A method has been developed to simultaneously compute matrix corrections from a composite spectrum of multi-target energy-dispersive (EDXRF) and multicrystal wavelength—dispersive (WDXRF) x-ray fluorescence systems, A serial line installed between the WDXRF and EDXRF spectrometers via a PDF 11/34a computer allows acquired wavelength data to be digitally transformed into an energy spectrum. The low-energy x-ray information from the WDXRF unit is then coupled with the backscatter coherent/incoherent information from the EDXRF unit, enabling enhanced quantitative analysis for low-atomic-number (low-Z) elements. The peak resolution obtainable from the WDXRF spectra often removes the necessity for peak-overlap corrections.

Backscatter intensities obtained from the EDXRF unit are used to provide information on total sample mass and to correct for matrix effects. The resulting backscatter fundamental-parameter (BFP) calculations generally provide an accurate analysis of samples without prior knowledge of the sample matrix. Such an approach is particularly useful for samples in which quantities of carbon, oxygen, and other low-Z constituents cannot be explicitly determined.

Regions of interest (ROI) are created by the computer code “PREP” and processed by the BFP code "MSAP" an extension of the “SAP3” computer program for quantitative multielement analysis by energy-dispersive x-ray fluorescence,

The design, construction and operation of toroidal focusing X-ray monochromators have been described in detail by Marcus, et al. (1980) and by Furnas, et al. (1982), Marcus, et al. used 100 mechanically damaged, singly bent LiF (200) (2d = 4.02 Å) single crystals in a toroidal array to focus Cu Kα characteristic X-rays (8.04 keV, 1.54 Å, Θ = 22.6 deg). The diameter of the LiF toroid was 166 mm and the source-detector distance was 400 mm. Furnas, et al. used a series of singly bent, highly oriented graphite (2d = 6.72 Å) crystals, also in a toroidal array, to focus Pb Lα, Se Kα, Th Lα and U Lα X-rays (10.5 - 13.6 keV, 1.18 - 0.91 Å, Θ= 10.1 - 7.8 deg). Their system dimensions were not disclosed. The LiF and graphite crystals were both curved along the direction of X-ray propagation. That is, the cylindrical axes were orthogonal to the X-ray path.

Profile changes of copper Lα (L3-V) and Lβ (L2-V) X-ray fluorescence spectra are interpreted. It is shown that the intensity of the high energy shoulder of the Cu L X-ray spectra has a relation to the intensity of the so-called ‘shake-up’ satellite in 2p X-ray photoelectron spectra; the high energy shoulder of the divalent copper La is weak for covalent compounds and strong for ionic compounds. It is also shown that the Lβ/Lα intensity ratio changes with the change of copper concentration of the analyte as well as the change of chemical state of the analyte.

The Fuji Imaging Plate (IP) is a 2-dimensional detector in which a latent X-ray image is stored as a distribution of color centers on a photostimulable phosphor (BaFBr:Eu2+) screen. It has a large effective area, wide dynamic range and high sensitivity. Thus it has been widely used not only in medical but also in scientific and industrial fields. Particularly in X-ray structure analysis, mainly of proteins, it has been used extensively and achieved good results.

On the other hand, few applications have been reported in the field except for structure analysis, in spite of the superior performance of the IP which will give significant advantages in various measurements which have been done using an X-ray film such as electric device and fiber specimen.

Therefore we report here the basic performance of R-AXIS II(Rigaku Automated X-Ray Imaging System II), an IP reader made by Rigaku, and some applications of X-ray diffraction measurements using IP.

For time-resolved diffraction studies under high temperature and/or high pressure, we designed a new diffractometer incorporating a curved position sensitive detector and tested the rapid intensity measurement and the resolution of the angular dispersive diffraction. The diffraction profiles were compared with those from energy dispersive diffraction. Rapid intensity collection has been carried out with a CAMAC module. A curved position sensitive detector with a 120° working angular region was installed on the off-centered four circle diffractometer. Only a few seconds were needed to obtain a whole powder diffraction because of the extremely high counting efficiency due to the streamer mode.

Time-resolved observations of the dehydration reactions of Mg(OH)2 and Ca(OH)2, have been undertaken by angular dispersive and energy dispersive x-ray powder diffraction at high temperature. The in situ observations of the dehydration process provide kinetic information, such as the reaction rate, the apparent activation energy and the dehydration mechanism.

The XANES (X-ray absorption near edge structure) spectra of copper(II) ions in solid state and in solution of the square-planar copper(II) complexes with tetraaza macrocycles were measured. The peaks in the measured XANES spectra shifted to lower energy side with increasing the electron density of central copper(II) ions. The molecular orbital calculations for the complexes were carried out by the DV-Xα method, and the theoretical XANES spectra were estimated. The clear chemical shift obtained by this XANES study is evaluated and leads to a new concept of π-back donation between the copper(II) complexes and counter anion in aqueous solution.

