TY - JOUR A1 - Zhang, X. A1 - Zhang, J. A1 - Wang, H. A1 - Rogal, J: A1 - Li, H.-Y. A1 - Wei, S.-H. A1 - Hickel, Tilmann T1 - Defect-characterized phase transition kinetics N2 - Phase transitions are a common phenomenon in condensed matter and act as a critical degree of freedom that can be employed to tailor the mechanical or electronic properties of materials. Understanding the fundamental mechanisms of the thermodynamics and kinetics of phase transitions is, thus, at the core of modern materials design. Conventionally, studies of phase transitions have, to a large extent, focused on pristine bulk phases. However, realistic materials exist in a complex form; their microstructures consist of different point and extended defects. The presence of defects impacts the thermodynamics and kinetics of phase transitions, but has been commonly ignored or treated separately. In recent years, with the significant advances in theoretical and experimental techniques, there has been an increasing research interest in modeling and characterizing how defects impact or even dictate phase transitions. The present review systematically discusses the recent progress in understanding the kinetics of defect-characterized phase transitions, derives the key mechanisms underlying these phase transitions, and envisions the remaining challenges and fruitful research directions. We hope that these discussions and insights will help to inspire future research and development in the field. KW - Kinetics KW - Atomistic models KW - Phase transitions KW - Defects PY - 2022 DO - https://doi.org/10.1063/5.0117234 SN - 1931-9401 VL - 9 IS - 4 SP - 1 EP - 42 PB - AIP CY - New York, NY AN - OPUS4-56507 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zhang, Kun A1 - Carrod, Andrew J. A1 - Del Giorgio, Elena A1 - Hughes, Joseph A1 - Rurack, Knut A1 - Bennet, Francesca A1 - Hodoroaba, Vasile-Dan A1 - Harrad, Stuart A1 - Pikramenou, Zoe T1 - Luminescence Lifetime-Based Sensing Platform Based on Cyclometalated Iridium(III) Complexes for the Detection of Perfluorooctanoic Acid in Aqueous Samples N2 - Luminescence lifetimes are an attractive analytical method for detection due to its high sensitivity and stability. Iridium probes exhibit luminescence with long excited-state lifetimes, which are sensitive to the local environment. Perfluorooctanoic acid (PFOA) is listed as a chemical of high concern regarding its toxicity and is classified as a “forever chemical”. In addition to strict limits on the presence of PFOA in drinking water, environmental contamination from industrial effluent or chemical spills requires rapid, simple, accurate, and cost-effective analysis in order to aid containment. Herein, we report the fabrication and function of a novel and facile luminescence sensor for PFOA based on iridium modified on gold surfaces. These surfaces were modified with lipophilic iridium complexes bearing alkyl chains, namely, IrC6 and IrC12, and Zonyl-FSA surfactant. Upon addition of PFOA, the modified surfaces IrC6-FSA@Au and IrC12-FSA @Au show the largest change in the red luminescence signal with changes in the luminescence lifetime that allow monitoring of PFOA concentrations in aqueous solutions. The platform was tested for the measurement of PFOA in aqueous samples spiked with known concentrations of PFOA and demonstrated the capacity to determine PFOA at concentrations >100 μg/L (240 nM). KW - Perfluorooctanoic Acid (PFOA) KW - Cyclometalated iridium (III) complexes KW - Luminescent lifetime KW - Optically active surfaces KW - ToF-SIMS PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594535 UR - https://pubs.acs.org/doi/10.1021/acs.analchem.3c04289 DO - https://doi.org/10.1021/acs.analchem.3c04289 VL - 96 IS - 4 SP - 1565 EP - 1575 PB - American Chemical Society (ACS) AN - OPUS4-59453 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zauer, M. A1 - Prinz, Carsten A1 - Adolphs, J. A1 - Emmerling, Franziska A1 - Wagenführ, A. T1 - Sorption surfaces and energies of untreated and thermally modified wood evaluated by means of excess surface work (ESW) N2 - Water vapor sorption surface areas and sorption energies of untreated and thermally modified Norway spruce [Picea abies (L.) Karst.], sycamore maple (Acer pseudoplatanus L.) and European ash (Fraxinus excelcior L.) were investigated by means of dynamic vapor sorption (DVS) measurements and excess surface work (ESW) evaluation method, respectively. Adsorption and desorption experiments in the hygroscopic range and desorption tests from water saturation were conducted. Thermodynamically, ESW is the sum of the surface free energy and the isothermal isobaric work of sorption. From the amount adsorbed in the first Minimum a specific surface area similar to the BET surface area can be obtained. The results show that untreated spruce has a significantly higher specific water vapor Sorption surface and sorption energy compared to both hardwoods maple and ash. Thermal modification of the woods leads to a significant