The least-squares method with complete component library spectra is applied to the quantitative analysis of X-ray fluorescence spectral intensities. An approach is outlined for application to the general case of thick homogeneous samples at high counting rates, A simplified approach can be taken with the more specific case represented, by atmospheric particulates collected on filters. The details and sample results of this approach for this specific case are given for an energy dispersive X-ray fluorescence analyzer. The results indicate that the least-squares method as developed and applied here is valid and should prove generally useful to X-ray analysts.

The possibility that primary recrystallization textures are influenced by local inhomogeneities of deformation induced in the regions of grain boundaries has been confirmed by comparing the cold rolling and the annealing textures of polycrystalline pure irons which were different in the grain size prior to cold rolling. Analyses were made for the effects of deformation on crystals, namely storage of lattice strain and orientation spread, with application of X-ray diffraction techniques, in order to elucidate the role of in homogeneities of deformation on recrystallization texture formation. Apparent correspondence was found between the orientation dependence of stored strain energy and the textural change on recrystallization. This is a scribed to oriented nucleation in high energy blocks, in the case of originally large-grain material in which the effects of inhomogeneities of deformation are small. But discrepancies arise on this basis in originally small - grain material in which the effects of inhomogeneities of deformation are thought to be considerable. The discrepancy is inferred to arise as an effect of local inhomogeneities of deformation, from the change in the trend of rotational orientation spreads from, a stable orientation and the extent of development of potential nuclei of recrystallization at high energy blocks in the orientation spreads. The change is considered to give rise to the variation in amount of microstrain distribution, which is expressed in recovery characteristics of lattice strains and in the dependence of microstrains on the column length as analyzed by following the procedure of Warren-Averbach.

Compositions in the tantalum-carbon system were prepared by carburizing high-purity tantalum wires. The microstructures so produced exhibit regions of a characteristic striated structure identical to those observed by earlier investigators. There are disparities in the literature as to the origin of such structures in the tantalum—carbon system. They have been variously described as “twins,” “striated structure,” “precipitate,” and “structure of unknown origin.” This paper presents conclusive evidence that the structures in question are the result of precipitation on cooling. In addition, a coherent precipitation model is applied in which it is shown that the lattice relationship {0001}Ta2C‖{Klll}TaC can exist with less than 0.5% misfit. This relationship is shown to completely explain the occurrence and characteristic appearance of the observed micro structures. Correlations between chemical analysis, X-ray diffraction results, metallography, and microhardness measurements confirm the proposed precipitation model.

Ferrites are promising materials for enabling solar-thermochemical cycles. Such cycles utilize solar-thermal energy to reduce the metal oxide, which is then re-oxidized by H2O or CO2, producing H2 or CO, respectively. Mixing ferrites with zirconia or yttria-stabilized zirconia (YSZ) greatly improves their cyclabilities. In order to understand this system, we have studied the behavior of iron oxide/8YSZ (8 mol-% Y2O3 in ZrO2) using in situ X-ray diffraction and thermogravimetric analyses at temperatures up to 1500 °C and under controlled atmosphere. The solubility of iron oxide in 8YSZ measured by XRD at room temperature was 9.4 mol-% Fe. The solubility increased to at least 10.4 mol-% Fe when heated between 800 and 1000 °C under inert atmosphere. Furthermore iron was found to migrate in and out of the 8YSZ phase as the temperature and oxidation state of the iron changed. In samples containing >9.4 mol-% Fe, stepwise heating to 1400 °C under helium caused reduction of Fe2O3 to Fe3O4 to FeO. Exposure of the FeO-containing material to CO2 at 1100 °C re-oxidized FeO to Fe3O4 with evolution of CO. Thermogravimetric analysis during thermochemical cycling of materials with a range of iron contents showed that samples with mostly dissolved iron utilized a greater proportion of the iron atoms present than did samples possessing a greater fraction of un-dissolved iron oxides.

Structures of two K2SnX(PO4)3(X=Fe,Yb) phosphates, obtained by conventional solid state reaction techniques at 950 °C, were determined at room temperature by X-ray powder diffraction using Rietveld analysis. The two materials exhibit the langbeinite-type structure (P213 space group, Z=4). Cubic unit cell parameter values are: a=9.9217(4) Å and a=10.1583(4) Å for K2SnFe(PO4)3 and K2SnYb(PO4)3, respectively. Structural refinements show that the two crystallographically independent octahedral sites (of symmetry 3) have a mixed Sn∕X (X=Fe,Yb) population although ordering is stronger in the Yb phase than in the Fe phase.

Barium titanyl oxalate tetrahydrate, Ba(TiO)(C2O4)2.4H2O, has been investigated by means of X-ray powder diffraction. Precise powder diffraction data were obtained by a conventional diffractometer with strictly monochromatic radiation. Unit cell dimensions were determined by an indexing program based on the variation of parameters by successive dichotomies. A monoclinic cell was found, a=14.044(2)Å, b=13.812(2)Å, c=13.382(2)Å, β=91.48(1); V=2594.9Å3, which is characterized by the figures of merit M20=46.5 and F30=107(0.0056, 50). The complete powder pattern was reviewed by means of the program NBS*AIDS83 and the 81 first lines were indexed. Structural imperfections were not detected from the diffraction line widths, which are comparable to the instrumental resolution.

