Suchergebnisse

A pressure-induced interaction between core electrons, the core-level crossing (CLC) transition, has been observed in hcp Os at P approximate to 400 GPa [L. Dubrovinsky et al., Nature (London) 525, 226 (2015)]. By carrying out a systematic theoretical study for all metals of the 5d series (Hf, Ta, W, Re, Os, Ir, Pt, Au) we have found that the CLC transition is a general effect for this series of metals. While in Pt it occurs at approximate to 1500 GPa, at a pressure substantially higher than in Os, in Ir it occurs already at 80 GPa. Moreover, we predict that in Re the CLC transition may take place already at ambient pressure. We explain the effect of the CLC and analyze the shift of the transition pressure across the series within the Thomas-Fermi model. In particular, we show that the effect has many common features with the atomic collapse in rare-earth elements. ; Funding Agencies|Swedish Government Strategic Research Area Grant Swedish e-Science Research Centre (SeRC); Ministry of Education and Science of the Russian Federation in the framework of Increase Competitiveness Program of MISiS; Swedish Foundation for Strategic Research (SSF) program SRL [10-0026]; Swedish Research Council (VR) [2015-04391]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; Ministry of Education and Science of the Russian Federation [14.Y26.31.0005]; German Research Foundation (DFG); Federal Ministry of Education and Research (BMBF), Germany; DFG [DU 954-8/1]; BMBF (PT-DESY) [5K13WC3, O5K2013, 2]; Act 211 Government of the Russian Federation [02.A03.21.0006]; Knut and Alice Wallenberg Foundation [2012.0083, 2014-2019]

Carbon has a low solid solubility in bcc tungsten at equilibrium. However, metastable supersaturated solid solutions can be synthesized with magnetron sputtering. Here, we present a systematic study on the phase stability and mechanical properties of such supersaturated W-C solid solutions. H-2h scans show a split of the 200/020 and the 002 peaks for supersaturated films which is explained by a tetragonal distortion of the bcc structure. This split increases with increasing C content and is maximized at 4 at.% C, where we observe an a/b axis of 3.15-3.16 A and a c-axis of 3.21-3.22 A. We performed first-principles calculations of lattice parameters, mixing enthalpies, elastic constants and polycrystalline elastic moduli for cubic and tetragonal W-C solid solutions. Calculations show that tetragonal structure is more stable than the bcc supersaturated solid solution and the calculated lattice parameters and Youngs moduli follow the same trends as the experimental ones as a function of C concentration. The results suggest that supersaturated films with lattice distortion can be used as a design approach to improve the properties of transition metal films with a bcc structure. (c) 2022 The Authors. Published by Elsevier Ltd. ; Funding Agencies|Knut and Alice Wallenberg Foundation (Wallenberg Scholar Grant) [KAW-2018.0194]; Swedish Research Council (VR)Swedish Research Council [2018-04834, 2019-05403]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University, Faculty Grant SFOMatLiU [2009 00971]; Swedish Foundation for Strategic Research through the Future Research Leaders 6 program [FFL 15-0290]; RFBRRussian Foundation for Basic Research (RFBR) [20-02-00178]; Swedish Research Council at the National Supercomputer Center (NSC) [2018-05973]

Body centered cubic (bcc) Ti-based alloys are of interest for multiple technological applications ranging from aerospace technology to biomedicine. However, these alloys are usually unstable at low temperatures. Indeed, the calculated elastic modulus C of bcc Ti-V alloys with low V concentrations is negative at 0 K temperature, indicating their mechanical instability. Here, we investigate elastic moduli of the Ti-V system in the vicinity of mechanical instability theoretically and experimentally. Our calculations predict that mechanical stabilization of bcc Ti-V alloys, which is governed by the hardening of C , is possible at as low V concentration as 18 at.%. We synthesize single-phase bcc alloys with as little as 22 at.% of V with low values of Youngs modulus. Moreover, we predict strong concentration dependence of anisotropy of Youngs modulus in these alloys that can also be used in tuning the alloy composition to design materials for specific applications. ; Funding Agencies|Swedish Research Council (VR)Swedish Research Council [2018-04834]; VINN Excellence Center Functional Nanoscale Materials (FunMat-2) [2016-05156]; Swedish Government Strategic Research Areas in Materials Science on Functional Materials at Linkoping University [2009-00971]; RFBRRussian Foundation for Basic Research (RFBR) [20-02-00178]

Due to their high melting temperature, high-temperature oxidation resistance and outstanding mechanical properties, TaxZr1-xC solid solutions are promising ultra-high temperature ceramics (UHTC). However, accelerated knowledge-based development of UHTCs solid solutions requires reliable data regarding the properties of the solution phases in the whole interval of concentrations. At present, there are contradictory reports regarding the existence of the miscibility gap in Ta-Zr-C system at temperatures below 900 degrees C. In this work, we carry out ab-initio calculations of the thermodynamic properties of TaxZr1-xC alloys and demonstrate that the solid solutions should not decompose into TaC and ZrC end member compounds. We synthesize single-phase samples of TaxZr1-xC with compositions x = 0.9, 0.8, 0.6, and 0.3 by self-propagating high-temperature synthesis (SHS) and anneal the samples for 40 h. We do not observe any sign of the decomposition of the solid solution during the annealing, corroborating the conclusions obtained by theoretical simulations. (C) 2018 Elsevier B.V. All rights reserved. ; Funding Agencies|Ministry of Education and Science of the Russian Federation [14.Y26.31.0005, K2-2017-080]; Russian Science Foundation [17-79-10173]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]

Recent theoretical investigations [A. B. Belonoshko et aL Nat. Geosci. 10, 312 (2017)] revealed the occurrence of the concerted migration of several atoms in bcc Fe at inner-core temperatures and pressures. Here, we combine first-principles and semiempirical atomistic simulations to show that a diffusion mechanism analogous to the one predicted for bcc iron at extreme conditions is also operative and of relevance for the high-temperature bcc phase of pure Ti at ambient pressure. The mechanism entails a rapid collective movement of numerous (from two to dozens) neighbors along tangled closed-loop paths in defect-free crystal regions. We argue that this phenomenon closely resembles the diffusion behavior of superionics and liquid metals. Furthermore, we suggest that concerted migration is the atomistic manifestation of vanishingly small co-mode phonon frequencies previously detected via neutron scattering and the mechanism underlying anomalously large and markedly non-Arrhenius self-diffusivities characteristic of bcc Ti. ; Funding Agencies|Olle Engkvist Foundation; Swedish Research Council (VR) [2015-04391, 2014-4750]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFOMat-LiU) [2009-00971]; VINN Excellence Center Functional Nanoscale Materials (FunMat-2) [2016-05156]

We develop a method to accurately and efficiently determine the vibrational free energy as a function of temperature and volume for substitutional alloys from first principles. Taking Ti1-xAlxN alloy as a model system, we calculate the isostructural phase diagram by finding the global minimum of the free energy corresponding to the true equilibrium state of the system. We demonstrate that the vibrational contribution including anharmonicity and temperature dependence of the mixing enthalpy have a decisive impact on the calculated phase diagram of a Ti1-xAlxN alloy, lowering the maximum temperature for the miscibility gap from 6560 to 2860 K. Our local chemical composition measurements on thermally aged Ti0.5Al0.5N alloys agree with the calculated phase diagram. ; Funding Agencies|Swedish Foundation for Strategic Research Programs (Stiftelsen for Strategisk Forskning) [SRL10-0026, RMA08-0069]; FUNCASE; Swedish Research Council (Vetenskapsradet) [2012-4401, 621-2011-4426, 2015-04391, 637-2013-7296, 621-2011-4417, 330-2014-6336]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; Swedish Governmental Agency for Innovation Systems (Vinnova) through the M-ERA.net project MC2; SECO Tools AB; Marie Sklodowska Curie Actions, Cofund [INCA 600398]; Erasmus Mundus Joint European Doctoral Programme DocMASE; Ministry of Education and Science of the Russian Federation [K2-2016-013]; Deutsche Forschungsgemeinschaft; Federal State Government of Saarland [INST 256/298-1 FUGG]

Beryllium oxides have been extensively studied due to their unique chemical properties and important technological applications. Typically, in inorganic compounds beryllium is tetrahedrally coordinated by oxygen atoms. Herein based on results of in situ single crystal X-ray diffraction studies and ab initio calculations we report on the high-pressure behavior of CaBe2P2O8, to the best of our knowledge the first compound showing a step-wise transition of Be coordination from tetrahedral (4) to octahedral (6) through trigonal bipyramidal (5). It is remarkable that the same transformation route is observed for phosphorus. Our theoretical analysis suggests that the sequence of structural transitions of CaBe2P2O8 is associated with the electronic transformation from predominantly molecular orbitals at low pressure to the state with overlapping electronic clouds of anions orbitals. ; Funding Agencies|Ministry of Science and High Education of the Russian Federation [K2-2019-001]; Russian Foundation for Basic Research [19-02-00871]; Swedish Research Council (VR) [2015-04391]; Swedish Government Strategic Research Areas in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; SeRC

The TiN/SiNx nanocomposite and nanolaminate systems are the archetype for super if not ultrahard materials. Yet, the nature of the SiNx tissue phase is debated. Here, we show by atomically resolved electron microscopy methods that SiNx is epitaxially stabilized in a NaCl structure on the adjacent TiN(001) surfaces. Additionally, electron energy loss spectroscopy, supported by first-principles density functional theory calculations infer that SiNx hosts Si vacancies. ; Funding Agencies|Swedish Research Council (VR) [2008-405, 2012-4359, 2015-04391, 2016-04412]; Swedish Foundation for Strategic Research (SSF) through FunCase; SRL [10-0026]; M. Bergwall foundation; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; Ministry of Education and Science of the Russian Federation [14.Y26.31.0005, K2-2017-080]; [RIF 14-0074]

We provide experimental and theoretical evidence for a pressure-induced Mott insulator-metal transition in Fe2O3 characterized by site-selective delocalization of the electrons. Density functional plus dynamical mean field theory (DFT + DMFT) calculations, along with Mossbauer spectroscopy, x-ray diffraction, and electrical transport measurements on Fe2O3 up to 100 GPa, reveal this site-selective Mott transition between 50 and 68 GPa, such that the metallization can be described by ((FE3+HS)-F-VI)(2)O-3 [R (3) over barc structure]-amp;gt;(50) (GPa) (Fe-VIII(3+HS) Fe-VI(M))O-3 [P2(1)/n structure]-amp;gt;(68 Gpa)(Fe-VI(M))(2)O-3[Aba2/PPv structure]. Within the P2(1)/n crystal structure, characterized by two distinct coordination sites (VI and VIII), we observe equal abundances of ferric ions (Fe3+) and ions having delocalized electrons (Fe-M), and only at higher pressures is a fully metallic high-pressure structure obtained, all at room temperature. Thereby, the transition is characterized by delocalization/metallization of the 3d electrons on half the Fe sites, with a site-dependent collapse of local moments. Above approximately 50 GPa, Fe2O3 is a strongly correlated metal with reduced electron mobility (large band renormalizations) of m*/m similar to 4 and 6 near the Fermi level. Importantly, upon decompression, we observe a site-selective (metallic) to conventional Mott insulator phase transition (Fe-VIII(3+HS) Fe-VI(M))O-3 -amp;gt;(50) (GPa)(Fe-VIII(3+HS) Fe-VI(3+HS))O-3 within the same P2(1)/n structure, indicating a decoupling of the electronic and lattice degrees of freedom. Our results offer a model for understanding insulator-metal transitions in correlated electron materials, showing that the interplay of electronic correlations and crystal structure may result in rather complex behavior of the electronic and magnetic states of such compounds. ; Funding Agencies|Israeli Science Foundation [1189/14]; U.S. Department of Energy; Swedish Research Council (VR) [2015-04391]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFOMatLiU) [2009 00971]; Swedish e-Science Research Centre (SeRC); Deutsche Forschungsgemeinschaft through Transregio [TRR 80]; Russian Science Foundation [18-12-00492]; Ministry of Education and Science of the Russian Federation [K3-2016-027]

The remarkable mechanical properties of high-entropy alloys can be further improved by interstitial alloying. In this work we employ density functional theory calculations to study the solution energies of dilute carbon interstitial atoms in tetrahedral and octahedral sites in bcc HfNbTiVZr. Our results indicate that carbon interstitials in tetrahedral sites are unstable, and the preferred octahedral sites present a large spread in the energy of solution. The inclusion of carbon interstitials induces large structural relaxations with long-range effects. The effect of local chemical environment on the energy of solution is investigated by performing a local cluster expansion including studies of its correlation with the carbon atomic Voronoi volume. However, the spread in solution energetics cannot be explained with a local environment analysis only pointing towards a complex, long-range influence of interstitial carbon in this alloy. ; Funding Agencies|Swedish Research Council (VR)Swedish Research Council [2019-05403, 2018-04834]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University, Faculty Grant SFOMatLiU [2009 00971]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [KAW2018.0194]; Swedish Foundation for Strategic Research through the Future Research Leaders 6 program [FFL 15-0290]; RFBRRussian Foundation for Basic Research (RFBR) [20-02-00178]; NordForsk Nordic Neutron Science Programme through the functional hydrides (FunHy) project [81942]

The chelating gadolinium-complex is routinely used as magnetic resonance imaging (MRI) -contrast enhancer. However, several safety issues have recently been reported by FDA and PRAC. There is an urgent need for the next generation of safer MRI-contrast enhancers, with improved local contrast and targeting capabilities. Cerium oxide nanoparticles (CeNPs) are designed with fractions of up to 50% gadolinium to utilize the superior MRI-contrast properties of gadolinium. CeNPs are well-tolerated in vivo and have redox properties making them suitable for biomedical applications, for example scavenging purposes on the tissue-and cellular level and during tumor treatment to reduce in vivo inflammatory processes. Our near edge X-ray absorption fine structure (NEXAFS) studies show that implementation of gadolinium changes the initial co-existence of oxidation states Ce3+ and Ce4+ of cerium, thereby affecting the scavenging properties of the nanoparticles. Based on ab initio electronic structure calculations, we describe the most prominent spectral features for the respective oxidation states. The as-prepared gadolinium-implemented CeNPs are 3-5 nm in size, have r(1)-relaxivities between 7-13 mM(-1) s(-1) and show clear antioxidative properties, all of which means they are promising theranostic agents for use in future biomedical applications. ; Funding Agencies|Swedish Research Council [621-2013-5357]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; Knut and Alice Wallenberg Foundation [2012.0083 CTS 15:507]; Centre in Nano Science and Nano technology at LiTH (CeNano) at Linkoping University; CoTXS; Ministry of Education and Science of the Russian Federation [14.Y26.31.0005, K2-2017-080, 211]

The large class of layered ceramics encompasses both van der Waals (vdW) and non-vdW solids. While intercalation of noble metals in vdW solids is known, formation of compounds by incorporation of noble-metal layers in non-vdW layered solids is largely unexplored. Here, we show formation of Ti3AuC2 and Ti3Au2C2 phases with up to 31% lattice swelling by a substitutional solid-state reaction of Au into Ti3SiC2 single-crystal thin films with simultaneous out-diffusion of Si. Ti3IrC2 is subsequently produced by a substitution reaction of Ir for Au in Ti3Au2C2. These phases form Ohmic electrical contacts to SiC and remain stable after 1,000 h of ageing at 600 degrees C in air. The present results, by combined analytical electron microscopy and ab initio calculations, open avenues for processing of noble-metal-containing layered ceramics that have not been synthesized from elemental sources, along with tunable properties such as stable electrical contacts for high-temperature power electronics or gas sensors. ; Funding Agencies|VINN Excellence Center in research and innovation on Functional Nanoscale Materials (FunMat) by the Swedish Governmental Agency for Innovation Systems (VINNOVA); Swedish Government Strategic Research Areas in Materials Science on Functional Materials at Linkoping University [2009 00971]; Swedish Foundation for Strategic Research through the Future Research Leaders 5 Program; Synergy Grant FUNCASE, Functional Carbides and Advanced Surface Engineering; e-Science Research Centre (SeRC); Swedish Research Council (VR) [2014-4750]; European Research Council under the European Community [335383]; Knut and Alice Wallenberg Foundation

Dynamic nuclear polarization (DNP) is an attractive method for initializing nuclear spins that are strongly coupled to optically active electron spins because it functions at room temperature and does not require strong magnetic fields. In this Letter, we theoretically demonstrate that DNP, with near-unity polarization efficiency, can be generally realized in weakly coupled electron spin-nuclear spin systems. Furthermore, we theoretically and experimentally show that the nuclear spin polarization can be reversed by magnetic field variations as small as 0.8 Gauss. This mechanism offers new avenues for DNP-based sensors and radio-frequency free control of nuclear qubits. ; Funding Agencies|Knut & Alice Wallenberg Foundation; Swedish Research Council (VR) [2015-04391]; Swedish Foundation for Strategic Research program SRL Grant [10-0026]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; Ministry of Education and Science of the Russian Federation [14.Y26.31.0005]; Swedish National Infrastructure for Computing [SNIC 2013/1-331, SNIC 2014/1-420]; "Lendulet program" of the Hungarian Academy of Sciences; NSF [EFMA-1641099]; UChicago NSF-MRSEC; AFOSR, AFOSR-MURI, ARO

The 5d transition metals have attracted specific interest for high-pressure studies due to their extraordinary stability and intriguing electronic properties. In particular, iridium metal has been proposed to exhibit a recently discovered pressure-induced electronic transition, the so-called core-level crossing transition at the lowest pressure among all the 5d transition metals. Here, we report an experimental structural characterization of iridium by x-ray probes sensitive to both long- and short-range order in matter. Synchrotron-based powder x-ray diffraction results highlight a large stability range (up to 1.4 Mbar) of the low-pressure phase. The compressibility behaviour was characterized by an accurate determination of the pressure-volume equation of state, with a bulk modulus of 339(3) GPa and its derivative of 5.3(1). X-ray absorption spectroscopy, which probes the local structure and the empty density of electronic states above the Fermi level, was also utilized. The remarkable agreement observed between experimental and calculated spectra validates the reliability of theoretical predictions of the pressure dependence of the electronic structure of iridium in the studied interval of compressions. ; Funding Agencies|Spanish Ministry of Science, Innovation and Universities; Spanish Research Agency (AEI); European Fund for Regional Development (FEDER) [MAT2016-75586-C4-1/2-P]; Generalitat Valenciana [Prometeo/2018/123]; Spanish Mineco Project [FIS2017-83295-P]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; Ministry of Science and High Education of the Russian Federation [K2-2019-001]; "Juan de la Cierva" fellowship [FJCI-2016-27921]; "Ramon y Cajal" fellowship [RYC-2015-17482]

In this work we present a comprehensive study of the domain structure of a nickel oxide single crystal grown by floating zone melting and suggest a correlation between point defects and the observed domain structure. The properties and structure of domains dictate the dynamics of resistive switching, water splitting and gas sensing, to name but a few. Investigating the correlation between point defects and domain structure can provide a deeper understanding of their formation and structure, which potentially allows one to tailor domain structure and the dynamics of the aforementioned applications. A range of inhomogeneities are observed by diffraction and microscopy techniques. X-ray and low-energy electron diffraction reveal domains on the submicron- and nanometer-scales, respectively. In turn, these domains are visualised by atomic force and scanning tunneling microscopy (STM), respectively. A comprehensive transmission electron microscopy (TEM) study reveals inhomogeneities ranging from domains of varying size, misorientation of domains, variation of the lattice constant and bending of lattice planes. X-ray photoelectron spectroscopy and electron energy-loss spectroscopy indicate the crystal is Ni deficient. Density functional theory calculations-considering the spatial and electronic disturbance induced by the favourable nickel vacancy-reveal a nanoscale distortion comparable to STM and TEM observations. The different inhomogeneities are understood in terms of the structural relaxation induced by ordering of nickel vacancies, which is predicted to be favourable. ; Funding Agencies|Russian Science FoundationRussian Science Foundation (RSF) [18-12-00492]; RFBRRussian Foundation for Basic Research (RFBR) [19-29-03021]; Research Facility Center at the ISSP of RAS; Erasmus Plus mobility Grants [2016-1-IE02-KA107-000479, 2017-1-IE02-KA107-000538 2018-1-IE02-KA107-000589]; Ministry of Science and Higher Education of the Russian Federation [K2-2019-001, 211]; Swedish Research Council (VR)Swedish Research Council [2019-05600]; Swedish Government Strategic Research Areas in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; Irish Research Council Laureate AwardIrish Research Council for Science, Engineering and Technology [IRCLA/2019/171]