Quantitative phase analysis

The powder XRD analysis of the components present in a mixture was one of the first applications carried out with this methodology. In fact, in 1919, Hull was the first to apply the XRD methodology in chemical analysis [43], However, Klug and Alexander [36] gave a big impetus to the development of the XRD phase analysis method. 

The absorption factor for a sample in the form of a plate located in the sample holder of a Bragg-Brentano geometry powder diffractometer is given by [4] 

from Equation 4.2, the integrated intensity of the ith peak in the XRD profile of the mixture is calculated by the addition of all the contributions to this peak from all the phases present in the mixture [30,31,38-40] 

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In the simplest case, this system can be solved using the method of multilinear regression [30,31,40], In some cases, it is necessary to experimentally determine p the mass absorption coefficient of the mixture [39,40], To carry out this procedure, a monochromatic CuKa radiation was used, and with the help of the following equation [39,40] 

When the nature of the material s crystalhne phases is known, the volume of each of the phases present can be determined. We saw in Chapter 1 that the integrated intensity of each peak in a given phase is directly proportional to the volume of the phase. Therefore, quantitative phase analysis is performed from the very precise measurement of these integrated intensities. Quantitative phase analysis should not be confused, of course, with the quantitative chemical analysis which is used to determine the amount of each element present in a sample. The first quantitative phase analysis by X-ray diffraction was conducted in 1925 on a ceramic material, in order to determine the amount of mullite in burned clays [NAV 25]. Despite the fact that this type of quantitative measurement has existed for 80 years, these analyses remain very difficult to conduct [BIS 89, TOR 99a, TOR 99b] and require experimental precautions which we will now discuss. However, we should point out that X-ray diffraction is virtually the only method available for quantitative phase analysis.  

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Quantitative Phase Analysis. Once the identity of the components in a sample are known, it is possible to determine the quantitative composition of the sample. There are several different methods for doing a quantitative analysis, but the most rehable method is to use mixtures of known composition as standards. The computer can determine quantitatively the relative amounts of each component in the unknown sample. For accurate calculations of relative amounts in the unknown sample, it is necessary that the sample and standards have uniform distributions of crystaUites. Often the sample and standards are rotated during data collection to provide a more even distribution of crystaUites which diffract. 

Quantitative Phase Analysis by Rietveld Refinement. The quantitative analysis can be performed through the Rietveld method because the number of the elemental cells of each phase is NccKV, where K and are the refined scale factor and the cell volumes, respectively. So, the weight fraction of the /th phase is given by ... 

The use of Equation (22) is very general, but it is also possible, with accurate measurements and data treatment, to perform the quantitative phase analysis in semi-crystalline materials without using any internal standard. This procedure is possible only if the chemical compositions of all the phases, including the amorphous one, are known. If the composition of the amorphous phase is unknown, the quantitative analysis without using any internal standard can still be used provided that the chemical composition of the whole sample is available [51]. This approach, until now, has been developed only for the XRD with Bragg-Brentano geometry that is one of the most diffused techniques in powder diffraction laboratories. 

This procedure allows quantitative phase analysis without using any internal standard, but it requires the knowledge of the composition of the sample and a careful treatment of the experimental data, which have to be corrected for the air scattering. 

Quantitative ir spectroscopy, 74 239 Quantitative phase analysis diffractometers in, 26 428 Quantitative Structure-Activity... 

Peplinski B, Schultze D, Wenzel J (2001) Interlaboratory comparison (round robin) on the application of the Rietveld method to quantitative phase analysis by X-ray and neutron diffraction. In Delhez R, Mittemeijer EJ (eds) Proc 7th European powder diffraction conference (EPDIC-7), Barcelona, Spain, 20th 23rd May 2000, Trans Tech Publications Ltd, Switzerland, p 124... 

Toraya H, Tsusaka S. 1995. Quantitative phase analysis using the whole-powder-pattem decomposition method. I. Solution from knowledge of chemical compositions. J. Appl. Cryst. 28 392-399. 

A simple example of the use of XRD for quantitative phase analysis is as follows the phase composition of a perovskite was determined using the obtained XRD diffraction pattern. The x-ray diffractograms were obtained in a Siemens D5000 x-ray diffractometer, in a vertical setup 0-20 geometry in the range 15° < 20 < 75°, with a Cu Ka radiation source, Ni filter, and graphite monochromator [32],... 

