Improved powder XRD patterns for the titanium suboxides, TinO2n−1 (4≤n≤9), have been calculated from published single-crystal structures. To provide the best match with experimental data, the entire diffraction traces were simulated, and d-spacings and intensities extracted in the same manner as from experimental traces. The accuracy of the new patterns has been verified by comparison with measured powder patterns, particularly in the case of the n=4 and n=5 compounds where single-phase powders can be prepared relatively easily. Difficulties experienced preparing higher homologues have been related to the thermodynamic properties of this system.

A strategy for qualitative X-ray phase analysis of complex multiphase solids is illustrated through the analysis of eight fixed-bed gasification ashes. Coal from the same lignite formation was gasified in three different reactors. Despite the differences in gasifiers and their operating conditions, all of the ash specimens had the same basic crystalline phase assemblage: silicates and aluminosilicates (merwinite, dicalcium silicates, melilite, nepheline, carnegieite and a sodalite structure phase), oxides (ferrite spinels, hematite and periclase), calcite and residual lignite minerals (quartz, plagioclase). The identification strategy relied on a bulk chemical analysis of each ash and used manual methods with the JCPDS-ICDD search manuals for the Powder Diffraction File. Grain picking, size separations, magnetic enrichment, separation by hardness, dissolution of water soluble phases, and further crystallization of the ash through heat treatment all figured in the identification strategy. Identification of more than a dozen minor and trace phases resulted from these additional methods. Several trials with an automated search/match system demonstrated the difficulties of analyses of such complex phase assemblages. The need for SEM characterization of the ashes to accompany the XRD analyses is discussed.

The following new or updated patterns are submitted by the JCPDS Research Associateship at the National Bureau of Standards. The patterns are a continuation of the series of standard X-ray diffraction powder patterns published previously in the NBS Circular 539, the NBS Monograph 25, and in this journal. The methods of producing these reference patterns are described in this journal, Vol. 1, No. 1, p. 40 (1986).

The data for each phase apply to the specific sample described. A sample was mixed with one or two internal standards: silicon (SRM640a), silver, tungsten, or fluorophlogopite (SRM675). Expected 2-theta values for these standards are specified in the methods described (ibid.). Data, from which the reported 2-theta values were determined, were measured with a computer controlled diffractometer. Computer programs were used to locate peak positions and calibrate the patterns as well as to perform variable indexing and least squares cell refinement. A check on the overall internal consistency of the data was also provided by a computer program.

Ongoing software developments for creating three-dimensional (3D) printed crystallographic models seamlessly from Crystallographic Information Framework (CIF) data (*.cif files) are reported. Color versus monochrome printing is briefly discussed. Recommendations are made on the basis of our preliminary printing efforts. A brief outlook on new materials for 3D printing is given.

To enable mechanical milling of small (0.1–1.0 g) samples, a cylindrical grinding vessel machined from polypropylene and furnished with tungsten carbide rods has been designed and produced for use inside the conventional jar of a McCrone Micronizing Mill. The vessel is about one-seventh the volume of the conventional jar supplied by the manufacturer. The conditions of milling for both the conventional and the miniaturized-grinding assemblies were tested using quartz sand as a limiting case. The median grain sizes of the resultant powders were measured by an X-ray gravitational-sedimentation method, with contamination from the grinding media measured by Rietveld refinement and by instrumental neutron activation analysis. The use of tungsten carbide grinding elements permits rapid wet milling of a small sample to the same median grain size in about one-third of the time required by a regular sample ground in corundum. The relative contamination (by tungsten carbide on a weight basis) using the miniaturized-grinding assembly is about 6(1)% of the proportion of corundum contamination yielded by the conventional grinding assembly.

The structures of orthorhombic (a=5.5686(2)Å, b=9.8946 (2)Å, c=3.19369(12Å) and cubic (a=9.177(3)Å) Cd2SnO4were refined by Rietveld analysis of X-ray powder diffraction patterns. Both of these polymorphs were chemically treated with hydrogen gas mixtures at 400°C, resulting in a colour change from yellow to green. Small structural changes were observed for the orthorhombic material, which underwent a uniform contraction (≈0.02%) of cell size and movement of some oxygen atoms towards the tin atoms. Evidence for loss of structural oxygen was sought, but could not be found above the detection limit of 0.3%. Cubic Cd2SnO4possesses the spinel structure with a large (at least 65%) degree of inversion. Samples prepared with a smaller cell have so far proved unsuitable for Reitveld analysis.

