Journal of Cleaner Production 262 (2020) 121385

Contents lists available at ScienceDirect

Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Coupling effect of g-dicalcium silicate and slag on carbonation

resistance of low carbon materials
Z.X. Chen a, 1, S.H. Chu b, *, 1, Y.S. Lee a, H.S. Lee a
a
Department of Architectural Engineering, Hanyang University, South Korea
b
The University of Hong Kong, Hong Kong, China

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

Article history: In this paper, the combined use of g-dicalcium silicate and slag for possible coupling effect on carbon-
Received 29 December 2019 ation resistance was investigated. The potential of the use of g-C2S to impart carbonation immunity to
Received in revised form slag blended materials at early age has not been fully explored so far. In this regard, 15, 30 and 50% slag
14 March 2020
blended cement paste and mortar samples containing 0, 5, 10, 15, 20% of g-C2S in replacement of cement
Accepted 26 March 2020
Available online 2 April 2020
were manufactured before undergoing accelerated carbonation for 3, 7 and 28 days. Then, techniques of
X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis
Handling editor: Baoshan Huang (TGA) and Mercury Intrusion Porosimetry (MIP) were utilized to analyze the carbonation characteristics.
Results show that the carbonation of g-C2S in the presence of slag is effective in CO2 sequestration, pore
Keywords: refinement and surface hardening. Moreover, an optimum combination of g-C2S and slag exists for
Carbonation achieving the smallest carbonation depth which is 78% lower than the observed maximum, from which
Low carbon certain coupling effect was identified. Lastly, a conceptual model was presented to probe into the
g-C2S mechanism. Such research shall be conducive to the search for next-generation low carbon concrete with
Slag
improved durability.
Coupling effect
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction increases rapidly and nowadays accounts for 7e8% of global

Durability and sustainability are of essential importance for
modern concrete structures (Falikman et al., 2018). Regarding the
durability, carbonation is one of the determining factors and rep-
resents a larger concern for reinforced concrete structures (Parrott,
1990). Carbonation occurs to concrete when atmospheric CO2 dif-
fuses through unsaturated pore network and/or existing cracks in
concrete and dissolves in pore solution. The acidification of the pore
solution induces the dissolution of the hydrates and then a
decrease in pH value. Subsequently, corrosion of steel reinforce-
ment is initiated as the passive film is destroyed. The key to tackle
such problem lies in the enhancement of the carbonation resistance
of concrete. One innovative way to achieve it is to impart carbon-
ation immunity to concrete at early age, during which CO2 is se-
questrated and the rapid surface hardening of concrete would offer
improved carbonation resistance in long term.
Regarding the sustainability, global cement production
* Corresponding author.
E-mail address: shchu@connect.hku.hk (S.H. Chu).
1
These authors contributed equally to this study and share first authorship.
anthropogenic carbon dioxide emissions (Miller and Myers, 2020).
In view of such high environmental impact, various attempts have
been made to develop new sustainable materials without greatly
compromising the performance (Bentz et al., 2015; Schmidt et al.,
2018; Chu, 2019). Among the attempts, the adoption of supple-
mentary cementitious materials (SCMs) has been prevalent (Chu
and Kwan, 2019a, b; Diaz-Loya et al., 2019; Jiang et al., 2018), dur-
ing which problems like low carbonation resistance may emerge
simultaneously (Shah and Bishnoi, 2018). In fact, carbonation is also
a common type of attack in cement-based materials (Kim et al.,
2014; Liu et al., 2017; Phung et al., 2015), especially when SCMs
are incorporated (Gruyaert et al., 2013; Wu and Ye, 2017). However,
few attentions have been paid to the better utilization and opti-
mization of existing chemical ingredients inside clinker to coun-
teract the above negative effect.
In this paper, g-dicalcium silicate, which is a common type of
ingredient but quite often deliberately avoided in cement due to its
incredibly low hydraulic activity, was re-examined for possible
coupling effect with SCMs arising from its intrinsic attributes of low
carbon and high carbonation activity (Ashraf, 2018; Ashraf and
Olek, 2018a; Guan et al., 2016). Dicalcium silicate, referred to C2S,

