An Evaluation of the Rietveld Method for Modal Analysis at CANMET

"The Rietveld numerical method was used to calculate the relative abundances of phases in both synthetic binary mixtures and synthetic and natural ores, using X-ray diffraction data. The results were compared with those of image analysis and a chemical method. The ranges of the relative errors were estimated. The Rietveld method is found to be acceptable for determining the abundances of major and minor phases and the amorphous component of partially crystalline samples. In complex mixtures, where there are several trace phases (~<2 wt%) present, the technique becomes less accurate. It is most useful as an alternative technique to image analysis when sample preparation is problematic or sample particle sizes are sub-micron. It is a manual method which requires user input during the fitting process, but is both simpler and faster than image analysis due to the reduced set up time and sample preparation required. It is now implemented at CANMET as a technique for quantitative analysis.INTRODUCTIONUntil recently, the Applied Mineralogy group at CANMET used only image analysis and chemical techniques to determine phase quantities. An effort to develop quantitative X-ray diffraction (XRD) has been on-going for several years. Initially, the reference intensity ratio (RIR) method with external standards was tried with some success (Szymanski and Petruk, 1989). The main difficulty with this technique was finding adequate standard material for each phase present in the sample. This shortcoming made the method ultimately impractical, given the wide variety of materials which come to the laboratory for analysis.The Rietveld refinement method of quantitative XRD (Hill et al 1993, Mumme et al 1996), in contrast, requires no standards and requires minimal sample preparation and therefore a more rapid turnaround compared to image analysis. The Rietveld method also has advantages over image analysis in that it can identify and quantify polymorphs, ultra fine materials and many types of hydroxide products. As well, it is useful for analyzing materials such as bauxite or talc, which do not polish well enough for making mounts of the quality required for image analysis. To quantify amorphous material and phases which are present in amounts below the detection limit of XRD, the addition of a standard material is still required. However, in such cases only one standard is needed, which is alumina."