A nonlinear optical material, o–chlorobenzol–benzoyl thiourea (C14H11ClN2OS), has been characterized by X-ray powder diffraction. Experimental values of 2θ corrected for systematic errors, relative peak intensities, values of d, and the Miller indices of 78 observed reflection with 2θ up to 72° are reported. The powder diffraction data have been evaluated, and the figures-of-merit are reported. The unit cell parameters least-squares refined from 28 nonoverlapping peaks of the monoclinic compound with a P2 space group are a=13.2797(4) Å, b=12.4058(8) Å, c=8.1561(2) Å, β=95.398(1)°, V=1337.7(4) Å3, Z=4, Dx=1.444 g/cm3. © 1997 International Centre for Diffraction Data.

Crystal structure of the skutterudite-related phase has been refined by the Rietveld method from X-ray powder diffraction data. Refined crystallographic data for CoSn1.5Te1.5 are a=12.9063(2) Å, c=15.7837(3) Å, V=2276.89(4) Å3, space group R3 (No. 148), Z=24, and Dx=7.50 g/cm3. The crystal structure of the title compound can be viewed as a modification of the skutterudite structure (CoAs3)—it is isostructural with CoGe1.5Te1.5 and IrSn1.5Te1.5. In the structure of CoSn1.5Te1.5, the Sn and Te atoms exhibit long-range ordering, which results in lowering of the original cubic symmetry of the skutterudite structure to the trigonal one.

Stress in the early stages of growth has been measured in α-Al2O3 (alumina) scales formed on FeCrAl- and NiAl-based alloys during heating in air at 1000 °C to 1200 °C. Scale thickness ranges from 0.5 to 5 μm, times from 5 to 720 min. Stress was measured using the multiple-tilt method. In order to measure the thinnest scales at the earliest times, focused, monochromatic synchrotron radiation was used for high intensity, and a fixed, small angle of incidence was used along with an appropriate wavelength to maximize scattering from the film relative to the background from the substrate. Depending on the composition, transient tensile stresses of up to 1.2 GPa were observed, with maximum stress at times ranging from >10 h at 1000 °C to <10 min at 1200 °C. Thermal stresses induced by an abrupt temperature change were found to relax much more quickly, suggesting that the kinetics observed during isothermal growth reflect a dynamic competition between stress generation and stress relaxation. These results challenge commonly accepted models of growth stress in scales that predict that a compressive stress will be generated as the metal converts to a larger-volume oxide in a constrained location such as an interface. The observed tensile stress may be due to another mechanism altogether (e.g., grain coalescence), or to the conversion of a transitional Al2O3 to the equilibrium α-Al2O3 phase. For one composition, transitional Al2O3 is observed during the period of tensile stress

In the absence of single crystals, silver(I) 3,5-dimethylpyrazolate, [Ag(dmpz)]3, has been structurally characterized by ab initio X-ray powder diffraction, using conventional laboratory data. Its crystals are triclinic, P1¯, with a=8.0876(10), b=11.1204(13), c=11.6136(16) Å, α=68.293(6), β=78.350(7), and γ=81.243(6)°. The structure has been solved by Patterson, difference Fourier, and geometrical modeling, and ultimately refined by the Rietveld method down to Rp=0.068, Rwp=0.085, and RF=0.055, for 4300 observations in the 17<2θ<103° range. Each molecule consists of a cyclic, trimeric assembly of Ag(dmpz) fragments, with the dmpz ligand bridging, in the exo-bidentate mode, nonbonded Ag…Ag edges.

Doubly curved crystal (DCC) X-ray optics provide an enabling technology for new portable, remote, and in situ applications of monochromatic X-rays for composition and structure analysis of amorphous, polycrystalline, and crystalline solids. Femtogram sensitivity for surface contamination, parts-per-billion (ppb) impurity levels for solids, and composition, structure and uniformity of thin films with compact, low power (20–50 W) source optic combinations are possible.