https://doi.org/10.1016/j.jclepro.2020.121385
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
2 Z.X. Chen et al. / Journal of Cleaner Production 262 (2020) 121385
has five polymorphs, namely, a, aH0 , aL0 , b and g-C2S. For pure C2S,
a-C2S, aH0 -C2S, aL0 -C2S and b-C2S exist in an unstable form under
normal temperature and tend to transform into g-C2S (Mu et al.,
2018a；Mu et al., 2019) and the transformation of b-C2S to g-C2S
induces large volume increase for easier pulverization of the clinker
ball (Mu et al., 2018a). To vividly show the conversion relationships
among these five forms of C2S, a schematic diagram is given in Fig. 1.
As an undesirable component in cement (Zhou et al., 2018), g-C2S is
generally avoided using rapid cooling method during cement pro-
duction (Elhoweris et al., 2018).
Despite the fact that the g-C2S can hardly react with water, the
presence of water would facilitate the rapid reaction of g-C2S with
CO2 to form calcium carbonates and highly polymerized silica gel,
which is called carbonation (Ashraf and Olek, 2018a; Moon and
Choi, 2019). Different from the traditional carbonation process of
b-C2S where CO2 mainly reacts with Ca ions released from calcium
hydroxide (Ca(OH)2), g-C2S reacts directly with H2CO3 to precipi-
tate as various forms of calcium carbonate (CaCO3) and silica gel as
shown in the following formulas (Saito et al., 2007),
CO2 þ H2O / H2CO3
(2CaO)$SiO2 (g-C2S) þ 2H2CO3 / 2CaCO3 þ SiO2 þ 2H2O (gel)
Apparently, the carbonation of g-C2S consumes CO2 whilst the
manufacturing of g-C2S generates less CO2 than that of cement
(Guan et al., 2016). Therefore, the use of g-C2S in cement is an
effective low carbon technique that has been underestimated
before.
Apart from it, in-depth research on the use of g-C2S in
conjunction with slag for the production of low carbon rapid sur-
face hardening materials seems rare and wider applications have
also been hindered. In early age, rapid surface hardening could be
achieved by utilizing the high carbonation reactivity of g-C2S to
form a densified surface to inhibit further ingress of CO2 (Garrault,
2001; Salvoldi et al., 2015). In other words, the surface densification
would help to impart carbonation immunity to concrete for much-
improved resistance to the environmental attack in a later stage. It
should be noted that an excessive amount of g-C2S might also
impair the quality of the mixture. However, the optimum addition
of g-C2S to cement to develop carbonation immune concrete is yet
to be explored.
Above all, the introduction of g-C2S into slag blended cement-
based materials could contribute significantly to the CO2 reduc-
tion in construction industry, thus necessitate wider and deeper
research on this important topic. Despite that supplementary
cementitious materials (SCMs) have been widely used in con-
struction industry for reduced cement content and higher perfor-
mance, studies combining these two environmental-friendly
materials, i.e., g-C2S and slag, have been rare that most studies have
focused on the single use of g-C2S or SCM. Even for the studies on
Fig. 1. C2S in five polymorphous forms.
their combined use, possible coupling effect between them is yet to
be revealed. Therefore, to facilitate the development of
geC2Sebased materials, there is an urgent need to fill the research
gap by probing into the carbonation characteristics of cement-
based materials incorporating both g-C2S and SCM.
2. Literature review
In the development of low carbon durable construction mate-
rials, two raw materials, namely, g-C2S and slag, were considered
herein. In fact, both of them are not new. g-C2S is an undesired
component in cement exhibiting little hydraulic activity and slag is
an industrial by-product. Interestingly, their combined use might
give rise to certain coupling effect that has been ignored or
underestimated before. The possible coupling effect comes from
the fact that g-C2S could partially counterpart the negative effect on
carbonation resistance brought by slag and slag could offer
appropriate alkali environment that facilitates the activation of g-
C2S.
Pioneering works on the activation of g-C2S are not rare where
alkali activation is widely used for g-C2S containing materials and
pure g-C2S. For instance, (Shi, 2002) and Shi and Hu (2003) re-
ported steel ladle slag fines, consisting mainly of g-C2S, showed
significant cementitious property with alkaline activator of Na2SiO3
solution. Kriskova et al. (2014) used Na2CO3 and NaOH solution to
activate synthetic g-C2S at ambient temperature and reported the
hydration of g-C2S started earlier and the total heat release was
higher with the Na2CO3 solution which has a lower alkalinity than
the NaOH solution. Salman et al. (2014) and Salman et al. (2015)
used alkali (NaOH, KOH, Na2SiO3, K2SiO3) solutions to improve
the hydration activity of g-C2S containing stainless steel slag and
reported the strengths of K activated samples were generally lower
than Na activated samples, particularly at early age.
More recently, Ashraf (2018) argued that g-C2S would react
directly with HCO 3 (pH ~ 6.3e10.3) produced by dissolving gaseous
CO2 in water which consumed Ca ions released by g-C2S to form
CaCO3. Interestingly, Ashraf (2018) compared the effects of Na2CO3,
NaHCO3, Na2SiO3, and NaOH activators on the hydration reactions
of g-C2S pastes and concluded that NaOH, which exhibited the
highest alkalinity, showed the least effectiveness and the lowest
total heat release among all of the activators, indicating that a high
alkalinity would not always favor the activation of g-C2S. Apart
from it, Yip et al. (2005) and Burciaga-Díaz et al. (2013) reported
that a high pH value would lower down the solubility of Ca ions.
Hence, it could be inferred that an excessively high alkalinity would
inhibit the formation of HCO 3 and thus the carbonation of g-C2S. A
median pH value of around 9.0 might be preferred for the
carbonation of g-C2S because it enables the formation of denser
vaterite CaCO3 which is the main carbonation product of g-C2S as
pointed out by Choi et al. (2018).
In spite of the effectiveness, the above alkali activation methods
do take a long time to fully activate the g-C2S, which is unrealistic
and costly for on-site concrete production. Meanwhile, there is an
increasing need to mitigate the intensifying global warming by CO2
capture, storage and sequestration in construction (Gartner and
Hirao, 2015; Sanna et al., 2014; Xuan et al., 2016). In fact, acceler-
ated carbonation of g-C2S is gaining attention because the rapid
reaction between g-C2S and CO2 in the presence of water as catalyst
would consume large amounts of CO2. More importantly, the rapid
surface hardening due to the formation of carbonation products can
inhibit further ingress of harmful matters (Savija
and Lukovic,
2016), thus improving the durability of cement-based materials
by imparting certain carbonation immunity at early age (Mabudo
et al., 2016; Pan et al., 2017). For instance, Saito et al. (2007) re-
ported 80% g-C2S in replacement of cement would lead to the least
 Z.X. Chen et al. / Journal of Cleaner Production 262 (2020) 121385 3

