This contribution presents a measurement protocol and a data-reduction workflow for obtaining single-crystal X-ray total-scattering datasets that capture both Bragg-peak and diffuse-scattering intensities on an absolute (electrons 2 per atom) scale. It demonstrates that the intensity scale factor derived from crystallographic refinements using Bragg peaks is in reasonable agreement with the scale obtained by matching the scattering function, computed via spherical integration of the 3D total-scattering signal, to the theoretical coherent baseline. This baseline is calculated from the Debye–Waller factor. The latter scaling approach can be applied to diffuse scattering without including Bragg peaks. These results lay the groundwork for structural refinements using large atomic configurations while simultaneously fitting Bragg intensities and diffuse scattering from a single crystal. Moreover, with the convergence between the two scaling methods, the Bragg and diffuse components can be obtained from the same total-scattering dataset, as achieved in this work, or measured independently.

Local structural correlations are encoded in diffuse scattering, but identifying atomic motifs that produce specific diffuse features can be challenging. We introduce MOSAIC, a computational framework for this task when an atomistic configuration is available and a phase-bearing scattering amplitude can be calculated. Our approach relies on applying the Fourier filter to this amplitude over the reciprocal-space regions encompassing the scattering features of interest to obtain maps of atomic displacements and site occupancies responsible for those features. The method is effective in interrogating the nature and spatial distributions of interatomic correlations in large-scale structural models, such as obtained using Reverse Monte Carlo refinements from experimental data, molecular dynamics, or Monte Carlo simulations, or 2D structural projections derived from atomic-resolution electron microscopy images.

Relaxor ferroelectrics underpin high-performance actuators and sensors, yet the nature of polar heterogeneities driving their broadband dielectric response remains debated. Using a unified, multimodal structural refinement framework- simultaneously fitting complementary X-ray and neutron total scattering, X-ray absorption spectra, and diffuse scattering-we reconstruct 3D mesoscale polarization maps in the classic relaxor system PbMg1/3Nb2/3O3-PbTiO3. We uncover self-organized swirling polarization textures with half-skyrmion (meron) vortices, challenging models of independent polar nanoregions. These textures, characterized by smooth changes in the polarization direction, originate from overlapping volumes in which the projections of locally correlated polarization vectors onto each volume's long axis share the same sign. Vortex cores correlate strongly with local charge and strain gradients imposed by compositional heterogeneities. In this work, our results suggest that chemical disorder, acting via depolarizing and strain fields, stabilizes topological vortex textures of the polarization field, offering a route for engineering new dielectric and ferroelectric functionalities.

The properties of the hexagonal P2 sodium cobaltate, Na0.7CoO2 (NCO) phase densified using the conventional and cold sintering methods were investigated, and we demonstrated that the cold sintering method yields NCO with a relative density of over 98 % (compared to 90 % attained after conventional sintering) while maintaining high room temperature conductivity (10(-2) Scm(-1)). In X-ray diffraction, the original P2-phase framework is retained regardless of the sintering process, and the magnetic properties of NCO strongly depend on the densification route. Cold-sintered samples showed a classic paramagnetic response down to 2 K, while conventionally sintered samples developed a spin-glass behaviour below 6 K. The emergence of the spin-glass state on conventionally sintered ceramics was attributed to the enhanced disorder of Co3+ and Co4+ ions. A multitude of complex superstructures associated with Na ordering was identified for both cold and conventionally sintered NCO in electron diffraction.

We report the results of an international interlaboratory study of the flexural strength of alumina fabricated across six laboratories using the vat photopolymerization ceramic additive manufacturing (AM) technology. The mechanical testing of all the specimens, 142 in total, was performed at the National Institute of Standards and Technology (NIST) according to the well-established four-point bending method standardized for traditional ceramics. Overall, the existing ASTM standard for the four-point bend testing proved adequate for AM ceramics, with several modifications to the specimen requirements to account for the specifics of AM processes. Critical flaws that caused failure were identified in all but two cases using optical fractography augmented with the imaging of fracture surfaces in a scanning electron microscope. The flexural strength data, analyzed following the Weibull statistics, exhibited considerable variation among the specimen sets manufactured by different laboratories. This variability correlated with the presence of many distinct critical flaws. We identified seven types of flaws that accounted for the failure of 94% of specimens. The prevalent flaws depend on the printing direction relative to the specimen's geometry. We discuss the nature of these flaws and their relation to the printing and post-processing conditions. Removal of several types of critical flaws will significantly improve mechanical properties of ceramic parts built using vat-photopolymerization AM.

This article presents a perspective on the state of the art in the structure determination of microporous carbon-capture materials and paths toward future progress in this field, as discussed the NIST workshop of the same title.

(1−x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-PT) perovskite-like solid solutions are recognized for their outstanding electromechanical properties, which are of technological importance. However, some significant aspects of the crystal structures and domain assemblages in this system and the role of these characteristics in defining the functional performance of PMN-PT remain uncertain. Here, we used synchrotron x-ray diffraction to investigate the phase transition linking the paraelectric (cubic) and ferroelectric (tetragonal) phases in a single crystal of 0.65PMN-0.35PT. We analyzed the evolution of reciprocal-space maps across this transition. These maps were collected using small temperature step (1 K) and a high reciprocal-space resolution to reveal changes in the splitting of Bragg peaks caused by the formation of ferroelastic domains in the low-symmetry phase. Our results uncovered a two-phase state, cubic plus tetragonal phases, which exists over a narrow temperature range of only ≈4 K and exhibits a thermal hysteresis of ≈1.8 K. Remarkably, within this state, the lattice parameter of the cubic phase, aC, matches the orientational average of the lattice parameters for the tetragonal polymorph, 23aT+13cT. We discuss the implications of this matching, highlighting the possibility of it being realized by the formation of an assemblage of tetragonal twin domains separated from the cubic phase by a strain-free {110} boundary, as in the “adaptive phase” but without domain miniaturization.

This study considers critical data reduction steps and data analysis approaches required to determine explicitly the atomic arrangements in nanoparticles from time-of-flight neutron total scattering. A practical procedure is described for removing parasitic backgrounds caused by the incoherent scattering of hydrogen inevitably present in most nanoparticle samples and normalizing the recovered coherent scattering intensities onto an absolute scale. A model-free analysis is presented of a pair-distribution function derived from total scattering that can be used to determine thermal expansion coefficients and particle sizes directly from experimental data without knowledge of the material's structure. Finally, atomistic whole-nanoparticle refinements of yttrium-doped ceria nanoparticles from neutron total-scattering data are demonstrated using the reverse Monte Carlo method implemented in the RMCProfile software. These results reveal a strong dependence of the cation–oxygen and oxygen–oxygen distances on the coordination numbers, which leads to gradients of these distances near the particle surface. The details are dependent on the surface coverage by ligands and adsorbates and on the structure of grain boundaries in nanocrystalline agglomerates. The refined models confirm the expectations of more substantial disorder at particle surfaces, with a distorted surface layer extending over several coordination shells. The results highlight the feasibility of whole-nanoparticle refinements from neutron data, calling for further development of data reduction and analysis procedures.

The NIST Workshop: Integrating Crystallographic and Computational Approaches to Carbon-Capture Materials for the Mitigation of Climate Change took place from October 31–November 1, 2023 at the National Cybersecurity Center of Excellence (NCCoE) Compound in Rockville, MD, which is an off-campus NIST facility. This workshop provided a forum for experimentalists and theorists working on the structural aspects of CO 2 capture and sequestration materials to review the current state of the art in this field and discuss opportunities for collaborative research required to develop tools for rapid determination of the structure and its effect on the direct air capture performance in porous solid sorbents. We had a total of 33 international participants (18 invited speakers) from 17 institutions who were experimentalists and theorists from academia, government, and industry. The workshop was a great success.

