TY - JOUR A1 - Serebrennikova, P. A1 - Komarov, V. A1 - Sukhikh, A. A1 - Khranenko, S. A1 - Zadesenetz, A. A1 - Gromilov, S A1 - Yusenko, Kirill T1 - [NiEn3](MoO4)0.5(WO4)0.5 co-crystals as single-source precursors for ternary refractory Ni-Mo-W alloys N2 - The co-crystallisation of [NiEn3](NO3)2 (En = ethylenediamine) with Na2MoO4 and Na2WO4 from a water solution results in the formation of [NiEn3](MoO4)0.5(WO4)0.5 co-crystals. According to the X-ray diffraction analysis of eight single crystals, the parameters of the hexagonal unit cell (space group P–31c, Z = 2) vary in the following intervals: a = 9.2332(3)–9.2566(6); c = 9.9512(12)–9.9753(7) Å with the Mo/W ratio changing from 0.513(3)/0.487(3) to 0.078(4)/0.895(9). The thermal decomposition of [NiEn3](MoO4)0.5(WO4)0.5 individual crystals obtained by co-crystallisation was performed in He and H2 atmospheres. The ex situ X-ray study of thermal decomposition products shows the formation of nanocrystalline refractory alloys and carbide composites containing ternary Ni–Mo–W phases. The formation of carbon–nitride phases at certain stages of heating up to 1000 °C were shown. KW - Single source precursors KW - Phase diagrams PY - 2021 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-540123 VL - 11 IS - 12 SP - 1 EP - 12 PB - MDPI CY - Basel AN - OPUS4-54012 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yusenko, Kirill A1 - Khandarkhaeva, S. A1 - Bykov, M. A1 - Fedotenko, T. A1 - Hanfland, M. A1 - Sukhikh, A. A1 - Gromilov, S. A1 - Dubrovinsky, L. T1 - Face-centered cubic refractory alloys prepared from single-source precursors N2 - Three binary fcc-structured alloys (fcc–Ir0.50Pt0.50, fcc Rh0.66Pt0.33 and fcc–Rh0.50Pd0.50) were 14 prepared from [Ir(NH3)5Cl][PtCl6], [Ir(NH3)5Cl][PtBr6], [Rh(NH3)5Cl]2[PtCl6]Cl2 and 15 [Rh(NH3)5Cl][PdCl4]·H2O, respectively, as single-source precursors. All alloys were prepared by 16 thermal decomposition in gaseous hydrogen flow below 800 °C. Fcc–Ir0.50Pt0.50 and fcc–Rh0.50Pd0.50 17 correspond to miscibility gaps on binary metallic phase diagrams and can be considered as 18 metastable alloys. Detailed comparison of [Ir(NH3)5Cl][PtCl6] and [Ir(NH3)5Cl][PtBr6] crystal 19 structures suggests that two isoformular salts are not isostructural. In [Ir(NH3)5Cl][PtBr6], specific 20 Br…Br interactions are responsible for crystal structure arrangement. Room temperature 21 compressibility of fcc–Ir0.50Pt0.50, fcc–Rh0.66Pt0.33 and fcc–Rh0.50Pd0.50 has been investigated up to 50 GPa 22 in diamond anvil cells. All investigated fcc-structured binary alloys are stable under compression. 23 Atomic volumes and bulk moduli show good agreement with ideal solutions model. For fcc–24 Ir0.50Pt0.50, V0/Z = 14.597(6) Å3·atom-1, B0 = 321(6) GPa, B0' = 6(1); for fcc–Rh0.66Pt0.33, V0/Z = 14.211(3) 25 Å3·atom-1, B0 =259(1) GPa, B0' = 6.66(9); for fcc–Rh0.50Pd0.50, V0/Z = 14.18(2) Å3·atom-1, B0 =223(4) GPa, 26 B0' = 5.0(3). KW - High-pressure KW - Refractory alloys KW - Platinum group metals KW - Single-source precursors PY - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-508176 VL - 13 IS - 6 SP - 1418 PB - MDPI CY - Basel AN - OPUS4-50817 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yusenko, Kirill A1 - Sukhikh, A. A1 - Kraus, Werner A1 - Gromilov, S. T1 - Synthesis and Crystal Chemistry of Octahedral Rhodium(III) Chloroamines N2 - Rhodium(III) octahedral complexes with amine and chloride ligands are the most common starting compounds for preparing catalytically active rhodium(I) and rhodium(III) species. Despite intensive study during the last 100 years, synthesis and crystal structures of rhodium(III) complexes were described only briefly. Some [RhClx(NH3)6-x] compounds are still unknown. In this study, available information about synthetic protocols and the crystal structures of possible [RhClx(NH3)6−x] octahedral species are summarized and critically analyzed. Unknown crystal structuresof(NH4)2[Rh(NH3)Cl5],trans–[Rh(NH3)4Cl2]Cl·H2O,andcis–[Rh(NH3)4Cl2]Clarereported based on high quality single crystal X-ray diffraction data. The crystal structure of [Rh(NH3)5Cl]Cl2 was redetermined. All available crystal structures with octahedral complexes [RhClx(NH3)6-x] were analyzed in terms of their packings and pseudo-translational sublattices. Pseudo-translation lattices suggest face-centered cubic and hexagonal closed-packed sub-cells, where Rh atoms occupy nearly ideal lattices. KW - Pseudo-translationalsublattices KW - Rhodiumcomplexes KW - Ligandsubstitution KW - Crystalstructure PY - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-508194 VL - 25 IS - 4 SP - 768 PB - MDPI CY - Basel AN - OPUS4-50819 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Baek, W. A1 - Gromilov, S. A1 - Kuklin, A. A1 - Kovaleva, E. A1 - Fedorov, A. A1 - Sukhikh, Alex A1 - Hanfland, M. A1 - Pomogaev, V. A1 - Melchakova, Y. A1 - Avramov, P. A1 - Yusenko, Kirill T1 - Unique Nanomechanical Properties of Diamond-Lonsdaleite Biphases: Combined Exp and Theor consideration of popigai impact diamonds N2 - For the first time, lonsdaleite-rich impact diamonds from one of the largest Popigai impact crater (Northern Siberia) with a high concentration of structural defects are investigated under hydrostatic compression up to 25 GPa. It is found that, depending on the nature of a sample, the bulk modulus for lonsdaleite experimentally obtained by X-ray diffraction in diamond-anvil cells is systematically lower and equal to 93.3−100.5% of the average values of the bulk moduli of a diamond matrix. Density functional theory calculations reveal possible coexistence of a number of diamond/lonsdaleite and twin diamond biphases. Among the different mutual configurations, separate inclusions of one lonsdaleite (001) plane per four diamond (111) demonstrate the lowest energy per carbon atom, suggesting a favorable formation of single-layer lonsdaleite (001) fragments inserted in the diamond matrix. Calculated formation energies and experimental diamond (311) and lonsdaleite (331) powder X-ray diffraction patterns indicate that all biphases could be formed under high-temperature, high-pressure conditions. Following the equation of states, the bulk modulus of the diamond (111)/lonsdaleite (001) biphase is the largest one among all bulk moduli, including pristine diamond and lonsdaleite. KW - Compressibility KW - Lonsdaleite KW - Impact diamonds PY - 2019 U6 - https://doi.org/10.1021/acs.nanolett.8b04421 VL - 19 IS - 9 SP - 1570 EP - 1576 PB - ACS AN - OPUS4-47403 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Khandarhaeva, S. A1 - Fedotenko, T. A1 - Pakhomova, A. A1 - Gromilov, S. A1 - Dubrovinsky, L. A1 - Dubrovinskaia, N. A1 - Yusenko, Kirill T1 - Equations of state of rhodium, iridium and their alloys up to 70 GPa N2 - Knowledge of the compressional and thermal behaviour of metals and alloys is of a high fundamental and applied value. In this work, we studied the behaviour of Ir, Rh, and their fcc-structured alloys, Ir0.42Rh0.58 and Ir0.26Os0.05Pt0.31Rh0.23Ru0.15, up to 70 GPa using the diamond anvil cell technique with synchrotron X-ray diffraction. We found that all these materials are structurally stable upon room-temperature hydrostatic compression in the whole pressure interval, as well as upon heating to 2273 K both at ambient and high pressure. Rh, Ir0.42Rh0.58 and Ir0.26Os0.05Pt0.31Rh0.23Ru0.15 were investigated under static compression for the first time. According to our data, the compressibility of Ir, Rh, fcc–Ir0.42Rh0.58, and fcc Ir0.26Os0.05Pt0.31Rh0.23Ru0.15, can be described with the 3rd order Birch-Murnaghan equation of state with the following parameters: V0 = 14.14(6) Å3·atom−1, B0 = 341(10) GPa, and B0' = 4.7(3); V0 = 13.73(7) Å3·atom−1, B0 = 301(9) GPa, and B0' = 3.1(2); V0 = 13.90(8) Å3·atom−1, B0 = 317(17) GPa, and B0' = 6.0(5); V0 = 14.16(9) Å3·atom−1, B0 = 300(22) GPa, B0' = 6(1), where V0 is the unit cell volume, B0 and B0' – are the bulk modulus and its pressure derivative. KW - EOS KW - Rh-Ir alloys KW - High-entropy alloys KW - High-pressure PY - 2019 U6 - https://doi.org/10.1016/j.jallcom.2019.02.206 VL - 788 SP - 212 EP - 218 PB - Elsevier B.V. AN - OPUS4-47404 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -