Structure solution of the Al69.2Cu20Cr10.8 ϕ phase

The stable ϕ phase that forms below ∼923 K around the Al69.2Cu20.0Cr10.8 composition was found to be hexagonal [P63, a = 11.045 (2), c = 12.688 (2) Å] and isostructural to the earlier reported Al6.2Cu2Re X phase [Samuha, Grushko & Meshi (2016). J. Alloys Compd. 670, 18–24]. Using the structural model of the latter, a successful Rietveld refinement of the XRD data for Al69.5Cu20.0Cr10.5 was performed. Both ϕ and X were found to be structurally related to the Al72.6Cu11.0Cr16.4 ζ phase [P63/m, a = 17.714, c = 12.591 Å; Sugiyama, Saito & Hiraga (2002). J. Alloys Compd. 342, 148–152], with a close lattice parameter c and a τ-times-larger lattice parameter a (τ is the golden mean). The structural relationship between ζ and ϕ was established on the basis of the similarity of their layered structures and common features. Additionally, the strong-reflections approach was successfully applied for the modeling of the ϕ phase based on the structural model of the ζ phase. The latter and the experimental structural model (retrieved following Rietveld refinement) were found to be essentially identical.

Quantitative phase analysis and microstructural characterization of urinary tract calculi with X-ray diffraction Rietveld analysis on a Caribbean island

In the twin-island state of Trinidad and Tobago, urinary stone analysis is not routinely performed. This study investigates, via powder X-ray diffraction, 52 urinary tract calculi collected from hospitals in Trinidad. Of these, 46 stones were analysed with Rietveld refinement for quantitative analysis and materials characterization. Refined unit-cell, microstructural and weight fraction parameters were obtained, with the last being used for stone classification. The results revealed seven distinct mineralogical phases of varying frequency: calcium oxalate monohydrate (COM, 58%), calcium oxalate dihydrate (COD, 23%), carbonated apatite (APA, 48%), brushite (BRU, 6%), struvite (STR, 42%), uric acid (UA, 23%) and ammonium acid urate (AAU, 19%). The average refined crystallite sizes were 1352 ± 90 Å (COM), 1921 ± 285 Å (COD), 83 ± 5 Å (APA), 1172 ± 9 Å (BRU), 1843 ± 138 Å (STR), 981 ± 87 Å (UA) and 292 ± 83 Å (AAU). Subsequently, 36.5% of stones were categorized as phosphates, 34.6% as oxalates, 13.5% as uric acid/urates and 15.4% as mixed compositions. The study findings highlight the importance of stone analysis as a necessary step towards disease management of local patients, and endorse the application of Rietveld refinement as a natural extension to diffraction-based kidney stone investigations.

Psilocybin: crystal structure solutions enable phase analysis of prior art and recently patented examples

Psilocybin {systematic name: 3-[2-(dimethylamino)ethyl]-1H-indol-4-yl dihydrogen phosphate} is a zwitterionic tryptamine natural product found in numerous species of fungi known for their psychoactive properties. Following its structural elucidation and chemical synthesis in 1959, purified synthetic psilocybin has been evaluated in clinical trials and has shown promise in the treatment of various mental health disorders. In a recent process-scale crystallization investigation, three crystalline forms of psilocybin were repeatedly observed: Hydrate A, Polymorph A, and Polymorph B. The crystal structure for Hydrate A was solved previously by single-crystal X-ray diffraction. This article presents new crystal structure solutions for the two anhydrates, Polymorphs A and B, based on Rietveld refinement using laboratory and synchrotron X-ray diffraction data, and density functional theory (DFT) calculations. Utilizing the three solved structures, an investigation was conducted via Rietveld method (RM) based quantitative phase analysis (QPA) to estimate the contribution of the three different forms in powder X-ray diffraction (PXRD) patterns provided by different sources of bulk psilocybin produced between 1963 and 2021. Over the last 57 years, each of these samples quantitatively reflect one or more of the hydrate and anhydrate polymorphs. In addition to quantitatively evaluating the composition of each sample, this article evaluates correlations between the crystal forms present, corresponding process methods, sample age, and storage conditions. Furthermore, revision is recommended on characterizations in recently granted patents that include descriptions of crystalline psilocybin inappropriately reported as a single-phase `isostructural variant.' Rietveld refinement demonstrated that the claimed material was composed of approximately 81% Polymorph A and 19% Polymorph B, both of which have been identified in historical samples. In this article, we show conclusively that all published data can be explained in terms of three well-defined forms of psilocybin and that no additional forms are needed to explain the diffraction patterns.

The supports’ tendency to generate oxygen vacancies and the Ni/ZrO2 and Ni/Mg(Al)O catalysts performance in the CO2 methanation

The Ni/ZrO2, Ni/Mg(Al)O, and Ni/SiO2 catalysts were employed in the CO2 methanation. The catalysts were characterized by XPS, XRF, XRD (Rietveld refinement method), TPR, EPR, BET, CO2+H2-TPSR, CO+H2-TPSR, CO2-TPD, CO-TPD,...