In-situ, high temperature X-ray diffraction (XRD) is an extremely useful tool for studying, monitoring or investigating crystal structure modifications as well as phase transformations in crystalline material during thermal treatments in controlled atmospheres. This technique has been used to investigate the thermal behavior of materials such as carbonate minerals, ceramic fibers, coating pigments, etc. The advantages of such a technique over the conventional practice, where samples are heat treated in a separate oven and then analyzed by XRD include: consistency of sample placement; preservation of high temperature structures to facilitate observation of metastable phases that are unstable upon exposure to outside atmosphere or during cooling; real time monitoring of reactions that occur, and products that are formed at a desired temperature or environment; and need for multiple samples or analysis.

The major advantage of secondary-target X-ray fluorescence analysis is the enchancement of sensitivity and detection limit of an element or small group of elements with similiar atomic numbers by selecting a target material which produces X-rays slightly higher than the absorption edges of the analysis of interest. Secondary target excitation systems are, however, being employed for simultaneous determinations of a large range of elements. Thus, it was decided to compare the application of a simple secondary target X-ray fluorescence system with excitation from a Cd-109 annular radioisotope source.

A simple secondary target X-ray fluorescence system was constructed and optimized which operates at less than 800 kilowatts. The “relative” elemental sensitivities of this system. and a radioisotope system with a Cd-109 annular source were compared by the analysis of the 1-2-3-multi-spectral standard from Chemplex which contains 1.23% of 53 elements. The characteristic X-rays were collected with the same Si(Li) detector and analyzed with the same Apple lie microprocessor with a Nucleus ADC/interface card. Finally, the secondary target system described herein with a molybdenum X-ray tube and zirconium or cadmium target produced similiar elemental sensitivities as a Cd-109 annular source of about 7.5 mCi and 5.0 mCi intensity respectively.

The exact compositions of the Victoria Crosses held in custody by the Australian War Memorial were needed so that its conservation staff could formulate a proper strategy for their conservation. This analytical study not only provided the required information but it resolved important ambiguities in the historical record.

A procedure for the accurate determination of unit-cell parameters using conventional Xray powder diffractometry is described. Two important factors in the procedure are: 1) the use of high-resolution-type diffractometer, which can suppress the axial beam divergence and thus gives nearly symmetric diffraction profiles in the low 2θ region and 2) the use of a new algorithm for systematic peak shift correction during the least-squares determination of unit-cell parameters of a sample with an internal standard [Toraya & Kitamura (1990). J. Appl. Cryst. 23 , 282-285]. The procedure has been tested by measuring successively the unit-cell parameter of W, CeO2, and Si in three mixtures, Si+W, W+CeO2, and CeO2+Si: the unit-cell parameter of W, which was first determined by using NIST SRM 640b Si powder as an internal standard reference material, was used as a standard reference value to determine the unit-cell parameter of CeO; in the next W+CeO2 mixture, and so on. The difference between the end value of observed Si unit-cell parameters and the starting value of 5.430940(35) Å were just 1 to 5 p.p.m. High accuracy is attainable in measuring the uni-cell parameters even with the conventional powder diffractometry provided with the nearly symmetric diffraction profile and the algorithm for peak shift correction used in the present study.

The basic diffraction techniques for examining the stress tensor are reviewed, with particular emphasis on what can be done without knowing the unstressed lattice parameter(s). Examples are given of the residual stresses in thin films, how to measure the bonding and yield stress in composites and separating the micro and macrostresses to examine load sharing between phases.

In recent years, for the development of magnetic tape, it has become increasingly important that the elemental content be determined accurately and rapidly. In the past, the elemental content of magnetic tape was determined by calibration analysis using a wavelength dispersive X-ray fluorescence spectrometer(WDXRF). For calibration analysis many standard samples and large amount of sample were needed. Preparation of sample for calibration analysis, as well as for inductively coupled plasma emission spectral analysis(ICP) was difficult. On the other hand, for thin layer fundamental parameter analysis(we call TLFP) using a WDXRF, a few standard samples and l.pss sample are needed and preparation of the sample is easy. The superiority of TLFP analysis can be seen In comparison with calibration analysis and IOP analysis in Table 1. For this reason, this study has established a method for accurate and rapid determination of the elemental composition of oxide magnetic tape by TLFP analysis using a WDXRF.

