Cement and Concrete Research 52 (2013) 169–181

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Cement and Concrete Research

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Effect of temperature on the hydration of Portland cement blended with

siliceous fly ash
Florian Deschner a,⁎, Barbara Lothenbach a, Frank Winnefeld a, Jürgen Neubauer b
a
Empa, Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Concrete and Construction Chemistry, Überlandstrasse 129, 8600 Dübendorf, Switzerland
b
GeoZentrum Nordbayern, Mineralogy, University of Erlangen-Nuremberg, 91054 Erlangen, Germany

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

Article history: The effect of temperature on the hydration of Portland cement pastes blended with 50 wt.% of siliceous fly ash is
Received 14 March 2013 investigated within a temperature range of 7 to 80 °C.
Accepted 9 July 2013 The elevation of temperature accelerates both the hydration of OPC and fly ash. Due to the enhanced pozzolanic
reaction of the fly ash, the change of the composition of the C–S–H and the pore solution towards lower Ca and
Keywords:
higher Al and Si concentrations is shifted towards earlier hydration times. Above 50 °C, the reaction of fly ash also
Fly ash (D)
Blended cement (D)
contributes to the formation of siliceous hydrogarnet. At 80 °C, ettringite and AFm are destabilised and the re-
Temperature (A) leased sulphate is partially incorporated into the C–S–H. The observed changes of the phase assemblage in depen-
Hydration (A) dence of the temperature are confirmed by thermodynamic modelling.
Modelling (E) The increasingly heterogeneous microstructure at elevated temperatures shows an increased density of the C–S–H
and a higher coarse porosity.
© 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Cementitious materials are exposed to a vast range of temperatures
due to factors like local climatic conditions, externally applied heat in
precast concrete or heat due to the exothermic nature of the hydration
process. Several studies investigated the impact of temperature on the
hydration kinetics, the hydrate assemblage, microstructure and durabil-
ity of ordinary Portland cement (OPC) in a temperature range between
5 and 60 °C [1–8]. In accordance with the Arrhenius law, the augmenta-
tion of temperature leads to the increase of the hydration rate of OPC
and therefore to increased early compressive strength [1]. The temper-
ature sensitivity of the hydration rate is indicated by the apparent acti-
vation energy, which was determined for OPC and cements blended
with fly ash, slag and other supplementary cementing materials [9,10].
At later hydration times, the rate of strength development diminishes,
so that after a certain time span, the compressive strength at high tem-
peratures is lower than for samples hydrated at lower temperatures.
This effect is related to the microstructure development of the cement
paste [1–3,5,8,11]. The rapidly forming initial hydration products at
elevated temperatures are distributed heterogeneously, the density of
the C–S–H is increased and at above 47 °C, ettringite and monocar-
bonate are destabilised to monosulphate and calcite. This leads to a
higher coarse porosity and reduced compressive strength [2,3,12,13].
At lower temperatures, the hydration rate is reduced allowing the
dissolved ions more time for diffusion before the hydrates precipitate.
This leads to the formation of a less polymerised C–S–H with higher
⁎ Corresponding author. Tel.: +41 58 765 4535; fax: +41 58 765 4035.
E-mail address: florian.deschner@gmail.com (F. Deschner).
gel-porosity [13–15] and a cement paste with a more even distribution
of the hydrate phases. Hence, the coarse porosity is reduced and the
compressive strength increased [1,7].
Furthermore, the chemistry of the pore solution is affected by the
temperature due to the change of the solubility of the hydrate phases.
For example, the increase of the temperature in neat OPC leads to a
higher solubility of ettringite and thus to an increase of the sulphate
concentrations in the pore solution [3,4,16,17].
Although the effect of temperature on the hydration of neat OPC is
well studied, there are few studies about fly ash blended OPC at differ-
ent temperatures [11,15]. The present study shows a consistent set of
data of the hydration of a Portland cement containing 50 wt.% of sili-
ceous fly ash between 7 and 80 °C. The hydrate phase assemblage, the
composition of the C–S–H, the development of the microstructure and
the composition of the pore solution at hydration times between 1
and 180 days were investigated. The results are compared to the analy-
sis of reference samples containing 50 wt.% of quartz powder instead of
fly ash to allow the observation of the effect of temperature on the reac-
tion of fly ash.
2. Materials and methods
2.1. Raw materials
An OPC (CEM I 42.5 N) and a siliceous fly ash (type V according to EN
197-1) have been used as raw materials. The chemical and mineralogi-
cal compositions of these materials were determined by means of X-ray
fluorescence (XRF) and quantitative X-ray diffraction [18] (Table 1,
reproduced from [19]). The average composition of the fly ash glass

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170 F. Deschner et al. / Cement and Concrete Research 52 (2013) 169–181

Table 1
Composition and density of the raw materials.

XRF-analysisa [wt.%] Mineralogical phase compositionb [wt.%] Average composition of

the fly ash glass [wt.%]

FA OPC FA OPC FA

SiO2 50.9 19.4 Mullite 8.2 C3S 57.1 SiO2 54.1

Al2O3 24.7 5.2 Quartz 7.0 β C2S 7.9 Al2O3 23.4
Fe2O3 7.3 3.6 Hematite 0.7 α′ C2S 9.3 Fe2O3 7.1
CaO 3.7 62.1 Magnetite 0.8 C4AF 13.0 CaO 4.6
MgO 1.8 1.8 Amorphous 83.3 C3A cubic 2.0 MgO 2.2
K2O 3.9 1.2 C3A orthorh. 2.0 K2O 5.0
Na2O 0.9 0.3 Calcite 0.4 Na2O 1.1
TiO2 1.1 0.2 Periclase 1.0 TiO2 1.4
Mn2O3 0.1 0.1 Bassanite 2.6 Mn2O3 0.1
P2O5 0.8 0.6 Anhydrite 2.8 P2O5 0.9
SO3 0.4c 3.7 Arcanite 0.5 SO3 b0.1
SrO 0.3 Dolomite 0.5
LOI 3.5 1.1 Magnesite 0.3
C 2.7d Siderite 0.2
Quartz 0.2
Ankerite 0.2
Sum 99.1 99.5 100 100 100
a
Standard deviation of the XRF analyses is b0.1 wt.% for all oxides except SiO2 (0.5 wt.%).
b
Standard deviation ranges from 0.1 to 0.6 wt.%.
c
SO3 content determined by combustion analysis.
d
C-content (part of the LOI) determined by combustion analysis.

was calculated by subtracting the crystalline phases and the readily sol-
uble alkalis from the total composition of the fly ash and normalizing
the results to 100 wt.%. As reference material, a quartz powder, which
showed no pozzolanic activity at 23 °C up to 90 days of hydration was
used [19]. The particle size distribution of the quartz powder is similar
to that of the fly ash (graph shown in [19]).
2.2. Preparation of cement pastes
All raw materials and mixing tools used for the preparation of the ce-
ment pastes were equilibrated at the respective temperature for 1 day
before use. Cement paste samples containing 50 wt.% of OPC and
50 wt.% of fly ash (OPC-FA) or 50 wt.% of quartz powder (OPC-Qz), re-
spectively, were prepared according to EN 196-3 with a water-to-
binder ratio (w/b) of 0.5. The samples were cast in 500 ml and 60 ml
polyethylene flasks, sealed and stored at 7, 23, 40, 50 and 80 °C. The
500 ml samples were used for the extraction of the pore solution and
the 60 ml samples for the analysis of the solid phases. The solid phases
were analysed by means of TGA in N2-atmosphere, XRD, and scanning
electron microscopy (SEM).
2.3. Thermogravimetric analyses (TGA)
The hydrated samples were crushed, immersed in isopropanol for
15 min, washed with diethylether, and filtered. Afterwards, the samples
were dried for 10 min at 40 °C to evaporate the remaining diethylether
and analysed in a Mettler Toledo TGA/SDTA 851e device at a heating
rate of 20 K/min in N2-atmosphere. The analysed bound water of all
hydrate phases (H) and the crystal water within Ca(OH)2 (HCH) were
determined by the weight loss in the temperature intervals 50–500 °C
and 400–470 °C. The exact boundaries for the temperature interval of
portlandite were read from the derivative curve (DTG). The results are
expressed as percentage of the dry sample weight at 500 °C [20]. Triple
preparation and measurement of the samples after 1, 2 and 7 days of
hydration at 23 °C shows an absolute error of up to 2 wt.% for the
bound water, and up to 0.6 wt.% for the water loss related to the decom-
position of Ca(OH)2. This includes the errors caused by preparation and
measurement.
2.4. X-ray diffraction (XRD) measurements
5 mm thick discs of the hardened paste samples with a diameter of
30 mm were sliced from the cast samples, immersed in isopropanol
for 2 days to stop the hydration and stored under N2-atmosphere
until measurement. Measurements were performed in a PANalytical
X'Pert Pro MPD diffractometer with attached X'Celerator detector.
2.5. Analysis of the pore solution
The pore solutions of the hardened samples were extracted by the
steel die method [21] using pressures up to 250 MPa. The solutions
were filtered immediately with nylon filters with a mesh size of
0.45 μm. The free OH− concentrations of the pore solutions were calcu-
lated from pH measurements with a pH electrode, calibrated against
KOH solutions with known concentrations. The K, Na, Ca, Al, Si and sul-
phur concentrations were measured by means of inductively coupled
plasma optical emission spectroscopy (ICP-OES). The standard devia-
tion of the measured elemental concentrations ranges between 5 and
10%.
2.6. Scanning electron microscopy (SEM)
The hydration was stopped by cutting the sample into slices of 5 mm
thickness with a diameter of 30 mm and keeping them for 3 days in
isopropanol and drying them for 3 days at 40 °C. Subsequently, the
samples were impregnated with a modified bisphenol-A-epoxy-resin
and polished by polycrystalline diamond suspension at grades from
9 μm down to 1/4 μm. Finally, the samples were carbon-coated and in-
vestigated under high vacuum conditions in a Philips ESEM FEG XL 30.
EDX measurements of the hydrate phases were carried out at a beam
voltage of 10 keV and 10 mm working distance. The content of coarse
pores (pore size N 0.6 μm) was determined by means of image analysis
of 600 images per sample at magnification of 2000. The upper threshold
for the grey level segmentation of pores was determined by the mini-
mum point between the peak of pores and the brighter hydration prod-
ucts peak in the histogram of the sum of all 600 images [22,23]. The
error of the quantification of the coarse porosity is estimated to be
± 3%.
 F. Deschner et al. / Cement and Concrete Research 52 (2013) 169–181
2.7. Compressive strength of mortar samples
Mortar prisms (40 × 40 × 160 mm3) were prepared according to
EN 196-1 and cured at 7, 20, 40, 50 and 80 °C. After demoulding, two
mortar prisms per testing age were stored inside sealed boxes filled
with distilled water at the appropriate temperature until testing. The
compressive strength was tested according to EN 196‐1.
2.8. Thermodynamic modelling
The stable phase assemblage of the investigated cementitious sys-
tems at thermodynamic equilibrium was calculated in dependence of
the temperature. The calculations were performed with the help of
the Gibbs free energy minimisation programme GEMS [24,25] together
with the thermodynamic data from the PSI-GEMS database [26] ex-
panded with additional data for solids that are expected to form under
cementitious conditions [4,27–29]. For the sake of simplicity, the crys-
talline phases in the fly ash were considered as inert and the glass
phase of the fly ash was assumed to dissolve uniformly.
GEMS was also used to calculate the activities of the aqueous species
in the investigated pore solutions by the extended Debye–Hueckel
equation [30]. From the activities, the saturation indices (SI) of the
solid phases were calculated. The SI with respect to the solids are
given by log(IAP/KS0), where KS0 is the theoretical solubility product
of the respective solid, while IAP is the ion activity product calculated
from the measured concentrations. A positive SI implies oversaturation,
a negative value undersaturation. As the use of SI can be misleading
when comparing phases which dissociate into a different number of
ions, effective SI were calculated by dividing the SI by the number of
ions participating in the reactions to form the solids, as described by
Lothenbach et al. [4].
3. Results and discussion
3.1. Compressive strength
Fig. 1a shows a positive influence of elevated temperature on the
early compressive strength of the reference sample OPC-Qz. After
28 days, the OPC-Qz samples hydrated at 7 to 40 °C show similar
strength. At 50 °C, a late increase of strength is observed compared to
OPC-Qz at 40 °C. And at 80 °C, a strong increase of compressive strength
from 23.4 to 71.9 MPa is detected between 7 and 180 days. This effect is
probably related to the temperature induced pozzolanic reaction of the
quartz powder.
The development of the compressive strength of OPC-FA between 1
and 180 days is shown in Fig. 1b. Between 7 and 40 °C, the compressive
strength shows a positive correlation with the temperature throughout
the whole hydration time. After 1 day of hydration at 50 and 80 °C, the
70 a) OPC-Qz
Compressive strength [MPa]
60 7 °C
20 °C
50 40 °C
50 °C
40 80 °C
30
20
10
0
1 10
Time [d]
Fig. 1. Development of the compressive strength of (a) OPC-Qz and (b) OPC-FA at temperatures ranging from 7 to 80 °C.
171
strength is higher than at lower temperatures. Afterwards however, the
rate of strength increase at these high temperatures is lower, and there-
fore the late strength values are lower than at 40 °C. At 80 °C, this effect
is pronounced: the high early strength of 21.8 MPa after 1 day of hydra-
tion is followed by a slow increase of strength resulting in 36.8 MPa
after 180 days. In contrast to OPC-Qz, no relevant increase of the com-
pressive strength is found after 7 days of hydration at 80 °C.
In comparison to the reference sample OPC-Qz (Fig. 1a), the com-
pressive strength of the fly ash blended cement pastes at 20 °C is clearly
higher after 28 days. This additional strength is related to the pozzolanic
reaction of the fly ash, while the quartz powder in the reference shows
no significant pozzolanic reactivity at this temperature [31]. From 7 to
50 °C, the rise of compressive strength in OPC-FA compared to OPC-Qz
is shifting to earlier hydration times and thereby indicating a faster hy-
dration of fly ash at higher temperatures.
3.2. Content of portlandite and bound water
Fig. 2a–e shows the portlandite contents (CH) and bound water of all
hydrate phases other than portlandite (H*), determined by means of
TGA. H* is calculated by subtracting the content of crystal water of
portlandite in the sample from the amount of total bound water (H).
For each temperature CH and H* in OPC-FA is compared to the reference
sample OPC-Qz. The beginning of the portlandite consumption related
to the pozzolanic reaction is indicated by the relative decrease of the
portlandite content in OPC-FA compared to OPC-Qz. It shows that the
start of the pozzolanic reaction is shifting to earlier hydration times at el-
evated temperatures. The onset of portlandite consumption in OPC-FA is
found at 7 °C after 90 days, at 23 °C after 7 days, at 40 °C after 1 day, at
50 °C after 16 h, and at 80 °C before 16 h of hydration. The difference
between H* in OPC-FA and H* in OPC-Qz is related to the amount of hy-
dration products formed by the pozzolanic reaction of fly ash. The point
at which H* of OPC-FA is starting to be higher than H* in OPC-Qz is
shifting towards earlier hydration times at elevated temperatures and
correlates well with the beginning decrease of portlandite.
The decrease of the portlandite content in the OPC-Qz samples ob-
served at 40, 50 and 80 °C indicates a pozzolanic reaction of the quartz
in the reference samples. The rate of the quartz reaction increases
with temperature. Surprisingly at 80 °C, the reaction of the quartz con-
tinues while the fly ash reacts much slower after the first hours. This
could be related to a hindrance of the further fly ash reaction at the
high dissolved Al concentrations observed in these samples.
3.3. Characterization of hydration products
3.3.1. X-ray diffraction (XRD)
Figs. 3 and 4 show details of the XRD patterns of the samples after 1
and 180 days of hydration. In addition to anhydrous Portland cement
b) OPC-FA
7 °C
20 °C
40 °C
50 °C
80 °C
100 1 10 100
Time [d]
172 F. Deschner et al. / Cement and Concrete Research 52 (2013) 169–181

