Neutron Diffraction Research Articles

Noncentrosymmetric Triangular Magnet CaMnTeO6: Strong Quantum Fluctuations and Role of s0 versus s2 Electronic States in Competing Exchange Interactions.

Noncentrosymmetric triangular magnets offer a unique platform for realizing strong quantum fluctuations. However, designing these quantum materials remains an open challenge attributable to a knowledge gap in the tunability of competing exchange interactions at the atomic level. Here, a new noncentrosymmetric triangular S=3/2 magnet CaMnTeO6 is created based on careful chemical and physical considerations. The model material displays competing magnetic interactions and features nonlinear optical responses with the capability of generating coherent photons. The incommensurate magnetic ground state of CaMnTeO6 with an unusually large spin rotation angle of 127°(1) indicates that the anisotropic interlayer exchange is strong and competing with the isotropic interlayer Heisenberg interaction. The moment of 1.39(1)µB, extracted from low-temperature heat capacity and neutron diffraction measurements, is only 46% of the expected value of the static moment 3µB. This reduction indicates the presence of strong quantum fluctuations in the half-integer spin S=3/2 CaMnTeO6 magnet, which is rare. By comparing the spin-polarized band structure, chemical bonding, and physical properties of AMnTeO6 (A=Ca, Sr, Pb), how quantum-chemical interpretation can illuminate insights into the fundamentals of magnetic exchange interactions, providing a powerful tool for modulating spin dynamics with atomically precise control is demonstrated.

Correlating Structure with Spectroscopy in Ascorbate Peroxidase Compound II.

Structural and spectroscopic investigations of compound II in ascorbate peroxidase (APX) have yielded conflicting conclusions regarding the protonation state of the crucial Fe(IV) intermediate. Neutron diffraction and crystallographic data support an iron(IV)-hydroxo formulation, whereas Mössbauer, X-ray absorption (XAS), and nuclear resonance vibrational spectroscopy (NRVS) studies appear consistent with an iron(IV)-oxo species. Here we examine APX with spectroscopy-oriented QM/MM calculations and extensive exploration of the conformational space for both possible formulations of compound II. We establish that irrespective of variations in the orientation of a vicinal arginine residue and potential reorganization of proximal water molecules and hydrogen bonding, the Fe-O distances for the oxo and hydroxo forms consistently fall within distinct, narrow, and nonoverlapping ranges. The accuracy of geometric parameters is validated by coupled-cluster calculations with the domain-based local pair natural orbital approach, DLPNO-CCSD(T). QM/MM calculations of spectroscopic properties are conducted for all structural variants, encompassing Mössbauer, optical, X-ray absorption, and X-ray emission spectroscopies and NRVS. All spectroscopic observations can be assigned uniquely to an Fe(IV)═O form. A terminal hydroxy group cannot be reconciled with the spectroscopic data. Under no conditions can the Fe(IV)═O distance be sufficiently elongated to approach the crystallographically reported Fe-O distance. The latter is consistent only with a hydroxo species, either Fe(IV) or Fe(III). Our findings strongly support the Fe(IV)═O formulation of APX-II and highlight unresolved discrepancies in the nature of samples used across different experimental studies.

Microstructure and residual stress evolution during cyclic elastoplastic deformation of AISI316L fabricated via laser powder bed fusion

In metal additive manufacturing (MAM), microstructural properties such as texture, residual stresses, and dislocation density have emerged as key factors ruling the resulting mechanical performances. In this study, cylindrical AISI 316L specimens, fabricated with laser powder bed fusion (LPBF), were tested under cyclic elastoplastic (EP) deformation using a constant strain amplitude to highlight the evolution of residual stresses (RS), dislocation density and texture with increasing number of EP cycles, N, across the hardening-softening (H–S) transition stage, in the attempt to find correlations between relevant microstructural parameters and macroscopic properties. The structural and microstructural analysis is carried out through whole powder pattern modeling (WPPM) of neutron diffraction (ND) data and Electron Back-Scattering Diffraction (EBSD) analysis. The H–S transition is found to occur within 7–9 cycles, with RS fading out already after 5 cycles. Across the H–S transition, the trend of the maximum tensile stress correlates closely with the trend of WPPM-calculated total dislocation density, suggesting a major role of dislocations’ characteristics in the evolution of macroscopic mechanical properties. EBSD analysis reveals the rearrangement of geometrically necessary dislocations (GND) into cellular structures, and moderate grain refinement, which are deemed to be responsible for the quick fading of RS in the very early stage of EP loading. ND-based texture analysis reveals a (220) preferential orientation retained throughout the EP tests but with orientation density functions (ODFs) changing non-monotonically with N, suggesting preliminary partial randomization of grains around the deformation axis followed by the recovery of crystallographic anisotropy and more localized ODFs.

Hydrogenation of silicon-bearing hexagonal close-packed iron and its implications for density deficits in the inner core

To investigate silicon effects on the hydrogen-induced volume expansion of iron, neutron diffraction and X-ray diffraction experiments were conducted to examine hcp-Fe0.95Si0.05 under high pressures and high temperatures. Neutron diffraction experiments were performed on the deuterated hcp-Fe0.95Si0.05 at 13.5 GPa and 900 K, and at 12.1 GPa and 300 K. The hydrogen occupancy was determined from the obtained profiles using Rietveld analysis. By combining the P–V–T equation of state of hcp-Fe0.95Si0.05, the present results indicate that the hydrogen-induced volume expansion of hcp-Fe0.95Si0.05 is 10% greater than that of pure hcp iron. Using the obtained values, we estimated the hydrogen content that would reproduce the density deficit in the inner core, which was 50% less than that without the effect of silicon. Possible hydrogen content, x, in the inner core and the outer core was calculated to be 0.07 and 0.12–0.15, respectively when reproducing the density deficit of the inner core with hcp-Fe0.95Si0.05Hx.

High valley-degeneracy electron gas at double perovskite - strontium titanate interface

Emergent phenomena such as two-dimensional electron gas (2DEG) and interfacial superconductivity and ferromagnetism are generally built on the interface between insulating oxide thin films and substrates, e.g., LaAlO3/SrTiO3, where the 2D profiles of these electronic states are precisely confined at the interface of two insulators. Herein we report a high-mobility electron gas state with unusual symmetry at the interface of the Sr2CrMoO6/SrTiO3 (110) heterostructures, the fermiology of which follows the cubic crystallographic symmetry rather than the two-dimensional interface itself, resulting in the identical Shubnikov-de Haas oscillations with applied magnetic field along all the twelve equivalent [110] crystallographic directions of SrTiO3, distinctly different from the 2D nature of the electron gas reported previously. Neutron diffraction verifies the predicted ferrimagnetic ordering between Cr and Mo moments. This, together with the magnetic hysteresis loops and negative magnetoresistance in low-field region, suggests possible spin polarization of itinerant electrons. Therefore, a quasi-3D profile, high mobility (up to 104 cm2 V−1 s−1) and possibly spin polarized electronic state is observed in the double-perovskite-based oxide heterostructures. This finding of the electronic properties in Sr2CrMoO6/SrTiO3 (110) heterostructure expands the knowledge of interfacial physics, as well as shines light on oxide-based electronics and spintronics research.

Study of the structure and properties of interstitial alloys TixMo1 – xCyNz

Developing the new materials with improved properties suggests study of the crystal structure and properties of multicomponent interstitial alloys. We present the results of studying the crystal structure and microhardness of TixMo1 – xCyNz interstitial alloys in massive samples with different ratios of concentrations of constituent elements. The samples obtained by self-propagating high-temperature synthesis were subjected to homogenizing annealing at 2600 K for 8 h and cooled together with the furnace. Data of neutron diffraction revealed that the alloys have a face-centered cubic crystal structure in which Ti and Mo atoms, as well as C and N, are intersubstituted and statistically located in the 4b positions and octahedral 4a positions, respectively. The Rietveld method was used to determine crystallite sizes, dislocation densities, and microstrain using X-ray diffraction patterns. The microhardness of the samples was determined by the Vickers method. It is shown that the crystallite sizes determined by the Williamson-Hall and Scherrer methods differ significantly, whereas the patterns of crystallite growth in size, as well as regularities of changes in the dislocation density and microstrains follow change in the concentration of the components in the composition. As the carbon content in the alloy increases, the crystallite sizes and microstrains decrease, and the dislocation density increases. It is revealed that the smaller the crystallite size and the higher the dislocation density, the more microhardness is displaced towards increasing the carbon content. With a change in the ratio of components in TixMo1 – xCyNz as the crystallite size and microstrains decrease and dislocation density increases, the microhardness of the alloy increases by 1.5 – 2 times compared to binary carbide and titanium nitride. The results obtained can be applied to the use of interstitial alloys in instrumental and high-temperature engineering.

Real-time evolution of texture and temperature during friction stir processing of a magnesium alloy: An operando neutron diffraction study

The real-time development of texture and the evolution of temperature during friction stir processing (FSP) of a Mg alloy were investigated using an operando neutron diffraction measurement. A novel approach was applied in this study where the real-time, quasi-steady state measurements performed as a function of position during FSP are converted to a Lagrangian dataset that reveals the transient behavior as a function of time. The in-situ FSP was carried out under two different thermo-mechanical processing conditions represented by the Zener-Hollomon parameter, Z. The results show that: (i) a shear texture develops from the initial strong basal texture with the peak temperature reaching about 774 K during a low-Z processing and (ii) a strong off-normal texture develops with a peak temperature of 616 K during a high-Z processing. Moreover, time-temperature-texture diagrams were established to reveal the real-time development of the texture during the processing for both the low Z and high Z processing conditions. The changes in texture will be discussed in terms of plastic deformation mechanisms active during various stages of the FSP under the two different processing conditions.

Microscopic insights of the extraordinary work-hardening due to phase transformation

Commercial 316 L stainless steel is known for its appreciable strength and ductility, as well as strong resistance against corrosion and radiation damage. Remarkably, upon cooling, 316 L maintains high ductility while the strength increases significantly, making the alloy an excellent choice for applications at low temperatures. Despite these attractive properties, the physical mechanisms underlying the outstanding low-temperature mechanical properties have not been established. Here, we report an in situ neutron diffraction study of 316 L that reveals an extraordinary work-hardening rate (WHR) of ∼7 GPa at 15 K. Detailed analyses show that the major contribution to the excellent strength and ductility comes from the transformation-induced plasticity (TRIP) effect, introduced by the austenite-to-martensite (γ-to-α′) phase transition. A dramatic increase in the WHR is observed along with the transformation; the WHR declined when the austenite phase is exhausted. During plastic deformation, the volume-fraction weighted phase stress and stress contribution from the α′-martensite increase significantly. The neutron diffraction data further suggest that the γ-to-α′ phase transformation was mediated by the ε-martensite, as evidenced by the concurrent decline of the ε phase with the γ phase. This study sheds light on the extraordinary work-hardening effect due to phase transformation, which will provide guidance in the design of complex alloys.

Correlation of microstructure, mechanical properties, and residual stress of 17-4 PH stainless steel fabricated by laser powder bed fusion

17-4 precipitation hardening (PH) stainless steel is a multi-purpose engineering alloy offering an excellent trade-off between strength, toughness, and corrosion properties. It is commonly employed in additive manufacturing via laser powder bed fusion owing to its good weldability. However, there are remaining gaps in the processing-structure-property relationships for AM 17-4 PH that need to be addressed. For instance, discrepancies in literature regarding the as-built microstructure, subsequent development of the matrix phase upon heat treatment, as well as the as-built residual stress should be addressed to enable reproducible printing of 17-4 builds with superior properties. As such, this work applies a comprehensive characterisation and testing approach to 17-4 PH builds fabricated with different processing parameters, both in the as-built state and after standard heat treatments. Tensile properties in as-built samples both along and normal to the build direction were benchmarked against standard wrought samples in the solution annealed and quenched condition (CA). When testing along the build direction, higher ductility was observed for samples produced with a higher laser power (energy density) due to the promotion of interlayer cohesion and, hence, reduction of interlayer defects. Following the CA heat treatment, the austenite volume fraction increased to ∼35 %, resulting in a lower yield stress and greater work hardening capacity than the as-built specimens due to the transformation induced plasticity effect. Neutron diffraction revealed a slight reduction in the magnitude of residual stress with laser power. A concentric scanning strategy led to a higher magnitude of residual stress than a bidirectional raster pattern.

Investigation of O/N Ordering in Perovskite-Type Oxynitrides La1−xYxTa(O,N)3 on Long Range and Short Scale

Oxynitrides such as LaTa(O,N)3 are attractive materials as photoelectrodes for photoelectrocatalytic solar water splitting. The potential anionic ordering in their perovskite-type structure has been shown to impact the materials’ properties. Given the importance attributed to it, the present study reports a detailed experimental analysis supported by simulations of the anionic ordering of La1−xYxTa(O,N)3. The influence of O/N and yttrium content on the anionic order was assessed. Neutron diffraction analysis was performed on four different nominal compositions—LaTaON2, LaTaO2N, La0.9Y0.1TaON2, and La0.9Y0.1TaO2N—at 10 K and 300 K to study potential long-range ordering. Neutron pair distribution function (PDF) analysis was performed on all samples at 10 K and on non-Y-substituted samples at 300 K to evaluate short-range ordering. There was no evidence of long-range O/N order in any of the compounds. In contrast, at a short range (1.5 Å ≤ r < 6 Å), a Pnma (a−b+a−) tilting pattern and local cis-ordering of the anions were seen. The latter faded rapidly, leaving the Pnma tilting pattern in a 6 Å ≤ r ≤ 11 Å range. At higher distances, the PDF analysis agreed with the Imma (a−b0a−) O/N disordered long-range structure. As the O/N content changed, not much difference in behavior was observed. Yttrium substitution introduced some disorder in the structure; nonetheless, it showed marginal influence on octahedral tilting and anionic ordering.

Molecular interactions with bilayer membrane stacks using neutron and X-ray diffraction

Lamellar unit cell reconstruction from neutron and X-ray diffraction data provides information about the disposition and position of molecules and molecular segments with respect to the bilayer. When supplemented with the judicious use of molecular deuteration, the technique probes the molecular interactions and conformations within the bilayer membrane and the water layer which constitute the crystallographic unit cell. The perspective is model independent, and potentially, with a higher degree of resolution than is available with other techniques. In the case of neutron diffraction the measurement consists of carefully normalised diffracted intensity under conditions of contrast variation of the water layer. The subsequent Fourier reconstruction of the unit cell is made using the phase information from variation of peak intensities with contrast. Although the phase problem is not as easily solved for the corresponding X-ray measurements, an intuitive approach can often suffice. Here we discuss the two complimentary techniques as probes of scattering length density profiles of a bilayer, and how such a perspective provides information about the location and orientation of molecules within or between lipid bilayers. Within the basic paradigm of lamellar phases this method has provided, for example, detailed insights into the location and interaction of cryoprotectants and stress proteins, of the mechanisms of actions of viral proteins, antimicrobial compounds and drugs, and the underlying structure of the stratum corneum. In this paper we review these techniques and provide examples of the systems that have been examined. We finish with a future outlook on the use of these techniques to improve our understanding of the interactions of membranes with biomolecules.

A redox switch allows binding of Fe(II) and Fe(III) ions in the cyanobacterial iron-binding protein FutA from Prochlorococcus

The marine cyanobacterium Prochlorococcus is a main contributor to global photosynthesis, whilst being limited by iron availability. Cyanobacterial genomes generally encode two different types of FutA iron-binding proteins: periplasmic FutA2 ABC transporter subunits bind Fe(III), while cytosolic FutA1 binds Fe(II). Owing to their small size and their economized genome Prochlorococcus ecotypes typically possess a single futA gene. How the encoded FutA protein might bind different Fe oxidation states was previously unknown. Here, we use structural biology techniques at room temperature to probe the dynamic behavior of FutA. Neutron diffraction confirmed four negatively charged tyrosinates, that together with a neutral water molecule coordinate iron in trigonal bipyramidal geometry. Positioning of the positively charged Arg103 side chain in the second coordination shell yields an overall charge-neutral Fe(III) binding state in structures determined by neutron diffraction and serial femtosecond crystallography. Conventional rotation X-ray crystallography using a home source revealed X-ray-induced photoreduction of the iron center with observation of the Fe(II) binding state; here, an additional positioning of the Arg203 side chain in the second coordination shell maintained an overall charge neutral Fe(II) binding site. Dose series using serial synchrotron crystallography and an XFEL X-ray pump-probe approach capture the transition between Fe(III) and Fe(II) states, revealing how Arg203 operates as a switch to accommodate the different iron oxidation states. This switching ability of the Prochlorococcus FutA protein may reflect ecological adaptation by genome streamlining and loss of specialized FutA proteins.

