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Quantitative Phase Analysis from Neutron Powder Diffraction Data Using the Rietveid
Method
BY R. J. HILL
CSIRO Division of Mineral Chemistry, PO Box 124, Port Melbourne, Victoria 3207, Australia
AND C. J. HOWARD
Australian Nuclear Science and Technology Organisation, Lucas Heights Research Laboratories,
Private Mail Bag l, Menai, New South Wales 2234, Australia
The whole-pattern fitting methods are of two kinds. formulation for the step intensity Yi which gives an
In the Rietveld method (Rietveld, 1969), the diffraction absolute calculation of the number of neutrons diffrac-
profile is calculated using the unit-cell dimensions to ted. The analysis of the neutron powder diffraction
determine the peak positions, and the atomic po- pattern by Sabine (1980) provides a suitable starting
sitional and thermal displacement parameters as a point.
model for the peak intensities. On the other hand, in Sabine (1980) showed that, in the single-phase case,
the 'pattern-decomposition' technique, the step-scan for a single peak with a Gaussian line shape, the
data are decomposed into their component Bragg number of neutrons received by a counter at an angle
reflections without reference to the crystal structure 20 is given by
(other than the unit-cell dimensions); that is, the
y(20) = ~023hwvp'JNc2F 2 exp ( - 2W)
calculated peak intensities are themselves variables in
the fitting procedure (Sonneveld & Visser, 1975). x a exp ( - px2)t(81tr2p sin 0 sin 20) - l,
The pattern-decomposition method provides a con-
venient means of measuring more accurately the
(2)
relative peak intensities and, therefore, of determining where 4'o, z are the neutron flux and wavelength, r is the
the usual (experimentally derived) calibration curves specimen-to-counter distance, h, w, t are the aperture
(Toraya et al., 1984) and Rp values (Smith et al., 1986). height and width and the counting time, p', p are the
The Rietveld method calculates the peak intensities actual and theoretical densities, v is the specimen
directly from crystal structure parameters, and so it volume, N~ is the number of unit cells per unit volume
has the advantage of permitting the determination of (i.e. l/V, where V is the unit-cell volume of the material),
phase abundance without precalibration of either the F, exp ( - 214/) are the structure factor per unit cell and
experimental or calculated kind (Werner et al., 1979; an (overall) Debye-Waller factor for the intensities, J is
Weiss et al., 1983). Of course, the same advantage is the reflection multiplicity, x is 2(0 - Ok), where Ok is the
present when integrated intensities are obtained by Bragg angle for the kth reflection, p is 4H-21n2, a is
calculation but in this case the deconvolution of 2 H - l ( r t - l l n 2 ) 1/2, and H is the full-width of the re-
overlapping peaks in complex diffraction patterns flection at half-maximum intensity. This equation is
remains a serious limitation of the method. To date, based on kinematic theory, and takes no account of
the general utility of both the calculated-constant and absorption.
fitted-profile (Rietveld) methods has been diminished The calculated contribution from the peak to the
by (i) confusion about the definition of 'absolute', number of neutrons received by the counter at the
'relative', and 'instrumental' scale factors (Hubbard et angle 20i, denoted Yic, can be recast as
al., 1976) and (ii) problems associated with the treat- Yi~ = SJkLklFkl2GiR, (3)
ment of preferred orientation (Weiss et al., 1983) and
absorption (Hubbard et al., 1976; Werner et al., 1979). where S is the scale factor, Jk is the reflection multi-
In this paper we derive a simple relationship be- plicity, L k is the Lorentz factor (sin Ok sin 2 0 k ) - 1 , f k
tween phase abundance and the Rietveld scale factor, is the structure factor, including displacement
and test this on data from Rietveld refinements of factors [[Fk[2 corresponds to F 2 exp ( - 2 W ) in (2)],
high-resolution neutron powder diffraction patterns and Gig is a normalized Gaussian profile function
collected on binary mixtures of ruffle/corundum, ru- [ a e x p ( - p x 2) in (2)]. The scale factor contains
tile/quartz and silicon/quartz. We argue that, for other quantities from (2) and is
quantitative phase analysis, neutron powder diffrac- S=(p'N2v/p)C (4)
tion offers distinct advantages over the more com-
monly used X-ray technique in that (i) the diffraction where C -- (~o23hwt)/(8/tr2).
patterns are representative of the bulk sample, rather Equation (3), with (4), holds when profiles are non-
than surface regions, (ii) absorption in the individual Gaussian, provided only that Gig is correctly norma-
phases can be effectively ignored, and (iii) the data are lized. When more than one diffraction peak con-
more extensive [because neutron scattering lengths do tributes at an angle 20i, the calculated count is a
not decrease with (sin 0)/2], leading to more accurate summation over contributing peaks k,
estimates of thermal displacement parameters, and
hence to more reliable scale factors. Yic = S ~ JkLklFkl2Gik . (5)
k
With the addition of the background, denoted Yib at
Theory 20i, the total calculated count is
The Rietveld method is commonly applied to powder
diffraction patterns in which counts are recorded for Y,c = Y,b + S~,JkLkIFkIEG,k • (6)
k
equal effective times at equal intervals of 20. For
quantitative analysis, it is useful to start with a When more than one phase is present, which is the
R. J. H I L L A N D C. J. H O W A R D 469
case in quantitative phase analysis, a summation over Windsor (1982)] are given by (8), but with a different
contributing phases p is performed: expression for the pattern constant C. The masses and
scales are therefore related again by (11).
Y,c = Y,b + ~Sp~JkpLkplFkplZG,kp (7) We note that (11) applies as well to the common
p k
cases of X-ray diffraction with Debye-Scherrer and
where now
Bragg-Brentano geometries. The X-ray intensity can
Sp = (p'pN{pv/pp)C. (8) be derived from that discussed above for fixed-
Equation (7) can be recognized as the step intensity wavelength neutron diffraction by multiplication by
calculated in Rietveld-method computer programs. In the electronic factor (e2/mecZ) 2. With this factor in the
particular, apart from the omission of a preferred constant C, (8) holds, and relation (11) follows.
orientation factor, it is exactly the quantity computed There are several points to be noted in connection
in the program described by Hill & Howard (1986). with the application of (10) and (11) in quantitative
The factor Sp is the usual scale factor for the pth phase. analysis:
Equation (8), resulting from comparison with Sabine's (i) It is essential that the structure factors and the
exposition, gives this scale factor explicitly. constants which multiply them are correctly com-
We now consider (8) in more detail. First we note puted. Specifically, it is necessary to ensure that the
!
t h a t ppl)=-rap, the mass of the phase p present in the correct site multiplicities are used for atoms in special
sample. In addition, Nip = 1/VZp, and ppVp is the mass positions [see Hill & Howard (1986), p. 9].
of phase p in one unit cell of the crystalline pth phase. (ii) The effects of absorption can be incorporated
We can write ppVp = ZpMp, where Mp is the mass per into the phase-analysis theory by including a trans-
formula unit of phase p, and Zp is the number of mission factor in (7). In the case of Bragg-Brentano
formula units per unit cell. So (8) can be written as diffraction from a specimen of effectively infinite thick-
ness, the transmission factor is angle-independent [i.e.
Sp = mp/( ZpM v Vp)C (9) 1/2#, where/~ is the linear absorption coefficient (Klug
where C [(4)] is constant in the recording of the & Alexander, 1974)]; this is simply included in the
diffraction pattern. This shows that multiphase refine- pattern constant C, so (10) and (11) still apply. In the
ment of a mixture of phases will yield scale factors Debye-Scherrer case for/~r < 1 (where r is the radius
of the cylindrical specimen), the analytical approxi-
Sp w. mp/( ZpM pVp) (10) mation to the transmission factor given by Rouse,
or that the masses of the component phases are given Cooper, York & Chakera (1970), and discussed by
by Hewat (1979), can be used. When this is applied to
each term in the summation over phases in (7), each Sp
mp ~ Sp(ZpMpVt, ) (11)
incorporates the same correction factor and the rela-
where Sp is the scale factor obtained for phase p in the tionships (10) and (11) are again unaffected. Correc-
Rietveld analysis.* This relationship is the foundation tions for absorption in other diffraction geometries
of the present work; it gives the relative weight of any remain to be determined, but are generally not ex-
component, and provides an absolute weight fraction pected to affect the phase-analysis results when/~r is
if an internal standard is introduced in a known small and/or the diffraction peaks from all phases are
proportion. If all phases are identified and crystalline, more or less uniformly distributed with respect to
the sum of the weight fractions is unity and the angle.
