Defect Fluorite Phase Research Articles

Phase transformations in oxides above 2000°C: experimental technique development

ABSTRACTThe oxidation of boride and carbide-based ultra-high-temperature ceramics is the primary limiting factor for their use as aerodynamic surfaces. Understanding the behaviour of the oxides that can result from oxidation of metal borides and carbides at very high temperatures is essential to optimise and tailor the performance of these materials; yet experimental thermodynamic and structural data for refractory oxides above 2000°C are mostly absent. The following techniques that can be applied to fill this gap are discussed: (i) commercial ultra-high-temperature differential thermal analysis for investigation of phase transformations and melting in inert environments to 2500°C, (ii) a combination of laser heating with a splittable nozzle aerodynamic levitator for splat quenching and drop calorimetry from temperatures limited only by sample evaporation, (iii) synchrotron X-ray and neutron diffraction on laser-heated aerodynamically levitated oxide samples for in situ observation of phase transformations in variable atmospheres, refinement of high-temperature structures and thermal expansion. Recent experimental findings include anomalous thermal expansion of the defect fluorite phase of YSZ, thermodynamics of pyrochlore–fluorite transformation from high-temperature structure refinements, and measurement of thermal expansion to the melting temperatures and fusion enthalpies of Zr, Hf, La, Yb and Lu oxides. These methods provide temperatures, enthalpies and volume change for phase transformations above 2000°C, which are required for thermodynamic assessments and calculation of phase diagrams of multicomponent systems.

Energetic Ion Irradiation-Induced Disordered Nanochannels for Fast Ion Conduction

Atomically disordered oxides are seen as suitable candidate for fast oxygen conduction due to their remarkable enhancement in oxygen diffusivity compared with ordered oxides. In particular, disordered derivatives of pyrochlore-structured oxides (A2B2O7) are seen as an interesting prospect due to the intrinsic existence of oxygen vacancies in their lattice. Using energetic ion irradiation, we demonstrated fabrication of structurally disordered nanoscale channels in A2B2O7 (A = Gd, Yb; B = Ti, Zr) that act as selective pathways for fast oxygen conduction. Atomic-level characterization revealed that the amorphous core and surrounding defect-fluorite phase in the nanochannels exhibited distorted and differently coordinated Ti-O polyhedra, with very similar electronic structure. The formation of defect-fluorite structure is facilitated by a decrease in the difference between the ionic radii of A- and B-site cations in the lattice.

Effect of substrate temperature on microstructure and nanomechanical properties of Gd2Zr2O7 coatings prepared by EB-PVD technique

In the present work, gadolinium zirconate (Gd2Zr2O7) coatings have been developed on Inconel-718 substrates by electron beam physical vapor deposition (EB-PVD) technique. The structural, morphological and mechanical properties as a function of substrate temperature have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), nanoindentation and scratch tests. XRD analysis revealed that the coatings showed cubic defect fluorite phase, and no secondary phase formation was observed in the coatings during deposition. The decrease in the lattice constant of the fluorite phase with increasing deposition temperature was explained on the basis of strain relaxation and vacancy concentration. Increased surface roughness of the coatings has been found with increasing substrate temperature as a result of increased crystallite size. An improved coating adhesion achieved for the coating deposited at higher substrate temperature of 973 K was confirmed by scratch test. Nanoindentation measurements indicated higher hardness (7.7 GPa) and resistance to plastic deformation and better capability to accommodate deformation energy for the coatings prepared at higher deposition temperature.

Structure Evolution and Reactivity of the Sc(2- x)V xO3+δ (0 ≤ x ≤ 2.0) System.

Solid oxide fuel cells (SOFCs) are solid-state electrochemical devices that directly convert chemical energy of fuels into electricity with high efficiency. Because of their fuel flexibility, low emissions, high conversion efficiency, no moving parts, and quiet operation, they are considered as a promising energy conversion technology for low carbon future needs. Solid-state oxide and proton conducting electrolytes play a crucial role in improving the performance and market acceptability of SOFCs. Defect fluorite phases are some of the most promising fast oxide ion conductors for use as electrolytes in SOFCs. We report the synthesis, structure, phase diagram, and high-temperature reactivity of the Sc(2- x)V xO3+δ (0 ≤ x ≤ 2.00) oxide defect model system. For all Sc(2- x)V xO3.0 phases with x ≤ 1.08 phase-pure bixbyite-type structures are found, whereas for x ≥ 1.68 phase-pure corundum structures are reported, with a miscibility gap found for 1.08 < x < 1.68. Structural details obtained from the simultaneous Rietveld refinements using powder neutron and X-ray diffraction data are reported for the bixbyite phases, demonstrating a slight V3+ preference toward the 8b site. In situ X-ray diffraction experiments were used to explore the oxidation of the Sc(2- x)V xO3.0 phases. In all cases ScVO4 was found as a final product, accompanied by Sc2O3 for x < 1.0 and V2O5 when x > 1.0; however, the oxidative pathway varied greatly throughout the series. Comments are made on different synthesis strategies, including the effect on crystallinity, reaction times, rate-limiting steps, and reaction pathways. This work provides insight into the mechanisms of solid-state reactions and strategic guidelines for targeted materials synthesis.

Swift-heavy ion irradiation response and annealing behavior of A2TiO5 (A = Nd, Gd, and Yb)

The structural responses of A2BO5 (A = Nd, Gd, and Yb; B = Ti) compositions irradiated by high-energy Au ions (2.2GeV) were investigated using transmission electron microscopy, synchrotron X-ray diffraction and Raman spectroscopy. The extent of irradiation-induced amorphization depends on the size of the A-site cation, with smaller lanthanides having less susceptibility to the accumulation of radiation damage. In the track-overlapping regime, complete amorphization is observed in all three compounds, despite the ability of Yb2TiO5 to incorporate a great deal of structural disorder into its initial defect-fluorite structure (Fm-3m). This is attributed to the high cation radius ratio (A:B = 2:1), which reduces the stability of the structure upon ion irradiation. The fully-amorphized samples were subsequently isochronally heated at temperature intervals from 100°C to 850°C. X-ray diffraction analysis indicated a similar damage recovery process in Nd2TiO5 and Gd2TiO5, where both compositions recover their original structures (Pnma) at 850°C. In contrast, Yb2TiO5 exhibited recrystallization of a metastable, non-equilibrium orthorhombic phase at ~ 550°C, prior to a transformation to the stable defect-fluorite phase (Fm-3m) at 625°C. These compositional variations in radiation tolerance and thermal recovery processes are described in terms of the energetics of disordering during the damage and recrystallization processes.

(High Temperature Materials Division J. Bruce Wagner, Jr. Award Address) Disorder and Transport in Pyrochlore Oxides

Numerous avenues are currently being explored to enhance ionic conductivity in solid oxide materials, including dopants, nano-structuring, and strain engineering. Their effect on material properties, specifically mobile carrier concentration and mobility, needs to be understood and ultimately exploited to develop advanced functional materials. Crystalline disorder in complex oxides can have a pronounced effect on mass transport, but the role of disorder within the complex landscape of material and microstructural defects is not uniquely understood.In this work, we seek to explore the relationship between intrinsic disorder and oxygen ion conduction. We are using radiation damage, not to study the fundamental damage response, but rather as a tool to induce and control the extent of disorder in oxide materials. The pyrochlore compounds, A2B2O7, consist of both ordered cation and anion sublattices. The introduction of anti-site disorder, where the A and B cations switch positions, is accompanied by increasing disorder on the anion sublattice, and complete randomization of the A- and B-site cations results in the defect fluorite phase. Several workers have previously studied the influence of structural disorder on ionic conductivity by introducing disorder through dopants, temperature, or pressure. It has previously been suggested that disorder increases carrier concentration by freeing the fixed vacancy from the ordered anion sublattice of the pyrochlore structure, while order, on the other hand, may serve to increase mobility by providing a preferential ion transport pathway. This is in contrast to recent modeling results that indicate that both carrier concentration and mobility increase with disorder. In the present work we have chosen to investigate the end members of the Gd2(ZrxTi1-x)2O7 system in order to gain a better understanding of the interplay between disorder and ionic transport. Gd2Zr2O7 is an intrinsic fast-ion conductor that is also very radiation tolerant, whereas Gd2Ti2O7 is a poor ionic conductor that is much more susceptible to amorphization under irradiation than the zirconates. Electrochemical Impedance Spectroscopy is used to measure the conductivity of materials with varying degrees of irradiation-induced structural disorder in order to better understand how the underlying transport mechanisms depend on crystalline disorder. Acknowledgements This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.

Engineered thermal barrier coatings deposited by suspension plasma spray

Yttria stabilized zirconia (YSZ) is susceptible to CMAS (Calcium Magnesium Alumino Silicates) attack at high temperatures (>1200°C) which limits its durability. New ceramic materials which can overcome these high temperature challenges are highly desirable. This work investigates the feasibility of depositing two variations of three ceramic layered thermal barrier coatings. The first variation comprised of yttria as the top ceramic layer with gadolinium zirconate (GZ) as the intermediate layer and YSZ as the base layer. The second variation comprised of Yttrium Aluminum Garnet (YAG) as the top layer with gadolinium zirconate as the intermediate layer and YSZ as the base layer. Microstructural analysis of the as sprayed three layered TBCs were performed by SEM/EDS. Columnar microstructures with a relatively dense top layer were obtained in both the variations. The porosity content of the TBCs was measured by water intrusion and image analysis methods. Phase composition of each layer of the as sprayed TBCs was analyzed using XRD. YAG showed an amorphous phase whereas GZ showed a cubic defect fluorite phase and tetragonal phase was observed in YSZ. In the case of yttria, monoclinic and cubic phases were observed.

Erosion Performance of Gadolinium Zirconate-Based Thermal Barrier Coatings Processed by Suspension Plasma Spray

7-8 wt.% Yttria-stabilized zirconia (YSZ) is the standard thermal barrier coating (TBC) material used by the gas turbines industry due to its excellent thermal and thermo-mechanical properties up to 1200 °C. The need for improvement in gas turbine efficiency has led to an increase in the turbine inlet gas temperature. However, above 1200 °C, YSZ has issues such as poor sintering resistance, poor phase stability and susceptibility to calcium magnesium alumino silicates (CMAS) degradation. Gadolinium zirconate (GZ) is considered as one of the promising top coat candidates for TBC applications at high temperatures (>1200 °C) due to its low thermal conductivity, good sintering resistance and CMAS attack resistance. Single-layer 8YSZ, double-layer GZ/YSZ and triple-layer GZdense/GZ/YSZ TBCs were deposited by suspension plasma spray (SPS) process. Microstructural analysis was carried out by scanning electron microscopy (SEM). A columnar microstructure was observed in the single-, double- and triple-layer TBCs. Phase analysis of the as-sprayed TBCs was carried out using XRD (x-ray diffraction) where a tetragonal prime phase of zirconia in the single-layer YSZ TBC and a cubic defect fluorite phase of GZ in the double and triple-layer TBCs was observed. Porosity measurements of the as-sprayed TBCs were made by water intrusion method and image analysis method. The as-sprayed GZ-based multi-layered TBCs were subjected to erosion test at room temperature, and their erosion resistance was compared with single-layer 8YSZ. It was shown that the erosion resistance of 8YSZ single-layer TBC was higher than GZ-based multi-layered TBCs. Among the multi-layered TBCs, triple-layer TBC was slightly better than double layer in terms of erosion resistance. The eroded TBCs were cold-mounted and analyzed by SEM.

Disorder and Conductivity in Pyrochlore Thin Films

Numerous avenues are currently being explored to enhance ionic conductivity in solid oxide materials including dopants, nano-structuring, and strain engineering. Their effect on material properties, specifically mobile carrier concentration and mobility, needs to be understood and ultimately exploited to develop advanced functional materials. In this work, we seek to explore the relationship between intrinsic disorder and oxygen ion conduction. The pyrochlore compounds, A2B2O7, consist of both ordered cation and anion sublattices. The introduction of anti-site disorder, where the A and B cations switch positions, is accompanied by increasing disorder on the anion sublattice, and complete randomization of the A- and B-site cations results in the defect fluorite phase. Several workers have previously studied the influence of structural disorder on ionic conductivity by introducing disorder through dopants, temperature or pressure. It has previously been suggested that disorder increases carrier concentration by freeing the fixed vacancy from the ordered anion sublattice of the pyrochlore structure, while order, on the other hand, may serve to increase mobility by providing a preferential ion transport pathway. This is in contrast to recent modeling results that indicate that both carrier concentration and mobility increase with disorder. In order to better understand the interplay of disorder and ionic transport, the present work utilizes irradiation as a tool to introduce, and control the extent of, structural disorder in pyrochlore oxide thin films. We have chosen to investigate the end members of the Gd2(ZrxTi1-x)2O7 system as Gd2Zr2O7 is an intrinsic fast-ion conductor that is also very rad tolerant whereas Gd2Ti2O7 is a poor ionic conductor that is much more susceptible to amorphization under irradiation than the zirconates. Electrochemical Impedance spectroscopy is used to measure the conductivity of materials with varying degrees of structural disorder in order to better understand how the underlying transport mechanisms depend on crystalline disorder. Acknowledgements This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.

Failure analysis of Gd2Zr2O7/YSZ multi-layered thermal barrier coatings subjected to thermal cyclic fatigue

8 wt.% yttria stabilized zirconia (8YSZ) is the standard ceramic top coat material used in thermal barrier coatings (TBCs) due to its excellent thermo-physical and thermo-mechanical properties. However, above 1200 °C, YSZ has issues such as susceptibility to CMAS (Calcium Magnesium Alumino Silicates) attack and enhanced sintering which could lead to catastrophic failure of the TBC. Pyrochlores of rare earth zirconate composition such as gadolinium zirconate have shown to be resistant to CMAS attack and at the same time possess several other attractive properties. However, poor thermal cycling life of single layer gadolinium zirconate (GZ) TBC compared to single layer YSZ has been reported. Therefore, a double layered GZ/YSZ TBC with YSZ as the intermediate coating and GZ as the top coat and a single layer 8YSZ were deposited by the axial suspension plasma spray process. Additionally, a triple layer TBC (GZdense/GZ/YSZ) comprising of denser GZ coating on top of GZ/YSZ TBC was deposited. SEM analysis revealed a columnar microstructure in the single, double and triple layer TBCs. XRD analysis confirmed the presence of tetragonal prime and defect fluorite phases in the top surface of YSZ and GZ based as sprayed TBCs respectively. The single layer YSZ and GZ/YSZ multi-layered TBCs were subjected to thermal cyclic fatigue (TCF) testing at 1100 °C and 1200 °C. The triple layer TBC showed a higher thermal cyclic life at both the temperatures compared to the single and double layer TBCs. The failed TBCs at 1100 °C were analyzed by SEM/EDS and image analysis. It was found that the failure modes in single layer YSZ and GZ based TBCs were different.

Bubble formation and lattice parameter changes resulting from He irradiation of defect-fluorite Gd2Zr2O7

Pyrochlores have long been considered as potential candidates for advanced ceramic waste-forms for the immobilization of radioactive waste nuclides. This work provides evidence that Gd2Zr2O7, often considered the most radiation tolerant pyrochlore, could be susceptible to radiation damage in the form of bubble nucleation at the highest He doses expected over geological time. Ion irradiations were utilized to experimentally simulate the radiation damage and He accumulation produced by α-decay. Samples were pre-damaged using 7 MeV Au3+ to induce the pyrochlore to defect-fluorite phase transformation, which would occur due to α-recoil damage within several hundred years of storage in a Gd2Zr2O7 waste-form. These samples were then implanted to various He concentrations in order to study the long-term effects of He accumulation. Helium bubbles 1–3 nm in diameter were observed in TEM at a concentration of 4.6 at.% He. Some bubbles remained isolated, while others formed chains 10–30 nm in length parallel to the surface. GIXRD measurements showed lattice swelling after irradiating pristine Gd2Zr2O7 with 7 MeV Au3+ to a fluence of 2.2 × 1015 Au/cm2. An increase in lattice swelling was also measured after 2.2 × 1015 Au/cm2 + 2 × 1015 He/cm2 and 2.2 × 1015 Au/cm2 + 2 × 1016 He/cm2. A decrease in lattice swelling was measured after irradiation with 2.2 × 1015 Au/cm2 + 2 × 1017 He/cm2, the fluence where bubbles and bubble chains were observed in TEM. Bubble chains are thought to form in order to reduce lattice strain normal to the surface, which is produced by the Au and He irradiation damage.

Insights on dramatic radial fluctuations in track formation by energetic ions.

We report on unexpected dramatic radial variations in ion tracks formed by irradiation with energetic ions (2.3 GeV 208Pb) at a constant electronic energy-loss (~42 keV/nm) in pyrochlore-structured Gd2TiZrO7. Though previous studies have shown track formation and average track diameter measurements in the Gd2TixZr(1−x)O7 system, the present work clearly reveals the importance of the recrystallization process in ion track formation in this system, which leads to more morphological complexities in tracks than currently accepted behavior. The ion track profile is usually considered to be diametrically uniform for a constant value of electronic energy-loss. This study reveals the diameter variations to be as large as ~40% within an extremely short incremental track length of ~20 nm. Our molecular dynamics simulations show that these fluctuations in diameter of amorphous core and overall track diameter are attributed to the partial substitution of Ti atoms by Zr atoms, which have a large difference in ionic radii, on the B-site in pyrochlore lattice. This random distribution of Ti and Zr atoms leads to a local competition between amorphous phase formation (favored by Ti atoms) and defect-fluorite phase formation (favored by Zr atoms) during the recrystallization process and finally introduces large radial variations in track morphology.

Disorder and Ionic Transport in Pyrochlore/Defect Fluorite Oxide Thin Films

Numerous avenues are currently being explored to enhance ionic conductivity in solid oxide materials including dopants, nano-structuring, and strain engineering. Their effect on material properties, specifically mobile carrier concentration and mobility, needs to be understood and ultimately exploited to develop advanced functional materials. In this work, we seek to explore the relationship between intrinsic disorder and oxygen ion conduction. The pyrochlore compounds, A2B2O7, consist of both ordered cation and anion sublattices. The introduction of anti-site disorder, where the A and B cations switch positions, is accompanied by increasing disorder on the anion sublattice, and complete randomization of the A- and B-site cations results in the defect fluorite phase. Several workers have previously studied the influence of structural disorder on ionic conductivity by introducing disorder through dopants, temperature or pressure. In the present work, we are using irradiation as a tool to introduce, and control the extent of, structural disorder in pyrochlore oxide thin films. We have chosen to investigate the end members of the Gd2(ZrxTi1-x)2O7 system as Gd2Zr2O7 is an intrinsic fast-ion conductor that is also very rad tolerant whereas Gd2Ti2O7 is a comparatively poor ionic conductor that is much more susceptible to amorphization under irradiation than the zirconates. Electrochemical Impedance spectroscopy is used to measure the conductivity of materials with varying degrees of structural disorder in order to better understand how the underlying transport mechanisms depend on crystalline disorder.

Transformation from pyrochlore to fluorite by diffraction and X-ray spectroscopy

We have studied the long-range average and local structures in a number of zirconium containing materials of the type A2B2O7 ( A = Ln or Y; B = Zr, Hf or Sn) using synchrotron X-ray and neutron powder diffraction and X-ray absorption spectroscopy. Studies of the system Gd2-xTbxZr2O7 include neutron diffraction data, obtained at λ ≍ 0.497 Å to minimise absorption, not only provide evidence for independent ordering of the anion and cation sublattices, but also suggest that the disorder transition across the pyrochlore-defect fluorite boundary of Ln2Zr2O7 is rather gradual. In general we observe that while the diffraction data indicate a clear phase transition from ordered pyrochlore to disordered defect-fluorite at specific compositions corresponding to a critical ionic radius ratio of the A and B cations (rA/rB) x ~ 1.0-1.2, X-ray absorption near-edge structure (XANES) results reveal a gradual structural evolution across the compositional range. These findings provide experimental evidence that the local disorder occurs long before the pyrochlore to defect-fluorite phase boundary as determined by X-ray diffraction, and the extent of disorder continues to develop throughout the defect-fluorite region. Where possible the experimental results were supplemented by ab initio atomic scale simulations, which provide a mechanism for disorder to initiate in the pyrochlore structure. Further, the coordination numbers of the cations in both the defect-fluorite and pyrochlore structures were predicted, and the trends agree well with the experimental XANES results. X-ray absorption measurements at the Zr L3-edge, which showed a gradual increase in the effective coordination number of the Zr from near 6-coordinate in the pyrochlore rich samples to near 7-coordinate in the defect fluorites.

High conductivity of La2Zr2O7nanofibers by phase control

We report an oxygen ionic conductivity of 0.016 S cm−1 in La2Zr2O7 nanofibers at 500 °C, which is ∼400 times higher than traditional La2Zr2O7 bulk materials. The highly enhanced conductivity of our La2Zr2O7 nanofibers can mainly be attributed to a novel mixed phase structure. We found that a defect fluorite to pyrochlore phase transition occurred at 875 °C. By precise control of calcination conditions, we successfully tuned the ratio of defect fluorite and pyrochlore phases, and further demonstrated that nanofibers with a mixed phase structure have higher conductivity due to an interface lattice mismatch between the two phases. The remarkably high conductivity and facile manufacturing of the La2Zr2O7 nanofibers make them a promising material for high performance SOFCs and oxygen sensors. Moreover, our study provides a new strategy to design solid electrolytes with high conductivity by phase control.

Gradual Structural Evolution from Pyrochlore to Defect-Fluorite in Y2Sn2–xZrxO7: Average vs Local Structure

We have studied the long-range average and local structures in Y2Sn2–xZrxO7 (x = 0–2.0) using synchrotron X-ray powder diffraction and X-ray absorption spectroscopy, respectively, and by theoretical methods. While the diffraction data indicate a clear phase transition from ordered pyrochlore to disordered defect-fluorite at x ∼ 1.0–1.2, X-ray absorption near-edge structure (XANES) results at the Zr L3- and Y L2-edges reveal a gradual structural evolution across the whole compositional range. These findings provide experimental evidence that the local disorder occurs long before the pyrochlore to defect-fluorite phase boundary, as determined by X-ray diffraction, and the extent of disorder continues to develop throughout the defect-fluorite region. The Zr and Y L-edge spectra are very sensitive to changes in the local structure; such sensitivity enables us to reveal the progressive nature of the phase transition. Experimental results are supported by ab initio atomic scale simulations, which provide a mech...

Anion Disorder in Lanthanoid Zirconates Gd2–xTbxZr2O7

The pyrochlore-defect fluorite order-disorder transition has been studied for a series of oxides of the type Gd(2-x)Tb(x)Zr2O7 by a combination of diffraction and spectroscopy techniques. Synchrotron X-ray diffraction data suggest an abrupt transition from the coexistence of pyrochlore and defect fluorite phases to a single defect fluorite phase with increasing Tb content. However neutron diffraction data, obtained at λ ≈ 0.497 Å for all Gd-containing samples to minimize absorption, not only provide evidence for independent ordering of the anion and cation sublattices but also suggest that the disorder transition across the pyrochlore-defect fluorite boundary of Ln2Zr2O7 is rather gradual. Such disorder was also evident in X-ray absorption measurements at the Zr L3-edge, which showed a gradual increase in the effective coordination number of the Zr from near 6-coordinate in the pyrochlore rich samples to near 7-coordinate in the Tb rich defect fluorites. These results indicate the presence of ordered domains throughout the defect fluorite region, and demonstrate the gradual nature of the order-disorder transition across the Gd(2-x)Tb(x)Zr2O7 series.

