (2010)
    Freestanding Fe70Pd30 foils with a thickness of about 60 μm were fabricated using the splat-quenching technique. A shift of the martensitic transformation temperatures as a function of different annealing treatments (600 °C, 700 °C, 800 °C, 900 °C, 1000 °C for 15 min) was observed by temperature-dependent X-ray diffraction (XRD), resistance and magnetization measurements. The sample annealed at 800 °C showed the highest degree of crystallinity for the (200) fcc austenite peak and no secondary phases. Samples annealed below 800 °C kept austenite remainders even at -25 °C. The transformation temperatures, determined by all three-measurement methods, showed an increase with increasing annealing temperature. © 2009 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.intermet.2009.12.019
  • 2010 • 47 Direct synthesis of pure complex aluminium hydrides by cryomilling
    Pommerin, A. and Weidenthaler, C. and Schüth, F. and Felderhoff, M.
    Scripta Materialia 62 576-578 (2010)
    Simple mechanochemical procedures can be used for the solid-state preparation of stable complex aluminium hydrides as hydrogen storage materials. For the synthesis of unstable complex hydrides, cryomilling at temperatures at which product decomposition does not take place under milling conditions appears to be a viable method. To probe the potential of cryomilling for the synthesis of complex aluminium hydrides, the reactions of different alkaline hydrides with AlH3 were tested under these conditions. © 2009 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.scriptamat.2009.12.041
  • 2010 • 46 Effect of strain hardening on texture development in cold rolled Al-Mg alloy
    Liu, W.C. and Man, C.-S. and Raabe, D.
    Materials Science and Engineering A 527 1249-1254 (2010)
    The hot band of a continuous cast Al-Mg alloy possesses a typical deformed structure and a strong β fiber rolling texture. The hot band was heat-treated at 260 °C for 3 h to generate different degrees of strain hardening. The hot band and its counterpart after recovery treatment were cold rolled to different reductions along the original transverse direction. The effect of strain hardening on texture evolution was investigated by X-ray diffraction. The results show that a high degree of strain hardening reduces the formation rate of the β fiber rolling texture. © 2009 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.msea.2009.09.059
  • 2010 • 45 Effects of annealing on properties of ZnO thin films prepared by electrochemical deposition in chloride medium
    Lupan, O. and Pauporté, T. and Chow, L. and Viana, B. and Pellé, F. and Ono, L.K. and Roldan Cuenya, B. and Heinrich, H.
    Applied Surface Science 256 1895-1907 (2010)
    The development of cost-effective and low-temperature synthesis techniques for the growth of high-quality zinc oxide thin films is paramount for fabrication of ZnO-based optoelectronic devices, especially ultraviolet (UV)-light-emitting diodes, lasers and detectors. We demonstrate that the properties, especially UV emission, observed at room temperature, of electrodeposited ZnO thin films from chloride medium (at 70 °C) on fluor-doped tin oxide (FTO) substrates is strongly influenced by the post-growth thermal annealing treatments. X-ray diffraction (XRD) measurements show that the films have preferably grown along (0 0 2) direction. Thermal annealing in the temperature range of 150-400 °C in air has been carried out for these ZnO thin films. The as-grown films contain chlorine which is partially removed after annealing at 400 °C. Morphological changes upon annealing are discussed in the light of compositional changes observed in the ZnO crystals that constitute the film. The optical quality of ZnO thin films was improved after post-deposition thermal treatment at 150 °C and 400 °C in our experiments due to the reducing of defects levels and of chlorine content. The transmission and absorption spectra become steeper and the optical bandgap red shifted to the single-crystal value. These findings demonstrate that electrodeposition have potential for the growth of high-quality ZnO thin films with reduced defects for device applications. © 2009 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.apsusc.2009.10.032
  • 2010 • 44 Effects of annealing on the microstructure and the mechanical properties of EB-PVD thermal barrier coatings
    Zotov, N. and Bartsch, M. and Chernova, L. and Schmidt, D.A. and Havenith, M. and Eggeler, G.
    Surface and Coatings Technology 205 452-464 (2010)
    The effects of thermal annealing at 1000°C in air on the microstructure and the mechanical properties (Young's modulus and hardness) of thermal barrier coatings consisting of a 4mol% Y2O3 partially stabilized ZrO2 top coat and a NiCoCrAlY bond coat, deposited by electron beam physical vapour deposition on nickel-based superalloy IN 625, have been investigated using X-ray diffraction, Raman spectroscopy, scanning electron microscopy (SEM), image analysis and nanoindentation. During annealing, the ceramic top coat undergoes sintering and recrystallization. These processes lead to stress relaxation, an increase of the intra-columnar porosity and the number of large pores as measured by image analysis of SEM micrographs. An increase of the grain size of the γ-phase in the bond coat, accompanied by changes in the morphology of γ-grains with annealing time, is also observed. Correlations between these microstructural changes in the top coat and the bond coat and their mechanical properties are established and discussed. © 2010 Elsevier B.V.
    view abstractdoi: 10.1016/j.surfcoat.2010.07.008
  • 2010 • 43 Effects of annealing time on the structural and magnetic properties of L10 FePt thin films
    Zotov, N. and Hiergeist, R. and Savan, A. and Ludwig, Al.
    Thin Solid Films 518 4977-4985 (2010)
    Thermal annealing of [Fe 1.65 nm/Pt 1.84 nm]50 multilayers at 673 K for various annealing times between 60 and 12000 s leads to the direct formation of the fully ordered L10 FePt phase with (111) texture. The average grain sizes, determined from X-ray diffraction size-strain analysis, are smaller than the critical size for multi-domain FePt particles, suggesting the presence of single-domain (SD) grains. The coercivity increases with annealing time and increasing grain size and reaches values of about 955 kA/m. The remanence values are typical for randomly oriented weakly-interacting particles. A decrease of the remanence with annealing time suggests a decrease of the intergrain exchange interactions with annealing time. Analysis of minor loops and the initial magnetization curves shows the presence of a broad distribution of critical fields, which the individual SD particles have to overcome for the magnetization reversal. © 2010 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.tsf.2010.03.076
  • 2010 • 42 Effects of focused ion beam milling and pre-straining on the microstructure of directionally solidified molybdenum pillars: A Laue diffraction analysis
    Zimmermann, J. and Van Petegem, S. and Bei, H. and Grolimund, D. and George, E.P. and Van Swygenhoven, H.
    Scripta Materialia 62 746-749 (2010)
    White beam Laue micro-diffraction was performed on directionally solidified, single-crystal Mo pillars in the as-grown state, after focused ion beam (FIB) milling and after pre-straining. The Laue diffraction peaks from the as-grown pillars are very sharp and show no broadening, similar to those from single-crystal Si wafers. Significant broadening and streaking of the peaks occurred after FIB milling and pre-straining, indicative of the damage these treatments induce in the nearly perfect crystal structure of the directionally solidified Mo pillars. © 2010 Acta Materialia Inc.
    view abstractdoi: 10.1016/j.scriptamat.2010.02.013
  • 2010 • 41 Epitaxially stabilized TiN/(Ti,Fe,Co)N multilayer thin films in (pseudo-)fcc crystal structure by sequential magnetron sputter deposition
    Klever, C. and Seemann, K. and Stüber, M. and Ulrich, S. and Brunken, H. and Ludwig, Al. and Leiste, H.
