A method to quantitatively analyze the surface regions of metals, alloys, and coatings using proton-excited X-ray emission (PEX) has been utilized in two areas of metallurgy research. This paper describes application of the technique to (1) the development of erosion- and corrosion-resistant coatings, and (2) the study of structural failures in turbine alloys.

The technology for the electrodeposition of erosion- and corrosionresistant TiB2 coatings from molten-salt electrolytes has been developed in order to provide protective coatings for valve components in coal gasification plants. Analyses by PEX and X-ray diffraction have played the key role in the determination of the optimum electrolysis parameters required to obtain adherent, erosion-resistant TiB2 coatings. From these studies, the erosion resistance of a TiB2 coating can be predicted on the basis of (1) the amount of Cr and Fe impurities codeposited during electrolysis and (2) the degree of orientation of the TiB2 crystal structure along the (110) or (100) planes.

PEX was used for analytical studies of a Nimonic 105 alloy turbine blade and an A-286 alloy turbine wheel from a San Diego, California, power generating station gas turbine that suffered a catastrophic failure in November 1974. Analyses of the turbine blade in the region at which the rupture occurred showed alloy composition changes that included decreases of 80%, 78%, 52%, and 50% of Al, Ti, Cr, and Co, respectively, and an increase of 2500% in Fe. Alloy composition changes were also found at the failure interface of the turbine wheel; these included decreases of 43%, 21%, and 15% in Hi, Cr, and Ti, respectively, and increases of 248% and 714% in Si and Al, respectively.

A semiconductor detector x-ray spectrometer has been constructed for the analysis of elements in air particulate specimens. The excitation radiation is provided, either directly or indirectly, using a low power (40 watts) Ag anode x-ray tube. Less than 100 ng for most of the elements in the range Mg → Zr, Pb are easily detected within two 1-minute counting intervals. A calibration technique for light element analysis and an experimental method which compensates for particle size effects will be discussed.

Monte Carlo simulation is used to determine the effects of selfabsorption for the low energy X-rays of light elements in the size range front 1 to 20 μm. Calculations are performed for a wide angle Fe-55 radioisotope-excited energy dispersive XRF system. Results are obtained for sulfur attenuation in thin layers, long cylinders, and spheres composed of various matrix materials. The enhancement effect is also treated for the transition region between thin and thick layer samples as well as in spheres of various sizes. Results are also comrpared to fixed angle analytical models.

In the case of X-ray fluorescence analysis of aerosol loaded filters, the X-ray absorption effect Is due to particulate matter absorption and to filter material absorption. The latter contribution is of a predominant importance in many practical cases. It can be calculated from the ratio of the X-ray intensities measured from the front and back side of the filters. The sandwich geometry obtained by folding the filters in two with the loaded side inwards during the measurement renders the filter material absorption correction much simpler and often more accurate, and offers distinct additional advantages.

REX is a Fortran program for analysis of spectra obtained in PIXE analysis. The underlying model is still under development; however, one year of experience has demonstrated REX's capability to be a fast reliable tool. The modeling of the different components and effects of the physical model is briefly discussed. Evidence is shown that secondary effects mostly due to Compton-scattering in and around the detector are important factors. In order to assure that heavy elements are recorded with sufficient sensitivity during short bombardment times, low energy X-rays are suppressed but not completely absorbed by use of a Mylar absorber with a hole. Such an absorber sometimes introduces severe problems for other techniques of spectrum analysis. However, to REX there is only the job to find the transmission curve of the absorber.

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 discovery of a very simple and useful relationship between the absorption coefficient of a particular element and the ratio of incoherent to coherent scattering by the sample containing the element is discussed. By measuring the absorption coefficients for a few elements in a few samples, absorption coefficients for many elements in an entire set of similar samples can be obtained.

The design and application of a newly-developed Siemens multichannel wavelength x-ray fluorescence spectrometer that has been specially adapted to the needs of the Environmental Protection Agency for rapid analysis of particulate samples is described. The system consists of sixteen fixed-wavelength spectrometers which are optimized for sixteen pre-selected elements and a computer-operated scanning channel which is used to determine additional elements that might be desired on a given sample. A minicomputer operates the instrument and custom-designed sample changer and processes the data.

Requirements for standards suitable for air pollution samples and the approaches used for the preparation of thin layer standards are discussed. Sensitivities, detection limits for elements of interest in air pollution, and the relative merits of aerosol filter types for x-ray fluorescence analysis have been determined. The system has been used to measure the elemental composition of a large number of samples from stationary source emissions, mobile sources, and ambient air.

An automatic time sequence filter sampler has been developed for atmospheric aerosol particle sampling of ambient air and subsequent analysis for elemental composition using the proton, beam of a Van de Graaff accelerator. Some features of the operation of the sampler are given, the retention of particles by the filter material are discussed, examples of the type of data obtained are presented, and some approaches to the numerical analysis of data for environmental interpretation are considered. Lines for further development and improvement in this type of sampler are indicated.

Atmospheric aerosol particles have been sampled near a Los Angeles freeway and analyzed by proton-induced X-ray emission, PIXE, as a sulfur baseline study in September 1974 before 1975-model auto mobiles, equipped with catalytic emission control devices, appeared in large numbers. The sampling plan was optimized a c cording to the requirements of X-ray analysis techniques, fluctuations in air flow across the freeway, and the time and particlesise resolution of the aerosol sampling equipment. During five selected two-hour intervals with cross wind conditions, particles were collected as a function of size by six cascade impactorsope rating simultaneously on three towers at 2 and 7 meters above road level 35 meters upwind and 35 meters downwind of the traffic lanes. Particles as a function of time were sampled continuously, for the 100-hour duration of the experiment, from the three 7-meter heights using time series streaker filter samplers with two-hour time resolution. Precise analyses of S, Cl, K, Ca, Fe, Br, and. Pb established relationships which permit estimates to be made of future increases in particulate sulfur as a consequence of increased sulfate emissions from catalytic automobiles.

Vacuum x-ray fluorescence spectrometers are used routinely in our laboratory to analyze automotive exhaust particulate emissions. However, a problem has developed in the analyses of samples collected from cars equipped with catalytic converters. The catalytic converters which were developed to decrease the carbon monoxide and unburned hydrocarbon emissions from auto exhausts, also produce sulfuric acid through the oxidation of part of the SO2 emissions. The sulfuric acid aerosol which is collected with the particulate emissions causes problems in the use of a vacuum spectrometer. If the samples are analyzed as , collected, the sulfuric acid would be pumped off the collection filters resulting in the loss of sulfur from the samples and contamination of the spectrometer. A technique was needed to fix the sulfuric acid so that it would remain on the filters. Exposure of the samples to ammonia gave the needed stability. Details of the technique in cluding standard preparation procedures are described. The results obtained with samples exposed to ammonia at various concentrations and periods of time are presented.

Energy-dispersive X-ray fluorescence might advantageously be used for the determination of trace metals in water. Suspended material can straightforwardly be collected on a 0.45 μm pore-size Nuclepore membrane by filtration. Dissolved ion analysis usually requires a physical or chemical enrichment step. Spotting a 1.5 ml water sample on a Whatman-41 filter within a 29 mm diameter hydrophobic ring and drying by a cold air stream from underneath yielded a 50 ppb sensitivity for many elements, and a 18% accuracy. Filtration of a 200 ml water sample at the natural pH through a pair of Chelest-100 chelating ion-exchange resin loaded filter papers allowed 1-5 ppb sensitivities but suffered from the combination of limited load capacity and significant uptake of usually abundant alkali earth metals.

The growing need for multielement analytical capability is currently being emphasized by the ever broadening governmental regulations on metallic pollutants in water sources. These new regulations cover more elements and are more restrictive in the type and amounts allowable in waste water and natural sources. For example, the California Public Health Law of 1970 states that 0.01 ppm arsenic, 1.0 ppm barium, 0.01 cadmium, 0.05 ppm manganese and 5.0 ppm zinc are the limiting concentrations of these elements in drinking water. Monitoring programs, both for compliance-enforcement and general survey work, have become a greater burden on both governmental agencies and private inductries. While trace analysis in solutions presents certain difficulties to the analytical chemist, regardless of the technique used, the results of this study indicate that x-ray analysis provides a more useful analytical tool for routine work and offers multielement capability with minimal sample preparation.

Particulate reference samples have been prepared for the standardization of x-ray fluorescence spectrometers used in the analysis of air particulate matter. Uniform layers of reground orchard leaves of known composition, i.e., National Bureau of Standards Standard Reference Material SRM 1571, were deposited on membrane filters and coated with a thin polymer film for protection against abrasion and moisture. These samples have been prepared with areal densities of 0.1 to 5.0 mg/cm2.

The purpose of this work was to develop accurate calibration standards which were fully characterized in terms of uniformity and concentration using fundamental measuring methods. Three similar sets of vacuum deposits were commercially made, each set containing the single deposits CuS, KCl, CaF2, Cr, Fe, Cu, RbNO3, SrF2, MoO3 , BaF2, and Pb. Thickness variations in each deposit were measured with PIXEA (proton induced x-ray excitation analysis) measurements taken at 6 to 8 positions along the deposit diameters. Relative elemental concentrations on corresponding deposits from each set were measured using multiple XRF intercomparisons. One set of deposits was destructively analyzed at the National Bureau of Standards with isotope dilution thermal ionization mass spectrometry (IDMS) in order to calibrate the remaining sets of vacuum deposits. The calibrated deposits were compared with standards from two commercial sources. For seven elements heavier than chlorine there was an average deviation of 13.5% between the calibrated deposits and the commercial standards. Disagreements as large as 15% were observed between standards from the two commercial suppliers.

X-ray fluorescence spectroscopy is being used to measure the elemental composition of fish tissues. The elemental data are then subjected to pattern recognition procedures in an attempt to discriminate fish stocks.

A quantitative x-ray fluorescence (XRF) analytical system has been developed with the emphasis on small sample size. The system employs a two kilowatt tungsten anode x-ray tube, and an 80 mm2 lithium drifted silicon x-ray detector arranged in a compact geometry. Operation at 55 kV and 20 m A give a sensitivity of 153 counts/min/ng at Z=42 (molybdenum). A computer controlled target changer makes it capable of analyzing 32 targets automatically. The sample target is rotated during irradiation, so that the average sample position is defined to 0.2 mm. Several sets of 5 to 9 calibration targets have exhibited a standard deviation of less than 1%.

Methods have been developed for autopsy tissue analysis using a proton-induced X-ray emission (PIXE) system optimized for thin sample analysis. The system uses 2 MeV protons, thus limiting sample thickness to several milligrams per square centimeter. Calibration was accomplished with standard solutions spotted onto Nuclepore filters, which were subsequently irradiated in a uniform proton flux. X-ray yields measured with a Si (Li) detector were corrected for proton energy loss in the filter matrix as well as X-ray attenuation. Corrections for proton energy loss were determined from empirical parameters relating proton energy to X-ray cross sections. Typical filter thickness and penetration of the sample solution into the filter matrix were measured allowing calculation of proton energy attenuation and X-ray absorption corrections. The method was used in routine analyses for sixteen elements in seven types of human tissue. Accuracy was evaluated with standard reference materials and atomic absorption analyses.

The proton beam from the 4 MV Van de Graaff at the University of Florida has been used in conjunction with a 5 mm thick lithium drifted silicon, Si (Li), x-ray detector to do elemental analysis of biomedical samples by proton-induced x-ray emission (PIXE). Several hundred samples, mostly autopsy organs ashed at high, temperature, have been analyzed by this method. The main object of the research is the correlation between human diseases and trace element levels. The target mass has been determined by monitoring the elastically scattered protons from the sample. This technique considerably reduces the target preparation time by eliminating careful weighings or doping of each individual sample.

The high-density and high-temperature plasma conditions required for successful laser-initiated fusion make x-ray diagnostics a valuable tool in this exciting field. Measurements of the hard x-ray bremsstrahlung continuum emitted from laser targets provide insight into the complex laser-plasma coupling physics and the subsequent electronic energy transport. X-ray techniques are important in the selection and assay of microballoon targets for current compression experiments. X-ray imaging experiments and diffraction spectroscopy of highly stripped atoms can provide information about the symmetry, density and temperature of laser targets. Extremely high temporal and spatial resolution may be required for definitive diagnostic information on compressed targets. While laser-produced plasmas are interesting as possible intense x-ray sources and as a possible means of achieving x-ray lasing, those topics are outside the scope of this review.