A standard test method for the determination of RIR values by x-ray diffraction

Abstract

The measurement of x-ray diffraction line intensities is the basis for quantitative phase analysis (see for example, Chung (1974), Davis (1986), and Hubbard and Snyder (1988)). While there are many sources of error in such measurements, in recent years computer automation of powder diffractometers and associated analytical software has made such measurements more practical and accurate. For example, profile fitting software has made it possible to determine integrated peak areas and to deconvolute overlapping lines. Another problem which affects quantitative analysis is the systematic error in instrument sensitivity as a function of 20 diffraction angle. This effect has been partially responsible for poor reproducibility of relative intensities between laboratories (Schreiner and Kimmel (1987), and Jenkins and Schreiner (1989)). But, because the error is systematic, corrections may be made by using a standard such as the National Institute of Standards and Technology SRM 1976 alumina plate (NIST 1991). These and other advances have led to a renewed interest in the determination of I/Ic (also called RIR - Reference Intensity Ratio) values for crystalline substances (e.g., Snyder (1992)). I/Ic is defined as the ratio of the intensity of the strongest line of an analyte to the corundum (113) line when the analyte is mixed 50:50 by weight with corundum. We present here a standard procedure used in our laboratory to experimentally measure I/Ic values, and which explicitly incorporates profile fitting and instrument sensitivity corrections. The procedure is written in the format of an ASTM (American Society for Testing and Materials) standard test method, however, inter-laboratory round robin tests have not been carried out to determine precision and bias associated with the method. While the method calls for corundum as the internal standard, another standard material, s, may be used, in which case the procedure will result in a ratio I/Is. Hubbard and Snyder (1988) have shown how to convert between I/Is and I/Ic. This method is based on the procedure routinely published in NBS Monograph 25 until 1986. It is augmented with corrections for the angularly dependent instrument sensitivity and with calculations of I/Ic for both variable and fixed divergence slit configurations. A Quattro Pro spreadsheet is used in our laboratory to do the calculations. An example of the spreadsheet is given in the appendix for one of two I/Ic runs of MgCO3. We also utilize the corundum in the I/Ic runs as an internal standard to determine displacement error corrections for preparation of digitized patterns of pure analyte phases. These patterns are submitted to the International Centre for Diffraction Data for inclusion in a whole pattern data file planned for some time in the future. The notation used here is the standard notation developed for the RIR method by Hubbard and Snyder (1988) and systematically extended by Snyder (1992). A table of the notation is given in the Terminology section below.