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Electronic Structure and Spin Correlations in Novel Magnetic Structures

The research has advanced understanding of the interrelation between the crystal structure and magnetism in several materials which are or can be of interest for the development of improved, specialized or more cost-effective permanent magnets, as well as in selected materials for biomedical and catalytic applications. Fundamental aspects of ferromagnetism were investigated for Mn-Ge, Co-V and Co-Ge nanoclusters and for melt-spun Co-Sn alloys. New solution-chemistry synthesis methods were designed and tested for Fe-Pt, Fe3C and Fe3O4 nanoparticles. Off-stoichiometric Laves phases in the Fe-Si-Zr, Fe-Nb and Fe-Ta systems, as well as Fe5(Si,Ge)B2 compounds were assessed as new rare-earth-free permanent magnet materials; all except the Fe-Si-Zr Laves phases were found to be promising enough to merit a further exploration. A new method for manufacturing rare-earth-free magnets based on the MnBi compound was developed; by purposely avoiding oxidation-sensitive fine single-crystalline powders, the new method yields magnets with a 50% larger energy storage capacity. Studies of rare-earth-lean permanent-magnet materials (lean compared to the currently predominant Nd-Fe-B materials) were focused on the tetragonal compound of the ThMn12 structure type and included both discovery and characterization of new formulations and exploration of new fabrication/processing techniques. Among the most significant achievements were successful preparation of a vanadium-lean SmFe11V compound, the first observation of thermomechanically induced texture in nanocrystalline Sm(Fe,V)12 alloys, and a breakthrough reduction-diffusion synthesis of Sm1-xZrx(Fe0.8Co0.2)11.2Ti0.8 single-crystal particles with a coercivity as high as 12.6 kOe. Several experiments aimed at improvement of the Nd-Fe-B magnet have also been undertaken including a five-fold increase of the coercivity through a grain-boundary diffusion treatment of a Nd10Fe84B6 nanocrystalline alloy.

36 MATERIALS SCIENCE↗

Apollo 14 very low titanium glasses - Melting experiments in iron-platinum alloy capsules

This paper describes two techniques that have been developed to produce Fe-Pt alloy capsules for hgh-pressure experiments, and reports liquidus-phase relations of the Apollo 14 very low titanium glasses determined using Fe-rich capsules (a/Fe/ approximately 0.6). The liquid is multiply saturated with olivine and clinopyroxene at equal to or greater than 22 kbar. The multiple saturation is at least 3 kbar higher than that determined using pure Fe capsules and corresponds to a source region at least 60 km deeper if olivine and clinopyroxene were the residual phases. However, independent data on iron activity or oxygen fugacity of the glasses are still needed in order to choose a container of optimum composition. Preliminary experiments in Fe-poor alloy capsules suggest that the valence state of iron and the crystallization sequence in the melt have changed, possibly as a result of oxidizing materials entrapped during the iron-plating processes. The FeO content of the charge decreases linearly with increasing run duration in experiments using pure Fe capsules. The observation that iron-rich globules grow with time suggests that the equilibrium Fe (bleb) + Fe2O3 (liq) = 3 FeO (liq) might be established in the liquid at high pressure. If this explanation is correct, an appreciable amount of 'FeO' in the liquid could actually be Fe2O3, and some natural lunar volcanic glasses may contain ferric iron as well.

Chen, H.-K.↗

A Transmission Electron Microscopy Study of a Refractory Metal Grain from a Calcium-Aluminum-Rich Inclusion in the Leoville CV3 Chondrite

Introduction: Calcium-aluminum-rich inclusions (CAIs) are an important component of chondritic meteorites. They can contain materials that are thermodynamically predicted and isotopically age dated to be among the first-formed solids in our solar system [1-5]. Observed in some CAIs are micron to sub-micron sized inclusions rich in Fe, Ni, and high-Z elements such as Pt, Os, Ir and W, in the form of refractory metal nuggets (RMNs), fremdlinges, and ‘nugget like objects’ (NLOs) [1,6]. Refractory siderophile elements such as Os, Ir and Ru are thermodynamically predicted to condense at temperatures well in excess of the major CAI phases such as melilite, perovskite, spinel and hibonite [2,7-9]. These refractory metal inclusions in CAIs can therefore serve as probes into the thermodynamic landscape of the early solar protoplanetary disk. Here we report on a refractory grain identified in a CAI of the Leoville CV3 chondrite. This work is part of an ongoing effort to gain insight into the thermochemistry of the early solar system through systematic analyses of the structure and chemistry of various components in CAIs [10-13]. Sample and Analytical Techniques: A fluffy type A CAI (Fig. 1A) was identified in a section of the Leoville, CV3 chondrite (Center for Meteorite Studies, Arizona State University collection, #821_C_3) using a JOEL-JXA 8530F electron microprobe at Arizona State University. Backscattered electron (BSE) imaging and energy-dispersive X-ray spectroscopy (EDS) were used to identify refractory metal grains in the CAI using a Thermo Fisher (formerly FEI) Helios NanoLab 660 G3 focused-ion-beam scanning-electron microscope (FIBSEM) located at the Kuiper Materials Imaging and Characterization Facility (KMICF) at the Lunar and Planetary Laboratory, University of Arizona. The FIB is equipped with an EDAX EDS system. We selected one of the larger (micron-sized) refractory metal grains, designated as ‘Spud’ (Fig. 1B) for further analysis. ‘Spud’ was extracted and thinned to electron transparency (<100 nm) using the FIB-SEM located in KMICF, following methods described by [14- 15]. The FIB section was analyzed using a 200 keV Hitachi HF5000 scanning transmission electron microscope (S/TEM) located at KMICF. The HF5000 is equipped with cold-field emission gun, 3rd-order spherical aberration corrector for STEM imaging, and an Oxford Instruments X-Max N 100 TLE energydispersive spectroscopy (EDS) system with dual 100 mm2 windowless silicon-drift detectors (Ω = 2.0 sr). Selected-area electron-diffraction (SAED) patterns were acquired to aid in determination of crystallinity and phase. Results: The mineralogy, texture, and morphology of the CAI are consistent with that of a fluffy type A (FTA) CAI [16]. BSE imaging at high magnifications revealed grains with high contrast, indicative of compositions rich in elements of higher atomic number relative to surrounding material. These high-Z grains have sizes that range from ∼250 nm to 4 µm. EDS analyses confirm that the bright grains are metal-rich inclusions. A minor fraction of the grains are composed of only Fe and Ni, but the majority (∼60%) of the identified inclusions also contained various refractory siderophiles including Os, Ru, Zr, Ir and Mo. EDS analysis on the FIB-SEM of Spud shows that it contains Fe, Ni, Mo and Ru. High-angle annular dark-field (HAAFD) imaging and EDS mapping in the TEM (Fig. 2) show that Spud occurs in melilite (Ca1.9Al1.99Si1.06O7). Spud contains a subhedral to anhedral morphology and is compositionally heterogenous (polyphasic, Fig. 2). Local spatial correlation occurs among Fe, Ni, and Pt, and also among Os, Ru, and Mo. SAED patterns show that the Fe-Ni-Pt, Fe-Os-Mo-Ru and Fe-Pt regions are crystalline. Discussion: CAIs can contain various types of inclusions rich in Fe, Ni and refractory siderophiles such as Os, Ru, W and Pt [1]. RMNs are micron-sized, single phase alloy grains and can contain Os, Ir, Ru and Rh [1,7,17]. NLOs are also micron-sized inclusions, but contain two phases, a refractory metal, and an oxide [6]. Fremdlinge are the largest of such inclusions (tens of microns in size) and are complex aggregates of Fe-Ni alloy, silicates, oxides, and sulfides [1,17]. While the size of Spud matches previous descriptions of RMNs and NLOs, Spud is neither a single-phase alloy like RMNs, nor does it contain one metal phase and one oxide like NLOs. Spud does not match the above described categories of refractory metal inclusions. The presence of refractory siderophiles such as Mo, Os, Ru, and Pt suggests a high-temperature origin. Thermodynamic modelling by [7] indicates condensation temperatures of 1917 K, 1693 K, 1613 K and 1415 K for Os, Mo, Ru and Pt respectively. These models also show that following the initial condensation of a refractory metal, alloying of solutes such as Fe, Ni and W, occurs in levels proportional to their partial pressures in the surrounding gas. Such alloying occurs at temperatures above the condensation temperatures of common CAI phases such as melilite (1529 K), perovskite (1441 K), spinel (197 K) and forsterite (1354 K) [2]. The polyphasic nature of Spud could be the result of such high-temperature alloying, possibly shortly after the condensation of Mo and Ru at 1693 K and 1613 K respectively. That Spud occurs as an inclusion is consistent with it having formed prior to and at temperature above that of its host melilite in this FTA CAI, which is qualitatively consistent with such prior thermodynamic modeling. Further, the polyphasic nature of Spud is similar to refractory grains from a FTA CAI in the Northwest Africa (NWA) 8323, CV3 chondrite [11-13]. These data suggest that such refractory metal grains could have been widespread in the inner and early solar protoplanetary disk and represent some of the earliest formed solids to have condensed. Acknowledgments: Research and instrumentation supported by NASA grants #NNX12AL47G, #NNX15AJ22G and #80NSSC19K0509, and NSF grants #1531243 and #0619599. Fig 2. STEM data on ‘Spud’. HAADF Image (Top) False-color EDS Maps (Bottom) References: [1] MacPherson G. J. (2014) T. of Geochem. Vol I: Met. And Cosmochem. Processes, 139-179. [2] Lodders K. (2003) ApJ, 591, 1220-1247. [3] Ebel D. S. (2006) Met. & the Early S. Sys. II., 253- 277. [4] Amelin Y. (2002) Science, 297, 1678-1683. [5] Connelly J.N. et.al. (2012) Science, 338, 651-655. [6] Schwander D. et al. (2015) GCA, 18, 70-87. [7] Palme H. and Wlotzka F. (1976) EPSL, 33, 45-60. [8] Berg T. et al. (2009) ApJ, 702, 172-176. [9] Liffman K. et al. (2021) Icarus, 221, 89-105. [10] Zega T.J. et al. (2021) PSJ, 2, 115. [11] Ramprasad T. et al. (2020) LPSC LI, Abstract #2472. [12] Ramprasad T. et al. (2021) Microscopy & Microanalysis, S1, 2792-2794. [13] Ramprasad T. et al. (2021) 84th MetSoc, Abstract #6123. [14] Zega T.J. et al. (2007) MAPS, 42, 1373-1386. [15] Ramprasad T. et al. (2022) MAPS, in revision. [16] Grossman L. (1975), GCA, 39, 433-454. [17] El Goresy A. et al. (1978) LPSC IX, Abstract#1100

T. Ramprasad↗

Materials Data on Fe3Pt by Materials Project

Fe3Pt is Uranium Silicide structured and crystallizes in the tetragonal P4/mmm space group. The structure is three-dimensional. there are two inequivalent Fe sites. In the first Fe site, Fe is bonded to eight Fe and four equivalent Pt atoms to form distorted FeFe8Pt4 cuboctahedra that share corners with twelve equivalent FeFe8Pt4 cuboctahedra, edges with eight equivalent PtFe12 cuboctahedra, edges with sixteen FeFe8Pt4 cuboctahedra, faces with four equivalent PtFe12 cuboctahedra, and faces with fourteen FeFe8Pt4 cuboctahedra. There are four shorter (2.62 Å) and four longer (2.71 Å) Fe–Fe bond lengths. All Fe–Pt bond lengths are 2.62 Å. In the second Fe site, Fe is bonded to eight equivalent Fe and four equivalent Pt atoms to form FeFe8Pt4 cuboctahedra that share corners with twelve equivalent FeFe8Pt4 cuboctahedra, edges with eight equivalent PtFe12 cuboctahedra, edges with sixteen equivalent FeFe8Pt4 cuboctahedra, faces with four equivalent PtFe12 cuboctahedra, and faces with fourteen FeFe8Pt4 cuboctahedra. All Fe–Pt bond lengths are 2.71 Å. Pt is bonded to twelve Fe atoms to form PtFe12 cuboctahedra that share corners with twelve equivalent PtFe12 cuboctahedra, edges with twenty-four FeFe8Pt4 cuboctahedra, faces with six equivalent PtFe12 cuboctahedra, and faces with twelve FeFe8Pt4 cuboctahedra.

36 MATERIALS SCIENCE↗

Materials Data on Fe3Pt by Materials Project

Fe3Pt is Uranium Silicide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Fe is bonded to eight equivalent Fe and four equivalent Pt atoms to form distorted FeFe8Pt4 cuboctahedra that share corners with twelve equivalent FeFe8Pt4 cuboctahedra, edges with eight equivalent PtFe12 cuboctahedra, edges with sixteen equivalent FeFe8Pt4 cuboctahedra, faces with four equivalent PtFe12 cuboctahedra, and faces with fourteen equivalent FeFe8Pt4 cuboctahedra. All Fe–Fe bond lengths are 2.65 Å. All Fe–Pt bond lengths are 2.65 Å. Pt is bonded to twelve equivalent Fe atoms to form PtFe12 cuboctahedra that share corners with twelve equivalent PtFe12 cuboctahedra, edges with twenty-four equivalent FeFe8Pt4 cuboctahedra, faces with six equivalent PtFe12 cuboctahedra, and faces with twelve equivalent FeFe8Pt4 cuboctahedra.

36 MATERIALS SCIENCE↗

Materials Data on FePt by Materials Project

FePt is Tetraauricupride structured and crystallizes in the tetragonal P4/mmm space group. The structure is three-dimensional. Fe2+ is bonded in a distorted body-centered cubic geometry to eight equivalent Pt2- atoms. All Fe–Pt bond lengths are 2.70 Å. Pt2- is bonded to eight equivalent Fe2+ and four equivalent Pt2- atoms to form a mixture of distorted corner, edge, and face-sharing PtFe8Pt4 cuboctahedra. All Pt–Pt bond lengths are 2.73 Å.

36 MATERIALS SCIENCE↗

Materials Data on FePt3 by Materials Project

FePt3 is Uranium Silicide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Fe2+ is bonded to twelve equivalent Pt+0.67- atoms to form FePt12 cuboctahedra that share corners with twelve equivalent FePt12 cuboctahedra, edges with twenty-four equivalent PtFe4Pt8 cuboctahedra, faces with six equivalent FePt12 cuboctahedra, and faces with twelve equivalent PtFe4Pt8 cuboctahedra. All Fe–Pt bond lengths are 2.74 Å. Pt+0.67- is bonded to four equivalent Fe2+ and eight equivalent Pt+0.67- atoms to form distorted PtFe4Pt8 cuboctahedra that share corners with twelve equivalent PtFe4Pt8 cuboctahedra, edges with eight equivalent FePt12 cuboctahedra, edges with sixteen equivalent PtFe4Pt8 cuboctahedra, faces with four equivalent FePt12 cuboctahedra, and faces with fourteen equivalent PtFe4Pt8 cuboctahedra. All Pt–Pt bond lengths are 2.74 Å.

36 MATERIALS SCIENCE↗

Materials Data on Fe2Pt by Materials Project

Fe2Pt is beta-derived structured and crystallizes in the trigonal P-3m1 space group. The structure is three-dimensional. Fe is bonded to nine equivalent Fe and three equivalent Pt atoms to form distorted FeFe9Pt3 cuboctahedra that share corners with three equivalent PtFe6Pt6 cuboctahedra, corners with nine equivalent FeFe9Pt3 cuboctahedra, edges with nine equivalent PtFe6Pt6 cuboctahedra, edges with fifteen equivalent FeFe9Pt3 cuboctahedra, faces with six equivalent PtFe6Pt6 cuboctahedra, and faces with twelve equivalent FeFe9Pt3 cuboctahedra. There are three shorter (2.36 Å) and six longer (2.62 Å) Fe–Fe bond lengths. All Fe–Pt bond lengths are 2.69 Å. Pt is bonded to six equivalent Fe and six equivalent Pt atoms to form PtFe6Pt6 cuboctahedra that share corners with six equivalent FeFe9Pt3 cuboctahedra, corners with six equivalent PtFe6Pt6 cuboctahedra, edges with six equivalent PtFe6Pt6 cuboctahedra, edges with eighteen equivalent FeFe9Pt3 cuboctahedra, faces with six equivalent PtFe6Pt6 cuboctahedra, and faces with twelve equivalent FeFe9Pt3 cuboctahedra. All Pt–Pt bond lengths are 2.62 Å.

