The analysis of thin insulating films occurring in various stages of the manufacture of integrated circuits has in the past been difficult, if not impossible. Their dimensions usually preclude analysis by conventional chemical techniques, hence very little is known concerning their relative stoichiometrics. However, by microprobe analysis, films as thin as 540 Å (∼18μg/cm2) have been successfully analyzed. In general, two different approaches are taken, depending on the film thickness. Usually, films thicker than 2500 Å (∼50μg/cm2) are analyzed by conventional microprobe techniques. A computer program, called MAGIC, has been written, which converts the raw X-ray intensities to chemical composition. All data are corrected for dead time, background, absorption, atomic number effects, and fluorescence by characteristic radiation, if required. A minimum of input is required, only the chemical symbols. X-ray lines employed, and the accelerating voltage being necessary in addition to the raw X-ray intensities. All constants such as atomic weights, critical excitation potentials, X-ray wavelengths, and absorption coefficients are stored or calculated internally, which reduces the errors and time associated with looking up and key-punching these values. New fluorescent yields are used for K and L radiation. No fluorescence correction is made for M radiation. The use of this correction program generally gives results, accurate to about 2 to 4%, relative to the amount present. For films thinner than 2500 Å, a new model is proposed which allows the X-ray spectra from the film and substrate to be unfolded to give the composition of the film only. To accomplish this, the atomic number correction of Duncumb and deCasa employed in MAGIC has been used in conjunction with a mean electron energy concept. Results obtained to date through the use of this model have been surprisingly good, being of the order of 5% relative to the amount present. Potential errors and uncertainties are discussed, and results given which illustrate the accuracy of the two methods.

Literature data pertaining to the crystal chemistry, crystallography, and X-ray powder-diffraction properties of phases reported in the system BaO-CuOx are compiled. Reported phases include BaCuO2−2.12, BaCuO2.26−2.39, BaCuO2.5, Ba2CuO3+x, Ba2Cu3O5+x, BaCu2O2+x, Ba3Cu5O8, Ba3CuO4, BaCu3O4, Ba3Cu2O4+x, Ba5Cu3O6+x, and BaCu2O3. The existence of some of these phases, however, still has to be verified. Most of these compounds are nonstoichiometric in oxygen. Their oxygen content, and in some cases even their crystal structures, vary with oxygen partial pressure. There are also reported indications that the cations Ba and Cu are not stoichiometric in the cubic BaCuO2-type compounds.

Phase composition estimates by X-ray powder diffraction and Rietveld analysis are becoming more widely used in the cement industry. The ASTM C01.23 Compositional Analysis subcommittee developed test method C 1365, “Standard Test Method for Determination of the Proportion of Phases in Portland Cement and Portland-Cement Clinker Using X-Ray Powder Diffraction Analysis.” A round-robin analysis involving 11 laboratories was initiated to assess the precision and bias of this approach and to develop guidelines for Rietveld analysis of hydraulic cements. Four cements were prepared using NIST SRM clinkers spiked with known amounts of one or more of the following minerals: gypsum, bassanite, anhydrite, and calcite. Specimens were provided with instructions that laboratories analyze the whole cement, collect data in triplicate, and repack the specimen for each run. The results of the round robin were used to estimate interlaboratory and intralaboratory precision and bias of phase abundance determinations. The results show an improvement over previous cement round-robin studies utilizing traditional internal-standard-based, peak-area-measurement methods.

The following fifteen reference patterns of boride, silicide and oxide ceramics represent the first group of ceramic phases measured at the National Bureau of Standards under the project “High Quality Reference Patterns and Total Digital Powder Patterns of Technologically Important Ceramic Phases”. The support and interest of the JCPDS-ICDD in this project is gratefully acknowledged.

The general methods of producing these X-ray powder diffraction reference patterns are described in this journal, Vol. 1, No. 1, pg. 40(1986).

Nanocrystals of Zn1−xMxO (M=Mn, Co, or Ni) were grown using proteic sol-gel process, and the crystalline phases were identified by X-ray diffraction and Rietveld refinement. The nanocrystals have hexagonal wurtzite structure, with space group P63mc. The insertion of Mn2+ in the place of Zn2+ provoked an increase in the size of the nanocrystals, and the insertion of Co2+ or Ni2+ caused a reduction in the sizes of the nanocrystals, as compared to pure ZnO. This occurred because these three transition metals have very different ionic radii (Co2+=0.58 A˚, Mn2+=0.66 A˚, Ni2+=0.55 A˚, and Zn2+=0.60 A˚).

A pragmatic, easily applied theory of the extended X-ray absorption fine structure found on the high-energy side of absorption edges is developed. This simple model can be successfully applied to determinations of interatomic distances, and it accounts for differences in Kronig structure on different absorption edges in the same material. Quantitative agreement with experimental data is good.

Kesterite (Cu2ZnSnS4, CZTS) powders were produced by reactive high-energy milling, starting from stoichiometric mixtures of the elemental components. CZTS forms fine crystals with a cubic structure, which evolves to the stable tetragonal form after thermal treatment. Tablets were produced by cold pressing of the ball milled powder, and sintered up to 660 °C. Seebeck coefficient, electrical resistivity, and thermal diffusivity were measured on the sintered tablets, pointing out the positive effect of CZTS nanostructure and of the rather large fraction of porosity: thermal conductivity is rather low (from ~0.8 W/(m K) at 20 °C to ~0.42 W/(m K) at 500 °C), while electrical conduction is not seriously hindered (electrical resistivity from ~8500 µΩ m at 40 °C to ~2000 µΩ m at 400 °C). Preliminary results of thermoelectric behavior are promising.

Cu-paddle-wheel-based Cu3(BTC)2 (nicknamed Cu-BTC, where BTC ≡ benzene 1,3,5-tricarboxylate) is a metal organic framework (MOF) compound that adopts a zeolite-like topology. We have determined the pore-size distribution using the Gelb and Gubbins technique, the microstructure using small-angle neutron scattering and (ultra) small-angle X-ray scattering (USAXS\SAXS) techniques, and X-ray powder diffraction reference patterns for both dehydrated d-Cu-BTC [Cu3(C9H3O6)2] and hydrated h-Cu-BTC [Cu3(C9H3O6)2(H2O)6.96] using the Rietveld refinement technique. Both samples were confirmed to be cubic Fm $\bar 3$ m (no. 225), with lattice parameters of a = 26.279 19(3) Å, V = 18 148.31(6) Å3 for d-Cu-BTC, and a = 26.3103(11) Å, and V = 18 213(2) Å3 for h-Cu-BTC. The structure of d-Cu-BTC contains three main pores of which the diameters are approximately, in decreasing order, 12.6, 10.6, and 5.0 Å. The free volume for d-Cu-BTC is approximately (71.85 ± 0.05)% of the total volume and is reduced to approximately (61.33 ± 0.03)% for the h-Cu-BTC structure. The d-Cu-BTC phase undergoes microstructural changes when exposed to moisture in air. The reference X-ray powder patterns for these two materials have been determined for inclusion in the Powder Diffraction File.

Verification tests of the forward modeling technique for near-field high energy X-ray diffraction microscopy are conducted using two simulated microstructures containing uniformly distributed orientations. Comparison between the simulated and reconstructed microstructures is examined with consideration to both crystallographic orientation and spatial geometric accuracy. To probe the dependence of results on experimental parameters, simulated data sets use two different detector configurations and different simulated experimental protocols; in each case, the parameters mimic the experimental geometry used at Advanced Photon Source beamline 1-ID. Results indicate that element orientations are distinguishable to less than 0.1°, while spatial geometric accuracy is limited by the detector resolution.

