RIETVELD ANALYSIS OF COMPLEX MIXTURES.

WHAT
CAN WE DO?

Ryan S. Winburn

Division of Science, 500 University Ave. W, Minot State University, Minot, ND 58707

ABSTRACT

Rietveld Quantitative X-Ray Diffraction (RQXRD) has become commonplace for the analysis of
everything from industrial materials, such as concrete, to geologic materials, such as bauxite ores
or igneous rocks. The recent report on the IUCR Round Robin study on quantitative analysis
indicates that accurate results may not always be obtained when using RQXRD, even with
simple three-phase mixtures. What can we do when we have samples with many phases and a
large amorphous content? And what kind of errors can we expect?

Coal combustion by-products (CCBs) are a diverse set of complex materials. They can be as
simple as four phases in a significant amorphous matrix (>50%) or as complex as twelve or more
phases in a significant amorphous matrix (>50%). The studies and results reported here have
focused primarily on this class of materials, both actual CCB materials and synthetic mixtures
having compositions resembling those found in CCB materials. A refinement protocol has been
developed for these types of materials and the corresponding estimated errors have been
determined. In developing this protocol, a number of different effects and refined parameters
have been investigated. These effects include the scan time, internal standard (both material and
particle size), divergence slit type, and refined parameters (such as specimen displacement and
preferred orientation). In addition, the effects of microabsorption have been examined in a
qualitative fashion. The methodology has been examined both with and without the Brindley
correction.

INTRODUCTION

If one wants to quantify the components of a complex mixture of solids, the only recourse may
be to use quantitative X-ray diffraction (QXRD). In some cases, quantification may be possible
using bulk sample chemical analysis by X-ray fluorescence (XRF) and/or atomic emission or
absorption spectroscopy. However, this is only effective in cases where the composition of each
phase is accurately known and if a sufficient number of phases contain unique elements (not
found in other phases). Many mixtures of solids that are of interest chemically, geochemically,
or for engineering applications do not meet these constraints.

Coal combustion by-products (CCBs) are one such class of complex mixtures. CCBs are the
solid waste generated from the burning of coal for the production of power and subsequent
emission control methods. For the year 1995, in excess of 92 million tons of CCB materials
were produced in the United States, with less than 25% (23 million tons) being used in an
application and the remaining 75+% disposed in landfills or storage ponds [1]. One potential use
for these materials is as structural materials or as admixtures in structural materials. One concern
over the use of these materials is the lack of knowledge of the long-term behavior of many of
CopyrightJCPDS - International Centre for Diffraction Data 2003, Advances in X-ray Analysis, Volume 46. 210
these materials when they are exposed to the environment. In some cases, the materials undergo
a mineralogical alteration similar to natural diagenesis. This diagenesis may result in lower
strengths and increased permeability. In these cases, although initial tests indicate high
strengths, the resulting material more closely resembles a soil than a concrete over time.

The mineralogy of the CCB materials varies depending on the initial coal source, burning
conditions, method of ash collection and any subsequent treatment (i.e., flue gas desulfurization,
etc.). In all cases, there is also a non-crystalline phase present (up to >90% of the material). The
crystalline portion of the material is readily characterized by x-ray diffraction, while the
amorphous portion is not. The variability of CCB materials necessitates the examination and
characterization of these materials, not only for elemental composition, but also for
mineralogical composition before their use in a particular application.

Coal combustion by-products are difficult to analyze by traditional XRD methods. They exhibit
many strong peak overlaps, preferred orientation, peak broadening due to small crystallite size
and/or strain, low intensities, possible microabsorption effects and potential solid solution
behavior. Previously, CCB materials were quantified using the Reference Intensity Ratio (RIR)
method. The RIR is the ratio of a particular reflection of the analyte phase to the intensity of the
single, strongest reflection from an internal standard (in a 50:50 mixture). This RIR value can
then be used to determine the amount of that material in an unknown mixture. Unfortunately,
each of the above factors exhibited by CCBs pose a problem in the RIR method.

The Rietveld method [2] is based on a least squares minimization of the difference between a
calculated diffraction pattern and one obtained experimentally. Because the Rietveld method
uses the entire pattern in the quantification, overlapping peaks pose less of a problem. In
addition, effects such as preferred orientation, solid solutions and peak broadening can be
modeled.

The Rietveld method was originally developed for the determination of structural information
from neutron diffraction of powders [2]. Use of this methodology for the quantitative analysis of
mixtures of powders was introduced in the late 1970's to late 1980's [3-9] but has not been tested
on complex, multi-phase systems until quite recently [10,11]. The Rietveld method offers
superior performance over the RIR method due to:

1. Use of the entire diffraction pattern, rather than one peak. This has the advantage of
reducing the effects of preferred orientation, instrumental factors, overlapping reflections
and extinction.
2. Peak profiles can be modeled more effectively, resulting in superior deconvolution of
overlapping reflections.
3. The inclusion of crystal structure information. This allows for factors such as solid
solutions and variable occupancies to be accounted for, a distinct advantage when dealing
with CCBs and geological samples.
4. Factors such as the background, preferred orientation, absorption, and extinction can be
modeled, allowing for the precision and accuracy of the method to be superior to other
methods used for these analyses in the past [12].

CopyrightJCPDS - International Centre for Diffraction Data 2003, Advances in X-ray Analysis, Volume 46. 211
There are many excellent sources of background information on the Rietveld method [3-6,13-
18]. The one necessary piece of information required for the Rietveld method is accurate
structure information. Many of the structures required for the analysis of CCB materials and
other complex materials are well known, particularly for phases which are compositionally and
structurally invariable. However, some phases exhibit variable composition and structure and
may pose problems for researchers interested in using the Rietveld method.

While much work has been done with the development of the Rietveld method to improve the
models used in the analyses, there are still a number of experimental and instrumental
considerations that can affect the accuracy of ones results. This paper will focus on data
accumulated over a number of years when dealing with complex mixtures, such as CCBs (both
real-life samples and synthetic materials), and geologic materials, such as igneous rocks and
heavy mineral separates from sandstones. Specifically, experimental and instrumental
considerations for improving (or at least not decreasing) the accuracy of the results obtained
when using RQXRD will be reported.

METHODS

Data were collected using Bragg-Brentano geometry and a slit configuration of 1 degree fixed
divergence and anti-scatter slits with a 0.2mm receiving slit. Scans were taken from 20 to 80
degrees 2! with a 2 second count time, unless otherwise specified. The data was analyzed using
the General Structure Analysis System (GSAS) [19]. The refinement protocol used has been
described previously [11,12] and was developed to minimize the number of refined variables
while yielding results within the desired accuracy (+/- 10% relative error for the majority of
refinements). The refinement protocol includes refining a Chebyshev polynomial background
function (the number of parameters refined is dependent on the background), the phase-element
fractions (weight fractions), lattice parameters of each phase, the specimen displacement (shft)
and Lorentzian particle size broadening (LX) terms of the Hastings, Cox, Thompson profile
function [20], and preferred orientation (if necessary).

Determination of the instrument parameter file is critical in this protocol. The correct description
of the instrument allows for many of the variables to be fixed during the refinement of
quantitative samples. A number of different materials are available for determining the
instrumental parameters, including the National Institute of Standards and Technology (NIST)
Standard Reference Materials (SRMs) 660a (LaB
6
), 676 (Al
2
O
3
) and 1976 (alumina plate).
Techniques for determining the instrumental parameters have been outlined previously [11,21].
The instrumental parameters used for this research were determined using SRM 1976, which was
chosen for its availability, ease of use, and simultaneous calibration of intensities. The major
downfall of using this to determine the instrumental parameters is that the material is oriented,
which needs to be accounted for in the Rietveld refinement. It should be noted here that many
scientists favor SRM 660b for the determination of instrumental parameters due to its lack of
orientation.



CopyrightJCPDS - International Centre for Diffraction Data 2003, Advances in X-ray Analysis, Volume 46. 212
RESULTS AND DISCUSSION

Scan Parameters

Initial considerations for dealing with CCB materials focused on developing a methodology,
including scan parameters, that would allow rapid refinement of a large number of specimens.
Typical structure determination scans or high accuracy data can take 12 hours or more to collect,
which significantly reduces the number of data sets that can be collected in a day. A number of
different scan parameters were examined, ranging from the parameters outlined previously in the
Methods section (shortest time examined, 1 hour and 6 minutes) to a set of scan parameters that
collected data from 20-140 degrees 2!, with a 0.02 degree step and 8 second count time
(approximately 11 hours). There was no significant difference between the results obtained with
the different scan parameters as indicated in Table 1, which compares the two extremes. A side
note of concern when using longer scans with complex mixtures is that occasionally the data set
contains too much information and overloads the program, causing errors.

Table 1. Comparison of Long and Short Scan Parameters (Relative Error in Parentheses)

Phase Reference RQXRD (long) RQXRD (short)
Hematite 26.8 27.3 (2%) 26.7 (1%)
Calcite 25.2 24.8 (2%) 24.0 (5%)
Al
2
O
3
3.6 4.2 (18%) 4.2 (18%)
Cr
2
O
3
11.0 10.6 (4%) 10.3 (7%)
ZnO 7.1 6.9 (3%) 6.9 (3%)
Silicon 7.3 7.6 (4%) 8.1 (10%)
Cristobalite 3.5 4.1 (16%) 4.0 (12%)
Quartz 13.4 14.1 (5%) 13.7 (2%)
Weighted Relative Error 5.6% 5.5%

Fixed vs. Variable Slits

One of the concerns when using the Rietveld method is that the counting statistics are valid only
when using data collected with fixed divergence slits (constant irradiated volume). When using
variable divergence slits (constant irradiated area) one can use a 1/sin ! conversion factor to
obtain pseudo-fixed slit data. There has been concern over the validity of this conversion when
using RQXRD. The validity of using the 1/sin ! conversion was examined using NIST SRM Fly
Ash materials (SRMs 1633a, 1633b, 2689, 2690 and 2691). For these materials, there is no
significant difference between the fixed slit data and the variable slit data as shown in Table 2.

Choice of Internal Standard and Microabsorption

The choice of internal standard is generally based on a number of factors; including potential
overlaps with other phases in the material, the absorption coefficient of the internal standard and
the mixture, and the particle size of the internal standard. The last two factors mentioned
generally are of concern for microabsorption effects. It appears that both the choice of the
internal standard material and the particle size of the internal standard play a role in the resulting
CopyrightJCPDS - International Centre for Diffraction Data 2003, Advances in X-ray Analysis, Volume 46. 213
accuracy of the RQXRD as shown in Table 3. The rutile internal standards both appear to be
more accurate than the alumina internal standard. Also, the smaller particle size rutile internal
standard appears to yield more accurate results overall than the larger particle size rutile material.

Table 2. Comparison of Fixed vs. Variable Slit Data for SRM 1633b.

Phase Fixed Variable
Quartz 5.6 5.7
Mullite 20.0 20.8
Hematite 2.2 2.2
Magnetite 1.4 1.3
Gypsum 0.7 0.8
Amorphous 70.1 70.9

Table 3. Comparison of Internal Standards on Synthetic Mixture

Phase Reference Alumina Rutile (0.4 "m) Rutile (0.9 "m)
Zincite 24.9 20.8 22.0 21.7
Cr
2
O
3
24.3 20.4 22.0 22.1
Quartz 24.9 21.7 23.6 24.8
Ceria 23.9 15.7 18.9 16.4

The phase with the largest error is the ceria, which is due to microabsorption effects. These
results are typical from what has been seen when dealing with synthetic CCB materials; the rutile
internal standards tend to be more accurate than the alumina with smaller particle sizes being
more accurate than larger particle sizes. This is contrary to the current belief about
microabsorption in that you should choose an internal standard with a linear absorption
coefficient near that of the material being analyzed. CCB materials generally have a linear
absorption coefficient between 200 and 300 cm
-1
. Alumina has a linear absorption coefficient of
approximately 125 cm
-1
and rutile is around 550 cm
-1
. This would indicate that alumina should
be equivalent to, or slightly better than the rutile internal standard. However, if one examines the
absorption characteristics of the individual phases in the materials it becomes apparent that the
rutile may be better suited for these materials due to its proximity to the average of the two
extremes in CCBS. The two extremes in CCB materials are quartz (80 cm
-1
) and magnetite
(1150 cm
-1
). More details on the effects of microabsorption in complex mixtures can be found in
Reference 21.

If microabsorption is a severe problem, the Brindley correction may be applied [23]. While is
some cases the Brindley correction can decrease the level of accuracy [22,24], in extreme cases,
it tends to normalize the errors in a system, yielding errors in the same range, irregardless of the
absorption characteristics of the material or the internal standard [22].

Data collected using different energies further indicates that microabsorption may be a problem
in CCB materials, for which the Brindley correction may not be applied due to the lack of
knowledge about particle sizes of individual phases. Data was collected on the SRM Fly Ash
materials using both copper and iron anodes. The resulting RQXRD data indicated a large
variation in the results, particularly for the iron containing phases (Table 4). Unfortunately,
CopyrightJCPDS - International Centre for Diffraction Data 2003, Advances in X-ray Analysis, Volume 46. 214
these SRMs are not certified for crystalline phase content and so the true values for each phase
are not known. With this in mind, a number of possibilities that explain this variance can be
proposed: the large variation could be the result of the lower power exhibited by the iron tube;
the variation could be due to microabsorption (the difference in linear absorption coefficient
between the silicon and iron containing phases decrease significantly when iron radiation is
used); or the iron tube could be artificially increasing the intensity of iron containing materials.

Table 4. Effect of X-Ray Source on RQXRD Results for SRM 1633a.

Phase Copper Iron
Quartz 6.8 8.6
Mullite 20.7 22.9
Magnetite 3.0 6.6
Hematite 1.3 2.8
Amorphous 68.2 59.2

Amorphous Content

Amorphous content is dealt with by using an internal standard and normalizing the data relative
to it, then taking the crystalline content and subtracting from one hundred to obtain the percent
amorphous material. In complex mixtures there is real concern about the effect of significant
amorphous material on the accuracy of RQXRD. For instance, in CCBs the amount of
amorphous material can range from 40% to over 90% [25]. The influence of the amorphous
content of materials on the accuracy of RQXRD has been studied. Typical results indicate there
is no loss of accuracy (with perhaps an increase in the accuracy) when significant amorphous
material is present (Table 5). The mixture containing the amorphous material was prepared by
diluting the original mixture (first data set in table) with amorphous silica gel.

Table 5. Effect of Amorphous Content on Accuracy in RQXRD (Relative Error in
Parentheses)

Phase Reference RQXRD Reference RQXRD
Hematite 27.7 30.6 (11%) 9.2 9.8 (6%)
Calcite 26.9 28.5 (6%) 9.0 7.9 (12%)
Corundum 10.9 12.1 (13%) 3.6 3.7 (3%)
Cr
2
O
3
11.2 11.3 (0%) 3.7 3.5 (6%)
ZnO 7.7 7.9 (2%) 2.6 2.5 (3%)
Silicon 7.2 7.7 (7%) 2.2 2.4 (3%)
Cristobalite 3.6 3.9 (7%) 1.2 1.1 (8%)
Quartz 3.1 3.1 (2%) 1.1 1.0 (7%)
Amorphous - - 66.7 68.3 (3%)
Weighted Relative Error 6.9% 4.0%

In order to assess the accuracy of the methodology at the extreme levels of amorphous content
that are occasionally seen in CCBs, a mixture containing eight crystalline phases at
approximately 1% each with 92% amorphous content was prepared and analyzed. While the
errors for this system tended to be slightly larger than typically seen, the overall results are quite
CopyrightJCPDS - International Centre for Diffraction Data 2003, Advances in X-ray Analysis, Volume 46. 215
promising (Table 6), giving less than 1% relative error in the amorphous content (0.2% absolute
error). In addition, the higher relative errors are expected due to the small values for each
crystalline component. The two phases with largest deviation are portlandite and periclase. The
large error (and low value) for the periclase is believed to be due to the small number of periclase
peaks (three) in the scan region. The difficulty with portlandite is believed to stem from the
particle size broadening, which in the case of portlandite yields broad peaks with low intensity.
The small broad peaks are difficult to distinguish from the background and the low intensity
tends to yield values that are too low.

Table 6. Accuracy of RQXRD on Materials with Significant Amorphous Content (Relative
Error in Parentheses)

Phase Reference RQXRD
Quartz 1.0 0.9 (10%)
Calcite 1.0 1.2 (22%)
Gypsum 1.0 1.4 (48%)
Hematite 1.0 1.3 (32%)
Anhydrite 1.0 1.1 (10%)
Periclase 1.0 0.5 (49%)
Magnetite 0.6 0.7 (7%)
Portlandite 1.0 0.4 (63%)
Amorphous 92.3 92.5 (0%)

Materials With More Than Nine Phases

One of the main drawbacks with using GSAS for RQXRD is its limitation of only allowing a
maximum of nine phases per refinement. This problem has been addressed previously [11,12]
and the solution relies on an averaging technique of multiple refinements. This technique has
also been successfully applied to complex geologic samples, including an igneous rock sample
from the central Cascades in Oregon and heavy mineral separates from a sandstone taken from
southwestern North Dakota [26,27]. Typical results using the averaging technique are found in
Table 7.

Preferred Orientation

A point of debate among scientists using RQXRD is the use of models to correct for preferred
orientation, particularly spherical harmonics. The points of view range from indiscriminate use
of orientation functions through the use of spherical harmonics invalidating the results obtained
in a refinement. It is not my place here to argue for or against any point, but a common theme in
the data collected in these experiments is that careful use of preferred orientation will yield more
accurate results than without the correction. Careful use of preferred orientation is the addition
of a small number of spherical harmonics terms in order to slightly improve the fit of the refined
data. If the difference plot yields a perfect fit, the data has been over-corrected and inaccurate
results will be obtained. Table 8 details the effects of spherical harmonics order on the relative
error in gypsum in an eight-phase mixture (the gypsum is at approximately the 5% level). Note,
the minimum in the errors occurs when 4
th
order harmonics are used. When 4
th
order harmonics
CopyrightJCPDS - International Centre for Diffraction Data 2003, Advances in X-ray Analysis, Volume 46. 216
are utilized, orientation is still evident in the gypsum pattern. When 8
th
order harmonics are
utilized, the orientation is barely evident and by 12
th
order the fit for gypsum looks perfect.

Table 7. RQXRD Results for Complex Mixtures Containing More than Nine Phases
(Relative Error in Parentheses).

Phase Reference RQXRD
Quartz 7.3 6.8 (6%)
Mullite 4.8 4.2 (12%)
Hematite 1.7 1.5 (8%)
Magnetite 0.4 0.3 (21%)
Periclase 1.6 2.0 (21%)
Calcite 3.1 2.8 (9%)
Merwinite 2.6 2.9 (14%)
Tricalcium Aluminate 2.2 1.7 (20%)
Anhydrite 3.4 4.0 (16%)
Brownmillerite 0.9 0.7 (21%)
Melilite 1.6 2.1 (25%)
Amorphous 70.5 71.0 (1%)

Table 8. Comparison of Relative Errors for Gypsum Using Different Spherical Harmonics
Orders

Spherical Harmonics Order 0 4 8 12
Gypsum Relative Error 26.9% 4.3% 40.8% 82.0%


A second example of the utility/necessity of using preferred orientation functions is outlined in
Reference 27, where a heavy mineral separate from a sandstone is examined. This sample
contains four different oriented materials, two of which are severely oriented as confirmed by
viewing the consistent cleavage planes in scanning electron microscope (SEM) images. Without
the use of orientation, the data yields both inaccurate crystalline phase data (due to overlapping
of orientated phases) and amorphous information (due to the internal standard being over-
emphasized). Inclusion of spherical harmonics (up to 12
th
order on some phases) yields results
that compare favorably well with optical point counting and energy dispersive x-ray analysis
(EDX) within the SEM.

CONCLUSIONS

The Rietveld method can be used to obtain results with reasonable accuracy. However, care
must be taken to ensure physically meaningful values are obtained from the refinement. This can
most easily be accomplished by fixing as many variables that are instrument dependent as
possible within the instrument parameter file. Then, following a well-defined refinement
protocol, one can generally obtain consistent, if not accurate, results. However, the method is
not perfect yet, as indicated by the large spread in some results for the IUCR Quantitative
Analysis Round Robin [24].
CopyrightJCPDS - International Centre for Diffraction Data 2003, Advances in X-ray Analysis, Volume 46. 217

The factors investigated here that had little bearing on the accuracy of the RQXRD results
included the slit type (fixed vs. variable), the amorphous content and refinements on materials
with more than nine phases. Factors that did have bearing on the accuracy of the RQXRD results
tended to have some connection to microabsorption. The choice of internal standard, both
material and particle size, has an effect on the RQXRD accuracy. In addition, the choice of x-ray
tube used has some effect on the results of the experiment.

While these results give users some confidence in the method, more data needs to be collected.
In particular, the effects of microabsorption and tube type need to be addressed more fully in
order to increase the accuracy of the methodology.

ACKNOWLEDGEMENTS

I would like to acknowledge a number of people who have aided me in this research over the
years: Dr. Greg McCarthy, Dean Grier, Bryan Jarabek, Stephanie Lerach, Renee Peterson and
Marissa Wisdom from North Dakota State University; Dr. John Webster, Chris Cool, Robin
Gonzalez, Tim Lorbiecke, Brad McIntyre, Brad Pederson, Roy Kight and Tom Edwards from
Minot State University; Jim Cathcart, Bill Betterton, Steve Sutley and Michael Brownsfield from
the United States Geological Survey in Denver, CO. I would also like to acknowledge the
Department of Energy, North Dakota EPSCoR, the Minot State University Small Grants
Program and the Minot State University College Research Grants Program for their financial
support for portions of this research.

REFERENCES

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