On-line X-ray diffraction for quantitative phase analysis:

Application in the Portland cement industry

Nicola V. Y. Scarlett and Ian C. Madsen
CSIRO Minerals, Box 312, Clayton South, Victoria 3169, Australia
Con Manias and David Retallack
Fuel and Combustion Technology Pty. Ltd. (FCT), 20 Stirling Street, Thebarton SA 5031, Australia
(Received 8 September 2000; accepted 12 October 2000)
The aim of this work was to design, construct, install, and commission an on-line, X-ray diffraction
(XRD) analyzer capable of continuously monitoring phase abundances for use in process plant
control. This has been achieved through a joint project between CSIRO Minerals and Fuel &
Combustion Technology Pty. Ltd. with an instrument designed for use in a Portland cement
manufacturing plant. Key factors in tailoring such an instrument to the cement industry were (i) the
handling and presentation of a dry sample and (ii) the development of an analytical method suitable
for the complex suite of phases contained within Portland cement. The instrument incorporates
continuous flow of sample through the diffractometer using a purpose-built sample presentation
stage. The XRD data are collected simultaneously using a wide range (120 20) position sensitive
detector, thus enabling rapid collection of the full diffraction pattern. The data are then analyzed
using a Rietveld analysis method to obtain a quantitative estimate of each of the phases present. The
instrument is controlled by a PC linked to the diffractometer through a purpose built interface. The
phase abundance information is then transmitted to the central computer in the cement plant where
it can be used for the control of mill parameters such as temperature and retention times as well as
gypsum feed rate. 2001 International Centre for Diffraction Data. [DOI: 10.1154/1.1359796]

I. INTRODUCTION the Rietveld method to extract the quantitative phase analy-

Many processing industries require routine analysis at
various stages of processing as a means of controlling the
quality of their products. Frequently, this consists of an ' 'off-
line" chemical analysis obtained by sub-sampling the pro-
cessing line and sending the material to the site laboratory
for analysis. This "batch" mode of operation often incurs
sampling problems and poor turnaround times, both of which
can limit the usefulness of the results for plant control.
In many cases, knowledge of the phase, rather than the
elemental, abundances is required to assess the processing
conditions. In the Portland cement industry, phase abundance
determination has traditionally been achieved in an "off-
line" manner either by:
Optical microscopy using point counting techniques
(Campbell, 1986); or
Use of the Bogue (Bogue, 1929) method where phase
abundances are derived by reduction of the chemical
analyses assuming a detailed composition for each phase.
Optical microscopy is very labor intensive and can be se-
verely affected by sampling errors. The Bogue method often
produces considerable error due to variation in the phase
composition resulting from changes in the feed-stock and/or
processing conditions. Further discussion of the errors in
these methods can be found in Madsen and Scarlett (1999)
and references therein.
Both optical microscopy and the Bogue method are con-
sidered to be too slow to be directly incorporated into a plant
control circuit since the results may not be available for sev-
eral hours. An alternative is to use X-ray diffraction methods
with a continuously moving stream of material and to apply
sis. This "on-line" determination of phase abundance has
some significant advantages, namely:
XRD determines the phase abundances directly from the
crystallography of the phases present, not by inference
from other measurements (e.g., chemical analysis).
The moving sample significantly reduces the problems as-
sociated with particle statistics encountered in conven-
tional "stationary sample" XRD instruments. Therefore,
larger particle sizes can be tolerated without affecting the
reliability of peak intensity measurements, and hence the
phase abundances.
The turn-around time for the analysis is very rapid (of the
order of 1-10 min), thus enabling their direct use in plant
control.
CSIRO Minerals and Fuel & Combustion Technology Pty.
Ltd. have collaborated in the design and construction of an
on-line XRD instrument for the cement industry. The follow-
ing steps were involved in the development of the instru-
ment:
(1) Selection of XRD instrument geometry and components
required;
(2) Determination of the applicability of the phase suite to
quantitative phase analysis via the Rietveld method and
development of a suitably accurate and fast refinement
strategy;
(3) Devising a method for rapid data collection;
(4) Design and construction of a sample presenter for the
continuous feeding of a sample suitable for X-ray dif-
fraction studies; and

71 Powder Diffraction 16 (2), June 2001 0885-7156/2001/16(2)/71 /10/$18.00 2001 JCPDS-ICDD 71

 TABLE I. Phases present in Portland cement clinker.

Typical concentration
Phase Nominal formula (wt. %) Comments

C3S Ca3SiO5 50-70 Seven known polymorphsthree present in clinker

C2S Ca2SiO4 15-30 Five known polymorphs/J-C2S known to be present in
clinker, but some evidence for presence of another two
C4AF C:a4(Al;tFe, -,) 4 O 1 0 5-15 Only one polymorph, but composition varies
(0.0<;t<0.5)
C3A Ca3Al2O6 5-10 Two polymorphscubic and orthorhombic
Lime Ca, _ ,Mg.O 0.5-2 Mg substitution for Ca (0.0<;t<0.02)
Hydrates rapidly to portlanditeCa(OH)2

(5) Design and coding of software for (i) remote control of
the instrument, (ii) data acquisition and analysis, and (iii)
reporting of results to the site computer.
II. EXPERIMENTAL
A. Cement analysis
1. Portland cement production and phases produced
The methodology of production for Portland cement is
well documented (Taylor, 1990) and will not be repeated in
detail here. In summary the process involves:
Feed material consisting mainly of CaO, SiO2, A12O3, and
Fe2O3 is prepared by milling predetermined quantities of
limestone, shale, sand and iron oxide.
The mixture is heated in a rotating kiln at approximately
1400 C. The limestone decomposes and calcium silicate,
calcium-aluminate, and calcium-alumino-ferrite phases are
formed in "clinkers" of approximately 1-3 cm in diam-
eter. The composition of the feed materials as well as kiln
conditions can affect the final clinker properties and com-
position. Table I describes the clinker phases and their
nominal compositions.
Portland cement is prepared by grinding the clinkers in a
ball mill with approximately 5 wt. % each of gypsum
(CaSO4.2H2O) and limestone. The mill temperature rises
to about 130 C during grinding, causing partial decompo-
sition of the gypsum to form hemihydrate
(CaSO4.0.5H2O) and occasionally anhydrite (CaSO4).
Table II gives the additional phases present in Portland
cement.
At two crucial stages in the manufacture, phase abundance
estimations can be used to provide feedback for plant con-
trol. First, analysis of the clinker material provides informa-
tion for control of kiln parameters such as temperature pro-
file, residence times, and excess oxygen. Second, analysis of
Portland cement provides quality assessment of the finished
product as it is produced rather than relying on testing of
material at the time of dispatch to the customer. The mea-
surement of the mineralogy allows (i) control of the setting
time (estimated from the gypsum, hemihydrate and C3A ra-
tios), and (ii) control of the weighfeeders for gypsum, lime-
stone, and clinker in the feed to the mill.
2. Phase abundance determination procedure
Traditional quantitative phase analysis using XRD has
been carried out using single peak methods based upon either
peak heights or integrated intensities (Klug and Alexander,
1974; Cullity, 1978; Jenkins and Snyder, 1996). The appli-
cation of such methods to the quantitative analysis of cement
and clinker phases has not been entirely successful in the
past (Aldridge, 1982). This is due to the high degree of over-
lap between the main peaks of the major phases leaving few
free-standing peaks available for the measurement of inte-
grated intensities. In order to avoid the overlap problem,
relatively weak peaks are often selected for analysis, leading
to large counting errors in the determination of peak inten-
sity. Figure 1 shows an observed XRD pattern for clinker
plus the individual components (calculated to represent typi-
cal clinker composition) for each of the major phases and
clearly demonstrates the high degree of overlap in the region
31 to 35 26 (CuKa) where most phases have their strongest
reflections.
Additional complications in the XRD analysis of Port-
land cement include:
Most of the phases display variable amounts of atomic
substitution (solid solution) which can have a substantial
influence on the measured peak positions for a particular
sample.
Variation of the degree of crystallinity of the phases can
affect the width and shape and hence the degree of overlap
between the observed diffraction peaks.

TABLE II. Phases present in Portland cement in addition to those present in clinker.

Nominal Typical concentration

Phase formula (wt. %) Comments

Gypsum CaSO4.2H2O 2-5 Exhibits severe preferred orientation

Hemihydrate CaSO4.;tH2O 2-5 Hydration state varies ( 0 . 3 < J : < 0 . 8 )
Anhydrite CaSO4 0-3
Calcite CaCO3 0-5 Exhibits preferred orientation
Quartz SiO2 0-3

72 Powder Diffr., Vol. 16, No. 2, June 2001 Scarlett et al. 72

 90
Observed
-C3S
A
70
60
C4AF I 1
f 50
C3A
1
\
40
C2S A V The potential for refinement of the crystal chemistry of the
30
Lime
\J!S
/
K \ V; \
20 / conditions.
31 32 33 34 35
29 ()
Figure 1. Observed XRD pattern (CuKa) for a sample of Portland cement
clinker showing the individual components (calculated to represent their
abundance in a typical clinker) for each of the major phases. Note that the
y-axis is depicted as the square root of the actual intensities to improve the
clarity for the minor phases.
C3S (as defined in Table I) exhibits strong preferred ori-
entation about the (001) crystallographic direction. This
affects not only its own relative peak intensities, but also
the derived peak intensities of overlapping phases, espe-
cially C2S.
In recent years it has been recognized that peak overlap prob-
lems (and, to a lesser extent, preferred orientation) can be
largely solved by using the entire diffraction pattern for
analysis, rather than a small number of preselected, free-
standing peaks. The Rietveld method (Rietveld, 1969;
Young, 1993) uses a model which includes the crystal struc-
ture for each phase, the pattern background, and peak width
and shape parameters to generate a calculated diffraction pat-
tern which is then compared with observed diffraction data.
Parameters in the model are varied through a least-squares
process to minimize the difference between the calculated
and observed patterns.
For each phase a scale factor is included to adjust the
intensity or "height" of the calculated pattern. In a multi-
phase sample consisting of n phases, there is a relatively
simple relationship between the Rietveld scale factor and the
relative abundance of phase i [Eq. (1)]. This technique was
first proposed by Hill (1983) and further developed and
tested by Hill and Howard (1987) and is given by:
Si(ZMV)t
(1)
where w, = weight fraction of phase /, 5 = refined Rietveld
scale factor, ZMV'= the "calibration constant" where Z is
the number of formula units per unit cell, M is the mass of
the formula unit, and V is the volume of the unit cell.
The Rietveld method is now widely used (Madsen et al.,
2001) for phase abundance determination from diffraction
data since no calibration is required; in this case knowledge
of the crystal structure provides the calibration constant. It
73 Powder Diffr., Vol. 16, No. 2, June 2001
should be noted that the so-called ZMV method provides a
dynamic calibration throughout the refinement process but
provides only relative phase abundance, i.e., the analyzed
phases are normalized to 100%.
The advantages of the Rietveld method for the quantita-
tive phase analysis of Portland cement are:
The use of the entire diffraction pattern (where tens or
hundreds of peaks may contribute to the analysis) rather
than just one or two peaks as in conventional methods.
component phasesthe structural parameters may then
contain information which can be correlated to processing
The reduction of peak overlap difficulties since the ob-
served data are compared with a calculated pattern which
is the sum of the component phase contributions.
However, some of the disadvantages of the method are the
requirements for:
Detailed crystallographic knowledge of all phases present.
Not all of the structures are well defined for the clinker
phases, i.e., reported structures may not calculate intensi-
ties which match those observed.
Data which cover a wide angular range need to be col-
lected.
Potentially long computational times. Many of the phases
present in cement and clinker have complex crystal struc-
tures that generate many peaks in the calculated pattern.
The computational time is proportional to the number of
peaks in the calculation. In addition, some phases are poly-
morphic and may be present as a mixture of two or more
forms within a single material.
Calculation of relative rather than absolute phase abun-
dances. This does not account for the presence of any
amorphous component in the sample stream. In the case of
the Portland cement industry the amount of amorphous
content was deemed to be of an insignificant level and thus
quantification of relative phase abundances is adequate for
plant control. If large amounts of amorphous material were
a regular component of another sample stream it may be
possible to include an assessment of the amount by mea-
surement of the area of the amorphous peak. In many in-
dustrial applications the appearance of trends in the rela-
tive proportions of phases is still useful for plant control
even if absolute quantification is not possible.
The need for long data sets and computational times has
the potential to reduce the efficacy of the method as a tool
for rapid feedback of results for the purpose of plant con-
trol.
Modified Rietveld approach. In order to address the dif-
ficulties of ill-defined structures and long computational
times, a modified Rietveld approach (Taylor and Rui, 1992)
has been taken to the analysis of Portland cement. Where the
conventional Rietveld method utilizes crystal structure infor-
mation to generate peak intensities, the modified approach
uses intensities based, in part, on intensities observed in
"real" materials. This technique is particularly useful for the
analysis of C3S since the reported structural information
does generate peak intensities which accurately reflect those
observed in real clinker material. In summary, the method-
On-line X-ray diffraction for quantitative phase 73
ology (described more fully in Taylor and Rui, 1992; Mad-
sen and Scarlett, 1999) comprises:
Calculate the structure factors using the partially known
structure and write to a text file.
Manually modify the structure factors according to the ob-
served intensities to obtain a better fit during Rietveld re-
finement.
Adjust the absolute scale of the modified structure factors
to ensure compliance of the ZMV relationship used for
derivation of phase abundances.
During analysis, read the structure factors from the file
rather than generate them from the crystal structure. To
speed up processing it is also possible to read in unmodi-
fied values of the structure factors rather than repeatedly
calculate them from the structure throughout the refine- Figure 2. The upper cabinet of the on-line XRD instrument showing the
ment. In the case of the Portland cement detailed here, all continuous feed sample presenter.
phases were read in from structure factor files from which
the very weak reflections (less than 0.5% of the maximum
for the phase) had been omitted to further speed the calcu- that the diffraction patterns are reported in terms of channel
lations. numbers rather than diffraction angle required by the Ri-
etveld program. This has been overcome by devising a cali-
Although detailed structural knowledge is not required for bration routine that is relatively easy to use in a plant envi-
this approach, it is necessary to know the unit cell of the ronment. However, small residual errors remain in the
phase in question (i.e., all peaks must be able to be indexed) reported 20 values and must be accommodated by the Ri-
to adjust the peak positions if necessary. etveld refinement software (Coelho et al, 1997). Additional
In this work only the structure factors for C3S were problems are caused by the inability to place a post-
modified (based on the average intensities observed from diffraction monochromator in the instrument, resulting in an
several "real" clinker samples) in order to provide the best increase in pattern background due to sample fluorescence
match between the calculated and observed XRD patterns. (Figure 3). This difficulty can be partially solved by using
Madsen and Scarlett (1999) have noted that the XRD pattern CoKa radiation to eliminate the generation of FeA"a fluores-
of cement clinker exhibits a peak at approximately 36.8 26
(CuKa) which can be attributed to C3S (ICDD-PDF,
1995card number 31-301). In addition, the peak can be A
indexed using the structure of Mumme (1995) but is not 500

generated with significant intensity by any of the structures I

400 i I
used for pattern calculation. Modified structure factors for a |
Intensity (coun

this peak have also been included in the modified C3S file.
While this approach was effective in improving the gen- !
eral level of fit between the observed and calculated patterns i , i
in these samples, additional modifications to the structure
factor files may be required for clinker or cement samples 100

from other sources. Changes to the source of raw materials

0
or to kiln operating conditions at a particular location may 10 20 30 40 50 60 70 80
also produce minor changes in the observed peak intensities. 29 H

B. Instrument design
1. X-ray diffractometer
_ 4000
The diffractometer used for the XRD analyzer was com-
posed of (i) an Inel CPS 120 curved detector plus electronic
control panel, (ii) interface card, (iii) X-ray generator with $

RS232 interface, (iv) a graphite, incident beam monochro-

mator (v) Co target tube, and (vi) a purpose-built instrument
cabinet. It is the use of the curved detector, which allows the
simultaneous collection of 120 20 of data, that forms the
basis of the on-line XRD analyzer. The resolution of this
detector is of the order of 0.03 20. It is the only one cur- 26 f)
rently available capable of simultaneously collecting the an-
gular range required for this application. Figure 2 shows the Figure 3. X-ray diffraction data collected using the on-line analyzer using
diffractometer with the sample presenter in place. total collection times of 1 min (A) and 10 min (B) duration. Note (i) the
relatively high pattern background due to sample fluorescence and (ii) the
There remain some problems inherent in the use of the general improvement in the definition of the minor phases above the pattern
curved detector in this application. The most important is background with increased counting time.

74 Powder Diffr., Vol. 16, No. 2, June 2001 Scarlett et al. 74

 point, thus providing a representative sample for analysis.
:. 9
\

This should be compared to conventional laboratory based

\ , measurements (using X-ray fluorescence spectrometry)
where only about 5 kg of material is sampled over a 2-4 h
period and then sub-sampled down to a few grams for analy-
sis.
The sample presenter provides a smooth, flat sample sur-
face of constant height by means of a roller and knife-edge
system. Following irradiation, the sample is withdrawn by
means of a scraper and vacuum system that returns the ma-
terial to the cement storage bin. The rate at which the sample
passes through the diffractometer can be adjusted to vary the
total amount of sample examined in each analysis. Figure 4
shows the sample presenter mounted on the diffractometer.
The ability to examine a continuous stream of sample in this
manner significantly increases the number of crystallites ex-
amined during the data collection, and hence improves the
Figure 4. Sample presenter for on-line XRD cement analyzer showing the
sample feed tube (A), the body of the presenter (B), and the sample surface precision of the quantitative phase analyses.
(C).

cence. However, the presence of high concentrations of cal-
cium in the samples still causes problems due to CaKa fluo-
rescence. While much of the CaKa is absorbed in the air gap
between the sample and the detector, there is still sufficient
to increase the pattern background and hence increase the
lower limits of detection for the minor phases.
2. Sample feeder and presenter
The sample handling devices have been purpose-built to
provide a continuous flow of material from the cement mill,
through the diffractometer, and back to the cement hopper.
While the total amount of cement manufactured is some 75
tonnes per hour, only a fraction of this (several kg/h) is
passed through the XRD analyzer. The grinding process in
the mill ensures uniform mixing of material at the sampling
3. Software/instrument controller
The operation of the on-line diffractometer is controlled
remotely by a PC. Purpose-written software (Figure 5) con-
trols all aspects of the operation of the instrument including
power on/off, checking of instrument status parameters, cali-
bration of the detector, control of the XRD instrument pa-
rameters, collection and analysis of data, and the reporting of
results to the plant operating room.
Data quality can be controlled through the use of a data
collection regime in which single data sets (typically of 60 s
duration) are collected and several (typically ten) are
summed prior to Rietveld analysis. The benefits of this re-
gime include (i) improvement of the X-ray counting statistics
through the addition of multiple data sets, and (ii) the gen-
eration of rapid analyses (every 1 min) which are based on
the running sum of the previous ten data sets. The software

Eh U * Cat

p PHASE WSUlT
c
q-77
^
Figure 5. The main screen for the soft-
imTiaCwftr [ i MM
Brila 7 437 ware interface for the on-line XRD ce-
M* 5 623 ment analyzer. Features include (i)
Frtb o/Ts display of the number of data sets re-
AkJimtro '43f.
quired for analysis and the number al-
Almnta-c J0O1
ready collected, (ii) the elapsed time
Una UXO
for the current data set, (iii) controls to
FMInto '343
power the XRD analyzer up and down
Sjwum --
as well as to start data collection and
.(6!4
Rietveld analysis, (iv) display of the
Mvdto KP4
quantitative phase abundances and de-
Cafcto 4 H.'t
rived oxide contents for the most re-
cently analyzed data set, and (v) the
OiMb L *4
RFKKX ?*=
status of various sections of the instru-
ment.
U) f.4 ,--.;.

ua I8f37

ALMMl MESSAGE |MLgr.lnMml

y Mctwolr Wad Dronii| 1334

75 Powder Diffr., Vol. 16, No. 2, June 2001 On-line X-ray diffraction for quantitative phase 75

Figure 6. The on-line XRD cement analyzer installed in the purpose-built
instrument room adjacent to the cement mill. The upper cabinet houses the
XRD instrumentation and sample presenter, while the lower cabinet houses
the generator, detector electronics, and computer.
allows the setting of both the data collection time and the
number of data sets prior to analysis.
The instrument described here employs a flat graphite,
incident beam monochromator. Data quality could be im-
proved by the inclusion of a multi-layer mirror in the inci-
dent beam path to provide an increase in pattern intensity of
about 5 to 10 times. Adequate data could then be collected in
a total of 1-2 min.
4. Instrument construction and installation
The XRD instrument is housed in a purpose-built cabinet
(Figure 6) comprised of two sections that can be sealed to
exclude dust and separated for transportation. The upper sec-
tion houses the INEL XRD instrument and sample presenter,
while the lower section houses the detector electronics,
X-ray generator, instrument interface, and computer. The
lower cabinet is equipped with a heat exchanger to remove
the excess heat generated by the electronics. The upper cabi-
net section has been designed to minimize the risks of radia-
tion leakage, with special attention paid to the conditions
likely to be encountered in a plant installation.
III. RESULTS AND DISCUSSION
A. Verification of analytical method
One of the difficulties with the analysis of cement and
clinker is in establishing a "true" quantitative phase analysis
76 Powder Diffr., Vol. 16, No. 2, June 2001
(QPA) with which to compare results from XRD phase
analysis. The industry standard methods of point counting or
the Bogue method both suffer severe limitations (Madsen
and Scarlett, 1999). However, given that the Bogue method
is the most commonly used benchmark, it was necessary
from an industrial point of view to relate the method de-
scribed here to it. More accurate verification of the analytical
method was obtained by comparing "reduced oxide" values
calculated from the Rietveld QPA and the detailed phase
compositions obtained from microprobe analysis against the
oxide values measured by X-ray fluorescence.
A series of samples of plant material were provided
along with their relevant Bogue and XRF analyses for veri-
fication work. XRD data were collected on these samples
using a traditional Bragg-Brentano geometry, scanning dif-
fractometer incorporating a post-diffraction monochromator
to eliminate sample fluorescence. This provided high quality
data sets with good counting statistics and high peak-to-
background ratios.
The results of QPA using the modified Rietveld ap-
proach are compared with the Bogue results in Figure 7,
while a comparison of the oxide contents from XRF and the
XRD "reduced oxides" is shown in Figure 8. Table III
shows the standard deviation (s.d.) for each method derived
from the covariance between the (i) XRD and Bogue, and (ii)
XRD and XRF oxide estimates using the method of Grubbs
(1948). Also included is the mean difference between the
estimates for each of the major phases (BogueXRD) and
oxides (XRFXRD reduced oxides). The individual s.d.'s
provide a measure of the precision of each analysis method,
while the mean difference provides an indication of the over-
all accuracy (incorporating the bias present in each method).
For the most abundant phases (C3S and C2S), the high
s.d. values reflect relatively poor precision in the determina-
tion, with the Bogue being much poorer than XRD. For the
other phases (C4AF and C3A) both methods contribute ap-
proximately equally to the overall error estimate. For all
phases, the large values of the average difference indicates
relatively poor accuracy when attempting to use Bogue re-
sults as a point of comparison for the XRD analyses.
For all of the major oxide components, the s.d. values
are generally much lower than for the phase data with the
XRF estimates and those derived from XRD contributing
approximately equally to the overall error estimate. In addi-
tion, the values for average difference for the oxides are
much lower than those given for the phase abundances.
These results show that the comparison of reduced oxides
calculated from XRD results with XRF measurements is a
more reliable measure of success of the XRD analysis than
comparison of XRD phase abundances with the Bogue
method.
1. Sensitivity of lime measurement
Lime (CaO) is present in clinker at a level of approxi-
mately 0.2-3 wt. % and is a useful indicator for kiln operat-
ing conditions. Ideally, an accuracy of 0.1 wt. % is re-
quired in the analysis, but 0.2 wt. % is useful for obtaining
trends. Verification of the accuracy of lime measurement by
XRD was achieved by preparing a synthetic sample consist-
ing of clinker with various known lime additions. XRD data
were collected using a conventional, laboratory based scan-
Scarlett et al. 76
 70

60

50

c
n
a 40

30

a.
S 20
CD C3S
C2S
10 C4AF
x C3A-0
1:1

10 20 30 40 50 60 70 5 10 15
XRD Phase Abundance (wt%) XRD Phase Abundance (wt%)

Figure 7. Comparison of quantitative phase abundance determination for plant samples using the modified Rietveld approach with that from Bouge analysis.
"A" shows all phases present simultaneously. " B " is an expansion of " A " which shows the minor phases in greater detail.

ning diffractometer incorporating a dry nitrogen atmosphere
and a sample stage heated to 110 C to prevent the hydration
of lime to portlandite. The results of the analyses are com-
pared with the known additions in Table IV. The results
indicate that lime can be measured to an accuracy of about
0.2 wt. % at levels up to 2 wt. % which should be sufficient
for obtaining trends in the lime content. Future developments
will aim to improve the level of accuracy of the method.
The estimation of the lime (CaO) content will only be
effective for freshly manufactured clinker since lime readily
hydrates to portlandite [Ca(OH)2]. It is unlikely that lime
will be detected in finished cement since extended storage
periods for the clinker and the use of a water spray to control
mill temperature will ensure that all of the lime has hydrated.
The presence of portlandite provides an indication of
pre-hydration (related to problems with cement mill water
sprays or clinker storage) and is a factor used in the predic-
tion of cement strength (Manias et al, 2000). While portlan-
dite can be included in the quantitative phase analysis, it
should be noted that the crystallite size of portlandite is rela-
tively small. This results in broad diffraction peaks that are
not readily observed above the pattern background unless the
counting statistics are adequate. The instrument operators

o
A B /
60
/ 5

50
/ I.
a
u
XRI F Oxide Abundar

IS 40
o
c
I 30
/
/
CaO CaO

S / SiO2 SiO2

Li- 20
* AI2O3 / A AI2O3
ce
x / x Fe2O3 / x Fe2O3

/ MgO
1
MgO
+ Na2O
10 / + Na2O
- K2O - K2O
1:1
0 / 1:1
n
10 20 30 40 50 60 70 1 2 3 4 5
XRD "Reduced Oxide" Abundance (wt%) XRD "Reduced Oxide" Abundance (wt%)

Figure 8. Comparison of reduced oxide values derived from XRD phase abundances with analyzed values from X-ray fluorescence for the same suite of
samples as shown in Figure 7. Once again " A " shows all phases present simultaneously and " B " is an expansion of " A " which shows the minor phases
in greater detail.

77 Powder Diffr., Vol. 16, No. 2, June 2001 On-line X-ray diffraction for quantitative phase 77
TABLE III. Estimates of the covariance and average difference for (i)
Bogue and XRD for the major phases and (ii) XRF oxide estimates and the A
"reduced oxides" derived from XRD. The average difference is defined as
the mean of (BogueXRD phase estimate) or (XRFXRD reduced oxide) C3S
16 i
for each determination.

Standard deviation C4AF

Derived from covariance

Phase Bogue XRD Average difference C3A O

9
C3S 4.38 0.85 2.3 o
C2S 4.08 1.57 -2.8 8
o C2S o
C4AF 0.25 0.40 -1.6 6 ID
C3A -1.4 O
0.36 0.37
4

Standard deviation
Derived from covariance 17:00 19:00 21:00 23:00 1:00 3:00 5:00 7:00

Oxide XRF oxides XRD reduced oxides Average difference Time (hours:minutes)

CaO 0.42 0.37 -0.75

SiO 2 0.30 0.29 -0.47
A12O3 0.15 0.24 -0.09
Fe 2 O 3 0.10 0.15 -0.02
MgO 0.03 0.08 -0.29

must consider the importance of counting statistics when se-

lecting the data collection times. s
E

B. Laboratory based stability testing

Prior to the installation of the on-line XRD analyzer,
extensive laboratory based testing was conducted to deter-
mine the stability of the instrument. Some of these tests in-
volved the collection of data from a recirculating sample
over a period of 15 h. Data sets of 60 s duration were col-
lected continuously and analyses carried out on the summa-
tion of ten sets. The result of this was the production of a
QPA result every 1 min which is the average of the previous
ten minutes of data collection. Figure 9 shows the results of
these stability trials for the major phases contained within the
Portland cement. Table V shows the means, standard devia-
tions, and % relative standard deviations (%RSD) for these
results. The maximum deviation over the course of 15 h was
3.70% relative in the gypsum (for example) which was
present at a level of about 3 wt. %. This indicates good re-
producibility and internal stability of the instrument in a
laboratory environment.
C. Plant based testing
Testing similar to that carried out in the laboratory was
also carried out in the plant as part of the on-line XRD in-
TABLE IV. Results of quantitative phase analysis for known lime additions
to a sample of cement clinker. The figures in brackets for the analyzed
values represent the errors derived from the errors in the Rietveld scale
factors. The line of best fit is given by ana!yzed=0.8994*Weighed
+ 0.1016, K2 = 0.9923.
Weighed Analyzed Bias
(wt. %) (wt. %) (wt. %)
I
$
21:00 23:00 1:00 3:00
17:00 19:00
Time (hours:minutes)
Figure 9. Results of laboratory based stability testing for on-line cement
analyzer over a 15 h period for (A) C3S, C4AF, C3A, and C2S and (B)
Gypsum and Hemihydrate. For the duration of the test, the same cement
sample was allowed to remain on the sample presenter. For (A), the left
hand scale refers to the amount of C3S present, while the right hand scale
refers to the amount of all other phases. For (B), the left hand scale refers to
the amount of gypsum present, while the right hand scale refers to the
amount hemihydrate.
strument's commissioning process. In this instance, the ce-
ment manufacturers were interested in trialing faster turn-
around times than those considered in the laboratory so
analyses were carried out on single data sets of 80 s duration.
The sample was fed continuously from the cement mill and
data were collected over a period of 8.5 h. The QPA results
for the major phases obtained during plant testing are shown
in Figure 10 and Table VI. Note that the cement used in this
trial was not the same as that used in the laboratory trials, so
the magnitude of the results will be slightly different.
TABLE V. Means, standard deviations and % relative standard deviations
(RSD) for laboratory based stability trials. Individual analyses were based
on the rolling sum of 10X60 second data sets.

0.00 0.17(0.10) 0.17 = 815 C3S C2S C4AF C3A Gypsum Hemihydrate
0.47 0.31(0.10) -0.16
0.91 1.13(0.12) 0.22 Mean 58.47 8.08 11.86 8.84 3.02 3.40
1.95 1.78(0.14) -0.17 S.D. 0.38 0.23 0.27 0.17 0.11 0.09
5.00 4.61(0.16) -0.39 %RSD 0.64 2.81 2.31 1.98 3.70 2.71

78 Powder Diffr., Vol. 16, No. 2, June 2001 Scarlett et al. 78

 the material fed continuously from the cement mill. While
A .
correlation of the QPA results with actual mill operating con-
ditions has not been performed to date, the variations ob-
served in the gypsum/hemihydrate values (Figure 10) could
C3S
provide valuable data for control of the mill operating con-
ditions.

C4AF

S 50 IV. CONCLUSIONS
V)
o
o I An on-line, X-ray diffraction instrument capable of con-
tinuously monitoring phase abundances has been constructed
45
and installed in an operational cement plant. This has been
' C2S
achieved through (i) the use of a curved, position sensitive
0
detector to simultaneously collect wide-range diffraction
8:30 9:30 10:30 11:30 12:30 13:30 14:30 15:30 16:30 17:30 data, (ii) the incorporation of a continuous feed mechanism
T i m e (hours:minutes)
for sample presentation, and (iii) the use of a modified Ri-
etveld approach for quantitative phase analysis, thus provid-
B ing more accurate analyses than conventional methods.
* * Gypsum The continuous nature of the sample feed significantly
-- - - '-;. :\:- ./ : - reduces the problems associated with obtaining a representa-
% tive sample by more traditional methods of sampling. An
' ."'. '. " . . . additional benefit of the use of a moving sample is the in-
crease in the total number of particles examined during the
s
g data collection. This leads to increased accuracy in the peak

o intensities and hence the quantitative phase analyses.
In its current configuration, this instrument can be used
-: .?r*X*,' * 5"
- a . . . . . to analyze any multi-phase system that is amenable to analy-

r Hemihydrate
sis by powder X-ray diffraction. The instrument can be rap-
idly reconfigured to allow a "single sample" mode of op-
eration for the periodic investigation of smaller samples for
8:30 9:30 10:30 11:30 12.30 13:30 14:30 15:30 16:30 17:30
research purposes. Currently, the sample feed system is lim-
Time (houre:minutes) ited to dry feed materials but work is in progress to allow for
the continuous analysis of slurry samples resulting from min-
Figure 10. Results of plant based stability testing for the on-line cement eral processing operations.
analyzer over an 8 h period for C3S, C2S, C4AF, and C3A (A) and Gyp-
sums and Hemihydrate (B). During testing, the sample was fed continuously
from the cement mill. For (A), the left hand scale refers to the amount of
C3S present, while the right hand scale refers to the amount of all other ACKNOWLEDGMENTS
phases. For (B), the left hand scale refers to the amount of gypsum present,
while the right hand scale refers to the amount hemihydrate. The solid lines Edmund Schneider is gratefully acknowledged for his
represent the mean of each set of analyses in this diagram while the dotted input to the design and construction of the sample feed and
lines represent 2 esds derived from the laboratory based testing and show presentation system. The staff of the Birkenhead works of
the limits of variability that can be expected from instrumental variation Adelaide Brighton Management Ltd. are gratefully acknowl-
alone.
edged for their assistance during installation and commis-
sioning of the XRD cement analyzer. Dr. Cheryl Lim and Dr.
In addition to quantitative phase analyses, Figure 10 Nick Cutmore of CSIRO Minerals are gratefully acknowl-
shows the mean for the plant based results as well as lines edged for their reviewing of an early version of the manu-
representing 2 estimated standard deviations (esd) derived script.
from the laboratory based testing. The 2 esd lines indicate
the limit of variation that could be attributed to instrument Aldridge, L. P. (1982). "Accuracy and precision of phase analysis in Port-
land cement by Bogue, microscopic and X-ray diffraction methods,"
stability alone. For the sulphate phases (gypsum and hemi- Cem. Concr. Res. 12, 381-398.
hydrate) variations are apparent which exceed these limits Bogue, R. H. (1929). "Calculation of the compounds in Portland cement,"
and could be attributed to variability in the composition of Ind. Eng. Chem. 1, 192-197.
Campbell, D. H. (1986). "Microscopical examination and interpretation of
Portland cement and clinker," Portland Cement Association, USA, Li-
TABLE VI. Means, standard deviations, and % relative standard deviations brary of Congress catalogue card number 85-63563.
(%RDS) for plant based trials. Individual analyses were based on single 80 Coelho, A. A., Madsen, I. C , and Cheary, R. W. (1997). "A New Rietveld
second data sets. refinement program using a fundamental parameters approach to synthe-
sizing line profiles," Proceedings of Crystal XX, The Twentieth Meet-
n = 315 C3S C2S C4AF C3A Gypsum Hemihydrate ing of the Society of Crystallographers in Australia, April 2-5, 1997,
Queenstown, New Zealand.
Mean 61.71 6.65 12.60 7.10 3.33 2.14 Cullity, B. D. (1978). Elements of X-ray Diffraction, 2nd ed. (Addison Wes-
S.D. 1.48 0.95 0.92 0.63 0.50 1.60 ley, New York).
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