It has been found possible to determine quickly the concentrations of molybdenum and ruthenium in non-radioactive alloys representative of high burn-up reactor fuels by the method of X-ray emission spectrometry. Preliminary steps of chemical dissolution and separation are not required. The alloys, essentially ternaries of molybdenum and ruthenium with uranium, are being studied because they are considered to typify the alloys which will result from cycling uranium fuel elements through the sequence of fabrication, use and pyro.metallurgical processing.

The analytical procedure involves sampling of the ingot by slicing with a silicon carbide wheel at the plane of interest and reducing the surface to the flatness and finish obtained by a five-minute grinding and polishing operation. In the X-ray spectrograph the flat surface is examined for the intensities of its molybdenum and ruthenium K emission lines, with counting times of one to eight minutes. Calibration plots of intensity versus chemically determined weight per cent are established and used for subsequent sets of analyses.

Emission-concentration proportionality Is one of the main features of electronprobe mlcroanalysis. It can be interpreted by taking simultaneously Into account the Z/A factor of Webster's law of deceleration and the variation with atomic number of the backscattering ratio. The baclcscattering ratio itself can be deduced approximately from experimental distribution curves of thecharacteristicemisslonjejqpertments on copper-gold alloys show good agreement with the theoretical predictions. An important practical consequence is that regulation of the electron beam falling onto the specimen leads to better results than regulation of the current passing through it. The different corrections are discussed, with special reference to the fluorescence induced by the general continuous spectrum. The case of insulating materials is considered separately; preliminary experiments seem to show that their behavior is not essentially different from that of conducting materials.

The use of glancing angles of incidence enables X-ray Absorption Spectroscopy to be measured as a function of depth from the surface of a material into the bulk. As x-rays rather than photoelectrons are detected, a UHV environment is not required and instead surfaces and interfaces can be examined under realistic operational conditions. Whilst the reflected beam carries the fine structure of concentrated species in the imaginary part of the refractive index, this is obscured by the contribution from the real part for angles greater than ϕc, the critical angle for total external reflection. Measuring the x-ray fluorescence offers more flexibility, particularly for dilute systems. The use of synchrotron radiation in conjunction with a multi-element Solid State Detector enables impurity loadings down to a few 1019 cm-3 to be measured which for ion implants is equivalent to around half-monolayer coverage at the surface. This sensitivity makes it practical to examine impurities in semiconductors at realistic dopant levels.

Spectrographic analysis of light elements by soft and ultrasoft fluorescent x-rays has become a useful technique for many applications of elemental analysis, using single crystals, soap multilayers and a combination of total reflection and filtering.

Instead of the wavelength dispersive method based on Bragg reflection which provides high resolution combined with low reflecting intensity, monochromatization combining total reflection by a selected mirror and an appropriate filter offered an alternative approach in order to increase measurable intensity with reasonable spectral resolution.

Recently, the use of synthetic multilayers, which are prepared by sputter/evaporation techniques, has been introduced for the detection of soft and ultrasoft x-rays. Studies on the use of these new wavelength dispersing devices have been conducted and it has been found that the reflectivity of these devices is very high compared with single crystals and soap multilayers and that their resolving power is fairly good.

An application of energy dispersive diffractometry to the measurement of residual strains (stresses) in the interior of industrial materials is described with particular emphasis on the use of high energy (up to 250 keV) x-ray photons. The use of high energy photons permits better penetration into materials. Hence diffraction data for evaluating bulk residual strains can be obtained in the transmission geometry in contrast with the conventional angular dispersive diffractometry, which uses Bragg reflections from the surface of materials. The reliability and sensitivity (detectability of small strains) of the energy dispersive method are demonstrated through its application to mapping of residual stress distributions across weld zones in Alaskan pipe line segments (API5LX65). The detectability of strain variations within materials depends on x-ray optical resolution and statistics.

The oscillation from a linear relation in the 20 vs. sin2ψ diagram has been a most important problem in X-ray stress measurement. There are, therefore, a number of papers concerned with the X-ray elastic constant, lattice strains under stresses and evaluation of stresses of textured materials.

The purpose of the present study is to analyze the three-dimensional orientation distribution of steel sheets by means of the Vector method proposed by Ruer and Baro, and to calculate the elastic modulus of textured sheets by means of a finite element method (FEM) using the three-dimensional orientation distribution, and then to calculate the strain/stress ratios vs. the directions defined by the angles between the specimen normal and the normal to the diffracting planes.

The state of stress in a material, as represented by the stress tensor, can be measured using x-ray or neutron diffraction techniques. A stress tensor measured using diffraction represents an experimental estimate of the true state of stress in the material. The measured stress tensor will include both instrumental and counting statistical errors. With careful measurement techniques, instrumental errors can be minimized, and accurate results can be obtained. The errors in the measured stress tensor that are due to counting statistics can be estimated using well established error propagation techniques. Unfortunately, these errors cannot be analytically propagated through the solution to the eigenvalue problem which yields the principal stresses and directions. Without estimates of the errors associated with the principal stresses and directions, the values determined for these quantities are of limited value.

Due to the current high interest in characterizing epitaxially deposited thin films required by the electronics industry as well as the increased attention in elucidating reactions between solid surfaces and the environment (e.g., corrosion), investigators have increased their efforts in developing X-ray procedures for analyzing films and surfaces less than 2 μm thick. For example, an entire session of the 1985 Denver Conference on Applications of X-ray Analysis was devoted to this subject and an excellent review of X-ray diffraction techniques for characterizing thin films was recently published by Segmuller (1). Specific techniques include grazing incidence diffraction (2, 3), double crystal diffraction (3), and the use of the Seemann-Bohlin focusing geometry (4, 5).

In a number of laboratories data from the X-ray pole-figure goniometer are now processed numerically to obtain a suite of complete and normalized pole- figures. From these pole-figures the preferred orientat ion of the grains in a monomineralic aggregate is determined using spherical harmonic analysis and represented as a frequency distribution of the Euler angles Ψ, θ, ø, termed the “orientation distribution function” (ODF),When the frequency density of grain orientations is plotted in a Cartesian coordinate system with Ψ, θ, ø, as axes,it must have a translation periodicity Of 2π or less along each of the axes, because the Euler Angles are angles of rotation.

With a new irradiation chamber a comparison of three excitation modes under same conditions and with the same material has been done. The results of this comparison are presented in the following manner: - Barltla scattering (graphite) versus Bragg reflection (HOPS) - Bragg reflection (Mo) versus secondary target fluorescence (Mo) - secondary target fluorescence (Sn) versus Barkla scattering (graphite) Excitation spectra and detection sensitivities of a NBS standard will be discussed for the different modes. The Barkla scattering was found to be the best excitation mode for a wide elemental range.

The diffraction, reflection, absorption, fluorescence, and the electronic emission that results from the interaction with ultrasoft X-rays (λ > 10 A) are presented as practical bases for microanalysis. Recent developments on sources and detectors for the ultrasoft X-radiations are described. A preliminary report on a current investigation on low-energy photo-Auger electron analysis and on a new type of low-energy electron spectrometer is also presented.

Solid solutions are pervasive in minerals and in industrial inorganic materials. The analyst is often called upon to provide qualitative and quantitative X-ray phase analysis for specimens containing solid solutions when all that is available are Powder Diffraction File (PDF) data or commercial standards for the end members. In an earlier paper (1) we presented several examples of substantial errors in accuracy of quantitative analysis that can arise when the crystallinity and composition of the analyte standard do not match those of the analyte in the sample of interest. We recommended that to obtain more accurate quantitative analyses, one should determine the analyte composition (e.g., from XRF on grains seen in a SEM or from comparison of cell parameters with those of the end members) and synthesize an analyte standard with this composition and with a crystallinity approximating that of the analyte (e.g., as determined from peak breadth or α1/ α2 splitting).

This paper describes a technique of measuring the volume percent retained austenite in steel using ordinary filtered X-radiation and an X-ray diffractometer. As compared with conventional rate-meter recordings or microphotometer traces of diffraction peaks, the subject technique extends the range of austenite determinations from the usual 7 % down to 1 %. It markedly improves over the entire range of measurement.

Essentially, the technique consists of step scanning the profile of each selected martensite and austenite diffraction line and recording the corresponding intensity within a known probable error. The step-scanning, fixed-count, and counting-rate, recording operations are performed automatically by a counting-rate computer. The integrated intensity of each diffraction line is obtained by summation of intensity increments above background in accordance with the “trapezoidal rule.” For hardened steel, the best peak-to-background ratio is secured using filtered Cr Ka radiation with the vanadium filter located in the diffracted beam. The volume percent retained austenite is determined by direct comparison of the integrated intensity of an austenite line with the integrated intensity of a marten site line and from the relationships between intensity and concentration for the martensitic and austenitic phases.

An application of the subject technique was its use in determining the retained austenite behavior of carburized 9310 steel. The volume percent austenite retained on the surfaces of as-quenched specimens was determined as a function of carburizing potential. The amount of retained austenite subsequently transformed by various combinations of tempering, refrigerating, and retempering treatments was successively ascertained. The amount of retained austenite determined using the subject technique compared closely with the amount of retained austenite measured by metallographic examination. However, the reproducibility of results was better for the X-ray method as compared to metallographie examination. The nondestructive nature of the X-ray method permitted successive measurements on the same surface following repeated thermal treatments.

