An X-ray small-angle scattering instrument is described which is used for recording X-ray diffraction patterns or small-angle X-ray scattering curves in an angular region very close to the direct beam. The measurement of X-ray intensity is accomplished with standard geiger or scintillation counter techniques. The instrument is designed for use with a spot-focus or vertical-line X-ray source, In essence, it is a multiple-reflection double-crystal diffractometer, based on a concept developed by Bonse and Hart, employing two grooved perfect germanium crystals arranged in the parallel position. Multiple diffraction from these crystals produces a monochromated X-ray beam which can be several millimeters wide while still exhibiting extremely high angular resolution. As a result, effective sample volumes can be employed with maximum volume-to-thickness ratios. The principal features of the instrument are discussed with emphasis on the advantages of this device over those employing complex slit systems and film-re cording techniques, Data are presented to illustrate the operation, intensity, and resolution of the unit.

Three variables in the identification of crystalline multiphase unknowns by computer search/match methods were examined: presence or absence of chemical information; varying quality of d-I diffraction data; use of a large data base vs a data base having about 10% as many entries--both contain the unknown phases. The results showed that the search/match using average quality d-I data with chemical information was quite successful, while that obtained using higher quality d-I data alone missed one of four phases. It took only half the time to obtain the average d-I data plus chemistry as it did to obtain the higher quality data. Searching the smaller data base with the higher quality data alone resulted in an identification of all phases with high reliability.

To assure an adequate supply of such critical metals as nickel and chromium, extraction procedures must be developed to process low grade domestic sources. In optimizing these procedures it is essential to use suitable analytical procedures to characterize the materials, identify phase transformations, and determine metal and mineral association of the critical metallic elements through all stages of the process. Evaluation of complex sources such as laterites requires special material handling techniques coupled with X-ray diffraction and with optical and SEM analyses of many individual particles. A joint study by the Bureau of Mines and the Denver Research Institute using these procedures has resulted in optimizing a new modification of an extraction process.

On-stream X-ray fluorescence analyzers have been available for about 20 years. They have been used with great success and they have made an effective process control possible in many concentrators. They have, however, one severe drawback. Normally the sample that ought to be measured is in slurry form and it would be difficult and expensive to prepare it into more conventional form used in ordinary laboratory practice. The main constituent of slurry is water and normally some kind of plastic film is needed to keep slurry apart from the measuring system at least when the slurry system is malfunctioning. Already these two things are sufficient to set a limit to the lightest element that can be measured with reasonable accuracy and precision. This means that minerals that contain only such low atomic number elements as e.g. Mg, Al, Si and P remain out of reach. Difficulties arise also in cases where the interesting element is not only in the solid material but also in the solution part of the slurry. In great many cases the interesting element occurs in several minerals at the same time which causes certain problems with the accuracy. Fortunately this problem does not set such a basic limitation as a too low Z does unless only one of these minerals is of interest, which may make the whole method worthless.

A review of the basic physical principles of the gas proportional scintillation counter is presented. Its performance is discussed and compared with that of other room-temperature detectors in regard to applications to portable instruments for energy-dispersive X-ray fluorescence analysis. It is concluded that the gas proportional scintillation counter is definitely superior to all other room-temperature detectors, except the mercuric iodide (HgI2) detector. For large areas or soft X-rays it is also superior to the HgI2 detector.

Total Reflection X-Ray Fluorescence Analysis (TXRF) has become a powerful analytical tool for trace element analysis. Because of its advantages in excitation and background reduction TXRF has been applied for the analysis of light elements (C,O,F,Na,...). A special Ge(HP) detector offering an ultra thin window in combination with a spectrometer specially designed for the requirements of light element analysis was used. Also a new windowless X-ray tube for efficient excitation of the light elements was tested. The system was checked with standard aqueous solutions; detection limits in the ng range (7 ng for O) are obtained.

Previous work on modification of the collagen lattice, presented at these meetings, has served to confirm the Ramachandran proposal for the structure of this important protein, together with information on the lengths and tensile strengths of these bonds, including hydrogen bonds, hydrophobe bonds, and Vander Waals attractions. Rat tail tendons were suspended in 2 M aqueous solutions of dimethylsulfoxide, acetone, trimethylamineoxide and 1,4-cyclohexanedione, all of which showed evidence of ligation by expansion of the collagen lattice and refinement of the 100 spot in the x-ray diffraction pattern run by rotation on the collagen fiber axis. In the case of trimethylamineoxide and cyclohexanedione, oriented crystallization also occurred, with the long direction of the molecule in the plane perpendicular to the fiber axis of collagen. With the monofunctional ligands, the -C=0 group forms a hydrogen bond to the N-H group in the Ramachandran standard revised model, leaving the methyl groups to form the hydrophobe bond.

The primary X-ray analyzer is used for nondestructive spectrochemical analysis of solid specimens. Accelerated electron beams bombard the specimen surface directly and generate primary X-rays which are measured in a vacuum spectrometer. The method of primary X-ray spectroscopy is superior to the fluorescence X-ray spectroscopy because (1) detectable sensitivity for such light elements as magnesium and aluminum is very high, and (2) the correction of the measured value for self-absorption of X-rays by the specimen itself is low. The performance of the instrument and applications are reported.

We have developed an algorithm for calculating the x-ray tube continuum based on the eqidistribution proposed by Love and Scott, extended the description of white and characteristic radiation given by Wiederschwinger et al for the energy range 10 to 50 keV to the low energy range from 5 to 30 keV, and compared the results from this algorithm to those responses obtained from algorithms using the absorption correction of Pochou and Pichoir, Philibert, Sewell and Pella. The comparison to other models showed a significandy better performance by our model.

Techniques of determining spot size and sensitivity of the instrument will be developed. Spot sizes of the order of 5 microns have been obtained with the possibility remaining for improvement- Preliminary sensitivity measurements indicate that micro-microgram quantities of some elements are sufficient to be detected. Difficulties involved in finding desired target areas will be discussed. The inhomogeneities of standard samples used for conventional fluorescense X-ray quantitative analyses precludes their use for microemission techniques at least in some cases. Possible ways of determining homogeneity will be discussed. Analysis which can be performed to advantage may be classed into several categories.

• 1. The changes in composition occurring in grain boundaries can be detected and compared with the base material.

• 2. An inclusion, in a metallic material can be brought under the electron probe and analyzed independently of the base material.

• 3. Changes in composition across a boundary between solid phases can be measured.

• 4. Diffusion coefficients between solid phases may be determined.

• 5. Thickness of thin films and variations in film thickness can be measured.

Examples of the instrument's performance will be given in some of these categories.

Analysis of sample composition and/or thickness in a routine, process-control or monitoring environment generally requires rapid turn-around time with minimal sample handling. X-ray Fluorescence (XRF) is well-suited for these kinds of analyses and has been applied to various bulk and thin sample applications (1-7). This technique is rapid, precise, non-destructive, and requires minimal sample handling.

X-ray Fluorescence is generally considered a secondary analysis technique, that is, instrumentation must be calibrated using known standards before unknown samples may be analyzed (quantitative analysis). Continuing work on standardless approaches, particularly for Energy-Dispersive XRF (EOXRF) systems, relax this requirement for some samples but the large share of XRF analyses still require calibration with standards. A number of mathematical and non-matheraatical techniques have been devised to calibrate XRF measurements for many different sample types (1,2,8,9).

A commercial powder diffractometer linked to an IBM 1800 time sharing computer is used for the precision determination of lattice parameters on single crystals with Bond's method of measuring the angle between two diffracting positions of the crystal, symmetric to the incident x—ray beam. A remote x-ray tube and collimator allows a high angle Bragg reflection to be measured easily in these two positions with only one detector. After scanning the two diffraction line profiles, the peak positions and the lattice parameter are determined on line by the computer. Several methods for determining the peak position are discussed. Using these techniques, the lattice parameter of silicon has been determined on two crystals of high purity and perfection to a0 = 5.43093 ± 0.00002 Å and a0 = 5.43095 ± 0.00002 Å at 25°C. These values are in excellent agreement with Bond's result, a0 = 5.430935 ± 0.000019 Å, and they differ slightly from the value a0 = 5.43074 ± 0.00017 Å, the mean value of, lattice parameters measured on silicon powder in 16 laboratories under the I.U.Cr. precision lattice parameter project.

A versatile double-crystal X-ray spectrometer has been developed for the precise measurement of X-ray diffraction line widths to tenths of seconds. The device can be employed in either the parallel or antiparallel arrangement for rocking curve studies and can also be used in anomalous X-ray transmission experiments with nearly perfect crystals.

A detailed description of the instrument is given as well as some results concerning the Darwin theory of X-ray diffraction line widths and Borrmann effects.

An active recording x-ray crystal spectrometer for extended x-ray absorption fine structure (EXAFS) has been built using a position sensitive detector of the self scanning photodiode array (SSPA) type. The SSPA detector has energy and position sensitivity for x-rays. The spectrometer was applied to the measurement for EXAFS of the several compounds in foil, powder and liquid states. The spectra can be obtained rapidly, and compare very well with other methods. We found that the SSPA detector is very useful for the measurement of EXAFS.

The properties of particle-induced X-ray emission, PIXE, and secondary target mode X-ray fluorescence, XRF, applied to the analysis of unprepared drill cores in open air have been evaluated. Typical detection limits for elements heavier than Mg have been determined for a PIXE-system with an external 2.55 MeV proton beam and for an XRF-system with Ti, Mo and Tb secondary targets. These two systems were found to have similar detection limits for most elements in a typical geological sample. The heterogeneous composition of drill cores prevents the performance of accurate matrix corrections, though calculations using fundamental parameters show that in the PIXE analysis of elements heavier than Ca, these corrections are much less sensitive to variations in the matrix composition than in the XRF analysis.

Primary beam transmission filters in energy dispersive X-ray fluorescence (EDXRF) analysis are used to shape the spectral output of the X-ray tube. The effective use of these filters allows the optimization of excitation conditions for each different analysis. Filters are used in two basic ways in EDXRF; either as edge filters or as white filters. The proper choice of filter and excitation conditions optimizes the analysis of a particular element or spectral region by shaping the primary radiation to reduce background and to maximize excitation.

X-ray fluorescence excited by a monochromatic collimated Mo-Kα beam at grazing incidence is measured as a function of the angle of incidence. Monochromatic excitation guarantees a well-defined penetration depth and enables a simple analytical description of the fluorescence intensity. This method is applied to a system of thin Cu and Ti metallization layers on a Si wafer and to As dopant concentration profiles in Si wafers.Thereby, the effect of annealing can be analyzed non-destructively.

Basic lead azides are obtained by the slow thermal decomposition of PbN6 at temperatures up to 200°C in oxygen, argon, and air containing varying amounts of moisture. The decomposition diagrams show several stages due to the formation of different phases, two of which have been separated. One phase can be identified as a tetragonal deformed cubic lattice. Further slow decompositions of the basic lead azide at 250°C lead to tetragonal lead oxide. The structure of the other isolated phase Is of lower symmetry and has not yet been classified. The results of this investigation are also compared with the work of previous investigators.

A prototype Environmental Monitoring Device (EMD) has been developed as a simple means for inexpensive, routine determination of site severities. The EMD is a cartridge that can be connected to an inexpensive pumping unit to collect an atmospheric sample. The field procedures are extremely simple and have been done routinely by individuals with no chemical training. Four filters within the cartridge selectively react with and permanently trap pollutants from the air drawn through the cartridge. The first filter collects particulates. The second is o-tolidine impregnated Whatman #41 filter paper to collect gaseous chlorine species. Silver nitrate impregnated paper collects reactive sulfur gases, and the fourth filter paper is impregnated with sodium hydroxide to react with and collect sulfur dioxide. After atmospheric sampling, the cartridges are returned via mail to a central analytical lab. Procedures have been developed for easy and rapid determination of the quantities of pollutants on the filters by energy dispersive X-ray fluorescence. Laboratory and field measurements from a number of locations within the IBM Corporation have been made and will be reported. The EMD approach is providing a large data base on indoor atmospheric pollutants that could affect electronic equipment. The approach could easily be extended to numerous other applications.

The diffractometer employs dual fixed detectors and a moving, vertically mounted X-ray tube. Lattice strain is measured in two specimen directions simultaneously. The drive has three concentric shafts; the outer driven by a cone drive worm and gear; a middle fixed shaft supporting the detectors and an inner shaft geared in a 1:2 ratio carrying the specimen mount. Scanning angles are measured to an accuracy of ±0.001°. A large range of specimen sizes can be accommodated.