High-temperature X-ray diffraction with concurrent gas chromatography (GC) was employed in the study of iron disulfide (FeS2) cathode pellets disassembled from thermal batteries. When FeS2 cathode materials were analyzed in an air environment, reaction of the KCl and LiCl salt phases led to the formation of Li2(SO4) and KFe2S3 phases beginning at ~230 °C. These phases subsequently reacted to generate various forms of potassium iron sulfates in the 280–500 °C range, with the final products resulting in a β-Fe2O3 phase and K2(SO4). Independent simultaneous thermal analysis coupled with mass spectroscopy (MS) augmented the diffraction results and supported the overall picture of FeS2 decomposition. Both gas analysis measurements (i.e. GC and MS) from the independent experiments confirmed the formation of SO2 off-gas species during the breakdown of the FeS2. In contrast, characterization of the same cathode material under inert conditions showed the persistence of the initial FeS2 phase throughout the entire temperature range of analysis.

Leucites are silicate framework structures with some of the silicon framework cations partially replaced by divalent or trivalent cations. A monovalent extraframework alkali metal cation is also incorporated to balance the charges. We have previously reported Pbca leucite structures with the stoichiometries Cs2X2+Si5O12 (X = Mg, Mn, Co, Ni, Cu, Zn, Cd) and Rb2X2+Si5O12 (X = Mg, Mn, Ni, Cd). These orthorhombic leucite structures have all the silicon and non-silicon framework cations completely ordered onto separate crystallographic sites. This structure has five distinct Si sites and 1 X site; there are also two distinct sites for the extra-framework Cs or Rb. We have recently synthesised leucite analogues with two different extra-framework cations, these have the stoichiometry RbCsX2+Si5O12 (X = Mg, Ni, Cd). The initial Rietveld refinements assumed 50% Cs and 50% Rb on each of the two extra-framework cation sites. The refined structures for X = Ni and Cd have (within error limits) complete extra-framework cation site disorder. However, for X = Mg there is partial ordering of the extra-framework cation sites, the site occupancies are:- Cs1 0.37(3), Rb1 0.63(3), Cs2 0.63(3), Rb2 0.37(3).

Powder X-ray diffraction patterns for three forms of MIL-53(Al), a metal organic framework (MOF) compound with breathing characteristics, were investigated using the Rietveld refinement method. These three samples are referred to as the MIL-53(Al)as-syn (the as synthesized sample), orthorhombic, Pnma, a = 17.064(2) Å, b = 6.6069(9) Å, c = 12.1636(13) Å, V = 1371.3(2) Å3, Z = 4), MIL-53(Al)LT-H (low-temperature hydrated phase, monoclinic P21/c, a = 19.4993(8) Å, b = 15.2347(6) Å, c = 6.5687(3) Å, β = 104.219(4) °, V = 1891.55(10) Å3, Z = 8), and MIL-53(Al)HT-D (high-temperature dehydrated phase, Imma, a = 6.6324(5) Å, b = 16.736(2) Å, c = 12.840(2), V = 1425.2(2) Å3, Z = 4). The crystal structures of the “as-syn” sample and the HT-D sample are confirmed to be the commonly adopted ones. However, the structure of the MIL-53(Al)LT-H phase is confirmed to be monoclinic with a space group of P21/c instead of the commonly accepted space group Cc, resulting in a cell volume double in size. The structure has two slightly different types of channel. The pore volumes and pore surface area were estimated to be 0.11766 (8) cm3/g and 1461.3(10) m2/g for MIL-53(Al)HT-D (high-temperature dehydrated phase), and 0.08628 (5) cm3/g and 1401.6 (10) m2/g for MIL-53(Al)as-syn phases, respectively. The powder patterns for the MIL-53(Al)as-syn and MIL-53(Al)HT-D phases are reported in this paper.

This mini review summarizes recent advances in experimental thermodynamics of metal–organic frameworks (MOFs). Taking advantage of the development in mechanochemistry, near-room temperature solution calorimetry, and low-temperature heat capacity measurements, the energetic landscape, entropy trends, and Gibbs free energy evolutions of MOFs with true polymorphism [Zn(MeIm)2, Zn(EtIm)2, and Zn(CF3Im)2] as framework topology varies were thoroughly explored by integrated calorimetric and computational methodologies. In addition, the formation enthalpies of MOFs with ultrahigh porosity (MOF-177 and UMCM-1) and the simplest structure (metal formates) have been determined. The studies summarized below highlight the complex interplays among interrelated compositional, chemical, and topological (structural) factors in the determination of the thermodynamic parameters of MOFs.

We use density functional theory meta-generalized gradient approximation TPSS + D3(BJ) + U + J calculations to investigate the energetics and geometry of water molecules in the flexible metal-organic framework material Materials of Institut Lavoisier (MIL)-53(Cr) as a function of cell volume. The critical concentration of water to cause the transition from the large pore (lp) to the narrow pore (np) structure is estimated to be about 0.13 water molecule per Cr. At a concentration x = 1 water molecule per Cr, the zero-temperature np and lp configurations each have a hydrogen bond between the H of each framework hydroxyl group and water oxygen (OW). At intermediate volumes, water dimer-like configurations are observed. A concentration x = 1.25 leads to hydrogen bonding between water molecules in the np phase that is absent for x = 1. Our results suggest possible mechanisms for pore closing in hydrated MIL-53(Cr).

Structural variation of LiMn1.5Ni0.5O4 spinel cathode during the Li+ extraction/insertion reaction was studied using operando X-ray diffraction. It was found that the reaction in the voltage range from 3.5 to 4.9 V consisted of two consecutive two-phase reactions, where three spinel phases of LiMn1.5Ni0.5O4, Li0.5Mn1.5Ni0.5O4 and Mn1.5Ni0.5O4 were identified and the lattice volume change in the whole reaction was evaluated as 6%. The reactions were symmetric and reversible under low-current conditions, but some asymmetries were detected during high current operation. Furthermore, a two-phase reaction between cubic and tetragonal phases was observed in the low-voltage reaction at 2.1–3.5 V, where the lattice volume change was approximately 4.9%. The rate-determining step was discussed based on these operando results.

A commercially available combined X-ray diffraction – differential scanning calorimetry (XRD-DSC) stage was adapted for studies of gas loading in microporous materials, including metal organic frameworks (MOFs). Insertion of a custom-built humid atmosphere swing chamber (HASC) between a humidity generator and the XRD-DSC stage facilitates both humid atmosphere and vacuum swing gas loading. The HASC is necessary to buffer between the humidity generator and the XRD-DSC stage, allowing the gas mixture to homogenize prior to sample exposure, so that both humid atmosphere and vacuum swings could be performed. The changes in XRD can be used to follow structural changes, including collapse, which is indicative of a lack of microporosity upon activation, and the flexibity of frameworks upon gas sorption–desorption cycles. Measurements of the area under the DSC curve allows for calculation of the isosteric heat of adsorption (Qst; kJ molGAS−1). Vacuum-atmosphere swing experiments performed at different pressure steps allow for the reconstruction of the enthalpy of gas adsorption before and after a phase transition. These modes of operation are illustrated in three case studies from a program of exploratory MOF synthesis used to discover novel materials for selective gas sorption from humid gas streams: (1) gas binding in Stony Brook metal organic framework-1, (2) zeolitic imidazolate framework-7 response to variable pressure vacuum-atmosphere swing, and (3) high throughput evaluation of the selectivity of novel MOFs synthesized from customized linkers.

Advancements in computer technology have enabled three-dimensional (3D) reconstruction, data-stitching, and manipulation of 3D data obtained on X-ray imaging systems such as micro-computed tomography (μ-CT). Likewise, intuitive evaluation of these 3D datasets can be enhanced by recent advances in virtual reality (VR) hardware and software. Additionally, the generation, viewing, and manipulation of 3D X-ray diffraction datasets, such as pole figures employed for texture analysis, can also benefit from these advanced visualization techniques. We present newly-developed protocols for porting 3D data (as TIFF-stacks) into a Unity gaming software platform so that data may be toured, manipulated, and evaluated within a more-intuitive VR environment through the use of game-like controls and 3D headsets. We demonstrate this capability by rendering μ-CT data of a polymer dogbone test bar at various stages of in situ mechanical strain. An additional experiment is presented showing 3D XRD data collected on an aluminum test block with vias. These 3D XRD data for texture analysis (χ, ϕ, 2θ dimensions) enables the viewer to visually inspect 3D pole figures and detect the presence or absence of in-plane residual macrostrain. These two examples serve to illustrate the benefits of this new methodology for multidimensional analysis.