sulfate ion penetration as a result of denser pore structure from 3. Materials and methods
accelerated carbonation. Saphouvong et al. (2012) reported the
surface densification as a result of the use of 40e80% g-C2S with 3.1. Materials
accelerated carbonation could prevent steel from corrosion.
In addition, Higuchi et al. (2014) developed a new type of con- 3.1.1. Synthesis of g-C2S
crete named CO2-SUICOM using g-C2S and fly ash in pursuit of zero The g-C2S used in this study was prepared by mixing and
or negative carbon dioxide emission, without compromising the grinding calcium carbonate and silica dioxide powders in a Ca/Si
strength. Ghouleh et al. (2015) applied accelerated carbonation to a ratio of 2:1 (with reference to the Ca/Si ratio in g-C2S) and then
high-strength KOBM steel slag binder containing g-C2S and ach- were placed in a muffle furnace for calcination. In the calcination
ieved a strength of 80 MPa in 2 h. Sung et al. (2015) applied process, the temperature was increased in 10  C/min until reached
accelerated carbonation to g-C2S binders and observed improved 900  C and then maintained for 1 h to ensure that a decarburization
strength and finer pore structure. Guan et al. (2016) obtained a g- reaction as complete as possible (Morioka et al., 2010). Immediately
C2S based mortar strength of up to 60 MPa in 5 h by tailoring the after that, the temperature was raised to 1450  C and maintained
carbonation conditions and argued that the carbonation products for another hour (Na et al., 2015). After the calcination, the samples
of g-C2S have a layered structure with CaCO3 outside and silica gel were cooled down at room temperature. During the slow cooling
inside. The CO2 uptake results from thermal analysis revealed that process, the conversion from b-C2S to g-C2S which has a lower
the carbonation process could enable a sequestration of up to density leads to a volume expansion accompanied by the afore-
230 kg of CO2 per 1 ton of g-C2S binder (Guan et al., 2016), which is mentioned pulverization of materials.
of great significance to the development of low carbon materials. After the g-C2S was synthesized, X-ray Diffraction (XRD) was
Chang et al. (2016) reported g-C2S and b-C2S absorbed 18.3% and performed for the phase identification and quantification of the
9.2% CO2, respectively, after accelerated carbonation for 2 h. synthetic g-C2S, where RIGAKU D/MAX-2500 was used with CuKa
Recently, Lu et al. (2018) synthesized a low-calcium clinker con- radiation of 100 mA and 40 kV. The obtained XRD results of syn-
taining C3S2-geC2SeC2AS (Ca2Al2SiO7) to achieve a compressive thetic g-C2S after performing Rietveld refinement using software
strength of about 60 MPa after accelerated carbonation for 24 h. Mu Profex are presented in Fig. 2. The chemical compositions of syn-
et al. (2018a), Mu et al. (2018b) developed g-C2S based mortar thetic g-C2S obtained from X-ray Fluorescence (XRF) are tubulated
exhibiting rapid strength gain and CO2 uptake of 18.6% by mass of g- in the second row of Table 1. It can be seen that the synthetic g-C2S
C2S after accelerated carbonation for 24 h. Zhou et al. (2018) applied has a very high purity exceeding 90%. To control the particle size
accelerated carbonation for a novel carbonated 0e3 piezoelectric g- and guarantee the quality, the synthetic g-C2S was sieved using a
C2S composite for over 2 h and attained a rapid strength gain of 150 mm sieve and only the particles finer than 150 mm were adopted
38.5 MPa. Moon and Choi (2019) developed CO2 fixation materials in this study.
using stainless-steel argon oxygen decarburization slag which con-
tains g-C2S and observed increased strength and the CO2 capture
capacity as a result of accelerated carbonation. In summary, the re- 3.1.2. Sample preparation and curing method
ported CO2 uptake of 1 g of g-C2S varied between 0.18 and 0.40 g, Type CEM 1 cement and slag, the chemical compositions of
demonstrating enormous potential for CO2 sequestration. which are tabulated in the third and fourth rows of Table 1, were
On the other hand, slag is widely used in the construction used as cementitious materials in this study (Shi, 2004). Sand with
(Humbert and Castro-Gomes, 2019; Wang and Lee, 2019; Yang a maximum particle size of 2.36 mm was adopted for making of slag
et al., 2020). The partial replacement of ordinary Portland cement blended cement mortar. The mixture proportions of slag blended
by such industrial by-product can effectively lower down the cement paste and slag blended cement mortar are tabulated in
cement consumption and hydration temperature and improve the Table 2 and Table 3, respectively. The water to binder (W/B) ratios of
€
durability (Ozbay et al., 2016; Rashad, 2018). However, it might also slag blended cement paste and cement mortar and samples were
impair the carbonation resistance of concrete. The addition of slag fixed at 0.50. Both slag and g-C2S were added to replace the cement
would reduce the amount of Portlandite and bring down the
alkalinity (Ashraf, 2016) of the mixture to below that of pure
cement mixture. Such appropriate lower alkalinity and minor
amount of Na ions and K ions might favor the activation process
because the g-C2S reacts with H2CO3 (Ashraf, 2018) and an exces-
sively high alkalinity would destroy such environment. In other
words, there might exist an optimum alkalinity that best facilitates
the activation process and the co-presence of cement and SCM of
slag might be a solution to achieve it.
From the literature review, it can be inferred that: (1) from the
perspective of carbonation resistance, g-C2S has little hydraulic
activity and needs a demanding alkali environment for carbon-
ation, while slag is less carbonation-resistant but can offer appro-
priate alkali environment; (2) from the perspective of cleaner
production, the g-C2S generates less CO2 during production and
captures more CO2 during carbonation (Ashraf and Olek, 2018b),
while the slag lowers down the cement consumption and absorbs
CO2 (Wang et al., 2019); (3) hence, the combined use of g-C2S and
slag at appropriate ratio might yield certain coupling effect on the
long-term carbonation resistance and environmental friendliness.
However, the optimum combination of g-C2S and slag for mini-
mizing the environmental impact and maximizing the carbonation Fig. 2. XRD results of synthetic g-C2S (g: g eC2S, b: b-C2S).
resistance and the associated mechanism are yet to be explored.
4 Z.X. Chen et al. / Journal of Cleaner Production 262 (2020) 121385