The ceramic cold sintering process (CSP) offers an eco-friendly approach to producing fully dense ceramics at low temperatures. However, an incomplete mechanistic understanding hinders its optimization and widespread adoption. In this study, we analyze the microstructural and structural changes in ZnO, a model CSP system, using in situ synchrotron-based high-energy small-angle X-ray scattering and X-ray diffraction techniques. Our results reveal the time evolution of ZnO particles' surface area and roughness, reflecting the dissolution and re-precipitation processes that enable densification. The in situ measurements supply valuable kinetic data for these stages of CSP. Alongside microstructural changes and densification, we observed the evolution of secondary phases representing reaction products between ZnO and acetic acid, the solvent used. The initial ZnO/solvent mixture's dominant secondary phase is attributed to zinc acetate, which is gradually replaced by a zinc soap-type structure during CSP. This structure has a large (≈ 21 Å) lattice parameter and is assumed to have a layered nature. The formation of this soap phase, which is retained in the sintered product as an intergranular component, appears to be a signature of successful cold sintering as it facilitates mass transport, leading to densification. Our study underscores the potential of in situ synchrotron characterization for revealing microstructural and phase-evolution details during CSP. These findings, which would be challenging to obtain through ex situ measurements, provide crucial data to guide and validate theoretical models, ultimately enhancing CSP's effectiveness and adoption.

Measuring local polar ordering is key to understanding ferroelectricity in thin films, especially for systems with small domains or significant disorder. Scanning nanobeam electron diffraction (NBED) provides an effective local probe of lattice parameters, local fields, polarization directions, and charge densities, which can be analyzed using a relatively low beam dose over large fields of view. However, quantitatively extracting the magnitudes and directions of polarization vectors from NBED remains challenging. Here, we use a cepstral approach, similar to a pair distribution function, to determine local polar displacements that drive ferroelectricity from NBED patterns. Because polar distortions generate asymmetry in the diffraction pattern intensity, we can efficiently recover the underlying displacements from the imaginary part of the cepstrum transform. We investigate the limits of this technique using analytical and simulated data and give experimental examples, achieving the order of 1.1 pm precision and mapping of polar displacements with nanometer resolution.

We have examined the lattice vibrations and the energy landscape of the isoelectronic diamond and zincblende semiconductor series CuBr, ZnSe, GaAs, and Ge. Vibrations are found to be an increasing function of ionicity, with the cation sublattice always vibrating more strongly than the anion sublattice. These findings are consistent with density functional theory (DFT) calculations of the energy landscape and temperature-dependent molecular dynamics simulations of the atomic-position fluctuations. For CuBr, inclusion of the Cu 3d Hubbard U term is found necessary to stabilize the zincblende structure and to bring its vibrational amplitudes into agreement with experiment. In addition, vibrations are found to strongly affect the CuBr near-edge x-ray absorption fine structure that we have successfully modeled by including displacements in our theoretical Bethe-Salpeter equation calculations. Reverse Monte Carlo structural refinements using large atomic configurations to simultaneously fit x-ray absorption and x-ray total-scattering data support these conclusions, and they reveal strong Cu-Br first-neighbor correlations and asymmetric distributions of interatomic distances in the temperature ranges of both negative and positive thermal expansion. Delineation of the CuBr valence band photoelectron spectrum into its Cu 3d and Br 4p states uniquely reveals their covalent mixing and further supports the DFT results.

We communicate a feasibility study for high-resolution structural characterization of biomacromolecules in aqueous solution from X-ray scattering experiments measured over a range of scattering vectors (q) that is approximately two orders of magnitude wider than used previously for such systems. Scattering data with such an extended q-range enables the recovery of the underlying real-space atomic pair distribution function, which facilitates structure determination. We demonstrate the potential of this method for biomacromolecules using several types of cyclodextrins (CD) as model systems. We successfully identified deviations of the tilting angles for the glycosidic units in CDs in aqueous solutions relative to their values in the crystalline forms of these molecules. Such level of structural detail is inaccessible from standard small angle scattering measurements. Our results call for further exploration of ultra-wide-angle X-ray scattering measurements for biomacromolecules.

Here, we summarize a panel discussion on the direct ink writing (DIW) of ceramics, organized and moderated by the National Institute of Standards and Technology at the American Ceramic Society's 46th International Conference on Advanced Ceramics and Composites in January 2022. The panel reviewed the current state of the art in DIW, focusing on research directions, standards development, and data needs required to facilitate industrial adoption of these technologies. The panel agreed to form working groups for (1) exploring how the community can work together to develop and curate public databases of feedstock characteristics and properties of end-products and (2) organizing an international round-robin to compare performance properties of DIW-manufactured ceramics, potentially tied to ASTM/ISO standards development.

