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Accuracy in Rietveld Quantitative Phase Analysis

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Article in Journal of Applied Crystallography · March 2003

DOI: 10.1107/S002188980301375X

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 electronic reprint
Journal of
Applied
Crystallography
ISSN 0021-8898

Accuracy in Rietveld quantitative phase analysis of Portland cements

A. G. De la Torre and M. A. G. Aranda

Copyright © International Union of Crystallography

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J. Appl. Cryst. (2003). 36, 1169–1176 De la Torre and Aranda  Portland cements
 research papers
Journal of
Applied
Accuracy in Rietveld quantitative phase analysis of
Crystallography Portland cements
ISSN 0021-8898

A. G. De la Torre and M. A. G. Aranda*

Received 19 February 2003
Accepted 16 June 2003
Departamento de QuõÂmica InorgaÂnica, CristalografõÂa y MineralogõÂa, Universidad de MaÂlaga, 29071
MaÂlaga, Spain. Correspondence e-mail: g_aranda@uma.es

# 2003 International Union of Crystallography
Printed in Great Britain ± all rights reserved
The polymorphs that constitute most Portland cements have been synthesized:
tricalcium silicate, dicalcium silicate, aluminate, ferrite, gypsum, bassanite and
calcite. They have been used to prepare arti®cial mixtures, i.e. white Portland
clinker, grey Portland clinker and two types of grey Portland cements.
Quantitative mineralogical analyses of these mixtures have been obtained by
laboratory X-ray powder diffraction ( = 1.54 A Ê ) and the Rietveld method. To
assess the accuracy of these analyses, high-energy synchrotron X-ray powder
data ( = 0.40 A Ê ) for the same mixtures have also been studied. Furthermore,
synchrotron X-ray powder data were collected for binary mixtures of the
polymorphs and a corundum standard. This was done to determine the presence
of impurity crystalline phases in the synthesized samples and to check the
presence of non-negligible amorphous phase contents. The errors in the
synchrotron X-ray analyses are quite low (usually smaller than 1 wt%). The
relative errors in the laboratory X-ray analyses are of the order of 2% for the
main phases and increase to approximately 5±10% for the low-content
components. These errors are acceptable in the factory environment and the
routine application of this methodology in the cement industry is being
implemented.

1. Introduction In the cement industry, QPA using X-ray powder diffrac-

X-ray powder diffractometry has been used as an analytical
technique for a long time (Klug & Alexander, 1974; Zevin &
Kimmel, 1995). In recent years, there has been great interest in
the application of the Rietveld method (Rietveld, 1969) to
obtain quantitative phase analysis (QPA) of simple mixtures
(Hill & Howard, 1987; Bish & Howard, 1988; Madsen et al.,
2001) using X-ray powder diffraction. This methodology is
standardless but the crystal structures for every crystalline
phase in the sample must be known as the process consists of
the comparison between the measured and calculated powder
diffraction patterns. QPA by the Rietveld method gives phase
fractions normalized to 100% crystalline phases, while the
amorphous/non-diffracting/non-de®ned crystalline content is
not usually accounted for.
Inherent bene®ts of QPA using the Rietveld method have
encouraged its application to complex mixtures (Scarlett et al.,
2002), and to industrial materials such as Portland cements
(De la Torre, Cabeza et al., 2001; Taylor et al., 2000; Neubauer
& Sieber, 1996), aluminous cements (Guirado et al., 2000),
archaeological ceramics (Kockelmann & Kirfel, 2001),
mineralized Portland cements (Pajares et al., 2002) and
calcium sulphoaluminate cements (Schmidt & PoÈllmann,
2000). The Rietveld methodology has also been used to
determine indirectly the amorphous content in a given crys-
talline sample by adding a suitable standard (De la Torre,
Bruque & Aranda, 2001).
tometry and the Rietveld method is the most auspicious
alternative to control on-line the production process (Schmidt
& Kern, 2001). Much effort to develop prototype systems has
been exerted recently (Manias et al., 2000; Scarlett et al., 2001),
allowing the mineralogical compositions of the clinker and
cement streams to be followed on-line in a factory. To date,
X-ray ¯uorescence (XRF) provides the elemental composition
used to infer the mineralogical composition of these materials
by means of Bogue calculations (Bogue, 1929). Problems with
this methodology are well known (Taylor, 1997) and mainly
arise from the lack of thermodynamical equilibrium in the kiln
and because it does not take into account the elemental
substitutions in a given phase, which is usually important in
these phases. Nevertheless, the Bogue method is still in
worldwide use to estimate the main phase fractions as part of
quality control.
To implement the Rietveld methodology for these mixtures,
it is essential to have the crystallographic description for every
phase that may be present. White Portland clinkers have three
phases and grey Portland clinkers have an additional fourth
phase. Cement nomenclature will be used hereinafter, i.e. C =
CaO, S = SiO2, A = Al2O3, F = Fe2O3, S = SO3, C = CO2 and H =
H2O. The main phase, alite (C3S or Ca3SiO5), has seven
polymorphs (Taylor & Aldridge, 1993), but the complex
monoclinic superstructure is usually present in Portland
cements because of the stabilization effect of the Al3+ and

J. Appl. Cryst. (2003). 36, 1169±1176 De la Torre and Aranda  Portland cements 1169
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research papers
Mg2+ elemental substitution (De la Torre et al., 2002). The sample volume yields a better determination of the true
second phase, belite (C2S or Ca2SiO4), has ®ve polymorphs, crystalline contents of the arti®cial mixtures. This work is a
but in the industrial samples, the  phase is usually present
(Mumme et al., 1996). Aluminate (C3A or Ca3Al2O6) may
crystallize in four polymorphs depending upon the alkaline
content (Na, K); the cubic and orthorhombic phases are
commonly present in cements (Goetz-Neunhoeffer &
Neubauer, 1997). In grey Portland clinkers, ferrite (C4AF or
Ca4Al2Fe2O10) is also present and it crystallizes in an orthor-
hombic structure that can be primitive or body-centred
depending upon the Fe/Al ratio. The body-centred polymorph
is usually found in clinkers (Guirado et al., 1996). In ®nal grey
Portland cements, three additional phases are usually found:
gypsum (CSH2 or CaSO4.2H2O), bassanite (CSH0.5 or
CaSO4.0.5H2O) and calcite (CC or CaCO3). Bassanite is not
added but it is formed in the cement mills as a result of the
partial dehydration of gypsum at the milling temperature.
The application of Rietveld methodology to laboratory
powder diffraction data of these systems has some known
handicaps that can be partially overcome (De la Torre et al.,
2002) to obtain relatively reliable QPA. Although the preci-
-Al2O3 (99.997% from Alfa) were weighed to obtain 6 g
sion of the laboratory studies can be estimated, the accuracy of
such analyses is not known and it is dif®cult to measure.
However, knowledge of the accuracy of these analyses is very
important if this methodology is to be transferred to industry.
To evaluate this, the use of commercial samples is not
adequate since the `true' mineralogical compositions are not
known and it is very dif®cult to measure them by other
techniques to an acceptable low error level.
In order to evaluate the accuracy of Rietveld QPA of
Portland cements, arti®cial samples have been prepared by
mixing suitable synthesized phases in the appropriate
proportions. Hence, an expected mineralogical phase fraction,
step forward in the application of the Rietveld method to
ordinary Portland cements.
2. Experimental section
2.1. Specimen and sample preparation
2.1.1. Synthesis of pure phases. The appropriate poly-
morphs of the main constituents of Portland clinkers (mono-
clinic C3S, monoclinic C2S, cubic C3A and orthorhombic
C4AF) were synthesized. Polycrystalline CaCO3 was used as
received (99.95% from Alfa). Polycrystalline CaSO4.2H2O
was prepared by carefully grinding a piece of a high-quality
gypsum single crystal. Bassanite was synthesized by grinding
3 g of gypsum single crystal. The powder was heated at 365 K
for 24 h and then to 373 K for another 24 h.
C3S-alite. Adequate amounts of CaCO3, Mg(OH)2.4Mg-
CO3.5H2O (99% from Aldrich), SiO2 (99.7% from ABCR)
and
of (Ca2.93Mg0.07)O3(SiO2)0.98(Al2O3)0.01. This Mg/Ca and Si/Al
elemental substitution stabilizes the monoclinic alite structure
at room temperature. The mixture was ground in an agate ball
mill at 200 r.p.m. for 30 min and heated at 1273 K in a Pt
crucible for 6 h. The resulting solid was ground in an agate ball
mill at 200 r.p.m. for 30 min, pelletized, heated at 1723 K for
6 h (10 K minÿ1 heating rate) and cooled by turning off the
furnace (5 h to 423 K). Finally, the mixture was ground in an
agate mortar, pelletized, and heated at 1773 K for 6 h twice, as
previously described.
C2S-belite. Dicalcium silicate has several polymorphs but
the elemental substitution and the thermal cooling in Portland
our `true mineralogical composition', is available and we can clinkers stabilize the  form. -Ca2SiO4 is stable above 953 K
determine the accuracy of the procedure. Laboratory X-ray and it must be (meta)stabilized at room temperature. The
powder diffraction patterns may have several non-random stable polymorph at room temperature is the
phase
errors, such as poor sample averaging, preferred orientation or
transformation on
texture, optical aberrations which change with 2, etc. There-
fore, high-energy parallel synchrotron X-ray powder diffrac-
tion data have been collected for all samples as these data are
(Nettleship et al., 1992), and the !
cooling has to be avoided. It is known that this transformation
is precluded if the C2S particle size is small and the cooling
rate is high. A mixture of the stoichiometric proportions of
almost free from these errors, providing the best analyses that
can be obtained. Furthermore, this may be slightly compli-
cated by the presence of non-diffracting regions in the
prepared polymorphs. In order to check this, all `pure' arti®-
cial phases were mixed with a crystalline standard, -Al2O3, to
obtain a set of corrected crystalline phase fractions. Related
studies where QPA Rietveld analyses using laboratory data
were compared with the results of optical microscopy have
-Al2O3 was prepared to obtain 3 g of cubic
been reported (Neubauer et al., 1997; Neubauer, 1998; FuÈll-
mann et al., 2001; Walenta et al., 2001; Kern, 2001).
The main aim of this work is to evaluate the accuracy of
Rietveld QPA for Portland clinkers and cements using
laboratory X-ray powder diffraction data. The use of
synchrotron radiation has several advantages: (i) the high-
resolution synchrotron data allows one to distinguish the
-Al2O3 and Fe2O3 (99.95% from Alfa). The mixture was
appropriate polymorph and to know if the structural
descriptions for the phases are adequate; (ii) the large tested
1170 De la Torre and Aranda  Portland cements
electronic reprint
CaCO3 and SiO2 was prepared to obtain 5 g of -Ca2SiO4. The
mixture was heated at 1273 K for 4 h, cooled and ground in an
agate ball mill at 100 r.p.m. for 1 h. The powdered sample was
pelletized and heated in a platinum crucible at 1473 K for 1 h
(20 K minÿ1 heating rate) and quenched in air. The sample
underwent this treatment three times.
C3A-aluminate. A mixture of stoichiometric amounts of
CaCO3 and
Ca3Al2O6. The sample was ground in an agate mortar and
heated at 1273 K for 6 h. The product was pelletized and
heated at 1723 K with a heating rate of 10 K minÿ1 for 6 h and
cooled by turning off the furnace.
C4AF-ferrite. 5 g of orthorhombic Ca4Al2Fe2O10 was
synthesized by mixing stoichiometric proportions of CaCO3,
heated at 1273 K during 4 h and the resulting product was
ground in an agate mortar and pelletized. The pellets were
J. Appl. Cryst. (2003). 36, 1169±1176
 research papers
Table 1 number of particles, 40, were studied for each phase.
Weight fractions for binary mixtures and synchrotron X-ray powder Gypsum and bassanite were not studied as they are not stable
diffraction results, along with RF and Rwp values.
in vacuum under the electron beam. Linear absorption coef-
Binary Weighed SXRPD RF Rwp Ê and  = 1.54 A
®cients, , for  = 0.40 A Ê X-rays are also given
mixture (Wi) (%) (Ri) (wt%) (%) (%) fc
in Table 2.
C3S 49.85 47.75 (6) 5.41 10.8 0.9194 Four mixtures, imitating commercial Portland samples, were
-Al2O3 50.15 52.25 (7) 2.20 prepared. The simplest mixture is the arti®cial white Portland
C2S 49.55 50.29 (4) 2.57 7.6 1.0300
-Al2O3 50.45 49.71 (5) 2.22 clinker (AWC), which contains three phases. The arti®cial grey
C3A² 50.14 49.68 (4) 4.72 7.5 0.9818 Portland clinker (AGC) contains four phases. Two arti®cial
-Al2O3 49.86 50.32 (5) 2.89 Portland cements (labelled AC1 and AC2) were also prepared,
C3A³ 50.14 49.30 (3) 3.87 6.9 0.9670
-Al2O3 49.86 50.70 (3) 2.05 which contain six and seven crystalline phases, respectively.
C4AF 50.02 47.91 (4) 3.59 7.9 0.9190 The weighed fractions are given in Tables 3±6.
-Al2O3 49.98 52.09 (4) 2.95
Gypsum 50.00 50.26 (4) 2.67 6.0 1.0105
-Al2O3 50.00 49.74 (4) 1.64 2.2. X-ray data collection
Bassanite 49.87 49.24 (6) 3.72 8.0 0.9751
-Al2O3 50.13 50.76 (6) 1.53 Synchrotron X-ray powder diffraction (SXRPD) patterns
CaCO3 51.03 52.58 (4) 3.21 6.5 1.0641 have been collected on the ID31 diffractometer of ESRF,
-Al2O3 48.97 47.42 (4) 1.98 European Synchrotron Radiation Facility (Grenoble, France),
using a short penetrating wavelength  = 0.400269 A Ê
² Measured in a capillary of 2 mm. ³ Measured in a capillary of 1 mm.
(30.97 keV) selected with a double-crystal Si (111) mono-
heated at 1623 K for 12 h (10 K minÿ1 heating rate) and chromator and calibrated with NIST Si (a = 5.43094 A Ê ). The
cooled by turning off the furnace. The synthesis temperature standard Debye±Scherrer con®guration was used. Samples
was well below the melting temperature. were loaded in borosilicate glass capillaries (diameter 2 mm)
The crystalline standard used to prepare the binary and rotated during data collection. The overall measuring time
mixtures was -Al2O3. This compound was synthesized from was 100 min in order to obtain very good statistics over the

-Al2O3. The solid was ground in an agate ball mill at 200 angular range 2.5±30 (in 2) (9.15±0.77 A Ê ). The data from the
r.p.m. for 30 min and heated at 1373 K for 4 h in a Pt crucible. multi-analyser Si(111) stage coupled with the nine scintillation
The oxide was cooled by turning off the furnace and ground in detectors were normalized and summed to 0.002 step size
an agate mortar for 5 min. A second thermal treatment was with local software to produce the ®nal raw data.
carried out at 1473 K for 6 h. The resulting solid was ground in Laboratory X-ray powder diffraction, LXRPD, patterns
an agate mortar and sieved (<0.125 mm) prior to being were recorded on a Siemens D5000 /2 diffractometer (¯at
weighed. The crystallinity of this compound has been studied re¯ection mode) by using Cu K1,2 radiation (1.542 A Ê ) with a
in previous work (De la Torre, Bruque & Aranda, 2001). secondary curved graphite monochromator and a goniometer
2.1.2. Artificial mixtures. Seven binary mixtures of the radius of 220 mm. The diffractometer optic used to collect the
`pure' cement phases with the -Al2O3 standard were clinker samples comprised a ®xed aperture slit of 2 mm, one
prepared and analysed by synchrotron X-ray powder diffrac- scattered-radiation slit of 2 mm after the sample, followed by a
tion. In order to obtain good particle dispersion, each mixture system of secondary Soller slits and the detector slit of 0.2 mm.
(800 mg) was ground in an agate mortar for 30 min. The The diffractometer optic used to collect the cement samples
weighed fractions of each binary mixture are shown in Table 1. (with gypsum and bassanite) comprised a ®xed aperture slit of
The average particle size, d, for each pure cement phase is 1 mm, one scattered-radiation slit of 1 mm after the sample,
shown in Table 2. The sizes were estimated from a scanning followed by a system of secondary Soller slits and the detector
electron microscope (SEM) characterization using a Jeol SM slit of 0.1 mm. The X-ray tube operating conditions were
840 electron microscope with gold-metallized samples. A large 40 kV and 30 mA for clinkers and 40 kV and 40 mA for

Table 2
Mean particle size, linear absorption coef®cients, unit-cell parameters and reference for the structural description of the studied phases.
C3S C2S C3A C4AF CSH2 CSH0.5 CC A

d (mm) 8 2 15 15 ± ± 10 0.3
 = 0.4 AÊ (cmÿ1) 6.0 5.7 5.1 10.6 2.5 3.6 3.7 1.9
 = 1.54 AÊ (cmÿ1) 314 303 267 495 139 195 197 120
Space group Cm P21/n Pa3 Ibm2 I2/c I2 
R3c 
R3c
Ê)
a (A 33.1043 (2) 5.51124 (3) 15.26783 (2) 5.56501 (2) 5.67798 (4) 12.0153 (2) 4.99117 (1) 4.76011 (2)
b (AÊ) 7.03783 (4) 6.75397 (3) 15.26783 14.51501 (5) 15.2090 (1) 6.9445 (2) ± ±
Ê)
c (A 18.5263 (1) 9.31335 (5) 15.26783 5.34628 (2) 6.52670 (5) 12.6818 (1) 17.06772 (4) 12.99457 (6)
 ( ) 94.141 (1) 94.574 (1) ± ± 118.478 (1) 89.824 (2) ± ±
V (A Ê 3) 4305.0 (6) 345.565 (4) 3559.03 (1) 431.853 (3) 495.425 (5) 1058.17 (2) 368.222 (1) 254.992 (2)
Reference De la Torre et al. Mumme et al. Mondal & Colville & De la Torre et al. Bezou et al. Maslen et al. This work
(2002) (1995) Jeffery (1975) Geller (1971)² (unpublished) (1995) (1995)

² Occupation factors in the text.

J. Appl. Cryst. (2003). 36, 1169±1176 De la Torre and Aranda  Portland cements 1171
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research papers
cements. All samples were loaded in a methacrylate holder by
gently sample-front pressing and they were rotated during
data collection at 15 r.p.m. to obtain better powder averaging.
The 2 range was 10±70 , in 0.03 steps, counting between 15
and 25 s per step. The data for the four arti®cial mixtures were
collected twice; the samples were reground (5 min) and
reloaded in the holder.
2.3. X-ray data analysis
The powder patterns were re®ned by the Rietveld method
with the GSAS suite of programs (Larson & Von Dreele, 1994)
by using a pseudo-Voigt peak shape function (Thompson et al.,
1987) with the asymmetry correction of Finger et al. (1994)
included. Some phases present anisotropic line shape broad-
ening, which has to be taken into account. For very high-
resolution synchrotron data, the approach based on multi-
dimensional distribution of lattice metrics reported by
Stephens (1999) and included in GSAS is encouraged. Some
phases showed preferred orientation in the LXRPD patterns.
For simple texture effects, the March±Dollase correction
(Dollase, 1986) was used (gypsum along [010], bassanite along
[100], calcite along [104] and C4AF along [020]). A minor
correction for gypsum and bassanite was also used in the
SXRPD re®nements. The texture effect of C3S, for front-
loaded samples, in the LXRPD patterns is complex. These
texture effects increase as the C3S particle sizes are larger, and
are exacerbated for patterns collected from cement pellets.
There is no doubt that the spherical-harmonic correction (Von
Dreele, 1997) gives much better ®ts and results for this phase

Table 3
Comparison of the weight fractions for arti®cial white Portland clinker.
Weighed and corrected weighed mass fractions are compared with the QPA from SXRPD and LXRPD analyses by the Rietveld method. Rwp values are also given.
Weighed (%) Weighedc (%) SXRPD (wt%) LXRPD1 (wt%) LXRPD2 (wt%)

C3S 79.98 78.33 79.53 (5) 78.3 (1) 79.0 (1)

C2S 15.01 16.47 15.10 (13) 17.3 (4) 16.2 (4)
C3A 5.01 5.20 5.37 (6) 4.4 (1) 4.8 (1)

Rwp (%) ± ± 12.5 7.5 7.7

Table 4
Comparison of the weight fractions for arti®cial grey Portland clinker as in Table 3.
Weighed (%) Weighedc (%) SXRPD (wt%) LXRPD1 (wt%) LXRPD2 (wt%)

C3S 60.00 58.25 60.15 (8) 60.5 (2) 62.6 (1)

C2S 20.00 21.75 20.24 (10) 22.8 (2) 20.0 (2)
C3A 10.00 10.29 9.59 (6) 8.5 (1) 9.4 (1)
C4AF 10.00 9.70 10.02 (7) 8.2 (2) 8.0 (2)

Rwp (%) ± ± 11.2 6.5 6.9

Table 5
Comparison of the weight fractions for arti®cial grey Portland cement-1 as in Table 3.
Weighed (%) Weighedc (%) SXRPD (wt%) LXRPD1 (wt%) LXRPD2 (wt%)

C3S 62.00 60.35 61.64 (7) 61.1 (2) 60.9 (2)

C2S 15.00 16.36 15.16 (10) 17.7 (5) 17.2 (5)
C3A 5.00 5.16 5.52 (5) 5.1 (1) 5.3 (1)
C4AF 10.00 9.73 9.49 (6) 7.6 (1) 8.0 (1)
Gypsum 4.00 4.28 4.29 (6) 3.9 (1) 4.1 (2)
Bassanite 4.00 4.13 3.90 (6) 4.6 (2) 4.5 (2)

Rwp (%) ± ± 10.6 10.3 12.6

Table 6
Comparison of the weight fractions for arti®cial grey Portland cement-2 as in Table 3.
Weighed (%) Weighedc (%) SXRPD1 (wt%) SXRPD2 (wt%) LXRPD1 (wt%) LXRPD2 (wt%)

C3S 65.00 63.05 64.06 (6) 63.78 (6) 62.7 (2) 62.2 (2)
C2S 10.00 10.87 9.66 (11) 9.69 (11) 11.5 (3) 10.8 (3)
C3A 5.00 5.14 5.36 (5) 5.50 (4) 5.1 (2) 5.2 (1)
C4AF 5.00 4.85 4.76 (5) 4.94 (5) 4.4 (2) 5.1 (2)
Gypsum 5.00 5.33 5.49 (7) 5.54 (7) 4.9 (1) 4.9 (2)
Bassanite 5.00 5.14 4.96 (6) 4.85 (6) 5.5 (2) 5.6 (2)
CaCO3 5.00 5.61 5.71 (6) 5.70 (6) 5.9 (1) 6.2 (2)

Rwp (%) ± ± 11.1 11.1 11.2 12.2

1172 De la Torre and Aranda  Portland cements J. Appl. Cryst. (2003). 36, 1169±1176
electronic reprint

in LXRPD patterns collected in ¯at geometry. A value of 1 for
the texture index represents an ideal random powder whereas
1 would stand for a single crystal.
The references for the crystal structures used to calculate
powder patterns are given in Table 2. When anisotropic
vibration temperature factors are reported, these were
converted to the corresponding isotropic values and intro-
duced in the Rietveld analyses. The structure of -Al2O3 used
in all binary Rietveld re®nements has Al at (0, 0, 0.35227) and
O at (0.69396, 0, 1/4) (Maslen et al., 1993). The thermal
coef®cients were Uiso = 0.004 A Ê 2 for both atoms.
There are several reports (e.g. Scho®eld et al., 1996)
describing the crystal structure of gypsum. However, the ®ne
structural details of such a simple inorganic solid,
CaSO4.2H2O, are not well known. This is due to problems with
the single crystals, which present spots with irregular shapes
(for twin-free crystals). The positional parameters are not
greatly affected but the thermal parameters vary enormously
in the reported structures. We are carrying out a structural and
microstructural study of gypsum with ultra-high resolution
synchrotron powder diffraction which will be reported else-
where.
-C2S were detected in
research papers
The re®ned overall parameters were background coef®-
cients, cell parameters, zero-shift error, peak shape para-
meters, preferred orientation (when appropriate) and phase
fractions. Brindley correction was not applied. The peak shape
parameters (GW and LY) were re®ned freely for each phase in
the synchrotron patterns. However, the strong peak over-
lapping in the laboratory X-ray patterns did not allow free
re®nements of these parameters. For alite, we could re®ne
both GW and LY; for the remaining phases GW was set to
5.0 (0.01 )2 and only LY was re®ned.
3. Results
3.1. Binary mixtures
The ®rst step of this work was to characterize each `pure'
single phase with SXRPD data of binary mixtures with -
Al2O3. Quantitative phase results for these analyses are given
in Table 1. From the results of these analyses, we can calculate
a correction factor, fc, that takes into account the deviation of
the SXRPD Rietveld re®ned phase fractions from the weighed
ones. The unit-cell parameters for the studied phases are
reported in Table 2 for the sake of comparison with the
corresponding values for commercial Portland clinkers and
cements.
The SXRPD pattern of the alite + Al2O3 sample showed
that alite was a pure crystalline phase and belite was not
observed. Three synthesized samples were not completely
pure phase. (i) Diffraction peaks from
the SXRPD pattern of the -C2S + -Al2O3 binary mixture.
The Rietveld analysis of the three phases gave: 50.18 (4)% for
-C2S (wt%).
-C2S was that reported
Figure 1
(a) Low-angle region of an LXRPD2 Rietveld plot ( = 1.54 A
arti®cial Portland cement-2 with the main diffraction peaks labelled. The
phases are: C3S, C2S, C4AF, C3A, CSH0.5, CSH2 and CC. (b)
Intermediate-angle region of the LXRPD2 Rietveld plot ( = 1.54 A
for arti®cial Portland cement-2 as in (a).
J. Appl. Cryst. (2003). 36, 1169±1176
electronic reprint
-C2S, 49.68 (5)% for -Al2O3 and 0.14 (2)% for
The crystal structure description for
by Mumme et al. (1995). (ii) Anhydrite, CaSO4, was detected
as an impurity in the bassanite sample. This phase was
described with the crystal structure published by Kirfel & Will
(1980). The Rietveld result for the CaSO4.0.5H2O + -Al2O3
binary mixture was 48.86 (6)% for bassanite, 50.45 (5)% for
corundum and 0.69 (2)% for anhydrite (wt%). (iii) C3A was
detected in the C4AF + -Al2O3 binary mixture. The re®ne-
ment with the three phases converged to: 47.83 (4)% for
C4AF, 52.03 (4)% for -Al2O3 and 0.14 (1)% for C3A (wt%).
However, the impurity content was always smaller than 1%
and becomes very dilute in the prepared arti®cial mixtures.
The Rietveld analyses of the SXRPD patterns of the arti®cial
mixtures did not evidence these impurities. Hence, we report
the analysis of these three samples as two-phase mixtures in
Table 1.
The crystal structure of C4AF was re®ned starting from that
reported (Colville & Geller, 1971). This structure has two sites
for Al and Fe atoms, one tetrahedral and the other octahedral.
It is known that the Fe/Al ratios in these two sites depend
upon the synthesis, mainly the cooling rate. The Fe/Al ratios
Ê ) for
were constrained to full occupancy and to maintain the
nominal stoichiometry, overall Fe/Al = 1. Fe content
Ê) converged to 70.2 (2)% at the octahedral site [0, 0, 0.0023 (2)]
and, therefore, to 29.8% in the tetrahedral site [0.9257 (2), 1/4,
De la Torre and Aranda  Portland cements 1173
research papers
0.9534 (1)]. Isotropic thermal parameters were also re®ned.
This re®ned structure was used for the structural description
of C4AF in the arti®cial mixtures.
SXRPD data for the C3A mixture were collected twice.
Firstly, the sample was loaded in a capillary of 2 mm and
secondly in a 1 mm capillary. Rietveld results for both analyses
are given in Table 1. The main diffraction peak for C3A
created problems in the ®tting because it had a smaller
experimental intensity than that calculated from the structure.
All other peaks were ®tted nicely, so secondary extinction was
the likely cause of this intensity problem. We recorded an
additional pattern with a 1 mm capillary to rule out the
saturation problem in the detectors. The recorded intensity of
the main peak presented the same problem. The extinction
correction implemented in GSAS improved the ®t but the
problem was still present. Therefore, this region (8.46±8.53
2) was removed from all the patterns where C3A was present.
We also have problems with the main peak of CaCO3 (7.39±
7.71 2), again arising from secondary extinction. However,
the discrepancy for the main peak of this compound was
smaller. This region was also removed from the re®nement of
the binary mixture pattern. Secondary extinction was not
observed in any LXRPD pattern.
The Rwp values for all re®nements are given in Tables 1 and
3±6. We also report RF for each phase in Table 1 in order to
illustrate the quality of the ®tting for each phase. It should be
noted that this R factor depends on the agreement between
the recorded pattern and the structural description for that
phase.
3.2. Artificial mixtures
The four arti®cial Portland mixtures have been analysed by
the Rietveld method using both SXRPD and LXRPD data.
The results for the AWC sample are given in Table 3. They
include the weighed fractions, the corrected crystalline
weighed fractions (using fc), the re®ned fractions from the
analysis of the SXRPD pattern and the re®ned fractions from
the study of both LXRPD patterns.
The results for the AGC sample, with four phases, are given
in Table 4. Similar results for the AC1 sample, with six phases,
are given in Table 5. The results for the AC2 sample, with
seven phases (®ve being at low contents, 5 wt%) are given in
Table 6. SXRPD data for the AC2 sample were measured and
analysed twice in order to evaluate the precision in the QPA of
these type of data. The Rietveld plots of the LXRPD2 data for
AC2 are shown in Fig. 1.
4. Discussion
The objective of this work is to evaluate the accuracy of QPA
of Portland cement mixtures by using LXRPD data analysed
with the Rietveld method. The standard mixtures were
analysed with high-energy parallel synchrotron X-rays in
order to obtain the best possible QPA results using the Riet-
veld method. Furthermore, by analysing the binary mixtures
with corundum, we can obtain a set of corrected crystalline
1174 De la Torre and Aranda  Portland cements
electronic reprint
weighed fractions that would account for deviations if strong
amorphous content is present in some `pure' crystalline phase.
We must note that weighed fractions included all the mass but
the QPA with the Rietveld method only accounts for the
crystalline fractions. It must be emphasized that the poly-
morphs used in this study are those present in the commercial
Portland clinkers and cements. Thus, the results of this study
with arti®cial mixtures can be directly exported to the analyses
of commercial samples.
4.1. Binary mixtures
It should be noted that the errors stated in Table 1 are those
only arising from the counting statistics of the patterns. The
correction factor, fc, for each phase is inferred using the
RpWs/RsWp ratio, where Wp and Rp stand for the weighed
fraction and the Rietveld result for the characterized phase,
respectively, and Ws and Rs stand for the same values for the
standard. In an ideal case, the fc value must be 1.00. The fc
value departs from 1.0 because (i) it may cause problems in
the samples (minor crystalline phase not de®ned, amorphous
and non-coherently diffracting regions, etc.), (ii) the particle
statistics (powder averaging) are not ideal, (iii) problems
describing the peak shape, and (iv) inadequacies in the
structural descriptions of some phases. The fc values reported
in Table 1 do not deviate very importantly from 1.0, which
indicates that the samples do not have large amounts of
amorphous phases and that the structural descriptions for
those phases are adequate. This is also independently shown in
Table 1 by the low value of the RF factors for these phases.
The SXRPD pattern for the C3A binary mixture was
collected twice. The results are quite close but not identical.
The relative error is smaller than 1% (absolute error lower
than 0.5%) indicating a high precision in the SXRPD analysis.
The fc value used for C3A was the average, 0.9744. fc values
were used to obtain the corrected crystalline mass fractions for
arti®cial mixtures, Weighedc which are given in Tables 3±6. It
must be noted that C3A powder diffraction peaks are extre-
mely sharp with a full width at half-maximum (FWHM) of
0.005 , while the FWHM for -Al2O3 was 0.009 . Owing to the
short wavelength used, microabsorption is not an important
problem in the SXRPD analyses (see Table 2). However,
secondary extinction was observed for C3A and CC in the
SXRPD patterns (high-energy X-rays) but not in the LXRPD
patterns (low-energy X-rays). This effect was likely caused by
the combination of high-energy X-rays, large particle sizes and
the mosaic block size of the powder grains for the two phases.
4.2. Artificial mixtures
We will focus now on the core part of this work with the
results shown Tables 3±6. Comparing the weighed fractions
and the corrected weighed fractions, we inferred that the non-
diffracting regions in the `pure' phases are not very important
since these values do not differ signi®cantly. Furthermore, the
QPA obtained from the Rietveld re®nement of the SXRPD
patterns agree fairly well with these values. It should be noted
J. Appl. Cryst. (2003). 36, 1169±1176

that the two main drawbacks of QPA using the Rietveld
re®nement and powder diffraction (microabsorption and poor
powder averaging of the different phases) are overcome by
high-energy synchrotron powder diffraction working in
Debye±Scherrer geometry with wide capillaries.
The QPA of SXRPD data of Portland cements is both
precise and accurate. The precision in the SXRPD data
analyses is very high, as shown in Table 6 (AC2 sample) where
two analyses with data recorded from two different capillaries
are presented. This is a very complex case with seven phases,
®ve of them being at the 5 wt% level. The relative errors
between the two analyses (precision) in the two main phases
are smaller than 0.5%, and in the low-content phases they are
smaller than 3% (absolute errors always lower than 0.3%).
Furthermore, the SXRPD data analyses are also considered to
be accurate because the determined weight fractions agree
fairly well with the Weighed and Weighedc values; see Tables
3±6. It should be noted that the QPA values from the
synchrotron studies are systematically slightly closer to the
weighed fractions than to the corrected values. The relative
errors compared with the Weighed and Weighedc values
(accuracy) are of the order of 1% for the main phases and of
the order of 3±4% for the low-content phases. These results
are outstanding and they clearly show that the high-energy
SXRPD method is the more appropriate method to char-
acterize/certify standard mixtures for QPA using powder
diffraction.
However, SXRPD is an expensive technique to char-
acterize/certify standard mixtures and routine QPA using
powder diffraction has to be carried out in-house with
laboratory X-ray devices. Tables 3±6 present a comparison of
LXRPD data, the SXRPD results and Weighed and Weighedc
values. We have repeated each analysis to evaluate the
precision and accuracy of the QPA using LXRPD data of
Portland cements mixtures. At this point, it is important to
estimate and compare the active sample volumes in both the
SXRPD and LXRPD techniques. For SXRPD patterns
recorded in transmission, the calculation of the irradiated
volume is easy. Taking into account the beam size (4 mm
horizontal and 2 mm vertical), the capillary radius of 1 mm,
and for an approximate capillary compaction coef®cient of
50%, the irradiated volume was 6.3 mm3. For LXRPD
patterns recorded in re¯ection, the calculation of the irra-
diated volume is approximate. Furthermore, it changes with
the slits used in the clinker and cements studies. For a 2, 2,
0.2 mm set of slits (clinkers), the beam size at 20 (2) was
10 mm  16 mm wide. For an average linear absorption
coef®cient of 300 cmÿ1 and an attenuation of 80%, the
resulting surface-perpendicular penetration depth at this
angle was 5 mm. Thus, the calculated active sample volume was
0.7 mm3. For a 1, 1, 0.1 mm set of slits (cements), the beam
size at 20 (2) was 6 mm  16 mm wide. In this case, the
calculated active sample volume was 0.4 mm3. Hence, the
irradiated sample volume in SXRPD is an order of magnitude
larger than those in LXRPD, which leads to better particle
statistics and to a higher precision and accuracy in the QPA.
Rotation of the holder during LXRPD data collection
J. Appl. Cryst. (2003). 36, 1169±1176
electronic reprint
research papers
improves the particles averaging in these `relatively small'
probing volumes.
AWC is the simplest mixture; the results are shown in Table
3. The QPA results for the AGC sample are shown in Table 4.
The values are satisfactory as the relative errors from the
LXRPD data are of the order of 2% for the main phases and
of the order of 8% for the low-content phases. It should be
noted that C4AF is invariably underestimated in all LXRPD
analyses (see Tables 4±6). This is due to microabsorption
effect in this phase. The linear absorption coef®cient of the
AWC mixture for Cu K1,2 is approximately 320 cmÿ1 and the
 value for C4AF is larger at 495 cmÿ1. The microabsorption
effect is more pronounced in our arti®cial mixtures as the
average particle size of C4AF is large, 15 mm (see Table 2).
Furthermore, this phase showed a small preferred orientation
effect, which was corrected as described in the experimental
section. However, these problems are not important in
commercial samples, in which the particle size of this phase is
small (<1±2 mm) as it is the last crystallizing fraction on
cooling in the kiln.
The QPA results for the AC1 sample are shown in Table 5.
The results are very satisfactory since the values obtained
from the LXRPD analyses are quite close to those expected.
The main difference is the above-described underestimation
of C4AF due to microabsorption. It must be noted that the
relative errors in the low-content phases are not very high,
being smaller than 10%.
The QPA results for the AC2 sample are shown in Table 6.
This is the most complex case with seven crystalline phases.
Composite cements may contain mineral additions such as
limestone. Quanti®cation of this phase is not an easy task since
the most intense peaks are overlapped with those arising from
tricalcium silicate. However, its quanti®cation is possible and,
furthermore, the relative errors in the low-content phases are
not very high, being of the order of 10±15% for these phases.
The quality of the re®nements is good, as evidenced in the
difference curves of Fig. 1, which are quite ¯at.
It should be noted that the texture effect for C3S in these
arti®cial mixtures is not pronounced where alite particles have
been grown in the solid state. This is much more important for
commercial samples. This is likely due to the difference in the
particle sizes for the different phases. In the studied samples,
the particle sizes are similar; however, for commercial samples
the particle sizes for C3S are much larger than those of the
other minor phases and, consequently, become more orien-
tated (De la Torre & Aranda, 2003). Furthermore, alite of
commercial Portland cements grows in the liquid phase, which
leads to well de®ned crystals. The alite particles with large and
clean surfaces exhibit strong preferred orientation.
5. Conclusions
We have shown that quanti®cation of Portland cement
mixtures is possible with laboratory powder diffraction data
and the Rietveld method. Firstly, the structural descriptions of
the phases are adequate. Secondly, good quanti®cations of the
Portland cement phases can be obtained with relative errors of
De la Torre and Aranda  Portland cements 1175
research papers
the order of 2±3% for the main phases and 5±10% for the low-
content phases. Finally, high-energy synchrotron powder
diffraction is highly appropriate to characterize standard
mixtures for QPA using powder diffraction.
We thank the ESRF, Grenoble, for providing synchrotron
X-ray beam time on ID31.
References
Bezou, C., Nonat, A., Mutin, J. C., Christensen, A. N. & Lehmann, M.
S. (1995). J. Solid State Chem. 117, 165±176.
Bish, D. L. & Howard, S. A. (1988). J. Appl. Cryst. 21, 86±91.
Bogue, R. H. (1929). Ind. Eng. Chem. (Anal. Ed.) 1, 192.
Colville, A. A. & Geller, S. (1971). Acta Cryst. B27, 2311±2315.
De la Torre, A. G. & Aranda, M. A. G. (2003). Proceedings of the 11th
International Congress on the Chemistry of Cement, pp. 135±144.
Durban, South Africa. ISBN 0-958-40858-0.
De la Torre, A. G., Bruque, S. & Aranda, M. A. G. (2001). J. Appl.
Cryst. 34, 196±202.
De la Torre, A. G., Bruque, S., Campo, J. & Aranda, M. A. G. (2002).
Cement Concrete Res. 32, 1347±1356.
De la Torre, A. G., Cabeza, A., Calvente, A., Bruque, S. & Aranda, M.
A. G. (2001). Anal. Chem. 73, 151±156.
Dollase, W. A. (1986). J. Appl. Cryst. 19, 267±272.
Finger, L. W., Cox, D. E. & Jephcoat, A. P. (1994). J. Appl. Cryst. 27,
892±900.
FuÈllmann, T., Walenta, G., PoÈllmann, H., Gimenez, M., Lauzon, C.,
Hagopian-Babikian, S., Dalrymple, T. & Noon, P. (2001). Int.
Cement Rev. 2, 41±43.
Goetz-Neunhoeffer, F. & Neubauer J. (1997). Proceedings of the 10th
International Congress on the Chemistry of Cement, Gothenburg,
edited by H. Justnes.
Guirado, F., GalõÂ, S. & ChinchoÂn, S. (1996). World Cement Res. Dev.
pp. 73±76.
Guirado, F., GalõÂ, S. & ChinchoÂn, S. (2000). Cement Concrete Res. 30,
1023±1029.
Hill, R. J. & Howard, C. J. (1987). J. Appl. Cryst. 20, 467±474.
Kern, A. (2001). Accuracy in Powder Diffraction III. Gaithersburg:
NIST.
Kirfel, A. & Will, G. (1980). Acta Cryst. B36, 2881±2890.
Klug, H. & Alexander, L. E. (1974). X-ray Diffraction Procedures.
New York: John Wiley.
Kockelmann, W. & Kirfel, A. (2001). J. Archaeol. Sci. 28, 213±222.
Larson, A. C. & Von Dreele, R. B. (1994). GSAS ± General Structural
Analysis System, Los Alamos National Laboratory Report No. LA-
UR-86-748.
1176 De la Torre and Aranda  Portland cements
View publication stats
electronic reprint
Madsen, I. C., Scarlett, N. V. Y., Cranswick, L. M. D. & Lwin. T.
(2001). J. Appl. Cryst. 34, 409±426.
Manias, C., Retallack, D. & Madsen, I. C. (2000). World Cement,
February, pp. 78±81.
Maslen, E. N., Streltsov, V. A., Streltsova, N. R. & Ishizawa, N. (1995).
Acta Cryst. B51, 929±939.
Maslen, E. N., Streltsov, V. A., Streltsova, N. R., Ishizawa, N. & Satow,
Y. (1993). Acta Cryst. B49, 973±980.
Mondal, P. & Jeffery, J. W. (1975). Acta Cryst. B31, 689±697.
Mumme, W., Cranswick L. & Chakoumakos B. (1996). Neues Jahrb
Mineral.-Abhandlungen, 170, 171±188.
Mumme, W. G., Hill, R. J., Bushnell-Wye, G. & Segnit, E. R. (1995).
Neues Jahrb Mineral.-Abhandlungen, 169, 35±68.
Nettleship, I., Slavick, K. G., Kim, Y. J. & Kriven W. M. (1992). J. Am.
Ceram. Soc. 75, 2400±2406.
Neubauer, J. (1998). Proceedings of the 20th International Conference
on Cement Microscopy, Guadalajara, pp. 103±119.
Neubauer, J., PoÈllmann, H. & Meyer, H. W. (1997). Proceedings of the
10th International Congress on the Chemistry of Cement, pp. 7±18,
3v007.
Neubauer, J. & Sieber, R. (1996). Mater. Sci. Forum, 228±231, 807±
812.
Pajares, I., De la Torre, A. G., MartõÂnez-RamõÂrez, S., Puertas, F.,
Blanco-Varela, M. T. & Aranda, M. A. G. (2002). Powder Diffr. 17,
281±286.
Rietveld, H. M. (1969). J. Appl. Cryst. 2, 65±71.
Scarlett, N. V. Y., Madsen, I. C., Cranswick, L. M. D., Lwin. T.,
Groleau, E., Stephenson, G., Aylmore, M. & Agron-Olshina, N.
(2002). J. Appl. Cryst. 35, 383±400.
Scarlett, N. V. Y., Madsen, I. C., Manias, C. & Retallack, D. (2001).
Powder Diffr. 16, 71±80.
Schmidt, R. & Kern, A. (2001). World Cement, February, pp. 2±8.
Schmidt, R. & PoÈllmann, H. (2000). Mater. Sci. Forum, 321±324,
1022±1027.
Scho®eld, P. F., Knight, K. S. & Stretton, I. C. (1996). Am. Mineral. 81,
847±851.
Stephens, P. W. (1999). J. Appl. Cryst. 32, 281±289.
Taylor, H. F. W. (1997). Cement Chemistry. London: Thomas Telford.
Taylor, J. C., Hinczak, I. & Matulis, C. E. (2000). Powder Diffr. 15, 7±
18.
Taylor, J. C. & Aldridge, L. P. (1993). Powder Diffr. 3, 138±144.
Thompson, P., Cox, D. E. & Hasting, J. B. (1987). J. Appl. Cryst. 20,
79±83.
Von Dreele, R. B. (1997). J. Appl. Cryst. 30, 517±525.
Walenta, G., FuÈlmann, T., GimeÂnez, M., Leroy, I., Friedle, R., Schnedl,
G., Hartung, D., Staupendahl, G., Lauzon, C. & Decay, D. (2001).
International Cement Review, June, pp. 51±54.
Zevin, L. S. & Kimmel G. (1995). Quantitative X-ray Diffractometry.
New York: Springer-Verlag.
J. Appl. Cryst. (2003). 36, 1169±1176