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Copyright(c)JCPDS-International Centre for Diffraction Data 2001,Advances in X-ray Analysis,Vol.

44

TEXTURE CHARACTERIZATION IN X-RAY AND NEUTRON POWDER


DIFFRACTION DATA USING THE GENERALIZED
SPHERICAL-HARMONIC
H. Sitepua,c,d , H.J. Praska and M.D. Vaudinb
NIST Center for Neutron Research, Gaithersburg, MD 20899, USA. bNIST Ceramics Division,
Gaithersburg, MD 20899, USA. cSUNY Center for Thermal Spray Research, Department of
Materials Science and Engineering, Stony Brook, NY 11794, USA. dNow at the Institut fr
Geologie, Mineralogie und Geophysik, Ruhr-Universitt Bochum, Universittsstrasse 150,
44780 Bochum, Germany.
a

ABSTRACT
Crystallographic texture or preferred orientation can cause serious systematic errors in
quantitative phase analysis of crystalline materials using powder diffraction data. In the present
study, parallel modeling with x-ray diffraction data was carried out in order to compare the nearsurface characterizations texture information with the bulk obtained with neutron diffraction.
This paper will describe the general applicability of the March and the generalized sphericalharmonic models with particular reference to x-ray and neutron diffraction data of highlyoriented molybdite and calcite specimens.
INTRODUCTION
Texture is an important feature of the characterization of powders utilizing the x-ray diffraction
(XRD) method because it manifests itself by variation of the intensities of particular (hkl)
reflections. This phenomenon is commonly observed in XRD patterns measured with a powder
diffractometer. It is possible to extract preferred orientation information from such patterns if the
pattern for a randomly oriented specimen can be modeled, or simulated, from knowledge of the
crystal structure parameters and various other factors (e.g. line broadening) which influence the
pattern. Neutron diffraction (ND) may also be used to characterize the texture character of
materials. The pertinent attribute of ND with respect to texture is the small attenuation
coefficients of neutrons for most materials relative to x-ray absorption. Therefore ND texture
information is gained from the bulk of the sample, whereas the XRD response is typically from
the near-surface. Thus, XRD and ND are excellent complementary tools for characterizing
texture from the near-surface into the bulk of the materials.
The March1 model was shown by Dollase2 to provide an excellent descriptor of preferred
orientation for Rietveld3 refinement of calcite and huntite XRD data. The model was successfully
applied to Rietveld modeling of gibbsite XRD data4 producing accurate atomic parameters with
low crystallographic R-parameters (RWP = 1.5 Rexp), but proved to be deficient for XRD data
obtained from molybdite, calcite and kaolinite subjected to high pressures5. Subsequently,
Sitepu6 and Sitepu, OConnor and Li7,8 showed that in contrast to the XRD results, the atomic
parameters from ND analysis using the March model are correct for the bulk material, with
superior goodness-of-fit indices; the results were not substantially influenced by the pressing
procedure. Sitepu6 suggested that generalized spherical-harmonic (GSH) modeling9 should be
employed for the analysis of XRD and ND data from materials with more substantial levels of

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preferred orientation. Sitepu and Prask10 successfully applied the March model and the GSH
method to preferred orientation corrections for ND data of highly-oriented calcite powder
prepared at a pressure of 380 MPa, about twice the highest pressure used in the previous study6.
The study reported here seeks to extend the work of Sitepu6 on the general applicability of the
March and the GSH formulations for modeling preferred orientation with both XRD and ND
data, with reference to: (i) the reliability of both the March model and the GSH approach and (ii)
their use in correcting powder diffraction intensities for preferred orientation bias.
EXPERIMENTAL
The molybdite (MoO3) and calcite (CaCO3) starting materials were analytical reagents. In the
present work a very substantial level of preferred orientation was introduced by uniaxial-pressing
at pressures of (380 5) MPa and (530 5) MPa. These pressures are two and three times higher
than the highest pressure conducted previously by Sitepu6 in examining the validity of the March
preferred orientation model for powder diffraction characterization of materials. For XRD,
approximately 2g of powder was compacted in a cylindrical steel die 13mm in diameter.
Multiple discs were pressed for the ND experiment as the relatively weak beam intensities
required use of larger specimens. Seven discs were stacked together into a cylinder
approximately 6 mm high to maximize the use of neutron beam. All of the samples were spun
during the data collection to improve particle statistics.
Patterns were measured with an XRD diffractometer equipped with a sample spinner, position
sensitive detector and focussing incident beam monochromator tuned to transmit only the CuK1
component of the CuK doublet. The texture axis was assumed to be normal to the specimen
surface in the Rietveld refinement, permitting the use of a sample spinner to reduce the effect of
particle counting statistics. Data were collected from 20 to 152 2 in step size of 0.01 using a
scan rate of 1 degree per minute. The low angle limit of 20 was chosen to ensure that the
condition of constant volume of illumination was met for the refined data.
The ND data were collected at room temperature using the BT-1 32-detector high-resolution
powder diffractometer at the NIST Center for Neutron Research Reactor. A Cu(311)
monochromator with a 90 take-off angle, wavelength 1.5402 and 15 minutes incident
collimation were employed. Data were collected over the range of 3 to 168 2 with total
counting time approximately 8 hours per sample. The scan range was 10, with a step size of
0.05, so that each data point was collected in two adjacent detectors. The data from the 32
detectors were then processed to yield a single histogram using interpolations between adjacent
observations to correct for zero-point offsets and detector sensitivities.
RIETVELD CALCULATIONS
The Rietveld refinements were performed with the GSAS software package11. The refinement
strategy was similar to that described by Sitepu6, with the difference that in the present study,
two textured phases were employed, one with March parameter r and volume fraction f and one
with March parameter 1 and volume fraction (1-f). This is the so-called March-Dollase approach
in which the parameters r and f are refined. The fraction would often refine to a reasonable value
with a statistically significant reduction in the Rietveld analysis goodness-of-fit index. If the

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Copyright(c)JCPDS-International Centre for Diffraction Data 2001,Advances in X-ray Analysis,Vol.44

result diverged, r was fixed at the value obtained from the previous successful refinement, and
the refinement was repeated until a reasonable result was obtained. Then, the March preferred
orientation r-parameter was refined once more. If the refinements which included f converge to
an f value near one without a significant reduction in the value of the goodness-of-fit index, it
was concluded that f was 1.0. The same conclusion was made also if the refinements which
included f failed to reach convergence with the March r-parameter of nearly 1.0.
Once the March-Dollase refinement had been completed, the atomic parameters were used as the
starting point for the GSH texture calculation (with the r-parameter fixed to 1.0). The default
values for the goniometer angles , and were fixed at (0, 0 and 0) and (0, 90 and 0),
respectively for XRD and ND data9. The initial values for GSH coefficients were all set to zero.
Unlike the case of crystal structure refinements, the orthogonalities of the spherical harmonics
resulted in very rapid convergence with no requirement for well-chosen initial values for the
GSH coefficients. The default sample texture symmetry was chosen to be cylindrical (fiber
texture); and the maximum harmonic order of L = 6 was selected after calculations with L = 8
and L = 10 showed no additional improvement. The crystallographic R-factors are given in Table
1 along with the March r and f parameters.
Table 1 compares the Rietveld refinement results for parallel calculations involving the March
model and GSH. Even though the spherical-harmonic description of texture effects on XRD and
ND intensities is a more flexible approach than the March model, employing more fitting
parameters, the figures of merit derived from the spherical-harmonic model in the study (the
crystallographic R-factors: RP , RWP and R( F 2 ) ) are not significantly better than those obtained
from the March model. However, for both materials and both models the R-factors were better
for the ND case than the XRD. It is noted, though, that the goodness-of-fit still substantially
exceeded the expected value, 2 = 1.00, when either the March model or the GSH formalism
was employed.
The r values for XRD and ND given in Table 1 are less than and greater than one, respectively.
This occurs because for XRD the texture axis (pressing direction) lies in the plane of diffraction
but for ND the texture axis is normal to the plane of diffraction. In both cases the specimen is
rotated about the texture axis, resulting in a complex relationship between the r values
determined in the two different geometries. This relationship has not yet been determined. The
ND r values for both calcite and molybdite for the two pressures are all very similar. The higher
texture detected by XRD is due to the fact that neutrons can penetrate through the whole
specimen whereas x-rays only penetrate a few tens of microns into the materials. Thus the ND
results represent the texture of the specimen averaged over its entire volume, and the XRD
results are sensitive to the near-surface region of the specimen, which is the region most affected
by the pressing procedure.
The spatial inhomogeneity in pressing-induced texture was confirmed by XRD rocking curve
measurements made on the calcite specimen pressed at 380 MPa. The rocking curve from the
outer pressed surface of the specimen showed significant texture but a rocking curve obtained
from a surface produced by cutting 10 m off the specimen (parallel to the pressed surface)
showed no detectable texture. As with the March model, the capacity of the GSH to provide
satisfactory agreement steadily diminishes for XRD data with increasing preferred orientation.

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Copyright(c)JCPDS-International Centre for Diffraction Data 2001,Advances in X-ray Analysis,Vol.44

Figure 1 shows that the agreement between the measured (a) and calculated patterns improved
dramatically when either the March model (b) or the GSH method (c) was employed in the
Rietveld refinement. The observed data are indicated by plus signs and the calculated profile is
the continuous line in the same field. The sets of vertical lines below the profiles represent the
positions of all possible Bragg reflections. The lower plot is the difference between the measured
and calculated patterns on the same scale as the measured and calculated patterns.
While Table 1 shows that for both materials the XRD results indicate higher levels of texture
than the ND results, it also shows that the goodness-of-fit for the ND data is in all cases better
than for the XRD data. The better goodness-of-fit for ND data can be attributed to the generally
lower preferred orientation levels detected by neutrons in the bulk material, which results in a
flatter texture profile that is more likely to be well fit by a model function. The fact that the
March method, with one or two fitting parameters, was as successful as the spherical-harmonic
approach, with a larger number of fitting parameters (six were actually used), is somewhat
surprising. Therefore, it can be concluded that both these techniques can be used to correct the xray and neutron diffraction intensities due to the effects of preferred orientation for the purposes
of determining crystal structure information. Finally, the correction of pattern intensities with
either the March r-parameter or the GSH coefficients substantially improved the agreement
between the measured and calculated intensities.
ACKNOWLEDGMENT
Thanks to B. Toby and J. Stalick of the NIST Centre for Neutron Research for invaluable
contributions in interpreting data. The authors would like also to thank R.B. Von Dreele for his
help with the Rietveld refinement with the generalized spherical-harmonic approach. Also thanks
to Q.Z. Huang and J. Barnes for helpful discussions.
REFERENCES
[1] March, A., Z. Kristallogr, 1932, 81, 285-297.
[2] Dollase, W.A., J. Appl. Cryst, 1986, 19, 267-272.
[3] Rietveld, H.M., J. Appl. Cryst, 1969, 2, 65-71.
[4] OConnor, B.H.; Li, D.Y.; Sitepu, H., Adv. X-ray Analysis, 1991, 34, 409-415.
[5] OConnor, B.H.; Li, D.Y.; Sitepu, H., Adv. X-ray Analysis, 1992, 35, 277-283.
[6] Sitepu, H., PhD Thesis, Curtin University of Technology, Perth, WA, 1998.
[7] Sitepu, H.; OConnor, B.H.; Li, D.Y., To be submitted, 2000a.
[8] Sitepu, H.; OConnor, B.H.; Li, D.Y., To be submitted, 2000b.
[9] Von Dreele, R.B., J. Appl. Cryst, 1997, 30, 517-525.
[10] Sitepu, H.; Prask, H.J., Submitted to Journal of Materials Science, 2000.
[11] Larson, A.C.; Von Dreele, R.B., GSAS: General Structure Analysis System. Los Alamos
National Laboratory Report LAUR, 86-748. Los Alamos, New Mexico, 1986.
[12] Kihlborg, L., Arkiv for Kemi, 1963, 21, 357-364.
[13] Maslen, E.N.; Streltsov; V.A.; Stretsova; N.R., Acta Cryst, 1995, B51, 929-939.

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Copyright(c)JCPDS-International Centre for Diffraction Data 2001,Advances in X-ray Analysis,Vol.44

Table 1. Summary of XRD and ND Rietveld refinement results for molybdite and calcite using
the March model and the generalized spherical harmonic formalism. Results for specimens
pressed at pressures of 380 MPa and 530 MPa are given in the first and second lines,
respectively. The number in parentheses gives the estimated standard uncertainty for the least
significant figure of the parameter.

The structural models used for the molybdite and calcite were those described by Kihlborg12
and Maslen et a113, respectively. The preferred orientation directions used for the XRD
refinements were <010> for molybdite12 and <104> for calcite2. For ND, the preferred
orientation directions for molybdite were <010> and for calcite was <001> as the <001>
gave ND pattern fits superior6 to those obtained with the <104> direction.

Parameter

March Model
XRD

Spherical-Harmonic
XRD

ND

ND

13.41
10.08*
18.31
15.24*
19.78
12.72*
13.05
9.65*
0.434(2)
0.312(2) *
0.860(1)
0.845(5)*

4.99
4.47*
6.03
5.39*
5.24
4.02*
4.31
2.14*
1.267(2)
1.298(2) *
1.000
1.000*

14.52
12.23*
19.60
17.73*
24.32
18.81*
14.96
13.07*
1.000 (fixed)

4.16
3.80*
5.37
4.82*
3.44
2.34*
3.42
1.71*
1.000(fixed)

1.000 (fixed)

1.000(fixed)

14.46
9.15*
21.28
13.47*
16.45
24.38*
3.62
10.56*
0.423(2)
0.403(2) *
0.657(3)
0.706(1)*

4.90
6.40*
6.49
8.16*
2.41
2.94*
3.97
1.87*
1.248(4)
1.264(6) *
1.000
1.000*

14.40
9.10*
20.72
12.77*
14.17
24.61*
3.43
9.50*
1.000 (fixed)

4.83
6.26*
6.37
8.00*
2.89
3.03*
3.84
1.80*
1.000 (fixed)

1.000 (fixed)

1.000(fixed)

Molybdite

RP
RWP
R( F 2 )

2
r

f
Calcite

RP
RWP
R( F 2 )

2
r

Results for a pressure of 530 MPa

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Copyright(c)JCPDS-International Centre for Diffraction Data 2001,Advances in X-ray Analysis,Vol.44

Counts

10000

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(a)

5000

Counts

10000

(b)

5000

Counts

10000

(c)

5000

0
20

40

60

80

100

2q (deg)

120

140

160

Figure 1. Agreement between calculated and measured ND patterns for calcite specimens
pressed at pressures of 530 MPa following Rietveld refinement with (a) random orientation, (b)
the March and (c) the generalized spherical harmonic models for preferred orientation.