absolute weight fractions can again be obtained. (iii) Since the analysis is in kinematic theory only,
Although the derivation and experimental tests of the presence of extinction will directly affect the scale
(11) described in this paper are specific to fixed- factors in (7) and hence change the phase masses
wavelength neutron powder diffraction, it is clear that derived from (11).
the equation also applies in other circumstances. In (iv) The samples should be free, as far as is possible,
particular, the argument above can be repeated for from preferred orientation. It is likely that a Rietveld
time-of-flight neutron powder diffraction at fixed refinement will still be able to produce good estimates
angle. The intensities in this case are simply related to of the scale factors when there is a small degree of
those obtained in fixed-wavelength powder diffraction preferred orientation since the effects are 'averaged
(Buras & Gerward, 1975). It can be shown that the out' if the range of diffraction angles is large. The
scale factors obtained from Rietveld analysis of time- widely used correction for preferred orientation pro-
of-flight data [with multiphase versions of programs posed by Rietveld (1969) does not conserve scattering
such as that described by Von Dreele, Jorgensen & material, and so seriously affects the scale factors; it
should not be invoked. On the other hand, the March
function (Dollase, 1986) is correctly normalized and
*We note that a rather similar relationship has been given by
Werner et al. (1979), but it lacks the unit-cell volume Vr an omission can be safely used to treat preferred orientation in
which we cannot understand. quantitative phase analysis.
470 QLIANTITATIVE PHASE ANALYSIS FROM N E U T R O N POWDER DIFFRACTION DATA
(v) Problems related to sample mixing, sampling of pure anatase by heating at 1475 K for 2 h, ground in
the mixture, and number of crystallites measured, an acetone slurry in a tungsten carbide mill for 10 min
have been discussed by Klug & Alexander (1974) in and annealed at 1075 K for 2 h; the corundum was
connection with X-ray quantitative analysis. Since the a sample of either 'Linde C' (1.0 ~tm) or 'Linde A'
volumes sampled by neutrons are very much larger (0"3 ~tm) annealed at 1075 K for 4 h.
than those in an X-ray experiment, these problems are Pairs of these phases were combined in the propor-
rare in neutron analysis. tions shown in Table 1 (by weighing to at least four
(vi) Amorphous or poorly crystalline material does significant figures) to yield a volume of approximately
not contribute to diffraction peaks, and so is not 15cm 3. The mixtures were homogenized by hand
determined by (11). It has been suggested (Klug & grinding in a pestle and mortar and loaded into a 16
Alexander, 1974; Altree-Williams, Byrnes & Jordan, x 50 mm vanadium can for neutron powder diffrac-
1981) that there may be a significant fraction of tion data collection.
amorphous surface material in chemically pure pow- Diffraction data for the pure phases and binary
ders, especially in samples that have undergone ex- mixtures were recorded at 295 K on the eight-counter
tensive milling. The amount of amorphous material in fixed-wavelength high-resolution powder diffractom-
a mixture may be determined by the addition of a eter (HRPD) at the Australian Nuclear Science and
known weight of (crystalline) internal standard prior Technology Organisation's research reactor HIFAR
to the phase analysis. at Lucas Heights, New South Wales. This instrument
(in an earlier single-counter configuration) has been
described by Howard, Ball, Davis & Elcombe (1983).
Experimental The data were recorded under monitor control at
Equation (11) was tested using various binary intervals of 0.05 ° between 15 and 160° 20 using a
mixtures of the phases silicon (Si), 0t-quartz (SiO2), wavelength of 1.893 A (except Si, for which the wave-
rutile (TiO2) and corundum (A1203). These materials length was 1-377 A). Several mixtures were remea-
were selected primarily because of their availability in sured using 1"377 ,~, neutrons as a test for the possible
pure form, but also because their crystal structures are effects of extinction. The scattering lengths used for Si,
well characterized and display an acceptable range of O, AI and Ti were 4.149, 5.805, 3.449 and -3.438 fm,
structural complexity; relevant details of their crystal respectively.
structures are provided in Table 1, along with the The least-squares structure and profile refinements
ZMV values appropriate for use in (11). were performed with the Rietveld analysis program
The sample of Si was a commercial laboratory LHPM1 described .by Hill & Howard (1986). The
reagent chemical that had been extensively character- background was defined by a three-parameter poly-
ized in earlier X-ray and neutron diffraction studies; nomial in 20", where n had values between 0 and 2,
the ~-quartz was a commercial ( - 2 0 0 # ) sample of and was refined simultaneously with the unit-cell,
silica digested in 2 M HC1 to remove impurities and zero-point, scale, peak-width/shape/asymmetry and
heated at 1075 K for 2 h; the rutile was prepared from crystal-structure parameters. The peak shape was
R. J. HILL AND C. J. HOWARD 471
(o) J Discussion
The Rietveld refinement results presented in Table 2
show that the crystal-structure parameters and unit-
cell dimensions derived for all four phases are statisti-
cally independent of their abundance in the binary
mixture studied, at least down to the level of l0 w t % .
I A 1 , 1 I , I 1 I i
1.0
Ouontitotive Anolysis" 3:7 TiOz:AIzO 3
t-
O 0.8
c_ 0.6
O
f,,_
t i Il
"- 0.4
O
,---, 0.2
21r)
4-
.-- 0.0
I I I I I I I II I II I I I I I I I I I II I I I II
I I I I I I I I I I I I I I II II I II I I II II I I II I -
r"
' -' - - - ~ - ± ' T- I-" " " ~ - ; - : - "-" ~ " ~ - ~ ~ ":" ~ ~ ~ ; - - ~ - -- ~ " J ~
, I , I ~ I ~ 1 ~ I ~ I
Table 2. Fractional atomic coordinates, isotropic displacement parameters and refinement agreement indices for
each phase determined from single-crystal X-ray data and by Rietveld analysis of neutron powder data obtained
from binary mixtures
TiO2/SiO 2
TiO2/AI20 3 (Linde C) mixtures mixture
X-ray single
Parameter crystal 0% TiO 2 10% TiO 2 30% TiO 2 50% TiO 2 70% TiO 2 100% TiO 2 50% TiO 2
TiO2 (rutile)
a (A) 4-5845( 1)* - 4"5960(1) 4"5959(1) 4-5954(1) 4"5956(l) 4.5951(1) 4.5957(1)
c (A) 2"9533(1) - 2"9603(1) 2"9603(1) 2"9600(1) 2"9602(1) 2.9599(1) 2.9601(1)
Ti B(/k 2) 0-62 - 0.28(12) 0-57(6) 0-60(4) 0-53(3) 0-60(2) 0-60(4)
O x 0-30493(7) - 0.3049(4) 0.3051(2) 0-3049(1) 0.3050(1) 0.3050(1) 0"3050(1)
B (A 2) 0.67 - 0-34(7) 0.50(3) 0.45(2) 0.51(2) 0"48(2) 0"54(2)
R8 (%)t 1.0 - 1-69 2.09 1.91 1"83 1"65 1"84
AI20 3 (corundum)
a(A) 4"7602(4)++ 4"7611(1) 4"7613(1) 4.7612(1) 4"7607(1) 4"7609(1)
c (A) 12.993(2) 12-9977(2) 12"9980(2) 12"9978(2) 12"9966(2) 12.9971(2)
AI z 0.35216(1) ff3522(1) 0"3522(1) 0"3521(1) 0-3520(1) 0"3521(2)
B (A 2) 0.18 0-31(3) 0-32(3) 0-27(3) 0.22(4) 0-31(5)
O x 0-30624(4) 0.3064(l) 0.3064(1) 0.3064(1) 0-3065(2) 0-3068(2)
B (,~2) 0.21 0-29(2) 0.32(2) 0.30(2) 0.22(2) 0.26(3)
R n (%) 4.4 0-88 0-63 1.01 1.52 1.06
Rwp (%) - 6.71 6.09 6.02 5.95 5.96 5"97
GofF 1.14 1.22 1"17 1.25 1"32 1"32 1"48
TiO2/SiO 2
Si/SiO 2 mixtures mixture
In particular, the atomic coordinates and thermal phase (Table 2). There are relatively large systematic
displacement parameters do not vary by more than 2.5 differences in the unit-cell dimensions obtained from
combined e.s.d.'s, and the unit-cell dimensions are all the X-ray and neutron data. The neutron values are,
within five combined e.s.d.'s. As expected, the param- however, internally consistent; they differ from the X-
eter errors increase as the proportion of the phase ray results only as a result of the inherent uncertainty
declines in the mixture. in the neutron wavelength value. Taken together, the
The crystal structural parameters (i.e. atomic co- results displayed in Table 2 lend confidence to the
ordinates and thermal parameters) obtained from the parameter values obtained from Rietveld analysis in
neutron powder refinements are in close agreement cases where a particular phase cannot be completely
with the results of single-crystal X-ray studies of each isolated from other crystalline compounds.
R. J. HILL AND C. J. HOWARD 473
Table 3. Theoretical and experimental phase-analysis Secondly, when examined closely, the diffraction
results pattern from 'Linde A' corundum was observed to
contain two small 'humps' in the background at 48
Composition (wt%) and 86 ° 20, suggesting that this sample contains a
Mixture Scale factor Experimental* As weighed
small amount of a poorly crystalline phase. In con-
TiO2 0"331(6) 9"8(2) 10 trast, the background in the diffraction pattern ob-
Ai203"I 0"1953(9) 90"2(2) 90
tained from 'Linde C' corundum was completely fiat.
TiO2 1"165(9) 30-4(3) 30 The inaccuracy of the analyses of the mixture contain-
AI2 ° 3 j" O"1708(9) 69.6(3) 70
ing 'Linde A' corundum (i.e. a shortfall of 3-4 wt% for
TiO 2 2.070(12) 50.5(3) 50 this phase; Table 3) is therefore attributed to the
A120 3"t 0-1300(8) 49.5(3) 50
presence of this component. This observation under-
TiO2 2.936(14) 70.5(3) 70 scores the importance of 'standard' sample character-
AI203"I" 0.0785(7) 29.5(3) 30 ization prior to phase analysis, even in the case of
TiO 2 2.560(15) 50.7(3) 50 commonly used materials such as the 'Linde'
SiO 2 1.221(6) 49.3(3) 50 corundums, and warns of the potential for uninten-
TiO2 3.589(22) 53-4(3) 50 tionally incorporating systematic errors into experi-
AI203 + 0"2007(15) 46"6(3) 50 mental calibration constants.
Si 0"3778(25) 48"3(3) 50 Although no unusual features were encountered in
SiO 2 0"7154(36) 51"7(3) 50 the patterns for Si o r SiO2, the shortfall of 1.7 wt% for
*Calculated from the scale-factor value using equation (11) and
Si in the analysis of the 1-1 mixture of these two
the Z M V value in Table 1. compounds (Table 3) suggests that the Si component
t'Linde C' corundum. contains a small amount of surface amorphous
~.'Linde A' corundum. material.
requires no standards (other than a knowledge of the HOWARD,C. J., BALL,C. J., DAVIS,R. L. & ELCOMBE,M. M.
crystal structure parameters) or laborious calibration (1983). Aust. J. Phys. 36, 507-518.
procedure and can be performed with both X-ray and HUBBARD,C. R., EVANS,E. H. & SMITH,O. K. (1976). J. Appl.
neutron powder diffraction data. Applications of the Cryst. 9, 169-174.
KLUG, H. P. & ALEXANDER,L. E. (1974). X-ray Diffraction
quantitative analysis technique described above are Procedures for Polycrystalline and Amorphous Materials.
being presented elsewhere for the specific cases of New York: Wiley.
zirconia ceramics (Howard, Hill & Reichert, in prepa- LE PAGE, Y. & I)ONNAY, G. (1976). Acta Cryst. B32,
ration), and lead-acid battery materials (Hill, Jessel & 2456-2459.
Rand, in preparation). LEWIS, J., SCHWARZENBACH,D. & FLACK,H. D. (1982). Acta
Cryst. A38, 733-739.
RIETVELD,H. M. (1969). J. Appl. Cryst. 2, 65-71.
We thank Ms J. Hodge of the Physics Department, ROUSE, K. D., COOPER, M. J., YORK, E. J. & CHAKERA, A.
New South Wales Institute of Technology, for prepar- (1970). Acta Cryst. A26, 682-691.
ing the futile specimen, and Mr M. A. M. Sufi, from SABINE,T. M. (1980). Aust. J. Phys. 33, 565-572.
the Nuclear Energy Unit, Puspati, Malaysia, for SHINTANI, H., SATO, S. & SAITO, Y. (1975). Acta Cryst. B31,
assistance with data analysis. 1981-1982.
SMITH, D. K., JOHNSON,G. G. & RUUD, C. O. (1986). Adv.
X-ray Anal. 29, 217-224.
SONNEVELD, E. J. & VISSER, J. W. (1975). J. Appl. Cryst. 8,
1-7.
References TORAYA, H., YOSHIMURA,M. & SOMIYA,S. (1984). J. Am
ALEXANDER,L. E. (1977). Adv. X-ray Anal. 20, 1-13 Ceram. Soc. 67, C 119-C 121.
ALTREE-WILLIAMS, S. (1978). Anal. Chem. 50, 1272-1275. VON DREELE, R. B., JORGENSEN, J. D. & WINDSOR, C. G.
ALTREE-WILLIAMS, S., BYRNES, J. G. & JORDAN, B. (1981). (1982). J. Appl. Cryst. 15, 581-589.
Analyst (London), 106, 69-75. WEISS, Z., KRAJi(~EK, J., SMRt~OK, U & FIALA, J. (1983).
BURAS, B. & GERWARD,L. (1975). Acta Cryst. A31, 372-374. J. Appl. Cryst. 16, 493-497.
CAGLIOTI, G., PAOLETTI, A. & RICCI, F. P. (1958). Nucl. WERNER, P.-E., SALOME,S., MALMROS,G. & THOMAS,J. O.
lnstrum. 3, 223-228. (1979). J. Appl. Cryst. 12, 107-109.
CHUNG, F. H. (1974). J. Appl. Cryst. 7, 519-525. WINDSOR,C. G., SINCLAIR,R. N., FAULKNER,S., RAINEY,V. &
CLARK, G. L. & REYNOLDS, D. H. (1936). Ind. Eng. Chem. SLATTERY, G. F. (1984). In Microstructural Character-
Anal. Ed. 8, 3640. ization of Materials by Non-Microscopical Techniques.
DOLLASE,W. A. (1986). J. Appl. Cryst. 19, 267-272. Proc. 5th Riso Int. Symp. Metall. Mater. Sci., 3-7 Septem-
HEWAT, A. W. (1979). Acta Cryst. A35, 248. ber 1984, pp. 583-588, edited by N. HESSELANDERSON,M.
HILL, R. J. (1982). J. Power Sources, 8, 175-196. ELDRUP, N. HANSEN, D. JUUL JENSEN, T. LEFFERS, H.
HILL, R. J. & HOWARD, C. J. (1986). Australian Atomic LILHOLT, O. B. PEDERSEN & B. N. SINGH. Riso National
Energy Commission (now ANSTO) Report No. Ml12. Laboratory, Roskilde, Denmark.
Lucas Heights Research Laboratories, New South Wales, YOUNG, R. A., PRINCE, E. & SPARKS, R. A. (1982). J. Appl.
Australia. Cryst. 15, 357-359.