a) 7 °C b) 23 °C
30 20 30 20
28 Bound H2O Portlandite 28 Bound H2O Portlandite
OPC-FA OPC-FA 18 OPC-FA OPC-FA 18
26 26
CH [g/100g dry binder]

CH [g/100g dry binder]

24 OPC-Qz OPC-Qz OPC-Qz

H* [g/100g dry binder]

24

H* [g/100g dry binder]

OPC-Qz 16 16
22 22
14 14
20 20
18 12 18 12
16 16
10 10
14 14
12 8 12 8
10 10
6 6
8 8
6 4 6 4
4 4
2 2
2 2
0 0 0 0
1 10 100 1 10 100
Time [d] Time [d]

c) 40 °C d) 50 °C
30 20 30 20
28 Bound H2O Portlandite 28 Bound H2O Portlandite
OPC-FA 18 OPC-FA OPC-FA 18
26 OPC-FA 26

CH [g/100g dry binder]

CH [g/100g dry binder]

24 OPC-Qz 16 24 OPC-Qz OPC-Qz 16

H* [g/100g dry binder]

H* [g/100g dry binder]

OPC-Qz
22 22
14 14
20 20
18 12 18 12
16 16
10 10
14 14
12 8 12 8
10 10
6 6
8 8
6 4 6 4
4 4
2 2
2 2
0 0 0 0
1 10 100 1 10 100
Time [d] Time [d]

e) 80 °C
30 20
28 Bound H2O Portlandite
OPC-FA 18
26 OPC-FA
CH [g/100g dry binder]

H* [g/100g dry binder]

24 OPC-Qz OPC-Qz 16
22
14
20
18 12
16
10
14
12 8
10
6
8
6 4
4
2
2
0 0
1 10 100
Time [d]

Fig. 2. Comparison of the content of portlandite (dashed lines) and bound water (solid lines) in OPC-FA and OPC-Qz at (a) 7 °C, (b) 23 °C, (c) 40 °C, (d) 50 °C and (e) 80 °C.

clinker phases and fly ash minerals, the diffractograms of OPC-FA show minor amounts of AFm phases. Due to the relatively high content of sul-
the formation of portlandite, ettringite, monosulphate and an AFm phate and magnesium in the Portland cement, the majority of Al is
phase, which is most likely a ternary solid solution of AFm phases con- bound within ettringite and possibly hydrotalcite in OPC-Qz. In OPC-
taining sulphate, carbonate and hydroxide [32,33]. FA, the fly ash dissolution leads to the release of Al and the increase of
After 1 day of hydration (Fig. 3) the diffractograms of OPC-Qz and the Al-to-sulphate ratio and thereby promotes the formation of AFm
OPC-FA are similar. At 7 and 23 °C the main hydrate phases are port- phases. At 80 °C, OPC-FA and OPC-Qz do not show any more reflections
landite and ettringite. The increase of the temperature to 40 or 50 °C related to the presence of ettringite and AFm phases.
leads to the formation of monosulphate in addition to ettringite and The presence of siliceous hydrogarnet is found after 180 days of hy-
portlandite. At 80 °C ettringite is not stable and an AFm phase is formed dration in OPC-FA and OPC-Qz. While the diffractograms at 50 °C and
instead. lower temperatures show only minor amounts of siliceous hydrogarnet,
After 180 days of hydration at 7 and 23 °C, portlandite, ettringite, at 80 °C siliceous hydrogarnet is one of the main hydrate phases. This is
monosulphate, a solid solution of AFm phases and monocarbonate are related to the kinetic hindrance of the formation of hydrogrossular
present in both samples (Fig. 4). At 40 and 50 °C, ettringite and below 50 °C.
portlandite persist in both samples. However, while OPC-FA shows the The change of the stable phase assemblage from ettringite and
presence of monosulphate and other AFm phases, OPC-Qz shows only monosulphate to siliceous hydrogarnet is related to the temperature
 F. Deschner et al. / Cement and Concrete Research 52 (2013) 169–181 173

a) OPC-Qz b) OPC-FA
CH Qz Qz CH CH Qz CH
Ms Ms
AFmss AFmss Mu Mu
E F E E EF E F E E EF
80 °C

50 °C

40 °C

23 °C

7 °C
8 10 12 14 16 18 20 22 24 26 28 30 8 10 12 14 16 18 20 22 24 26 28 30
°2 Theta °2 Theta

Fig. 3. Comparison of XRD data of (a) OPC-Qz and (b) OPC-FA after 1 day of hydration at 7, 23, 40, 50 and 80 °C. E—ettringite, Ms—monosulphate, AFmss—solid solution of AFm phases, CH—
portlandite, F—ferrite, Mu—mullite, Qz—quartz.

dependent solubility of these phases and the availability of Al, Ca, sul-
phate and hydroxide [4].
3.3.2. Analysis of the C–S–H composition by SEM-EDX
EDX point analyses were targeted at the outer product in the matrix
of hydrates and the inner product of fly ash or clinker in order to char-
acterize the composition of the C–S–H phase. Due to the interaction vol-
ume of electrons with the specimen and the intergrowth of hydrates,
the detected X-rays of one spot often consist of the signal of a mix of
two or more phases [34]. To derive the composition of a phase, element
ratio plots are used [35,36].
The Al/Ca versus Si/Ca plot of OPC-FA hydrated for 180 days at 7,
50 and 80 °C is shown in Fig. 5. The scatter of data points towards
high Si/Ca and high Al/Ca ratios is due to the presence of fly ash particles
within the excited sample volume of some EDX point analyses. The Al/Si
ratio of C–S–H is determined by the slope of a line, which is drawn
through the points with the lowest Al/Ca ratio and represents mixed
analyses of portlandite and C–S–H without AFm or ettringite. The range
of Si/Ca ratios of the C–S–H is represented by the bulk of data points
along this line. OPC-FA at 7 °C shows a range of Si/Ca values between
0.5 and 0.7 or Ca/Si ratios between 1.4 and 2.0. This variance is in
agreement with transmission electron microanalyses of C–S–H in fly
ash blended white Portland cement [37].
The Ca/Si, Al/Si and S/Si atomic ratios of OPC-FA and OPC-Qz after
180 days of hydration at temperatures ranging from 7 to 80 °C are
given in Table 2. The C–S–H composition of OPC-Qz hydrated for
180 days at 80 °C shows a significant reduction of the Ca/Si ratio com-
pared to lower temperatures. This is on one hand related to the reduced
solubility of Ca(OH)2 at elevated temperatures. On the other hand the
quartz powder is being dissolved at high temperatures and the addi-
tionally provided Si is probably incorporated into the C–S–H in a similar
way as during the hydration of silica fume blended OPC [15,38,39].
Compared to the reference sample, the C–S–H of the fly ash blended
Portland cement is characterised by lower Ca/Si and higher Al/Si ratios.
This change of the C–S–H composition is related to the additional Si,
provided by the fly ash dissolution, which is incorporated in the C–S–H
and results in longer silicate chain lengths [37,40,41]. This effect and
the provision of Al from the dissolution of fly ash leads to an increased
uptake of aluminium, which is substituting the Si atoms located in the
bridging tetrahedra of the silicate chains [42–44].
The comparison of the C–S–H compositions of OPC-FA hydrated at
different temperatures shows that the Ca/Si ratio decreases with in-
creasing temperature and the Al/Si ratio of the C–S–H increases from 7

a) OPC-Qz b) OPC-FA
CH Qz Qz CSH CH Qz CSH
Ms Ms
HG HG
AFmss HG HG AFmss HG Mu Mu
E F E E EF E F E E E F
80 °C

50 °C

40 °C

23 °C

7 °C
8 10 12 14 16 18 20 22 24 26 28 30 8 10 12 14 16 18 20 22 24 26 28 30
Mc °2 Theta CH Mc Mu °2 Theta CH

Fig. 4. Comparison of XRD data of (a) OPC-Qz and (b) OPC-FA after 180 days of hydration at 7, 23, 40, 50 and 80 °C. E—ettringite, Ms—monosulphate, AFmss—solid solution of
hemicarbonate and OH− substituted monosulphate, CH—portlandite, HG—hydrogarnet, F—ferrite, Mu—mullite, Qz—quartz.
174 F. Deschner et al. / Cement and Concrete Research 52 (2013) 169–181

Fig. 5. Plot of Al/Ca versus Si/Ca atomic ratios of the EDX measurements focussed on hydrate phases in OPC-FA hydrated for 180 days at 7, 50 and 80 °C. Ettr—ettringite, CH—portlandite,
C2ASH8—strätlingite, C3AH6—katoite, C3ASH4—hydrogrossular, Jen—jennite, Tob—tobermorite.

to 50 °C. This is probably related to the enhanced reactivity of fly ash at measured increased concentrations of dissolved Al and S in the pore
higher temperatures, the increased release of Si and Al ions from the fly solution.
ash dissolution and the increased degree of polymerisation of the C–S–H
at higher temperatures [13–15,45].
The uptake of sulphate in the C–S–H has been shown to be depen- 3.4. Analysis of the pore solutions
dent on the temperature and time of hydration [12,46]. The S/Si ratios
of the C–S–H in OPC-FA hydrated at 7 to 50 °C are about 0.04–0.05 The development of the elemental concentrations in the pore solu-
(Table 2). However, at a hydration temperature of 80 °C, the S/Si ratio tion of fly ash blended OPC has been described by various studies
of the C–S–H in OPC-FA is significantly increased to about 0.09. This is [19,20,47,48]. On one hand, the consumption of portlandite by the poz-
related to the increased solubility of ettringite at 80 °C and the thereby zolanic reaction causes a decrease of the Ca concentrations in the pore
increased availability of sulphate in the pore solution [17]. This effect solutions. On the other hand, the release of Al and Si from the dis-
agrees with investigations on the sulphate concentrations of C–S–H in solving fly ash leads to the increase of the Al and Si concentrations.
plain OPC at elevated temperatures [12,46]. In OPC-Qz the S/Si ratio in- Additionally, the hydroxide concentrations tend to decrease due to
creases slightly, in agreement with the less distinct increase of dissolved the enhanced binding of alkalis in the C–S–H formed by the pozzola-
sulphate in the pore solution. A similar observation has been made in an nic reaction [45,49–51].
unpublished study including microanalyses of the C–S–H of Portland The progress of the Ca, Al, Si, alkali and sulphate concentrations in
cement pastes blended with 50 wt.% silica fume hydrated at 80 °C OPC-Qz and OPC-FA at temperatures ranging from 7 to 80 °C is shown
(personal communication by Dr. B. Lothenbach). in Fig. 7. All elemental concentrations of the investigated pore solutions
To show the relation between the amount of Al and S incorporated in are also given in the appendix in Tables A.1 and A.2.
the C–S–H and the concentration of these elements in the pore solution, Fig. 7a shows that the Ca concentrations in the reference sample
the measured Al/Si or S/Si ratios of the C–S–H are plotted against the OPC-Qz are slightly decreased at elevated temperature, which agrees
measured concentrations of the pore solution (Fig. 6). The presented with the decreased solubility of portlandite. In OPC-FA, a significant
data is expanded by published data from other studies dedicated to drop of the Ca concentrations related to the pozzolanic reaction is ob-
the characterisation of synthesized C–S–H [44,46]. It shows that the in- served. The drop of the Ca concentrations is shifting to earlier hydration
creased amount of Al and S incorporated in the C–S–H agrees with the times by increasing the temperature from 7 to 50 °C due to the faster
onset of the pozzolanic reaction and the faster consumption of Ca(OH)2.
At 80 °C, the effect of the faster onset of the pozzolanic reaction is ob-
Table 2 served in the low measured Ca concentration at 1 day of hydration. Af-
Ca/Si, Al/Si and S/Si ratios of the EDX analyses of the C–S–H in OPC-FA and OPC-Qz after terwards the Ca concentration at 80 °C is higher than at 40 and 50 °C
180 days of hydration at 7, 23, 40, 50 and 80 °C. and the Al and Si concentrations are equal to those of OPC-FA at 40 and
Temperature 7 °C 23 °Ca 40 °C 50 °C 80 °C 50 °C. This is related to the fast reaction of fly ash at 80 °C up to 1 day
and a relatively low rate of reaction at later hydration times, as observed
OPC-FA
Ca/Si 1.7 ± 0.3 1.3 ± 0.2 1.4 ± 0.3 1.4 ± 0.3 1.1 ± 0.2 by the rate of portlandite consumption measured by TGA (Section 3.2)
Al/Si 0.14 ± 0.03 0.17 ± 0.03 0.19 ± 0.02 0.19 ± 0.02 0.19 ± 0.02 and the development of compressive strength (Section 3.1).
S/Si 0.05 ± 0.02 0.04 ± 0.02 0.04 ± 0.02 0.04 ± 0.02 0.09 ± 0.02 Fig. 7b shows the Al concentrations of the pore solution in OPC-Qz
OPC-Qz and OPC-FA. Up to 2 days of hydration the Al concentrations in OPC-
Ca/Si 1.8 ± 0.2 1.6 ± 0.3 1.7 ± 0.3 1.7 ± 0.3 1.2 ± 0.2 Qz are higher at 40–80 °C compared to lower temperatures. This is
Al/Si 0.07 ± 0.02 0.08 ± 0.02 0.08 ± 0.02 0.08 ± 0.02 0.05 ± 0.02 due to the higher ettringite solubility at higher temperature [17]. The
S/Si 0.05 ± 0.02 0.05 ± 0.02 0.05 ± 0.02 0.06 ± 0.02 0.06 ± 0.02 decrease at later ages could be related to the formation of siliceous
a
Data at 23 °C acquired from 250 day old samples (reproduced from [19]). hydrogarnet and Al uptake by C–S–H.
 F. Deschner et al. / Cement and Concrete Research 52 (2013) 169–181
a)
0.20 OPC-Qz
Atomic Al/Si ratio in the C-S-H
OPC-FA
Pardal et al.
0.15
0.10
0.05
0.00
0.01 0.1
Al [mM]
Fig. 6. Dependency of the incorporation of Al and S in C–S–H on the pore solution chemistry. (a) Relation between the Al/Si atomic ratio of the C–S–H and the concentration of dissolved Al.
(b) Relation between the S/Si atomic ratio of the C–S–H and the concentration of dissolved S.
In OPC-FA, the increase of the Al concentrations related to the reac-
tion of fly ash is shifting towards earlier times at higher temperatures
due to the faster onset of the pozzolanic reaction, which is expected
to lead to an increased Al uptake in C–S–H. The acceleration of the poz-
zolanic reaction by higher temperature is also observed for the Si con-
centrations (Fig. 7c).
The progress of the alkali concentrations in OPC-FA is shown in
Fig. 7d. The effect of temperature on the alkali concentrations is not
straight forward compared to the other elements. There are several fac-
tors which influence the concentration of alkalis in the pore solution:
• The rate of the clinker reaction and the related release of alkalis into
the pore solution
• The rate of the fly ash reaction and the related release of alkalis into
the pore solution
• The alkali binding capacity of the hydrate phases, which is related to
the amount and composition of the C–S–H [50]
• The decrease of the volume of pore solution.
At early hydration times, the enhanced clinker dissolution leads to
increased alkali concentrations at elevated temperatures. Therefore
the highest alkali concentrations are found at 80 °C and the lowest at
7 °C. As long as the fly ash or the quartz powder is not reacting, the alkali
concentrations in the solution are increasing due to the ongoing dissolu-
tion of clinker minerals and the reduction of the pore solution volume.
This effect is clearly observed in OPC-FA at 7 °C where the reaction of
fly ash is just slowly starting between 90 and 180 days. At higher tem-
peratures, a reduction of the alkali concentrations is observed due to
the enhanced binding of alkalis on the increased amounts of C–S–H dur-
ing the main reaction of the fly ash. Hence, the reduction of alkalis in the
pore solution is related to the temperature dependent reactivity of fly
ash. A similar effect is observed for OPC-Qz when the quartz powder
starts to react at temperatures of 40 °C and higher. At 80 °C, the concen-
tration of alkalis in OPC-Qz after 7 and 28 days of hydration is signifi-
cantly lower than in OPC-FA. This may be related to a higher C–S–H
content, and hence enhanced binding of alkalis in OPC-Qz compared
to OPC-FA.
Fig. 7e shows the sulphate concentrations in the pore solutions of
OPC-Qz and OPC-FA. At elevated temperatures an increase of sulphate
is observed due to the increased solubility of ettringite at higher tem-
perature [17]. A similar increase of sulphate concentrations with tem-
perature was also observed in silica fume blended and neat Portland
cements [3,15,45,52]. The lower sulphate concentrations in OPC-Qz
compared to OPC-FA agree with the sulphate concentrations found in
the C–S–H.
175
b)
0.12
OPC-Qz
Atomic S/Si ratio in the C-S-H
OPC-FA
0.10
Barbarulo et al.
0.08
0.06
0.04
0.02
0.00
1 10 0.1 1 10 100
S [mM]
The effective saturation indices of portlandite, ettringite, monosul-
phate and strätlingite, calculated from the elemental concentrations in
the pore solutions, are shown and discussed in Appendix B.
3.5. Microstructure
The effect of temperature on the microstructure of the investigated
samples is studied by back-scattered electron (BSE) images of OPC-FA
and OPC-Qz after 180 days of hydration (Fig. 8). The main difference be-
tween the samples hydrated at different temperatures is found regard-
ing the porosity of the matrix and the grey level of the C–S–H.
Fig. 8a and b shows a very low matrix porosity in the samples hy-
drated at 7 °C. Most of the visible pores in the microstructure are hollow
shell, so called “Hadley” grains [53] or internal fly ash pores. At higher
temperatures, the microstructure is more heterogeneous and the poros-
ity is higher compared to lower temperatures as shown by the example
images of OPC-FA and OPC-Qz at 50 and 80 °C (Fig. 8c–f).
Another temperature dependent parameter of the microstructure
is the grey level of the C–S–H in BSE images. In all investigated samples
at 7 °C, lower grey levels of the C–S–H are observed compared to higher
temperatures. The intensity of the grey level in the BSE image of a
polished sample is dependent on the electron density of the analysed
sample volume, which is mainly related to the atomic number of the
analysed elements and the density or microporosity, respectively.
Since the C–S–H at 7 °C has a higher Ca content compared to the C–S–
H of the samples hydrated at higher temperatures (as shown in
Fig. 5), the decreased grey levels have to be related to a higher micropo-
rosity or lower density, respectively. Similar findings have been report-
ed for the hydration of neat OPC mortars [2,8] and recently also for fly
ash blended Portland cement [11].
The relation between the microstructure of the paste samples
and the compressive strength of the mortar samples is not yet fully
understood. Fig. 9 shows the compressive strength of the mortar sam-
ples plotted versus the coarse porosity (pores N 0.6 μm). Although the
graph shows a general trend of increased strength with decreased po-
rosity, the compressive strength of samples with low coarse porosity
varies significantly depending on the temperature and time of hydra-
tion. This effect can also visually be seen from the comparison of the
BSE images shown in Fig. 8a and c. Although OPC-FA after 180 days of
hydration at 50 °C has the highest compressive strength, it shows a
higher coarse porosity than the same sample hydrated at 7 °C. This ef-
fect is pronounced in OPC-Qz: At 80 °C, the OPC-Qz mortar shows by
far the highest compressive strength after 180 days, although the coarse
porosity is clearly lower than at 7 °C. On one hand, this may indicate,
176 F. Deschner et al. / Cement and Concrete Research 52 (2013) 169–181

that in addition to the content of coarse pores other factors such as the
interfacial transition zone at the aggregates in mortars, the hydrate
phase assemblage and the mechanic properties of the hydration prod-
ucts play an important role. On the other hand, the variance of compres-
sive strength values at low porosity is similar to other studies and is
probably related to the uncertainty caused by the fact that fine capillary
pores with a diameter of less than 0.6 μm are not identified by this
image analysis procedure [8].
4. Modelling of the hydrate phase assemblage at
different temperatures
The effect of temperature on the hydrate phase assemblage of OPC-
Qz and OPC-FA after 180 days of hydration is simulated by using a
simplified model with constant reaction degrees of C3S, C2S, C3A and
C4AF. The assumed reaction degrees after 180 days of hydration (100%
for C3S, 86% for C2S, 93% for C3A and 90% for C4AF) are based on an exper-
imental study showing only slight variations of the OPC reaction degree
after 180 days within a temperature range between 5 and 40 °C [11].
In order to calculate the phase assemblage the following aspects are
included in the model:
• The variance of the Ca/Si ratio of the C–S–H is accounted for by using a
solid-solution model with jennite (C1.67–S–H2.1) and tobermorite
(C0.83–S–H1.33) as end-members. The Al and sulphate uptake in the
C–S–H is adapted to the measured Al/Si and S/Si ratios (Section 3.3.2).
• The formation of siliceous hydrogarnet is restricted. Significant quan-
tities of this phase have been reported only for cements hydrated at

a) Calcium
100
7 °C 7 °C
OPC-Qz 23 °C OPC-FA 23 °C
40 °C 40 °C
50 °C 50 °C
10 80 °C 80 °C
Ca [mM]

0.1
1 10 100 1 10 100
Time [d] Time [d]

b) Aluminium
10
7 °C
23 °C
40 °C
50 °C
1 80 °C
Al [mM]

0.1 7 °C
23 °C
40 °C
OPC-Qz OPC-FA 50 °C
80 °C
0.01
1 10 100 1 10 100
Time [d] Time [d]

c) Silicium
10
7 °C
OPC-Qz 23 °C OPC-FA
40 °C
50 °C
1 80 °C
Si [mM]

0.1 7 °C
23 °C
40 °C
50 °C
80 °C
0.01
1 10 100 1 10 100
Time [d] Time [d]

Fig. 7. Development of the (a) Ca, (b) Al, (c) Si, (d) alkali and (e) sulphate concentrations in OPC-FA and OPC-Qz hydrated at 7, 23, 40, 50 and 80 °C.
 F. Deschner et al. / Cement and Concrete Research 52 (2013) 169–181 177

d) Sodium and potassium

600
500

400

Na+K [mM] 300

200 7 °C 7 °C
23 °C 23 °C
40 °C 40 °C
OPC-Qz 50 °C OPC-FA 50 °C
80 °C 80 °C
100
1 10 100 1 10 100
Time [d] Time [d]

e) Sulphate
100
SO4 [mM]

10

7 °C 7 °C
1
23 °C 23 °C
40 °C 40 °C
OPC-Qz 50 °C OPC-FA 50 °C
80 °C 80 °C
0.1
1 10 100 1 10 100
Time [d] Time [d]

Fig. 7 (continued).

higher temperatures [4,29,54–56] or in the presence of Fe(OH)3
[57,58]. Since the formation of Al siliceous hydrogarnet (hydro-
grossular) is kinetically hindered at room temperature, it is exclud-
ed from the calculations at temperatures up to 50 °C. However, Fe
siliceous hydrogarnet (hydroandradite) may form also at lower
temperatures.
With these implementations, the development of the phase assem-
blage after approximately 180 days of hydration is calculated as a func-
tion of temperature and expressed as percentage of the original volume
of the raw materials and water (Figs. 10 and 11).
In the reference system OPC-Qz, the TGA experiments (Section 3.2)
show the consumption of portlandite by the pozzolanic reaction of the
quartz powder at temperatures between 40 and 80 °C. This is taken
into account in the model by the adaption of the reaction degree of
the quartz powder at a given temperature to fit the experimentally
measured portlandite content.
Fig. 10 shows the calculated change of the phase assemblage, exclud-
ing the formation of hydrogrossular up to 50 °C. At low temperatures,
C–S–H, hydrotalcite, ettringite, monocarbonate, hydroandradite and
portlandite are predicted to form. At higher temperatures the pozzolanic
reaction of the quartz powder leads to the consumption of portlandite
and the formation of C–S–H. Due to the binding of Al in the C–S–H, the
content of monocarbonate is reduced with increasing temperature until
this phase disappears at 50 °C, in agreement with the XRD results
shown in Fig. 4. Ettringite is predicted to be stable up to 72 °C.
Hydrotalcite persists throughout the modelled temperature range.
In OPC-FA, the calculated average composition of the glass phase
is used as input for the model, since the crystalline fraction of the fly
ash shows no reaction [19,59,60]. The reaction degree of fly ash at a
given temperature is adapted to fit the measured portlandite content
(Section 3.2).
Fig. 11a shows the calculated change of the phase assemblage in
OPC-FA up to 50 °C. Due to the increased amount of reacted fly ash
glass, the elevation of temperature leads to the consumption of port-
landite and the formation of additional C–S–H. Additionally, aluminate
is provided by the fly ash dissolution and contributes to the forma-
tion of monosulphate starting from 30 °C. This process leads to the
destabilisation of ettringite at 50 °C.
For the modelling of the temperature interval between 50 and 90 °C,
the formation of hydrogrossular is allowed in addition to hydro-
andradite (Fig. 11b). The presence of hydrogrossular affects the amount
of ettringite and AFm. Due to the high Al content of the siliceous
hydrogarnet, the ratio of available sulphate to aluminate is increased,
and hence ettringite persists up to 74 °C while no more AFm phases
are predicted to form. Hydrotalcite persists throughout the modelled
temperature range.
Comparing the modelled development of hydrate phases in the two
systems shows lower amounts of C–S–H in OPC-FA compared to OPC-Qz
at temperatures above 50 °C. This may be responsible for the observed
lower compressive strength of OPC-FA at 80 °C compared to OPC-Qz
(Fig. 1). As a consequence of the lower C-S-H content in OPC-FA, less al-
kali are bound within the C-S-H, which agrees well with the observed
higher alkali concentrations in the pore solution (Section 3.4). As at
80 °C, in the OPC-FA and the OPC-Qz where neither ettringite nor
monosulphate is present, the sulphate is distributed between the pore
solution and the C–S–H. Hence, the lower content of C–S–H in OPC-FA
is responsible for the observed increased S/Si ratio in the C–S–H
(Section 3.3.2) and the higher sulphate concentrations in the pore solu-
tion (Section 3.4).
178 F. Deschner et al. / Cement and Concrete Research 52 (2013) 169–181

a) OPC-FA 7 °C b) OPC-Qz 7 °C

20 µm 20 µm

c) OPC-FA 50 °C d) OPC-Qz 50 °C

20 µm 20 µm

e) OPC-FA 80 °C f) OPC-Qz 80 °C

20 µm 20 µm

Fig. 8. BSE images of the microstructure of OPC-FA and OPC-Qz after 180 days of hydration at 7, 50 and 80 °C.

60
7 °C
5. Conclusions
Compressive strength [MPa]

20 °C
50
40 °C
50 °C This study shows the effect of temperature on the hydration kinetics,
40 80 °C the change of the phase assemblage and the microstructure in Portland
cement blended with 50 wt.% of siliceous fly ash in comparison to a ref-
30 erence sample with 50 wt.% of quartz powder.
First of all, the temperature is affecting the OPC hydration, which
20 leads to enhanced early compressive strength at elevated temperatures.
Besides the well-known effects of temperature on the OPC hydration, a
10 strong influence of temperature on the reactivity of fly ash is observed.
The beginning pozzolanic reaction of the fly ash, as indicated by the con-
0 sumption of portlandite, and the change of the pore solution chemistry
0 10 20 30 40
is shifting towards earlier hydration times at elevated temperatures.
Coarse porosity [%]
The increase of the temperature from 7 to 23 °C shifts the start of the
Fig. 9. Compressive strength of OPC-FA plotted versus the coarse porosity. The error of the pozzolanic reaction from 90 days to 7 days. At 50 °C the fly ash reaction
coarse porosity is estimated to be ±3%. starts after 1 day of hydration.
 F. Deschner et al. / Cement and Concrete Research 52 (2013) 169–181 179

a) b) the interfacial transition zone at the aggregates in mortars, the hy-

100 drate phase assemblage and the mechanic properties of the hydration
products, play an important role for the development of compressive
pore solution
80 strength.
% of original volume

siliceous hydrogarnet

60
Acknowledgements

portlandite
The authors wish to acknowledge the BASF Construction Chemicals
40 ettringite
hydrotalcite
GmbH and Schwenk Zement KG for the analytical and financial support.
C-S-H monocarbonate STEAG Power Minerals GmbH is acknowledged for the provision of the
fly ash. Thanks are extended to Julien Keraudy for the technical support
20
anhydrous Qz and Boris Ingold for the preparation and polishing of the samples for the
anhydrous OPC
SEM investigations.
0
10 20 30 40 50 50 60 70 80 90
Temperature [°C] Appendix A. Elemental concentrations of the pore solutions

Fig. 10. Modelled change of the phase assemblage in OPC-Qz after approximately 180 days The elemental concentrations of the pore solution in OPC-Qz and
as a function of temperature. (a) Calculation excluding the formation of hydrogrossular OPC-FA are shown in Tables A.1 and A.2.
below 50 °C and (b) including hydrogrossular above 50 °C.

Table A.1
At advanced hydration times the effect of temperature on the hydra- Elemental concentrations in the pore solutions of OPC-Qz at 7, 23, 40, 50 and 80 °C.

tion is governed by the enhanced pozzolanic reaction of the fly ash. The Temperature Time [d] K Na Ca Si S Al Fe Cl OH−
typical effects of the pozzolanic reaction on the hydration, like the mM
consumption of portlandite, the release of Al and Si into the pore solu-
7 °C 1 192 26 8.5 0.1 30.4 0.02 0.003 3.66 166
tion and the formation of additional C–S–H are accelerated at elevated
2 184 42 4.4 0.2 3.0 0.14 0.004 1.67 245
temperatures. Al and alkalis are partially incorporated into the C–S–H 7 228 47 3.9 0.2 5.3 0.17 0.002 1.27 303
and the remaining Al contributes to the formation of AFm phases and 28 251 64 3.4 0.2 5.9 0.15 0.005 0.51 296
to the formation of Al containing siliceous hydrogarnet at higher 90 276 93 2.8 0.3 2.0 0.24 0.004 0.33 352
temperatures. 180 295 92 1.5 0.1 7.7 0.15 0.003 0.15 381
23 °C 1 228 45 3.7 0.1 4.8 0.15 0.002 n.a. 283
At 80 °C, Al containing siliceous hydrogarnet forms while ettringite 2 289 74 3.6 0.1 0.9 0.12 0.002 n.a. 311
and AFm phases are destabilised. The released sulphate is partially 7 263 70 2.9 0.1 4.4 0.12 0.002 n.a. 332
enriched in the pore solution and partially incorporated into C–S–H 28 322 97 2.5 0.1 1.8 0.10 0.003 n.a. 323
and siliceous hydrogarnet. 90 303 95 2.2 0.1 3.1 0.11 0.003 n.a. 317
250 205 56 2.1 0.1 7.5 0.13 0.005 n.a. 277
The microstructure of the fly ash blended Portland cement is affect-
40 °C 1 216 53 2.3 0.2 8.9 0.59 0.003 1.33 308
ed in a similar way as OPC by the change of temperature. At 7 °C homo- 2 222 73 2.1 0.2 5.6 0.53 0.007 1.33 296
geneously distributed hydration products and a low content of coarse 7 249 66 2.3 0.1 11.7 0.14 0.002 0.69 327
pores (pores N 0.6 μm) are found. The C–S–H phases show relatively 28 207 59 2.1 0.1 17.5 0.10 0.003 0.42 244
low grey values due to their high microporosity. The increase of temper- 90 186 68 1.9 0.2 20.6 0.11 0.004 0.33 231
180 178 58 1.0 0.2 25.9 0.11 0.002 0.34 214
ature leads to a more heterogeneous distribution of the hydration 50 °C 1 227 58 2.6 0.2 17.4 0.50 0.003 1.23 285
products and the formation of a C–S–H with a lower microporosity, 2 226 76 2.3 0.2 14.8 0.36 0.007 0.95 274
and hence higher grey levels. The amount of coarse porosity increases 7 246 67 2.2 0.2 36.0 0.10 0.002 n.a. 251
with temperature. 28 213 59 2.2 0.1 43.2 0.13 0.004 0.78 216
90 236 86 3.2 0.3 50.8 0.11 0.005 0.38 190
The correlation between the coarse porosity and the compressive
180 172 57 1.4 0.2 42.3 0.09 0.002 0.23 169
strength is not perfectly clear and indicates that other factors, such as 80 °C 1 248 67 2.7 0.2 71.7 0.65 0.006 0.70 88
2 185 65 2.6 0.2 62.1 0.21 0.003 0.40 173
7 209 57 4.0 0.1 83.8 0.06 0.003 0.40 151
a) b)
100 n.a. = not available.

pore solution
80 Table A.2
% of original volume

Elemental concentrations in the pore solutions of OPC-FA at 7, 23, 40, 50 and 80 °C.
monosulphate siliceous hydrogarnet
60 Temperature Time [d] K Na Ca Si S Al Fe Cl OH−
portlandite mM
ettringite 7 °C 1 177 31 10.3 0.1 34.2 0.01 0.004 3.84 194
40
monocarbonate 2 171 47 4.0 0.2 5.2 0.43 0.005 2.30 254
C-S-H
hydrotalcite 7 211 53 3.8 0.2 5.4 0.16 0.003 1.62 303
20 28 221 60 3.6 0.1 6.0 0.12 0.005 0.70 296
glass fraction of FA
anhydrous OPC
90 275 95 1.9 0.2 1.9 0.28 0.004 0.70 352
180 297 98 0.5 0.5 7.8 1.75 0.002 0.30 381
crystalline fraction of FA 23 °C 1 262 68 3.7 0.1 5.8 0.02 0.002 1.24 276
0
10 20 30 40 50 50 60 70 80 90 2 294 86 3.4 0.1 0.9 0.13 0.002 0.75 311
7 322 104 3.0 0.1 1.1 0.13 0.002 0.97 270
Temperature [°C]
28 231 72 1.7 0.3 5.5 1.36 0.004 0.47 285
90 202 84 1.5 0.7 8.8 3.75 0.005 0.74 234
Fig. 11. Modelled change of the phase assemblage in OPC-FA after approximately 180 days 250 254 97 0.5 1.2 13.9 3.57 0.003 0.10 236
as a function of temperature. (a) Calculation excluding the formation of hydrogrossular
below 50 °C and (b) including hydrogrossular above 50 °C. (continued on next page)
180 F. Deschner et al. / Cement and Concrete Research 52 (2013) 169–181

Table A.2 (continued) these phases from the XRD patterns (Section 3.3.1). The effective SI of
Temperature Time [d] K Na Ca Si S Al Fe Cl OH− strätlingite indicate that it is not expected to precipitate.
mM In OPC-FA, the effective SI of portlandite (Table B.1) changes from
oversaturation to undersaturation with ongoing hydration at 7–50 °C.
40 °C 1 235 64 2.4 0.2 8.4 0.49 0.005 1.82 308
2 180 73 1.1 0.3 5.7 0.54 0.004 1.77 308
This effect is due to the consumption of portlandite by the pozzolanic re-
7 199 62 0.6 1.2 20.8 5.09 0.002 2.81 251 action of fly ash. When the rate of portlandite consumption by the poz-
28 179 59 0.7 1.1 25.5 4.01 0.003 2.67 234 zolanic reaction overcomes the formation rate of portlandite by the
90 200 84 0.4 1.3 23.3 2.30 0.004 2.65 250 reaction of the OPC, the effective SI yields negative values. The time of
180 222 81 0.2 1.5 38.9 3.49 0.004 3.18 241
the decrease of the effective SI of portlandite therefore depends on the
50 °C 1 207 57 1.7 0.3 13.5 0.66 0.003 1.79 275
2 221 84 0.7 0.8 30.0 2.73 0.013 2.71 255 reaction rate of OPC and fly ash, and hence on the temperature during
7 194 61 0.6 1.3 46.6 3.38 0.003 3.38 215 hydration. The data agrees with the portlandite consumption measured
28 212 68 0.7 0.8 50.9 3.37 0.007 5.15 200 by means of TGA (Fig. 2).
90 217 89 0.5 1.4 49.7 2.40 0.004 3.08 213 The effective SI of ettringite and monosulphate in OPC-FA are affect-
180 239 86 0.3 1.5 63.0 3.20 0.002 2.96 214
80 °C 1 268 86 1.4 0.7 154.6 3.89 0.006 3.06 227
ed in a similar way as in OPC-Qz. The reaction of fly ash shows no signif-
2 271 109 1.3 1.0 149.0 2.60 0.006 3.96 104 icant effect on the effective SI of these phases.
7 303 98 1.3 1.1 166.9 3.12 0.003 5.89 124 The effective SI of strätlingite turns positive with ongoing hydration.
28 305 100 1.6 0.6 174.9 2.96 0.005 5.08 98 This effect is typically observed in fly ash blended samples due to the
consumption of Ca(OH)2 and the provision of Al and Si by the reaction
of the fly ash. Due to the enhanced reactivity of fly ash at higher temper-
Appendix B. Effective saturation indices atures, the increase of the effective SI of strätlingite is shifted towards
earlier hydration times. In fact, OPC-FA does not show the formation
The effective saturation indices (SI) of portlandite, ettringite, mono- of strätlingite due to the presence of siliceous hydrogarnet, as shown
sulphate and strätlingite in OPC-Qz and OPC-FA at temperatures ranging by XRD (Section 3.3.1) and thermodynamic modelling (Section 4).
from 7 to 80 °C are shown in Table B.1. The effective SI of portlandite in
the reference sample OPC-Qz at different temperatures shows a minor References
effect of the temperature. At higher temperatures after 180 days of hy-
[1] J.I. Escalante-Garcia, J.H. Sharp, Effect of temperature on the hydration of the main
dration, the effective SI of portlandite is slightly reduced compared to clinker phases in Portland cements: part I, neat cements, Cem. Concr. Res. 28
lower temperatures. Also the SI of ettringite and monosulphate show (1998) 1245–1257.
[2] K.O. Kjellsen, R.J. Detwiler, O.E. Gjørv, Development of microstructures in plain
lower values at elevated temperatures. This is related to a faster hydra-
cement pastes hydrated at different temperatures, Cem. Concr. Res. 21 (1991)
tion kinetic at higher temperatures. The pore solutions are thus nearer to 179–189.
the thermodynamic equilibrium. [3] B. Lothenbach, F. Winnefeld, C. Alder, E. Wieland, P. Lunk, Effect of temperature on
At 80 °C, the pore solution is undersaturated with respect to et- the pore solution, microstructure and hydration products of Portland cement pastes,
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