Table 1 3.2. Test methods

Chemical composition of cement, synthetic g-C2S and slag (by weight %).

Chemical composition CaO SiO2 Al2O3 Fe2O3 MgO SO3 3.2.1. XRD and Fourier-transform infrared spectroscopy (FT-IR)
Synthetic g-C2S 63.58 35.55 0.09 0.23 0.36 0.05
XRD and FT-IR were used to evaluate the accelerated carbon-
Cement 65.14 18.02 3.04 3.08 2.95 4.24 ation products of the paste and mortar samples containing g-C2S.
Slag 43.00 31.5 15.02 0.53 5.59 0.06 Before the tests, the cement paste samples were ground into
powder finer than 150 mm at 84 days. FT-IR was performed using a
PerkinElmer Spectrum Two FT-IR Spectrometer (L160000A). Spec-
tral analysis was performed over the range of 400e4000 cm1 at a
Table 2 resolution of 4 cm1.
Mix proportions of slag blended cement paste samples.

Samples Binder (weight %) W/B ratio S/B ratio 3.2.2. Thermogravimetry analysis (TGA)
Cement Slag g-C2S To quantify the CO2 capture during the accelerated carbonation
process, the calcium carbonate content of carbonated cement paste
A0-P 85 15 0 0.50 3.0
A5-P 80 5
was used as an indicator and analyzed by thermogravimetry anal-
A10-P 75 10 ysis (TGA). Similarly, each batch of cement paste samples was
A20-P 65 20 ground into a powder finer than 150 mm at 84 days before TGA test.
B0eP 70 30 0 Then, powders were heated from room temperature to 1000  C at a
B5eP 65 5
heating rate of 10  C/min, during which a continuous flow of ni-
B10eP 60 10
B20eP 50 20 trogen (N2) gas was supplied.
C0eP 50 50 0
C5eP 45 5 3.2.3. Mercury Intrusion Porosimetry (MIP)
C10eP 40 10 Mercury intrusion porosimetry (MIP) is one of most widely used
C2 0-P 30 20
techniques for characterizing the pore size distributions in litera-
ture [32]. To assess the differences in pore structures of the cement
mortar, MIP was performed for samples with and without accel-
erated carbonation, using Micromeritics AutoPore iv 9500. Besides,
Table 3
Mix proportions of slag blended cement mortar samples. the surface part of samples was separated from samples for further
evaluation of the pore volume and pore size distributions of
Samples Binder (weight %) W/B ratio
carbonated samples. The pore diameter analyzed in this study was
Cement Slag g-C2S ranged between 0.003 and 370 mm.
A0-M 85 15 0 0.50
A5-M 80 5 3.2.4. Carbonation depth measurement
A10-M 75 10 Cement mortar samples were sealed with epoxy resin while a
A20-M 65 20
pair of two opposite rectangular surfaces were exposed before
B0-M 70 30 0
B5-M 65 5 accelerated carbonation. Then, the test samples were placed in a
B10-M 60 10 CO2 chamber (relative humidity of 60%, CO2 concentration of 5%,
B20-M 50 20 temperature of 20  C) for the accelerated carbonation. The sealed
C0-M 50 50 0
samples were cut perpendicular to the unsealed surfaces after 3, 7,
C5-M 45 5
C10-M 40 10 and 28 days of accelerated carbonation. The carbonation depths
C20-M 30 20 were measured using 1% phenolphthalein pH indicator. For each
mortar mix at each curing age, three samples were measured for
the determination of carbonation depth. To obtain as high mea-
by mass, in the replacement ratios of 15%, 30% and 50% for slag and surement accuracy as possible, 12 carbonation depth data were
replacement ratios of 0%, 5%, 10% and 20% for g-C2S, respectively. All measured for each sample and then averaged to the final carbon-
of the slag blended cement mortar samples have a sand to binder ation depth result.
(S/B) ratio of 3.0. The slag blended cement paste samples and
cement mortar samples were prepared according to KS L 5109, 4. Results and discussions
before they were cast into three 40  40  160 mm and three
35  35  10 mm moulds, respectively. 4.1. XRD results
Both slag blended cement paste and mortar samples were
demolded after 24 h. After demolded, the samples were placed in Fig. 4 and Fig. 5 depict the XRD results. From the figures, the
water (temperature of 20 ± 2  C) for curing until the age of 28 days effect of accelerated carbonation on the crystalline phase of slag
and were dried in a constant temperature chamber (relative hu- blended cement paste samples was revealed. Hydration products of
midity of 60%, temperature of 20  C) for another 28 days. After that, cement, such as ettringite and Portlandite (also referred to as CH),
a portion of the cement paste and all the cement mortar samples could be identified from the diffraction peaks in Fig. 4. The observed
was transformed into a CO2 chamber (relative humidity of 60%, CO2 diffraction peaks of quartz mainly come from cement clinkers and/
concentration of 5%, temperature of 20  C) for accelerated or synthetic g-C2S. As the g-C2S replacement ratio increased, the
carbonation curing for 28 days, whilst the remaining samples were diffraction peaks associated with g-C2S became more visible,
kept in the chamber. For clearer illustration, the accelerated especially at 2q degrees of 20.5 , 22 and 32 . The diffraction peaks
carbonation curing process and characterization methods adopted of g-C2S became conspicuous for the samples containing 10% and
for all of the paste and mortar examples in this study are tabulated 20% g-C2S. Moreover, it was found that, at the same slag replace-
in Table 4. As a supplement to the table, a flowchart describing the ment ratio, the main diffraction peaks of Portlandite decreased
investigation procedure is presented in Fig. 3. significantly at 2q degrees of 18 and 34 . Such decreases in Por-
tlandite were caused by the increasing content of g-C2S in
 Z.X. Chen et al. / Journal of Cleaner Production 262 (2020) 121385 5

Table 4
Curing process and characterization methods of the paste and mortar samples.

Curing process Characterization methods Samples

Slag blended cement paste 28 days water curing XRD A0-P B0eP C0eP
þ56 days air curing FT-IR A5-P B5eP C5eP
A10-P B10eP C10eP
A20-P B20eP C20eP
28 days water curing þ28 days air curing þ3, 7, 28 days accelerated carbonation XRD A0-PC B0-PC C0-PC
FT-IR A5-PC B5-PC C5-PC
TGA A10-PC B10-PC C10-PC
pH A20-PC 20-PC C20-PC
Slag blended cement mortar 28 days water curing þ56 days air curing MIP A0-M B0-M C0-M
A5-M B5-M C5-M
A10-M B10-M C10-M
A20-M B20-M C20-M
28 days water curing þ28 days air curing þ3, 7, 28 days accelerated carbonation pH A0-MC B0-MC C0-MC
A5-MC B5-MC C5-MC
A10-MC B10-MC C10-MC
A20-MC B20-MC C20-MC
MIP A0-MC B0-MC C0-MC
A5-MC B5-MC C5-MC
A20-MC B20-MC C20-MC

Fig. 3. Flowchart describing the investigation procedure.

Fig. 5. The XRD results of carbonated slag blended cement paste samples.
Fig. 4. The XRD results of noncarbonated slag blended cement paste samples.

replacement ratio of cement. In addition, the powder samples were
placed in open air and may react with CO2, during which CaCO3
would be formed as revealed by the diffraction peaks of calcite and
vaterite.
Substantial differences occur to the diffraction peaks after the
accelerated carbonation. First, the diffraction peaks of hydration
products were basically absent after carbonation, while the peaks
of the three polymorphs of calcium carbonate, namely, calcite,
aragonite and vaterite, became more visible, as shown in Fig. 5.
Second, the diffraction peaks of vaterite are more pronounced with
the addition of g-C2S, especially when an appropriate amount of
6 Z.X. Chen et al. / Journal of Cleaner Production 262 (2020) 121385
slag is included. Third, the combination of 5% g-C2S and 30% slag
appears to be associated with the largest increase in carbonation
product of vaterite as evidenced by narrowing difference between
peaks of calcite and vaterite. Lastly, the vaterite, calcite and
aragonite are the possible carbonation products of g-C2S for the
observed samples. Interestingly, g-C2S and vaterite have a similar
crystalline structure and their CaeO bond lengths are also similar.
Hence, the topotactic reaction of g-C2S might be prone to generate
vaterite during the accelerated carbonation. Nevertheless, discus-
sions on the main carbonation products of g-C2S are still ongoing as
the metastable phases of aragonite and vaterite tend to convert to
more stable phase of calcite.
4.2. FT-IR results
The FT-IR spectra of noncarbonated cement paste at 84 days is
shown in Fig. 6. The shapes of the FT-IR spectra of the non-
carbonated samples appeared quite similar to each other, indi-
cating that the hydration products in these samples were also quite
similar, mainly consisting of CeSeH gel, Portlandite, calcite and
vaterite etc.
The noncarbonated samples show a weak peak at 3640 cm1,
which is due to HeO stretching vibrations of Portlandite. The peaks
at approximately 1450 cm1 correspond to the asymmetric
stretching vibration of v3 CeO from three polymorphs of calcium
carbonate (calcite, vaterite, and aragonite). The peak near 970 cm1
is due to the Q2 vibration of the v2 SieO bond in the hydrate product
CeSeH which cannot be detected by XRD (Borges et al., 2010; Shi
et al., 2012).The peaks at 870 cm1 were assigned to the out-of-
plane bending vibration of v2 CeO from calcite and vaterite,
respectively. As mentioned in previous sections, the formation of
calcium carbonate is caused by the reaction of the sample with
dissolved CO2. In addition, a broad band at the interval of
650e670 cm1 can be assigned to stretching vibrations of SieOeSi
from SiO4.
Fig. 6 depicts the FT-IR spectra of the noncarbonated cement
paste samples at 84 days, while Fig. 7 depicts the FT-IR spectra of
the carbonated cement paste samples at 84 days. Comparisons
between Figs. 6 and 7 reveal the effect of carbonation on the FT-IR
spectra at various combinations of g-C2S and slag. Due to the
carbonation of Portlandite, peaks of OeH stretching vibrations
were absent at 3640 cm1. The peaks at approximately 1400 cm1,
870 cm1 were sharper and more visible compared to the FT-IR
Fig. 6. The FT-IR spectra of noncarbonated slag blended cement paste samples.
spectra of the noncarbonated samples. Moreover, new peaks
emerged at 850 cm1, 745 cm1 and 715 cm1 which are attributed
to out-of-plane bending vibration of v2 CeO from calcite and
vaterite, formation of vaterite, and the in-plane bending vibration
of v4 CeO from calcite and aragonite, respectively (Shi et al., 2012).
The appearance of the broad asymmetrical peaks at approxi-
mately 1410 cm1 demonstrated that a lower crystallinity calcium
carbonate was formed during the accelerated carbonation process.
Another interesting observation is that the peaks of the SieOeSi
band that appeared at approximately 970 cm1 in the FT-IR spec-
trum of the noncarbonated samples were shifted to approximately
1070 cm1 in the FT-IR spectrum of the carbonated samples. Such
observed phenomenon indicated that the accelerated carbonation
of CeSeH gel also contributed to the formation of amorphous sil-
icate gel (Bernal et al., 2013; Zou et al., 2020). In previous studies,
researchers have reported that the carbonation process of CeSeH
gel involved mainly two steps, namely, the dissolution of calcium
ions from the CeSeH gel structure and the formation of the
amorphous silica gel (Ashraf and Olek, 2016; Savija
and Lukovi c,
2016; Wu and Ye, 2017). However, the amorphous silica gel is
considered to contribute to the coarsening of the pore structure and
thus should be carefully controlled. Therefore, a dilemma exists
that carbonation is beneficial to g-C2S while detrimental to CeSeH
gel. Fortunately, the key to solve this problem lies in the accelerated
carbonation of g-C2S to acquire rapid surface hardening property,
after which further ingress of CO2, water and hazardous chemicals
would be unlikely to happen readily.
4.3. Quantification of CO2 capture
Completely carbonated (confirmed by 1% phenolphthalein so-
lution) cement paste samples were measured by TGA. The ther-
mogravimetric (TG) and differential thermogravimetry (DTG)
results of each sample are shown in Fig. 8 and Fig. 9. The DTG re-
sults were actually calculated from the TGA results. From Fig. 9, it
can be observed that all of the samples exhibit more or less similar
DTG patterns. The peaks appeared at range of 40e200  C are mainly
caused by the decomposition of free water and/or evaporation of
physically adsorbed water in CeSeH and/or SiO2 gel. The humps in
the region of 500e650  C and 650e750  C are due to the decom-
position of poorly crystallized CaCO3 and in the region of
750e850  C are due to the decomposition of well crystallized
CaCO3. According to previous researchers, the mass loss at
Fig. 7. The FT-IR spectra of carbonated slag blended cement paste samples.
 Z.X. Chen et al. / Journal of Cleaner Production 262 (2020) 121385 7

Fig. 9. DTG results of carbonated slag blended cement paste.

Fig. 8. TGA results of carbonated slag blended cement paste.

8 Z.X. Chen et al. / Journal of Cleaner Production 262 (2020) 121385

750e850  C was due to the decomposition of calcite, vaterite, and

aragonite. Thus, it may be considered that the mass loss occurs
between 500 and 850  C is very likely associated with the
decomposition of calcium carbonates of varying crystallinity (Mo
et al., 2017). Therefore, the mass loss in this range can be used to
evaluate the total amount of CO2 capture of the slag blended
cement paste samples during the accelerated carbonation process.
Fig. 8 shows the TGA results of the carbonated slag blended
cement paste samples. From the figure, the mass loss between 500
and 850  C was calculated and tabulated in Table 5. From the table,
it can be seen that the CO2 capture was increased dramatically by
16e31% when the slag replacement ratio was lowered down from
50% to 30%. Such increases in CO2 capture are probably due to the
increasing amount of substance for hydration. When the slag
replacement ratio was further decreased to 15%, there was a slight
increase in CO2 capture, suggesting that the addition of a suitable
amount of slag would not seriously affect the CO2 capture while the
slag content should be not set too high to avoid adverse effects.
Moreover, it was found that, at the same slag replacement ratio, the
CO2 capture would be further increased by 0.2e2.5% with the
addition of g-C2S, demonstrating the g-C2S would contribute to the
CO2 sequestration by providing more substance for reaction.