    Journal of Physics D: Applied Physics 43 (2010)
    Multilayer thin films were grown by non-reactive sequential magnetron sputter deposition from ceramic TiN and metallic FeCo targets addressing a combination of wear resistance and sensoric functionality. Coatings with bilayer period values ranging from 449 nm down to 2.6 nm were grown with the total amount of either material maintained constant. The multilayer thin films were post-annealed ex situ at 600 °C for 60 min in vacuum. X-ray diffraction results imply the multilayer thin films undergo significant changes in their crystalline structure when the bilayer period is decreased. Using high-resolution transmission electron microscopy as well as selected-area electron diffraction it is shown that in the case of multilayer thin films with bilayer periods of several tens of nanometres and higher, FeCo layers and TiN layers in their respective common CsCl-and NaCl-type crystal structures alternate. In contrast, in the multilayer thin films with bilayer periods of only a few nanometres, grain growth across the interfaces between the individual layers takes place and a strongly textured microstructure is formed which features columns in (pseudo-)fcc crystal structure grown in heteroepitaxial growth mode. It is suggested that the experimental findings imply the latter multilayer thin films to be alternately composed of TiN layers and (Ti,Fe,Co)N solid solution layers which have been formed by a solid-state reaction during the deposition process. As a consequence, heteroepitaxially stabilized columnar grains in strongly textured (pseudo-)fcc crystal structure are formed. This crystal structure is preserved after the annealing procedure which qualifies these coatings for use in applications where temperatures of up to 600 °C are reached. © 2010 IOP Publishing Ltd.
    view abstractdoi: 10.1088/0022-3727/43/39/395406
  • 2010 • 40 Experimental and computer simulation determination of the structural changes occurring through the liquid-glass transition in Cu-Zr alloys
    Mendelev, M.I. and Kramer, M.J. and Ott, R.T. and Sordelet, D.J. and Besser, M.F. and Kreyssig, A. and Goldman, A.I. and Wessels, V. and Sahu, K.K. and Kelton, K.F. and Hyers, R.W. and Canepari, S. and Rogers, J.R.
    Philosophical Magazine 90 3795-3815 (2010)
    Molecular dynamics (MD) simulations were performed of the structural changes occurring through the liquid-glass transition in Cu-Zr alloys. The total scattering functions (TSF), and their associated primary diffuse scattering peak positions (Kp), heights (Kh) and full-widths at half maximum (KFWHM) were used as metrics to compare the simulations to high-energy X-ray scattering data. The residuals of difference between the model and experimental TSFs are ∼0.03 for the liquids and about 0.07 for the glasses. Over the compositional range studied, Zr1-xCux (0.1 ≤ x ≤ 0.9), Kp, Kh and KFWHM show a strong dependence on composition and temperature. The simulation and experimental data correlate well between each other. MD simulation revealed that the Cu-Zr bonds undergo the largest changes during cooling of the liquid, whereas the Cu-Cu bonds change the least. Changes in the partial-pair correlations are more readily seen in the second and third shells. The Voronoi polyhedra (VP) in glasses are dominated by only a few select types that are compositionally dependent. The relative concentrations of the dominant VPs rapidly change in their relative proportion in the deeply undercooled liquid. The experimentally determined region of best glass formability, xCu 65%, shows the largest temperature dependent changes for the deeply undercooled liquid in the MD simulation. This region also exhibits very strong temperature dependence for the diffusivity and the total energy of the system. These data point to a strong topological change in the best glass-forming alloys and a concurrent change in the VP chemistry in the deeply undercooled liquid. © 2010 Taylor &amp; Francis.
    view abstractdoi: 10.1080/14786435.2010.494585
  • 2010 • 39 Formation, stability and crystal structure of the r phase in Mo-Re-Si alloys
    Bei, H. and Yang, Y. and Viswanathan, G.B. and Rawn, C.J. and George, E.P. and Tiley, J. and Chang, Y.A.
    Acta Materialia 58 6027-6034 (2010)
    The formation, stability and crystal structure of the σ phase in Mo-Re-Si alloys were investigated. Guided by thermodynamic calculations, six critically selected alloys were arc melted and annealed at 1600 °C for 150 h. Their as-cast and annealed microstructures, including phase fractions and distributions, the compositions of the constituent phases and the crystal structure of the r phase were analyzed by thermodynamic modeling coupled with experimental characterization by scanning electron microscopy, electron probe microanalysis, X-ray diffraction and transmission electron microscopy. Two key findings resulted from this work. One is the large homogeneity range of the r phase region, extending from binary Mo-Re to ternary Mo-Re-Si. The other is the formation of a r phase in Mo-rich alloys either through the peritectic reaction of liquid + Moss → σ or primary solidification. These findings are important in understanding the effects of Re on the microstructure and providing guidance on the design of Mo-Re-Si alloys. © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actamat.2010.07.020
  • 2010 • 38 Growth and characterization of ti-ta-o thin films on si substrates by liquid injection MOCVD for high-k applications from modified titanium and tantalum precursors
    Devi, A. and Hellwig, M. and Barreca, D. and Parala, H. and Thomas, R. and Becker, H.-W. and Katiyar, R.S. and Fischer, R.A. and Tondello, E.
    Chemical Vapor Deposition 16 157-165 (2010)
    Titanium oxide (TiO2) and titanium-tantalum oxide (Ti-Ta-O) thin films are deposited by liquid injection (LI) metal-organic (MO) CVD using metal amide-malonate complexes, [Ti(NR2)2 (dbml) 2], and tantalum, [Ta(NMe2)2 (dbml)] (R Me, Et; dbml di-tert-butylmalonato). TiO2 and Ti-Ta-O films are deposited on Si(100) in the temperature ranges 350-650°C and 500-700°C, respectively. The structure, morphology, and chemical composition of the films are evaluated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), Rutherford backscattering spectroscopy (RBS), and X-ray photoelectron spectroscopy (XPS). The electrical properties of the films, namely the dielectric properties, are assessed by carrying out capacitance-voltage (C-V) measurements on metal-oxide-semiconductor (MOS) capacitor structures.
    view abstractdoi: 10.1002/cvde.200906813
  • 2010 • 37 Growth of crystalline Gd2O3 thin films with a high-quality interface on Si(100) by low-temperature H2O-assisted atomic layer deposition
    Milanov, A.P. and Xu, K. and Laha, A. and Bugiel, E. and Ranjith, R. and Schwendt, D. and Osten, H.J. and Parala, H. and Fischer, R.A. and Devi, A.
    Journal of the American Chemical Society 132 36-37 (2010)
    (Figure Presented) This work documents the first example of deposition of high-quality Gd2O3 thin films in a surface-controlled, self-limiting manner by a water-based atomic layer deposition (ALD) process using the engineered homoleptic gadolinium guanidinate precursor [Gd(DPDMG) 3]. The potential of this class of compound is demonstrated in terms of a true ALD process, exhibiting pronounced growth rates, a high-quality interface between the film and the substrate without the need for any additional surface treatment prior to the film deposition, and most importantly, encouraging electrical properties. © 2010 American Chemical Society.
    view abstractdoi: 10.1021/ja909102j
  • 2010 • 36 High-pressure SAXS study of folded and unfolded ensembles of proteins
    Schroer, M.A. and Paulus, M. and Jeworrek, C. and Krywka, C. and Schmacke, S. and Zhai, Y. and Wieland, D.C.F. and Sahle, C.J. and Chimenti, M. and Royer, C.A. and Garcia-Moreno, B. and Tolan, M. and Winter, R.
