Cement and Concrete Research 67 (2015) 122–130

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Cement and Concrete Research

journal homepage: http://ees.elsevier.com/CEMCON/default.asp

Study on the hydration and microstructure of Portland cement

containing diethanol-isopropanolamine
Suhua Ma ⁎, Weifeng Li, Shenbiao Zhang, Yueyang Hu, Xiaodong Shen
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009, China

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

Article history: Diethanol-isopropanolamine (DEIPA) is a tertiary alkanolamine used in the formulation of cement grinding-aid
Received 23 May 2014 additives and concrete early-strength agents. In this research, isothermal calorimetry was used to study the hy-
Accepted 12 September 2014 dration kinetics of Portland cement with DEIPA. A combination of X-ray powder diffraction (XRPD), scanning
Available online 4 October 2014
electron microscopy (SEM), differential scanning calorimetry (DSC)–thermogravimetric (TG) analysis and
micro-Raman spectroscopy was used to investigate the phase development in the process of hydration. Mercury
Keywords:
DEIPA
intrusion porosimetry was used to study the pore size distribution and porosity. The results indicate that DEIPA
Hydration kinetics (A) promotes the formation of ettringite (AFt) and enhances the second hydration rate of the aluminate and ferrite
Microstructure (B) phases, the transformation of AFt into monosulfoaluminate (AFm) and the formation of microcrystalline
Portland cement (D) portlandite (CH) at early stages. At later stages, DEIPA accelerates the hydration of alite and reduces the pore
size and porosity.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction
Faced with global energy-saving and emission-reducing require-
ments, the cement industry is being confronted with extensive press
coverage. To achieve energy savings and emission reductions for ce-
ment, in addition to improving equipment, one approach involves in-
creasing the grindability of cement using a grinding agent, thus
reducing the power consumption. Another approach is to improve the
properties of cement by using additives. Hence, chemical additives are
becoming increasingly popular in materials based on cement.
Ethanolamine is a type of chemical additive used primarily in
cement grinding agents. Typical ethanolamine components in-
clude triethanolamine (TEA), triisopropanolamine (TIPA), methyl-
diethanolamine (MDEA) and diethanol-isopropanolamine (DEIPA).
Several studies have been conducted on TEA and TIPA. It was reported
[1] that TEA could significantly increase the early compressive strength,
especially before 3 d, and reduce the later strength. However, TIPA
could improve the later strength. Gartner [2,3] observed that the effect
of TIPA on the compressive strength at 28 d was dependent on the C4AF
content in cement. The compressive strength at 28 d could be increased
by 10%–22.8% if the C4AF content was more than 7.6%. J. Wray and P.
Sandberg [4] observed that TIPA could increase the compressive
strength to 65 MPa at 28 d if the lime saturation factor was decreased
from 0.98 to 0.96. With respect to mechanistic explanations, it has
been reported [5–7] that TEA accelerates the dissolution of C3A and
C3S to form hydration products (AFt, CH and C-S-H) in the early stages,
which result in an increase in the compressive strength. However, with
the ongoing hydration, TEA is adsorbed on the surface of CH due to its
low steric hindrance and precipitates along with CH when the concen-
tration of Ca2 + reaches saturation [8,9]. TEA precipitation causes its
concentration in solution to decrease, thus reducing its action at later
stages. For TIPA [2,10], its concentration in solution does not decrease
significantly due to its higher steric hindrance compared with TEA.
TIPA can also form a complex with Fe3+ and accelerate the hydration
of C4AF, even when the gypsum has been fully consumed. Consequent-
ly, TIPA can enhance the later compressive strength.
To date, there have been only a few studies on DEIPA. Riding [11]
demonstrated the effect of 0.02% DEIPA on the early strength enhance-
ment of blend cement systems. The aim of the research presented here-
in was to determine the effect of various dosages of DEIPA on the
hydration kinetics and microstructure of Portland cement to increase
our understanding of the function of DEIPA. It is hoped that this further
understanding will lead to more efficient use of Portland cement, with
energy-saving and emission-reducing benefits in manufacture and
application.
2. Experimental details
2.1. Materials

⁎ Corresponding author at: Room 111, College of Materials Science and Engineering,
Nanjing Tech University, No. 5 Xinmofan Road, Gulou District, Nanjing, China. Tel./fax:
+86 2583587813.
E-mail address: yc982@163.com (S. Ma).
The Portland cement used in this work was produced by intergrinding
Portland cement clinker with 5.0% gypsum in a 500 mm × 500 mm ball
mill. The chemical compositions of gypsum are shown in Table 1. The

http://dx.doi.org/10.1016/j.cemconres.2014.09.002
0008-8846/© 2014 Elsevier Ltd. All rights reserved.
 S. Ma et al. / Cement and Concrete Research 67 (2015) 122–130 123

Table 1 a
Chemical compositions of gypsum measured by XRF.

Chemical CaO MgO Fe2O3 Al2O3 SiO2 K2O SO3 P2O5 TiO2 LOI
composition 31.84 0.21 0.08 0.27 0.78 0.04 45.93 0.02 0.01 20.64

Table 2
The chemical and phase compositions of the clinker as determined by chemical analysis
and Bogue calculation.

Chemical composition CaO SiO2 Al2O3 Fe2O3 SO3 MgO Loss

65.70 21.60 5.51 3.39 0.41 1.65 0.46
Phase composition C3S C2 S C3A C4AF f-CaO
60.76 16.96 7.24 10.67 0.42

chemical and phase compositions are listed in Table 2 for the Portland
cement clinker, and its PSD is shown in Fig. 1. Research-grade DEIPA
was added using a dosage by weight of cement of 0.01%, 0.02%, 0.03%,
0.04%, 0.05% and 0.1%. Deionised water was used as the mixing water
in the paste experiments. b
2.2. Methodology

2.2.1. Paste preparation

All of the experiments were performed on cement paste with a
water-to-cement ratio of 0.5 to study the effect of various DEIPA dos-
ages on the phase and microstructural developments. Cement pastes
were prepared by mixing cement and water using a laboratory mixer
for 2 min at 500 rpm. The fresh pastes were poured into plastic bottles.
The bottles were sealed and then stored in a curing box with a humidity
of 98% and a temperature of 20 °C. The hydration was stopped after 1 h,
2 h, 3 h, 6 h, 12 h, 24 h, 3 d and 28 d by submerging small pieces in al-
cohol. The pieces were stored in an oven at 40 °C for 1 d to dry. Some
dried pieces were ground and all particles passed through a sieve with
80 um for the XRD, DSC–TG and micro-Raman spectroscopy experi-
ments. The other pieces were retained for SEM and MIP experiments.

2.2.2. Isothermal calorimetry
An 8-channel isothermal calorimeter (TAM Air from Thermometric
AB, Sweden) operating at 20 °C was used to measure the hydration
heat flow of cement with and without DEIPA. The hydration experi-
ments were run for 3 d to examine the effect of DEIPA on the hydration
kinetics of Portland cement.
2.2.3. X-ray powder diffraction
The phase development was investigated on a Rigaku SmartLab
3000A diffractometer with CuKα radiation (λ = 0.154 nm). The X-ray
tube was operated at 35 kV and 30 mA. The optics configuration
Fig. 2. Heat flow vs. hydration time for cement with and without DEIPA.
includes a fixed divergence slit (1/2°) and a D/teX Ultra detector. The
measurements were collected using a θ–θ reflection geometry. Data
were collected from 10° to 70° in the continuous mode.
2.2.4. Differential scanning calorimetry–thermogravimetric analysis
Thermal analysis was performed on a NETZSCH STA-449C instru-
ment with a combined TG and DSC system. A portion of the above pow-
der was heated from 30 °C to 1000 °C at a heating rate of 10 °C/min
under N2 atmosphere. The amounts of bound water were deduced
from the weight loss between 30 °C and 400 °C. The amounts of CH
were deduced from the weight loss between 400 °C and 500 °C.

2.2.5. Micro-Raman spectroscopy analysis

Laser-Raman spectroscopy is complementary to IR spectroscopy,
which can also be used to analyse cement minerals and hydration

Table 3
Cumulative heat of cement with and without DEIPA hydrated for different times.

Hydration time/h Dosages of DEIPA

Blank 0.01% 0.02% 0.03% 0.05% 0.1%

1 27.26 16.16 17.44 16.89 16.89 19.41

2 28.64 17.51 18.76 18.28 18.23 20.86
3 30.32 19.05 20.26 19.76 19.65 22.17
6 41.51 29.73 30.68 29.90 29.107 30.57
12 83.28 72.49 75.23 75.75 75.857 80.97
24 140.07 134.15 139.55 139.79 137.00 136.76
48 182.16 185.48 192.16 193.58 191.90 196.8
72 205.97 211.28 217.78 219.87 219.22 226.57
Fig. 1. The PSD curve for the Portland cement.
124 S. Ma et al. / Cement and Concrete Research 67 (2015) 122–130

a) Cements hydrated for 1h

b) Cements hydrated for 2h

 S. Ma et al. / Cement and Concrete Research 67 (2015) 122–130 125

c) Cements hydrated for 3h

d) Cements hydrated for 6h

126 S. Ma et al. / Cement and Concrete Research 67 (2015) 122–130
e) Cements hydrated for different ages
Fig. 3. Selected XRD patterns of cements hydrated for different ages.
products by studying their molecular vibration. Raman spectra were re-
corded on a Thermo Scientific DXR micro-Raman spectrometer over the
range of 50 cm−1 to 3400 cm−1. Excitation was provided at 532 nm by a
diode pump solid-state laser with a maximum power of 10 mW.
2.2.6. Scanning electron microscopy analysis
For the morphology investigations, some pieces were coated with
carbon and examined using a JSM-5900 SEM operated at 30 kV.
2.2.7. Mercury intrusion porosimetry analysis
The porosity and pore size distribution were studied using a
Quantachrome PoreMaster GT60 mercury intrusion porosimeter capa-
ble of generating high pressures in the range of 20 psia to 20,000 psia
and low pressures in the range of 1.1 psia to 20 psia. The porosimeter
can be used to measure pore sizes ranging from 0.0035 μm to 400 μm.
The pore radii were calculated according to the Washburn equation,
r = −2γcos θ/P, where r is the pore entry radius in which mercury is
being intruded, γ is the surface tension, and θ and P are the contact an-
gles of mercury with the solid and the applied pressure, respectively.
3. Results and discussion
3.1. Hydration kinetics
Fig. 2 presents the heat evolution curves for cements with and with-
out DEIPA, which were obtained using conduction calorimetry. The heat
release curves are characterised by the presence of two peaks in 72 h
(see Fig. 2(a)). The initial peak is assigned to the dissolution of free
lime, the partial dissolution of anhydrite, aluminate, alite and the initial
precipitation of AFt [12–14]. The second peak is primarily attributed to
the rapid dissolution of alite and the precipitation of the CH and C-S-H
phases [15]. A small amount of ferrite and belite also dissolved during
this period. However, the second peak is widened due to the second hy-
dration of the aluminate phase occurring between 13 and 15 h. In addi-
tion to the two peaks, a clear induction period is observed following the
initial peak until an age of approximately 1.5 h. Fig. 2(b) shows the clear
difference between the blank cement and the cement with DEIPA.
DEIPA delays the induction period and activates the second reaction of
the aluminate phase. As more DEIPA is added, the second reaction oc-
curs earlier and faster compared with the blank cement.
The cumulative heat was calculated (see Table 3) according to the
heat flow. The cumulative heat of cement with DEIPA is lower in 24 h,
compared to the blank cement. However, for a hydration age of more
than 48 h, the cumulative heat is greater for the cement with DEIPA. It
suggests that DEIPA promotes the hydration reaction of cement parti-
cles at ages beyond 48 h, which leads probably to the decreasement in
porosity of the cement paste.
3.2. Solid phase assemblage
3.2.1. X-ray powder diffraction analysis
DEIPA was observed to have a significant effect on the hydration ki-
netics of cement, as shown in Fig. 2, and the effect on phase development
was further investigated. Fig. 3 shows the effect of increased DEIPA dos-
age on the phase assemblages at different stages. At the age of 1 h, AFt be-
gins to form due to the nucleation and growth of Al3+, SO2− 4 , Ca
2+
and
−
OH in solution from the dissolution of the aluminate and/or ferrite
phases and anhydrite (see Fig. 3(a)). The characteristic peak intensity
 S. Ma et al. / Cement and Concrete Research 67 (2015) 122–130 127

Fig. 6. Raman spectra of cements hydrated for 3 d.

At an age of 3 h, the CH content is lower for the cement pastes with

more than 0.05% DEIPA compared to the other pastes (see Fig. 3(c)).
However, the differences in the alite content are not significant. As pre-
viously reported by Gartner [2], the triisopropanolamine remained in
the solution for a sufficient time to promote the hydration of C4AF
after all of the free gypsum had been consumed. The hydration of the
C4AF phase could result in a decrease in the CH content due to their

Fig. 4. TG/DSC curves of cements hydrated for 3 d.

of gypsum (2θ = 11.5–11.8°, d = 7.64 μm) indicates that DEIPA accel-

erates the dissolution of gypsum. No other hydrates are observed in
the XRD patterns for these pastes at this age, except for AFt. As hydra-
tion continues, CH formed due to the hydration reaction of alite at 2 h,
when the induction period was near its end (see Fig. 3(b)). The AFt con-
tent is significantly higher for the cement pastes with DEIPA compared
to the blank cement paste. However, the corresponding levels of alumi-
nate and ferrite phases show no clear difference. Hence, DEIPA may de-
crease the amounts of SO2− 4 , Al
3+
and Fe3+ merged into C-S-H or the
saturation concentration of SO2− 4 , Al3+
and Fe3+ in solution. b