Rietveld Refinement and X-ray Absorption Study on the Bonding States of Lanthanum-Based Perovskite-Type Oxides La1-xCexCoO3

Metal-oxygen bonding of the Ce-doped LaCoO3 system remains largely unexplored despite extensive studies on its magnetic properties. Here, we investigate the structure and local structure of nanoscale La1-xCexCoO3, with x = 0, 0.2, and 0.4, using the Rietveld refinement and synchrotron X-ray absorption techniques, complemented by topological analysis of experimental electron density and electron energy distribution. The Rietveld refinement results show that LaCoO3 subject to Ce addition is best interpretable by a model of cubic symmetry in contrast to the pristine LaCoO3, conventionally described by either a monoclinic model or a rhombohedral model. Ce4+/Co2+ are more evidently compatible dopants than Ce3+ for insertion into the main lattice. X-ray absorption data evidence the partially filled La 5d-band of the pristine LaCoO3 in accordance with the presence of La–O bonds with the shared-type atomic interaction. With increasing x, the increased Ce spectroscopic valence and enhanced La–O ionic bonding are noticeable. Characterization of the local structures around Co species also provides evidence to support the findings of the Rietveld refinement analysis.

Role of Ti3AlC2 MAX phase on characteristics of in-situ synthesized TiAl intermetallics. Part II: Phase evolution

In this research, the 2nd part of a series of papers on the processing and characterization of TiAl–Ti3AlC2 composites, the phase evolution during the manufacturing process was investigated by X-ray diffraction (XRD) analysis and Rietveld refinement method. Metallic Ti and Al powders with different amounts of previously-synthesized Ti3AlC2 additives (10, 15, 20, 25 and 30 wt%) were ball-milled and densified by spark plasma sintering (SPS) under 40 MPa for 7 min at 900 °C. Before the sintering process, XRD test verified that the powder mixtures contained metallic Ti and Al as well as Ti3AlC2 and TiC (lateral phase synthesized with Ti3AlC2) phases. In the sintered composites, the in-situ synthesis of TiAl and Ti3Al intermetallics as well as the presence of Ti3AlC2 and the formation and Ti2AlC MAX phases were disclosed. The weight percentage of each phase in the final composition of the samples and the crystallite size of different phases were calculated by the Rietveld refinement method based on the XRD patterns. The size of Ti3AlC2 crystallites in sintered samples was compared with the crystallite size of synthesized Ti3AlC2 powder.

Linking Serpentinization and Weathering of Peridotite: A Study on the Mineralogical and Geochemical Evolution of the Sta. Cruz Nickel Laterite Deposit, Zambales, Philippines

While there are extensive studies on the mineralogy and geochemistry of laterites worldwide, the temporal and spatial mineralogical development of a typical nickel laterite profile is still poorly constrained. In this study, we present a detailed mineralogical and geochemical characterization of samples systematically collected from a nickel laterite profile at the Sta. Cruz nickel laterite deposit, Zambales, Philippines, to describe the temporal and spatial development of the laterite profile. Wavelength-dispersive X-ray fluorescence spectroscopy (WDSXRF), mass balance-element mobility calculations, transmitted and reflected light microscopy, and previously reported results from coupled X-ray diffraction (XRD) and Rietveld refinement analyses, reveal that the laterite profile investigated is composed of two main horizons: the limonite and saprolite zones, separated by a thin transitional zone. The main zones are further subdivided into subzones based primarily on the mineral assemblage and major element chemistry: upper limonite, lower limonite, transitional zone, upper saprolite, and lower saprolite. Late-stage garnierite veins were observed cutting the upper and lower saprolite subzones. Investigation of the structure of goethite within the limonite zone via Rietveld refinement show that the crystallinity of goethite decreases with increasing Ni content and increasing crystallite size. This suggests that upwards through the limonite zone, as goethite ages, its crystallinity increases which possibly results in the removal of Ni from its crystal structure and eventual remobilization to the lower laterite zones. We propose a spatio-temporal model of the formation of the Sta. Cruz laterite consisting of four stages: (1) early-stage alteration, (2) continued serpentinization and volume expansion, (3) late stage serpentinization and incipient oxide formation, and (4) goethite ageing and garnierite formation.

Fifty years of Rietveld refinement: Methodology and guidelines in superconductors and functional magnetic nanoadsorbents

The Rietveld refinement method has taken high relevance since its creation. Nowadays, it is an useful tool in many fields of industry, materials science, and technology. For these reasons, it becomes a need for scientists and engineers whom pretend to use it for proper analysis of their materials. However, the initiation in the method can be slow, taking into account the accelerated rhythm of the research and economic demands. Thus, this work is an intend to fulfill this hole, providing the basic foundations and methodology of the Rietveld refinement in a brief way, this along with the results of its application in superconducting samples of Yttrium Barium Copper Oxide and magnesium diboride, and functional magnetic nanoadsorbents of maghemite and a multiphasic composite (iron oxide, hydroxyapatite and secondary phases). In the process, an in-detail protocol was designed and provided. It was concluded that the samples were successfully refined and that this work represents a fast introduction to the Rietveld method for which beginners can obtain good results while making correct interpretations ofthe whole refinement process.