Cement and Concrete Research 64 (2014) 89–98

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Cement and Concrete Research

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Use of X-ray diffraction to quantify amorphous supplementary

cementitious materials in anhydrous and hydrated blended cements
R. Snellings a,⁎, A. Salze a, K.L. Scrivener a
a
Laboratory of Construction Materials, Institute of Materials, Ecole Polytechnique Fédérale de Lausanne (EPFL), Switzerland

a r t i c l e i n f o a b s t r a c t

Article history: The content of individual amorphous supplementary cementitious materials (SCMs) in anhydrous and hydrated
Received 11 April 2014 blended cements was quantified by the PONKCS [1] X-ray diffraction (XRD) method. The analytical precision and
Accepted 26 June 2014 accuracy of the method were assessed through comparison to a series of mixes of known phase composition and
Available online 13 July 2014
of increasing complexity. A 2σ precision smaller than 2–3 wt.% and an accuracy better than 2 wt.% were achieved
for SCMs in mixes with quartz, anhydrous Portland cement, and hydrated Portland cement.
Keywords:
X-ray diffraction (B)
The extent of reaction of SCMs in hydrating binders measured by XRD was 1) internally consistent as confirmed
Blended cement (D) through the standard addition method and 2) showed a linear correlation to the cumulative heat release as
Amorphous material (B) measured independently by isothermal conduction calorimetry.
Cement manufacture (E) The advantages, limitations and applicability of the method are discussed with reference to existing methods that
Kinetics (A) measure the degree of reaction of SCMs in blended cements.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction
In present-day society the cement industry fulfils a pivotal role in the
recycling of waste streams into construction materials. In particular, the
partial replacement of Portland clinker by supplementary cementitious
materials (SCMs) offers the opportunity to reuse large volumes of
industrial by-products, notably blast furnace slag and fly ash. As the
reactivity of SCMs is lower than that of clinker, cement replacement
levels are mainly limited by the early-age strength gain. Further
decreases in clinker contents will depend on an improved control and
understanding of the SCM reactivity in blended cements. Key to
unravelling the parameters governing SCM reactivity is the accurate
measurement of the degree of reaction of SCMs in hydrating blended ce-
ments. To this purpose, a range of different methods has been applied
with mixed results. All reported methods are subject to more or less
serious limitations [2]. Recent studies deemed selective dissolution
approaches [3,4] unreliable, showing large, unrealistic discrepancies
with other methods and problems with interlaboratory reproducibility
[5,6]. Application of image analysis to electron microscopy images and
element maps has shown promising results for blast furnace slag [6],
and to some extent for fly ash [7,8]. However, the proposed approaches
are time-demanding and cannot resolve the reaction of particles smaller
⁎ Corresponding author at: MXG 234, LMC IMX STI EPFL, Station 12, CH-1015 Ecublens,
Switzerland. Tel.: +41 21 693 72 52; fax: +41 21 693 58 00.
E-mail addresses: ruben.snellings@epfl.ch (R. Snellings), karen.scrivener@epfl.ch
(K.L. Scrivener).
than about 2 μm, rendering the method unsuitable for fine materials
such as silica fume and metakaolin. A more generally applicable method
makes use of 29Si and 27Al solid-state NMR spectroscopy. The method
has been successfully applied to binders containing blast furnace slag
[6,9], fly ash [10], and silica fume [11–13]. However, widespread use
will remain limited because access to solid-state NMR equipment is
restricted. 29Si NMR data acquisition is time-consuming (1–2 days per
measurement) and measurements are restricted to systems with low
levels of paramagnetic ions. It can thus be concluded that the direct
measurement of the degree of reaction of amorphous SCMs remains a
difficult task, and that a generally applicable, reliable and accessible
quantification method is still needed. In this respect, the present contri-
bution explores the potential of a novel X-ray diffraction (XRD) based
methodology.
Over recent years, XRD has become one of the most prominent ana-
lytical techniques in the characterisation of Portland cement based sys-
tems [14–20]. The main advantages of XRD are the ease and speed of
measurement and its accuracy compared to traditional quantitative
phase analysis methods such as Bogue calculations and optical micros-
copy [21,22]. Over the last decade, the success of XRD has been rooted
largely in advances in detector performance [23], and in the develop-
ment of powerful and user-friendly analysis software. Simultaneously,
quantification approaches shifted from single peak to full XRD profile
fitting methods such as the Rietveld method [24,25] and profile summa-
tion methods [26]. Its capability to accommodate adjustment of crystal
structure parameters has favoured strongly the use of the Rietveld
method as many cementitious phases display extensive chemical

http://dx.doi.org/10.1016/j.cemconres.2014.06.011
0008-8846/© 2014 Elsevier Ltd. All rights reserved.
90 R. Snellings et al. / Cement and Concrete Research 64 (2014) 89–98

variability. However, phase quantification by the Rietveld method
depends on two preconditions: 1) the quantified phase displays three-
dimensional structural periodicity i.e. is crystalline, and 2) the crystal
structure of the phase has been resolved. Nowadays the large majority
of crystalline phases encountered in cements have resolved crystal
structures and can be quantified.
Despite these advances, the quantification of individual amorphous
phases such as SCMs remains problematic. Common approaches
making use of internal and external standards can determine the total
amount of unknown and amorphous phases [27,28], but cannot distin-
guish between the individual contributions of different amorphous
phases [27,28]. In this respect, profile summation methods offer the ad-
vantage of relying only on a calibrated XRD profile of each individual
phase, which is also possible for amorphous phases.
The advantages of both Rietveld and profile summation methods
were combined recently in the Partial Or No Known Crystal Structure
(PONKCS) method [1]. The method is devised to be easily implementable
in common Rietveld refinement software for the simultaneous quantifi-
cation of phases calculated from crystal structure data and phases from
calibrated XRD profiles. In the field of cement, the PONKCS method has
been applied recently on alkali-activated metakaolin to determine the
extent of metakaolin reaction [29], and in the quantification of C–S–H
in hydrating alite pastes [30]. The quantification results were reported
to compare well to results from independent quantification methods
such as mass balance calculations, calorimetry and electron microscopy.
This paper describes the application of the PONKCS method to the
study of blended cements by XRD. The PONKCS method was used in com-
bination with the external standard method [31,32] and a determination
of the bound water to obtain a quantification of the degree of reaction of
several SCMs. The repeatability and accuracy of the quantification results
were assessed for anhydrous and hydrated blended cements containing
one or more amorphous components. The performance of the quantifica-
tion method is evaluated for increasingly complex systems going from
simple binary synthetic mixes over anhydrous blended cements to hy-
drated samples of portlandite–SCM model mixes and blended cements.
Both repeatability and accuracy errors are reported. Potential sources of
bias are identified and recommendations are made accordingly.
spectrometry is shown in Table 1 along with the sample mass absorp-
tion coefficients (MAC) calculated from the international tables of
crystallography for CuKa radiation [33]. The Loss On Ignition (LOI) was
considered as H2O, except for limestone where CO2 was used in the
calculation. An overview of the experimental sample matrix is given in
Table 2.
Simple binary mixes of quartz and slag were prepared at 10, 30, and
50 wt.% of slag content. The samples were mixed thoroughly by wet-
grinding in isopropanol in a McCrone micronizing mill for 10 min.
Resulting particle sizes (d50) were in the range of 3–5 μm. The 30 wt.%
slag sample was prepared twice to assess errors involved in sample
mixing and preparation. A second sample series consisted of ternary
mixes of quartz, slag and metakaolin in 2:1:1 and 1:1:2 weight propor-
tions. The 2:1:1 mix was weighed and mixed twice. Similar synthetic
samples were prepared of anhydrous grey cement and slag and/or
metakaolin to simulate the performance of the method in the analysis
of anhydrous blended cements. Binary mixes were prepared of cement
and slag at 20, 40, and 60 wt.% slag levels, and of cement and metakaolin
at 20, 30, and 40 wt.% metakaolin. One ternary mix of anhydrous cement
and two SCMs was tested at a 2:1:1 cement:slag:metakaolin weight
proportion to assess to what extent the two different amorphous phases
can be quantified in a mix with a complex multiphase material such as
Portland cement.
An additional level of complexity was introduced in mixes of white
cement hydrated for 7-years and fixed quantities of slag or metakaolin.
This system was selected as a way to evaluate the accuracy of the quan-
tification results for actual hydrated blended cements. To stop the hy-
dration of the white cement paste, the hardened paste was ground to
below 50 μm and immersed in isopropanol for 15 min. Afterwards the
isopropanol was evaporated in an oven at 40 °C and the powder was
stored in a desiccator over silica gel. The solvent exchange and drying
Table 2
Sample matrix giving the composition of the preblended simulated mixes, and the
hydrated cement mixes. AS stands for low (L) or high (H) alkali sulfate additions (detailed
in text).
Simulated mixes

Sample Slag MK Qtz OPC HWC

S10-Q90 10 90
2. Materials and methods S30_Q70 (2×) 30 70
S50_Q50 50 50
2.1. Materials, mix design, and sample preparation S25_M25_Q50 (2×) 25 25 50
S25_M50_Q25 25 50 25
S20_C80 20 80
The method was tested on a series of mixes of increasing complexity.
S40_C60 40 60
The materials used in the preparation of the mixes were: ground high- S60_C40 60 40
purity quartz (K13, Bernasconi), blast furnace slag (Dunkerque, M20_C80 20 80
Holcim), metakaolin (Burgess), limestone (Durcal 5/15, Omya), grey M30_C70 30 70
M40_C60 40 60
Portland cement (CEMI 52.5N, Heidelberg), and white Portland cement
S25_M25_C50 25 25 50
(Aalborg cement) hydrated for 7-years. The chemical composition S10_H90 10 90
of the anhydrous samples measured by X-ray fluorescence (XRF) S30_H70 30 70
S50_H50 50 50
M10_H90 10 90
Table 1
M20_H80 20 80
Chemical composition (wt.%) and mass absorption coefficients (MAC) of the grey Portland
M30_H70 30 70
cement (OPC), white Portland cement (WC), metakaolin (MK), blast furnace slag (Slag),
M40_H60 40 60
quartz, and limestone samples.
Hydrated cements
Oxides/wt.% OPC WC Slag MK Quartz Limestone
Samples CH MK AS Cc Qtz OPC Slag
SiO2 19.27 24.68 36.61 50.62 97.91 0.04
Al2O3 5.65 2.11 12.21 46.91 1.00 0.06 P-M 50 50
Fe2O3 3.63 0.43 0.85 0.38 0.05 0.05 P-M-LAS 50 50 L
CaO 63.65 68.67 41.59 0.02 0.02 56.53 P-M-HAS 50 50 H
MgO 1.62 0.58 7.18 0.09 – 0.10 P-M-LAS-Q 40 40 L 20
SO3 3.16 1.82 0.63 0.08 – – P-M-LAS-Cc20 40 40 L 20 (coarse)
Na2O 0.15 0.17 0.18 0.28 – 0.04 P-M-LAS-Cc6 40 40 L 20 (fine)
K2O 1.24 0.06 0.28 0.18 0.77 0.04 CEM-MK 30 70
TiO2 0.29 0.05 0.35 1.29 0.03 0.03 CEM-MK-Q 30 15 55
LOI 0.75 0.97 – 0 0.15 43.09 CEM-MK-Cc6 30 15 (fine) 55
MAC (cm2/g) 99.35 96.91 73.63 35.90 36.72 74.72 CEM-Slag 60 40
 R. Snellings et al. / Cement and Concrete Research 64 (2014) 89–98 91

(d50 of 6.3 μm) and quartz fillers replaced 15 wt.% of the Portland cement
in two additional metakaolin blended cements. 1.5 wt.% gypsum was
added to the metakaolin blended cements to balance the supply of alumi-
nate by metakaolin [34]. Pastes were prepared at a water to binder ratio of
0.4 and sealed-cured until analysis at 3, 7 and 28 days of hydration. All
pastes were cured in a 20 °C temperature controlled room.
Slices of the hydrating pastes were cut at the set times of hydration
and hydration stopped by solvent exchange in isopropanol for 7 days,
finely ground and measured by XRD.
To check the accuracy of the quantification for hydrating systems the
method of standard additions was used. 20 and 40 wt.% metakaolin
were mixed into hydration-stopped, dried powders of reacted model
systems. The accuracy of the quantification can then be assessed from
the intercept of the calibration curve between measured and added
metakaolin.

2.2. XRD data collection

Fig. 1. XRD patterns of grey Portland cement (OPC), hydrated white cement (HWC), blast
furnace slag (Slag), and metakaolin (MK). The measured (black) and fitted, calculated
(grey) XRD patterns are superimposed. The decomposition of HWC, slag and MK is
depicted in more detail to show the respective contributions of the amorphous phase
and the (accessory) crystalline phases.
procedure was designed to minimize the decomposition of the hydrate
phases. Binary mixes of the hydrated cement powder and slag were
prepared at 10, 30, and 50 wt.% of slag incorporation and at 10, 20, 30,
and 40 wt.% metakaolin incorporation. Mixing of the hydrated cement
containing samples was carried out by hand to preserve the hydrate
assemblage.
The measurement of the degree of SCM reaction was tested in two
different reacting systems. First, pastes of portlandite (chemical
grade), metakaolin and water with variable additional alkali and sulfate
(added as KOH and K2SO4) were prepared to simulate and analyse the
pozzolanic reaction. The portlandite to metakaolin weight ratio was
fixed to 1:1, while the water to binder ratio was kept at 1.2. The main
variables were the K2O/MK molar ratio of 0, 0.18, and 0.29 and the
SO3/MK molar ratio of 0, 0.16, and 0.27 for the samples called P-M,
P-M-LAS, and P-M-HAS, respectively. The effect of adding fine fillers
on the SCM degree of reaction was studied in mixes of portlandite:
metakaolin:filler in a 2:2:1 weight proportion. Finely ground quartz
(d50 of 13.7 μm), and two limestone samples of different fineness (d50
of 20.0 and 6.3 μm) were added to the P-M-LAS system, keeping all
other compositional ratios fixed. The samples were cast into plastic
containers and sealed cured until analysis at 1, 4, and 7 days of hydration.
A second series of hydrated samples were blended cements consisting of
grey Portland cement with 60 wt.% slag, or 30 wt.% metakaolin. Limestone
XRD data were collected using CuKα radiation on a PANalytical
X'Pert Pro diffractometer operated at 40 mA and 45 kV. Measurements
were made in flat-plate Bragg–Brentano θ–2θ geometry, incident
beam and receiving Soller slits of 0.04 rad were used and the incident
beam divergence slit was fixed at 0.25°. Air scattering was reduced
using a beam knife and a receiving antiscatter slit of 1° was positioned
in the diffracted beam path. An X'Celerator linear position-sensitive X-
ray detector with a length of 2.122 °2θ was used for data acquisition.
All scans were measured over an angular range of 8 to 70 °2θ with a
0.017 °2θ step size and accumulated time per step of 59.6 s, resulting
in a total measurement time of about 30 min per scan. All measure-
ments were carried out in triplicate to calculate repeatability errors.
Powder samples were prepared using the back-loading technique to
minimize preferred orientation effects and were repacked between
repeated measurements. During measurement the samples were spun
around the vertical goniometer axis to improve particle statistics.
2.3. XRD data analysis
Rietveld quantitative phase analysis was carried out using Topas-
Academic v4.1 software. The refinement strategy and structure models
for crystalline phases were as reported in [35]. The external standard
method was used to quantify the total amount of amorphous and un-
identified phases [31,32]. The external standard method calculates the
absolute weight fraction of a phase k by comparison of the refined
phase scale factor Sk to the scale factor Ss of an external rutile standard
(Kronos 2300 TiO2), measured under identical conditions. The calcula-
tion takes into account the (ZMV) phase constants and corrects for the

Table 3
Phase composition of the grey Portland cement (OPC), hydrated white Portland cement (HWC), metakaolin (MK), and blast furnace slag (Slag) as determined by XRD.

Phase OPC HWC Slag MK

g/100 g anhydrous g/100 g anhydrous g/100 g anhydrous g/100 g anhydrous

C3S 63.6
C2S 8.9 2.4
C3A cubic 1.3
C3A orthorhombic 5.2
Ferrite 14.2
Periclase 0.4
Anhydrite 4.0
Arcanite 2.3
Portlandite 25.1
Ettringite 4.4
Calcite 0.7
Quartz 0.6
Mullite 5.9
Anatase 1.5
Amorphous/C–S–H – 92.6 98.7 92.6
92 R. Snellings et al. / Cement and Concrete Research 64 (2014) 89–98

differences in mass absorption coefficients of the sample μ m and the

standard μms (124.6 cm2/g) according to:

ðZMV Þk sk μ
wk ¼   ws  m ð1Þ
ðZMV Þs ss μ ms

where Z represents the number of formula units in the unit cell, M is the
unit cell mass, and V the volume of phase k or standard s. The crystallinity
of the rutile standard ws was calibrated to be 96.4 wt.% using the external
standard approach and the certified NIST SRM 676a α-Al2O3. The (ZMV)k
phase constants are readily calculated for crystalline phases from the
refined crystal structure. However, for amorphous or nano-crystalline
phases α without known crystal structure, the phase constant (ZMV)α
needs to be calibrated separately. The phase constant can be deter-
mined by the internal standard method as in [1,36], or can be obtained
from a rearrangement of Eq. (1) using the external standard method if
the sample chemical composition and the weight fraction of the phase
of interest in the sample are known. Therefore, the calibration sample
needs to contain only the phase of interest, or the phase of interest Fig. 3. XRD pattern decomposition of a sample composed of 50 wt.% metakaolin, 25 wt.%
blast furnace slag, and 25 wt.% quartz.
and a series of accurately quantifiable crystalline phases.
Amorphous or nano-crystalline phases generally present a diffuse
scattering contribution or ‘hump’ which can be fitted using a so-called fraction was calculated by difference. The resulting phase composition
‘peaks phase’, consisting of a set of one or more peaks and a background is given in Table 3. The results for the hydrated white cement were
function. It was found that an appropriate choice of diffractometer set- recalculated to an anhydrous basis using the bound water. The content
tings and control on the background function parameters delivered of amorphous material was then adopted as phase fraction wα in the
the most robust quantification strategy. Beam overflow at low angles calculation of the calibrated phase constant by Eq. (1). It should be
should be avoided and a background function with as few coefficients noted that the phase constant value has no direct physical meaning as
as possible should be used. Here, a first order Chebyshev polynomial the constituent Z, M and V values are unknown.
was combined with a 1/2θ term to fit the background signal in both In the Rietveld quantitative phase analyses the calibrated peak
calibrations and analyses. phases were introduced as separately quantifiable phases. Except for
The diffuse scattering signals of slag and C–S–H (humps) were fitted the phase scale factor, all profile parameters were kept fixed during re-
using characteristic sets of pseudo Voigt peaks, the metakaolin peak was finement. As in the calibration measurements, the background signal
modelled using one asymmetric split pseudo Voigt peak. The calibration
of the phase constant (ZMV)α was derived by comparing the ‘peaks
phase’ scale factor of the fitted phase contribution in a reference sample
of known composition to the external standard measured under identi-
cal conditions. Knowing wα and μm, the (ZMV)α phase constant can be
calculated by setting Sα equal to 1 in the calibration sample. The obtain-
ed phase constant can then be used in Eq. (1) to quantify the weight
fraction of phase α in samples of unknown composition. The measured
and calculated XRD patterns of the SCMs (metakaolin and slag), the hy-
drated white cement (HWC) and the anhydrous grey Portland cement
(OPC) are shown Fig. 1. The calculated patterns were decomposed to
show the contribution of the main amorphous or nanocrystalline phases
present. Using the external standard method, first the concentrations of
the crystalline phases were determined and the amorphous weight

Fig. 2. Plot of the measured vs. weighed values (wt.%) of slag and metakaolin (MK) in their
respective preselected mixes with quartz. Error bars represent the 2σ repeatability inter- Fig. 4. XRD pattern decomposition of the simulated blended cements composed of:
val. The full grey line shows the 1:1 relationship, dashed lines depict a ±2 wt.% interval. a) 40 wt.% OPC, and 60 wt.% blast furnace slag, b) 50 wt.% OPC, 25 wt.% blast furnace slag,
Sample designations in bold indicate which amorphous component is plotted. and 25 wt.% metakaolin (MK). The difference curve is shown at the bottom of the graphs.
 R. Snellings et al. / Cement and Concrete Research 64 (2014) 89–98 93

was fitted using a first order Chebyshev polynomial and a 1/2θ term. The
profiles of slag and metakaolin were adopted from the calibration. The
C–S–H profile was based on the model obtained from the HWC
decomposition. As slight changes in C–S–H peak widths were observed
between different hydrating systems, a single lorentzian peak broaden-
ing parameter for all peaks was refined for the most advanced age of
hydration. This reparametrized C–S–H model was then used for all
previous ages. To calculate the mass absorption coefficients of the
hydrated pastes the water content of the paste was included as the
bound water content determined by the weight loss of samples heated
to 600 °C for 1 h in a laboratory furnace for solvent exchanged and dried
samples. Similarly, the calculation of the SCM degree of reaction needs
to be corrected for the dilution of the solid phases by the bound water
content of the paste.

2.4. Isothermal conduction calorimetry

Isothermal conduction calorimetry was used as an independent way

of following the degree of reaction over time. The heat released by the
pozzolanic reaction in the different portlandite–metakaolin model
systems was measured using a TAM Air calorimeter (TA Instruments).
15 g of paste was introduced into the calorimeter glass flasks and
the heat flow was measured at a constant temperature of 20 °C up to
7 days of hydration. The heat flow curves were integrated to obtain
the cumulative heat release.

3. Results

3.1. Anhydrous blends
In the following, the quantification results are discussed in terms of
absolute repeatability errors (95% or 2σ confidence interval assuming
a normal distribution of errors) and absolute bias (the difference be-
tween weighed and measured contents) reported in wt.%. The XRD
methodology was first applied to the quantification of the slag and
metakaolin content in simple binary mixes with quartz. The results
are shown graphically in Fig. 2. In the slag–quartz mixes the repeatabil-
ity (2σ) on slag quantification was always smaller than 0.5 wt.%. The 2σ
repeatability on separately prepared samples of identical mix was
somewhat higher, i.e. 0.9 wt.%. This means that sample preparation
and homogenization are more limiting the precision than the XRD
data collection and analysis procedure for the simple binary mixes.
The absolute accuracy was always better than 0.8 wt.% and the average
deviation from the as weighed composition was 0.5 wt.%.
Next the method was applied to the quartz–slag–metakaolin mixes
containing two amorphous phases. A measured and calculated XRD
Fig. 6. XRD pattern decomposition of the simulated hydrated blended cements composed
of: a) 70 wt.% HWC, and 30 wt.% blast furnace slag, b) 70 wt.% HWC, and 30 wt.% blast fur-
nace slag. The difference curve is shown at the bottom of the graphs.
pattern as well as the corresponding pattern decomposition is shown
in Fig. 3. The measured XRD pattern shows a single broad diffuse scat-
tering maximum. Using the calibrated peak profiles of the metakaolin
and slag components, good fits to the measured patterns were obtained.
The results are shown in Fig. 2. For both amorphous phases, the average
2σ repeatability was 0.36 wt.% and not higher than 0.72 wt.% for tripli-
cate measurements of the same sample. Separately prepared samples
of identical mix composition showed a 2σ repeatability of 0.3 wt.%.
The measured vs. weighed bias was 1.1 wt.% on average (max.
2.1 wt.%). The presence of multiple amorphous phases thus slightly
reduced the accuracy, however the results remain acceptable.
In a next step the precision and accuracy of the method were evalu-
ated for mixes of slag, metakaolin and grey Portland cement (OPC) as a
complex multiphase crystalline material. First binary mixes of OPC and

Fig. 5. Plot of the measured vs. weighed values (wt.%) of slag and metakaolin (MK) in the
simulated blended cements. Error bars represent the 2σ repeatability interval. The full Fig. 7. Plot of the measured vs. weighed values (wt.%) of slag and metakaolin (MK) in the
grey line shows the 1:1 relationship, dashed lines depict a ±2 wt.% interval. Sample simulated hydrated blended cements. Error bars represent the 2σ repeatability interval.
designations in bold indicate which amorphous component is plotted. The full grey line shows the 1:1 relationship, dashed lines depict a ±2 wt.% interval.
94 R. Snellings et al. / Cement and Concrete Research 64 (2014) 89–98

either slag or metakaolin were measured. Fig. 4a shows the pattern de-
composition of a blend of 40 wt.% OPC and 60 wt.% blast furnace slag.
The OPC and the blast furnace slag profiles are strongly overlapped
and incorrect fitting of the blast furnace contribution would lead to
significant deviations in the OPC quantification. Nevertheless, the
quantification results for the binary blended cements (Fig. 5) were
very repeatable with a 2σ repeatability smaller than 0.6 wt.% for the
slag blends and less than 1.2 wt.% for the metakaolin blended cements.
The accuracy was slightly less good compared to the quartz mixes, 0.8
wt.% on average for the slag blends (max. 2.0 wt.%), and 0.5 wt.% on
average for the metakaolin blends (max. 1.1 wt.%). The results show
that excellent analytical accuracy and precision on the quantification
of SCMs in anhydrous blended cements can be achieved if the SCM
profile is appropriately calibrated.
The advantage of the PONKCS method over methods that indirectly
quantify the amorphous content is highlighted by the analysis of the
XRD pattern of a ternary blended cement composed of grey cement,
metakaolin, and slag. The XRD pattern in Fig. 4b shows a relatively
low and indistinctive amorphous hump. Nevertheless, the pattern de-
composition enables both SCMs to be quantified separately with a
high level of precision (2σ of 0.8 wt.% on average) and good accuracy
(bias of 1.2–1.6 wt.%). Overall it can be concluded that for anhydrous
mixes the method enables the quantification of amorphous SCMs with
a precision better than 1 wt.% (2σ) and an accuracy better than 2 wt.%.
3.2. Hydrated systems
Hydrated blended cements mostly contain several amorphous or
nanocrystalline phases. Apart from the usually amorphous SCM, also
the C–S–H phase (and potentially also C–A–H phases) cannot be quan-
tified directly using Rietveld quantitative phase analysis. In addition, if
the scattering contribution of the C–S–H phase is incorrectly accounted
for, the deviations between the measured and calculated patterns may
be partially compensated by other phases, strongly decreasing the accu-
racy of the analysis.
As a first step in quantifying the SCM content in hydrated systems,
mixes of hydrated white cement (HWC), hydration-stopped and thus
containing a constant C–S–H phase, and fixed quantities of slag and
metakaolin were tested. Samples of representative XRD patterns are
shown in Fig. 6. The calculated pattern decomposition demonstrates
the extensive peak overlap between the C–S–H and the slag contribu-
tion in particular. The quantification results are compared to the as
weighed composition in Fig. 7. The results show that, even in the
case of extensive overlap, a very good correlation was found between
measured and weighed SCM contents. Absolute deviations were
0.33 wt.% on average (max. 0.6 wt.%) for the metakaolin–HWC mixes,
and 0.7 wt.% on average (max. 1.0 wt.%) for the slag–HWC mixes. The
analytical precision decreased however. In the slag–HWC samples an
average 2σ repeatability of 2.5 wt.% (max. 3.3 wt.%) was found, in the

Table 4
Initial content (corrected for the bound water content) and unreacted content of the main reactive phases, i.e. portlandite, cement and SCMs (metakaolin and blast furnace slag) and the
resulting extent of reaction.

Pozzolanic reaction model systems

Sample Age (days) Initial content (wt.%), bound water Unreacted content (wt.%) Extent of reaction (%)
corrected

Portlandite Metakaolin Portlandite Metakaolin Portlandite Metakaolin

P-M 1 46.4 43.0 40.7 40.1 12 7

4 38.1 35.3 23.5 26.9 38 24
7 36.9 34.2 12.3 19.3 67 44
P-M-LAS 1 36.5 33.8 12.9 22.5 65 33
4 34.1 31.6 8.5 19.0 75 40
7 33.2 30.7 7.9 17.6 76 43
P-M-HAS 1 34.9 32.4 11.3 22.3 68 31
4 32.5 30.1 8.3 18.7 74 38
7 32.2 29.8 7.5 17.4 77 42

Model systems with fillers

Age (days) Portlandite Metakaolin Portlandite Metakaolin Portlandite Metakaolin

P-M-LAS-Q 1 29.6 27.4 18.3 24.1 38 12

4 27.7 25.7 2.7 13.7 90 46
7 27.0 25.0 0.6 10.4 98 58
P-M-LAS-Cc20 1 29.6 27.4 13.9 21.2 53 22
4 27.5 25.5 1.1 13.6 96 46
7 27.3 25.3 0.5 12.5 98 51
P-M-LAS-Cc6 1 29.6 27.4 13.4 20.8 55 24
4 27.5 25.5 0.8 13.0 97 49
7 27.3 25.3 0.4 12.2 99 52

Blended cements

Age (days) Cement SCM Cement SCM Cement SCM

CEM-MK 3 62.3 24.7 16.2 24.0 74 3

7 58.9 23.4 13.9 21.7 76 7
28 56.0 22.2 8.3 17.5 85 21
CEM-MK-Q 3 53.0 21.0 12.3 20.1 77 4
7 50.1 19.9 10.8 18.0 79 10
28 48.4 19.2 5.3 14.6 89 24
CEM-MK-Cc6 3 51.9 20.6 12.9 19.0 75 8
7 49.7 19.7 11.6 17.3 77 12
28 48.0 19.1 6.1 14.5 87 24
CEM-Slag 3 35.5 52.6 6.7 46.7 81 11
7 34.8 51.5 2.7 39.6 92 23
28 33.3 49.4 1.5 31.8 96 36
 R. Snellings et al. / Cement and Concrete Research 64 (2014) 89–98
Fig. 8. Hydration assemblage of the P-M, P-M-LAS, P-M-HAS, and the MK blended cement
at 7 days of hydration. Ms, Hc, and Mc identify with monosulfoaluminate hydrate,
hemicarboaluminate hydrate, and monocarboaluminate hydrate.
metakaolin–HWC samples a better of precision of 1.5 wt.% on average
(max. 2.7 wt.%) was obtained. The decrease in precision was most
noted for the slag–HWC samples and was most likely due to the impor-
tant degree of peak overlap between both. The quantification results of
the C–S–H phase in the mixes showed very similar levels of accuracy
and precision as the SCMs. It can thus be concluded that also in blends
containing C–S–H an accuracy better than 2 wt.% can be expected,
however the measurement precision is lowered, advocating the use of
repeats.
Fig. 9. XRD pattern decomposition of the hydrated binders: a) P-M-LAS with quartz filler hydrated for 1 day, b) P-M-LAS with limestone (fine) filler hydrated for 1 day, c) blended cement
with 30 wt.% metakaolin (MK) and 15 wt.% limestone hydrated for 3 days, d) blended cement with 60 wt.% slag hydrated for 3 days. Ms, and Hc stand for monosulfoaluminate hydrate and
hemicarboaluminate hydrate, respectively.
95
The application of the method to the determination of the extent of
reaction of SCMs was first tested on simplified systems containing
metakaolin and portlandite with additional alkalis and sulfate to simu-
late the reaction environment of blended Portland cements. The
metakaolin content of the reacting system was determined at 1, 4, and
7 days and normalized to the initial content (bound water corrected)
in order to calculate the extent of reaction as presented in Table 4. The
effect of the various parameters (alkalis, sulfate, and presence of fillers)
on the degree of reaction is the subject of another study which will be
reported on later. Due to these variations there were some small differ-
ences in the hydrate assemblages formed (Fig. 8) but these are not
discussed in detail here. The focus here is just the degree of reaction of
the metakaolin component. An example of the XRD profile decomposi-
tion is shown in Fig. 9 for the P-M-LAS system with quartz and fine
limestone filler at 1 day of hydration.
The accuracy of the quantification results was cross-checked in two
ways. First, standard additions of 20 and 40 wt.% metakaolin were made
to selected reacted P-M-LAS model systems. The total metakaolin con-
tent was measured and plotted as a function of the metakaolin addition
in Fig. 10. The extrapolated intercept with the ordinate gives an estima-
tion of the metakaolin content in the original sample. These metakaolin
contents compared well to the directly measured content in the sam-
ples with differences of 0.9 wt.% on average (max 1.9 wt.%). Secondly,
the extent of the pozzolanic reaction measured by XRD was compared
to the overall cumulative heat released by the exothermal hydration re-
actions. Normalized by the initial content of metakaolin in Fig. 11a, the
cumulative heat release followed the same trends that were found by
quantitative XRD. Quantitatively, the cumulative heat release correlated
well with the extent of reaction measured by XRD in Fig. 11b. Neverthe-
less, the relationship between the extent of metakaolin reaction and the
96 R. Snellings et al. / Cement and Concrete Research 64 (2014) 89–98
Fig. 10. Measured vs. weighed, added metakaolin mass fractions. The correspondence
between the intercept of the trend line and the measured fraction in the original sample
without additions gives an indication of the level of accuracy of the quantification method.
Cc and Q refer to respectively the limestone and quartz fillers added to the reacting samples.
heat release also changes between systems due to changes in the
hydrate assemblage.
Finally, the extent of reaction of SCMs was measured for hydrated
blended cements. The SCM reaction was followed in blended cements
containing either slag (60 wt.%) or metakaolin (30 wt.%) with and
without fillers. Measured and calculated XRD patterns of metakaolin
and slag blended cements hydrated for 3 days are shown in Fig. 9. The
pattern decomposition shows the contributions of the various raw
materials and hydration products to the calculated XRD profile. The
calculated degrees of reaction of the OPC and the SCM are given in
Table 4. The results demonstrate that the degree of cement hydration
is enhanced by increasing levels of cement replacement (filler effect).
4. Discussion
The present paper demonstrates that the PONKCS method enables
the quantification of amorphous phases in complex materials such as
anhydrous and hydrated Portland cements with a level of precision
(2σ) of 2–3 wt.% and an accuracy better than 3 wt.%. Table 5 summa-
rizes the results on analytical precision and accuracy for the different
systems. The performance of the PONKCS method for amorphous
phases is therefore deemed comparable to that of the Rietveld method
for crystalline phases in cement systems [18,22,37]. It should be noted
that the estimated experimental errors on the SCM degree of reaction
Fig. 11. Cumulative heat release measured by calorimetry for pozzolanic reaction model systems with and without fillers (a), and plot of the measured amount of reacted metakaolin vs.
the cumulative heat released (b).
scale with the initial SCM content of the blend. The smaller the SCM
fraction in the blended cement the larger the error on the degree of
reaction. Moreover, the analytical accuracy will also decrease at high
degrees of reaction because of the relatively high detection limit of
amorphous phases. The levels of accuracy and precision established by
the present study indicate that the method is only practical for blended
cements with replacement levels higher than 10%. Below 10% replace-
ment, the accuracy of the method will be poor, due to the estimated
2–3 wt.% error on the SCM quantification. Moreover, detection limits
are relatively high for amorphous phases and it is doubtful whether
SCM residues below 3–5 wt.% can be reliably quantifiable.
The presented quantification method assumes that the peak phase
profiles and phase constants of the calibrated phases are representative
for the corresponding phases in the unknown sample. In the case of
blended cements, aberrations from this assumption may occur for
both SCMs and the C–S–H phase and reduce the accuracy of the method.
The decomposition method of the XRD patterns assumes a congruent
dissolution of the SCM component. At high pH this is a realistic assump-
tion for homogeneous SCMs such as slags and metakaolin [38]. For het-
erogeneous materials such as fly ashes, this condition may not hold and
the unreacted residue may change in composition due to differences in
reactivity of the various components. This may affect the peak phase
profile and the phase constant of the SCM and thus bias the quantifica-
tion results.
An added bias may originate from variations in the composition of
the precipitated C–S–H phase. The reaction of SCMs in blended cements
is known to decrease the Ca/Si ratio and, in the case of Al-rich SCMs such
as metakaolin, increase the Al uptake of the C–S–H phase [39]. In addi-
tion, both the morphology [40] and the XRD profile of the C–S–H [41]
were found to vary between OPC and a range of blended cements,
especially at later ages. The compositional and microstructural changes
encountered may affect the C–S–H peak phase profile and the calibrated
phase constant. The C–S–H model in this study was based on the C–S–H
phase formed in the white cement hydrated for 7 years. A better match
between the C–S–H model and the C–S–H in blended cements may be
obtained using peak phase models of synthetic C–S–H of the appropri-
ate composition and microstructure, or a model for C–S–H in fully
reacted blended cements. Obtaining a C–S–H model directly from
hydrated blended cements is experimentally difficult as it requires sep-
arating (and quantifying) the C–S–H phase contribution from other
amorphous or nanocrystalline phases present in the hydrated blended
cement (AFm phases, unreacted SCMs, …). Even so, XRD studies of syn-
thetic C–S–H of varying composition have not indicated significant
changes in the C–S–H XRD profiles with decreasing Ca/Si down to
 R. Snellings et al. / Cement and Concrete Research 64 (2014) 89–98
Table 5
Summary of the analytical precision (2σ) and accuracy for the different systems.
Anhydrous blends
Average (max.) wt.% Binary systems
Quartz (single phase) + SCM Anhydrous cement (multiphase) + SCM
Precision (2σ) 0.3 (0.9) 0.7 (1.2)
Accuracy 0.5 (0.8) 0.7 (2.0)
Hydrated blends
Average (max.) Weighed mix
Hydrated white cement + SCM
Precision (2σ) 2.0 (3.3)
Accuracy 0.5 (1.0)
a
Estimated by the standard addition method.
Ca/Si ratios of 1.0 [42,43]. In addition, incorporation of Al into C–S–H
was found to shift only the basal (002) peak and leave other peaks
unchanged [43–45]. The present study did not consider low-angle re-
flections and the C–S–H basal peak was not comprised in the present
model. Nevertheless, even if there are few indications that the C–S–H
XRD profile changes significantly with composition, the phase constant
may well vary and render the PONKCS method less suitable for the
quantification of the C–S–H phase. It should be noted however that an
inaccuracy in the determination of the C–S–H phase constant will only
change the quantification results by a constant factor, and that the
quantification of other phases is not affected.
5. Conclusions
The XRD based PONKCS method was successfully applied to
the quantification of the content and extent of reaction of SCMs in
anhydrous and hydrated blended cements. The PONKCS method was
implemented into Rietveld refinement software and combined with
an external standard approach to enable the quantification of crystalline
and individual amorphous phases. The quantification method and
approach was described in detail.
The analytical accuracy and precision of the method were evaluated
through an extensive series of model mixes of increasing complexity,
ranging from simple binary mixes of an SCM and a single crystalline
phase over ternary mixes of anhydrous grey Portland cement with
two separately measurable SCMs to mixes of hydrated cement and
SCMs. Overall, the precision (2σ) on the measured SCM content was
2–3 wt.% or less for triplicate analyses. The accuracy of the measurement
was better than 2 wt.%, even for the more complex mixes.
In hydrating binder systems the results were satisfactory in that
1) quantification results obtained by the standard addition method
corresponded to the initial measurement of the SCM content in the
original sample, and 2) the cumulative heat release measured by
calorimetry scaled linearly with the extent of SCM reaction.
The notable advantages of the application of the PONKCS method to
the measurement of the SCM content and extent of reaction are 1) the
widespread availability of XRD equipment, 2) the rapid data collection
(15–30 min), 3) the straightforward and fast data analysis, and
4) the potential general applicability to all SCMs. The method can be
implemented fairly easily into existing software packages for Rietveld
analysis by a skilled operator. The method is therefore likely to find a
more widespread use, both in research and in production control,
particularly because there are in principle no specific limitations regard-
ing the SCM type or composition.
Acknowledgements
RS gratefully acknowledges financial support of the European
Community under FP7-Marie Curie IEF grant 298337.
97
Ternary systems
Quartz (single phase) + 2 SCMs Anhydrous cement (multiphase) + 2 SCMs
0.4 (0.7) 0.8 (1.4)
1.1 (2.1) 1.4 (1.6)
Reacted system
Pozzolanic reaction model system
3.0 (4.2)
0.9 (1.9)a
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