Fig. 5. Mass loss curves of cements hydrated for 3 d. Fig. 7. Pore size distribution and cumulative volume of cements hydrated for 3 d.
128 S. Ma et al. / Cement and Concrete Research 67 (2015) 122–130

chemical reaction. But the characteristic peak intensity of C4AF indicates

almost no difference in the C4AF content for the different pastes evalu-
ated in this paper. Riding reported that DEIPA changes the CH morphol-
ogy and precipitation, thus decreasing its contents [11]. With respect to
the aluminate and ferrite phases, the hydration rate of ferrite appears to
be greater than that of the aluminate phase between 2 h and 3 h, which
corresponds to the acceleration period, while the AFt contents continue
to increase.
At an age of 6 h, most of the aluminate phase has reacted (see
Fig. 3(d)). Increasing the DEIPA dosage significantly increases the sec-
ond reactions of the aluminate and ferrite phases while some of the
CH is consumed and the transformation of AFt into AFm is promoted,
which is in agreement with the results from isothermal calorimetry.
However, DEIPA accelerates the hydration of alite if its content is greater
than 0.03%. Fig. 3(e) further illustrates that a large amount of AFt is
transformed into AFm for cement pastes with DEIPA, except for 0.01%
DEIPA after a hydration time of 12 h. With the ongoing hydration, the Fig. 8. The most probable aperture and value of −dV/(log D) vs. dosages of DEIPA for ce-
AFm content decreases due to environmental factors. After a hydration ments hydrated for 3 d.
duration of 28 d, monocarboaluminate phases form. The difference in
CH content gradually decreases due to the hydration of alite promoted
by DEIPA. 3.3. Microstructural analysis

3.3.1. Pore size distribution and porosity

3.2.2. Differential scanning calorimetry–thermogravimetric analysis The pore size distribution and cumulative volumes for cement
The heat flow and mass percent as a function of temperature for ce- hydrated for 3 d with and without DEIPA are presented in Fig. 7.
ment pastes hydrated for 3 d are presented in Fig. 4. Two peaks in the Fig. 7(a) illustrates that the pore size decreases significantly with in-
range of 50 °C to 300 °C were observed in the DSC curves (see creasing DEIPA dosage. The pore size distribution becomes narrow for
Fig. 4(a)). The first endothermic peak, at approximately 100 °C, is as- the cement paste with more than 0.01% DEIPA. A small amount of
cribed to the dehydration of C-S-H and AFt, and the second endothermic
peak, at approximately 140 °C, is attributed to the dehydration of AFm.
With increasing DEIPA, the first peak becomes smooth due to the de-
crease in AFt content. In contrast, the second peak sharpens due to the
increase in AFm content. No peak is observed near 140 °C for the
blank cement, which indicates that DEIPA promotes the transformation
(a)
of AFt into AFm. Fig. 4(b) shows that the mass loss in the range of 400 °C
to 500 °C is caused by the decomposition of CH. From the TG results, the
mass loss in the ranges of 30 °C to 400 °C and 400 °C to 500 °C vs. DEIPA
dosage is given in Fig. 5. The mass loss in the range of 30 °C to 400 °C is
caused by the dehydration of hydrates from the hydration of alite, the
aluminate phase and the ferrite phase. DEIPA promotes the hydration
of Portland cement. The difference in the CH content is minimal for
the cement pastes.

3.2.3. Micro-Raman spectroscopy analysis

The micro-Raman spectroscopy results for the cement hydrated for
3 d with and without DEIPA are presented in Fig. 6. The spectra in
Fig. 6 illustrate the general results obtained when the instrument was
used in a scanning mode ranging from 100 to 3350 cm−1. The ν1 SiO4
stretching vibration at 829 cm−1 clearly appears in the spectra of both
the blank cement paste and the cement paste with 0.02% DEIPA, indicat-
ing the presence of the alite phase. Compared to the vibration band at
832 cm−1 reported by S.S. Potgieter-Vermaak [16], the vibration band
is shifted. The vibration band at 829 cm−1 diminishes for the sample
with DEIPA, which suggests that DEIPA promotes the hydration of
alite. However, the C-S-H did not yield any Raman bands due to its
poor crystallinity. After 3 d of hydration with less alite, the ν1 SiO4
stretching vibration at 852 cm−1 resulting from β-C2S could also be ob-
served for the cement paste with 0.1% DEIPA, as reported by Bensted
[17]. With increasing DEIPA dosage, the symmetrical sulfate stretching
band (ν1 SO4) caused by monosulfoaluminate at 991 cm−1 becomes
stronger. It has been reported that the sharp band at 1114 cm−1 results
from the soda glass cell used [17] or ettringite [18]. The other crystalline
phase present in cement hydration, CH, is represented by a prominent
sharp peak at 355 cm−1 assigned to the Ca\O lattice vibration, as re-
ported by Sagrario [18]. Fig. 9. Pore size distribution and cumulative volume of cements hydrated for 28 d.
 S. Ma et al. / Cement and Concrete Research 67 (2015) 122–130
DEIPA has no significant effect on the pore size distribution. The pore
sizes primarily range from 0.03 μm to 2 μm for the blank cement and
the cement with 0.01% DEIPA and from 0.02 μm to 0.7 μm for the
other pastes. Based on the pore size distribution, the most probable ap-
erture and −dV/d(logD) vs. the DEIPA dosage are given in Fig. 8. This
figure clearly demonstrates that the most probable aperture decreases
while the value of −dV/d(logD) increases with increasing DEIPA dos-
age, indicating that DEIPA increases the volume of small pores. The me-
chanical properties of materials based on cement depend not only on
the pore size distribution but also on the porosity. Fig. 7(b) shows that
the cumulative pore volume decreases for the cement pastes with
DEIPA compared to the blank cement paste. When the pore size ranges
from 0.1 μm to 1 μm, the cumulative volume is significantly less for the
cement paste with more than 0.01% DEIPA compared to the other
pastes, indicating that DEIPA can reduce the size of large pores.
DEIPA exhibits only limited effects on the pore size distribution for
the cement pastes hydrated for 28 d, although the presence of DEIPA re-
sults in a decrease in the cumulative volumes (see Fig. 9). Based on the
cumulative volume, the pore size can be easily divided into three
ranges: 0.01 μm–0.04 μm, 0.04 μm–0.1 μm and 0.1 μm–1 μm. DEIPA sig-
nificantly reduces the volume of pores in the range of 0.1 μm–1 μm but
has only a limited effect on pores in the ranges of 0.01 μm–0.04 μm and
0.04 μm–0.1 μm. However, DEIPA clearly accelerates the volume reduc-
tion of intermediate pores for cement pastes at 3 d.
3.3.2. Morphology analysis
SEM images of the blank cement and cement with 0.05% DEIPA hy-
drated for 3 d are presented in Fig. 10. These images reveal that C-S-H
exhibits a network pattern for the blank cement paste, but a slender
pattern for the cement with 0.05% DEIPA. Numerous thin plates were
observed in large holes for the cement paste with 0.05% DEIPA (see
Fig. 10(c) and (d)). These thin plates are considered as AFm. Most of
the AFm are present in large pores and divide large pores into small
pores as a frame, which causes the most probable aperture to become
C-S-H
Fig. 10. SEM pictures of cement pastes hydrated for 3 d ((a): blank cement paste, (b), (c) and (d): cement paste with 0.05% DEIPA).
129
small (see Fig. 7(a)). On the other hand, the thin plates promote the
formation of C-S-H, whose size decreases due to the limited growth
space. The C-S-H fills the space between the thin plates and fabricates
a network structure to reduce the porosity.
4. Conclusions
The following conclusions can be drawn from this study on the effect
of DEIPA dosage on the hydration and microstructure of Portland
cement:
(1) In the initial stage, DEIPA promotes the formation of AFt but does
not accelerate the hydration of the aluminate or ferrite phases.
(2) DEIPA enhances the second hydration rate of the aluminate
phase and the transformation of AFt to AFm.
(3) In the early stages, DEIPA accelerates the formation of microcrys-
talline CH. As hydration continues, the difference in CH content
decreases for both cement with and without DEIPA, while
DEIPA accelerates the hydration of alite at later stages.
(4) DEIPA significantly decreases the pore size and porosity because
the large pores are divided by AFm as a frame and C-S-H fills the
space between AFm.
Acknowledgements
The authors are grateful for the financial support of the National
Natural Science Foundation of China (51202109), the Program for
Changjiang Scholars and Innovative Research Team in University
(IRT1146) and the National Building Materials Industry Technology
Innovation Programme (2013-M1-1). The support by the facilities of
the Modern Analysis and Testing Centre at Nanjing Tech University,
where the detailed microstructural analyses were performed, are also
acknowledged.
C-S-H
AFm
130 S. Ma et al. / Cement and Concrete Research 67 (2015) 122–130
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