Sauropod dinosaurs were typically one magnitude larger than any other living or extinct terrestrial animal. This sheer size of the sauropod leads to scale effects in their biology and physiology that still are inadequately understood. The only remnants of the sauropods are their fossilized bones. These fossilized bones have sustained burial for some hundred million years and thus may have experienced significant diagenetic changes. These diagenetic changes often do not affect bone preservation on the histological level, but may lead to significant alterations of the bone microstructure. Here the influence of diagenesis on the microstructure of fossilized sauropod bones using femur cross section of Brachiosaurus brancai that was excavated in the Tendaguru beds in Tanzania is investigated. The element distribution in this dinosaur bone is studied by a combination of micro-X-ray-fluorescence (μ-XRF) using synchrotron radiation and energy dispersive X-ray analyses (EDX) in the scanning electron microscope. These techniques reveal quantitative values of the element concentration at a macroscopic level combined with qualitative information at high spatial resolution of the distribution of Ca, Co, Cr, V, Pb, U, Sr, Y, and As in the fossil bones. This allows a differentiation between the remnants of the original bone apatite and pore filling minerals and also a visualization of damage, e.g., cracks introduced by diagenetic processes.

Laboratory powder X-ray microdiffraction with a focusing monocapillary and linear multichannel detector was applied to phase identification in fragments of painting layers of art works, canvas and wall paintings, and polychromes on wood. This method is useful in materials research of painting layers with complex stratigraphy, and it is indispensable in distinguishing inorganic pigments of different natural provenance and revealing degradation products. The advantage of X-ray microdiffraction is its nondestructive nature and no need of sample pretreatment. Samples after microdiffraction can hence be used for other analyses or archived. Another advantage is the possibility to work with samples smaller than 1 mm, which is particularly important in the analysis of artworks where the sample amount or size is a serious limit of using the laboratory techniques of materials research. The X-ray equipment used is more economical and more easily accessible than other microdiffraction techniques and is, hence, suitable for routine analytical work.

Standardized experimental and calculated X-ray powder diffraction data for a new synthetic zeolite, cesium titanium silicate, CsTiSi2O6.5, are reported. In addition, a structure model in space group Ia3d (230), which is isomorphous with the mineral pollucite (CsAlSi2O6·xH2O), is proposed for CsTiSi2O6.5. This structure model is the basis of the reported calculated X-ray powder diffraction data for CsTiSi2O6.5. The experimental pattern for CsTiSi2O6.5 shows this compound crystallizes in a body-centered cubic (BCC) unit cell with a=13.8423 (1) Å. The measured value of the reference intensity ratio (I/Ic) of CsTiSi2O6.5 is 2.37, while the contrasting calculated value of I/Ic is 4.45. The experimental density (Dm) of CsTiSi2O6.5 is 3.48±0.09 g/cm3, in agreement with the calculated density (Dx) of 3.42 g/cm3. Chemical analysis of CsTiSi2O6.5 by atomic absorption spectroscopy gives its composition as 54±2 wt% Cs; 23±2 wt% Ti; 23±2 wt% Si, which compares favorably with the theoretical composition of 56 wt% Cs; 20 wt% Ti; 24 wt% Si.

X-ray powder diffraction data, high resolution electron microscopy observation and refined unit cell parameters for δ-Al2O3 prepared from γ-Al2O3 are reported here. The new lattice parameters were a=7.9631(7) and c=23.3975(23) Å with space group P41212 (No. 92). The new data provide evidence for the simple tripling of the unit cell of the starting γ-Al2O3 spinel.

The X-Ray Powder Data File (XRPDF) enables one to identify the compounds in a sample. More often than not, however, a semi-quantitative analysis is wanted. Visual inspection of the pattern may give a vague impression of the composition, but the errors of such a result are usually not within reasonable limits. Clearly a less subjective and more accurate method is wanted. If the necessary data are printed on the cards, such a method will greatly enlarge the usefulness of the File.