The relative intensities ratios for the determination of the relative amounts of alpha and beta phases in silicon nitride and the relative amounts of delta yttrium disilicate (Y2Si2O7) and nitrogen apatite [Y5(SiO4)3N] are reported. These constants were determined using an iterative method applicable when the pure phases are not easily prepared. In addition, a calibration curve was obtained for the quantitative measurement of free silicon in silicon nitride over the range 0 to 0.3% by weight of Si.

Techniques for estimation of element levels directly in humans (noninvasive in vivo) or in samples (in vitro) from humans are reviewed. Toxic, nonessential, trace elements may cause temporary or permanent damage to various organs and tissues in humans. There is thus a need to control the concentrations. Knowledge of the relations between toxic effects and element concentration may be extracted from measurements in humans as well as in samples from humans and her environment. Applications traditionally include occupationally exposed subjects, but an increasing research area is studies of members of the general population and of patients undergoing therapy for malignant and other diseases. Most in vivo XRF studies deal with lead in bone and cadmium in kidneys. For retired lead workers, a clear association has been demonstrated between bone lead and blood lead, due to endogenous lead excretion from the skeleton. A study of mercury in vivo showed that the technique is capable of detecting mercury in heavily exposed worker’s kidneys. In vivo XRF in cancer and rheumatology patients has helped to understand how platinum and gold are retained in the human body. The newest in vivo applications include zinc in prostate gland and arsenic in skin.

X-ray powder diffraction data for buckminsterfullerene, C60 are reported. The crystal structure is a face-centered cubic unit cell with a = 14.165 (1) Å. The reference intensity ratio (I/Icor) is 2.20.

Powder X-ray diffraction data are reported for La0.6Sr0.4Co1−yFeyO3 (y=0.1, 0.25, 0.4, 0.6, 0.8, 1.0). The powders were prepared by thermal decomposition of metal-containing complex solutions. All compositions have rhombohedral unit cells. In hexagonal setting, the cell parameters are a=5.4388 Å, c=13.2355 Å for y=0.1; a=5.4427 Å, c=13.2542 Å for y=0.25; a=5.4530 Å, c=13.2838 Å for y=0.4; a=5.4769 Å, c=13.3175 Å for y=0.6; a=5.5057 Å, c=13.3918 Å for y=0.8; and a=5.5278 Å, c=13.4368 Å for y=1.0. The space group is probably R3c (167) for all compositions. The observed trends in the change of the pseudocubic cell parameter ac with increasing iron content can be explained in terms of substitution of Co4+ by Fe4+ when y<0.4, and substitution of Co3+ by Fe3+ when y≳0.4.

The fitting of a parabola by least squares regression to the upper portion of diffraction peaks is commonly used for determining lattice spacing in residual stress measurement. When Kα techniques are employed, the presence of the Kα doublet is shown to lead to significant potential error and non- linearities in lattice spacing as a function of Sin2ψ caused by variation in the degree of blending of the doublet. An algorithm is described for fitting Pearson VII distribution functions to determine the position of the Kα component, eliminating errors caused by defocusing of diffraction peaks of intermediate breadth. The method is applied to determine the subsurface residual stress distribution in ground TI-6 AI- 4 V, comparing directly the use of parabolic and Pearson VII peak profiles, and is shown to provide precision better than ± 1%% in elastic constant determination.

Plant surfaces are mostly covered with microscopic layers of wax which exhibit characteristic morphologies, visible under high magnification. Waxes belonging to three different types were investigated. Powder data of seven natural and three recrystallised waxes as well as of two isolated compounds are presented. The mainly crystalline nature of the studied plant waxes is proved. The correlation between morphology, chemical composition, and powder patterns is discussed.

The systems PbO–Bi2O3–P2O5/As2O5/V2O5 have been studied with respect to their compounds and solid solutions. A number of new compounds, particularly with high-Bi contents were found. Most of them are structurally closely related to the CaF2 and δ-Bi2O3 structures. Several binary and ternary solid solutions with P/As/V substitutions were investigated.

Physical and chemical analysis, X-ray astronomy and high temperature plasma diagnostics which utilize the ultrasoft X-radiations hare made evident a strong need for filling the gap in measured absorption coefficient data for the radiations between the conventional X-rays and the extreme ultraviolet. More than one hundred new coefficients have been measured in this laboratory on the gas state, atomic or molecular, containing He, C, N, 0, F, Ne, S, Cl, Ar, Kr and Xe using eleven fluorescent, characteristic wavelengths Al-Kα (8.34 A) through Be-K (113.8 A). The radiations were isolated by Bragg reflection from multilayer analyzers of the Langmuir-Blodgett type and by pulse height discriminating proportional counter intensity measurements.