Pressure-tuned quantum criticality in the large-D antiferromagnet DTN

Strongly correlated spin systems can be driven to quantum critical points via various routes. In particular, gapped quantum antiferromagnets can undergo phase transitions into a magnetically ordered state with applied pressure or magnetic field, acting as tuning parameters. These transitions are characterized by z = 1 or z = 2 dynamical critical exponents, determined by the linear and quadratic low-energy dispersion of spin excitations, respectively. Employing high-frequency susceptibility and ultrasound techniques, we demonstrate that the tetragonal easy-plane quantum antiferromagnet NiCl2 ⋅ 4SC(NH2)2 (aka DTN) undergoes a spin-gap closure transition at about 4.2 kbar, resulting in a pressure-induced magnetic ordering. The studies are complemented by high-pressure-electron spin-resonance measurements confirming the proposed scenario. Powder neutron diffraction measurements revealed that no lattice distortion occurs at this pressure and the high spin symmetry is preserved, establishing DTN as a perfect platform to investigate z = 1 quantum critical phenomena. The experimental observations are supported by DMRG calculations, allowing us to quantitatively describe the pressure-driven evolution of critical fields and spin-Hamiltonian parameters in DTN.

Tailored (La0.2 Pr0.2 Nd0.2 Tb0.2 Dy0.2 )2 Ce2 O7 as a Highly Active and Stable Nanocatalyst for the Oxygen Evolution Reaction.

Designing highly active and robust catalysts for the oxygen evolution reaction is key to improving the overall efficiency of the water splitting reaction. It has been previously demonstrated that evaporation induced self-assembly (EISA) can be used to synthesize highly porous and high surface area cerate-based fluorite nanocatalysts, and that substitution of Ce with 50% rare earth (RE) cations significantly improves electrocatalyst activity. Herein, the defect structure of the best performing nanocatalyst in the series are further explored, Nd2 Ce2 O7 , with a combination of neutron diffraction and neutron pair distribution function analysis. It is found that Nd3 + cation substitution for Ce in the CeO2 fluorite lattice introduces higher levels of oxygen Frenkel defects and induces a partially reduced RE1.5 Ce1.5 O5 + x phase with oxygen vacancy ordering. Significantly, it is demonstrated that the concentration of oxygen Frenkel defects and improved electrocatalytic activity can be further enhanced by increasing the compositional complexity (number of RE cations involved) in the substitution. The resulting novel compositionally-complex fluorite- (La0.2 Pr0.2 Nd0.2 Tb0.2 Dy0.2 )2 Ce2 O7 is shown to display a low OER overpotential of 210 mV at a current density of 10 mAcm-2 in 1M KOH, and excellent cycling stability. It is suggested that increasing the compositional complexity of fluorite nanocatalysts expands the ability to tailor catalystdesign.

Neutron Diffraction Residual Stress Study of a AA2219-T87 Self-Reacting Friction Stir Weld

Neutron Diffraction Residual Stress Study of a AA2219-T87 Self-Reacting Friction Stir Weld

Final physical design of engineering materials diffractometer at the China spallation neutron source

Neutron diffraction is a widely utilized technique in detecting microstructures and residual strains in large-scale engineering components. In this study, we present the final physical design of an upcoming neutron diffractometer for engineering materials at the China Spallation Neutron Source. Our primary objective is to minimize the experimental time required for precise diffraction peak determination. To achieve this, the design includes a neutron transport system, a neutron wavelength selection system, a diffracted neutron optical system, and a resolution and intensity regulation system. Notably, we optimized the wavelength bandwidth specifically for scientific experiments, while the neutron flux or integrated peak intensity were optimized through careful considerations of neutron transport. Additionally, we placed great emphasis on ensuring the uniformity of the neutron phase space to enhance measurement accuracy. Moreover, we optimized the combinations of resolution and integrated peak intensity based on the best figure of merit. Consequently, we successfully developed an advanced diffractometer that is poised to offer new capabilities for engineering material studies.

Phase evolution, defect chemistry, and electrical properties of Na0.5Bi0.5TiO3-BiNi0.5Ti0.5O3 solid solutions