The nanoscale structure of Sr0.61Ba0.39Nb2O6, a classic uniaxial relaxor ferroelectric crystallizing with the tetragonal tungsten bronze (TTB) structure and exhibiting an incommensurate modulation, has been determined by atomistic refinements using combined data from variable-temperature neutron total scattering, extended X-ray absorption fine structure, and threedimensional single-crystal diffuse scattering. We found the modulation to arise from the intergrowth of structural slabs featuring distinct types of octahedral rotations directed to minimize octahedral deformations. This modulation involves displacements of the A cations (Sr and Ba) but exerts no significant effect on the polar displacements of Nb. Our results demonstrated the coexistence of competing polar Gamma 3- and antipolar Gamma 2- modes for off-centering of Nb above the nominal ferroelectric transition temperature of 350 K. The nanoscale-correlated antipolar distortions, which exhibit their largest amplitudes at 425 K, are suppressed below the transition. We identified coupling between the polar off-centering of Nb on its two symmetrically distinct sites as a fundamental characteristic controlling the ferroelectric-to-relaxor crossover in TTBs. We then used it to propose a simple microscopic interpretation for the previously established empirical trend that links crystal-chemical parameters in these systems to their polar response.

A generic workflow for calibrating time-of-flight (TOF) instruments has been developed. Three major steps are involved in the workflow - automatic grouping of pixels, cross correlation, and calibration. At the stage of grouping, an unsupervised machine learning based clustering algorithm is introduced to group pixels 'next to' each other, in terms of peak properties. By grouping those similar pixels, the following cross correlation can be conducted more reliably, through which the statistics could be accumulated to further guarantee a reliable calibration against the nominal peak positions of standard sample (e.g., diamond). The calibration workflow has been successfully applied to NOMAD and POWGEN diffractometers at Spallation Neutron Source, Oak Ridge National Laboratory. It is worth noting that by applying this calibration workflow to replace the initially used pixel-by-pixel calibration routine on POWGEN diffractometer, the measurement time needed for diamond calibrant could be successfully reduced from ~10 hrs to ~3 hrs. Such a generic calibration workflow is expected to be generally applicable to TOF instruments which are seeking for the proper TOF-to-d transformation. On data analysis side, total scattering data modeling with RMCProfile package will be focused on and specifically, the implementation of arbitrary Bragg peak profile in a tabulated manner and the correction for finite instrument resolution effect going beyond the conventional Gaussian assumption will be discussed. Typically, the implementation of resolution correction enables the modelling to an otherwise-unreachable super-large length scale, e.g., 100 Å, following the supercell approach.

Alkaline niobate and tantalate perovskites have attracted attention as polar dielectrics for electronics and telecommunications. Here, we studied the polar behaviour, lattice dynamics, and local structure in conventionally processed K0.985Mn0.015TaO3±δ ceramics using a combination of variable-temperature dielectric and Raman spectroscopies, and X-ray absorption fine structure (XAFS) measurements, respectively. Mn doping induces a low-frequency dielectric relaxation in KTaO3 (KT), which follows the Arrhenius law with an activation energy U ≈ 105 meV and the characteristic relaxation time τ0 ≈ 4.6 × 10−14 s. Our XAFS results support preferential Mn occupancy of the cuboctahedral sites as Mn2+, with these cations strongly off-centred in the oversized oxygen cages. Such disordered Mn displacements generate electric dipoles, which are proposed as the source of the observed dielectric relaxation. We show that in Mn-doped ceramics, the low-frequency polar TO1 mode softens on cooling and, at low temperatures, exhibits a higher frequency than in undoped KT. This mode displays no detectable splitting, which contrasts with Li-doped KT that also contains off-centred Li+ species on the cuboctahedral sites. Therefore, we conclude that the coupling between the Mn displacements and the lattice is weaker than in the Li case, and Mn-doped KT therefore exhibits a dielectric relaxation but no ferroelectric transition.