reduction of water vapor Sorption surface and sorption energy. The determined surface area and energy are higher in desorption direction than in adsorption direction, whereby the highest values in Desorption direction from water saturation, especially for maple and ash, were obtained. The surface areas calculated by means of the ESW method are similar to the surface areas calculated by means of the BET method, particularly in adsorption direction. KW - Excess surface work KW - Dynamic vapor sorption KW - Wood KW - BET PY - 2018 DO - https://doi.org/10.1007/s00226-018-1021-2 SN - 1432-5225 SN - 0043-7719 VL - 52 IS - 4 SP - 957 EP - 969 PB - Springer CY - Berlin Heidelberg AN - OPUS4-44975 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zarinwall, A. A1 - Waniek, Tassilo A1 - Saadat, R. A1 - Braun, U. A1 - Sturm, Heinz A1 - Garnweitner, G. T1 - Comprehensive Characterization of APTES Surface Modifications of Hydrous Boehmite Nanoparticles N2 - Hydrous boehmite (γ-AlOOH) nanoparticles (BNP) show great potential as nanoscale filler for the fabrication of fiber reinforced nanocomposite materials. Notably, the particle−matrix interaction has been demonstrated to be decisive for improving the matrix-dominant mechanical properties in the past years. Tailoring the surface properties of the nanofiller enables to selectively design the interaction and thus to exploit the benefits of the nanocomposite in an optimal way. Here, an extensive study is presented on the binding of (3-aminopropyl)triethoxysilane (APTES), a common silane surface modifier, on BNP in correlation to different process parameters (concentration, time, temperature, and pH). Furthermore, a comprehensive characterization of the modified BNP was performed by using elemental analysis (EA), thermogravimetric analysis (TGA) coupled with mass spectrometry (TGA-MS), and Kaiser’s test (KT). The results show an increasing monolayer formation up to a complete surface coverage with rising APTES concentration, time, and temperature, resulting in a maximal grafting density of 1.3 molecules/nm². Unspecific multilayer formation was solely observed under acidic conditions. Comparison of TGA-MS results with data recorded from EA, TGA, and KT verified that TGA-MS is a convenient and highly suitable method to elucidate the ligand binding in detail. KW - Boehmite KW - Nanoparticle KW - Surface KW - APTES KW - Functionalization KW - BET KW - TGA KW - Grafting KW - Nanocomposite KW - Silane PY - 2020 DO - https://doi.org/10.1021/acs.langmuir.0c02682 VL - 37 IS - 1 SP - 171 EP - 179 PB - ACS Publications AN - OPUS4-51954 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CHAP A1 - Zarinwall, A. A1 - Waniek, Tassilo A1 - Finke, B. A1 - Sadaat, R. A1 - Sturm, Heinz A1 - Garnweitner, G. ED - Sinapius, M. ED - Ziegmann, G. T1 - Particle Surface Modification N2 - Whilst a decisive role of the particle-matrix interphase on the mechanical properties of nanoparticle-filled polymers has been demonstrated in the last years, the arbitrary design of this interphase remains a very challenging goal. In principle, this could be realized via an appropriate surfacemodification of the nanofiller prior to its incorporation in the polymer. For most systems, such as for boehmite nanofillers, however, the interaction of organic modifiers with the particle surface has not been studied in detail, and only single studies are known rather than systematic investiga- tions on the effects of different chemical functions anchored on the particle surface. In this chapter, we present an extensive study on the binding of APTES, a common silane surface modifier, with boehmite, and show that thermogravimetric analysis (TGA) coupled with mass spectrometry (MS) is a convenient and highly suitable method to elucidate the ligand binding in detail. Furthermore, a two-step coupling strategy is presented, demonstrating that based on APTES anchored to the parti- cle surface, the condensation of various carboxylic acids can be utilized to enable highly diverse chemical properties of the nanofillers, which leads to very different particle-matrix interactions in the nanocomposites. KW - APTES KW - Boehmite KW - Nanoparticle KW - TGA-MS PY - 2021 SN - 978-3-030-68522-5 SN - 978-3-030-68523-2 DO - https://doi.org/10.1007/978-3-030-68523-2 SN - 2194-8240 SN - 2194-8259 SP - 119 EP - 142 PB - Springer Nature Switzerland AG CY - Cham AN - OPUS4-53727 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yusenko, Kirill A1 - Zvereva, V. A1 - Martynova, S. A1 - Asanov, I. A1 - La Fontaine, C. A1 - Roudenko, O. A1 - Gubanov, A. A1 - Plyusnin, P. A1 - Korenev, S. A1 - Asanova, T. T1 - Insight of the thermal decomposition of ammonium hexahalogenoiridates(IV) and hexachloroiridate(III) N2 - Thermal decomposition of (NH4)3[IrCl6]·H2O, (NH4)2[IrCl6] and (NH4)2[IrBr6] in reductive and inert atmospheres has been investigated in situ using quick-EXAFS and temperature-resolved powder X-ray diffraction. For the first time, (NH4)2[Ir(NH3)Cl5] and (NH4)2[Ir(NH3)Br5] have been proven as intermediates of thermal decomposition of (NH4)3[IrCl6]·H2O, (NH4)2[IrCl6] and (NH4)2[IrBr6]. Thermal degradation of (NH4)2[IrCl6] and (NH4)2[IrBr6] is a more complex process as suggested previously and includes simultaneous formation of (NH4)2[Ir(NH3)Cl5] and (NH4)2[Ir(NH3)Br5] intermediates mixed with metallic iridium. In the inert atmosphere, complexes (NH4)[Ir(NH3)2Cl4] and (NH4)[Ir(NH3)2Br4] as well as [Ir(NH3)3Br3] were proposed as possible intermediates before formation of metallic iridium particles KW - Thermal decomposition KW - Iridium compounds KW - EXAFS KW - In situ PXRD PY - 2020 DO - https://doi.org/10.1039/D0CP02743J VL - 22 IS - 40 SP - 22923 EP - 22934 AN - OPUS4-51224 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 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-508194 DO - https://doi.org/10.3390/molecules25040768 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 - Yusenko, Kirill A1 - Spektor, K. A1 - Khandarkhaeva, S. A1 - Fedotenko, T. A1 - Pakhomova, A. A1 - Kupenko, I. A1 - Rohrbach, A. A1 - Klemme, S. A1 - Crichton, W. A. A1 - Dyachkova, T. V. A1 - Tyutyunnik, A. P. A1 - Zainulin, Y. G. A1 - Gramilov, S. A. A1 - Dubrovinsky, L. S. T1 - Decomposition of single-source precursors under high-temperature highpressure to access osmium–platinum refractory alloys N2 - Thermal decomposition of (NH4)2[OsxPt1-xCl6] as single-source precursors for Os-Pt binary alloys has been investigated under ambient and high pressure up to 40 GPa. Thermal decomposition of mixed-metal (NH4)2[OsxPt1-xCl6] precursor in hydrogen atmosphere (reductive environment) under ambient pressure results in formation of β-trans[Pt(NH3)2Cl2] and α-trans-[Pt(NH3)2Cl2] crystalline intermediates as well as single and twophase Os—Pt binary alloys. For the first time, direct thermal decomposition of coordination compound under pressure has been investigated. A formation of pure metallic alloys from single-source precursors under pressure has been shown. Miscibility between fcc- and hcpstructured alloys has been probed up to 50 GPa by in situ high-pressure X-ray diffraction. Miscibility gap between fcc- and hcp-structured alloys does not change its positions with pressure up to at least 50 GPa. KW - High-pressure high-temperature KW - Osmium KW - Platinum KW - Phase diagrams KW - Alloys KW - Single-source precursors PY - 2020 DO - https://doi.org/10.1016/j.jallcom.2019.152121 VL - 813 SP - 152121 PB - Elsevier AN - OPUS4-50019 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Yusenko, Kirill A1 - Smekhova, A. A1 - Kuzmin, A. T1 - Extended X-Ray absorption fine structure (exafs) to study local constitution of high-entropy alloys N2 - Modern design of superior multi-functional alloys composed of several principal components requires in-depth studies of their local structure for developing desired macroscopic properties. Herein, peculiarities of atomic arrangements on the local scale and electronic states of constituent elements in the single-phase face-centered cubic (fcc)- and body-centered cubic (bcc)-structured high-entropy Alx-CrFeCoNi alloys (x = 0.3 and 3, respectively) are explored by element-specific X-ray absorption spectroscopy in hard and soft X-ray energy ranges. Simulations based on the reverse Monte Carlo approach allow to perform a simultaneous fit of extended X-ray absorption fine structure spectra recorded at K absorption edges of each 3d constituent and to reconstruct the local environment within the first coordination shells of absorbers with high precision. T2 - SPP2006: ordering in high-entropy alloys CY - Online meeting DA - 05.10.2021 KW - EXAFS KW - High-entropy alloys PY - 2021 AN - OPUS4-54015 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yusenko, Kirill A1 - Petrushina, M. A1 - Dedova, E. A1 - Portnaygin, A. A1 - Papynov, E. A1 - Filatov, E. A1 - Korenev, S. A1 - Gubanov, A. T1 - Effect of temperature and pressure on mixed oxide solid solutions N2 - A hydrothermal synthesis of ZrW2-xMoxO8 (0 ≤ x ≤ 2) from the corresponding precursors is reported in this paper. High-temperature and high-pressure data are presented for the sample with x = 1.6. An increase in temperature initiates the phase transition from tetragonal precursor to orthorhombic-ZrW2-xMoxO8 (x = 1.6) with the subsequent formation of cubic and trigonal phases. The thermolysis parameter of the disordered cubic ZrW2-xMoxO8 (x = 1.6) phase is 803 K, and the coefficient of thermal expansion is α = -4.6∙10–6 K−1. Data on ZrW2-xMoxO8 (x = 1.6) structure as a function of pressure are obtained for the first time. Pressureinduced changes from cubic to orthorhombic ZrW2-xMoxO8 (x = 1.6) phase at 1.38 GPa are observed. The sample amorphization is irreversible during decompression. KW - Phase transition KW - High-pressure KW - Complex oxides PY - 2020 DO - https://doi.org/10.1016/j.inoche.2020.107965 VL - 117 SP - 107965 PB - Elsevier B.V. AN - OPUS4-50821 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -