467

J. Appl. Cryst. (1987). 20, 467-474

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

(Received 2 April 1987; accepted 23 June 1987)

Abstract 'standard' pattern. For the specific case of Bragg-

The weight of a phase in a mixture is proportional to
the product of the scale factor, as derived in a multi-
component Rietveld analysis of the powder diffraction
pattern, with the mass and volume of the unit cell. If
all phases are identified and crystalline, the weight
fraction W of phase p is given by
Wp = Sp( Z M IOp/~ S,( Z M IO,,
i
where S, Z, M and V are, respectively, the Rietveld
scale factor, the number of formula units per unit cell,
the mass of the formula unit and the unit-cell volume.
This is the basis of a method providing accurate phase
analyses without the need for standards or for labori-
ous experimental calibration procedures. The method
is demonstrated by measurements on binary mixtures
of rutile, corundum, silicon and quartz.
Introduction
X-ray powder diffraction has been used for quantita-
tive phase analysis since the mid-1930s (Clark &
Reynolds, 1936). By contrast, there has been, to the
best of our knowledge, only one application of neu-
tron powder diffraction to phase analysis, namely a
study of austenite in maraging steel by Windsor,
Sinclair, Faulkner, Rainey & Slattery (1984). The
methods rely on the fact that (i) each crystalline
component has a unique set of diffraction-peak po-
sitions and intensities, (ii) the diffraction patterns of
the components overlap without interference, and (iii)
the intensity of the pattern of each component is a
function of the amount present.
Diffraction measurements of phase abundance can
be performed in many ways [Klug & Alexander (1974)
and references therein], but all methods ultimately
rely on comparison of the intensity of a particular
peak (or set of peaks) from a phase in the sample with
the intensity of the corresponding peak(s) from a
Brentano geometry in which reference is made only to
phases present in a particular sample (i.e. the internal
standard and matrix-flushing methods), the effects of
matrix absorption can be ignored and the relationship
between phase abundance and diffraction-peak inten-
sity reduces to
Wp = ( lp';,)( W~/Rp), (1)
where Wp and W~are the weight percentages of phase p
and the standard phase s, Ip and I xare the intensities of
a peak or set of peaks from p and s, and Rp is the
'reference intensity ratio' ofp with respect to s (Klug &
Alexander, 1974; Chung, 1974).
Calibration of the relationship between peak inten-
sity and phase abundance [i.e. determination of the
value of Rp in (1)] is usually executed empirically, but
increasing use is being made of constants derived from
calculated diffraction-peak intensities (Hubbard,
Evans & Smith, 1976; Alexander, 1977; Altree-
Williams, 1978; Hill, 1982). The use of calculated
intensities has much to commend it since the constants
are then derived from an ideal model in which the
sample is composed of perfectly ordered and ran-
domly oriented crystallites (unless deliberately
altered), providing a 'standard' pattern free from
preferred-orientation, extinction, surface-roughness
and amorphous-component effects.
If step-scan diffraction data are collected, the deter-
mination of relative intensities need not be restricted
to individual peaks, or even to groups of peaks, but
can be extended to incorporate the entire diffraction
pattern by the use of 'whole-pattern' fitting procedures
(Werner, Salome, Malmros & Thomas, 1979; Weiss,
Kraji6ek, Smr6ok & Fiala, 1983; Toraya, Yoshimura &
Somiya, 1984; Smith, Johnson & Ruud, 1986). This
technique has the advantages of (i) permitting par-
tially overlapping (as well as free-standing) reflections
to contribute to the analysis, and of (ii) 'averaging out'
most of the effects of preferred orientation, extinction
and other systematic aberrations.

