This report will describe scientific activity in XRF as well as some practical application topics for Japan and China.

Two strategies are at present commonly used in studying and refining crystal structures from powder diffraction data: the total pattern refinement proposed by Rietveid (1969) and the two-step method originally proposed and applied by Will (Will et al., 1965). The latter one works by separating-the intensity determination of the individual peaks from the actual structure refinement, structure analysis or any structural calculation (tor example based on line broadening). Both methods have their merits, and their drawbacks.

Elastic constants as a function of crystallographic direction have been measured in polycrystalline alloy samples of 17-4PH stainless steel, Ni-Cr-Fe, and Ti-6%AI-4%V using a neutron diffraction technique. The results compare best with the constant stress model of Reuss. It is demonstrated that measurements of stress can be made sampling the bulk of the material using neutrons with an accuracy comparable to more conventional x-ray methods.

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.

Gold wires were vaporized by the exploding-wire phenomenon using a 20 μF capacitor bank charged to voltages up to 14 kV. The resulting condensate, an aerosol or metallic smoke, was collected on membrane filters and subjected to X-ray analysis to determine lattice constant, crystallite size, and behavior with isothermal annealing. Wire explosions were conducted in au ambient atmosphere of ait or nitrogen at barometric pressure. It is estimated that the quench rate for this material is of the order of 108 deg/sec from the melting point although no substrate is involved and it is expected that any effects of epitaxial origin on the structure would be minimized.

Before annealing, diffractograms showed broad peaks apparently shifted to the high-angle side. Line breadth may be attributed primarily to particle size broadening, since ft correlates well with size determined by electron microscopy, (β cos θ) is linear with θ, and [(β cos θ)/λ] is approximately constant for three radiations used. Crystallite size is of the order of 400 Å and is observed to decrease roughly with increasing voltage used for vaporization. The observed lattice decrement, approximately 0.2%, generally increases with voltage used for vaporization, and apparently correlates rather well with the inverse of sise as has been reported in some work on thin gold films. However, studies of colloidal gold particles do not show significant lattice shifts, although the particle size is less than 100 Å so that the decrements observed may be due to factors other than size alone. For this black, particulate material, some lattice decrement apparently persists even after protracted isothermal annealing below the melting point. Crystallite size increases with annealing but remains below about 1000 Å. Results suggest that the lattice decrements observed in condensed gold vapor are due to surface tension effects and the presence of vacancy aggregates.

The complex relationships among composition, roartensite start and finish temperatures, morphology of the martensite, residual stress distribution, and quenching conditions produce significant microstructural changes through a carburized case. Variations in the amount of retained austenite, the diffracting-particle size, and hardness were measured every 50μm in depth through a one percent carbon case on AISI-SAE 4320 steel. Measurement were made to a total depth of 2 mm. The percent retained austenite decreases from a maximum of 26% near the surface to a few percent in the bulk. It is shown that the x-ray diffracting-particle size of the martenaite phase is a structure parameter that changes when the martensite morphology goes from plate to lath type. The austenite phase diffracting-particle size is controlled hy the deformatioxis induced by the martensite formation.

Characteristic x rays have been produced for a variety of samples by bombardment with protons in the energy range from 75 keV to 5 MeV. The experiments were performed with two accelerators. For the low-energy studies (less than 150 keV), a Cockcroft-Walton accelerator was used. The higher-energy studies were done with a 5 MV Van de Graaff. The x rays were measured with high-resolution Si(Li) and Ge(Li) detectors. Yields for the cross section of characteristic K- and L-shell ionizations were measured for titanium, vanadium, chromium, manganeses iron, cobalt, nickel, copper, silver, gold, bismuth, and uranium. The experimental cross-sections have been compared to the theoretical predictions of the Born approximation for an interaction of this type.

Trace element analysis by 4-MeV proton bombardment of samples in the 10-12 gm range has also been performed. Some comments with regard to analysis with these sensitivities will be made.

A new method for the collection and analysis of high temperature Guinier x-ray data has been devised at The Dow Chemical Co. This technique can be used to monitor various types of structural transformation and thermal expansions up to 900°C. The thermal expansions of α-Al2O3 and two TiO2 structures, anatase and rutile, have been characterized for their use as high temperature internal standards.

A PDF 15/40 computer wich ADC and CAMAC interfaces is used to control data collection apparatus, acquire data, and reduce data to determine the elemental composition of aerosol samples. The background is subtracted from each energy spectrum, peak centers are located automatically using a Gaussian correlation technique, peak multiplets are resolved with Gaussian fits, peak energies are compared with entries in a table of x-ray lines for possible identification, multiple identification of peaks and line interferences are resolved, and the elemental amounts are determined from the areas of the Gaussian fits.

The analysis of dry powder samples for magnesium, sodium, and fluorine by X-ray and electron excitation has been studied. As in the case of heavier elements, the form of chemical combination influences the elemental sensitivity; sensitivity changes due to self-absorption can be adequately predicted using published absorption coefficients. Where both absorption and enhancement effects are possible, selection of X-ray target or excitation potential can. eliminate the enhancement problem. Matrix effects were found to be extremely variable and unpredictable. Finally, X-ray and electron excitation results are compared for the three elements in a series of geological samples. Efficiency of excitation was far better for electron excitation, but limits of detectability were lower for X-ray excitation due to significantly lower backgrounds.

A procedure and program are described for rapid, economical and simple production of fully quantitative, multi-element analyses from energy dispersive microprobe data. Methods are outlined for background shaping and scaling, comprehensive overlap correction, and adjustment for instrumental drift. Program facilities include the output of all coefficients required, built-in standard data, the option to use default standards when no working standards have been measured, and the ability to respecify standards during data processing.

The total soft x-ray emission of an electron-bombarded surface exhibits abrupt changes at the threshold potentials for the excitation of core levels of surface atoms. These features represent the excitation probabilities of the core states superimposed on a smoothly increasing background and can be sensitively detected by differentiating the x-ray emission with respect to sample potential. The application of this technique to the study of surface composition, chemical shifts, and band structure is discussed.

Magnesium has been shown to have a marked effect upon preprecipitation processes occurring in aluminum-13 wt.% zinc alloys containing 0.025, 0.098, 0.17, 0.19, 0.23, and 0.27 wt.% magnesium. X-ray small-angle scattering and resistance measurements have been used to monitor the rate of growth of Guinier-Preston zones in quenched foils and wires. The following results have been obtained: (a) small additions of magnesium noticeably decrease the rate of growth of G-P zones but the final zone size reached in the magnesium containing alloys is generally larger than in Al-Zn alloys quenched and aged under identical conditions; (b) the general pattern of preprecipitation found in Al-Zn alloys is not seriously changed by these small additions of magnesium; (c) the dependence of the rate of preprecipitation on quenching temperature is shown to be a function of magnesium content and aging temperature; (d) the dependence of the rate of preprecipitation on aging temperature is influenced by the range of aging temperature, magnesium content, and the quenching temperature.

The total reflection x-ray fluorescence (TXRF) method of analyzing elemental contents Is based on the small angle irradiation of thin samples placed on a total reflecting backing with a narrow photon beam. Two instrumental problems are to be solved here. The first is to form the narrow beam with a small angular deviation. The usual way to solve this problem is to use collimators with small solid angles. These angles must be less than the critical angle for x-ray total reflection, which, in the energy range 10 - 20 keV has an order of magnitude around 10−3 rad.

A series of nanostructured Fe/Ag metal films were produced at various substrate temperatures to determine their magnetic characteristics. The magnetic coercivity was found to increase with the diffracting-particle size which is process controlled. The films produced at low substrate temperature (<200°C) consisted of small metallic clusters of Ag (<100 Å). As the substrate temperature was increased, the films exhibited increased crystallinity and larger diffracting-particle size. The position of the maximum in the particlesize distribution function and the width of the function increased with substrate temperature.

The electron probe microanalyzer has found numerous applications in physical metallurgy. Some recent problems which have been studied with the microanalyzer constructed by the author at the California Institute of Technology include (1) determination of the penetration of chromium in chromized iron, (2) determinations of the concentration of nickel in taenite bands occurring in a fragment of meteorite from Canyon Diablo, (3) identification of intermediate phases in the as-cast structure of an alloy of titanium and copper, (4) identification of phases in the titanium—silver binary system, (5) determination of concentration fluctuations in a gold—copper alloy resulting from slow solidification, and (6) determination of the diffusion profile of nickel in single crystal sapphire.

The amphibole mineral, cummingtonite-grunerite, has been used as a tracer for taconite tailings discharged into Western Lake Superior. The discovery of many asbestiform amphibole fibers in the tailings and Western Lake Superior water lead to concern over fiber concentrations in municipal water supplies using this water. This concern was based on the association between human asbestos exposure and increased rates of cancer of the gastrointestinal tract and peritoneum. An x-ray diffraction external standard technique has been developed for rapid, inexpensive, semi-quantitative determinations of amphibole mass concentration in water. The average amphibole mass concentrations for different Western Lake Superior water intakes compare very well with the average electron microscope fiber counts for the same samples. Daily amphibole analysis of the Duluth water supply indicates an average amphibole concentration of 0.19 milligrams per liter.

Chemical analysis of geological materials such as nickel ores has been accomplished by atomic absorption (1,3) x-ray fluorescence (11,14) and conventional wet methods (10). Procedures utilizing these techniques are capable of producing excellent results but are often difficult and time consuming.

Minerals often present serious problems in chemical analysis by wet methods. X-ray analysis can therefore offer the analyst considerable savings in time providing the obstacles which exist are understood and minimized or eliminated. The most serious problems to solve are absorption and enhancement effects, mineralogical differences among samples, sample preparation, and particle size effects which often influence the intensities of the analytical lines. In addition, the element of interest may be of low concentration in a variable and unknown matrix.

Measurements on the heat affected zone of a weldment are presented using a gas filled position sensitive detector and a normal diffractometer equipped with a scintillation detector and a solid state detector. The sample, a surface ground titanium alloy, provided a difficult application for the X-ray technique from which a test of the real usefulness of the position sensitive detector could be made. The diffraction profile from the Ti alloy is very broad and the fluorescence produces a high background. The fluorescence is easily rejected using a solid state detector; however, the time of analysis is very long. With the position sensitive detector, the combination of increased energy discrimination over the scintillation detector and the simultaneous measurement of many data points over the broad peak enabled the measurements to be made for the same accuracy in much shorter times than for either the solid state detector or the scintillation detector.

Basic processing steps utilized in the fabrication of planar silicon devices include (a) substrate preparation, (b) epitaxial deposition, (c) thermal gvowth of silicon dioxide over the entire silicon wafer surface, (d) device pattern formation by photoetching techniques, and (e) diffusion of n-type or p-type elements through the holes to produce localized regions of desired conductivity, A detailed study of the various diffraction phenomena associated with such structures is presented. X-ray topographs of planar transistors show distinct contrast features such as excess diffraction intensity along the silicon oxide/silicon boundary and/or excess diffraction intensity inside the device area. The diffraction phenomena are discussed in terms of reversible elastic deformations, frozen-in lattice deformations, strain fields and imperfections generated by the various processing steps. A technique is presented to measure the sign of the elastic deformations. The phenomenon of stressjumping across semiconductors interfaces is described, and finally the implications of stress-strain relations on junction performance are stated.