    Biophysical Journal 99 3430-3437 (2010)
    A structural interpretation of the thermodynamic stability of proteins requires an understanding of the structural properties of the unfolded state. High-pressure small-angle x-ray scattering was used to measure the effects of temperature, pressure, denaturants, and stabilizing osmolytes on the radii of gyration of folded and unfolded state ensembles of staphylococcal nuclease. A set of variants with the internal Val-66 replaced with Ala, Tyr, or Arg was used to examine how changes in the volume and polarity of an internal microcavity affect the dimensions of the native state and the pressure sensitivity of the ensemble. The unfolded state ensembles achieved for these proteins with high pressure were more compact than those achieved at high temperature, and were all very sensitive to the presence of urea and glycerol. Substitutions at the hydrophobic core detectably altered the conformation of the protein, even in the folded state. The introduction of a charged residue, such as Arg, inside the hydrophobic interior of a protein could dramatically alter the structural properties, even those of the unfolded state. The data suggest that a charge at an internal position can interfere with the formation of transient hydrophobic clusters in the unfolded state, and ensure that the pressure-unfolded form of a protein occupies the maximum volume possible. Only at high temperatures does the radius of gyration of the unfolded state ensemble approach the value for a statistical random coil. © 2010 by the Biophysical Society.
    view abstractdoi: 10.1016/j.bpj.2010.09.046
  • 2010 • 35 Identification of magnetic properties of few nm sized FePt crystalline particles by characterizing the intrinsic atom order using aberration corrected S/TEM
    Biskupek, J. and Jinschek, J.R. and Wiedwald, U. and Bendele, M. and Han, L. and Ziemann, P. and Kaiser, U.
    Ultramicroscopy 110 820-825 (2010)
    Hard-magnetic nanomaterials like nanoparticles of FePt are of great interest because of their promising potential for data storage applications. The magnetic properties of FePt structures strongly differ whether the crystal phases are face centered cubic (fcc) or face centered tetragonal (fct). We evaluated aberration corrected HRTEM, electron diffraction and aberration corrected HAADF-STEM as methods to measure the chemical degree of order S that describes the ordering of Pt and Fe atoms within the crystals unit cells. S/TEM experiments are accompanied by image calculations. The findings are compared with results obtained from X-ray diffraction on a FePt film. Our results show that STEM is a reasonable fast approach over HRTEM and electron diffraction to locally determine the chemical degree of order S. © 2010 Elsevier B.V.
    view abstractdoi: 10.1016/j.ultramic.2010.02.043
  • 2010 • 34 In situ study of the polar ZnO(0001)-Zn surface in alkaline electrolytes
    Valtiner, M. and Torrelles, X. and Pareek, A. and Borodin, S. and Gies, H. and Grundmeier, G.
    Journal of Physical Chemistry C 114 15440-15447 (2010)
    We discuss how kinetic effects can be utilized to prepare polar ZnO(0001)-Zn surfaces as very well defined and single-crystalline surfaces by hydroxide stabilization of the polar face via a wet chemical etching process in 3N NaOH. An in situ AFM imaging study of the etching process is presented. In addition, measurement and analyses of grazing incidence X-ray diffraction experiments, reflectivity, and crystal truncation rods (CTRs) of the resulting ZnO(0001) surface structures in both dry and humid atmospheres are discussed. Analysis of the CTRs shows that these surfaces are topographically extremely flat, Zn-terminated, but covered with a defect-containing hydroxide/oxygen adlayer, which is adsorbed at hcp-hollow sites. This result is fully consistent with a stabilization of the polar surface by means of an adlayer of disordered hydroxides, which is adsorbed at hcp positions. Moreover, these studies indicate that the water structure at the solid/liquid interface is ordered within the first few layers, but no evidence for an "icelike" structure was found. Also, the pH-dependent stability of these hydroxide-stabilized ZnO(0001) surfaces within electrolyte solutions was investigated by means of an ex situ LEED approach. Hydroxides effectively stabilize the (0001) surface within a wide range of pH values between 11 and 4. In acidic solutions below pH 3.8, the formation of deep hexagonal etching pits is observed, whereas a crystalline structure with triangular reconstructions evolves between these etching pits. The origin of the hexagonal etching pits is discussed as a result of faster dissolution kinetics at dislocation sites. © 2010 American Chemical Society.
    view abstractdoi: 10.1021/jp1047024
  • 2010 • 33 Influence of the ball milling conditions on the preparation of rare earth aluminum hydrides
    Pommerin, A. and Felderhoff, M. and Schüth, F. and Weidenthaler, C.
    Scripta Materialia 63 1128-1131 (2010)
    The ball milling conditions in the preparation of rare earth aluminum hydrides from NaAlH4 and rare earth chlorides have a significant influence on product formation. Defined milling times and appropriate rotational speeds are required to obtain the desired products. It has been shown that starting directly from Na3AlH6 does not lead to the formation of REAlH6. Starting from rare earth iodides instead of chlorides allows dissolution of the alkali metal iodide formed and, therewith, the preparation of salt-free rare earth aluminum hydrides. © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.scriptamat.2010.08.020
  • 2010 • 32 Influence on diamonds during the spraying of diamond-bronze abrasive coatings
    Tillmann, W. and Vogli, E. and Nebel, J. and Buck, V. and Reuter, S.
    Journal of Thermal Spray Technology 19 350-357 (2010)
    Detonation spraying provides the opportunity to produce diamond grinding tools for the machining of stone, cement, and concrete. Especially the atmospheric conditions of the spraying process yield in a high production flexibility. However, during detonation spraying, the oxygenic atmosphere as well as the thermal and kinetic energy have an impact on the processed diamond. Despite its importance for the tools' performance, the influence of the spraying process on the superabrasive diamond is predominantly unknown. The potential decrease of the diamond durability and strength due to degradation effects during the production of sprayed diamond-CuSn 85/15 composites has not yet been determined. X-ray diffraction and Raman spectroscopy were used to verify thermally initiated surface reactions of the sprayed diamonds after exposure to the spraying process. Additionally, reference measurements on the degradation of diamonds in oxidizing and inert conditions were carried out to compare the spraying results. Differential thermal and thermogravimetric analyses were employed. To validate the mechanical properties of the diamond superabrasives, friability tests and fracture force tests were performed. It was found that under optimized detonation spraying conditions the thermal and mechanical impact remains low enough to ensure a good reliability of the processed diamonds. The diamond crystal structure endured the spraying process without detectable graphitization or oxidation. Deterioration indicators were not observed in SEM micrographs, x-ray diffraction patterns or Raman spectra. Furthermore, a high durability and strength of the sprayed diamonds were confirmed by mechanical testing. © 2009 ASM International.
    view abstractdoi: 10.1007/s11666-009-9418-y
  • 2010 • 31 Low-temperature martensitic transformation and deep cryogenic treatment of a tool steel
    Tyshchenko, A.I. and Theisen, W. and Oppenkowski, A. and Siebert, S. and Razumov, O.N. and Skoblik, A.P. and Sirosh, V.A. and Petrov, Y. and Gavriljuk, V.G.
    Materials Science and Engineering A 527 7027-7039 (2010)
    The tool steel X220CrVMo 13-4 (DIN 1.2380) containing (mass%) 2.2C, 13Cr, 4V, 1Mo and the binary alloy Fe-2.03. mass% C were studied using transmission electron microscopy, Mössbauer spectroscopy, X-ray diffraction and internal friction with the aim of shedding light on processes occurring during deep cryogenic treatment. It is shown that the carbon atoms are essentially immobile at temperatures below -50 °C, whereas carbon clustering in the virgin martensite occurs during heating above this temperature. An increase in the density of dislocations, the capture of immobile carbon atoms by moving dislocations, the strain-induced partial dissolution of the carbide phase, and the abnormally low tetragonality of the virgin martensite are found and interpreted in terms of plastic deformation that occurs during martensitic transformation at low temperatures where the virgin martensite is sufficiently ductile. © 2010 Elsevier B.V.
    view abstractdoi: 10.1016/j.msea.2010.07.056
  • 2010 • 30 MBE growth of cubic AlN on 3C-SiC substrate
    Schupp, T. and Rossbach, G. and Schley, P. and Goldhahn, R. and Rp̈ppischer, M. and Esser, N. and Cobet, C. and Lischka, K. and As, D.J.
    Physica Status Solidi (A) Applications and Materials Science 207 1365-1368 (2010)
    We present our recent results on the growth of cubic AlN (001) layers by plasma assisted molecular beam epitaxy (PAMBE) using freestanding 3C-SiC (001) substrate. For high-quality c-AlN layers reflection high-electron energy diffraction (RHEED) patterns in all azimuths show RHEED patterns of the cubic lattice, hexagonal reflections are absent. Highresolution X-ray diffraction (HRXRD) measurements confirm the cubic structure of the c-AlN layers with a lattice parameter of 4.373Å. Atomic force microscopy (AFM) scans show an atomically smooth surface with a roughness of 0.2nm RMS. Ellipsometry studies yield the dielectric function (DF) of c-AlN from 1 to 10eV. The direct gap is determined with 5.93eV at room temperature, while the indirect one is below 5.3 eV (onset of adsorption). The high-energy part of the DF is dominated by two transitions at 7.20 and 7.95 eV attributed to critical points of the band structure. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/pssa.200983437
  • 2010 • 29 Microstructure and magnetic properties of FeCo/Ti thin film multilayers annealed in nitrogen
    Brunken, H. and Somsen, C. and Savan, A. and Ludwig, Al.
    Thin Solid Films 519 770-774 (2010)
    Multifunctional nanocomposites consisting of at least one ferromagnetic phase (e.g. FeCo) and one protective, wear resistant phase (e.g. TiN) are of interest for applications as sensors or actuators in harsh environments. This paper reports on the fabrication and characterization of nanocomposite thin films, prepared from FeCo/Ti metallic precursor multilayer composition spreads using a combinatorial sputter-deposition system. After deposition, the composition spread was annealed in nitrogen (5 × 10 5 Pa pressure) at 850 °C for 1.5 h, leading to preferential nitriding of Ti to TiN, thus forming the protective phase. Automated energy dispersive X-ray analysis, Auger electron spectroscopy, X-ray diffraction measurements, transmission electron microscopy (TEM) and vibrating sample magnetometry were used for the characterization of the as deposited and nitrided composition spreads. As an unexpected result, the appearance of a Heusler phase (Co 2FeSi) in the nanocomposite was observed by TEM. After N 2 annealing, the nanocomposites show reduced saturation magnetization values μ 0M S between 0.5 and 0.95 T and improved coercive field values μ 0H c between 4 and 13.8 mT, dependent on the TiN content. © 2010 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.tsf.2010.09.008
  • 2010 • 28 Microstructures and mechanical properties of Al-base composite materials reinforced by Al-Cu-Fe particles
    Laplanche, G. and Joulain, A. and Bonneville, J. and Schaller, R. and El Kabir, T.
    Journal of Alloys and Compounds 493 453-460 (2010)
    In this study, we produced four composite materials with Al-based matrix reinforced by Al-Cu-Fe particles initially of the quasicrystalline (QC) phase. The processing route was a gas-pressure infiltration of QC particle preforms by molten commercial Al and Al alloys. The resulting composites were investigated by scanning electron microscopy (SEM) working in the energy dispersive spectroscopy (EDS) mode and by X-ray diffraction (XRD). It is shown that such a synthesis technique leads to the formation of various phases resulting from specific diffusion processes. Compression tests were performed at constant strain rate in the temperature range 290-770 K. The stress-strain curves look similar to those of Al-Cu-Fe poly-quasicrystals and show the yield point, the origin of which is however of very different nature. Composite deformation is recognised to occur through the rupture of a hard phase skeleton and localised plastic deformation in the matrix. © 2009 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.jallcom.2009.12.124
  • 2010 • 27 Novel synthetic pathway for new Zn-Zn-bonded compounds from dizincocene
    Gondzik, S. and Bläser, D. and Wölper, C. and Schulz, S.
    Chemistry - A European Journal 16 13599-13602 (2010)
    Making it new! A novel synthetic pathway for the synthesis of Zn-Zn-bonded complexes (see graphic) under mild reaction conditions is presented. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/chem.201002482
  • 2010 • 26 Optimization of mesh-based anodes for direct methanol fuel cells
    Chetty, R. and Scott, K. and Kundu, S. and Muhler, M.
    Journal of Fuel Cell Science and Technology 7 0310101-0310119 (2010)
    Platinum based binary and ternary catalysts were prepared by thermal decomposition onto a titanium mesh and were evaluated for the anodic oxidation of methanol. The binary Pt:Ru catalyst with a composition of 1:1 gave the highest performance for methanol oxidation at 80° C. The effect of temperature and time for thermal decomposition was optimized with respect to methanol oxidation, and the catalysts were characterized by cyclic voltammetry, linear sweep voltammetry, scanning electron microscopy, X-ray diffraction studies, and X-ray photoelectron spectroscopy. The best catalyst was evaluated in a single fuel cell, and the effect of methanol concentration, temperature, and oxygen/air flow was studied. The mesh-based fuel cell, operating at 80°C with 1 mol dm 3 methanol, gave maximum power densities of 38 mWcm -2 and 22 mWcm -2 with 1 bar (gauge) oxygen and air, respectively. © 2010 by ASME.
    view abstractdoi: 10.1115/1.3117605
  • 2010 • 25 Phase separation and Si nanocrystal formation in bulk SiO studied by x-ray scattering
    Feroughi, O.M. and Sternemann, C. and Sahle, Ch.J. and Schroer, M.A. and Sternemann, H. and Conrad, H. and Hohl, A. and Seidler, G.T. and Bradley, J. and Fister, T.T. and Balasubramanian, M. and Sakko, A. and Pirkkalainen, K. and ...
    Applied Physics Letters 96 (2010)
    We present an x-ray scattering study of the temperature-induced phase separation and Si nanocrystal formation in bulk amorphous SiOx with x≈1. X-ray Raman scattering at the Si LII,III -edge reveals a significant contribution of suboxides present in native amorphous SiO. The suboxide contribution decreases with increasing annealing temperature between 800-1200 °C pointing toward a phase separation of SiO into Si and SiO2 domains. In combination with x-ray diffraction and small angle x-ray scattering the SiO microstructure is found to be dominated by internal suboxide interfaces in the native state. For higher annealing temperatures above 900 °C growth of Si nanocrystals with rough surfaces embedded in a silicon oxide matrix can be observed. © 2010 American Institute of Physics.
    view abstractdoi: 10.1063/1.3323106
  • 2010 • 24 Photoluminescence studies on structural defects and room temperature ferromagnetism in Ni and Ni-H doped ZnO nanoparticles
    Tong, L.-N. and Cheng, T. and Han, H.-B. and Hu, J.-L. and He, X.-M. and Tong, Y. and Schneider, C.M.
    Journal of Applied Physics 108 (2010)
    We explore the effects of hydrogenated annealing on the crystal structure, room temperature ferromagnetism (RT-FM) and photoluminescence (PL) properties of Ni-doped ZnO (Zn1-xNixO, x=0.0 to 0.2) nanoparticles prepared by a sol-gel method. The x-ray photoelectron spectra and x-ray diffraction data provide evidence that Ni has been incorporated into the wurtzite ZnO lattice as Ni2+ ions substituting for Zn2+ ions at x0.05. A secondary phase of NiO type begins to form inside ZnO when x≤0.05 and segregates from ZnO host lattice at x=0.2, leading to a large variation in the lattice constants of ZnO. The magnetization measurements show that the saturation magnetization (Ms) increases with increasing Ni concentration in the single-phase Zn1-xNixO (x≤0.05) nanoparticles. The secondary phase formation reduces the magnetization of Zn1-xNixO (x=0.1 and 0.15), while the segregation of NiO from the ZnO lattice at x=0.2 is accompanied by a large increase in M s again. The PL measurements show that the UV emission intensity of single-phase Zn1-xNixO (x≤0.05) nanoparticles increases with a blueshift in the UV emission line when the Ni concentration increases, while the dominant green emission intensity decreases with increasing Ni dopant. The PL data strongly suggest that the FM in single-phase Zn 1-xNixO (x≤0.05) nanoparticles is intrinsically correlated with a doping induced increase in the electron concentration in the conduction band of Ni-doped ZnO. After H2 -annealing, the single-phase Zn1-x NixO:H (x≤0.05) nanoparticles show increases in both coercivity and saturation magnetization. The PL and diffuse reflectance spectra suggest that hydrogen-related shallow donors and an improved sample quality may be responsible for the H2-annealing induced enhancement of the RT-FM. The obvious correlation between FM and carrier concentration in Ni and Ni-H doped ZnO points towards a mechanism of carrier-mediated FM for Ni-doped ZnO diluted magnetic semiconductors. © 2010 American Institute of Physics.
    view abstractdoi: 10.1063/1.3460644
  • 2010 • 23 Rh-RhSx nanoparticles grafted on functionalized carbon nanotubes as catalyst for the oxygen reduction reaction
    Jin, C. and Xia, W. and Nagaiah, T.C. and Guo, J. and Chen, X. and Li, N. and Bron, M. and Schuhmann, W. and Muhler, M.