Starting in Germany (Garmisch Partenkirchen, 1986) we had the 1st ICRS (Int. Conf. on Residual Stresses). The second was held in France (Nancy, 1988), the third in Japan (Tokushima 1991). In all areas, the diffraction measurements furnish exceptional contributions, and in many cases they are the only methods capable of solving problems. Because of the importance of the diffraction methods, the literature on residualstress analysis (RSA) has enlarged in the last years, Figure 1.

Since Bednortz and Muller discovered high Tc oxide superconductors in 1986. many oxide superconductors are synthesized by many workers. These are YBCO system (Tc 90 K), BPSCCO system (110 K) and TBCCO system (125 K). Even now, the study of preparing higher Tc superconductors has been continued. The starting materials, in which the compositions are deiicatly variec, are mixed and high Tc oxide superconductors are prepared.

Residual stresses are found in the majority of multilayer thin film structures used in modem technology. The measurement and modeling of such stress fields and the elucidation of their effects on structural reliability and device operation has been a “growth area” in the literature, with contributions from authors in various scientific and engineering disciplines.

In this paper a review of the definitions of the residual stresses used by the authors in the various disciplines is presented and the mechanisms by which residual stresses may form in thin film systems is discussed.

The problem of background radiation in X-ray fluorescence trace element analysis of fused-glass iron ore samples is addressed. A first-order model of coherent and Comptcn scattering with primary absorption is presented and used to correct measurements. Overlap coefficients for elements in iron ores are presented. The importance of these corrections is demonstrated. The accuracy achieved with X-ray measurements after background corrections compares well with the accuracy of chemical analysis.

Intergranular residual stresses can exist in zirconium alloys, especially when there is a large distribution of grain orientations. The stresses result from the anisotropic plasticity and thermal expansion of the hexagonal close-packed crystal structure of α-zirconium. Apart from complicating the characterisation of materials using lattice parameter measurements, the intergranular stresses can significantly affect material behaviour, especially in nuclear reactor environments, and there is therefore a great deal of interest in their measurement.

The effects of specimen preparation and surface relaxation on X-ray diffraction measurements of lattice parameters of zirconium alloys have been investigated by comparing bulk neutron diffraction with X-ray diffraction on identical materials. The results show that: (i) intergranular or interphase residual stresses exist in dual-phase Zr-2.5Nb pressure tubes; (ii) the stresses normal to the surface of an X-ray diffraction specimen are not relieved completely when there are intergranular residual stresses in the material. One can conclude that intergranular stresses have to be considered when determining chemical compositions from lattice parameter measurements and also when measuring macroscopic residual stress using X-ray diffraction.

Objects of art and archaeology are relicts of the past, and art historians, archaeologists and conservators are constantly concerned with the questions of where, when or by whom such artifacts were made. Usually stylistic considerations can provide answers to these questions, but as styles were sometimes copied at locations and times quite different from those for which they were most characteristic, material analysis is often essential when one is attempting to infer how and of what materials an object was made. The use of several compounds e.g. as pigments in paintings, or the deliberate alloying of Cu with Sn, As, Sb and Pb, has varied greatly from region to region and from time to time and can be used to infer the geographic origin of an object or at least the origin of the materials, out of which it was made.

A self-consistent scheme is proposed for the evaluation of stressfields which vary strongly within the penetration depth of the X-rays in polycrystalline specimens which are elastically isotropic and homogeneous on a macroscopic scale. Very precise diffraction experiments have to be performed for practical applications.

XRF and Ion mfcroprobe analyses of fossils of known and uncertain provenance from the Lower-Middle Pleistocene locality of Kanjera. Kenya, are reported. The goal of this study was to develop a nondestructive technique of provenancixig fossils, which could be applied to the Kanjera sample. The fossils of known provenance were collected in the excavations of the 1987 Smithsonian Expedition. Three fossils of uncertain provenance, two specimens of Theropithecus oswaldi and a hominid fossil, were analyzed as test cases.

Both qualitative and quantitative XRF analyses of Kanjera fossils were carried out. In the qualitative analysis, the elemental peak areas from each fossil's XRF spectrum were calculated and normalized to the peak area of the incoherently scattered radiation. Results of the analysis showed that fossils from the Lower-Middle Pleistocene Kanjera Beds, for the most part, had higher levels of yttrium (Y) and zirconium (Zr) than those of the younger Apoko (Ap) Bed. black cotton soil (BCS) and modem bones (MD). The relative concentrations of uranium (U) v strontium (Sri and thorium (Th) were diagnostic of the Kanjera Bed of origin. These findings were confirmed by quantitative XRF and ion microprobe analyses of a subsample of Kanjera fossils. The T. oswaldi and hominid fossils had trace element concentrations suggestive of K2 and BCS provenances, respectively. These findings provide a framework for the qualitative XRF provenancing of other surface collected fossils from the locality.