Journal of Sustainable Cement-Based Materials

ISSN: 2165-0373 (Print) 2165-0381 (Online) Journal homepage: www.tandfonline.com/journals/tscm20

Hydration characteristics of slag-blended cement

at different temperatures

Fanghui Han & Peiyu Yan

To cite this article: Fanghui Han & Peiyu Yan (2015) Hydration characteristics of slag-blended
cement at different temperatures, Journal of Sustainable Cement-Based Materials, 4:1, 34-43,
DOI: 10.1080/21650373.2014.959089

To link to this article: https://doi.org/10.1080/21650373.2014.959089

Published online: 24 Sep 2014.

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Journal of Sustainable Cement-Based Materials, 2015
Vol. 4, No. 1, 34–43, http://dx.doi.org/10.1080/21650373.2014.959089

Hydration characteristics of slag-blended cement at different

temperatures
Fanghui Hana,b and Peiyu Yanb*
a
School of Chemical and Environmental Engineering, China University of Mining and
Technology (Beijing), Beijing, China; bKey Laboratory of Civil Engineering Safety and Durability
of China Education Ministry, Department of Civil Engineering, Tsinghua University, Beijing,
China
(Received 13 April 2014; accepted 25 August 2014)

The compressive strength of mortar, pore structure, hydration heat, and non-evaporable
water content of slag-blended cement used to prepare self-consolidating concrete were
investigated. The blended cement pastes were cured at different temperatures to simu-
late the condition of real concrete structure. The blended cement containing 30% of
slag possesses almost same characteristics as pure Portland cement. Incorporation of
70% of slag shows much lower properties than them. The dosage of slag in blended
cement should be controlled in a reasonable range. Elevated temperature activates the
hydration of binders but shortens the hydration continuing time, which results in a
coarse paste microstructure and a low final strength.
Keywords: cement; slag; strength; pore structure; hydration heat; hydration degree

1. Introduction binder.[9] What is more, due to the large

The mainstream bearing carrier of
skyscraper built now in many large cities
in China is steel–concrete composite
structure. High-strength self-consolidating
concrete (SCC) is used normally to fill
steel tube pillar.[1] The main benefits
from using SCC in building structure
consist in shortening the construction per-
iod and thus increasing productivity,
assuring compaction in the structure.[2]
Now supplementary cementitious
materials (SCM) as partial replacement of
Portland cement are used in SCC mix-
tures.[3,4] Fly ash, ground granulated
blast furnace slag and silica fume are the
most frequently applied SCM in SCC.
[5–8] The cost and the carbon footprint
of concrete can be significantly reduced
by lowering the amount of cement in the
volume of pillars, whose cross-section is
tens of m2, the temperature in the core of
pillars rises up to 70–80 °C in several
days after cast of concrete.[10] The use
of SCM in blended cements can reduce
the heat released during the hydration
process.[11,12] Slag-blended cement is
widely used in China to prepare high-
strength SCC.[13] The hydration and
property development of this kind of bin-
der is very sensitive to temperature.[14]
Therefore, it is obviously different for the
hydration of slag-blended cement in real
structure and under standard condition
(20 °C and 95% RH) in laboratory.
The compressive strength of mortar,
pore structure, exothermal characteristics,
and hydration degree of slag-blended
cement with different substituting ratios