    Journal of Materials Chemistry 20 736-742 (2010)
    Rhodium-rhodium sulfide nanoparticles supported on multi-walled carbon nanotubes (CNTs) were synthesized via a multi-step colloid route. The CNTs were first exposed to nitric acid to generate oxygen-containing functional groups, and then treated with thionyl chloride to generate acyl chloride groups. The grafting of thiol groups was subsequently carried out by reaction with 4-aminothiophenol. Colloidal rhodium nanoparticles were synthesized using rhodium chloride as metal source, sodium citrate as stabilizer, and sodium borohydride as reducing agent. The immobilization of the generated colloidal rhodium nanoparticles was achieved by adding the thiolated CNTs to the colloidal suspension. All these steps were monitored by X-ray photoelectron spectroscopy, which disclosed the presence of rhodium sulfide, whereas metallic rhodium was detected by X-ray diffraction, suggesting that the nanoparticles probably consist of a metallic Rh core covered by a sulfide layer. Scanning and transmission electron microscopy studies showed that the diameter of the catalyst particles was about 7 nm even at high Rh loadings. Rotating disc electrode measurements and cyclic voltammetry were employed to test the electrocatalytic activity in the oxygen reduction reaction in hydrochloric acid. Among all the synthesized catalysts with different rhodium loadings (4.3-21.9%), the 16.1% rhodium catalyst was found to be the most active catalyst. In comparison to the commercial E-TEK Pt/C catalyst, the 16.1% catalyst displayed a higher electrochemical stability in the highly corrosive electrolyte, as determined by stability tests with frequent current interruptions. © 2010 The Royal Society of Chemistry.
    view abstractdoi: 10.1039/b916192a
  • 2010 • 22 Salen-ligands based on a planar-chiral hydroxyferrocene moiety: Synthesis, coordination chemistry and use in asymmetric silylcyanation
    Niemeyer, J. and Cloppenburg, J. and Fröhlich, R. and Kehr, G. and Erker, G.
    Journal of Organometallic Chemistry 695 1801-1812 (2010)
    Condensation of the O-protected hydroxyferrocene carbaldehyde (Sp)-1 with suitable diamines, followed by liberation of the hydroxyferrocene moiety leads to a new type of ferrocene-based salen ligands (3). While the use of ethylenediamine in the condensation reaction yields the planar-chiral ethylene-bridged ligand [(Sp,Sp)-3a], reaction with the enantiomers of trans-1,2-cyclohexylendiamine gives rise to the corresponding diastereomeric cyclohexylene-bridged systems [(S,S,Sp,Sp)-3b and (R,R,Sp,Sp)-3c], which feature a combination of a planar-chiral ferrocene unit with a centrochiral diamine backbone. Starting with the ferrocene-aldehyde derivative (Rp)-1, the enantiomeric ligand series (3d/e/f) is accessible via the same synthetic route. The (Sp)-series of these newly developed N2O2-type ligands was used for the construction of the corresponding mononuclear bis(isopropoxy)titanium (4a/b/c), methylaluminum (5a/b/c) and chloroaluminum-complexes (6a/b/c), which were isolated in good yields and identified by X-ray diffraction in several cases. The aluminum complexes (5/6) were successfully used in the Lewis-acid catalyzed addition of trimethylsilylcyanide to benzaldehyde, yielding the corresponding cyanohydrins in 45-62% enantiomeric excess. © 2010 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.jorganchem.2010.04.008
  • 2010 • 21 Sol-gel-deposition of thin TiO2:Eu3+ thermographic phosphor films
    Nebatti, A. and Pflitsch, C. and Eckert, C. and Atakan, B.
    Progress in Organic Coatings 68 146-150 (2010)
    A relatively new promising method for surface temperature measurement is the use of thermographic phosphors. For this application, the temperature-dependent luminescence properties of europium(III)-doped anatase (TiO2:Eu3+) thin films were studied. The films were prepared by the sol-gel method using dip coating. The structures and the morphology of the films were determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. Electron dispersive X-ray spectroscopy (EDX) was used to verify the europium concentration within the films. For using the films as temperature sensors the optical properties are the main concern. Therefore, the emission spectra of the films were measured after ultraviolet laser excitation (355 nm). They indicate that the red characteristic emission (617 nm) of TiO2:Eu3+ due to the 5D0 →7F2 electric dipole transition is the strongest. The decay time constant of the exponential emission decay under UV excitation with a Nd:YAG laser (355 nm, f = 10 Hz) is strongly temperature dependent in the range from 200 °C up to 400 °C, making it useful for temperature evaluation. The temperature dependence was measured for the emission line at 617 nm; the results demonstrate that anatase doped europium(III) can be used as a thermographic phosphor. © 2009 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.porgcoat.2009.08.024
  • 2010 • 20 Spatially and size selective synthesis of Fe-based nanoparticles on ordered mesoporous supports as highly active and stable catalysts for ammonia decomposition
    Lu, A.-H. and Nitz, J.-J. and Comotti, M. and Weidenthaler, C. and Schlichte, K. and Lehmann, C.W. and Terasaki, O. and Schüth, F.
    Journal of the American Chemical Society 132 14152-14162 (2010)
    Uniform and highly dispersed γ-Fe 2O 3 nanoparticles with a diameter of ∼6 nm supported on CMK-5 carbons and C/SBA-15 composites were prepared via simple impregnation and thermal treatment. The nanostructures of these materials were characterized by XRD, Mössbauer spectroscopy, XPS, SEM, TEM, and nitrogen sorption. Due to the confinement effect of the mesoporous ordered matrices, γ-Fe 2O 3 nanoparticles were fully immobilized within the channels of the supports. Even at high Fe-loadings (up to about 12 wt %) on CMK-5 carbon no iron species were detected on the external surface of the carbon support by XPS analysis and electron microscopy. Fe 2O 3/CMK-5 showed the highest ammonia decomposition activity of all previously described Fe-based catalysts in this reaction. Complete ammonia decomposition was achieved at 700 °C and space velocities as high as 60 000 cm 3 g cat -1 h -1. At a space velocity of 7500 cm 3 g cat -1 h -1, complete ammonia conversion was maintained at 600 °C for 20 h. After the reaction, the immobilized γ-Fe 2O 3 nanoparticles were found to be converted to much smaller nanoparticles (γ-Fe 2O 3 and a small fraction of nitride), which were still embedded within the carbon matrix. The Fe 2O 3/CMK-5 catalyst is much more active than the benchmark NiO/Al 2O 3 catalyst at high space velocity, due to its highly developed mesoporosity. γ-Fe 2O 3 nanoparticles supported on carbon-silica composites are structurally much more stable over extended periods of time but less active than those supported on carbon. TEM observation reveals that iron-based nanoparticles penetrate through the carbon layer and then are anchored on the silica walls, thus preventing them from moving and sintering. In this way, the stability of the carbon-silica catalyst is improved. Comparison with the silica supported iron oxide catalyst reveals that the presence of a thin layer of carbon is essential for increased catalytic activity. © 2010 American Chemical Society.
    view abstractdoi: 10.1021/ja105308e
  • 2010 • 19 Sticking polydisperse hydrophobic magnetite nanoparticles to lipid membranes
    Paulus, M. and Degen, P. and Brenner, T. and Tiemeyer, S. and Struth, B. and Tolan, M. and Rehage, H.
    Langmuir 26 15945-15947 (2010)
    The formation of a layer of hydrophobic magnetite (Fe3O 4) nanoparticles stabilized by lauric acid is analyzed by in situ X-ray reflectivity measurements. The data analysis shows that the nanoparticles partially disperse their hydrophobic coating. Consequently, a Langmuir layer was formed by lauric acid molecules that can be compressed into an untilted condensed phase. A majority of the nanoparticles are attached to the Langmuir film integrating lauric acid residue on their surface into the Langmuir film. Hence, the particles at the liquid-gas interface can be identified as so-called Janus beads, which are amphiphilic solids having two sides with different functionality. © 2010 American Chemical Society.
    view abstractdoi: 10.1021/la102882j
  • 2010 • 18 Structural characterization of a completely alkyl-substituted Al-Sb Lewis acid-base adduct
    Schulz, S. and Kuczkowski, A. and Nieger, M. and Saxell, H.
    Journal of Organometallic Chemistry 695 2281-2283 (2010)
    The Lewis acid-base adduct t-Bu3Al-SbMe3 (1), which was synthesized by reaction of equimolar amounts of t-Bu3Al and trimethylstibine SbMe3, was characterized by multinuclear NMR ( 1H, 13C) spectroscopy, elemental analyses as well as by single crystal X-ray diffraction. © 2010 Elsevier B.V.
    view abstractdoi: 10.1016/j.jorganchem.2010.06.022
  • 2010 • 17 Study of Ni2 -Mn-Ga phase formation by magnetron sputtering film deposition at low temperature onto Si substrates and LaNi O3 /Pb (Ti,Zr) O3 buffer
    Figueiras, F. and Rauwel, E. and Amaral, V.S. and Vyshatko, N. and Kholkin, A.L. and Soyer, C. and Remiens, D. and Shvartsman, V.V. and Borisov, P. and Kleemann, W.
    Journal of Vacuum Science and Technology A: Vacuum, Surfaces and Films 28 6-10 (2010)
    Film deposition of Ni2 MnGa phaselike alloy by radio frequency (rf) magnetron sputtering was performed onto bare Si(100) substrates and LaNi O3 /Pb (Ti,Zr) O3 (LNO/PZT) ferroelectric buffer layer near room temperature. The prepared samples were characterized using conventional x-ray diffraction (XRD), superconducting quantum interference device, and electron dispersive x-ray spectroscopy from scanning electron microscope observations. The optimized films deposited under high rf power and low argon pressure present good surface quality and highly textured phase crystallization. The positioning distance between the substrate and the target-holder axis has some limited effect on the film's composition due to the specific diffusion behavior of each element in the sputtering plasma. Extended four pole high resolution XRD analysis allowed one to discriminate the intended Ni-Mn-Ga tetragonal martensitic phase induced by the (100) LNO/PZT oriented buffer. This low temperature process appears to be very promising, allowing separate control of the functional layer's properties, while trying to achieve high electromagnetoelastic coupling. © 2010 American Vacuum Society.
    view abstractdoi: 10.1116/1.3256200
  • 2010 • 16 Substrate influence on the optical and structural properties of pulsed laser deposited BiFeO3 epitaxial films
    Himcinschi, C. and Vrejoiu, I. and Friedrich, M. and Nikulina, E. and Ding, L. and Cobet, C. and Esser, N. and Alexe, M. and Rafaja, D. and Zahn, D.R.T.
    Journal of Applied Physics 107 (2010)
    Epitaxial BiFeO3 films pulsed laser deposited on SrTiO 3, Nb:doped SrTiO3, and DyScO3 were studied using variable angle spectroscopic ellipsometry, vacuum ultraviolet ellipsometry, micro-Raman spectroscopy, and x-ray diffraction. The energy band gap of the film deposited on DyScO3 is 2.75 eV, while the one for the film deposited on Nb:doped SrTiO3 is larger by 50 meV. The blueshift in the dielectric function of the BiFeO3 films deposited on Nb:doped SrTiO3 compared to the films deposited on DyScO3, indicates a larger compressive strain in the films deposited on Nb:doped SrTiO3. This is confirmed by Raman spectroscopy and by high resolution x-ray diffraction investigations. © 2010 American Institute of Physics.
    view abstractdoi: 10.1063/1.3437059
  • 2010 • 15 Suppression of Ni4Ti3 precipitation by grain size refinement in Ni-rich NiTi shape memory alloys
    Prokofiev, E.A. and Burow, J.A. and Payton, E.J. and Zarnetta, R. and Frenzel, J. and Gunderov, D.V. and Valiev, R.Z. and Eggeler, G.
    Advanced Engineering Materials 12 747-753 (2010)
    Severe plastic deformation (SPD) processes, such as equal channel angular pressing (ECAP) and high pressure torsion (HPT), are successfully employed to produce ultra fine grain (UFG) and nanocrystalline (NC) microstructures in a Ti-50.7 at% Ni shape memory alloy. The effect of grain size on subsequent Ni-rich particle precipitation during annealing is investigated by transmission electron microscopy (TEM), selected area electron diffraction (SAD, SAED), and X-ray diffraction (XRD). It is observed that Ni4Ti3 precipitation is suppressed in grains of cross-sectional equivalent diameter below approximately 150 nm, and that particle coarsening is inhibited by very fine grain sizes. The results suggest that fine grain sizes impede precipitation processes by disrupting the formation of selfaccommodating particle arrays and that the arrays locally compensate for coherency strains during nucleation and growth. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/adem.201000101
  • 2010 • 14 Surface modification of polypropylene microfiltration membrane via entrapment of an amphiphilic alkyl oligoethyleneglycolether
    Guo, H. and Ulbricht, M.
    Journal of Membrane Science 349 312-320 (2010)
    For surface hydrophilic and antifouling modification of polypropylene (PP) microfiltration membrane, the novel method for entrapment of the amphiphilic modifier octaethyleneglycol monooctadecylether (C18E8) was investigated in detail. The effects of the modification conditions on PP membrane and polymer structure were characterized by gas flow/pore dewetting, nitrogen adsorption/BET analysis, scanning electron microscopy and X-ray diffraction; surface properties were evaluated by ATR-FTIR spectroscopy and static water contact angle; filtration performance as well as antifouling property were investigated by water flux measurement, trans-membrane zeta potential, static and dynamic protein adsorption experiments. Furthermore, a stability study of the modified membrane was performed to offer a comprehensive understanding of this physical entrapment strategy. It can be concluded that both outer surface and inner pore walls of PP membrane were covered with oligoethylene glycol after entrapment modification by C18E8, with only very slight changes of membrane pore and polymer structures. Correspondingly, PP membrane surface hydrophilicity and antifouling performance were evidently improved. It was also found that the entrapped modifier has a tendency to leach out of the PP membrane in water at room temperature. However, after 8 weeks changes became very small, and the modified PP membrane surface still exhibited significant hydrophilicity and antifouling properties. © 2009 Elsevier B.V. All rights reserved.
    view abstractdoi: 10.1016/j.memsci.2009.11.062
  • 2010 • 13 Synthesis and characterization of ag- or sb-doped zno nanorods by a facile hydrothermal route
    Lupan, O. and Chow, L. and Ono, L.K. and Cuenya, B.R. and Chai, G. and Khallaf, H. and Park, S. and Schulte, A.