X-ray diffraction and electron microprobe analysis were used in combination to identify reaction phases that formed on the surfaces of low-carbon steel specimens reacted with a 75% basalt-25% bentonite mixture and anion-doped water in sealed pressure vessels at 100°C and 250°C. Reaction phases on specimen surfaces and in adhering geologic material were identified by conventional X-ray diffraction scans of entire specimens with intact reaction layers. Comparison of results from adhering geologic material and scans of selectively removed layers allowed establishment of approximate reaction gradients in the adhering packing material. Electron microprobe analysis of specimens in cross-section provided quantitative chemical analyses of adhering reaction phases, and identification of reaction layer composition gradients and thicknesses. Magnetite formed on the surface of specimens reacted at 250°C for 4 weeks. Iron-enriched clay was also observed on specimen surfaces and in the adjacent basalt-bentonite mixture. The 100°C experiments yielded surface films of a siderite-structure phase, (Fe,Ca,Mn)CO3, that were not observed in previous experiments with synthetic ground-water. Less extensive iron enrichment of the adjacent clays compared to that seen in the 250°C experiments was observed. The siderite-structure phase generally formed when no carbonate ion was present in the initial solution, implying dissolution of impurity calcite in the bentonite as the controlling factor in the reaction. The results demonstrate the utility of combining X-ray diffraction and electron microprobe analysis for characterization of reaction phases on alloys reacted with complex geologic materials.

Interest in advanced thermoplastic composites for use in high performance structures stems from their order of magnitude improvement in fracture toughness and delamination resistance over epoxy based composites, their strong solvent resistance, and the possibility of dramatically lower fabrication costs through processing flexibility. The chemical and mechanical properties of semicrystalline thermoplastics depend on the morphology of the material, such as the crystallinity content and spherulite size. We describe here the use of x-ray diffraction to characterize the degree of crystallinity of the polyetheretherketone-graphite composite system, a leading thermoplastic candidate for use in aerospace vehicles. In reflection, diffraction from the microcrystalline graphite fibers dominates the scattered signal and must be adequately accounted for. The technique is useful on large samples and for quality control. In transmission, the graphite signal is weak, thus simplifying data analysis; however, sample thickness must be limited.

Several interesting phenomena involving ultra-soft X-rays and synthetic multilayer crystals were studied as a result of the on-going process of improving the Rigaku Mode] 3630 Wafer Analyzer for the measurement of BPSG (1000-2500 Å) and other thin films.1-3 These phenomena can be divided into four categories; “ghost” peaks, diffraction from the substrate, fluorescence from the multilayer and higher order lines from the multilayer. Each of these is a potential snurce nf error in the measurement of ultra-soft X-rays, Fortunately, as will be shown, each can be readily dealt with.

Total-reflection X-ray fluorescence spectrometry, abbreviated as TXRF, is known for its high sensitivity down to the low pg-level or sub-ppb level, respectively, and its wide dynamic range of about three to four orders of magnitude (Yoneda and Horiuchi, 1971, Wobrauschek and Aiginger, 1980; Knoth and Schwenke, 1978 and 1980, Aiginger and Wobrausohek, 1985, Michaelis et al., 1985, Prange, 1987). Meanwhile several laboratories have purchased commercially available TXRF spectrometers and have started to report favourable about this technique. Applications have been reported from various disciplines: These are estuarine and marine water quality management and research, air pollution studies, mineralogical investigations, biology and medicine (Prange, 1987, Prange et al, 1985; Prange and Kremling, 1985, Prange et al., 1987, Stöβel and Prange, 1985, Michaelis, 1986, Ketelsen and Knöchel, 1985, Leland et al., 1987, von Bohlen et al., 1987, Junge et al., 1983, Hentschke et al., 1985, Hentschke et al., 1985, Gerwinski and Goetz, 1987, von Bohlen et al., 1987), In spite of its close kinship to conventional EDXRF , TXRF is quite different with respect to operation and performance and provides complementary capabilities.

This paper describes a set of interactive computer programs written in FORTRAN IV and implemented on a POP 11/34 equipped with RLO-2 ten Mbyte discs and an RSX-11M operating system to assist in x-ray diffraction phase analysis. The packing of the data base will be described along with the various interactive programs that access it. The search/match package is designed more as a set of aids for the diffractionist rather than as a single totally automated search/match program, the procedure adapted by many of the xray diffraction (XRD) equipment manufacturers. The approach taken allows the analyst to direct the analysis procedure by utilizing different search/match programs or specifying various options within a given program.

The development of intense synchrotron radiation sources during the last twenty years has enabled several types of x-ray spectroscopy and scattering techniques to come into practical use. One of the most significant methods for the characterization of extremely dilute samples is high resolution x-ray absorption-edge spectroscopy. The technique is usually divided into two separate methods according to whether the x-ray absorption near edge structure (XANES) or the extended x-ray absorption fine structure (EXAFS) is analyzed. XANES features are due mainly to bound-state electronic transitions just below, and on the low energy side of the edge, and to multiple scattering resonances on the top of the edge and at somewhat higher energies. EXAFS features are oscillations due to ejected photoelectron back scattering interference processes in the close vicinity of the absorber atom. XANES analysis is used to determine atom valence, atom site distortion from regular geometries, and other details of the atom site. EXAFS features can be analyzed to recover interatomic distances between the absorber atom and its first few shells of neighbors, as well as the number and types of these neighbors. Together these techniques can provide an atomspecific probe of die short-range structure within almost any type of condensed matter.