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At least 1,495 records · Page 83
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Stability of Solid Uranyl Peroxides under Irradiation

The effects of radiation on a variety of uranyl peroxide compounds were examined using γ-rays and 5 MeV He ions, the latter to simulate α-particles. The studied materials were studtite, [(UO 2 )(O 2 )(H 2 O)2](H 2 O) 2 , the salt of the U 60 uranyl peroxide cage cluster, Li 44 K 16 [(UO 2 )(O 2 )(OH)] 60 ·255H 2 O, the salt of U 60 Ox 30 uranyl peroxide oxalate cage cluster, Li 12 K 48 [{(UO 2 )(O 2 )} 60 (C 2 O 4 ) 30 ]·$n$H 2 O, and the salt of the U 24 Pp 12 (Pp = pyrophosphate) uranyl peroxide pyrophosphate cage cluster, Li 24 Na 24 [(UO 2 ) 24 (O 2 ) 24 (P2O7)12]·120H 2 O. Irradiated powders were characterized using powder X-ray diffraction, Raman spectroscopy, infrared spectroscopy, X-ray photoelectron spectroscopy, and UV–vis spectroscopy. A weakening of the uranyl bonds of U60 was found while studtite, U 60 Ox 30 , and U 24 Pp 12 were relatively stable to $γ$-irradiation. Studtite and U 60 are the most affected by α-irradiation forming an amorphous uranyl peroxide as characterized by Raman spectroscopy and powder X-ray diffraction while U 60 Ox 30 and U 24 Pp 12 show minor signs of the formation of an amorphous uranyl peroxide.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2013

On the crystal energy and structure of A{sub 2}Ti{sub n}O{sub 2n+1} (A=Li, Na, K) titanates by DFT calculations and neutron diffraction

First-principles quantum-mechanical calculations (CRYSTAL09 code, B3LYP functional) were performed on alkali titanates A{sub 2}Ti{sub n}O{sub 2n+1} with layered structure (n=3,4,6). Monoclinic structural types with unshifted (P2{sub 1}/m) and with shifted (C2/m) layers were considered. Crystal energies and full structural details were obtained for all Li, Na, and K phases. Neutron diffraction data were collected on powder samples of P2{sub 1}/m-Li{sub 2}Ti{sub 3}O{sub 7} (a=9.3146(3), b=3.7522(1), c=7.5447(3) Å, β=97.611(4)°) and C2/m-K{sub 2}Ti{sub 4}O{sub 9} (a=18.2578(8), b=3.79160(9), c=12.0242(4) Å, β=106.459(4)°) and their structures were Rietveld-refined. Computed energies show the P2{sub 1}/m arrangement as favoured over the C2/m one for n=3, and the opposite holds for n=6. In the n=4 case the P2{sub 1}/m configuration is predicted to be more stable for Li and Na, and the C2/m one for K titanates. Analysis of Li–O and K–O crystal-chemical environments from experiment and theory shows that the alkali atom bonding is stabilized/destabilized in the different phases consistently with the energy trend. - Graphical abstract: Display Omitted - Highlights: • The P2{sub 1}/m structure-type is found to be more stable for A{sub 2}Ti{sub 3}O{sub 7} layer titanates. • The C2/m structure-type is found to be more stable for A{sub 2}Ti{sub 6}O{sub 13} layer titanates. • Tetratitanates are predicted to prefer the P2{sub 1}/m (Li and Na) or C2/m (K) structure. • Li–O and K–O bond distances follow a trend consistent with computed phase energies.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Hydrogenation induced structure and property changes in GdGa

Hydrides GdGaH{sub x} were obtained by exposing the Zintl phase GdGa with the CrB structure to a hydrogen atmosphere at pressures from 1.5 to 50 bar and temperatures from 50 to 500 °C. Structural analysis by powder X-ray diffraction suggests that conditions with hydrogen pressures in a range between 15 and 50 bar and temperatures below 500 °C afford a uniform hydride phase with the NdGaH{sub 1.66} structure (Cmcm, a=3.9867(7) Å, b=12.024(2) Å, c=4.1009(6) Å) which hosts H in two distinct positions, H1 and H2. H1 is coordinated in a tetrahedral fashion by Gd atoms, whereas H2 atoms are inserted between Ga atoms. The assignment of the NdGaH{sub 1.66} structure is corroborated by first principles DFT calculations. Modeling of phase and structure stability as a function of composition resulted in excellent agreement with experimental lattice parameters when x=1.66 and revealed the presence of five-atom moieties Ga-H2-Ga-H2-Ga in GdGaH{sub 1.66}. From in situ powder X-ray diffraction using synchrotron radiation it was established that hydrogenation at temperatures above 200 °C affords a hydride with x≈1.3, which is stable up to 500 °C, and that additional H absorption, yielding GdGaH{sub 1.66}, takes place at lower temperatures. Consequently, GdGaH{sub 1.66} desorbs H above T=200 °C. Without the presence of hydrogen, hydrides GdGaH{sub x} decompose at temperatures above 300 °C into GdH{sub 2} and an unidentified Gd-Ga intermetallics. Thus the hydrogenation of GdGa is not reversible. From magnetic measurements the Curie-Weiss constant and effective magnetic moment of GdGaH{sub 1.66} were obtained. The former indicates antiferromagnetic interactions, the latter attains a value of ~8 μ{sub B} which is typical for compounds containing Gd{sup 3+}ions. - Graphical abstract: Ferromagnetic GdGa absorbs hydrogen in two steps to yield antiferromagnetic GdGaH{sub 1.66}. Display Omitted - Highlights: • Elucidation of hydrogen uptake behavior of the rare earth gallide GdGa by in situ diffraction. • H-incorporation in GdGa leads to the formation of chain-like polyanions Ga-H-Ga-H-Ga. • H-incorporation in GdGa changes magnetism from ferromagnetic to antiferromagnetic.

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

Recycling of additively printed anisotropic Nd-Fe-B bonded magnets

A high potential cost-effective and environmentally friendly method has been applied for recycling anisotropic Nd-Fe-B bonded magnets. Waste additively printed Hydrogenation-Disproportionation-Desorption-Recombination (HDDR) Nd-Fe-B anisotropic bonded magnet was pulverized into composite powder containing Nd-Fe-B particles and nylon binder through cryomilling at a liquid nitrogen temperature (~77 K) under Ar inert atmosphere. Then, the cryomilled composite powder was warm compacted into a bonded magnet. Further, the magnetic particles were aligned during post-compaction annealing under a magnetic field of 30 kOe. The recycled bonded magnets have a higher density (3% enhancement), but slightly inferior magnetic properties compared to the original magnets, i.e., the magnetic remanence, coercivity and maximum energy product are reduced by 2%, 3% and 8%, respectively. The scanning electron microscopy revealed that some HDDR Nd-Fe-B powder crumbled into fine particles during cryomilling. Powder X-ray diffraction showed a small amount of Nd-oxide impurity in the cryomilled powder. The slightly deteriorated magnetic properties are ascribed to the oxidation of Nd-Fe-B particles due to formation of fresh fracture surface during cryomilling. The approach enables the direct reuse of end-of-life bonded magnets in an economical and environmentally friendly way.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Martensite crystal structure in Ru-based high temperature shape memory alloys

Highlights: • A three level twinned microstructure is recognized in the β″ phase. • Wavy contrast boundaries which are typical for translation interfaces • Displacements are translations of tetragonal β′ phase, lost during transformation. • Six times bigger monoclinic cell is characterized by the disappearance of 5 translations. - Abstract: High temperature shape memory alloys RuNb and RuTa were investigated by X-ray diffraction in order to determine the structure of the low temperature β” martensite. Powder X-ray diffraction and Rietveld analysis confirm the monoclinic symmetry and allow a precise determination of the atom positions. The low temperature microstructure is the result of a martensitic transformation from a tetragonal β′ martensite. The analysis of how it is controlled by the space groups of the two phases and by their relative orientation is performed by transmission electron microscopy. A three level twinned microstructure is recognized in the β” phase. The investigation at the smallest scale twins reveals the presence of wavy contrast boundaries which are typical for translation interfaces. High resolution transmission electron microscopy images, accompanied by phase contrast imaging analysis, have been used to determine the translation vectors associated to the interfaces. These displacements are the translations of the tetragonal β′ phase which are lost during the transformation. The combination of X-ray diffraction and transmission electron microscopy investigation allows the suggestion of a global distortion mechanism that explains the atomic displacements in the β” form.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Organizing Chaos: Boosting Thermoelectric Properties by Ordering the Clathrate Framework of Ba 8 Cu 16 As 30

The type I clathrate, Ba 8 Cu 16 As 30 , is reinvestigated and found to have a low-temperature polymorph mP 108-Ba 8 Cu 16 As 30 with ordered Cu and As sites. In situ temperature-dependent powder X-ray diffraction experiments guided synthetic efforts toward the synthesis of the ordered monoclinic ( mP 108) and disordered cubic ( cP 54) polymorphs with high phase purity. While a transition from mP 108-Ba 8 Cu 16 As 30 to cP 54-Ba 8 Cu 16 As 30 is not directly observed, cP 54-Ba 8 Cu 16 As 30 is stabilized through quenching from high temperatures and is confirmed through high-resolution synchrotron powder X-ray diffraction. Further, combined theoretical predictions and experimental observations of the thermoelectric properties of both polymorphs reveal that the ordering of Cu and As atoms in the clathrate framework simultaneously enhances the Seebeck coefficient and electronic conductivity by increasing the hole effective mass and reducing the electronic scattering events. Consequently, the zT of mP 108-Ba 8 Cu 16 As 30 reaches a maximum of 0.2 at 575 K, an order of magnitude higher than that of cP 54-Ba 8 Cu 16 As 30 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Ultra-low thermal conductivities of hot-pressed attapulgite and its potential as thermal insulation material

In the past, there have been very few reports on thermal properties of attapulgite which is a widely used clay mineral. In this work, we report on extremely low thermal conductivities in attapulgite samples synthesized by hot-pressing. Attapulgite powder was hot-pressed at different temperatures into bulk samples, and a systematic study was conducted on the microstructures and thermal properties. Differential scanning calorimetry analysis shows that hot-pressing induces a rapid dehydration of the attapulgite powders. X-ray diffraction data and scanning/transmission electron microscopy reveal that the hot-pressed attapulgite features high porosity and complex microstructures, including an amorphous phase. As a result, the hot-pressed attapulgite exhibits thermal conductivity less than 2.5Wm -1 K -1 up to 600 °C. For one sample with porosity of 45.7%, the thermal conductivity is as low as 0.34Wm -1 K -1 at 50 °C. Finally, this suggests the potential of hotpressed attapulgite as a candidate for thermal barrier materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Formation of Ba 3 Nb 0.75 Mn 2.25 O 9 -6H during thermochemical reduction of Ba 4 NbMn 3 O 12 -12R

The resurgence of interest in hydrogen-related technologies has stimulated new studies aimed at advancing lesser-developed water-splitting processes, such as solar thermochemical hydrogen production (STCH). Progress in STCH has been largely hindered by a lack of new materials able to efficiently split water at a rate comparable to ceria under identical experimental conditions. BaCe 0.25 Mn 0.75 O 3 (BCM) recently demonstrated enhanced hydrogen production over ceria and has the potential to further our understanding of two-step thermochemical cycles. A significant feature of the 12R hexagonal perovskite structure of BCM is the tendency to, in part, form a 6H polytype at high temperatures and reducing environments ( i.e. , during the first step of the thermochemical cycle), which may serve to mitigate degradation of the complex oxide. An analogous compound, namely BaNb 0.25 Mn 0.75 O 3 (BNM) with a 12R structure was synthesized and displays nearly complete conversion to the 6H structure under identical reaction conditions as BCM. The structure of the BNM-6H polytype was determined from Rietveld refinement of synchrotron powder X-ray diffraction data and is presented within the context of the previously established BCM-6H structure.

08 HYDROGEN↗
DOE OSTI2014

Low temperature crystal structure and magnetic properties of RAl{sub 2}

Low temperature crystal structure and magnetic properties of RAl{sub 2} (R = Pr and Nd) have been studied using temperature dependent powder x-ray diffraction, magnetization, and heat capacity measurements. Unlike PrAl{sub 2}, NdAl{sub 2} retains cubic MgCu{sub 2}-type structure from room temperature down to 5 K, which is also confirmed from first principles electronic structure calculations. The magnetization measurements show both PrAl{sub 2} and NdAl{sub 2} order ferromagnetically at T{sub C} = 32 K and 77 K, respectively. However, the magnetization measurements show the former is a hard ferromagnet compared to the latter which is a soft ferromagnetic material. The magnetic entropy change obtained from heat capacity measurements at ΔH = 30 kOe for PrAl{sub 2} and NdAl{sub 2} are 3.15 J mol{sup −1} K{sup −1} and 1.18 J mol{sup −1} K{sup −1}, respectively.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

Crystal structures of two novel borate compounds MgInBO{sub 4} and MgIn{sub 7/8}B{sub 7/8}O{sub 29/8}

Two novel borate compounds MgInBO{sub 4} and MgIn{sub 7/8}B{sub 7/8}O{sub 29/8}, have been synthesized via solid-state reactions, and their crystal structures have been solved and refined from powder X-ray diffraction data. The compound MgInBO{sub 4}, which was obtained at 1190 °C, belongs to the warwickite family. It crystallizes in the Pnma space group (no. 62) with a=9.5443(1) Å, b=3.2771(1) Å, c=9.5228(1) Å, and Z=4. The fundamental building units are liner –Mg(In)O{sub 6}–[In(Mg)]{sub 2}O{sub 10}–Mg(In)O{sub 6}– chains and isolated BO{sub 3} triangles. The low-temperature phase, MgIn{sub 7/8}B{sub 7/8}O{sub 29/8}, whose crystal structure is solved ab initio by the charge-flipping method with standard chemical formula MgInBO{sub 4}, was prepared at 1080 °C. It crystallizes in the P12{sub 1}/n1 space group (no. 14) with a=17.0976(1) Å, b=3.2504(1) Å, c=5.3387(1) Å, β=96.0829(3)°, and Z=4. The structure of MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} contains [In(2)/Mg(2)]{sub 2}O{sub 10} groups, –MgO{sub 6}–InO{sub 6}– infinite ribbons and isolated BO{sub 3} triangles. The experiments and the differential thermal analysis (DTA) show the decompositions of MgInBO{sub 4} and MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} happen at about 1220 °C and 1180 °C, respectively. The comparative crystal chemistry from MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} to MgInBO{sub 4} has been discussed. Infrared spectra and UV–vis diffuse reflectance spectra of MgInBO{sub 4} and MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} were measured. - Graphical abstract: The structural transformation from the monoclinic MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} (P12{sub 1}/n1) to the orthorhombic MgInBO{sub 4} (Pnma). - Highlights: • Two novel borate compounds MgInBO{sub 4} and MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} have been synthesized via solid-state reactions for the first time. • The crystal structures of MgInBO{sub 4} and MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} have been solved and refined from powder X-ray diffraction data. • The possible crystal chemical analysis from MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} to MgInBO{sub 4} is discussed. • Infrared spectra and UV–vis diffuse reflectance spectra of MgInBO{sub 4} and MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} have been measured.

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

Li 21 Ge 8 P 3 S 34 : New Lithium Superionic Conductor with Unprecedented Structural Type

Abstract Lithium superionic conductors are pivotal for enabling all‐solid‐state batteries, which aim to replace liquid electrolytes and enhance safety. Herein, we report the discovery of an unprecedented lithium superionic conductor, Li 21 Ge 8 P 3 S 34 , featuring a novel structural type and a new composition in the Li–Ge–P–S system. This material exhibits high lithium ionic conductivity of approximately 1.0 mS cm −1 at 303 K with a low activation energy of 0.20(1) eV. It's unique crystal structure was elucidated using three‐dimensional electron diffraction (3D ED) and further refined through combined powder X‐ray and neutron diffraction analyses. The structure consists of alternating two‐dimensional slabs: one of corner‐sharing GeS 4 tetrahedra and the other of isolated PS 4 tetrahedra, enabling efficient lithium‐ion transport through a tetrahedrally interconnected network of 1D, 2D, and 3D diffusion pathways. This distinctive structural motif provides a novel design strategy for next‐generation solid electrolytes, broadening the structural landscape of lithium superionic conductors. With further advancements in compositional tuning and interfacial engineering, Li 21 Ge 8 P 3 S 34 could contribute to the development of high‐performance all‐solid‐state batteries.

Chemistry↗
DOE OSTI2018

Effect of Synthetic Method and Annealing Temperature on the Structure of Hollandite-Type Oxides

Hollandite is a class of metal oxide material with the general formula A 2 B 8 O 16 . Several methods have been used in the synthesis of this type of metal oxide, and the synthetic methods reported have typically employed high annealing temperatures between 1200 and 1300 °C. Appropriate synthetic methods must be employed to successfully synthesize these hollandite-type oxides at lower annealing temperatures. Hollandite compounds have been synthesized using ceramic (high annealing temperature only) and coprecipitation (high and low annealing temperatures) methods. Annealing temperatures ranging from 1200 to 700 °C have been employed in the thermal treatment process. In this work, powder X-ray diffraction and X-ray absorption near-edge spectroscopy (XANES) were conducted on hollandite-type oxides (Ba x Al 2 x Ti 8–2 x O 16–δ ; x = 1.2; and Ba x Al x Fe x Ti 8–2 x O 16–δ, Ba x Fe 2 x Ti 8–2 x O 16–δ ; x = 1.16). Structural comparisons between materials annealed in the temperature range from 1200 to 800 °C were made, and an examination of the XANES spectra and powder X-ray diffraction patterns has provided confirmation of the absence of significant structural changes in these hollandite materials. This study has shown that hollandite-type materials can be formed using annealing temperatures as low as 700–800 °C when a coprecipitation method is used, with little change to the local and long-range structures being detected.

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

Synthesis and Characterization of Silicon Carbide Ceramic Composites with CeO 2 Powder

This study pioneers the fabrication and characterization of silicon carbide (SiC) containing cerium dioxide (CeO 2 ). CeO 2 powder was tested as a surrogate for actinide oxide waste forms such as uranium dioxide (UO 2 ) and plutonium dioxide (PuO 2 ). Several syntheses were evaluated with varying amounts of preceramic polymer (SMP-10 resin) and CeO 2 containing either SiC fiber, carbon fiber, or no fibers. Scanning electron microscopy (SEM) was used to characterize morphology and compositional differences, and energy-dispersive x-ray spectroscopy (EDS) was used to provide semiquantitative elemental analysis. In addition, each sample was characterized by density, powder x-ray diffraction (pXRD), and Raman spectroscopy. Samples containing nearly more than four times CeO 2 powder than SMP-10 resin by mass had the best properties. This research establishes a unique synthesis for SiC containing high concentrations of CeO 2 powder to illustrate how it may be managed as a potential waste form.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

Role of annealing temperature on cation ordering in hydrothermally prepared zinc aluminate (ZnAl2O4) spinel

Highlights: • Investigation of the structural anomaly in Zinc Aluminate Spinel/ZAS (ZnAl{sub 2}O{sub 4}) by chemically inducing the defects by annealing temperature and synthetic pressure. • Hydrothermal synthesis of ZnAl{sub 2}O{sub 4} at 240 °C from nitrate precursors. • Study of the role of annealing temperature (300–900 °C) in tuning cation ordering. • Rietveld analysis of powder X-ray diffraction patterns and Raman spectroscopy to showcase disorder-order transition in ZnAl{sub 2}O{sub 4} spinels. - Abstract: Spinels (AB{sub 2}O{sub 4}) form a niche class of ceramics, which is rich in structural (dis)ordering due to the inherent mixing between the constituent tetrahedral and octahedral sites. The cations (A and B) can form antisite defects under the influence of external parameters like pressure, temperature and nuclear irradiation. The current study reports the formation and evolution of disorder-order structural transition in hydrothermally prepared zinc aluminate spinel ZnAl{sub 2}O{sub 4}. The effect of final calcination temperature (300–900 °C for 9 h) on the degree of cation ordering has been investigated with powder X-ray diffraction, Raman and {sup 27}Al solid-state NMR spectroscopy. Rietveld refinement revealed a gradual disorder to order structural transition accompanied by lower inversion parameter (i{sub s}) and smaller lattice parameter (a) with higher calcination temperature. It was further affirmed by Raman analysis and solid-state NMR spectroscopy probing the ZnO{sub 4} and AlO{sub 4} tetrahedra in spinel. Independent of the degree of cation ordering, nanometric particle size with high surface area was observed in ZnAl{sub 2}O{sub 4} spinel.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Quantitative Analysis of the Morphology of {101} and {001} Faceted Anatase TiO 2 Nanocrystals and Its Implication on Photocatalytic Activity

The atomistic structure and morphology (shape and size) of nanomaterials have strong influences on their physical and chemical properties. However, many characterization techniques focus exclusively on one length-scale regime or another when developing quantitative morphology/structural models. In this article, we demonstrate that powder X-ray diffraction and neutron pair distribution function (PDF) can be used to obtain accurate average morphology and atomistic structure of {001} and {101} faceted anatase TiO 2 nanocrystals based on differential evolution refinements using Debye scattering equation calculations. It is also demonstrated that the morphology polydispersity of TiO 2 nanocrystals can be effectively obtained from the diffraction data via a numerical refinement routine. The morphology refinement results are in good agreement with those from transmission electron microscopy and the modeling of small angle neutron scattering data. This method is successfully used to quantify the facet-specified photocatalytic hydrogen evolution activity of anatase TiO 2 nanocrystals with different {001} to {101} ratios. It is found that the sample with an intermediate amount of both {001} and {101} facets shows the best photocatalytic hydrogen evolution reaction (HER) activity. It is expected that the simultaneous structure and morphology refinement technique can be generally used to study the relationship between morphology and functionality of nanomaterials.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Zirconium-Based Metal–Organic Framework for Removal of Perrhenate from Water

Efficient removal of pertechnetate (TcO4 -) anions from liquid waste or melter off-gas solution for alternative treatment is one of the promising options to manage 99Tc in legacy nuclear waste. Safe immobilization of 99Tc is of major importance due to its long half-life (t1/2= 2.13 × 105 yrs) and environmental mobility. Different types of inorganic and solid state ion-exchange materials such as layered double hydroxides have been shown to absorb TcO4 - anions from water. However, both high capacity and selectivity have yet to be achieved in a single material. Herein, we show that a protonated version of an ultra-stable zirconium based metalorganic framework can adsorb perrhenate (ReO4 -) anions, a non-radioactive surrogate for TcO4 -, from water even in the presence of other common anions. Synchrotron based powder X-ray diffraction and molecular simulations were used to identify the position of the adsorbed ReO4 - (surrogate for TcO4 -) molecule within the framework.

Banerjee, Debasis↗
DOE OSTI2017

Pressure-dependence of the phase transitions and thermal expansion in zirconium and hafnium pyrovanadate

Low or negative thermal expansion (NTE) has been previously observed in members of the ZrP{sub 2}O{sub 7} family at temperatures higher than their order-disorder phase transitions. The thermoelastic properties and phase behavior of the low temperature superstructure and high temperature negative thermal expansion phases of ZrV{sub 2}O{sub 7} and HfV{sub 2}O{sub 7} were explored via in situ variable temperature/pressure powder x-ray diffraction measurements. The phase transition temperatures of ZrV{sub 2}O{sub 7} and HfV{sub 2}O{sub 7} exhibited a very strong dependence on pressure (∼700 K GPa), with moderate compression suppressing the formation of their NTE phases below 513 K. Compression also reduced the magnitude of the coefficients of thermal expansion in both the positive and negative thermal expansion phases. Additionally, the high temperature NTE phase of ZrV{sub 2}O{sub 7} was found to be twice as stiff as the low temperature positive thermal expansion superstructure (24 and 12 GPa respectively). - Graphical abstract: The temperature at which ZrV{sub 2}O{sub 7} transforms to a phase displaying negative thermal expansion is strongly pressure dependent. The high temperature form of ZrV{sub 2}O{sub 7} is elastically stiffer than the low temperature form. - Highlights: • The order-disorder phase transition temperatures in ZrV{sub 2}O{sub 7} and HfV{sub 2}O{sub 7} are strongly pressure dependent (∼700 K.GPa). • The high temperature (disordered) phase of ZrV{sub 2}O{sub 7} is much stiffer than the ambient temperature (ordered) phase. • Compression reduces the magnitude of the negative thermal expansion in the high temperature phase of ZrV{sub 2}O{sub 7}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