    Journal of Physical Chemistry C 114 12401-12408 (2010)
    ZnO nanorods doped with Ag and Sb have been synthesized by a facile hydrothermal technique. Crystal quality, morphology, chemical/electronic composition, local structure, and vibrational mode properties are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and micro-Raman spectroscopy. Evidence of dopant incorporation is demonstrated in the XPS measurements of both Sb-doped and Ag-doped ZnO nanorods. From XRD data, it was found that the doped ZnO nanorods have a lower degree of crystallinity. The lattice constants of doped ZnO nanorods were slightly larger than that of the pure samples. © 2010 American Chemical Society.
    view abstractdoi: 10.1021/jp910263n
  • 2010 • 12 Synthesis and characterization of ZnO nanowires for nanosensor applications
    Lupan, O. and Emelchenko, G.A. and Ursaki, V.V. and Chai, G. and Redkin, A.N. and Gruzintsev, A.N. and Tiginyanu, I.M. and Chow, L. and Ono, L.K. and Roldan Cuenya, B. and Heinrich, H. and Yakimov, E.E.
    Materials Research Bulletin 45 1026-1032 (2010)
    In this paper we report the synthesis of ZnO nanowires via chemical vapor deposition (CVD) at 650 °C. It will be shown that these nanowires are suitable for sensing applications. ZnO nanowires were grown with diameters ranging from 50 to 200 nm depending on the substrate position in a CVD synthesis reactor and the growth regimes. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), and Raman spectroscopy (RS) have been used to characterize the ZnO nanowires. To investigate the suitability of the CVD synthesized ZnO nanowires for gas sensing applications, a single ZnO nanowire device (50 nm in diameter) was fabricated using a focused ion beam (FIB). The response to H2 of a gas nanosensor based on an individual ZnO nanowire is also reported. © 2010 Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.materresbull.2010.03.027
  • 2010 • 11 Synthesis and x-ray crystal structures of tetranuclear zincamidinate complexes
    Gutschank, B. and Schulz, S. and Westphal, U. and Bläser, D. and Boese, R.
    Organometallics 29 2093-2097 (2010)
    Polynuclear amidinate zinc halide complexes of the general type{C[C(Ni-Pr)2ZnX]4} [X = Cl, 2; Br, 3; I, 4] were prepared in high yields via methyl/halide exchange reaction of {C[C(Ni-Pr) 2ZnMe]4} (1a) with AlX3. 2-4 were characterized by elemental analysis, multinuclear NMR, and IR spectroscopy and single-crystal X-ray diffraction. Computational calculations of halide-substituted complexes {C[C(Ni-Pr)2ZnX]4} [X = F-I] were performed to clarify the influence of the halide atom on the structural parameters of the complexes and to elucidate their electronic structure and bonding situation. The capability of these halide-substituted complexes to serve as suitable starting reagents for further salt elimination reactions was proven by reaction of 2 with LiR (R = Me, n-Bu) and EtMgBr, which yielded the corresponding Zn-alkyl species {C[C(Ni-Pr)2ZnR]4} [R = Me, 1a; n-Bu, 5; Et, 6]. © 2010 American Chemical Society.
    view abstractdoi: 10.1021/om100065w
  • 2010 • 10 Synthesis, structure, and reactivity of a tetranuclear amidinato zinc hydride complex
    Gutschank, B. and Schulz, S. and Bläser, D. and Boese, R. and Wölper, C.
    Organometallics 29 6133-6136 (2010)
    The tetranuclear amidinato zinc hydride complex (C[C(Ni-Pr) 2ZnH]4) (3) was synthesized by reaction of the Cl-substituted complex (C[C(Ni-Pr)2ZnCl]4) with CaH 2. 3 was found to react with phenylacetylene and acetylene at ambient temperature with elimination of H2 and subsequent formation of C[C(Ni-Pr)2ZnC≡CPh]4 (4) and (C[C(Ni-Pr) 2ZnC≡CH]4 (5), respectively. 3-5 have been characterized by multinuclear NMR (1H, 13C) and IR spectroscopy, elemental analyses, and single-crystal X-ray diffraction. © 2010 American Chemical Society.
    view abstractdoi: 10.1021/om100966d
  • 2010 • 9 The effect of annealing on the junction profile of CoFeB/MgO tunnel junctions
    He, H. and Zhernenkov, K. and Vadalá, M. and Akdogan, N. and Gorkov, D. and Abrudan, R.M. and Toperverg, B.P. and Zabel, H. and Kubota, H. and Yuasa, S.
    Journal of Applied Physics 108 (2010)
    The tunnelling magnetoresistance of CoFeB/MgO tunnel junctions is exceptionally high, although the electrodes and the barrier are grown at room temperature in the amorphous state. For their functionality annealing steps up to high temperatures are required. We have analyzed in detail the changes in the chemical and magnetization profile upon annealing up to 360°. The multilayers used for this study are similar to those which are used in magnetic tunnel junctions, however with five repeats. In particular, we have used hard non-resonant and soft resonant magnetic x-ray scattering in order to unravel any changes upon annealing. The multilayers exhibit superior structural quality, which hardly changes with annealing. Surprisingly, only little recrystallization of the CoFeB and the MgO layers can be discerned by x-ray diffraction. © 2010 American Institute of Physics.
    view abstractdoi: 10.1063/1.3483956
  • 2010 • 8 The release of nickel from nickel-titanium (NiTi) is strongly reduced by a sub-micrometer thin layer of calcium phosphate deposited by rf-magnetron sputtering
    Surmenev, R.A. and Ryabtseva, M.A. and Shesterikov, E.V. and Pichugin, V.F. and Peitsch, T. and Epple, M.
    Journal of Materials Science: Materials in Medicine 21 1233-1239 (2010)
    Thin calcium phosphate coatings were deposited on NiTi substrates (plates) by rf-magnetron sputtering. The release of nickel upon immersion in water or in saline solution (0.9% NaCl in water) was measured by atomic absorption spectroscopy (AAS) for 42 days. The coating was analyzed before and after immersion by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). After an initial burst during the first 7 days that was observed for all samples, the rate of nickel release decreased 0.4-0.5 ng cm-2 d-1 for a 0.5 μm-thick calcium phosphate coating (deposited at 290 W). This was much less than the release from uncoated NiTi (3.4-4.4 ng cm-2 d-1). Notably, the nickel release rate was not significantly different in pure water and in aqueous saline solution. © 2010 Springer Science+Business Media, LLC.
    view abstractdoi: 10.1007/s10856-010-3989-5
  • 2010 • 7 The resorption of nanocrystalline calcium phosphates by osteoclast-like cells
    Detsch, R. and Hagmeyer, D. and Neumann, M. and Schaefer, S. and Vortkamp, A. and Wuelling, M. and Ziegler, G. and Epple, M.
    Acta Biomaterialia 6 3223-3233 (2010)
    Nanocrystalline calcium phosphates containing carbonate have a high similarity to bone mineral. The reactions of bone cells (primary osteoblasts and osteoclast-like cells) on these materials as well as on sintered β-tricalcium phosphate and hydroxyapatite (HA) confirmed a good biocompatibility of the nanocrystalline samples. However, osteoclastic differentiation was constrained on the carbonate-rich samples, leading to a small number of osteoclast-like cells on the materials and few resorption pits. The grain size of the calcium phosphate ceramics (nano vs. micro) was less important than expected from to physico-chemical considerations. When comparing the nanocrystalline samples, the highest resorption rate was found for nano-HA with a low carbonate content, which strongly stimulated the differentiation of osteoclast-like cells on its surface. © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
    view abstractdoi: 10.1016/j.actbio.2010.03.003
  • 2010 • 6 The synthesis of highly loaded Cu/Al2O3 and Cu/Zno/Al2O3 catalysts by the two-step CVD of Cu IIdiethylamino-2-propoxide in a fluidized-bed reactor
    Becker, M. and D'Alnoncourt, R.N. and Kähler, K. and Sekulic, J. and Fischer, R.A. and Muhler, M.