Two methods may be used to measure the reference intensity ratio: (1) by measuring intensities from samples prepared by mixing the analyte and standard together in a known weight ratio and (2) measuring separately the intensities for the analyte peak and reference standard peak from pure phase preparations and by correcting the intensities with mass absorption coefficients. Both methods give identical results that are independent of the difference in mass absorption between analyte and standard. These reference intensity ratios may be universally applied to both matrix flushing and adiabatic procedures in multicomponent analysis providing that preferred orientation, microabsorption, and extinction can be eliminated or greatly minimized in the samples under analysis.

In this study, the application of (an)isotropic size determination using a recently proposed model for the double-Voigt approach is demonstrated and validated against line profile simulations using the Whole Powder Pattern Modelling approach. The fitting of simulated line profiles demonstrates that the attained crystallite sizes and morphologies are in very reasonable agreement with the simulated values and thus demonstrate that even in routine application scenarios credible size and morphology information can be obtained using the double-Voigt approximation. The aim of this contribution is to provide a comprehensive introduction to the problem, address the practical application of the developed model, and discuss the accuracy of the double-Voigt approach and derived size parameters. Mathematical formulations for the visualization of modeled morphologies, supporting the application of the recently developed macros, are additionally provided.

Synthetic analogs of naturally occurring nanoparticles have been studied by a range of X-ray techniques to determine their structure and chemistry, and relate these to their novel chemical properties and physical behavior. ZnS nanoparticles, formed in large concentrations naturally bymicrobial action, have an interesting core-shell structure with a highly distorted and strained outer layer. The strain propagates through the particles and produces unusual stiffness but can be relieved by changing the nature of the surface ligand binding. Weaker bound ligands allow high surface distortion, but strongly bound ligands relax this structure and reduce the overall strain. Only small amounts of ligand exchange causes transformations from the strained to the relaxed state. Most remarkably, minor point contacts between strained nanoparticles also relax the strain. Fe oxyhydroxide nanoparticles appear to go through structural transformations dependent on their size and formation conditions, and display a crystallographically oriented form of aggregation at the nanoscale that alters growth kinetics. At least one Fe oxyhydroxide mineral may only be stable on the nanoscale, and nonstoichiometry observed on the hematite surface suggests that for this phase and possibly other natural metal oxides, chemistry may be size dependent. Numerous questions exist on nanominerals formed in acid mine drainage sites and by reactions at interfaces.

2,4,6-Trimercapto-s-triazine, trisodium salt (ideally, Na3S3C3N3·9H2O), also known as TMT-55, is a white powder that is used to precipitate heavy metals from contaminated waters. Chemical analyses confirmed the nominal composition. TMT-55 crystals are uniaxial negative with indices of refraction (25 °C) of nε=1.520 and nω=1.675. The structure was determined by single-crystal methods at 25 and −110 °C. A powder pattern was determined and compared to a simulated pattern based on the 25 °C structure data. Crystal data at 25 °C are: R3;Z=6; a=17.600(1) Å and c=9.720(2) Å; V=2607.5(5) Å3; Dx=1.55 g/cm3.

Powder X-ray diffraction has become a routine procedure for the quantification of phases in mixtures. The most common method for this measurement is the Rietveld method, which generally returns the relative weight percentages of the crystalline components within the mixture. However, in many instances, it is also desirable to obtain an estimate of the amorphous content of a sample. There are several methods that may be used for this measurement and their accuracy has been assessed previously with a number of ideal, synthetic mixtures. Many samples, especially in the mineralogy sphere, are far from ideal and contain multiple phases of varying absorption contrast. This creates a microabsorption problem which affects the accuracy of the determination of both the crystalline and amorphous components. This paper assesses commonly used methods of amorphous determination with a series of synthetic samples designed to create a considerable microabsorption problem.

The crystal structure of Al7O3N5 was characterized by laboratory X-ray powder diffraction (CuKα1). The title compound is trigonal with a space group R3m (centrosymmetric). The hexagonal unit-cell dimensions (Z = 3) are a = 0.305 06(1) nm, c = 5.7216(1) nm, and V = 0.461 11(2) nm3. The initial structural model was derived by the charge-flipping method and refined by the Rietveld method. The final structural model showed the positional disordering of two of the four Al sites. The maximum-entropy method-based pattern fitting method was used to confirm the validity of the split-atom model, in which conventional structure bias caused by assuming intensity partitioning was minimized. The disordered crystal structure was successfully described by overlapping five types of domains with ordered atom arrangements. The distribution of atomic positions in one of the five types of domains can be achieved in the space group R3m. The atom arrangements in the four other domains are non-centrosymmetric with the space group R3m. Two of the four types of domains are related by a pseudo-symmetrical inversion, and the two remaining domains also have each other in the inversion pseudo-symmetry.