The pyrochlore to defect fluorite phase transition in Y2Sn2−xZrxO7

The system Y2Sn2−xZrxO7 (0.0 ≤ x ≤ 2.0) undergoes a phase transformation from ordered pyrochlore (Fdm) to defect fluorite (Fmm) actuated by the substitution of Zr for Sn. X-ray diffraction patterns map the retention of the pyrochlore structure up to x = 1.2. For samples with x = 1.4–2.0 the structure can be described as defect fluorite in broad terms. Electron diffraction patterns are consistent with this interpretation; however, they also demonstrate that the defect fluorite phase exhibits a strain driven compositional/displacive modulation that changes gradually with increasing Zr content. Raman spectra are consistent with gradual anion disorder up to x = 1.0 and highly disordered anion distributions inferred for x > 1.4, but the spectra also suggest the presence of residual order due to the modulated structure. The phase transformation in this system occurs at a higher Zr content than predicted by classical radius ratio models, consistent with the covalent character of Sn–O bonding. An unusual finding of this work comes from 119Sn MAS NMR and Sn L3-edge XANES analyses, indicating that Sn4+ prefers to occupy lattice sites with a 6-fold local coordination environment throughout the series. These results suggest that the incorporation of Sn or other metal cations having significant covalent bonding or a strong preference for octahedral coordination in pyrochlore-based materials may have a detrimental effect on ionic conductivity.

ChemInform Abstract: Topotactic Oxidation Pathway of ScTiO3 and High‐Temperature Structure Evolution of ScTiO3.5 and Sc4Ti3O12‐Type Phases.

AbstractThe formation of the new oxide defect fluorite phase (V) is monitored by XRD.

Topotactic Oxidation Pathway of ScTiO3 and High-Temperature Structure Evolution of ScTiO3.5 and Sc4Ti3O12-Type Phases

The novel oxide defect fluorite phase ScTiO(3.5) is formed during the topotactic oxidation of ScTiO(3) bixbyite. We report the oxidation pathway of ScTiO(3) and structure evolution of ScTiO(3.5), Sc(4)Ti(3)O(12), and related scandium-deficient phases as well as high-temperature phase transitions between room temperature and 1300 °Cusing in-situ X-ray diffraction. We provide the first detailed powder neutron diffraction study for ScTiO(3). ScTiO(3) crystallizes in the cubic bixbyite structure in space group Ia3 (206) with a = 9.7099(4) Å. The topotactic oxidation product ScTiO(3.5) crystallizes in an oxide defect fluorite structure in space group Fm3m (225) with a = 4.89199(5) Å. Thermogravimetric and differential thermal analysis experiments combined with in-situ X-ray powder diffraction studies illustrate a complex sequence of a topotactic oxidation pathway, phase segregation, and ion ordering at high temperatures. The optimized bulk synthesis for phase pure ScTiO(3.5) is presented. In contrast to the vanadium-based defect fluorite phases AVO(3.5+x) (A = Sc, In) the novel titanium analogue ScTiO(3.5) is stable over a wide temperature range. Above 950 °C ScTiO(3.5) undergoes decomposition with the final products being Sc(4)Ti(3)O(12) and TiO(2). Simultaneous Rietveld refinements against powder X-ray and neutron diffraction data showed that Sc(4)Ti(3)O(12) also exists in the defect fluorite structure in space group Fm3m (225) with a = 4.90077(4) Å. Sc(4)Ti(3)O(12) undergoes partial reduction in CO/Ar atmosphere to form Sc(4)Ti(3)O(11.69(2)).