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Problems and Solutions in Quantitative Analysis of Complex Mixtures by X-Ray Powder Diffraction

Published online by Cambridge University Press:  06 March 2019

David L. Bish  and
Steve J. Chipera
David L. Bish
Affiliation:
Earth & Space Sciences Division, M.S. D469 Los Alamos National Laboratory Los Alamos, NM 87545
Steve J. Chipera
Affiliation:
Earth & Space Sciences Division, M.S. D469 Los Alamos National Laboratory Los Alamos, NM 87545
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Abstract

In spite of the wide availability of automated diffractometers and advanced data reduction software, numerous traditional problems still exist that make highly precise and accurate quantitative analyses of complex mixtures difficult. The problems include particle statistics, primary extinction, microabsorption, preferred orientation, overlapping and broad reflections, variation in standard data with composition, availability of pure standards, and detection of amorphous and trace phases. Our analyses of rocks use the matrix flushing method on < 5μm particle-size material mixed with a 1.0-μm corundum internal standard to minimize the first four effects. Integrated intensities are used, and we employ several peaks from each phase whenever possible. We overcame overlap problems through iterative calculations using integral, multiple peaks or with profile refinement. Use of observed and calculated diffraction patterns for every phase enables us to predict the effects of composition and preferred orientation on RIRs. This allows us to correct for these effects if reference intensity ratios (RIRs) are known as a function of composition and orientation. Detection of amorphous phases is a significant problem, and standard mixtures reveal that amounts of amorphous components below 30% are difficult to detect. The poor detection limit and the nature of the diffraction band from amorphous phases make internal standard or spiking methods the best approach for analyzing samples containing amorphous materials. The Rietveld method of quantitative analysis has the potential to minimize all of the above problems. This method requires a knowledge of the crystal structures of all component crystalline phases, but no calibration data are necessary, structural and cell parameters can be varied during the refinement process, so that compositional effects can be accommodated and precise cell parameters can be obtained for every phase. Since this method fits the entire diffraction pattern and explicitly uses all reflections from every phase, complex, overlapped patterns can be easily analysed. In addition, this method presents the opportunity to correct for preferred orientation and microabsorption during data analysis.

Type
IV. Quantitative and Qualitative XRD Phase Analysis
Information
Advances in X-Ray Analysis , Volume 31: Thirty-Sixth Annual Conference on Applications of X-ray Analysis, August 3-7, 1987 , 1987 , pp. 295 - 308
Copyright
Copyright © International Centre for Diffraction Data 1987

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