C. Suryanarayanaand M. G. Norton, X-Ray Diffraction, A. Practical Approach , Plemnn Press, New York, 1998, An excellent elementary introduction to powdermethods with worked examples and exercises that allow the reader to work through determination of unit cell dimensions, crystalhte size, strain and quantitative phase analysis. Highly recommended for the novice. 

L. S. Zevin and G. Kimmel, in Quantitative X-Ray Diffractometry , ed. I. Mureinik, Springer, New York, 1995, More mathematical in nature with rigorous treatment of quantitative phase analysis. Contains a chapter on industrial apphcations. 

Quantitative phase analysis is used to determine the concentration of various phases that are present in a mixture after the identity of every phase has been established. Overall, the task may be quite complicated since several critical requirements and conditions should be met in order to achieve satisfactory accuracy of the analysis. 

In addition to instrumental factors, specimen preparation and properties introduce several key features that may have a detrimental influence on the accuracy of quantitative phase analysis. Sample-related factors cannot be avoided completely, but their effects should be minimized as much as possible and/or accounted for in all calculations. The main problems in quantitative analysis, borne by the nature and form of the employed sample are as follows ... 

Internal standard method is likely the most commonly used approach in a quantitative phase analysis. It is based on the following relationship ... 

On the other hand, measurement of peak intensities is not simply measurement of peak heights. First, the background should be extracted from the peaks. Second, the integrated intensity should be measured for quantitative analysis. It means that the total area under a peak should be measured. Three basic types of peaks are encountered when attempting quantitative phase analysis (Figure 2.26) ... 

The successful testing of DDM method for structure refinement purposes allows us to predict its applicability in other fields of powder diffraction, such as the analysis of microstructure and quantitative phase analysis (QPA). Trial runs of DDM for the XRD data supplied by the International Union of Crystallography Commission on Powder Diffraction for the Size-Strain and QPA round-robins gave encouraging results. Respective examples are included in the DDM program package. In particular, the biases in the phase contents determined by DDM refinement for the QPA round-robin samples from the weighted amounts were less than 1 wt.%. 

The residual difference after a successful DDM refinement or/and decomposition can be considered as a scattering component of the powder pattern free of Bragg diffraction. The separation of this component would facilitate the analysis of the amorphous fraction of the sample, the radial distribution function of the non-crystalline scatterers, the thermal diffuse scattering properties and other non-Bragg features of powder patterns. The background-independent profile treatment can be especially desirable in quantitative phase analysis when amorphous admixtures must be accounted for. Further extensions of DDM may involve Bayesian probability theory, which has been utilized efficiently in background estimation procedures and Rietveld refinement in the presence of impurities.DDM will also be useful at the initial steps of powder diffraction structure determination when the structure model is absent and the background line cannot be determined correctly. The direct space search methods of structure solution, in particular, may efficiently utilize DDM. 

This chapter focuses on the application of quantitative phase analysis (QPA) techniques for the extraction of phase abundance from diffraction data. Rather than repeat the extensive coverage of the QPA methodology covered in other texts, the focus will be on the basis and application of the most commonly used techniques. These were identified from participant responses to the recent round robin on QPA sponsored by the International Union of Crystallography (lUCr) Commission on Powder Diffraction (CPD). By far the greatest number of participants in that study used whole pattern (Rietveld based) methods but there are still several users of traditional single peak based methods and there are still many applications for which these methods suffice. Issues in the measurement of precision and accuracy will also be discussed. 

For quantitative phase analysis, the expression in the first square bracket of Equation (1) can be reduced to a constant for a particular experimental set-up while the expression in the second square bracket is a constant for reflection hkl for phase a. Therefore, the intensity, 7, of a reflection (or group of reflections), i, can be reduced to ... 

For quantitative phase analysis it is generally accepted that the peak intensities need to be measured to an accuracy of about 1 — 2% relative. The ability to achieve this is strongly influenced by the size of the crystallites in the sample reproducible diffraction intensities require a small crystallite size to ensure that there is uniform intensity around the Debye-Scherrer cone. 

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