The crystal structure of cobalt(II) acetate tetrahydrate, Co(C2H3O2)·4H2O, has been refined using single-crystal, laboratory powder, and synchrotron powder diffraction data, both individually and in various combinations. The compound crystallizes in the monoclinic space group P21/c, with a=4.80688(3), b=11.92012(7), c=8.45992(5) Å, β=94.3416(4)° at 27 °C, and Z=2. The crystal structure consists of discrete centrosymmetric trans-Co(C2H3O2)(H2O)4 complexes, linked by a three-dimensional network of hydrogen bonds. Each complex participates in 14 hydrogen bonds, 12 intermolecular, and 2 intramolecular. Compared to the single-crystal refinement, refinement of laboratory powder data yielded an average difference in bond distances of 0.02 Å, in bond angles of 3°, and in root mean square atomic displacements of 0.07 Å. The standard uncertainties of the bond distances were 0.01 Å, compared to the 0.001–0.002 Å in the single-crystal refinement. Refinement of the synchrotron powder data yielded improved accuracy and precision. It proved impossible to locate or refine hydrogen positions using a single-powder dataset, but the hydrogens could be refined using rigid groups in a joint refinement of the two powder datasets. Even from powder refinements, it is possible to obtain suitable accuracy and precision to distinguish C–O and C=O bonds, and to examine details of chemical bonding.

μPDSM, a powder diffraction search/match system, is derived from the original interactive time-sharing system written for the NIH/EPA Chemical Information System. Transformed and essentially rewritten, it still searches the entire JCPDS database, but on an inexpensive IBM PC microcomputer. In the transition from mainframe to micro, μPDSM has lost none of its speed or performance. Indeed, the basic discriminating power of the search/match algorithms had to be improved, since the Powder Diffraction File is some 50% larger than it was when The CIS version was in operation. While μPDSM will solve typical problems on a “push-button” mode, it provides an environment that promotes optimization of search parameters by the diffractionist, and provides all of the subfile and chemistry functions associated with larger systems.

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.

Representative compounds of the new family of magnetic materials Gd5−xNdxSi4 were analyzed by X-ray diffraction at the XRD1 beamline at Laboratório Nacional de Luz Síncrotron. To reduce X-ray absorption, thin layers of the powder samples were mounted outside the capillaries and measured in Debye–Scherrer geometry as usual. The XRD analyses and the magnetometry results indicate that the behavior of the magnetic transition temperature as a function of Nd content may be directly related to the average of the four smallest interatomic distances between different rare earth sites of the majority phase of each compound. The quality and consistency of the results show that the XRD1 beamline is able to perform satisfactory XRD experiments on high-absorption materials even off the best conditions.

A new structural model is proposed for cubic nitroprussides and the crystal structure for the complex salts of Fe(2+), Co(2+), and Ni(2+) refined in that model. In cubic nitroprussides the building unit, [Fe(CN)5NO]2−, and the assembling metal (M=Fe2+,Co2+,Ni2+), have ¾ occupancy with three formula units per cell (Z=3). This leads to certain structural disorder and to different local environments for the outer metal. The crystallographic results are supported by the Mössbauer and infrared data. The XRD powder patterns, index in a cubic cell (Fm3m space group), show a sinuous background because of diffuse scattering from positional disorder of the metal centers. Because of this, the crystal structures were refined allowing the metal centers to move from the (0,0,0) and (0,0,1/2) positions (away from positional symmetry restrictions). The refinement under these conditions leads to excellent agreement factors (Rwp, Rp, S), good pattern background fitting, and produced a refined structural model consistent with the crystal chemistry of nitroprussides. The studied materials are obtained as hydrates. On heating, the crystal water evolves, and below 100°C an anhydrous phase is obtained, preserving the framework of the original hydrates. The loss of the crystal water leads to cell contraction that represents around 2% of cell volume reduction. On cooling down from room temperature to 77 and 12 K, a slight expansion for the -M-N≡C-Fe-C≡N-M- chain length is observed, suggesting that at low temperature and reduction in the metals charge delocalization on the CN bridges takes place. For M=Fe and Co the crystal structure was also refined for the anhydrous phase at 12, 77, and 300 K.