36 MATERIALS SCIENCE↗

Materials Data on Fe3Pt by Materials Project

Fe3Pt crystallizes in the trigonal R-3m space group. The structure is three-dimensional. there are five inequivalent Fe sites. In the first Fe site, Fe is bonded to nine Fe and three equivalent Pt atoms to form distorted FeFe9Pt3 cuboctahedra that share corners with twelve equivalent FeFe9Pt3 cuboctahedra, edges with six equivalent PtFe6Pt6 cuboctahedra, edges with eighteen FeFe9Pt3 cuboctahedra, faces with six equivalent PtFe6Pt6 cuboctahedra, and faces with twelve FeFe9Pt3 cuboctahedra. There are three shorter (2.50 Å) and six longer (2.72 Å) Fe–Fe bond lengths. All Fe–Pt bond lengths are 2.69 Å. In the second Fe site, Fe is bonded to twelve Fe atoms to form FeFe12 cuboctahedra that share corners with six equivalent FeFe12 cuboctahedra, corners with six equivalent PtFe6Pt6 cuboctahedra, edges with six equivalent PtFe6Pt6 cuboctahedra, edges with eighteen FeFe9Pt3 cuboctahedra, and faces with eighteen FeFe9Pt3 cuboctahedra. All Fe–Fe bond lengths are 2.72 Å. In the third Fe site, Fe is bonded to nine Fe and three equivalent Pt atoms to form distorted FeFe9Pt3 cuboctahedra that share corners with seventeen FeFe9Pt3 cuboctahedra, edges with six equivalent PtFe6Pt6 cuboctahedra, edges with sixteen FeFe9Pt3 cuboctahedra, faces with six equivalent PtFe6Pt6 cuboctahedra, and faces with fifteen FeFe9Pt3 cuboctahedra. There are three shorter (2.50 Å) and six longer (2.72 Å) Fe–Fe bond lengths. All Fe–Pt bond lengths are 2.69 Å. In the fourth Fe site, Fe is bonded to sixteen Fe atoms to form FeFe16 cuboctahedra that share corners with six equivalent PtFe6Pt6 cuboctahedra, corners with sixteen FeFe9Pt3 cuboctahedra, edges with six equivalent PtFe6Pt6 cuboctahedra, edges with eighteen FeFe9Pt3 cuboctahedra, and faces with thirty-four FeFe9Pt3 cuboctahedra. There are a spread of Fe–Fe bond distances ranging from 2.50–5.45 Å. In the fifth Fe site, Fe is bonded to nine Fe and three equivalent Pt atoms to form distorted FeFe9Pt3 cuboctahedra that share corners with seventeen FeFe9Pt3 cuboctahedra, edges with six equivalent PtFe6Pt6 cuboctahedra, edges with sixteen FeFe9Pt3 cuboctahedra, faces with six equivalent PtFe6Pt6 cuboctahedra, and faces with fifteen FeFe9Pt3 cuboctahedra. All Fe–Fe bond lengths are 2.72 Å. All Fe–Pt bond lengths are 2.69 Å. Pt is bonded to six equivalent Fe and six equivalent Pt atoms to form distorted PtFe6Pt6 cuboctahedra that share corners with six equivalent FeFe12 cuboctahedra, corners with six equivalent PtFe6Pt6 cuboctahedra, edges with six equivalent PtFe6Pt6 cuboctahedra, edges with eighteen FeFe9Pt3 cuboctahedra, faces with six equivalent PtFe6Pt6 cuboctahedra, and faces with twelve equivalent FeFe9Pt3 cuboctahedra. All Pt–Pt bond lengths are 2.72 Å.

36 MATERIALS SCIENCE↗