*Corresponding author. Email: yanpy@tsinghua.edu.cn

© 2014 Taylor & Francis

 Journal of Sustainable Cement-Based Materials
of slag were investigated at different
temperatures in this paper.
2. Raw materials and experimental
methods
2.1. Raw materials
P.I 42.5 Portland cement and S95 ground
granulated blast furnace slag conforming
to Chinese National Standards GB175-
2007 and GB/T18046-2008, respectively,
were used. The specific surface areas of
cement and slag are 350 m2/kg and
442 m2/kg, respectively. The chemical
compositions of cement and slag are
given in Table 1. The ISO standard sand
was used for the strength test of mortars.
Three binders were prepared. Sample
Cem is pure Portland cement. Sample
SL30 contains 70% of Portland cement
and 30% of slag. Sample SL70 contains
30% of Portland cement and 70% of slag.
The water-to-binder ratio (W/B) for all
prepared binder pastes is 0.4.
2.2. Experimental methods
The compressive strength development of
mortar was investigated for slag-blended
cements hydrating at different tempera-
tures. For prepared mortar bars
(40 × 40 × 160 mm), the W/B and binder
to ISO standard sand ratio of mortar is 0.4
and 1/3, respectively. The mortars were
first cured in a fog room at 20 °C and 95%
RH for 1 d, and then they were stripped
from their molds and placed in a fog room
at 20, 45, and 60 °C for 6 d. Then the mor-
tars were placed in water at 20 °C until
testing ages. At the age of 3, 7, 40, and
90 d, the compressive strengths of mortars
Table 1. Chemical compositions of cement and slag (w/%).
Composition SiO2 Al2O3 Fe2O3 CaO
Cement 20.55 4.59 3.27 62.50
Slag 34.55 14.36 0.45 33.94
35
were measured as per Chinese National
Standard GB/T17671-1999.
The hydration heat evolution rate and
accumulative hydration heat of slag-
blended cement were measured by an iso-
thermal calorimeter (TAM Air) at 25, 45,
and 60 °C within 168 h. TAM Air has
eight parallel twin-chamber-measuring
channels: one chamber containing the
sample, another containing the reference.
After mixing homogeneously, the pastes
were immediately placed into the chamber
maintained at a constant temperature. The
hydration heat evolution rate and accumu-
lative hydration heat of slag-blended
cement can be continuously monitored as
a function of time.
The hardened pastes were prepared
for the measurement of pore characteris-
tics and hydration degree of slag-blended
cement pastes. The pastes were mixed
uniformly by a mechanical mixer for
3 min and then cast into plastic centri-
fuge tubes of 15 mm diameter and
80 mm length. The pastes were cured
under the condition of 20, 45, and 60 °C
for 7 d, and then cured in an environ-
mental chamber at 20 °C and 95% RH.
At the predetermined age, the pastes were
crushed to small pieces and put into ace-
tone to cease further hydration. Part of
the samples was ground until the pow-
ders all passed through 0.08 mm sieve
for the measurement of hydration degree.
The samples were dried at 65 °C till their
weight was constant before measurement.
The pore characteristics of hardened
pastes hydrating for 3 and 90 d were
determined with AUTOPORE II 9220
mercury intrusion porosimeter. As an
indication of hydration degree of binders,
MgO SO3 Na2Oeq f-CaO Cl− LOI
2.61 2.93 0.53 0.83 0.010 2.08
11.16 1.95 0.63 – – 0.70
36
the non-evaporable water contents of
pastes were examined by heating dry
paste powder to 1000 °C to constant
weight in an oven. The non-evaporable
water content is calculated according to
the following equation:
m1 m2
 WSL;C
Wne ¼ m1
1  WSL;C
WSL;C ¼ fSL  WSL;I þ fC  WC;I
where Wne is the non-evaporable water
content (%); m1 and m2 are the weights
of specimens before and after ignition,
respectively (g); fSL and fC are the weight
percent of slag and cement, respectively
(%); WSL,I and WC,I are the loss on igni-
tion of slag and cement, respectively (%).
3. Results and discussion
3.1. The compressive strength
development of mortar
The compressive strength development of
mortar of slag-blended cements cured at
different temperatures is shown in Table 2.
It is evident that the strength develop-
ment of all mortars depends on the curing
temperature and the dosage of mineral
admixture.
After 3 d of curing at 20 °C, the dif-
ferences in compressive strength between
pure Portland cement mortar and mortars
containing 30 and 70% of slag are
6 MPa and 14.1 MPa, respectively. After
90 d, the gaps become 1.8 and 5.1 MPa.
At early stage of hydration, the activity
of slag is lower than that of cement, but
the reaction of slag is activated by Ca
Table 2. Compressive strength of mortars cured at different temperatures (MPa).
Cured at 20 °C
Age Cem SL30 SL70
3 31.6 25.6 17.5
7 39.8 38.1 32.5
40 57.2 58.7 49.7
90 63.1 64.9 58
F. Han and P. Yan
(OH)2 at late stage. Burciaga-Díaz et al.
[15] found that alkali-activated slag paste
developed the highest strength of
120 MPa with 5% Na2O and Yang et al.
[16] presented that compressive strength
of the binder increased as slag content
increased at the same alkalinity level in
(1) alkali-activated fly ash and slag blends.
The strong alkali promotes the dissolu-
tion of slag particles, and cemetitious
(2) products are formed subsequently. Thus,
the compressive strengths of mortars con-
taining slag are higher in late period. At
45 and 60 °C, the gain of strength is
much more rapid and the improvement of
early-age strength is more significant for
mortars containing slag. The strength of
mortar containing 30% of slag is more or
less equivalent to that of pure Portland
cement mortar, but the mortar containing
70% of slag shows lower strength than
pure Portland cement mortar, especially
in the condition of high curing tempera-
ture. Due to the lower cement mass frac-
tion in blended cement SL70, a small
amount of calcium hydroxide produced
by the hydration of Portland cement can-
not activate the pozzolanic reaction of
slag. Therefore, an appropriate substitu-
tion of slag for cement will not hinder
the strength development of composite
binder. It has critical similarity to the
experimental results presented by Shi
et al. [17] that fly ash/slag and cement
must be in appropriate proportion.
As shown in Table 2, the early-age
strength of mortars increases, but the
late-age strength of mortars decreases
with an increase in curing temperature.
Cured at 45 °C Cured at 60 °C
Cem SL30 SL70 Cem SL30 SL70
39.4 40.6 31.5 36.6 37.8 27.6
47.8 52.6 40.1 44.8 41.6 32.6
55.4 52.2 44.1 48.3 50.9 32.6
59.5 56.8 46 54.8 53.9 37.4
 Journal of Sustainable Cement-Based Materials
At elevated temperatures, plenty of
hydration products are formed rapidly,
and then cover the surfaces of unhydrated
particles, which prevents further hydra-
tion of binders and retards the strength
development.[18,19] The non-uniform
distribution of hydration products also
leads to large pores in the paste micro-
structure.[20] It is noted that compressive
strength for mortars containing slag cured
at 45 °C is higher at early age and con-
tinues growth at late age. This elucidates
that an appropriate curing temperature is
beneficial, but an overtopped curing
temperature is harmful for the strength
development of slag-blended cement.[21]
3.2. The pore structure of slag-blended
cement
The pore distributions of slag-blended
cement pastes cured at different tempera-
tures for 3 and 90 d are shown in Figures
1 and 2, respectively. The main peak of
the sample is the most probable pore
diameter that means the highest fraction
of porosity. It can be seen in Figure 1(a)
that the pore sizes related to the most
probable pore diameter of pastes Cem
and SL30 are close to each other, but the
most probable pore diameter of paste
Cem is a little larger than that of paste
SL30. It is indicated that the pore struc-
ture of slag-blended cement paste blended
with a small amount of slag is finer. The
results are mainly concerned with the fil-
ler effect of slag at early stage of hydra-
tion. However, the pore size related to
the most probable pore diameter of paste
SL70 is larger and the peak is weaker
than other two pastes. Meanwhile, large
pores account for large proportion in
paste SL70. As a result, the strength of
mortar is lower, too (Table 2).
It can be observed from Figure 1(b)
that increasing temperature to 45 °C, the
pore size related to the most probable
pore diameter of paste Cem is larger than
that of slag-blended cement pastes, but
37
the peaks of slag-blended cement pastes
are stronger than that of pure Portland
cement paste. Small pores account for
large proportion in paste SL30 compared
to cement paste, so the strength of mortar
containing 30% of slag is higher than that
of pure Portland cement mortar’s
(Table 2). It is clear that the pore struc-
tures of all samples become finer when
raising temperature from 25 to 45 °C. As
shown in Figure 1(c), the pore structures
of samples cured at 60 °C are similar to
the samples cured at 45 °C, the most
probable pore diameter of pure Portland
cement paste is larger and the peak is
stronger than that of slag-blended cement
pastes, indicating that the pore structure
of pure Portland cement paste is coarser
than that of slag-blended cement paste.
Raising curing temperature to 60 °C, the
activity of slag is stimulated significantly,
more hydration products are generated in
a short time, and a dense structure is
formed, which results in high strength of
mortar at early age (Table 2).
As shown in Figure 2(a), the pore
structure of paste SL30 is finer than that
of paste Cem cured for 90 d at 20 °C. An
appropriate substitution of cement by slag
results in a dense paste structure. The
mortar strength is the same with or even
higher than that of pure Portland cement
mortar’s (Table 2). It is evident that the
pore size related to the most probable pore
diameter of paste Cem is larger and that
the peak is stronger than slag-blended
cement pastes as temperature increases
from 25 to 45 and 60 °C (Figure 2(b) and
(c)). The enhancing effect of elevated cur-
ing temperature on the contribution of
slag to the improvement of hardened paste
microstructure is considerable.[22] The
pore structures of all samples are coarser
after long-term curing under elevated tem-
perature compared to samples cured at
20 °C. Therefore, their strength decreases
with an increase in curing temperature
(Table 2). It is noted that the pore struc-
tures of slag-blended cement pastes cured
38 F. Han and P. Yan

Figure 1. The pore distribution of binder paste cured at different temperatures after 90 d. (a)
Paste cured at 20 °C. (b) Paste cured at 45 °C. (c) Paste cured at 60 °C.

at 60 °C are much finer, but the strength
is lower (Table 2) than that cured at
20 °C. It is due to the fact that not only
does the pore structure, but also the cohe-
sion of the compositions in slag-blended
cement, the distribution of hydration
products et al. influence the mortar
strength.[23,24]
3.3. Hydration heat characteristics of
slag-blended cement
The hydration heat evolution rate and
accumulative hydration heat of slag-
blended cements at different temperatures
are shown in Figures 3–5. It can be seen
in Figure 3 that the hydration of blended
cement continues for more than 20 h at
25 °C. The peak value of hydration heat
evolution rate and the accumulative
hydration heat decrease with an increase
in substituting ratio of slag. There is only
a little decrease for blended cement SL30
but an obvious decrease for blended
cement SL70 compared to pure Portland
cement. There are two separated maxi-
mums on the hydration heat evolution
rate curves of slag-blended cement. The
first maximum belongs to the hydration
of cement and the second maximum
belongs to the hydration of slag. There is
only a mini exothermal effect of slag and
main effect comes from cement clinker in
blended cement SL30. The exothermal
effect of slag is much larger in blended
cement SL70.
As shown in Figures 4 and 5, an
increase in temperature enhances the
intensity of hydration reaction but short-
ens its continuing time. The hydration
heat evolution rate increases greatly and
comes rapidly to the maximum at
elevated temperature. The maximum exo-
thermal rate of cement increases from
that lower than 10 J/g h at 25 °C to that
higher than 30 J/g h at 45 °C, as well as
almost 50 J/g h at 60 °C. The continuing
time of intense hydration for cement
 Journal of Sustainable Cement-Based Materials 39

Figure 2. The pore distribution of pastes cured at different temperatures for 3 d. (a) Paste cured
at 20 °C. (b) Paste cured at 45 °C. (c) Paste cured at 60 °C.

Figure 3. The hydration heat of pastes cured at 25 °C. (a) The hydration evolution rate curves
of paste. (b) The cumulative hydration heat curves of paste.

shortens from 20 h at 25 °C to 10 h at microstructure formed initially. The

60 °C. The hydration heat evolution rate
of binder hydrating at 25 °C decreases
slowly. There is still some hydration
reaction till 96 h. In this case, some
hydration products form continuously
for a long period to densify the paste
hydration heat evolution rate of binder
hydrating at 60 °C decreases quickly to
stop during 60 h. Short intensified reac-
tion produces lots of hydrates in a short
time to form a coarse paste microstruc-
ture, and little hydration products are
40 F. Han and P. Yan

Figure 4. The hydration heat of pastes cured at 45 °C. (a) The hydration evolution rate curves
of paste. (b) The cumulative hydration heat curves of paste.