The new compound, KCr3(SO4)2(OH)6, was prepared by low-hydrothermal synthesis. The structure was refined by the Rietveld technique in space group (Z = 3), a =7.2416(3) Å, c = 17.0788(9) Å, V = 775.63 Å3, Rp = 7.7, Rwp =10.1, RB = 6.8. The compound is isotypic with alunite, KAl3(SO4)2(OH)6. The temperature of decomposition under nitrogen atmosphere to a hitherto unknown form is about 550 K. The water content of alunite-type compounds is discussed.

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.

An increasingly frequent used sample holder, the zero-background holder (ZBH), is evaluated for use in external standard calibration of powder patterns. The effectiveness of the ZBH calibration method is determined by comparison to the conventional internal- and external-standard calibration techniques. The three calibration methods are compared using the results of lattice parameter refinements of test powders, using Si as the standard. Several test materials were used in the evaluation which cover a wide range of absorption coefficients so sample transparency effects can be distinguished from sample displacement effects. Results of the calibrations clearly indicate that the ZBH method gives precision and accuracy comparable to the internal-standard method, and significantly better than the external-standard technique. In addition, the ZBH method yields substantially better results than the internal-standard method for materials with low absorption coefficients. Low-angle calibrations are also made on a ZBH using a proposed standard, silver behenate, which has peaks from 1.5° to 20° 2θ. These calibrations have shown that if care is not taken to establish a monolayer of powder on the ZBH crystal, significant errors in refined lattice parameters will result.

Based on high purity constituents ternary AlFeSi intermetallic phases were prepared and annealed at 600°C for a month with compositions close to that of αH-AlFeSi (Al8Fe2Si) phase (∼8 wt.% Si, ∼32 wt.% Fe). The powder diffraction patterns and the chemical compositions of the different αH-AlFeSi intermetallic compounds formed as major components in the samples were investigated by X-ray powder diffraction and electron microprobe analysis, respectively.

A complete powder diffraction pattern is presented for the αH-AlFeSi intermetallic phase with 8 wt.% silicon and 33.5 wt.% iron content formed almost congruently. The refined cell parameters are given as

a = 12.4056 (7) Å

c = 26.236 (2) Å

Comparing the observed intensities with intensities calculated from single crystal data, gave very good agreement.

The lattice parameters of αH-AlFeSi phases with different silicon content were refined by the least-squares method. A contraction of the unit cell caused by the increase of the silicon content in the phase can be observed. Relative changes of the cell dimensions for 1 wt. % increase in silicon are −0.06%, −0.09 % and −0.21 % for the parameters a and c and for the unit cell volume, V, respectively.

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.

Icosahedral boron phosphide (B12P2) was directly synthesized from elemental powders by a high-temperature reaction under an argon pressure. Powder diffraction data were collected for two B12P2 samples, and diffraction patterns were compared with calculated patterns of phosphorus deficient crystals: B12+xP2−x for 0<;x<0.2. The as-synthesized B12P2 appears to be close to its ideal stoichiometry based on the consistency between the observed and the calculated values of the relative intensity for all diffraction planes below 90° 2θ.

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.

Powders of Al and Ti were blended and compacted, the compact then melted in an attempt to produce single phase Al3Ti. Optical microscopy of the cast and homogenized specimen revealed an almost single phase microstructure with minor amounts of a second phase. The composition of the matrix was measured using fully quantitative energy dispersive X-ray analysis. By use of X-ray diffractometry, the interplanar spacings and the associated integrated peak intensities were experimentally measured for the binary DO22 compound, Al3Ti. Using standard structure factor equations, the intensities were calculated for the various reflections. Good agreement was obtained between calculated and observed intensities.

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.