Micro-X-ray fluorescence (μ-XRF) is a rapidly evolving analytical technique which allows visualising the trace level metal distributions within a specimen in an essentially nondestructive manner. At second generation synchrotron radiation sources, detection limits at the sub-parts per million level can be obtained with micrometer resolution, while at third generation sources the spatial resolution can be better than 100 nm. Consequently, the analysis of metals within biological systems using micro- and nano-X-ray fluorescence imaging is a quickly developing field of research. Since X-ray fluorescence is a scanning technique, the elemental distribution within the sample should not change during analysis. Biological samples pose challenges in this context due to their high water content. A dehydration procedure is commonly used for sample preparation enabling an analysis of the sample under ambient temperature conditions. Unfortunately, a potential change in elemental redistribution during the sample preparation is difficult to verify experimentally and therefore cannot be excluded completely. Creating a cryogenic sample environment allowing an analysis of the sample under cryogenic condition is an attractive alternative but not available on a routine basis. In this article, we make a comparison between the elemental distributions obtained by micro-SR-XRF within a chemically fixed and a cryogenically frozen Daphnia magna, a model organism to study the environmental impact of metals. In what follows, we explore the potential of a dual detector setup for investigating a full ecotoxicological experiment. Next to conventional 2D analysis, dual detector X-ray fluorescence cryotomography is illustrated and the potential of its coupling with laboratory absorption micro-CT for investigating the tissue-specific elemental distributions within this model organism is highlighted.

Calcium hydroxyapatite (Ca10(PO4)6(OH)2) whiskers were prepared by using the technique of molten salt synthesis with the fluxing agent of potassium sulphate (K2SO4). A tentative x-ray diffraction (XRD) pattern was suggested for the produced whiskers. Phase purity, composition, and morphology of the whiskers were investigated by powder XRD, inductively coupled plasma-atomic emission spectroscopy, Fourier transform infrared spectroscopy, and scanning electron microscopy, respectively.

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.

The crystal structures of four samples of anhydrite, CaSO4, were obtained by Rietveld refinements using synchrotron high-resolution powder X-ray diffraction (HRPXRD) data and space group Amma. As an example, for one sample of anhydrite from Hants County, Nova Scotia, the unit-cell parameters are a = 7.00032(2), b = 6.99234(1), c = 6.24097(1) Å, and V = 305.487(1) Å3 with a > b. The eight-coordinated Ca atom has an average <Ca-O> distance of 2.4667(4) Å. The tetrahedral SO4 group has two independent S-O distances of 1.484(1) to O1 and 1.478(1) Å to O2 and an average <S-O> distance of 1.4810(5) Å. The three independent O-S-O angles [108.99(8) × 1, 110.38(3) × 4, 106.34(9)° × 1; average <O-S-O> [6] = 109.47(2)°] and S-O distances indicate that the geometry of the SO4 group is quite distorted in anhydrite. The four anhydrite samples have structural trends where the a, b, and c unit-cell parameters increase linearly with increasing unit-cell volume, V, and their average <Ca-O> and <S-O> distances are nearly constant. The grand mean <Ca-O> = 2.4660(2) Å, and grand mean <S-O> = 1.4848(3) Å, the latter is longer than 1.480(1) Å in celestite, SrSO4, as expected.

An interactive computer program to display, process and analyze raw powder X-ray diffraction data is described. The program extensively employs graphic means of input and output with the help of “pop-up” windows and menus. In addition to those tasks that are common to most primary raw data analyzing programs, it performs many functions which are generally assigned to separate secondary programs. These functions include on-screen correction of d-spacing with reference to a standard compound, calculation of peak width and crystallite size, subtraction of patterns for differential X-ray diffraction and unrestricted overlay of patterns. The advantages of an integrated single program to process X-ray diffraction data in mineral research are illustrated and discussed.

In this paper we propose a fitting procedure to describe the bandpass effect on all x radiation that passes through a focusing graphite monochromator used on the diffracted beam. The proposed bandpass function is: M(2θ)=1/(1+Kmon1sKmon2), with s=(2 sin θ)/λ, where Kmon1 and Kmon2 are constants which have been refined by means of a Rietveld analysis, using a physically modeled background (Riello et al., J. Appl. Crystallogr. 28, 115–120). We have investigated two polycrystalline powders: α-Al2O3 and a mixture of α and β-Si3N4. The so-obtained bandpass functions for these materials are close enough to conclude that they depend only on the used experimental setup (in the present case the X-Pert-Philips diffractometer with a graphite focusing monochromator). Knowledge of the bandpass function is important to suitably model the Compton scattering, which is a component of the background scattering. The present procedure allows one to avoid the direct experimental determination of the bandpass function, which requires the use of another monochromator (analyzer) and another tube with an intense white spectrum.