This paper is devoted to the X-ray diffraction study of bone fragments of Permian parareptile Deltavjatia vjatkensis obtained from the Kotelnich vertebrate fossil site, one of the richest of the Permian period, which is characterized by the excellent preservation of fossil remains because of their burial in a silty anaerobic environment similar to modern bogs. The bone is well-preserved and consists of fluorapatite, calcite, quartz, and dolomite. The refined apatite unit-cell parameters of a and b-axis (9.3526 ± 0.0001 and 9.3587 ± 0.0001) Å and c-axis (6.8930 ± 0.0001 and 6.8968 ± 0.0001) Å correspond to F-apatite. Crystallinity index determined as the full width at half maximum of the 002 reflection in degrees 2θ is 0.266–0.250, which is typical for Mesozoic vertebrate bones. Apatite crystallite size (length 70.3–74.9 nm, width 30.7–30.3 nm) in fossil pareiasaur bone is larger than in subfossil and recent mammal bone and is in a good agreement with the values for seismosaurus bone. Both crystallite size and aspect ratio (2.3–2.5) are independent of the fossil pareiasaur bone length.

Porphyrinic compounds are of increasing interest to the materials science community, yet little attention has been paid to crystallographically controlled voids and channels in these materials. We have conducted an initial survey of the voids and channels in a random subset of 1000 porphyrinic compounds with known crystal structures. From calculations using a rolling-probe subroutine, we have found that about 5% of these compounds have line-of-sight channels, which differ in their topology depending on the crystallography. A small but significant number of porphyrinic compounds have calculated void contents of >25 volume %. We discuss in detail the void and channel characteristics, including pore-size distribution, of four representative compounds, with technological implications.

In this paper, we will report about the implementation of the self-consistent Kröner–Eshelby model for the calculation of X-ray elastic constants for general, triclinic crystal symmetry. With applying appropriate symmetry relations, the point groups of higher crystal symmetries are covered as well. This simplifies the implementation effort to cover the calculations for any crystal symmetry. In the literature, several models can be found to estimate the polycrystalline elastic properties from single crystal elastic constants. In general, this is an intermediate step toward the calculation of the polycrystalline response to different techniques using X-rays, neutrons, or ultrasonic waves. In the case of X-ray residual stress analysis, the final goal is the calculation of X-ray Elastic constants. Contrary to the models of Reuss, Voigt, and Hill, the Kröner–Eshelby model has the benefit that, because of the implementation of the Eshelby inclusion model, it can be expanded to cover more complicated systems that exhibit multiple phases, inclusions or pores and that these can be optionally combined with a polycrystalline matrix that is anisotropic, i.e., contains texture. We will discuss a recent theoretical development where the approaches of calculating bounds of Reuss and Voigt, the tighter bounds of Hashin–Shtrikman and Dederichs–Zeller are brought together in one unifying model that converges to the self-consistent solution of Kröner–Eshelby. For the implementation of the Kröner–Eshelby model the well-known Voigt notation is adopted. The 4-rank tensor operations have been rewritten into 2-rank matrix operations. The practical difficulties of the Voigt notation, as usually concealed in the scientific literature, will be discussed. Last, we will show a practical X-ray example in which the various models are applied and compared.

A straightforward intuitive user-friendly compact graphical interface, PreDICT (Premier DICVOL Tool) has been developed to take full advantage of the new capabilities of the most recent version of the DICVOL14 Indexing Software. The latter, an updated version of DICVOL04, includes optimizations, e.g. for monoclinic and triclinic cases, a detailed review of the input data from the indexing solutions, cell centering tests, as well as the handling of a moderate number of impurity peaks. Among the most salient features of PreDICT, one can mention the ability (1) to use 2θ non-equistepped input 1D X-ray powder diffraction patterns as can be obtained from 2D detectors, (2) to strip laboratory data from its Kα2 contribution when present, (3) to generate 2θ equistepped output 1D X-ray powder diffraction patterns in both the “.XY” and “.GSA” formats. In addition, PreDICT allows for the following features: (1) full access to the native DICVOL14 input/output ASCII file system is retained, (2) for any selection of a DICVOL14 suggested unit cell, all predicted Bragg peaks up to a certain 2θMAX value are clearly displayed and indicated, thereby emphasizing the contribution of the unaccounted peaks (if any) to the 1D X-ray powder diffraction pattern under current investigation.

Based on the experimentally determined framework structure of porous MnO2 octahedral molecular sieve (OMS)-5, we used density functional theory-based calculations to evaluate the effect of Na+ cation on pore dimensionality and structural stability, and the interaction between CO2 and OMS-5. We quantified the formation energy of one CO2/unit tunnel and two CO2/unit tunnel, and projected the electronic density of states on the OMS-5 framework, CO2 molecules, and Na+ cations to reveal their individual contributions and bonding nature. Partial charge densities were also calculated to investigate CO2 adsorption behavior in the OMS-5. Our studies predict the initial stage and driving force for the adsorption of CO2 in the OMS-5, guiding the OMS material design for carbon capture and storage applications.