0021-8898/87/060467-08501.50 © 1987 International Union of Crystallography

468 QUANTITATIVE PHASE ANALYSIS F R O M N E U T R O N P O W D E R D I F F R A C T I O N DATA
The whole-pattern fitting methods are of two kinds.
In the Rietveld method (Rietveld, 1969), the diffraction
profile is calculated using the unit-cell dimensions to
determine the peak positions, and the atomic po-
sitional and thermal displacement parameters as a
model for the peak intensities. On the other hand, in
the 'pattern-decomposition' technique, the step-scan
data are decomposed into their component Bragg
reflections without reference to the crystal structure
(other than the unit-cell dimensions); that is, the
calculated peak intensities are themselves variables in
the fitting procedure (Sonneveld & Visser, 1975).
The pattern-decomposition method provides a con-
venient means of measuring more accurately the
relative peak intensities and, therefore, of determining
the usual (experimentally derived) calibration curves
(Toraya et al., 1984) and Rp values (Smith et al., 1986).
The Rietveld method calculates the peak intensities
directly from crystal structure parameters, and so it
has the advantage of permitting the determination of
phase abundance without precalibration of either the
experimental or calculated kind (Werner et al., 1979;
Weiss et al., 1983). Of course, the same advantage is
present when integrated intensities are obtained by
calculation but in this case the deconvolution of
overlapping peaks in complex diffraction patterns
remains a serious limitation of the method. To date,
the general utility of both the calculated-constant and
fitted-profile (Rietveld) methods has been diminished
by (i) confusion about the definition of 'absolute',
'relative', and 'instrumental' scale factors (Hubbard et
al., 1976) and (ii) problems associated with the treat-
ment of preferred orientation (Weiss et al., 1983) and
absorption (Hubbard et al., 1976; Werner et al., 1979).
In this paper we derive a simple relationship be-
tween phase abundance and the Rietveld scale factor,
and test this on data from Rietveld refinements of
high-resolution neutron powder diffraction patterns
collected on binary mixtures of ruffle/corundum, ru-
tile/quartz and silicon/quartz. We argue that, for
quantitative phase analysis, neutron powder diffrac-
tion offers distinct advantages over the more com-
monly used X-ray technique in that (i) the diffraction
patterns are representative of the bulk sample, rather
than surface regions, (ii) absorption in the individual
phases can be effectively ignored, and (iii) the data are
more extensive [because neutron scattering lengths do
not decrease with (sin 0)/2], leading to more accurate
estimates of thermal displacement parameters, and
hence to more reliable scale factors.
Theory
The Rietveld method is commonly applied to powder
diffraction patterns in which counts are recorded for
equal effective times at equal intervals of 20. For
quantitative analysis, it is useful to start with a
formulation for the step intensity Yi which gives an
absolute calculation of the number of neutrons diffrac-
ted. The analysis of the neutron powder diffraction
pattern by Sabine (1980) provides a suitable starting
point.
Sabine (1980) showed that, in the single-phase case,
for a single peak with a Gaussian line shape, the
number of neutrons received by a counter at an angle
20 is given by
y(20) = ~023hwvp'JNc2F 2 exp ( - 2W)
x a exp ( - px2)t(81tr2p sin 0 sin 20) - l,
(2)
where 4'o, z are the neutron flux and wavelength, r is the
specimen-to-counter distance, h, w, t are the aperture
height and width and the counting time, p', p are the
actual and theoretical densities, v is the specimen
volume, N~ is the number of unit cells per unit volume
(i.e. l/V, where V is the unit-cell volume of the material),
F, exp ( - 214/) are the structure factor per unit cell and
an (overall) Debye-Waller factor for the intensities, J is
the reflection multiplicity, x is 2(0 - Ok), where Ok is the
Bragg angle for the kth reflection, p is 4H-21n2, a is
2 H - l ( r t - l l n 2 ) 1/2, and H is the full-width of the re-
flection at half-maximum intensity. This equation is
based on kinematic theory, and takes no account of
absorption.
The calculated contribution from the peak to the
number of neutrons received by the counter at the
angle 20i, denoted Yic, can be recast as
Yi~ = SJkLklFkl2GiR, (3)
where S is the scale factor, Jk is the reflection multi-
plicity, L k is the Lorentz factor (sin Ok sin 2 0 k ) - 1 , f k
is the structure factor, including displacement
factors [[Fk[2 corresponds to F 2 exp ( - 2 W ) in (2)],
and Gig is a normalized Gaussian profile function
[ a e x p ( - p x 2) in (2)]. The scale factor contains
other quantities from (2) and is
S=(p'N2v/p)C (4)
where C -- (~o23hwt)/(8/tr2).
Equation (3), with (4), holds when profiles are non-
Gaussian, provided only that Gig is correctly norma-
lized. When more than one diffraction peak con-
tributes at an angle 20i, the calculated count is a
summation over contributing peaks k,
Yic = S ~ JkLklFkl2Gik . (5)
k
With the addition of the background, denoted Yib at
20i, the total calculated count is
Y,c = Y,b + S~,JkLkIFkIEG,k • (6)
k
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

Table 1. Summary of phase, sample and refinement details

Parameter Silicon ~t-Quartz Rutile Corundum
Formula Si SiO2 TiO2 AI2Oa
Space group Fd3m P3121 P42/mnm R~c
ZM V* 36027 20370 9985 156034
Wavelength (,~,) 1-377 1"893 1.893 1.893
20 scan range (o) 20-160 20-160 25-160 25-160
Max. step intensity (counts)t 1050 1910 1460 780
Number of unique reflections 21 41 28 36
Number of structural parameters:~ 2 8 5 6
Number of profile parameters 8 8 8 8
Mixtures examined: Rutile/corundum Rutile/quartz Silicon/quartz
1:9§ 1:1 l:l
3:7
1:1§
7:3
*Product of Z, the number of formula units in the unit cell, M, the mass of the formula unit (in atomic mass units), and I/, the unit-cell volume
(in A3).
t Represents the average value collected on each of eight detectors.
++Includes atomic positional and displacement parameters and unit-cell dimensions.
§These compositions were also examined using 'Linde A' corundum.

(v) Problems related to sample mixing, sampling of
the mixture, and number of crystallites measured,
have been discussed by Klug & Alexander (1974) in
connection with X-ray quantitative analysis. Since the
volumes sampled by neutrons are very much larger
than those in an X-ray experiment, these problems are
rare in neutron analysis.
(vi) Amorphous or poorly crystalline material does
not contribute to diffraction peaks, and so is not
determined by (11). It has been suggested (Klug &
Alexander, 1974; Altree-Williams, Byrnes & Jordan,
1981) that there may be a significant fraction of
amorphous surface material in chemically pure pow-
ders, especially in samples that have undergone ex-
tensive milling. The amount of amorphous material in
a mixture may be determined by the addition of a
known weight of (crystalline) internal standard prior
to the phase analysis.
Experimental
Equation (11) was tested using various binary
mixtures of the phases silicon (Si), 0t-quartz (SiO2),
rutile (TiO2) and corundum (A1203). These materials
were selected primarily because of their availability in
pure form, but also because their crystal structures are
well characterized and display an acceptable range of
structural complexity; relevant details of their crystal
structures are provided in Table 1, along with the
ZMV values appropriate for use in (11).
The sample of Si was a commercial laboratory
reagent chemical that had been extensively character-
ized in earlier X-ray and neutron diffraction studies;
the ~-quartz was a commercial ( - 2 0 0 # ) sample of
silica digested in 2 M HC1 to remove impurities and
heated at 1075 K for 2 h; the rutile was prepared from
pure anatase by heating at 1475 K for 2 h, ground in
an acetone slurry in a tungsten carbide mill for 10 min
and annealed at 1075 K for 2 h; the corundum was
a sample of either 'Linde C' (1.0 ~tm) or 'Linde A'
(0"3 ~tm) annealed at 1075 K for 4 h.
Pairs of these phases were combined in the propor-
tions shown in Table 1 (by weighing to at least four
significant figures) to yield a volume of approximately
15cm 3. The mixtures were homogenized by hand
grinding in a pestle and mortar and loaded into a 16
x 50 mm vanadium can for neutron powder diffrac-
tion data collection.
Diffraction data for the pure phases and binary
mixtures were recorded at 295 K on the eight-counter
fixed-wavelength high-resolution powder diffractom-
eter (HRPD) at the Australian Nuclear Science and
Technology Organisation's research reactor HIFAR
at Lucas Heights, New South Wales. This instrument
(in an earlier single-counter configuration) has been
described by Howard, Ball, Davis & Elcombe (1983).
The data were recorded under monitor control at
intervals of 0.05 ° between 15 and 160° 20 using a
wavelength of 1.893 A (except Si, for which the wave-
length was 1-377 A). Several mixtures were remea-
sured using 1"377 ,~, neutrons as a test for the possible
effects of extinction. The scattering lengths used for Si,
O, AI and Ti were 4.149, 5.805, 3.449 and -3.438 fm,
respectively.
The least-squares structure and profile refinements
were performed with the Rietveld analysis program
LHPM1 described .by Hill & Howard (1986). The
background was defined by a three-parameter poly-
nomial in 20", where n had values between 0 and 2,
and was refined simultaneously with the unit-cell,
zero-point, scale, peak-width/shape/asymmetry and
crystal-structure parameters. The peak shape was
 R. J. HILL AND C. J. HOWARD 471

Voigtian, with the widths of the Gaussian and

Lorentzian components coded to vary in accordance
with the Caglioti, Paoletti & Ricci (1958) function (to
model the effects of particle strain and the inherent
broadening due to the instrument) and with sec 0 (to
describe particle-size effects), respectively. The cal-
culated peak intensity was distributed over 3.5 peak
full-widths at h a l f - m a x i m u m on either side of the peak
(e) centre. Peak a s y m m e t r y was modelled by a sum of five
Voigtians. Convergence was assumed to have been
achieved when the p a r a m e t e r shifts in the final cycle of
refinement were less t h a n 10% of the associated
estimated s t a n d a r d deviation (e.s.d.). The observed*
neutron powder diffraction profiles for the TiO2 and
A120 a powders and their mixtures are presented in
Fig. 1, and the plot o u t p u t from a Rietveld analysis of
the diffraction pattern from the mixture of 30% (by
weight) TiO 2 with 70% A12Oa, is given in Fig. 2. A
(c) j~
j_ s u m m a r y of the structural p a r a m e t e r s from all refine-
ments of the pure phases and mixtures is given in
Table 2.

(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

20 q.O 60 80 100 120 1~0 160

28 [degreesD
* Listings of the observed step-scan neutron diffraction data for
Fig. 1. Neutron diffraction patterns from TiO 2 and 'Linde C' Al203 all mixtures have been deposited with the British Library Document
powders and their mixtures. The patterns are from (a) pure Supply Centre as Supplementary Publication No. SUP 44140
A1203, (b) 10 wt% TiO 2 with 90 wt% A1203, (c) 30% TiO2 with (49 pp.). Copies may be obtained through The Executive Secretary,
70% A1203, (d) 50% TiO2 with 50% A1203, (e) 70% TiO 2 with International Union of Crystallography, 5 Abbey Square, Chester
30o/o AI20 3, and (f) pure TiO2. CH1 2HU, England.

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

40 60 80 1O0 120 1~0 !60

28 [de9rees]
Fig. 2. Output from a Rietveld analysis of the diffraction pattern from a mixture of 30 wt% TiO 2 with 70 wt% AI203 [profile (c) in Fig. I].
The observed data are indicated by crosses and the calculated profile is the continuous line overlaying them. The short vertical lines below
the pattern represent the positions of all possible Bragg reflections for TiO2 (top row) and A1203 (bottom row). The lower curve is the
difference between the observed and calculated intensity at each step, plotted on the same scale. The analysis yields the scale factors, from
which the composition is derived.
472 QUANTITATIVE PHASE ANALYSIS F R O M N E U T R O N POWDER D I F F R A C T I O N DATA

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

0% Si 50% Si 100% Si 50% SiO 2

Si
a (A) - - 5.4320(1) 5.4321(1)
Si B(A:) - - 0-52(1) 0-50(1)
RB (%) - - 0"86 0"47
SiOz (0t-quartz)
a (/~,) 4"913~ 4"9153(1) 4"9144(1) - 4"9153(1)
c (/t~) 5.4052 5"4072(1) 5"4062(1) - 5-4071(1)
Si x 0"46987(9) 0-4700(2) 0-4698(4) - 0"4695(4)
B (A 2) 0"48 0"43(3) 0"48(3) - 0-50(5)
O x 0"4141(2) 0"4126(2) 0-4135(2) - 0"4126(3)
y 0"2681(2) 0"2667(2) 0-2671(3) - 0"2665(3)
z 0.2145(1) 0.2140(1) 0.2146(2) - 0-2141(2)
B (/~2) 1.02 0-95(2) 0-88(1) - 0.91(2)
Rn (%) 1.57 2.88 2.48 - 2.89
Rwp (%) - 6.29 5.92 6-61 5-98
GofF - 1.98 2.04 1.56 1.66
* Structural parameters from Shintani, Sato & Saito (1975); equivalent isotropic B only. Parenthesized figures here and elsewhere in the
tables represent the e.s.d, in terms of the least-significant figure to the left. No absorption corrections were applied during the analysis.
~fStandard Rietveld analysis agreement indices (Young, Prince & Sparks, 1982).
++Structural parameters from Lewis, Schwarzenback & Flack (1982); equivalent isotropic B only.
§Structural parameters from Le Page & Donnay (1976); equivalent isotropic B only.

In particular, the atomic coordinates and thermal
displacement parameters do not vary by more than 2.5
combined e.s.d.'s, and the unit-cell dimensions are all
within five combined e.s.d.'s. As expected, the param-
eter errors increase as the proportion of the phase
declines in the mixture.
The crystal structural parameters (i.e. atomic co-
ordinates and thermal parameters) obtained from the
neutron powder refinements are in close agreement
with the results of single-crystal X-ray studies of each
phase (Table 2). There are relatively large systematic
differences in the unit-cell dimensions obtained from
the X-ray and neutron data. The neutron values are,
however, internally consistent; they differ from the X-
ray results only as a result of the inherent uncertainty
in the neutron wavelength value. Taken together, the
results displayed in Table 2 lend confidence to the
parameter values obtained from Rietveld analysis in
cases where a particular phase cannot be completely
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.

The results of the phase-analysis determinations are Concluding remarks

summarized in Table 3 and Fig. 3. The agreement
The scale factors derived from Rietveld analysis of
between the experimental and as-weighed compo-
multi-phase powder diffraction data are related to the
sitions is satisfactory (i.e. within 2"5 e.s.d.'s) for the
phase composition of the mixture by a simple al-
rutile/'Linde C' corundum and rutile/quartz mixtures,
gorithm involving the product of the mass and volume
but there is an error of up to 3-4wt% for the
of the unit-cell contents of each phase. The method
rutile/'Linde A' corundum and silicon/quartz mixtures.
The scale factors (hence the weight percentages) are
reproducible to much less than one e.s.d, for repe- 1O0 [ , I I l , ] I ,:
titions of the experiment performed on completely
different samples. Errors of this relatively modest
magnitude are rarely obtained in X-ray phase- oo 80
...
t_
analytical procedures using calculated calibration ,4-

constants (Hubbard et al., 1976). Moreover, the smal- ~-o~

ler errors often quoted in the case of analyses per-
~% 60
t-
formed with experimentally determined calibration 4-- O~
D t3
constants may be grossly underestimated owing to the
incorporation of systematic errors (e.g. amorphous E
o
ca_

content, non-stoichiometry, extinction, absorption) L*-t -

'4..- 40
into the experimental constants; such camouflaging of C "--

errors cannot occur when calculated constants are

used, as in the present work. o 20
The rutile/'Linde A' corundum and silicon/quartz
mixtures have been re-examined in closer detail in an d
,,'"
attempt to explain their relatively poorer analytical 0 1 I I I I I I I
results. Firstly, diffraction data for the 1:1 mixtures 0 20 40 60 80 I00
were re-collected at a wavelength of 1.377 A, rather Composition as we ghed
than 1.893 A. No significant variation in the scale (weight per cent T i O 2]
factors (i.e. compositions) was observed for either
Fig. 3. Relationship between the composition determined from the
mixture, indicating that (i) extinction was not a major neutron diffraction pattern and the as-weighed sample compo-
problem, and (ii) the reproducibility of the analyses is sition (wt% TiO2) for the series of binary mixtures of 'Linde C'
again satisfactory for different experimental con- A120 3 and TiO2. Error estimates are smaller than the plotted
ditions. symbols for each analysis•
474 Q U A N T I T A T I VPHASE
E ANALYSIS FROM NEUTRON POWDER DIFFRACTION DATA
requires no standards (other than a knowledge of the
crystal structure parameters) or laborious calibration
procedure and can be performed with both X-ray and
neutron powder diffraction data. Applications of the
quantitative analysis technique described above are
being presented elsewhere for the specific cases of
zirconia ceramics (Howard, Hill & Reichert, in prepa-
ration), and lead-acid battery materials (Hill, Jessel &
Rand, in preparation).
We thank Ms J. Hodge of the Physics Department,
New South Wales Institute of Technology, for prepar-
ing the futile specimen, and Mr M. A. M. Sufi, from
the Nuclear Energy Unit, Puspati, Malaysia, for
assistance with data analysis.
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