Cement and Concrete Research 140 (2021) 106283

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Cement and Concrete Research

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Inhibition mechanisms of steel slag on the early-age hydration of cement

Shiyu Zhuang , Qiang Wang *
Department of Civil Engineering, Tsinghua University, Beijing 100084, China

A R T I C L E I N F O A B S T R A C T

Keywords: Steel slag inhibits the early-age hydration of cement. However, its mechanism is still unclear. In this paper, the
Steel slag early-age hydration kinetics and the evolution of the solid phases, aqueous species and microstructures in a
Cement cement-steel slag composite binder are investigated to explore how steel slag inhibits the early-age hydration of
Hydration
cement. Two novel phenomena are found: (1) steel slag slows the depletion of gypsum and reduces the formation
Microstructure
Pore solution
of ettringite, and (2) steel slag significantly inhibits the precipitation of CH and C–S–H. The results show that
the addition of steel slag increases the Ca concentration in the pore solution, reduces the supersaturation of the
pore solution with respect to CH and inhibits the nucleation and growth of C–S–H. Based on the above results,
the retardation mechanisms of steel slag on the initial setting of cement paste are explained.

1. Introduction hydration of cement-steel slag composite binder. Although it has been

As a by-product of steelmaking, steel slag accounts for 15–20 wt% of
crude steel production [1,2]. Statistics show that nearly 200 million tons
of steel slag are produced per year in the world [3,4], of which more
than 100 million tons are produced in China [5]. However, only
approximately 20% of the steel slag is utilized [6,7]. Most steel slag is
haphazardly abandoned, which leads to resource waste, land occupation
and environmental pollution. Considering that steel slag contains cal­
cium silicates (mainly C2S), which endow steel slag with hydraulic ac­
tivity [8], the use of the slag as a supplementary cementitious material
(SCM) is promising since it can produce the dual benefits of resource
utilization and environmental protection.
Studies have focused on the potential for steel slag as a SCM. C. Shi
et al. [9], M.P. Luxân et al. [10] and J. Li et al. [11] investigated the
mineralogical and microstructural characteristics of steel slag. L. Muh­
mood [12], Q. Wang [13], A.N. Murri [14], L. Kriskova [15], and G.
Qiana [16] studied the modification of the hydraulic activity of steel
slag, such as with remelting, water quenching, altering the mineral
compositions, prolonged milling in an ethanol suspension and autoclave
treatments. Some researchers investigated the cement-steel slag com­
posite binder. They mainly concentrated on the cementitious properties
and the macroscopic properties at later ages, such as the hydration
products [17–20], microstructure [17–19], soundness [21–26], volume
expansion [27], mechanical properties [28–31], transport properties
and durability (resistance to sulphate attack and permeability to chlo­
ride ions) [32]. However, few studies focused on the very early-age
widely reported that the hydration of cement-steel slag composite
binder is significantly slower than that of plain cement [17–19,33], this
knowledge is merely based on the isothermal calorimetry or the setting
time. Little is known about the early-age hydration kinetics as well as the
early-age evolution of the solid phases, aqueous species and micro­
structures of the cement-steel slag composite binder. In our previous
study, we found that steel slag inhibits the early-age hydration of cement
[20], but its mechanisms are still unclear. This is an interesting issue
because this behaviour is quite different from that of most of the SCMs. It
has been reported that granulated blast furnace slag [34–38], limestone
powder [34,39–42] and quartz [35,42,43] can accelerate cement hy­
dration. Since the SCMs provide both the filler effect (providing addi­
tional surface sites for the nucleation of hydrates) [34,39,44–46] and the
dilution effect (increasing the real water-to-cement ratio and providing
additional available water and space for the growth of hydrates)
[47–51], the presence of SCMs, even quartz or limestone powder, which
has a very low reactivity, can prompt the hydration of Portland cement
[38,42,52,53]. Although there are a number of studies focused on the
effect of SCMs on the cement hydration, little is known about the effect
of steel slag. Therefore, there remains a significant need for an in-depth
microscopic-level study on the early-age hydration kinetics as well as the
evolution of the solid phases, aqueous species and microstructures to
understand the inhibition mechanisms of steel slag on the early-age
hydration of cement.
There are several reasons that limit the widespread application of
steel slag as a SCM to replace a part of the cement, including the poor

* Corresponding author.
E-mail address: w-qiang@tsinghua.edu.cn (Q. Wang).

https://doi.org/10.1016/j.cemconres.2020.106283
Received 17 March 2020; Received in revised form 23 October 2020; Accepted 26 October 2020
Available online 9 November 2020
0008-8846/© 2020 Elsevier Ltd. All rights reserved.
S. Zhuang and Q. Wang
grindability (due to the presence of the RO phase) [11,12,17], soundness
problem (due to the presence of free CaO and MgO, which cause a po­
tential volume expansion) [5,27] and the heavy metal leaching problem
(due to the presence of Cr, Ni, V, As, Ba and Pb) [5,11,17]. In particular,
the significantly prolonged initial setting time of the composite paste
containing steel slag is one of the most important reasons [11,12,35,36].
It has been widely reported that the initial setting time of cement-steel
slag composite paste is much longer than that of plain cement
[18,19,54,55], which severely affects the setting, demoulding and
pumping. Although the replacement of Portland cement with other
SCMs, such as the granulated blast furnace slag or limestone powder,
also prolongs the setting time due to the dilution effect of SCMs [56–64],
their setting time is much less than that for steel slag. It is obvious that
the dilution effect cannot completely account for the significantly pro­
longed initial setting time, and other mechanisms should work. How­
ever, the retardation mechanisms are still unknown. It is well known
that the initial setting time is closely related to the very early-age hy­
dration of the cementitious materials because the initial setting is largely
affected by the evolution of the solid phases, aqueous species and mi­
crostructures caused by the very early-age hydration. Therefore, the
investigation on the inhibition mechanisms of steel slag on the early-age
hydration of cement plays an important role in explaining the retarda­
tion mechanisms of steel slag on the initial setting of cement paste. This
is another advantage and significant application of our research.
In this paper, an in-depth microscopic study is carried out to explore
the inhibition mechanisms of steel slag on the early-age hydration of
cement. In the beginning, the early-age hydration kinetics and the
evolution of the solid phases, aqueous species and microstructures are
investigated to explore how steel slag inhibits the early-age hydration of
cement. Then, the mechanisms of the novel findings are explained in
detail. Finally, the retardation mechanisms of steel slag on the initial
setting of cement paste are discussed based on both the novel findings
and the classical setting theory. To the best knowledge of the authors,
this is the first time the inhibition mechanisms of steel slag on the early-
age hydration of cement are discussed in depth. This study provides an
important complement the knowledge of supplementary cementitious
materials.
2. Experimental
2.1. Raw materials and mix proportions
Portland cement (P⋅I 42.5 compliant with GB 175-2007 and equiv­
alent to CEM I 42.5) and three types of steel slag (SS1, SS2, and SS3,
which are compliant with GB/T 32546) from various regions of China
were used as the raw materials. Their chemical composition, mineral
composition and particle size distribution are summarized in Table 1,
Figs. 1 and 2, respectively. The mineral composition of the steel slag
mainly includes calcium silicate (mainly C2S), calcium aluminate
(mainly C12A7), the RO phase (CaO-FeO-MgO-MnO solid solution), free
lime (f-CaO), calcium ferrite (mainly C2F), magnesium ferrite
(MgFe2O4), calcium aluminoferrite (CaAl8Fe4O19), ferric oxide (FeO)
and calcite (CaCO3). The densities of SS1, SS2 and SS3 are 3.56 g/cm3,
3.63 g/cm3 and 3.71 g/cm3, respectively. Plain cement paste and
cement-steel slag composite paste were prepared for testing. The
replacement level of the Portland cement by the steel slag was 30 wt%.
The water-to-binder ratio was 0.4.
Table 1
Chemical composition of materials (wt%).
CaO Al2O3 SiO2 Fe2O3 MgO P2O5
Cement 68.54 4.47 17.29 3.24 1.68 0.12
SS1 37.99 2.68 11.20 31.54 6.30 2.06
SS2 46.80 1.55 10.55 29.41 3.81 1.45
SS3 40.30 2.97 13.34 27.48 6.56 2.11
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Cement and Concrete Research 140 (2021) 106283
2.2. Test methods
2.2.1. Isothermal conduction calorimetry (ICC)
The hydration kinetics were monitored by using an isothermal
calorimeter (TAM Air 8-Channel Standard Volume Calorimeter) at
25 ◦ C. Before testing, the calorimeter was equilibrated at 25 ◦ C for 12 h.
6 g of binder was mixed ex situ with 1.8 g of deionized water in a 20 ml
glass ampoule with a stirrer for 1 min and then sealed and placed in the
calorimeter to record the evolution of the hydration heat with time for
60 h.
2.2.2. Initial setting time (IST)
The IST was measured with reference to the Chinese standard GB/T
1346 by using a Vicat apparatus. It should be noted that the standard
consistency was adopted for the IST test. This is because the initial
setting time is controlled by not only the hydration but also the initial
porosity of the paste. If the water-to-binder ratio is fixed like that in
other tests, since the density of steel slag is greater than that of cement,
the composite paste has a larger initial porosity than the cement paste,
which might lead to a significantly prolonged initial setting time than
that of the cement paste. As a result, it is impossible to directly compare
the hydration rate of the cement paste and the composite paste ac­
cording to the initial setting time. Before measuring the IST, the water
requirement for the paste to obtain the standard consistency was iden­
tified when the penetration depth of a plunger with a diameter of 10 ±
0.05 mm into the fresh paste was 34 ± 1 mm within 1.5 min after
mixing. Then, the initial setting time was determined as the time when
the penetration depth of a Vicat needle with a diameter of 1.13 ± 0.05
mm into the fresh paste with a standard consistency was 36 mm ± 1 mm.
2.2.3. Optical microscopy (OM), scanning electron microscopy (SEM),
energy dispersive spectrometry (EDS)
The morphological variation in the hydration products was observed
by using SEM (cold field emission, HITACHI SU8220). Both the plain
cement paste and the composite paste were prepared, sealed and stored
at 20 ± 1 ◦ C and 95 ± 5% relative humidity. At the selected ages, 1 g of
the paste was thoroughly mixed with 50 g of cold isopropanol in a
centrifugation tube to extract water from the paste and suspend the
hydration. The suspension was filtered, and the remaining solid was
dried at 40 ◦ C for 4 h and then used to prepare the samples. Prior to
imaging, the sample was coated with a carbon layer with a thickness of
approximately 10 nm to increase the conductivity [65]. The operating
voltage was 2 kV.
The steel slag raw material particles were observed by using OM
(Leica DM2500P), SEM and EDS (BRUKER FlatQuad) for additional
mineral characterization. The steel slag particles were impregnated by
an epoxy resin and manually polished for OM observation. Then, the
sample was coated with a carbon layer with a thickness of approxi­
mately 10 nm for SEM observation. The EDS element analysis of various
micro-zones with different morphologies was conducted at 20 kV with a
10 mm working distance to identify the mineral phases. Elemental
mapping was also performed to determine the element distribution of
the mineral phases.
2.2.4. Specific surface area (SSA)
The SSA of the solid particles was measured by a nitrogen adsorption
BET method using a Quantachrome Instruments Quadrasorb-SI-MP. The
SO3 Na2O K2 O MnO TiO2 Cr2O3 V2O5
2.83 0.20 0.89 0.07 0.39 0.01 0.01
0.53 0.16 0.05 5.42 1.29 0.23 0.36
0.40 0.15 0.04 3.95 0.88 0.26 0.57
0.11 0.11 0.04 4.43 1.47 0.40 0.54
S. Zhuang and Q. Wang
Fig. 1. XRD patterns of materials.
Fig. 2. Particle size distribution of materials.
SSA is calculated using the Brunauer-Emmett-Teller model [66,67].
During the early-age hydration of the paste, the SSA of the solid particles
continuously grows due to the formation of the hydration products [68].
Thus, the evolution of the SSA can qualitatively reflect the amount of
early-age hydration products (mainly C–S–H, since C–S–H has a
much larger SSA than CH) in the paste. Both the plain cement paste and
the composite paste were prepared, sealed and stored at 20 ± 1 ◦ C and
95 ± 5% relative humidity. At the selected ages, the samples for the
nitrogen adsorption BET method were prepared by using the same hy­
dration suspension and drying method as described in Section 2.2.3.
2.2.5. Thermogravimetric analysis (TGA)
The TGA was conducted by using a TA-Q5000 instrument to quali­
tatively identify the variation in the solid phases. Both the plain cement
paste and the composite paste were prepared, sealed and stored at 20 ±
1 ◦ C and 95 ± 5% relative humidity. At the selected ages, the samples for
the TGA were prepared using the same hydration suspension and drying
method as described in Section 2.2.3 and then ground to powder (≤75
μm). During the test, the powdered samples were heated from 20 ◦ C to
900 ◦ C at a rate of 10 ◦ C/min in a high-purity nitrogen atmosphere.
2.2.6. X-ray diffraction (XRD)
XRD patterns were collected by using a Bruker D8 powder diffrac­
tometer with scanning angles (2θ) ranging from 5◦ to 65◦ at a rate of 0.6
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Cement and Concrete Research 140 (2021) 106283
s/step and a step of 0.02◦ using a CuKα radiation source (λ = 1.5418 Å)
at 40 kV and 40 mA to identify the variation in the crystalline phases.
Both the plain cement paste and the composite paste were prepared,
sealed and stored at 20 ± 1 ◦ C and 95 ± 5% relative humidity. At the
selected ages, the samples for XRD were prepared using the same hy­
dration suspension and drying method as described in Section 2.2.3 and
then ground to powder (≤75 μm).
2.2.7. pH values of the pore solution
The pH values of the pore solution in the plain cement paste and the
composite paste were measured by using a METTLER TOLEDO FiveEasy
Plus pH metre. Both the plain cement paste and the composite paste
were prepared, sealed and stored at 20 ± 1 ◦ C and 95 ± 5% relative
humidity. At the selected ages, 20 g of the well-mixed paste was placed
in a centrifugation tube and immediately centrifuged at 15,000 rpm for
5 min using a high-speed centrifuge (Allegra 64R, Beckman Coulter). At
a selected hydration time, the well-mixed paste was centrifuged, and the
upper liquid was remained. Then, the remaining supernatant liquid was
filtered through a 0.22 μm membrane filter for the pH measurement.
2.2.8. Element concentration in the pore solution
The element concentration of the pore solution in the plain cement
paste and the composite paste was measured using inductively coupled
plasma optical emission spectrometry (ICP-OES, Agilent 5110). Both the
plain cement paste and the composite paste were prepared, sealed and
stored at 20 ± 1 ◦ C and 95 ± 5% relative humidity. At the selected ages,
20 g of the well-mixed paste was placed in a centrifugation tube and
immediately centrifuged at 15,000 rpm for 5 min using a high-speed
centrifuge (Allegra 64R, Beckman Coulter). The remaining superna­
tant liquid was filtered through a 0.22 μm membrane filter and acidified
with a 2 wt% dilute HNO3 solution for the element concentration
measurement.
2.2.9. Saturation index calculation
The saturation indices (SI) were calculated using PHREEQC software
with thermodynamic data from the CEMDATA18 database [69] ac­
cording to the measured element concentrations in and the pH values of
the pore solution to evaluate the saturation/undersaturation/supersat­
uration of the pore solution with respect to the anhydrous phases and the
respective hydrates. The SI can predict the phases that may precipitate
from the solution or become dissolved by the solution.
S. Zhuang and Q. Wang
3. Results
3.1. Initial setting time and hydration kinetics
The initial setting time is an important indicator of early-age hy­
dration. As Table 2 shows, the initial setting of the cement paste occurs
at approximately 3 h, while those of the composite paste containing steel
slag occur at 7–9 h, which are two to three times longer. This is
consistent with the literature [18,19,54,55]. The addition of steel slag
significantly prolongs the initial setting time, illustrating that steel slag
significantly retards the early-age hydration.
Fig. 3 shows the calorimetry curves of the cement paste and the
composite paste. Obviously, three exothermic peaks can be observed
from the heat flow curves of the composite paste. The peak that occurs at
approximately 5 h corresponds to the formation of ettringite because the
S concentration decreases sharply at this stage (Fig. 7(a)). The peak that
occurs at approximately 11 h is caused by the precipitation of CH and
C–S–H. There is a broad peak that occurs at 24 h or later. Compared
with the results for the cement paste, the presence of steel slag leads to a
significantly delayed second exothermic peak (i.e., the significantly
prolonged induction period), the markedly reduced peak value and the
obviously lower cumulative heat release, which is consistent with the
literature [11,19,20].
It is well known that the hydraulic activity of steel slag is much lower
than that of Portland cement [7,11,27] because (1) the cementitious
mineral phases (mainly C2S and C3S) in steel slag are significantly less
than those in cement [9,11,27,70]; (2) the cementitious mineral phases
in steel slag have a higher crystallinity than those in cement, since steel
slag is naturally cooled while cement is quenched [6,7,9,27]; and (3)
steel slag contains some inert phases without hydraulic activity, such as
the RO phase [6,7,9,27]. However, it seems that the lower reactivity of
steel slag cannot account for the significantly delayed and reduced main
exothermic peak. This is because the SCMs provide both the dilution
effect and the filler effect [34,39,44–46]. Although due to the dilution
effect, the replacement of Portland cement with SCMs prolongs the
setting time [11,12,35,36], the presence of SCMs, even inert quartz and
limestone powder that have a very low reactivity, can prompt the hy­
dration of Portland cement [34,35,39–43], including shortening the
induction period and increasing the main exothermic peak value when
the heat is normalized to the mass of Portland cement [38,42,52,71].
The dashed curves in Fig. 3 show the heat flow and the cumulative heat
normalized to the mass of Portland cement. It is obvious that when the
heat is normalized to the mass of Portland cement, the calorimetry
curves of the composite paste still indicate a significantly prolonged
induction period, a markedly reduced peak value and an obviously
decreased cumulative heat release. Therefore, it is evident that the lower
hydraulic activity of the steel slag is not the reason for the significantly
delayed main exothermic peak and the markedly reduced peak value;
other mechanisms work.
To continue the investigation, the heat flow and the cumulative heat
released by the cement part of the composite paste were calculated to
compare with those released by the cement paste. The calorimetry
curves of the calcium hydroxide-activated steel slag paste, which
simulate the hydration of steel slag in the composite paste, were
measured to deduct the heat flow and the cumulative heat released by
the steel slag part of the composite paste from the total heat flow and the
cumulative heat released by the composite paste to obtain that released
Table 2
Initial setting time of the samples.
Sample Initial setting time/min
PC 174
C-SS1 495
C-SS2 476
C-SS3 423
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Cement and Concrete Research 140 (2021) 106283
by the cement part of the composite paste, as shown in Fig. 4. It is
apparent from the figure that the calorimetry curves of the cement part
of the composite binder still indicate a significantly prolonged induction
period, a markedly reduced peak value and an obviously lower cumu­
lative heat release compared with those of the cement paste. This in­
dicates that steel slag significantly inhibits the early-age hydration of
cement. This is an interesting issue because this behaviour is quite
different from that of most SCMs, such as granulated blast furnace slag
[34–38], limestone powder [34,39–42] and quartz [35,42,43], which
promote the early-age hydration of cement. SS1 was selected as a
representative type of steel slag for further research.
3.2. Depletion of gypsum and formation of ettringite
Gypsum is one of the main components of cement. It is added to
cement to control the hydration of aluminium clinker for specific per­
formance requirements. As shown in Table 1 and Fig. 1, there is almost
no gypsum in the steel slag, so the gypsum content in the composite
binder is evidently less than that in the plain cement.
Fig. 5 shows the DTG curves of the paste. The mass loss peak at
approximately 107 ◦ C is attributed to gypsum [72–75]. The mass loss
peak of gypsum for the cement paste disappears between 5 h and 7 h,
while that for the composite paste disappears between 7 h and 10.5 h.
Fig. 6 shows the XRD patterns of the paste. The diffraction peak of
gypsum at 11.6◦ [72,76–78] for the cement paste disappears between 5
h and 7 h, while that for the composite paste disappears between 7 h and
10.5 h.
Fig. 7(a) shows the evolution of the S concentration in the pore so­
lution. The depletion of gypsum is generally considered to occur when
the S concentration is sharply reduced [71,79,80]. The S concentration
in the pore solution in the cement paste and the composite paste is
sharply reduced at 5.5 h and 7.5 h, respectively, indicating that the
depletion of gypsum occurs at 5.5 h and 7.5 h, respectively.
The results of the DTG, XRD and ICP-OES all indicate that the
depletion of gypsum in the composite paste occurs significantly later
than that in the cement paste. Considering the significantly lower gyp­
sum content in the composite binder, it can be concluded that the
dissolution rate of gypsum in the composite paste must be significantly
slower than that in the cement paste.
Fig. 7(b) compares the S concentration in the pore solution in the
composite paste and 70% of that cement paste, which represents the
theoretical S concentration attributed to the cement part of the com­
posite binder. With the addition of 30% steel slag, the S concentration is
reduced by approximately 10 mmol/l. This further indicates that steel
slag slows the depletion of gypsum.
The dissolution of gypsum provides S for ettringite, and thus, the
dissolution rate of gypsum significantly affects the formation of ettrin­
gite. Fig. 8a and b presents the SEM images of the paste at 5 h. A large
amount of needle-shaped ettringite can be observed in the cement paste,
while little needle-shaped ettringite is observed in the composite paste.
It is not until 10.5 h that a large amount of ettringite is observed in the
composite paste, but it is still obviously far less dense than that in the
cement paste at 5 h, as shown in Fig. 8(c). This phenomenon indicates
that steel slag significantly reduces the rate and amount of ettringite
formation.
In addition, in the cement paste, some plate-shaped hydration
products are observed (Fig. 9(a)). In the composite paste, instead of the
plate-shaped hydration products, a large number of cuboid-shaped hy­
dration products are observed (Fig. 9(b)).
3.3. Precipitation of CH and C–S–H
As Fig. 5 shows, a sharp mass loss peak due to the dehydroxylation of
CH is observed in the DTG curve of the cement paste at 5 h, which in­
dicates that a large amount of CH has been produced in the cement
paste. However, the mass loss peak due to the dehydroxylation of CH in
S. Zhuang and Q. Wang Cement and Concrete Research 140 (2021) 106283

Fig. 3. Calorimetry curves of the cement paste and the composite paste, (a) heat flow and (b) cumulative heat.

Fig. 4. Calorimetry curves of the cement part of the composite paste, (a) heat flow and (b) cumulative heat.

Fig. 5. DTG curves of (a) the cement paste and (b) the composite paste.

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S. Zhuang and Q. Wang Cement and Concrete Research 140 (2021) 106283

Fig. 6. XRD patterns of (a) the cement paste and (b) the composite paste.

Fig. 7. Element concentration in the pore solution of the cement paste and the composite paste, (a) and (b) S concentration, (c) Ca concentration.

6
S. Zhuang and Q. Wang
Fig. 8. SEM images of the cement paste and the composite paste.
Fig. 9. SEM images of (a) the cement paste and (b) the composite paste at 3 h.
the DTG curve of the composite paste at 5 h is relatively flat and weak
(the mass loss peak at approximately 360 ◦ C is not attributed to the
decomposition of hydration products of the composite binder since it
also appears in the DTG curve of the steel slag raw material [81]).
Similar results are shown in Fig. 6. A sharp diffraction peak of CH is
observed in the XRD pattern of the cement paste at 5 h, while the
diffraction peak of CH in the XRD patterns of the composite paste within
14 h is very weak at all times. Both results illustrate that the amount of
CH produced in the composite paste is much less than that in the cement
paste. Thus, steel slag significantly inhibits the precipitation of CH.
Fig. 10 shows the SSA of the solid phase. The rapid growth of the SSA
is mainly attributed to the fast precipitation of C–S–H due to its much
larger SSA than that of other hydration products [82]. The SSA of the
cement paste sharply increases from 3 h, which indicates a substantial
precipitation of C–S–H from this time. The SSA of the composite paste
remains rather stable during the first few hours. It is not until 10.5 h that
it begins to significantly grow, but it is still much smaller than 70% of
the cement paste, which is attributed to the cement part in the composite
binder. Both results reflect that the amount of C–S–H produced in the
composite paste is obviously less than that in the cement paste. Steel slag
significantly inhibits C–S–H precipitation.
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Cement and Concrete Research 140 (2021) 106283
4. Discussion
4.1. Inhibition mechanisms of steel slag on the precipitation of CH and
C–S–H
In general, the precipitation of CH or C–S–H can be inhibited in two
ways [83–91]. (1) The dissolution of anhydrous phases is inhibited.
Thus, the concentrations of relevant ions (cations) in the aqueous phase
are reduced, and the saturation index of CH or C–S–H is decreased. As
a result, the precipitation of CH or C–S–H is inhibited. (2) The
nucleation and growth of CH or C–S–H are disrupted. As a result,
although the supersaturation of CH or C–S–H exceeds the critical su­
persaturation, which is when C–S–H begins to precipitate, the pre­
cipitation of CH or C–S–H is inhibited. To explore the inhibition
mechanisms of steel slag on the precipitation of CH and C–S–H, the pH
values of the pore solution were measured (Fig. 11). The pH value of the
pore solution of the composite paste is significantly lower than that of
the cement paste. This is because the alkali content of the steel slag is
very low. As shown in Table 1, the Na2O content and K2O content of the
steel slag are 0.16 wt% and 0.05 wt%, respectively, which are much
lower than the 0.20 wt% and 0.89 wt% values of the cement,
S. Zhuang and Q. Wang Cement and Concrete Research 140 (2021) 106283

Fig. 10. The evolution of specific surface area of the solid phase in the cement Fig. 12. The saturation indices of CH in the cement paste and the compos­
paste and the composite paste. ite paste.

causes the supersaturation of the pore solution in the composite paste

with respect to CH to be lower than the critical supersaturation, which is
when CH begins to precipitate. As a result, steel slag inhibits the pre­
cipitation of CH.
Fig. 13 shows the saturation indices of C–S–H in the paste. The
saturation indices are always positive, reflecting that the pore solution
remains supersaturated with respect to C–S–H at any given time. The
TGA, XRD, SSA and SEM results all show that a large amount of C–S–H
has formed in the cement paste at 3 h, which indicates that the satura­
tion indices of C–S–H in the cement paste are higher than the critical
supersaturation, which is when C–S–H begins to precipitate. However,
although the saturation indices of C–S–H in the composite paste are
higher than those in the cement paste at any given time, which indicates
that the probability that ions collide to form a critical crystal nucleus in
the composite paste should be much larger, little C–S–H is formed in
the composite paste at the early age. Additionally, there are many “dot-
like” products in the composite paste (Fig. 14(a)) at the early age, which
are quite different from the “petal-like” products in the cement paste

Fig. 11. The pH values of the pore solution of the cement paste and the com­
posite paste.

respectively. The saturation indices were calculated based on the rele­

vant element concentrations and pH values to evaluate the under­
saturation/supersaturation of CH or C–S–H.
Fig. 12 shows the saturation indices of CH in the paste. The satura­
tion indices of CH are always positive, reflecting that the pore solution
remains supersaturated with respect to CH at any time. However, this
does not mean that CH will definitely precipitate because the formation
of crystal nuclei needs to break through the energy barrier, i.e., a crystal
nucleus with a critical size must be formed and is referred to as the
critical crystal nucleus. Supersaturation directly affects the formation of
critical crystal nuclei. The higher the supersaturation is, the higher the
relevant ion concentration, and thus the larger the probability that ions
successfully collide to form a critical crystal nucleus. It has been re­
ported that it is not until the saturation index reaches 0.4 that CH begins
to precipitate [80,92,93]. As shown in Fig. 12, the saturation indices of
CH in the cement paste are close to 0.4 after 3 h, while those in the
composite paste do not reach 0.4 before 14 h. This phenomenon in­
Fig. 13. The saturation indices of C–S–H in the cement paste and the com­
dicates that steel slag reduces the pH value of the pore solution and thus
posite paste.

8
S. Zhuang and Q. Wang
Fig. 14. The growth of C–S–H in the composite paste is inhibited.
(Fig. 14(b)). These “dot-like” products are considered to be the very
early-age morphology of C–S–H [65,94–98], indicating that steel slag
inhibits the nucleation and growth of C–S–H.
It is worth noting that some researchers believe that the P in the steel
slag may leach with the dissolution of the steel slag during the early-age
hydration process. Phosphate ions may combine with calcium ions to
form hydroxyapatite, which can adhere to the particle surface to inhibit
their further dissolution and hydration [81]. However, the ICP-OES re­
sults show that the P concentration in the pore solution of the composite
paste is nearly equal to that of the cement paste. In addition, neither
hydroxyapatite diffraction peak nor similar product morphology is
observed in the XRD and SEM results. In fact, according to our literature
research, P in steel slag is most likely to be present in C2S [99,100]. Since
the C2S in steel slag has a low hydraulic activity, it hardly hydrates at the
early age. As a result, P might not be available in the pore solution at the
early age and thus has little effect on inhibiting the early-age hydration
of cement.
To continue the investigation, we conduct a detailed mineral char­
acterization of the steel slag with optical microscopy and scanning
Fig. 15. Morphology of steel slag in the OM image (a) and the SEM images (SE mode (b) and BSE mode (c)).
9
Cement and Concrete Research 140 (2021) 106283
electron microscopy/energy dispersive spectrometry (SEM/EDS) to
identify the main mineral phases in the steel slag and confirm whether P
is present in the C2S. Element mappings were carried out to show the
element distribution. EDS element analysis of various micro-zones with
different morphologies was conducted to identify the mineral phases.
Fig. 15 shows the morphology of the steel slag in the OM image (a) and
the SEM images (SE mode (b) and BSE mode (c)). Fig. 16 shows the
element distribution of the steel slag. It can be seen that P has a very
similar distribution pattern with that of Si, a somewhat similar distri­
bution pattern with that of Ca but a completely different distribution
pattern with that of other elements, such as Fe, Al and Mg. Therefore, it
can be preliminarily determined that P in the steel slag is most likely to
be enriched in the calcium silicate phase. Table 3 shows the EDS element
analysis results of various micro-zones with different morphologies in
Fig. 15 (each zone was tested several times, and the average result is
reported). Upon referring to the XRD and XRF results as well as the
knowledge of the related literature, it can be seen that the mineral phase
with an irregular shape that is blue in the OM image but grey and rough
in the BSE image is the free lime (f-CaO); f-CaO always unevenly
S. Zhuang and Q. Wang Cement and Concrete Research 140 (2021) 106283

Fig. 16. Element distribution of steel slag.

Table 3
EDS element analysis result of steel slag.
Oxide CaO SiO2 Al2O3 P2O5 Fe2O3 MgO MnO TiO2 Cr2O3 Mineral composition

1 88.42 – – – 5.04 1.76 4.77 – – Free lime

2 85.37 – – – 6.17 2.98 5.48 – –
3 100 – – – – – – – –
4 – – – – 100 – – – – Free iron
5 62.81 1.22 8.98 – 16.22 2.74 – 8.02 – Calcium aluminoferrite
6 53.06 – 1.64 – 29.16 9.72 4.1 – 2.32
7 65.58 2.11 7.82 – 21.76 – – – –
8 1.58 – – – 20.2 67.19 11.03 –
9 4.48 – – – 33.12 45.94 16.46 – – RO phase
10 4.91 – – – 36.38 43.55 15.15 – –
11 36.24 35.75 – – 5.88 14.11 8.02 – – Composite phase: RO phase‑calcium silicate
12 67.52 30.25 – 2.23 – – – – – Calcium silicate
13 67.65 29.65 – 2.7 – – – – –
14 66.81 31.15 – 2.04 – – – – –
15 67.22 29.93 – 2.84 – – – – –
16 68.66 27.92 – 3.42 – – – – –
17 64.25 22.35 2.14 2.78 3.53 2.31 – 2.63 – Composite phase: calcium silicate‑calcium aluminoferrite-RO phase
18 65.04 29.61 0.57 2.97 – – – – – Composite phase: calcium silicate‑calcium aluminate
19 67.66 27 1.01 3.21 1.12 – – – – Composite phase: calcium silicate‑calcium aluminoferrite
20 59.14 6.75 7.75 0.75 11.67 4.14 1.51 8.3 – Composite phase: calcium silicate-RO phase‑calcium aluminate‑calcium
aluminoferrite

distributes between the calcium silicate and the RO phase and some­
times is symbiotic with some ferric oxides and manganese oxides. The
mineral phase with an irregular shape, which is white in the OM image
and bright white in the BSE image, is the free iron. The mineral phase,
which is light grey in the OM image and greyish white in the BSE image,
is the composite ferric phases. Among them, the phase that has a cross-
linked shape and a dark colour and is always wrapped by the calcium
silicate is the calcium aluminoferrite; the phase that has a small irregular
particle shape and a light colour is the RO phase. The mineral phase,
which is dark grey in the OM image and grey in the BSE image, is the
calcium silicate. Among them, the phase that has a round or leaf particle
shape and flat or smooth edges is C2S. C2S also wraps or coexists with the
calcium aluminoferrite and the f-CaO, which has a cross-linked shape. It
is worth noting that it is difficult to find the existence of C3S in both the
OM and the SEM results. In addition, there are also some composite
phases in the steel slag, such as the calcium silicate‑calcium alumi­
noferrite composite, calcium silicate‑calcium aluminate composite,
calcium silicate‑calcium aluminoferrite-RO phase composite and cal­
cium silicate-RO phase‑calcium aluminate‑calcium aluminoferrite
composite. The above analysis shows that the mineral composition of
the steel slag mainly includes the calcium silicate, RO phase, calcium
aluminoferrite, calcium aluminate, f-CaO and free iron.

10
S. Zhuang and Q. Wang
It can be seen in Table 3 that P is detected only in the calcium silicate
phase, with a P2O5 molar percentage of 2–3%. It is worth noting that the
actual CaO/SiO2 molar ratio of calcium silicate in the calcium silicate
phase is approximately 2, because P in steel slag exists in the form of
3CaO⋅P2O5 [101–104]. Combined with the morphological analysis, it is
determined to be C2S, indicating that the P in the steel slag is mainly
present in C2S, which is consistent with the results in the literature. Since
the C2S in steel slag has a low hydraulic activity, it hardly hydrates at the
early age. Therefore, P might not be visible in the pore solution at the
early age and thus has little effect on inhibiting the early-age hydration
of cement.
To further investigate whether P plays an important role, the steel
slag was leached in water and a calcium hydroxide solution with a pH of
12.5. Both the P content in the solid phase and the P concentration in the
liquid phase at the start and end of leaching were measured. The results
show that they are basically unchanged, which indicates that the
leaching of P from the steel slag can be neglected. Therefore, P has little
effect on inhibiting the early-age hydration of cement.
4.2. Retardation mechanisms of steel slag on the depletion of gypsum
Although the Ca content in the composite binder is significantly less
than that in the plain cement (Table 1), the Ca concentration in the pore
solution of the composite paste is significantly higher than that of the
cement paste throughout (Fig. 7(c)). This can explain why steel slag
slows the depletion of gypsum. Steel slag contributes to a higher Ca
concentration in the pore solution and thus leads to the dissolution
equilibrium of gypsum shifting to the left (Eq. (1)), which inhibits the
dissolution process and finally slows the depletion of gypsum.
CaSO4 (s) = Ca2+ (aq) + SO2−4 (aq) (1)
The higher Ca concentration in the pore solution of the composite
paste can be explained by the lower pH value of the pore solution of the
composite paste in comparison with that of the pore solution of the
cement paste, as shown in Fig. 11, because it has been reported
[53,105–108] that the pH value of the pore solution has a strong effect
on the Ca concentration and higher pH values decrease the Ca concen­
tration due to the precipitation of portlandite and the common ion ef­
fect. As mentioned above, the lower pH value of the pore solution of the
composite paste is caused by the much lower alkali content of the steel
slag in comparison to that of cement. In addition, it has also been re­
ported that although the pH value influences the Ca concentration, the
Ca concentration depends on the solubility of the phases present at the
particular stage of hydration [109]. Since the dissolution of calcium
aluminates is faster than that of gypsum [110–112], the Ca concentra­
tion in the pore solution at the very beginning is mainly derived from the
dissolution of calcium aluminates (the free CaO in steel slag is in a dead-
burnt state with a very low hydraulic activity, so it hardly reacts at the
early age [2,113]). According to Fig. 1, the main calcium aluminate
mineral in the steel slag is C12A7, which is quite different from the C3A in
the cement, in accordance with the literature [20,33]. It has been re­
ported that C12A7 is highly hydraulic and reacts very quickly with water
compared with the behaviour of C3A [114–116], which might also
explain why the steel slag leads to a higher Ca concentration in the pore
solution. Thermodynamic calculations may also provide further support.
The dissolution processes of C3A and C12A7 are shown in Eqs. (2) and
(3), respectively [69]. The Gibbs free energy of the reaction can be
calculated by Eq. (4) or Eq. (5), in which the enthalpy change, entropy
change and Gibbs free energy of formation are obtained from the
Table 4
The Gibbs free energy of formation of relevant substance.
C3A C12A7 H+ AlO−2 Ca2+ H2O
ΔfGΘ
m, B (kJ/mol) − 3382 − 18,451 0 − 827 − 553 − 237
11
Cement and Concrete Research 140 (2021) 106283
literature [69]. The results show that the Gibbs free energy of reaction
for the dissolution of C12A7 is obviously lower (Tables 4 and 5), which
indicates that the dissolution of C12A7 in water occurs more easily than
that of C3A.
(CaO)3 Al2 O3 + 4H+ = 2AlO−2 + 3Ca2+ + 2H2 O (2)
(CaO)3 (Al2 O3 ) + 10H+ = 14AlO−2 + 12Ca2+ + 5H2 O (3)
Δr GΘm = Δr HmΘ − TΔr SmΘ (4)
∑
Δr GΘm = vB Δf GΘm,B (5)
B
4.3. Retardation mechanisms of steel slag on the initial setting of cement
paste
As mentioned above, it has been widely reported that the presence of
steel slag significantly prolongs the initial setting time of the cement
paste [18,19,27,28,54,55,74], which limits the widespread application
of steel slag as a supplementary cementitious material to replace part of
cement since it affects the setting, demoulding and pumping. However,
its mechanisms are still unknown. It is obvious that the initial setting is
closely related to the early-age hydration of cementitious materials
because the initial setting should be largely affected by the evolution of
the solid phases, aqueous species and microstructures caused by the
early-age hydration. In this section, the retardation mechanisms of steel
slag on the initial setting of cement paste are preliminarily discussed
based on the evolution of the solid phases, aqueous species and micro­
structures of the cement-steel slag composite paste obtained above.
According to the well-known setting theory of cement [117–123],
the initial setting of cement paste depends on the establishment of a
continuous elastic solid network in the paste, which provides an initial
strength for the initial setting. This solid network is formed by the
overlap of the early-age hydration products (mainly the ettringite
[117–120] and the C–S–H [121–123]) on the surfaces of clinker grains
and the join of the amorphous C–S–H onto the nodes of the solid
network. Therefore, the quantity, type and morphology of the early-age
hydration products significantly affect the initial setting of cement paste.
The addition of steel slag significantly reduces the formation rate of
ettringite, which inhibits the overlap of the solid network. Steel slag
significantly inhibits the precipitation of C–S–H, which inhibits not
only the establishment of the solid network, but also the join onto the
nodes of the network. Additionally, steel slag contributes to the forma­
tion of cuboid-shaped products in the composite paste at the early age,
which have a significantly smaller SSA and lower meshing force than the
plate-shaped hydration products in cement paste. Thus, it might be
difficult for cuboid-shaped hydration products to engage and overlap
into an integrated whole as a network.
5. Conclusions
This study explores why steel slag inhibits the early-age hydration of
cement, unlike granulated blast furnace slag and limestone, which
promote the hydration of cement. Novel phenomena are found, and
their mechanisms are explained through an investigation of the early-
age hydration kinetics and the evolution of the solid phases, aqueous
species and microstructures of the cement-steel slag composite paste. In
addition, the retardation mechanisms of steel slag on the initial setting
Table 5
Calculation results of the Gibbs free energy of reaction.
ΔrHΘ
m (kJ/mol) ΔrSΘ
m (J/K/mol) ΔrGΘ
m (kJ/mol)
C3A dissolution − 492 − 296 − 403
C12A7 dissolution − 1490 − 1796 − 954
S. Zhuang and Q. Wang
of cement paste are discussed based on both the obtained findings and
the setting theory. The main conclusions are as follows.
(1) Steel slag significantly inhibits the precipitation of CH by
reducing the pH value of the pore solution. This leads to the su­
persaturation of the pore solution in the composite paste with
respect to CH being lower than the critical supersaturation, which
is when CH begins to precipitate. Steel slag significantly inhibits
the precipitation of C–S–H by inhibiting the nucleation and
growth of C–S–H.
(2) Steel slag slows the depletion of gypsum and thus reduces the
formation of ettringite by leading to a higher Ca concentration in
the pore solution of the composite paste. The higher Ca concen­
tration in the pore solution in the presence of steel slag can be
explained by the lower pH value of the pore solution of the
composite paste, which is caused by the much lower alkali con­
tent of steel slag in comparison to that of cement.
(3) The retardation of steel slag on the initial setting of cement paste
is attributed to the small formation rate and amount of ettringite,
the reduced amount of C–S–H and the formation of cuboid-
shaped hydration products caused by the addition of the steel
slag. These factors inhibit the overlap of the early-age crystalline
hydration products and the join of the amorphous C–S–H onto
the nodes, which are not conducive to the formation of the
network that provides an initial strength for initial setting.
CRediT authorship contribution statement
Shiyu Zhuang: Conceptualization, Data curation, Formal analysis,
Investigation, Methodology, Writing - original draft. Qiang Wang:
Conceptualization, Formal analysis, Funding acquisition, Supervision,
Validation, Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
Authors would like to acknowledge the National Natural Science
Foundation of China (No. 51822807).
References
[1] K. Horii, T. Kato, K. Sugahara, N. Tsutsumi, Y. Kitano, Overview of iron/steel slag
application and development of new utilization technologies, in: Nippon Steel &
Sumitomo Metal Technical Report, 2015.
[2] R. Jia, J. Liu, R. Jia, A study of factors that influence the hydration activity of
mono-component CaO and bi-component CaO/Ca2Fe2O5 systems, Cem. Concr.
Res. 91 (2017) 123–132.
[3] World Steel Association, Steel Statistical Yearbook 2016, 2016.
[4] World Steel Association, Fact sheet on co-products, in: WorldsteelOrg 2, 2018.
[5] J. Guo, Y. Bao, M. Wang, Steel slag in China: treatment, recycling, and
management, Waste Manag. 78 (2018) 318–330.
[6] H. Yi, G. Xu, H. Cheng, An overview of utilization of steel slag, Proced. Environ.
16 (2012) 791–801.
[7] J. Zhao, P. Yan, D. Wang, Research on mineral characteristics of converter steel
slag and its comprehensive utilization of internal and external recycle, J. Clean.
Prod. 156 (2017) 50–61.
[8] C. Shi, Steel slag—its production, processing, characteristics, and cementitious
properties, J. Mater. Civ. Eng. 16 (2004) 230–236.
[9] C. Shi, Characteristics and cementitious properties of ladle slag fines from steel
production, Cem. Concr. Res. 32 (2002) 459–462.
[10] M.P. Luxân, R. Sotolongo, F. Dorrego, E. Herrero, Characteristics of the slags
produced in the fusion of scrap steel by electric arc furnace, Cem. Concr. Res. 30
(2000) 517–519.
[11] J. Li, Q. Yu, J. Wei, T. Zhang, Structural characteristics and hydration kinetics of
modified steel slag, Cem. Concr. Res. 41 (3) (2011) 324–329.
[12] L. Muhmood, S. Vitta, D. Venkateswaran, Cementitious and pozzolanic behavior
of electric arc furnace steel slags, Cem. Concr. Res. 39 (2) (2009) 102–109.
12
Cement and Concrete Research 140 (2021) 106283
[13] Q. Wang, P. Yan, J. Feng, A discussion on improving hydration activity of steel
slag by altering its mineral compositions, J. Hazard. Mater. 186 (2011)
1070–1075.
[14] A.N. Murri, W.D.A. Rickard, M.C. Bignozzi, A.V. Riessen, High temperature
behaviour of ambient cured alkali-activated materials based on ladle slag, Cem.
Concr. Res. 43 (2013) 51–61.
[15] L. Kriskova, Y. Pontikes, Ö. Cizer, G. Mertens, W. Veulemans, D. Geysen, P.
T. Jones, L. Vandewalle, K.V. Balen, B. Blanpain, Effect of mechanical activation
on the hydraulic properties of stainless steel slags, Cem. Concr. Res. 42 (2012)
778–788.
[16] G. Qiana, D.D. Sun, J.H. Tay, Z. Lai, G. Xu, Autoclave properties of kirschsteinite-
based steel slag, Cem. Concr. Res. 32 (2002) 1377–1382.
[17] T. Zhang, Q. Yu, J. Wei, J. Li, P. Zhang, Preparation of high performance blended
cements and reclamation of iron concentrate from basic oxygen furnace steel slag,
Resour. Conserv. Recycl. 56 (1) (2011) 48–55.
[18] R.I. Iacobescu, G.N. Angelopoulos, P.T. Jones, B. Blanpain, Y. Pontikes, Ladle
metallurgy stainless steel slag as a raw material in Ordinary Portland Cement
production: a possibility for industrial symbiosis, J. Clean. Prod. 112 (2016)
872–881.
[19] T. Zhang, Q. Yu, J. Wei, J. Li, Investigation on mechanical properties, durability
and micro-structural development of steel slag blended cements, J. Therm. Anal.
Calorim. 110 (2012) 633–639.
[20] Q. Wang, P. Yan, S. Han, The influence of steel slag on the hydration of cement
during the hydration process of complex binder, Sci. China-Technol. Sci. 54 (2)
(2011) 388–394.
[21] F. Saly, L. Guo, R. Ma, C. Gu, W. Sun, Properties of steel slag and stainless-steel
slag as cement replacement materials: a comparative study, J. Wuhan. Univ.
Technol. 33 (6) (2018) 1444–1451.
[22] Q. Wang, D. Wang, S. Zhuang, The soundness of steel slag with different free CaO
and MgO contents, Constr. Build. Mater. 151 (2017) 138–146.
[23] M.S.H. Khan, A. Castel, A. Akbarnezhad, S. Foster, M. Smith, Utilisation of steel
furnace slag coarse aggregate in a low calcium fly ash geopolymer concrete, Cem.
Concr. Res. 89 (2016) 220–229.
[24] E. Anastasiou, K.G. Filikas, M. Stefanidou, Utilization of fine recycled aggregates
in concrete with fly ash and steel slag, Constr. Build. Mater. 50 (2014) 154–161.
[25] S. Saxena, A.R. Tembhurkar, Impact of use of steel slag as coarse aggregate and
wastewater on fresh and hardened properties of concrete, Constr. Build. Mater.
165 (2018) 126–137.
[26] Y. Xue, S. Wu, H. Hou, J. Zha, Experimental investigation of basic oxygen furnace
slag used as aggregate in asphalt mixture, J. Hazard. Mater. 138 (2) (2006)
261–268.
[27] S. Kourounis, S. Tsivilis, P.E. Tsakiridis, G.D. Papadimitriou, Z. Tsibouki,
Properties and hydration of blended cements with steelmaking slag, Cem. Concr.
Res. 37 (6) (2007) 815–822.
[28] L. Mo, F. Zhang, M. Deng, Mechanical performance and microstructure of the
calcium carbonate binders produced by carbonating steel slag paste under CO2
curing, Cem. Concr. Res. 88 (2016) 217–226.
[29] D. Adolfsson, R. Robinson, F. Engström, B. Björkman, Influence of mineralogy on
the hydraulic properties of ladle slag, Cem. Concr. Res. 41 (2011) 865–871.
[30] C. Shi, S. Hu, Cementitious properties of ladle slag fines under autoclave curing
conditions, Cem. Concr. Res. 33 (2003) 1851–1856.
[31] A. Monshi, M.K. Asgarani, Producing Portland cement from iron and steel slags
and limestone, Cem. Concr. Res. 29 (9) (1999) 1373–1377.
[32] Q. Wang, J. Yang, P. Yan, Cementitious properties of super-fine steel slag, Powder
Technol. 245 (8) (2013) 35–39.
[33] D. Ionescu, T.R. Meadowcroft, P.V. Barr, Early-age hydration kinetics of steel
slags, Adv. Cem. Res. 13 (1) (2001) 21–30.
[34] R.L. Sharma, S.P. Pandey, Influence of mineral additives on the hydration
characteristics of ordinary Portland cement, Cem. Concr. Res. 29 (1999)
1525–1529.
[35] E. Berodier, K. Scrivener, Understanding the filler effect on the nucleation and
growth of C-S-H, J. Am. Ceram. Soc. 97 (2014) 3764–3773.
[36] J. Zhou, G. Ye, K. Van Breugel, Hydration of Portland cement blended with blast
furnace slag at early age, editors, in: J. Marchand, B. Bissonnette, R. Gagné,
M. Jolin, F. Paradis (Eds.), Second International Symposium on Advances in
Concrete through Science and Engineering, Québec, 2006.
[37] J.I. Escalante-Garcia, J.H. Sharp, Effect of temperature on the hydration of the
main clinker phases in Portland cements: part II, blended cements, Cem. Concr.
Res. 28 (1998) 1259–1274.
[38] E. Gruyaert, N. Robeyst, N. De Belie, Study of the hydration of Portland cement
blended with blast-furnace slag by calorimetry and thermogravimetry, J. Therm.
Anal. Calorim. 102 (2010) 941–951.
[39] E.H. Kadri, S. Aggoun, G. DeSchutter, K. Ezziane, Combined effect of chemical
nature and fineness of mineral powders on Portland cement hydration, Mater.
Struct. 43 (2010) 665–673.
[40] G. Ye, X. Liu, G. De Schutter, A.M. Poppe, L. Taerwe, Influence of limestone
powder used as filler in SCC on hydration and microstructure of cement pastes,
Cem. Concr. Compos. 29 (2007) 94–102.
[41] G. Ye, X. Liu, A.M. Poppe, G. De Schutter, K. Van Breugel, Numerical simulation
of the hydration process and the development of microstructure of self-
compacting cement paste containing limestone as filler, Mater. Struct. 40 (2007)
865–875.
[42] A.-M. Poppe, G. De Schutter, Cement hydration in the presence of high filler
contents, Cem. Concr. Res. 35 (2005) 2290–2299.
S. Zhuang and Q. Wang
[43] A.M. Poppe, Influence of Fillers on Hydration and Properties of Self-compacting
Concrete (in Dutch). Doctoral thesis, Magnel Laboratory for Concrete Research,
Ghent University, Belgium, 2004.
[44] W.A. Gutteridge, J.A. Dalziel, Filler cement — the effect of the secondary
component on the hydration of Portland cement part 1: fine nonhydraulic filler,
Cem. Concr. Res. 20 (1990) 778–782.
[45] W.A. Gutteridge, J.A. Dalziel, Filler cement: the effect of the secondary
component on the hydration of Portland cement: part 2: fine hydraulic binders,
Cem. Concr. Res. 20 (1990) 853–861.
[46] J.J. Thomas, H.M. Jennings, J.J. Chen, Influence of nucleation seeding on the
hydration mechanisms of tricalcium silicate and cement, J. Phys. Chem. C 113
(2009) 4327–4334.
[47] P.Y. Yan, F. Zheng, Z.Q. Xu, Hydration of shrinkage-compensating binders with
different compositions and water-binder ratios, J. Therm. Anal. Calorim. 74
(2003) 201–209.
[48] J. Justs, M. Wyrzykowski, F. Winnefeld, D. Bajare, P. Lura, Influence of
superabsorbent polymers on hydration of cement pastes with low water-to-binder
ratio: a calorimetry study, J. Therm. Anal. Calorim. 115 (2014) 425–432.
[49] G. Baert, S. Hoste, G. De Schutter, N. De Belie, Reactivity of fly ash in cement
paste studied by means of thermogravimetry and isothermal calorimetry,
J. Therm. Anal. Calorim. 94 (2008) 485–492.
[50] D.P. Bentz, Influence of water-to-cement ratio on hydration kinetics: simple
models based on spatial considerations, Cem. Concr. Res. 36 (2006) 238–244.
[51] L. Lam, Y.L. Wong, C.S. Poom, Degree of hydration and gel/space ratio of high
volume fly ash/cement systems, Cem. Concr. Res. 30 (2000) 747–756.
[52] B. Lothenbach, K. Scrivener, R.D. Hooton, Supplementary cementitious materials,
Cem. Concr. Res. 41 (2011) 1244–1256.
[53] A. Schöler, B. Lothenbach, F. Winnefeld, M.B. Haha, M. Zajac, H. Ludwig, Early
hydration of SCM-blended Portland cements: a pore solution and isothermal
calorimetry study, Cem. Concr. Res. 93 (2017) 71–82.
[54] X. Wu, H. Zhu, X. Hou, H. Li, Study on steel slag and fly ash composite Portland
cement, Cem. Concr. Res. 29 (1999) 1103–1106.
[55] A. Altun, I. Yılmaz, Study on steel furnace slags with high MgO as additive in
Portland cement, Cem. Concr. Res. 32 (8) (2002) 1247–1249.
[56] H. Beushausen, M. Alexander, Y. Ballim, Early-age properties, strength
development and heat of hydration of concrete containing various South African
slags at different replacement ratios, Constr. Build. Mater. 29 (2012) 533–540.
[57] S. Zhang, Y. Zhang, Z. Li, Ultrasonic monitoring of setting and hardening of slag
blended cement under different curing temperatures by using embedded
piezoelectric transducers, Constr. Build. Mater. 159 (2018) 553–560.
[58] D. Le, Y. Sheen, M.N. Lam, Fresh and hardened properties of self-compacting
concrete with sugarcane bagasse ash–slag blended cement, Constr. Build. Mater.
185 (2018) 138–147.
[59] T. Perraki, E. Kontori, S. Tsivilis, G. Kakali, The effect of zeolite on the properties
and hydration of blended cements, Cem. Concr. Compos. 32 (2010) 128–133.
[60] D.P. Bentz, Activation energies of high-volume fly ash ternary blends: hydration
and setting, Cem. Concr. Compos. 53 (2014) 214–223.
[61] B. Yılmaz, A. Olgun, Studies on cement and mortar containing low-calcium fly
ash, limestone, and dolomitic limestone, Cem. Concr. Compos. 30 (2008)
194–201.
[62] E. Gulbandilar, Y. Kocak, Prediction of the effects of fly ash and silica fume on the
setting time of Portland cement with fuzzy logic, Neur. Comput. Appl. 22 (2013)
1485–1491.
[63] D. Snelson, S. Wild, M. O’Farrell, Setting times of Portland
cement–metakaolin–fly ash blends, J. Civ. Eng. Manage. 17 (2011) 55–62.
[64] K. Ezziane, E. Kadri, A. Hallal, R. Duval, Effect of mineral additives on the setting
of blended cement by the maturity method, Mater. Struct. 43 (2010) 393–401.
[65] Z. Zhang, G.W. Scherer, A. Bauer, Morphology of cementitious material during
early hydration, Cem. Concr. Res. 107 (2018) 85–100.
[66] S. Brunauer, P.H. Emmett, E. Teller, Adsorption of gases in multimolecular layers,
J. Am. Chem. Soc. 60 (1938) 309–319.
[67] S. Mantellato, M. Palacios, R.J. Flatt, Reliable specific surface area measurements
on anhydrous cements, Cem. Concr. Res. 67 (2015) 286–291.
[68] I. Odler, The BET-specific surface area of hydrated Portland cement and related
materials, Cem. Concr. Res. 33 (12) (2003) 2049–2056.
[69] B. Lothenbach, D.A. Kulik, T. Matschei, M. Balonis, L. Baquerizo, B. Dilnesa, G.
D. Miron, R.J. Myers, Cemdata18: a chemical thermodynamic database for
hydrated Portland cements and alkali-activated materials, Cem. Concr. Res. 115
(2019) 472–506.
[70] U.C. Shi, J. Qian, High performance cementing materials from industrial slags—a
review, Resour. Conserv. Recycl. 29 (3) (2000) 195–207.
[71] H. Tian, X. Kong, T. Su, D. Wang, Comparative study of two PCE superplasticizers
with varied charge density in Portland cement and sulfoaluminate cement
systems, Cem. Concr. Res. 115 (2019) 43–58.
[72] X. Wang, W. Ni, J. Li, S. Zhang, M. Hitch, R. Pascual, Carbonation of steel slag and
gypsum for building materials and associated reaction mechanisms, Cem. Concr.
Res. 125 (2019) 105893.
[73] W. Barbosa, R.D.P. Ramalho, K.F. Portella, Influence of gypsum fineness in the
first hours of cement paste: hydration kinetics and rheological behaviour, Constr.
Build. Mater. 184 (2018) 304–310.
[74] F. Winnefeld, L.H.J. Martin, C.J. Müller, B. Lothenbach, Using gypsum to control
hydration kinetics of CSA cements, Constr. Build. Mater. 155 (2017) 154–163.
[75] Y. Jeong, C.W. Hargis, S.C. Chun, J. Moon, The effect of water and gypsum
content on strätlingite formation in calcium sulfoaluminate-belite cement pastes,
Constr. Build. Mater. 166 (2018) 712–722.
13
Cement and Concrete Research 140 (2021) 106283
[76] H. Nguyen, P. Kinnunen, K. Gijbels, V. Carvelli, H. Sreenivasan, A.M. Kantola,
V. Telkki, W. Schroeyers, M. Illikainen, Ettringite-based binder from ladle slag
and gypsum — the effect of citric acid on fresh and hardened state properties,
Cem. Concr. Res. 123 (2019) 105800.
[77] F. Winnefeld, S. Barlag, Calorimetric and thermogravimetric study on the
influence of calcium sulfate on the hydration of ye’elimite, J. Therm. Anal.
Calorim. 101 (2010) 949–957.
[78] D. Jansen, A. Spies, J. Neubauer, D. Ectors, F. Goetz-Neunhoeffer, Studies on the
early hydration of two modifications of ye’elimite with gypsum, Cem. Concr. Res.
91 (2017) 106–116.
[79] J. Zhou, K. Zheng, Z. Liu, F. He, Chemical effect of nano-alumina on early-age
hydration of Portland cement, Cem. Concr. Res. 116 (2019) 159–167.
[80] B. Lothenbach, F. Winnefeld, Thermodynamic modelling of the hydration of
Portland cement, Cem. Concr. Res. 36 (2016) 209–226.
[81] N. Zhang, L. Wu, X. Liu, Y. Zhang, Structural characteristics and cementitious
behavior of basic oxygen furnace slag mud and electric arc furnace slag, Constr.
Build. Mater. 219 (2019) 11–18.
[82] J.J. Thomas, H.M. Jennings, A.J. Allen, The surface area of cement paste as
measured by neutron scattering: evidence for two C-S-H morphologies, Cem.
Concr. Res. 28 (6) (1998) 897–905.
[83] Y. Yan, A. Ouzia, C. Yu, J. Liu, K.L. Scrivener, Effect of a novel starch-based
temperature rise inhibitor on cement hydration and microstructure development,
Cem. Concr. Res. 129 (2020) 105961.
[84] M. Zajac, J. Skocek, B. Lothenbach, M.B. Haha, Late hydration kinetics:
indications from thermodynamic analysis of pore solution data, Cem. Concr. Res.
129 (2020) 105975.
[85] D. Marchon, R.J. Flatt, Impact of chemical admixtures on cement hydration, in:
Sci. Technol. Concr. Admixtures, Elsevier, 2016, pp. 279–304.
[86] B.J. Smith, A. Rawal, G.P. Funkhouser, L.R. Roberts, V. Gupta, J.N. Israelachvili,
B.F. Chmelka, Origins of saccharide-dependent hydration at aluminate, silicate,
and aluminosilicate surfaces, Proc. Natl. Acad. Sci. 108 (2011) 8949–8954.
[87] B.J. Smith, L.R. Roberts, G.P. Funkhouser, V. Gupta, B.F. Chmelka, Reactions and
surface interactions of saccharides in cement slurries, Langmuir 28 (2012)
14202–14217.
[88] R.P. Sangodkar, B.J. Smith, D. Gajan, A.J. Rossini, L.R. Roberts, G.P. Funkhouser,
A. Lesage, L. Emsley, B.F. Chmelka, Influences of dilute organic adsorbates on the
hydration of low-surface-area silicates, J. Am. Chem. Soc. 137 (2015) 8096–8112.
[89] X. Kong, S. Emmerling, J. Pakusch, M. Rueckel, J. Nieberle, Retardation effect of
styrene-acrylate copolymer latexes on cement hydration, Cem. Concr. Res. 75
(2015) 23–41.
[90] G. Möschner, B. Lothenbach, R. Figi, R. Kretzschmar, Influence of citric acid on
the hydration of Portland cement, Cem. Concr. Res. 39 (2009) 275–282.
[91] N.L. Thomas, J.D. Birchall, The retarding action of sugars on cement hydration,
Cem. Concr. Res. 13 (1983) 830–842.
[92] E. Gartner, I. Maruyama, J. Chen, A new model for the C-S-H phase formed during
the hydration of Portland cements, Cem. Concr. Res. 97 (2017) 95–106.
[93] H. Zhao, K. Jiang, R. Yang, Y. Tang, J. Liu, Experimental and theoretical analysis
on coupled effect of hydration, temperature and humidity in early-age cement-
based materials, Int. J. Heat Mass Transf. 146 (2020) 118784.
[94] F. Bellmann, G.W. Scherer, Analysis of C-S-H growth rates in supersaturated
conditions, Cem. Concr. Res. 103 (2018) 236–244.
[95] E. Ntafalias, P.G. Koutsoukos, Spontaneous precipitation of calcium silicate
hydrate in aqueous solutions, Cryst. Res. Technol. 45 (1) (2010) 39–47.
[96] X. Ouyang, D.A. Koleva, G. Ye, K. van Breugel, Understanding the adhesion
mechanisms between C-S-H and fillers, Cem. Concr. Res. 100 (2017) 275–283.
[97] M. Schönlein, J. Plank, A TEM study on the very early crystallization of C-S-H in
the presence of polycarboxylate superplasticizers: transformation from initial C-S-
H globules to nanofoils, Cem. Concr. Res. 869 (2018) 227–232.
[98] M. Delhorme, C. Labbez, M. Turesson, E. Lesniewska, C.E. Woodward, B. Jönsson,
Aggregation of calcium silicate hydrate nanoplatelets, Langmuir 32 (2016)
2058–2066.
[99] C. Du, X. Gao, S. Ueda, S. Kitamura, Separation and recovery of phosphorus from
steelmaking slag via a selective leaching-chemical precipitation process,
Hydrometallurgy 189 (2019) 105109.
[100] H. Suito, Y. Hayashida, Y. Takahashi, Mineralogical study of LD converter slags,
Tetsu-to-Hagane. 63 (8) (1977) 1252–1259.
[101] K. Ito, M. Yanagisawa, N. Sano, Phosphorus distribution between solid 2CaO⋅SiO2
and molten CaO-SiO2-FeO-Fe2O3 slags, Tetsu-to-Hagane 68 (2) (1982) 342–344.
[102] T. Teratoko, N. Maruoka, H. Shibata, S. Kitamura, Dissolution behavior of di-
calcium silicate and tricalcium phosphate solid solution and other phases of steel-
making slag in an aqueous solution, High Temp. Mater. Proc. 31 (2012) 329–338.
[103] M. Numata, N. Maruoka, S.J. Kim, S. Kitamura, Fundamental experiment to
extract phosphorous selectively from steelmaking slag by leaching, ISIJ Int. 54 (8)
(2014) 1983–1990.
[104] S. Wu, Y. Xue, Q. Ye, Y. Chen, Utilization of steel slag as aggregates for stone
mastic asphalt (SMA) mixtures, Build. Environ. 2 (42) (2007) 580–585.
[105] F. Deschner, F. Winnefeld, B. Lothenbach, S. Seufert, P. Schwesig, S. Dittrich,
Hydration of Portland cement with high replacement by siliceous fly ash, Cem.
Concr. Res. 42 (2012) 1389–1400.
[106] A. Kumar, G. Sant, C. Patapy, C. Gianocca, K.L. Scrivener, The influence of sodium
and potassium hydroxide on alite hydration: experiments and simulations, Cem.
Concr. Res. 42 (2012) 1513–1523.
[107] B. Mota, T. Matschei, K.L. Scrivener, The influence of sodium salts and gypsum on
alite hydration, Cem. Concr. Res. 75 (2015) 53–65.
S. Zhuang and Q. Wang
[108] G. Sant, A. Kumar, C. Patapy, G. Le Saout, K.L. Scrivener, The influence of sodium
and potassium hydroxide on volume changes in cementitious materials, Cem.
Concr. Res. 42 (2012) 1447–1455.
[109] O.A. Vollpracht, B. Lothenbach, R. Snellings, J. Haufe, The pore solution of
blended cements: a review, Mater. Struct. 49 (8) (2016) 3341–3367.
[110] T.S.Y. Hong, F.P. Glasser, Alkali binding in cement pastes. Part I. The C-S-H phase,
Cem. Concr. Res. 29 (12) (1999) 1893–1903.
[111] A. Quennoz, K.L. Scrivener, Hydration of C3A-gypsum systems, Cem. Concr. Res.
42 (2012) 1032–1041.
[112] D. Jansen, A. Spies, J. Neubauer, D. Ectors, F.G. Neunhoeffer, Studies on the early
hydration of two modifications of ye’elimite with gypsum, Cem. Concr. Res. 91
(2017) 106–116.
[113] G. Wang, Y.H. Wang, Z.L. Gao, Use of steel slag as a granular material: volume
expansion prediction and usability criteria, J. Hazard. Mater. 184 (2010)
555–560.
[114] B. Raab, S. Stöber, H. Pöllmann, Investigations of the hydration behaviour of pure
cement phases by different synthesis methods, in: C.H. Fentiman, R.J. Mangabhai,
K.L. Scrivener (Eds.), Proceedings of the Centenary Conference, Avignon, 2008,
pp. 79–92.
[115] F.M. Lea, High-alumina cement, in: The Chemistry of Cement and Concrete, 3rd
ed., Edward Arnold (Publishers) Ltd, Great Britain, 1970, pp. 490–527 (chapter
16).
14
Cement and Concrete Research 140 (2021) 106283
[116] I. Odler, Calcium Aluminate Cement, Special Inorganic Cements, E&FN Spon,
London & New York, 2000, pp. 173–201 (chapter 10).
[117] S.P. Jiang, J.C. Mutin, A. Nonat, Studies on mechanism and physico-chemical
parameters at the origin of the cement setting. I. The fundamental processes
involved during the cement setting, Cem. Concr. Res. 25 (4) (1995) 779–789.
[118] S.P. Jiang, J.C. Mutin, A. Nonat, Studies on mechanism and physico-chemical
parameters at the origin of the cement setting II. Physico-chemical parameters
determining the coagulation process, Cem. Concr. Res. 26 (3) (1996) 491–500.
[119] A. Nonat, J.C. Mutin, X. Lecoq, S.P. Jiang, Physico-chemical parameters
determining hydration and particle interactions during the setting of silicate
cements, Solid State Ionics 101–103 (1997) 923–930.
[120] A. Nonat, Interactions between chemical evolution (hydration) and physical
evolution (setting) in the case of tricalcium silicate, Mater. Struct. 27 (1999)
187–195.
[121] R. Ylmén, U. Jäglid, B. Steenari, I. Panas, Early hydration and setting of Portland
cement monitored by IR, SEM and Vicat techniques, Cement Concr. Res. 39 (5)
(2009) 433–439.
[122] Y. Chen, I. Odler, On the origin of Portland cement setting, Cem. Concr. Res. 22
(1992) 1130–1140.
[123] W. Scherer, J. Zhang, J.A. Quintanilla, S. Torquato, Hydration and percolation at
the setting point, Cem. Concr. Res. 42 (5) (2012) 665–672.