An improved method of alignment of a Philips diffractometer equipped with a theta-compensating slit is described. The method employs a special fluorescent screen which is flat to better than 10 microns. The procedure results in accurate alignment of the theta-compensating slit at low angles and assures reliable intensity data down to one degree two theta or less.

The value assignment of candidate Standard Reference Material (SRM®) 57b Silicon Metal provided an opportunity to develop an alkali reaction procedure as a precursor to borate fusion for the preparation of test specimens from the metal powder for X-ray fluorescence spectrometry (XRF). Suggested for this purpose by Blanchette in a 2002 Advances in X-ray Analysis article [45, 415–420 (2002)], the alkali reaction uses LiOH∙H2O to convert Si to Li2SiO3. Lithium silicate is fused with lithium borate flux without damage to platinum ware. Once specimens are fused and cast as beads, calibration standards are prepared to closely match the compositions of the specimens, allowing a linear calibration for each analyte. The XRF method yields results that are directly traceable to the mole through NIST SRM spectrometric solutions. The method was validated in two ways. First, the reaction was used on older SRMs for Si metal: SRM 57 and SRM 57a. Second, XRF results for candidate SRM 57b were compared to results obtained using prompt gamma-ray activation analysis (PGAA) and inductively coupled plasma optical emission spectrometry (ICPOES). Bias tests show the XRF results are accurate for the elements Al, S, Ca, Ti, Cr, Mn, Ni, Cu, and Zr. Levels of S, Ca, Cr, and Cu in candidate SRM 57b are near the limits of quantification of the borate fusion method. Iron results may be subject to a low bias. Phosphorus is not quantitatively retained during the alkali reaction and borate fusion. These elements, plus B, which cannot be determined after borate fusion, are listed in manufacturing specifications for Si metal.

Methods of chemical preparation and crystallographic data are reported for two new condensed phosphates: a hydrated cyclotriphosphate with a formula MnNa4(P3O9)2 4H2O and its anhydrous form MnNa4(P3O9)2. MnNa4(P3O9)2 4H2O is monoclinic P21/a with the following unit-cell dimensions: a=8.536(2) Å, b=14.309(3) Å, c=8.508(2) Å, β=96.452(2)°, and Z=2. MnNa4(P3O9)2 is monoclinic C2/c with the following unit-cell dimensions: a=13.198(2) Å, b=8.241(1) Å, c=14.228(2) Å, β=95.045(1)°, and Z=4.

A program has been written for rapid lattice parameter refinement which is designed to be applied to components in a mixture. This FORTRAN program employs a linear least-squares technique and is applicable to crystal systems with symmetry orthorhombic or higher. In addition to lattice parameters, a 2θ-zero can also be refined. Either approximate lattice parameters or a minimal set of indexed lines can be used as input. An example is given of its application to a AuMn two phase system.

CaMnO3 is a parent compound for various manganite systems exhibiting useful physical properties. Therefore, its structural and elastic properties are of general interest. In this paper, P–V equation of state of stoichiometric CaMnO3 is determined using energy dispersive X-ray diffraction. The measurements were carried out at a synchrotron beamline F2.1 (Hasylab, DESY) with samples compressed in a cubic-anvil diffraction press, MAX80, for pressures ranging up to 4.84 GPa. The experimental bulk modulus of CaMnO3, derived from the variation in the unit-cell volume with pressure by fitting the Birch–Murnaghan equation of state, is 154.4(3.3) GPa. The results are discussed on the basis of experimental and theoretical data for CaMnO3 and related compounds.

Ag–reduced graphene oxide (Ag/rGO) nanoparticle composites were synthesized through a facile one-step hydrothermal reaction using GO and silver carbonate (Ag2CO3) as raw materials. The homogeneous silver nanospheres with an average size of 50 nm well dispersed on the surface of rGO were obtained without other additives. During the formation process, GO both promotes the dispersion of Ag2CO3 in aqueous solution and acts as the substrate of silver cations, and the hydrolysis of Ag2CO3 provides silver cations and alkaline condition. Moreover, GO further serves as reducing agent to generate elemental silver in the alkaline condition. The as-prepared materials exhibit excellent surface-enhanced Raman scattering activities when used to detect the Raman signals of R6G absorbed on the Ag/rGO substrate.

Crystalline silica is known for its health hazards, and since 1997 has been listed as Group 1, Carcinogenic to Humans, by the International Agency for Research on Cancer. This issue is particularly important in the industrial environment, and there is still no method that allows quantification of the different polymorphs of crystalline silica. Many analytical methods have been proposed, and the major problem in almost all cases is attributable to the very large variety of matrixes encountered. This study evaluates the potential of X-ray diffraction techniques and an automated Rietveld analysis in order to overcome this problem and to adapt the quantitative analysis of quartz, the most prevalent crystalline silica polymorph, to routine analysis in the health and safety environment. Matrix simulations are done and many parameters are optimized. Sample preparation, the acquisition program, pattern treatment, and Rietveld refinement are evaluated, and a general procedure is determined. Automation of Rietveld refinement leads to a significant reduction in analysis time, but cannot be applied to every type of sample.