    Chemical Vapor Deposition 16 85-92 (2010)
    Highly loaded copper catalysts supported on alumina are synthesized applying the cyclic two-step CVD of the precursor copper(II)diethylamino-2- propoxide in a fluidized-bed reactor. Copper/zinc oxide/alumina composites are synthesized by either the CVD of the precursor bis[bis (trimethylsilyl) amido]zinc on Cu/Al2O3, or the CVD of the Cu precursor on Zn-pretreated alumina, impregnating with diethyl zinc in addition. The composites are extensively characterized by atomic absorption spectroscopy (AAS), elemental analysis (EA), mass spectrometry (MS), N2 physisorption, N2O reactive frontal chromatography (RFC), and X-ray diffraction (XRD). The Cu and ZnO nanoparticles originating from the efficient two-step procedure, consisting of adsorption and subsequent decomposition of the adsorbed species in two separated steps, are highly dispersed, X-ray amorphous, and, in the case of the Cu-containing catalysts, have high specific Cu surface areas. The catalytic activities are determined both in methanol synthesis, to judge the contact between the deposited Cu and ZnO nanoparticles, and in the steam reforming of methanol (SRM) to probe the stability of the Cu particles. The turn-over frequencies (TOF) in methanol synthesis of these Cu/ZnO/Al 2O3 catalysts are higher than that of a commercial ternary catalyst. The varied sequence of the CVD of Cu and ZnO on alumina leads to catalysts with similar activities in the case of similar specific Cu areas. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cvde.200906808
  • 2010 • 5 Unique features of the folding landscape of a repeat protein revealed by pressure perturbation
    Rouget, J.-B. and Schroer, M.A. and Jeworrek, C. and Pühse, M. and Saldana, J.-L. and Bessin, Y. and Tolan, M. and Barrick, D. and Winter, R. and Royer, C.A.
    Biophysical Journal 98 2712-2721 (2010)
    The volumetric properties of proteins yield information about the changes in packing and hydration between various states along the folding reaction coordinate and are also intimately linked to the energetics and dynamics of these conformations. These volumetric characteristics can be accessed via pressure perturbation methods. In this work, we report high-pressure unfolding studies of the ankyrin domain of the Notch receptor (Nank1-7) using fluorescence, small-angle x-ray scattering, and Fourier transform infrared spectroscopy. Both equilibrium and pressure-jump kinetic fluorescence experiments were consistent with a simple two-state folding/unfolding transition under pressure, with a rather small volume change for unfolding compared to proteins of similar molecular weight. High-pressure fluorescence, Fourier transform infrared spectroscopy, and small-angle x-ray scattering measurements revealed that increasing urea over a very small range leads to a more expanded pressure unfolded state with a significant decrease in helical content. These observations underscore the conformational diversity of the unfolded-state basin. The temperature dependence of pressure-jump fluorescence relaxation measurements demonstrated that at low temperatures, the folding transition state ensemble (TSE) lies close in volume to the folded state, consistent with significant dehydration at the barrier. In contrast, the thermal expansivity of the TSE was found to be equivalent to that of the unfolded state, indicating that the interactions that constrain the folded-state thermal expansivity have not been established at the folding barrier. This behavior reveals a high degree of plasticity of the TSE of Nank1-7. © 2010 by the Biophysical Society.
    view abstractdoi: 10.1016/j.bpj.2010.02.044
  • 2010 • 4 Very low temperature CO oxidation over colloidally deposited gold nanoparticles on Mg(OH)2 and MgO
    Jia, C.-N. and Liu, Y. and Bongard, H. and Schüth, F.
    Journal of the American Chemical Society 132 1520-1522 (2010)
    (Figure Presented) The colloidal deposition method was used to prepare Au/Mg(OH)2 (0.7 wt % gold) catalysts with gold particle sizes between 1.5 to 5 nm which exhibited very high activity for CO oxidation with specific rates higher than 3.7 molCO·h-1·g Au-1 even at temperatures as low as -89° C. © 2010 American Chemical Society.
    view abstractdoi: 10.1021/ja909351e
  • 2010 • 3 X-ray diffraction residual stress analysis on PVD-multilayer coatings
    Tillmann, W. and Selvadurai-Laßl, U. and Vogli, E. and Fischer, G. and Hoffmann, F.
    Materialwissenschaft und Werkstofftechnik 41 482-488 (2010)
    Hard and wear resistant thin layers provides significant improvements in tools employed in manufacturing industry and are recently of great interest to increase as well as to enhance the tools? performance and lifetime. Ceramic PVD-layers already feature a high hardness combined with a high abrasive wear resistance. However, such layers possess only a limited lifetime due to their low toughness. To increase the toughness as well as the durability of such layers multilayer systems are steadily developed. This research work presents the first results of the influence of the steel substrate pretreatments, multilayer designs and coating process parameters on the properties of two innovative PVD metal-ceramic multilayers, Ti/TiAIN and Cr/CrAIN. It was obviously that the substrate pretreatment and the multilayer design have a large influence on the layer properties and residual stresses. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/mawe.201000630
  • 2010 • 2 [cis-(1,3-diene) 2W(CO) 2] complexes as MOCVD precursors for the deposition of thin tungsten - Tungsten carbide films
    Jipa, I. and Heinemann, F.W. and Schneider, A. and Popovska, N. and Siddiqi, M.A. and Siddiqui, R.A. and Atakan, B. and Marbach, H. and Papp, C. and Steinrück, H.-P. and Zenneck, U.
    Chemical Vapor Deposition 16 239-247 (2010)
    Tungsten - tungsten carbide thin films are deposited by metal-organic (MO)CVD on silica-coated silicon wafers using [cis-(1,3-butadiene) 2W(CO) 2] and [cis-(1,3-cyclohexadiene) 2W(CO) 2], respectively, as tunable precursor complexes. The compounds are prepared through photochemical ligand exchange reactions from [W(CO) 6] and fully characterized, including X-ray structure determination and detailed differential thermal analysis (DTA)/thermogravimetry (TG) investigations. Gas-phase diffusion coefficients and the vapor pressure of the compounds are calculated. The MOCVD experiments are performed in a vertical cold-wall reactor and the exhaust gas is analyzed by gas chromatography (GC). X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), atomic force microscopy (AFM), and scanning electron microscopy (SEM) measurements are utilized for film characterization. Consequences of the high oxophilicity of freshly formed tungsten surfaces, consecutive surface reactions of the complex ligands, film growth, and film properties are discussed. Inside the layers, tungsten carbide is identified as the main component. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    view abstractdoi: 10.1002/cvde.201006852
  • 2010 • 1 γ-Fe2O3 nanoparticle adsorption at an OTS Langmuir monolayer
    Degen, P. and Paulus, M. and Leick, S. and Tolan, M. and Rehage, H.
    Colloid and Polymer Science 288 643-651 (2010)
    The assembling of magnetic nanoparticles in ordered structures as well as the preparation of very thin magnetic switchable polymer membranes is an important aim in many technical fields. We studied the influence of γ-Fe2O3 nanoparticles on the polymerization process and on the properties of the poly(organosiloxane)/nanoparticle-composite layer by surface rheological measurements, surface pressure/area (π/A) isotherm measurements, and Brewster angle microscopy. The adsorption process dynamics were studied by X-ray reflectivity and surface potential measurements. The results confirm the presence of attractive electrostatic interactions between the partial negatively charged monolayer and the positively charged nanoparticles. For further investigations, we prepared Langmuir-Blodgett layers of these polymer-nanoparticle composite and investigated them by atomic force microscopy and UV-Vis spectroscopy. We found that the concentration of nanoparticles was very low and the particles were mainly arranged below the polymer layer. © 2010 Springer-Verlag.
    view abstractdoi: 10.1007/s00396-010-2191-0