research papers

Journal of
Applied
Estimation of statistical uncertainties in quantitative
Crystallography phase analysis using the Rietveld method and the
ISSN 0021-8898
whole-powder-pattern decomposition method
Received 18 February 2000
Accepted 26 July 2000 H. Toraya

Ceramics Research Laboratory, Nagoya Institute of Technology, Asahigaoka, Tajimi 507-0071,

Japan. Correspondence e-mail: toraya@crl.nitech.ac.jp

Formulae for estimating statistical uncertainties in quantitative phase analysis

# 2000 International Union of Crystallography
Printed in Great Britain ± all rights reserved
using the Rietveld method and the whole-powder-pattern decomposition
method have been derived. The relative magnitude of statistical uncertainty
for a derived weight Pfraction of a component in a mixture is given by (Wm)/Wm
N
= (1/Wm ÿ 1)1/2F(D iˆ1 Yoi)ÿ1/2, where Wm is the weight fraction of the mth
component, F is the goodness-of-®t
P index, D (1) is a factor depending on the
degree of peak overlap, and Yoi is the total sum of pro®le intensities in the 2
range used for whole-powder-pattern
P ®tting. If the step width
2P in step
scanning is halved, Yoi is almost doubled; on the other hand, Yoi is
proportional to the ®xed counting time T. Therefore, (Wm)/Wm / (
2/T)1/2.
Extension of the 2 range for whole-powder-pattern ®tting towards the high-
angle region is not effective for improving the precision of the derived weight
fractions if the pro®le intensities in that region are weak. The formulae provide
guidelines for optimizing experimental parameters in order to obtain a required
precision.

1. Introduction (McCusker et al., 1999). Error estimation is required as a basis

The procedure of quantitative phase analysis (hereinafter
QPA) using X-ray powder diffraction is widely used in ®elds of
science and engineering for materials research. It is also an
important tool for quality and process control in industry.
Various kinds of materials are analysed: some of them consist
of just two or three components having high crystallinity, while
some contain more than ten components. Many researchers
and engineers, having different levels of skill in analytical
techniques, are involved in QPA. Moreover, high-volume
analysis is usually required. In these circumstances there are
many possible sources of error, as has been evidenced by two
of these tasks.
Optimization of experimental conditions for intensity data
collection to obtain required accuracy and precision in X-ray
analyses is an interesting problem from a methodological
viewpoint and has been extensively studied with respect to
Rietveld re®nement (Hill & Madsen, 1984, 1986). It is also
important for improving cost±performance in materials
research and industry. A purpose of the present study is to
derive formulae for estimating statistical uncertainties in QPA
using the Rietveld method (Rietveld, 1969) and the whole-
powder-pattern decomposition (WPPD) method based on the
QPA round robins conducted using - and -silicon nitrides
(Si3N4) (Toraya et al., 1999).
High accuracy and precision with high reproducibility are
desired in all X-ray analyses. Many round robins have been
conducted regarding the measurement of unit-cell parameters
(Parrish, 1960; Masciocchi & Artioli, 1996; Blanton et al.,
1995), Rietveld re®nement (Hill, 1992; Hill & Cranswick,
1994), QPA (Toraya et al., 1999) and so on. However, their
results have always shown large scatterings of measured
values beyond the declared precision. One of the practical
ways for improving accuracy and precision in these analyses is
standardization of analytical methods, as has been demon-
strated by the round robins of silicon nitrides (Toraya et al.,
1999); another is preparation of guidelines for mastering
techniques, as have been written for Rietveld re®nement
1324 H. Toraya  Quantitative phase analysis
Pawley algorithm (Pawley, 1981; Toraya, 1986).
2. Formula for weight fractions
Let us consider a mixture consisting of M components. A
whole-powder-pattern ®tting for a powder diffraction pattern
of the sample using either the Rietveld method or the WPPD
method provides scale factors Sok (k = 1 to M) and their
estimated standard deviations (or uncertainties) (Sok) for the
individual components. Formulae for deriving weight fractions
from the re®ned scale factors have been given by Hill &
Howard (1987) for the Rietveld method and by Toraya &
Tsusaka (1995) for the WPPD method. Their generalized form
can be written as
J. Appl. Cryst. (2000). 33, 1324±1328
 research papers
.P
M P
M P
M
Wm ˆ am Som ak Sok ; …1† Wk ˆ 1 and
Wk ˆ 0:
kˆ1 kˆ1 kˆ1

where Wm is the weight fraction of the mth component in the The (Wm) and
Wm values may be combined as a quadratic
sample and ak is the coef®cient given by ak = ZkMkUk (Zk is sum when they are independent, and a formula for total error
the number of chemical formula units in a unit cell, Mk is the in Wm, represented by E(Wm), is
molecular weight and Uk is the unit-cell volume) for the
Rietveld method, and ak = 1/k (k is the mass absorption E…Wm † ˆ ‰…Wm †2 ‡
Wm2 Š1=2 :
coef®cient) for the WPPD method.
In kinematical theory, the integrated intensity is propor-
tional to the square of the number of unit cells in a unit
volume, NU2 = 1/U2 (James, 1967), and thus to the irradiated 4. Estimated standard deviation of the scale factor
volume V of a specimen. In both single-line techniques (Klug The calculated pro®le intensity at the ith step, Yci, is expressed
& Alexander, 1974) and whole-powder-pattern ®ttings for by
QPA, the weight fraction Wk is derived from a volume fraction
Vk by multiplying by the density k. In most computer P
M
Yci ˆ Bi ‡ Sk Ycik ; …6†
programs for Rietveld re®nement, NU2 and V are customarily kˆ1
included in the scale factor. The form of the scale factor does
where Bi is the background intensity and Ycik is the pro®le
not in¯uence crystal structural parameters. In QPA, however,
intensity of the kth component, representing the powder
the form of the intensity formula, the physical meaning of the
diffraction pattern of each component. In the least-squares
scale factor and the form of the coef®cient ak are all related.
method, we minimize the function
For example, ak will be rewritten ak = ZkMkUkÿ1 when the
formula for the integrated intensity is written so as to include P
N

ˆ wi …Yoi ÿ Yci †2 ;
NU2 or 1/U2 in the computer programs for Rietveld re®nement. iˆ1
In the following discussion, the scale factor Sok is rede®ned in
the form where N is the number of observations and wi is the weight
assigned to the ith observation, Yoi. The wi value is
Sk ˆ ak Sok : …2†
wi ˆ 1=Yoi ; …7†
Equation (2) converts the relation Sok / Vk into Sk / Wk.
Then equation (1) is replaced with when only the counting statistics error is taken into account.
.P The estimated standard deviation of Sk is calculated by
M
Wm ˆ S m Sk : …3† …Sk † ˆ …Aÿ1 1=2
kˆ1 kk † F; …8†

Introduction of Sk requires that the intensity formula be where Aÿ1

kk is the kth diagonal element of the variance±
divided by ak before or after whole-powder-pattern ®tting for covariance matrix and F is the goodness-of-®t index given by
Rietveld re®nement or pattern decomposition. hPN i1=2 .
Fˆ wi …Yoi ÿ Yci †2 …N ÿ M†1=2
iˆ1

3. Error functions (Prince, 1995). If we re®ne only the scale factors in the whole-
Errors in the scale factors are both statistical and systematic, powder-pattern ®tting for QPA, the kk0 th element of the
and they are dominant factors in errors in Wm. Therefore, a normal equation matrix, Akk0 , is
formula for statistical uncertainty in Wm, represented by the
P
N
0
symbol (Wm), can be derived from the formula for error Akk0 ˆ wi Ycik Ycik : …9†
propagation in the form iˆ1
n Individual terms in equation (9) will have large values when k
…Wm † ˆ Wm …1 ÿ Wm †2 ‰ 2 …Sm †=Sm2 Š
= k0 , while they will be small when the peak heights of two
PM o1=2 patterns for the k and k0 th components are very different from
‡ Wk2 ‰ 2 …Sk †=Sk2 Š : …4† each other. Therefore, off-diagonal terms of the normal
k6ˆm
equation matrix are expected to be negligibly small. More-
On the other hand, a formula for systematic error in Wm, over, contributions of wi(Ycik )2 are large at peaks while they are

Wm, is represented by small at tails. Then a magnitude of the weight wi can be
h P
M i approximated by

Wm ˆ Wm …1 ÿ Wm †…
Sm =Sm † ÿ Wk …
Sk =Sk † ; …5†
k6ˆm wi ' D=Sk Ycik ; …10†
when the systematic errors in the scale factors,
Sk, are added where D is the factor to be adjusted depending on the degree
by a direct sum (Toraya, 1999). From equations (3) and (5), we of peak overlap. The D value may be close to 1 if the powder
obtain diffraction pattern is well resolved, and will decrease with

J. Appl. Cryst. (2000). 33, 1324±1328 H. Toraya  Quantitative phase analysis 1325
research papers
increasing overlap of peaks with the peaks of other compo- The proportionality of (Wm)/Wm / (
2 )1/2 will be consis-
nents. Therefore tent with the observation that the estimated standard devia-
hP
N iÿ1 tions of atomic parameters decrease linearly with the
Aÿ1
kk ' …Sk =D† Ycik : reciprocal square root of the number of steps in the pattern
iˆ1 (Hill & Madsen, 1986). However, it should be noted that the
From equation (6), factor that is signi®cant in equation (14) [and equation (15)] is
not the number of observations but the total sum of pro®le
P
M
intensities. Therefore, expansion of the 2 range for the whole-
Sk Ycik ˆ Yci ÿ Bi :
kˆ1 powder-pattern ®tting towards the high-angle region will not
be effective for improving precision when the pro®le inten-
Summing all terms gives
sities (Yoi) are weak.
P
M P
N P
N The average value of (Wm), expressed by the symbol
Sk Ycik ˆ …Yci ÿ Bi †: (W)av, can be calculated as a root-mean-square using equa-
kˆ1 iˆ1 iˆ1
tion (14):
P kto the de®nition of Sk by equation (2), the quan-
According h 1=2 . i . P 1=2
tities Yci represent the total scattered intensities for the P
M N
…W†av ˆ 1 ÿ Wm2 …M ÿ 1†1=2 F D Yoi :
respective components with the same weight in the mixture;P k
mˆ1 iˆ1

P k contributes to Yci.
thus nearly the same number of electrons …16†
If the total scattered intensities Yci are
P approximately the
If the weight fractions of individual components are all the
same for all components, a solution for Ycik is obtained by
same, having the weight fraction Wav = 1/M, equation (16)
PN PN .P M becomes
Ycik ' …Yci ÿ Bi † Sk : …11†
iˆ1 iˆ1 kˆ1 . P
N 1=2
1=2
…Wav †av =Wav ' …1=Wav †F D Yoi : …17†
If the background intensity is negligibly small, equation (8) iˆ1
becomes
 P M 1=2 . P N 1=2
…Sm † ' Sm Sk F D Yoi : …12†
kˆ1 iˆ1 6. Examples
Using equation (3), 6.1. Binary system
. P
N 1=2 The ®rst example is the binary system of - and -Si3N4,
…Sm †=Sm ' …1=Wm1=2 †F D Yoi : …13† samples of which were used for the QPA round robins (Toraya
iˆ1
et al., 1999). In the present study, Rietveld re®nements were
Equation (13) simply states that (Sm)/Sm / Wmÿ1=2 . Since conducted in two modes, I and II: only the scale factors were
heavier weights are assigned to components with weaker adjusted (after a re®nement of all pro®le parameters) in
intensities in equation (9), the increase of relative uncertainty re®nement mode I, and all pro®le parameters were re®ned
of the scale factor, (Sm)/Sm, for a minor component is a until their convergence in mode II. The estimated standard
reasonable output from the least-squares method. deviations of the scale factors in modes I and II are repre-
sented by (Sk)I and (Sk)II, respectively. (Sk) represents
and Rwp
values calculated by equation (12) using observed Sk P
5. Statistical uncertainty in weight fraction
values. The following relation was used to obtain F/( Yoi)1/2
Substituting equation (13) into equation (4), we obtain from the Rwp values:
. P N 1=2 ÿ P
1=2
…Wm †=Wm ˆ …1=Wm ÿ 1†1=2 F D Yoi : …14† F= Yoi ˆ Rwp =…N ÿ M†1=2 : …18†
iˆ1
These three kinds of estimated standard deviations are
The relative uncertainty of the mth weight fraction, (Wm)/ compared for sample C4 (W1:W2 = 95:5) and sample C9
Wm, is independent of the number of components, M, and the
weight fractions of the remaining components in the sample.
The term (Wmÿ1 ÿ 1)1/2 becomes Wmÿ1=2 when Wm  1. In that
case, (Wm)/Wm ' (Sm)/Sm.
Here, the step width and the ®xed counting time at each
step in step scanning the pro®le intensity are represented
P by
the symbols
2 and T, respectively.PIf
2 is halved, Yoi is
almost doubled. On the other hand, Yoi is proportional to T.
Therefore, equation (14) states that
(W1:W2 = 51:49) in Table 1 (k = 1 for -Si3N4 and k = 2 for -
Si3N4). Two kinds of estimated standard deviations for the
derived weight fractions were calculated by using equation
(14) assuming D = 1, and by using equation (4) plus the (Sk)I
values. They are expressed by (Wk) and (Wk)I, and given in
Table 2.
Differences between the (Sk) and (Sk)I values are just 10
to 20%, indicating that the equations are based on correct
assumptions. As was pointed out in x5, (Wm)/Wm ' (Sm)/Sm
for -Si3N4 with Wm of 0.05 and 0.49 for samples C4 and C9,
…Wm †=Wm / …
2=T†1=2 : …15†
respectively. Equations (12), (13) and (14) have ®ve factors

1326 H. Toraya  Quantitative phase analysis J. Appl. Cryst. (2000). 33, 1324±1328
 research papers
Table 1 (Wm)I/Wm by equation (4) in
Comparison of the estimated standard deviations of the scale factors. the present study. The (Wm)I/
PM
The scale factors are normalized by kˆ1 Sk = 1. Wm values are plotted in Fig. 1:
-Si3N4 -Si3N4 four plots, for example, of
Sample S1 (S1) (S1)I (S1)II S2 (S2) (S2)I (S2)II
CaCO3 correspond to the
(Wm)I/Wm values of P samples
C4 0.9472 0.0015 0.0017 0.0033 0.0528 0.0004 0.0005 0.0007 S10A to S10D. The F/( Yoi)1/2
C9 0.4990 0.0012 0.0015 0.0023 0.5010 0.0012 0.0015 0.0024
values for samples S10A to
S10D are reported to be in the
Table 2 range 0.00159±0.00166. Theoretical (Wm)/W Pm values, derived
Comparison of the estimated standard deviations for the weight fractions. by equation (14) using an average F/( Yoi)1/2 value of
The (W1) values were calculated using equation (14); the (W1)I values were 0.00163, were multiplied by a factor of 2.0, which corresponds
obtained via equation (4) and (S1)I. to a D value of 0.25 in equation (14), and they are plotted as a
Sample W1 (W1) (W1)I thick curved line in Fig. 1. The factor 2.0 was obtained as an
average ratio of (Wm)I/(Wm) for sample S10B, of which
C4 0.9472 0.0004 0.0005
C9 0.4990 0.0009 0.0010 weight fractions are all the same (Wk = 0.1 for all k). There-
fore, the theoretical value will be roughly half of the observed
value in the present case if we assume that D = 1 in equation
that could lead to the underestimation or overestimation of (14). The D value of 0.25 arises from dense peak overlaps in
(Sm) and (Wm). First is ignorance of parameter interactions
that increase when all pro®le parameters are re®ned in whole-
powder-pattern ®tting; this explains larger values of (Sk)II
than those of (Sk)I. Second is ignorance of the background
intensity. Rietveld re®nement of a single-phase -Si3N4
sample gives (S1) = 0.0017 and (S1)I = 0.0019 for a
normalized scale factor S1 = 1.0. A difference of 11% between
(S1) and (S1)I arises P from the second factor. P It can be
diminished if we use wi(Yoi ÿ Bi)2 instead of Yoi. The
third factor is ignorance of parameter interactions among the
scale factors. However, contributions of the off-diagonal terms
to the Aÿ1
kk in this case are generally much smaller compared to
those of the ®rst and second factors; they are just 1.5 and 2.3%
for samples C4 and C9, respectively.
The ®rst and second factors always lead to an under-
estimation of (Sm) and (Wm); the third factor also usually
underestimates them. The fourth factor is the parameter D in
the weight function de®ned by equation (10). With increasing Figure 1
overlap of the peaks with those of the remaining components, Plots of observed and calculated values of (Wm)I/Wm against Wm.
the magnitude of the weight decreases and the (Sm)/Sm value
increases. Therefore, equation (14) will, in principle, under-
estimate errors in QPA if we assume that D = 1. The ®fth
factor is the deviation from equality of the total scattered
intensities of individual components, which is assumed in
deriving equation (11). Since peaks of - and -Si3N4 are
relatively well resolved (Fig. 7 of Toraya et al., 1999), we could
assume that D = 1. However, the fourth and ®fth factors
appear to be appreciable in a ten-component system, as will be
discussed in the following section.

6.2. Ten-component system

The second example is a ten-component system consisting
of oxides and an oxygen compound in different ratios [samples
S10A, S10B, S10C and S10D as described by Hayashi &
Toraya (1999)]. The scale factors and their estimated standard
deviations, obtained in re®nement mode I (2 range 30.8±80 ), Figure 2 P
were provided by S. Hayashi and were used for calculating Variations of (Sk), (Sk)I, F and ( Yoi)ÿ1/2 with 2HAL.

J. Appl. Cryst. (2000). 33, 1324±1328 H. Toraya  Quantitative phase analysis 1327
research papers
the ten-component samples. It may be noted here that the
magnitude of the D value partly involves the second and third
factors discussed in x6.1.
The theoretical curve varies in proportion to (1/Wm ÿ 1)1/2
and the observed plots are distributed along the curve. We can
also see that the plots for materials containing heavy metal
elements, and thus with strong scattering power per unit
weight, are distributed below the curve, while those for
materials with relatively light elements are above the curve.
These distributions are considered to be the result primarily of
the ®fth factor discussed in x6.1.
Table 3 presents a comparison of observed (Wav)av/Wav
values with those calculated by equation (17), assuming a D
value of 0.25; good agreement between the observed and
calculated values is found.
6.3. Dependence on 2h range
2HAL represents the high-angle limit of the 2 range used
for whole-powder-pattern ®tting. In Fig. 2, the (Sk) and
(Sk)I values are plotted against 2HAL for -Si3N4 in sample

P 20ÿ1/22) together with the goodness-of-®t
C9 (low-angle limit
index F and ( Yoi) . The (Sk) and (Sk)I values run
parallel to each other. Magnitudes of their variations become
small when 2HALPexceeds 80 ; these changes conform with
the variation of ( Yoi)ÿ1/2 rather than that of F. The small
magnitudes in the high-angle region are in accordance with
the relation, as expected in x5, between (Sk) [and (Wk)] and
the 2 range used for whole-powder-pattern ®tting.
7. Conclusions
Formulae for estimating statistical uncertainties in QPA using
the Rietveld method and the whole-powder-pattern decom-
position method have been derived. The relative magnitude of
statistical uncertainty for the derived weight fraction [(Wm)/
Wm] hasPbeen shown to be proportional to (Wmÿ1/2 ÿ
1)1/2F(D Yoi)1/2 and, therefore, to (
2/T)1/2. Extension of
the 2 range for whole-powder-pattern ®tting towards the
high-angle region has little effect on improving the precision
of derived weight fractions if the pro®le intensities in that
region are weak. The well resolved pattern with larger D value
will give smaller (Wm)/Wm. Theoretical values were consis-
tent with the observed values for the samples of binary and
ten-component systems. When a powder diffraction pattern of
a mixture with a D value of 0.25 is scanned (typical
experimental conditions) in a 2 range of 20±80 at a step
width of 0.02 and it is analyzed at a reliability index Rwp of
10%, the expected (W)m/Wm value may be 1% for a
1328 H. Toraya  Quantitative phase analysis
Table 3
Comparison of calculated [equation (17)] and observed values (Wav)av/
Wav (%).
Sample
S10A S10B S10C S10D
(Wav)av/Wav from equation (17) 1.05 1.04 1.01 1.03
(Wav)av/Wav observed 0.95 0.97 0.94 1.00
component with Wm of 10%. The D value, which is a func-
tion of the peak overlap, is determined either by sampling
once under practical experimental conditions or by using
accumulated experimental data. The formulae for statistical
uncertainties will provide guidelines for optimizing experi-
mental parameters, such as scan range, step width and ®xed
counting time in step scanning, to obtain a speci®ed precision.
The author wishes to thank Mr S. Hayashi of the Ceramics
Laboratory, the Mie Prefectural Industrial Research Institute,
for his kind offer of the results of a quantitative phase analysis
of ten-component mixtures. He also wishes to thank Dr T. Ida
of Nagoya Institute of Technology for valuable comments.
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