Solid solutions of Na0.5Bi0.5TiO3 (NBT) and BiNi0.5Ti0.5O3 (BNiT) were prepared by a solid-state reaction route, and their electrical properties investigated by a combination of impedance spectroscopy and electromotive force measurements to explore the possibility of developing mixed ionic-electronic conductors based on NBT. Phase analysis showed that BNiT has a large solid solution limit in NBT (60 mol% based on X-ray diffraction), and the room temperature crystal structure changes from rhombohedral to pseudo-cubic with increasing BNiT content. Neutron diffraction revealed the coexistence of rhombohedral and tetragonal phases when the BNiT content ≥ 40 mol%. Electrically, incorporation of BNiT induces p-type electronic conduction into NBT by hopping of holes between Ni2+ (NiNix) and Ni3+ (NiNi·), and therefore changes the electrical conduction mechanism systematically from predominant oxide-ion conduction to mixed ionic-electronic conduction and then to predominant p-type electronic conduction. The total conductivity of the solid solutions showed a “V-shape” variation with increasing BNiT content. Possible mechanisms for the phase evolution and the conductivity-composition relationships are discussed. Achieving high levels of ionic and electronic conductivity simultaneously in NBT by introducing elements with variable oxidation states remains challenging due to the competition between an enhanced electronic component and a suppressed ionic component. Low levels of BNiT incorporation are, however, beneficial to reducing the dielectric loss of NBT for dielectric applications.

Low temperature heat capacities and magnetic properties of anhydrous and hydrated forms of manganous sulfate (MnSO4)

Manganese (II) sulfate (MnSO4), also known as manganous sulfate, has gained attention due to its low temperature magnetic properties. Following a study of its magnetic structure, manganese sulfate was proposed as being the first orthorhombic compound to have a spiral magnetic structure. It was predicted to have a three-step magnetic transition at low temperatures, which neutron diffraction studies have since confirmed. This work represents the first time that heat capacity data has been collected on MnSO4 and MnSO4 0.984(H2O) at low temperatures, which we report from 1.8 K to 300 K and comment on the presentation of the magnetic transition in the low temperature heat capacity region. Previous studies report the heat capacity of the anhydrous form above 50 K, and the data collected herein is compared with those previously published results. Theoretical fits of the heat capacity data are used to calculate the smoothed thermodynamic data, including Cp,m°, Δ0TSm°, Δ0THm°, andΦm°.

Structural and magnetic properties of YNi4-xCoxSi alloys

The transition-metal based alloy system YNi4-xCoxSi shows a second-order ferromagnetic-to-paramagnetic transition near room temperature. Here, the magnetic structure, the magnetocaloric properties and the magnetic anisotropy of YNi4-xCoxSi (x = 0–4) are investigated. For x = 3.5, 3.75 and 4.0 a Curie temperature near room temperature is observed with TC = 250, 283 and 310 K, respectively. In orientated YNi4-xCoxSi powder samples the c axis of the hexagonal crystal structure is found to be the easy magnetic axis, with a large dominant K2 anisotropy constant (K2 >K1 > 0). The magnetic structure and the preferred atomic position for Ni are demonstrated by neutron diffraction measurements. We have found a dramatic decrease in the magnetic moment at the 3g site in the CaCu5-type structure (space group P6/mmm), the saturation magnetization and the Curie temperature with increasing Ni concentration.

Charge Transport in the A6B2O17 (A = Zr, Hf; B = Nb, Ta) Superstructure Series

The electrical properties of the entropy stabilized oxides: Zr6Nb2O17, Zr6Ta2O17, Hf6Nb2O17 and Hf6Ta2O17 were characterized. The results and the electrical properties of the products (i.e. ZrO2, HfO2, Nb2O5 and Ta2O5) led us to hypothesize the A6B2O17 family is a series of mixed ionic-electronic conductors. Conductivity measurements in varying oxygen partial pressure were performed on A6Nb2O17 and A6Ta2O17. The results indicate that electrons are involved in conduction in A6Nb2O17 while holes play a role in conduction of A6Ta2O17. Between 900 °C–950 °C, the charge transport in the A6B2O17 system increases in Ar atmosphere. A combination of DTA/DSC and in situ high temperature X-ray diffraction was performed to identify a potential mechanism for this increase. In-situ high temperature X-ray diffraction in Ar does not show any phase transformation. Based on this, it is hypothesized that a change in the oxygen sub-lattice is the cause for the shift in high temperature conduction above 900 °C–950 °C. This could be: (i) Nb(Ta)4+- oxygen vacancy associate formation/dissociation, (ii) formation of oxygen/oxygen vacancy complexes (iii) ordering/disordering of oxygen vacancies and/or (iv) oxygen-based superstructure commensurate or incommensurate transitions. In-situ high temperature neutron diffraction up to 1050 °C is required to help elucidate the origins of this large increase in conductivity.