By means of a combined X-ray diffraction and metallographic study, two heretofore unrecognized phases, Zr4Fe and Zr2Fe, have been identified. Approximate verification of this finding has been made by Dr. David Levinson, using microprobe analysis. A tentative revision of the Zr-Fe phase diagram is proposed.

Software is described for complete computer control of residual stress measurements. One program (that incorporates either the two tilt method, the sins| procedure, or the Cohen-Marion technique) has been developed for use with either a normal detector or a position sensitive detector. The operator inputs the desired error in stress and various instrumental parameters that determine systematic errors. The counting strategy to obtain the total error is then determined by the software.

Employing this automated system, an investigation of a parabolic fit to the top of a diffraction profile indicates that a three point fit is satisfactory only for sharp profiles.

Legislation in the United States and Canada requires labelling of products containing ≥ 0.1 wt.% crystalline silica. Kaolin clays are used in a variety of industries and usually contain low levels of total (i.e., respirable plus non-respirable) quartz, even after beneficiation. X-ray diffraction procedures have been developed here which are suitable for the quantification of total quartz in commercial kaolins with accuracy sufficient to satisfy the legislation. Separation and analysis of the respirable fraction is not addressed in this paper; however, the procedures described would be applicable to such samples if sufficient were available. Use of the 50.1° 2θrather than the 26.6° 26 (CuKα) quartz peak avoids most of the potential problems of overlap with reflections from other accessory minerals. It is shown that profile fitting techniques and optimised experimental procedures allow the determination of quartz in bulk samples to ± 0.03 wt.% (95% confidence) at the 0.1 wt.% level, and ± 0.1 wt.% at the 1.0 wt.% level, with tolerable data collection times.

A new micro-X-ray flourescence (XRF) instrument was developed in combination with an atomic force microscope (AFM). A small pinhole of 5 or 10 μm was made on the AFM cantilever. The center of the micro-X-ray beam generated by a polycapillary X-ray lens was passed through the pinhole. The present experiment demonstrated that the size of the original X-ray beam of 48 μm produced by the polycapillary lens was reduced to about 10 μm. This instrument enables both observation of the surface morphology by the AFM and elemental analysis by micro-XRF.

A compilation has been made of the X-ray powder diffraction patterns of the high Tc superconductor and related phases in the systems of Ba-R-Cu-O, Sr-R-Cu-O and Ca-R-Cu-O, where R = yttrium and lanthanides. In addition to the patterns of compounds found in these systems, other related compounds included are cation substitution products of the high Tc phases of Ba2RCu2O6+x, potential reaction products with different types of sample containers, and selected thin-film substrates. The International Centre for Diffraction Data/Powder Diffraction file (ICDD/PDF) coverage includes Sets 1 to 41. A cross correlation of these phases with those reported in Phase Diagrams For Ceramists (PDFC), has also been completed. Results of these efforts are tabulated.

Potassium tetraperoxomolybdate (VI) K2[Mo(O2)4] was prepared, and its X-ray powder diffraction pattern was recorded at low temperature (258 K). The unit cell parameters were refined to a=10.7891(2) Å, α=64.925(3)°, space group R−3c (167), Z=6. The compound is isostructural with potassium tetraperoxotungstate (VI) K2[W(O2)4] (Stomberg, 1988). The sample of K2[Mo(O2)4] was characterized by analytical investigations, and the results of crystal structure refinement by Rietveld method are presented; final RP and RWP are 9.79% and 12.37%, respectively.

Quantitative X-ray diffraction (XRD) analysis is performed on 172 samples mainly containing paleosol sections of Unayzah and Basal Khuff clastics taken from the core of one well drilled by Saudi Aramco. Quantitative XRD bulk mineralogical determination is achieved using the Rietveld refinement method whereas quantitative XRD clay mineralogical determination of clay-size fraction is obtained using the reference intensity ratio method. The XRD results indicate that the samples from paleosol sections consist mainly of quartz and feldspar (microcline and albite) as framework constituents. Cement minerals include dolomite, hematite, anhydrite, siderite, gypsum, calcite, and pyrite. Clay minerals are important constituents in paleosols. The XRD results show that clay minerals in the samples are illite, mixed-layer illite/smectite, kaolinite, and chlorite. No discrete smectite is present in the samples. The clay mineral associations in these samples of paleosol sections can be classified into three types: Type I predominantly consists of illite and a mixed layer of illite/smectite; Type II of kaolinite; and Type III of illite and a mixed layer of illite/smectite, but also significant amounts of kaolinite. The change of clay mineral association type with sample depth can indicate the change of paleoclimate and paleoenvironment. For example, kaolinite usually forms under strongly leaching conditions such as abundant rainfall, good drainage, and acid waters. Therefore, XRD mineralogical data of paleosol sections are important for petroleum geologists to study paleoclimate and paleoenvironment and to predict the reservoir quality of the associated rock formations.