Figure 5. The hydration heat of pastes cured at 60 °C. (a) The hydration evolution rate curves
of paste. (b) The cumulative hydration heat curves of paste.

formed in late period. The initially
formed coarse paste microstructure is not
densified, which results in a high strength
at early age but does not enhance the
strength development of mortars at late
age (Table 2). There is similar regularity
of exothermal hydration for slag-blended
cement. There is a large gap between
blended cements SL30 and SL70, espe-
cially at 60 °C. Therefore, the mortar
strength of blended cement SL70 cured
at 60 °C is the lowest.
3.4. Non-evaporable water content of
slag-blended cement
The non-evaporable water content of slag-
blended cement pastes hydrating at differ-
ent temperatures is shown in Figure 6. The
non-evaporable water content of pastes
represents its quantity of hydrates as well
as hydration degree. Hydration of slag pro-
duces also C–S–H gel, which is similar to
the hydrates of Portland cement but with
low Ca/Si ratio.[25] Therefore, the quan-
tity of hydrates is comparable for the
blended cements containing different
percentages of slag.
As shown in Figure 6(a), the non-
evaporable water content of pastes cured
at 25 °C is low at the first hydrating day
and increases quasi-linearly in 7 d. Then
its increasing rate declines but it still
increases quasi-linearly till 90 d. The
pastes Cem and SL30 show almost the
same content but paste SL70 shows
 Journal of Sustainable Cement-Based Materials 41

Figure 6. The non-evaporable water content of binder pastes cured at different temperatures.
(a) Paste cured at 20 °C. (b) Paste cured at 45 °C. (c) Paste cured at 60 °C.

lower content than them. There is only 4. Conclusions

30% of cement clinker in blended cement
SL70. Its limited initial hydration prod-
ucts cannot excite fully the pozzolanic
reaction of slag. Therefore, its hydration
degree and strength development is low.
Elevated temperature excites the hydra-
tion activity of binders (Figures 4 and 5).
High non-evaporable water content of
pastes cured at elevated temperature
results in a high early strength, but its
low increasing rate results in a low
increasing rate of strength and a low final
strength. The non-evaporable water con-
tent of paste SL70 cured at 60 °C is
almost immobile after 28 d, which results
in a low and non-increasing strength. The
dosage of slag in slag-blended cement
should be controlled in a reasonable
range.
(1) The strength of mortar containing
30% of slag is more or less
equivalent to that of pure Port-
land cement mortar, but the
mortar containing 70% of slag
shows lower strength than pure
Portland cement mortar. An
increase in temperature increases
the early-age strength of mortars,
but decreases the late-age strength
of mortars. The dosage of slag in
slag-blended cement should be
controlled in a reasonable range.
(2) The pore structures of pastes
Cem and SL30 are almost same
at 20 °C curing for 3 d, but the
pore structure becomes finer for
paste SL30 than that for paste
42 F. Han and P. Yan
Cem curing for 90 d. The pore
structures of all samples are finer
after increasing in temperature to
45 and 60 °C at early stage of
hydration, but the pore structures
become coarser at late stage of
hydration compared to 25 °C.
(3) The peak value of hydration evo-
lution rate and the accumulative
hydration heat decrease with an
increase in substituting ratio of
slag. Elevated temperature can
activate the hydration of binders
but shortens the hydration contin-
uing time, which results in a
coarse paste microstructure and a
low final strength.
(4) Pure Portland cement paste and
blended cement paste containing
30% of slag show almost same
non-evaporable water content but
blended cement paste containing
70% of slag shows lower content
than them. High non-evaporable
water content of pastes is deter-
mined in early period at elevated
temperature, but the increasing
rate greatly decreases in late
period.
Acknowledgment
Authors would like to acknowledge the
finance support of the National Natural
Science Foundation of China (grant Nos.
U1134008 and 51278277).
Notes on contributors
Fanghui Han will receive her PhD from Uni-
versity of Mining and Technology (Beijing)
next year. She is interested in hydration mech-
anism and hydration kinetics of blended
cement containing mineral admixtures, such
as slag, fly ash and so on. She has published
three papers in Construction and Building
Materials, Thermochimica Acta, SCIENCE
CHINA Technology Sciences, respectively.
Peiyu Yan is a professor at Tsinghua Univer-
sity, PhD. He does researches mainly on
hydration properties of composite binder, the
composition, structure and properties of
cementitious materials, the durability of con-
crete and so on. He has published many
papers in all kinds of journals.
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