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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

IrGe 4 : A Predicted Weyl-Metal with a Chiral Crystal Structure

Polycrystalline IrGe4 was synthesized by annealing elements at 800 °C for 240 h, and the composition was confirmed by energy-dispersive X-ray spectroscopy. IrGe 4 adopts a chiral crystal structure (space group P3 1 21) instead of a polar crystal structure (P3 1 ), which was corroborated by the convergent-beam electron diffraction and Rietveld refinements using synchrotron powder X-ray diffraction data. The crystal structure features layers of IrGe 8 polyhedra along the b axis, and the layers are connected by edge- and corner-sharing. Each layer consists of corner-shared [Ir 3 Ge 20 ] trimers, which are formed by three IrGe 8 polyhedra connected by edge-sharing. Temperature-dependent resistivity indicates metallic behavior. The magnetoresistance increases with increasing applied magnetic field, and the nonsaturating magnetoresistance reaches 11.5% at 9 T and 10 K. The Hall resistivity suggests that holes are the majority carrier type, with a carrier concentration of 4.02 × 10 21 cm –3 at 300 K. In conclusion, electronic band structures calculated by density functional theory reveal a Weyl point with a chiral charge of +3 above the Fermi level.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Role of Fe Doping on Local Structure and Electrical and Magnetic Properties of PbTiO 3

In this work, the local structure and multiferroic properties of iron-doped lead titanate (PbTi 1-x Fe x O 3-δ ) samples was investigated over the entire composition range (x = 0-1). Inherent polarization in PbTiO 3 decreases due to Fe 3+ incorporation up to the solubility limit (x similar to 0.3), although homogeneous doping persists only up to x = 0.1. Ti prefers highly distorted oxygen octahedra for any x value, while Fe prefers more symmetric O-deficient polyhedra (Fe-O n ). The charge compensating oxygen vacancies induce local tilting of the Fe-O n polyhedra beyond a critical x value (x ≥ 0.2), promoting magnetic interaction between two adjacent Fe atoms. The strain induced by local heterogeneity could act as a coupling force between magnetic and ferroelectric properties. Fe-rich clusters evolve into ferromagnetic PbFe 12 O 19 with increased Fe doping. PbTi 1-x Fe x O 3-δ (x ≥ 0.3) samples therefore have separate origins for the ferroelectric (PbTi 1-x Fe x O 3-δ ) and magnetic (PbFe 12 O 19 ) phases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Deciphering the Distribution and Crystal-Chemical Environment of Arsenic, Lead, Silica, Phosphorus, Tin, and Zinc in a Porous Ferrihydrite Grain Using Transmission Electron Microscopy and Atom Probe Tomography

Here the interaction of contaminants and nutrients with soil constituents is controlled by processes in intergranular and intragranular pore spaces of organic matter or/and common secondary minerals such as ferrihydrite, ~Fe 3+ 10 O 14 (OH) 2 . This contribution shows that distribution and clustering of the contaminants As, P, Pb, Si, Sn, and Zn in a porous ferrihydrite grain is greatly affected by the heterogeneous size distribution and chemical composition of the pores as well as the ability of their polyhedra to polymerize with the same type of polyhedron. Transmission electron microscopy (TEM) and atom probe tomography (APT) studies are conducted on focused ion beam (FIB) sections extracted from a porous ferrihydrite grain from the smelter-impacted topsoil in Sudbury, Ontario, Canada. The ferrihydrite grain has pore spaces ranging in diameter from tens to hundreds of nanometers. TEM and scanning-TEM studies indicate that the surfaces of the pore walls are enriched in Si. APT data in conjunction with First Near Neighbor (1NN) analyses indicate different degrees of clustering of Pb, As, Sn, Zn, Si, and P within the sample and selected domains. Careful evaluations of 3D atomic plots and 1NN distances indicates the occurrence of polymerized arsenite-, silica-, Sn-, and Zn-polyhedra within pore spaces of the ferrihydrite. Deciphering adsorption, polymerization, and nucleation processes in porous Fe-(hydr)oxides and other soil constituents requires multianalytical approaches and, in this regard, we discuss the advantages and disadvantages of the combination of TEM and APT for characterizing complex environmental samples at the atomic to nanometer scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Elucidating the local structure of Li 1+ x Al x Ti 2– x (PO 4 ) 3 and Li 3 Al x Ti 2– x (PO 4 ) 3 ( x = 0, 0.3) via total scattering

Li 1+x Al x Ti 2–x (PO 4 ) 3 (LATP) and Li 3 Al x Ti 2–x (PO 4 ) 3 (x = 0, 0.3) are promising candidates in all-solid-state batteries due to their high room temperature conductivity of 10 –3 S cm –1 and air- and moisture-stability. They also exhibit unusual thermal expansion properties, with Li 1+x Al x Ti 2–x (PO 4 ) 3 showing near-zero thermal expansion along the a axis while Li 3 Al x Ti 2–x (PO 4 ) 3 exhibits polynomial positive thermal expansion along the a axis and polynomial negative thermal expansion along the c axis. A crucial component to understanding these properties is understanding the local structure. Total scattering is a powerful analytical technique as it provides information on the long-range, average structure as well as the local structure. Here, we report the first X-ray and neutron total scattering experiments performed on Li 1+x Al x Ti 2–x (PO 4 ) 3 and Li 3 Al x Ti 2–x (PO 4 ) 3 (x = 0, 0.3). We show that the PO 4 and TiO 6 polyhedra experience very little expansion of the P/Ti–O bonds up to 800 °C, nor is there much expansion when the Li content increases significantly. The minor thermal expansion of the nearest-neighbor bonds of the polyhedra is revealed to be the reason behind the unusual thermal expansion properties, causing the near-zero thermal expansion along a in Li 1+x Al x Ti 2–x (PO 4 ) 3 and moving as whole units in Li 3 Al x Ti 2–x (PO 4 ) 3 . The structural robustness of the framework is also the reason for the increased conductivity as Li content increases, as the framework remains undistorted as Li content increases, permitting Li-ion mobility as the number of charge carriers increases. Finally, this suggests that phosphate-based framework materials beyond LATP would also be a good material space to explore for new Li-ion (and other ion-) conducting materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Effect of rare earth size on network structure and glass forming ability in binary aluminum garnets

Rare earth aluminate glasses are potentially useful for optical, luminescence, and laser applications. As reluctant glass formers, these materials exhibit unconventional atomic structures. To better understand how their structures correlate with glass formation, we investigate two rare earth aluminum garnet melts, La 3 Al 5 O 12 (LAG) and Yb 3 Al 5 O 12 (YbAG), which represent the relative extremes of good and poor glass forming ability in rare earth aluminates. Structural models have been refined to high-energy X-ray diffraction data over 1340–2740 K. Both melts contain mixtures of AlO 4 , AlO 5 , and AlO 6 polyhedra, with larger fractions of [5] Al and [6] Al in YbAG. Extrapolation of the Al–O coordination distributions to the glass transition match closely with 27 Al nuclear magnetic resonance measurements of (La 1−z Y z ) 3 Al 5 O 12 glasses, z = 0 to 1. During cooling, the mean coordination numbers increase for La–O in LAG from 6.45(8) to 6.98(8) and for Yb–O in YbAG from 6.02(8) to 6.21(8). Linkedness among Al–O polyhedra at ∼2450 K is mostly corner-sharing, with 9% edge-sharing in LAG and 19% in YbAG. Among [4] Al units, both melts have 6% edge-sharing that convert to all corner-sharing upon cooling. Network connectivity is compared using a newly defined metric, K n , that is similar to the Q n distribution but that accounts for the edge-sharing and triply bonded oxygen present in these melts. The lower glass forming ability in YbAG as compared to LAG correlates with more edge-sharing, associated with the larger fractions of [5] Al and [6] Al, and lower connectivity among [4] Al units.

Wilke, Stephen K. [Materials Development, Inc., Ar↗
DOE OSTI2025

Structure of molten ytterbium aluminum garnet

Rare earth aluminum garnets are important materials in optical, dielectric, and thermal barrier applications. To advance the understanding of their melt processing and glass forming ability, we report the atomic structure of molten Yb 3 Al 5 O 12 over 1770–2630 K, which spans the equilibrium and supercooled liquid regimes. The melt density at T m = 2283 K is 5.50 g cm –3 , measured via silhouette imaging of electrostatically levitated drops over 1010–2420 K. Four separate structure measurements were made with aerodynamically levitated melts using x-ray and neutron diffraction with isotope substitution of Yb ( 172 Yb, 174 Yb, or nat Yb). Empirical potential structure refinement models were developed, which are in excellent agreement with the experiments. Coordination environments for Al–O are predominantly 4- and 5-coordinate, with a mean coordination of n AlO = 4.43(8), while Yb–O environments mostly range from 5- to 8-coordinate, with n YbO = 6.26(8). The cation–oxygen polyhedra are connected primarily by corner-sharing, with edge-sharing constituting up to ~1/3 of the connectivity among polyhedra with Yb or higher-coordinated Al–O. Structurally, the –Al–O– network in molten Yb 3 Al 5 O 12 appears conducive to glass formation: n OAl = 1.85(3), there are 1.86 AlO x –AlO x connections per Al atom (e.g., a mixture of Q 3 and Q 4 units), and the modal ring size is six cations. These characterize a network that is somewhat less constrained compared to SiO 2 glass, yet Yb 3 Al 5 O 12 cannot be quenched into crystal-free glass. Here, aluminum garnet compositions with larger rare earth cations do form glass, so these characterizations help reveal the structural characteristics corresponding to the limit of glass forming ability in rare earth aluminates.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Crystal structure of calcium-ferrite type NaAlSiO4 up to 45 GPa

Abstract Alkali-rich aluminous high-pressure phases including calcium-ferrite (CF) type NaAlSiO4 are thought to constitute ~20% by volume of subducted mid-ocean ridge basalt (MORB) under lower mantle conditions. As a potentially significant host for incompatible elements in the deep mantle, knowledge of the crystal structure and physical properties of CF-type phases is therefore important to understanding the crystal chemistry of alkali storage and recycling in the Earth’s mantle. We determined the evolution of the crystal structure of pure CF-NaAlSiO4 and Fe-bearing CF-NaAlSiO4 at pressures up to ~45 GPa using synchrotron-based, single-crystal X-ray diffraction. Using the high-pressure lattice parameters, we also determined a third-order Birch-Murnaghan equation of state, with V0 = 241.6(1) Å3, KT0 = 220(4) GPa, and KT0′ = 2.6(3) for Fe-free CF, and V0 = 244.2(2) Å3, KT0 = 211(6) GPa, and KT0′ = 2.6(3) for Fe-bearing CF. The addition of Fe into CF-NaAlSiO4 resulted in a 10 ± 5% decrease in the stiffest direction of linear compressibility along the c-axis, leading to stronger elastic anisotropy compared with the Fe-free CF phase. The NaO8 polyhedra volume is 2.6 times larger and about 60% more compressible than the octahedral (Al,Si)O6 sites, with K0NaO8 = 127 GPa and K0(Al,Si)O6 ~304 GPa. Raman spectra of the pure CF-type NaAlSiO4 sample shows that the pressure coefficient of the mean vibrational mode, 1.60(7) cm–1/GPa, is slightly higher than 1.36(6) cm−1/GPa obtained for the Fe-bearing CF-NaAlSiO4 sample. The ability of CF-type phases to contain incompatible elements such as Na beyond the stability field of jadeite requires larger and less-compressible NaO8 polyhedra. Detailed high-pressure crystallographic information for the CF phases provides knowledge on how large alkali metals are hosted in alumina framework structures with stability well into the lowermost mantle.

Geochemistry & Geophysics↗
DOE OSTI2023

Fundamentals of SrCoO 3-δ Based Oxygen Deficient Perovskites as Cathodes for Solid Oxide Fuel Cells

The local structure and oxygen stoichiometry in oxide systems have a profound impact on oxygen electrocatalysis encountered in metal-air batteries and solid oxide fuel cells (SOFCs). However, this knowledge is often obtained under conditions different from the real working conditions of the material, resulting in misinterpretation and misunderstanding. This PhD dissertation aims to obtain the structure and oxygen-stoichiometry information of a class of perovskite oxides under their real working conditions in solid oxide fuel cells. Several perovskite oxides were selected for the study: Sr 0.9 Y 0.1 CoO 3-δ (SYC10), Sr 0.9 Y 0.3 CoO 3-δ (SYC30), SrCo 0.9 Nb 0.1 O 3-δ (SCN10) and SrCo 0.9 Ta0.1O 3-δ (SCT10). The local crystal structure and oxygen stoichiometry of these materials were systematically characterized with in-situ neutron diffraction (ND). The oxygen stoichiometry was also measured by thermogravimetric analysis (TGA) and iodometric titration methods. To establish the correlation among structure, oxygen stoichiometry and oxygen reduction reaction (ORR) activity, high temperature electrochemical impedance spectroscopy, oxygen permeation and single cell testing were also performed. In chapter 2, SYC10 is described to have a more symmetrical structure and $V_o^{··}$ distribution, and higher $V_o^{··}$ concentration than SYC30. Molecular orbital energy analysis based on the local structure of the ORR-active Co1-polyhedra indicates SYC30 has a higher Fermi level relative to O-2p energy level in the active Co1-polyhedra, and thus a higher motional enthalpy for $V_o^{··}$ migration. However, the ORR activity of Y-doped SrCoO 3-δ (SCO) are found uncompetitive with other popular catalysts. In chapter 3 and 4, systematic structural studies are presented for Nb and Ta-doped SCO, namely SCN10 and SCT10, respectively. The methodology of unrevealing the structure-activity relationships in chapter 2 is also found applicable to SYC10, SCN10 and SCT10 as presented in chapter 5. The electrochemical tests indicate that SCT10 is the best catalyst due to its excellent thermal and electrochemical stability. In chapter 6, SCT10 is evaluated in a real solid oxide fuel cell in the form of nanoscaled SCT10 layer coating on the commercial (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ (LSCF). The bilayer structured cathode shows excellent properties of coarsening-resistant, Sr-segregation-free and high ORR-activity.

Yang, Tianrang↗
DOE OSTI2020

An efficient method to integrate polynomials over polytopes and curved solids

Here in this paper, we present an efficient approach to compute the integral of monomials and polynomials over polyhedra and regions defined by parametric curved boundary surfaces. We use Euler's theorem for homogeneous functions in combination with Stokes's theorem to reduce the integration of a monomial over a three-dimensional solid to its boundary. If the solid is a polytope, through a recursive application of these theorems, the integral is further reduced to just the evaluation of the monomial and its derivatives at the vertices of the polytope. The present approach is simpler than existing techniques that rely on repeated use of the divergence theorem, which require the antiderivative of the monomials and the projection of these functions onto hyperplanes. For convex and nonconvex polytopes, our approach does not introduce any approximation for the integration of monomials. For curved solid regions bounded by surfaces that admit a parameterization, the same approach yields simplified formulas to compute the integral of any homogeneous function, including monomials. For surfaces parameterized by polynomial surfaces (such as Bezier surface triangles and B-spline patches), the method yields machine-precision accuracy for the volumetric integration of monomials with an appropriate quadrature rule. Numerical examples over regions bounded by polynomial surfaces and rational surfaces are presented to establish the accuracy and efficiency of the method.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2023

Using small building blocks to assemble ultra-complex, multifaceted metal-organic frameworks with zeolitic, mesoporous subnetwork

The assembly of ultra-complex structures from simple building units remains a long-term challenge in chemistry. Using small molecular building blocks (MBBs) in a mixed-ligand approach permitted the assembly of unprecedented metal-organic frameworks (MOFs), M-kum-MOF-1 (M = Y, Tb), exhibiting extra-large mesoporous cavities with small access windows. The ultra-complex cage of M-kum-MOF-1 consists of 240 vertices bridged by 432 edges, leading to a 194 faces-containing tile. This tile exhibits more faces than in any periodic structures (zeolites, MOFs, metal-organic polyhedra [MOPs], etc.) known to date. M-kum-MOF-1 not only possess zeolitic features (anionic framework), but they also contain an underlying wse zeolitic topology, which is observed for the first time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

High‐Pressure Synthesis of Ultra‐Incompressible, Hard and Superconducting Tungsten Nitrides

Abstract Transition metal nitrides, particularly those of 5 d metals, are known for their outstanding properties, often relevant for industrial applications. Among these metal elements, tungsten is especially attractive given its low cost. In this high‐pressure investigation of the W–N system, two novel ultra‐incompressible tungsten nitride superconductors, namely W 2 N 3 and W 3 N 5 , are successfully synthesized at 35 and 56 GPa, respectively, through a direct reaction between N 2 and W in laser‐heated diamond anvil cells. Their crystal structure is determined using synchrotron single‐crystal X‐ray diffraction. While the W 2 N 3 solid's sole constituting nitrogen species are N 3‐ units, W 3 N 5 features both discrete N 3‐ as well as N 2 4‐ pernitride anions. The bulk modulus of W 2 N 3 and W 3 N 5 is experimentally determined to be 380(3) and 406(7) GPa, and their ultra‐incompressible behavior is rationalized by their constituting WN 7 polyhedra and their linkages. Importantly, both W 2 N 3 and W 3 N 5 are recoverable to ambient conditions and stable in air. Density functional theory calculations reveal W 2 N 3 and W 3 N 5 to have a Vickers hardness of 30 and 34 GPa, and superconducting transition temperatures at ambient pressure (50 GPa) of 11.6 K (9.8 K) and 9.4 K (7.2 K), respectively. Additionally, transport measurements performed at 50 GPa on W 2 N 3 corroborate with the calculations.

Chemistry↗
DOE OSTI2021

Deliberate Construction of Polyoxoniobates Exploiting the Carbonate Ligand

Abstract Polyoxometalates (POMs, metals=V V , Nb V , Ta V , Mo VI , W VI ) are molecular metal oxides that can be isolated without capping ligands. The high negative charge of polyoxoniobates (PONb) provides strong interactions with heterocations, advantageous for electrostatic assembly of modular materials. In four single‐crystal X‐ray structures, we demonstrate that carbonate combined with the very reactive decaniobate [Nb 10 O 28 ] 6− reassembles into a new decaniobate, [Nb 10 O 25 (CO 3 ) 6 ] 12− , featuring three carbonate‐ligated Nb‐polyhedra. These Nb‐sites can be replaced by heterometals (lanthanides), and the tridentate carbonate can serve as an anchor point to build niobate‐frameworks. Small‐angle X‐ray scattering and two additional X‐ray structures reveal that the reaction pathway proceeds through a Nb 24 ‐PONb intermediate, and the obtained PONb (with or without carbonate) is counterion, temperature, and solvent‐dependent (water or mixed water‐methanol). This provides an uncommon level of control for PONb chemistry.

Amiri, Mehran↗
DOE OSTI2022

Rational Design of Superconducting Metal Hydrides via Chemical Pressure Tuning**

Abstract The high critical superconducting temperatures ( T c s) of metal hydride phases with clathrate‐like hydrogen networks have generated great interest. Herein, we employ the Density Functional Theory‐Chemical Pressure (DFT‐CP) method to explain why certain electropositive elements adopt these structure types, whereas others distort the hydrogenic lattice, thereby decreasing the T c . The progressive opening of the H 24 polyhedra in MH 6 phases is shown to arise from internal pressures exerted by large metal atoms, some of which may favor an even higher hydrogen content that loosens the metal atom coordination environments. The stability of the LaH 10 and LaBH 8 phases is tied to stuffing of their shared hydrogen network with either additional hydrogen or boron atoms. The predictive capabilities of DFT‐CP are finally applied to the Y−X−H system to identify possible ternary additions yielding a superconducting phase stable to low pressures.

Hilleke, Katerina P.↗
DOE OSTI2023

Spatiotemporal Studies of Soluble Inorganic Nanostructures with X‐rays and Neutrons

Abstract This Review addresses the use of X‐ray and neutron scattering as well as X‐ray absorption to describe how inorganic nanostructured materials assemble, evolve, and function in solution. We first provide an overview of techniques and instrumentation (both large user facilities and benchtop). We review recent studies of soluble inorganic nanostructure assembly, covering the disciplines of materials synthesis, processes in nature, nuclear materials, and the widely applicable fundamental processes of hydrophobic interactions and ion pairing. Reviewed studies cover size regimes and length scales ranging from sub‐Ångström (coordination chemistry and ion pairing) to several nanometers (molecular clusters, i.e. polyoxometalates, polyoxocations, and metal‐organic polyhedra), to the mesoscale (supramolecular assembly processes). Reviewed studies predominantly exploit 1) SAXS/WAXS/SANS (small‐ and wide‐angle X‐ray or neutron scattering), 2) PDF (pair‐distribution function analysis of X‐ray total scattering), and 3) XANES and EXAFS (X‐ray absorption near‐edge structure and extended X‐ray absorption fine structure, respectively). While the scattering techniques provide structural information, X‐ray absorption yields the oxidation state in addition to the local coordination. Our goal for this Review is to provide information and inspiration for the inorganic/materials science communities that may benefit from elucidating the role of solution speciation in natural and synthetic processes.

Yin, Jia‐Fu↗
DOE OSTI2022

Rational Design of Superconducting Metal Hydrides via Chemical Pressure Tuning

The high critical superconducting temperatures (T c s) of metal hydride phases with clathrate-like hydrogen networks have generated great interest. Herein, we employ the Density Functional Theory-Chemical Pressure (DFT-CP) method to explain why certain electropositive elements adopt these structure types, whereas others distort the hydrogenic lattice, thereby decreasing the T c . The progressive opening of the H 24 polyhedra in MH 6 phases is shown to arise from internal pressures exerted by large metal atoms, some of which may favor an even higher hydrogen content that loosens the metal atom coordination environments. The stability of the LaH 10 and LaBH 8 phases is tied to stuffing of their shared hydrogen network with either additional hydrogen or boron atoms. Furthermore, the predictive capabilities of DFT-CP are finally applied to the Y-X-H system to identify possible ternary additions yielding a superconducting phase stable to low pressures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Spatiotemporal Studies of Soluble Inorganic Nanostructures with X‐rays and Neutrons

This Review addresses the use of X-ray and neutron scattering as well as X-ray absorption to describe how inorganic nanostructured materials assemble, evolve, and function in solution. We first provide an overview of techniques and instrumentation (both large user facilities and benchtop). We review recent studies of soluble inorganic nanostructure assembly, covering the disciplines of materials synthesis, processes in nature, nuclear materials, and the widely applicable fundamental processes of hydrophobic interactions and ion pairing. Reviewed studies cover size regimes and length scales ranging from sub-Ångström (coordination chemistry and ion pairing) to several nanometers (molecular clusters, i.e. polyoxometalates, polyoxocations, and metal-organic polyhedra), to the mesoscale (supramolecular assembly processes). Reviewed studies predominantly exploit 1) SAXS/WAXS/SANS (small- and wide-angle X-ray or neutron scattering), 2) PDF (pair-distribution function analysis of X-ray total scattering), and 3) XANES and EXAFS (X-ray absorption near-edge structure and extended X-ray absorption fine structure, respectively). While the scattering techniques provide structural information, X-ray absorption yields the oxidation state in addition to the local coordination. Our goal for this Review is to provide information and inspiration for the inorganic/materials science communities that may benefit from elucidating the role of solution speciation in natural and synthetic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Lattice Relaxations in Bixbyite‐Structured Rare‐Earth Sesquioxides

This report examines atomic relaxations in rare‐earth sesquioxides with the cubic bixbyite crystal structure. In particular, the experimentally determined unit cell atom positions in bixbyite compounds are compared to “ideal” bixbyite atom positions, where the concept of ideality is based on similarities between the bixbyite and fluorite crystal structures. Analyses indicate that all rare‐earth sesquioxide compounds deviate from ideality in similar ways and that there is a trend wherein the magnitudes of these atomic deviations decrease with increasing cationic size. The deviations from an ideal, fluorite‐like structure produce highly distorted coordination polyhedra and variations in metal‐oxygen bond lengths. A modified bond valence sum analysis revealed that the first nearest neighbor cation‐anion bond length variations lead to large (20%) variations in cation‐anion bond strength. This report also provides a qualitative analysis regarding the accuracy of atomic relaxed deviation parameters, based on x‐ray diffraction measurements. The analysis indicates that uncertainties in the accuracy of measured oxygen relaxed deviation parameters in bixbyite sesquioxides are likely much greater than the published uncertainties.

36 MATERIALS SCIENCE↗