4.4. MIP results

Fig. 10 depicts the pore size distributions of the noncarbonated

area as represented by the central part of the slag blended cement
mortar samples at 84 days. Fig. 11 depicts the pore size distributions
of carbonated area which is the surface part of the slag blended
cement mortar samples at 84 days. Compared with the incremental
pore volumes of noncarbonated area shown in Fig. 10, the incre-
mental pore volumes of carbonated area shown in Fig. 11 decreased
significantly. Such decreases in incremental pore volume after
carbonation are the overall result of the negative effect brought by
the formation of amorphous SiO2 gel during the carbonation of
CeSeH gel (Morandeau et al., 2014) and the positive effect attrib-
uted to the carbonation of g-C2S (Saito et al., 2010), demonstrating
that carbonation is remarkably effective in refining the pore size
and reducing the pore volume. The densified surface would be
greatly beneficial to the resistance to further ingress of CO2 and
environmental attack.
From the figures, it can be observed that the peak incremental
pore volumes generally occurred to the capillary pores finer than
1.0 mm (Dong et al., 2017). It is also interesting to note that, for the
noncarbonated areas, although the addition of g-C2S would in-
crease the peak incremental pore volumes, the pore size corre-
sponding to the peak incremental pore volumes becomes smaller,
especially at the slag replacement ratio of 30%. Such phenomenon
suggests that the slag replacement ratio has significant influences
and there is an optimum slag replacement ratio, which is 30%
herein, for achieving the lowest pore volume and the finest pore
size.
In fact, both the slag replacement ratio and the g-C2S replace-
ment ratio would affect the pore size distributions for the non-
carbonated and carbonated areas. Generally, the addition of g-C2S

Table 5
CO2 capture results of slag blended cement paste samples at 84 days.

Samples A0-PC A5-PC A10-PC A20-PC

CO2 capture (%) 22.1 23.2 23.0 23.0

Samples B0-PC B5-PC B10-PC B20-PC
Fig. 10. Pore size distributions of central part of slag blended mortar samples (non-
CO2 capture (%) 20.9 21.1 21.4 21.2
carbonated) at 84 days.
Samples C0-PC C5-PC C10-PC C20-PC
CO2 capture (%) 15.9 18.1 18.4 18.3
 Z.X. Chen et al. / Journal of Cleaner Production 262 (2020) 121385
Fig. 11. Pore size distributions of surface part of slag blended mortar samples
(carbonated) at 84 days.
9
would increase the volume of pores, particularly the pores with size
finer than 0.1 mm, for noncarbonated areas and the peak incre-
mental pore volumes always occur to the samples with the highest
g-C2S replacement ratio. On the contrary, after carbonation, the
addition of g-C2S would not increase the pore volumes, or even
slightly decrease the pore volumes at an optimum slag replacement
ratio, indicating that the addition of g-C2S should be accompanied
by a carbonation process to avoid the formation of increased pore
volume.
4.5. Carbonation depth results
The results of carbonation depths of mortar samples are tabu-
lated in Table 6. In addition, the percentage changes in carbonation
depth compared to the C20-M, the percentage changes in carbon-
ation depth due to the addition of g-C2S and slag after carbonation
for 28 days are respectively tabulated in the last three columns of
Table 6. Fig. 12 depicts the variation of carbonation depths with the
replacement ratios of g-C2S and slag. In each graphic of the figure,
the carbonation depths of slag blended cement mortar samples
undergone 3, 7 and 28 days of accelerated carbonation are shown at
increasing g-C2S replacement ratios. From the graphics, it can be
seen that the carbonation depths of all samples increased steadily
with the time of carbonation but at various rates. Moreover, at the
same slag replacement ratio, more clear distinctions between the
carbonation depths emerged for different g-C2S replacement ratios
until a bowl-shaped trend appeared as the carbonation progressed
to a later stage. For more in-depth analysis, the carbonation depths
of slag blended mortar samples undergone acceleration carbon-
ation for 28 days were studied individually.
The carbonation depth of slag blended mortar samples under-
gone 28 days of acceleration carbonation until the age of 84 days
after casting are plotted against the replacement ratio of g-C2S in
Fig. 13(a). As indicated in the figure, the mortar samples of A0-MC,
A5-MC, A10-MC, and A20-MC exhibited more or less similar
carbonation depths at slag replacement ratio of 15%. However, at
slag replacement ratios of 30%, the samples B5-MC and B10-MC
showed the lowest carbonation depths, which were lower than
the samples B0-MC and B20-MC, and B20-MC has the highest
carbonation depth. Similar trend occurs to the mortar samples with
slag replacement ratio of 50%, indicating that g-C2S is favourable
but an excessive amount would be detrimental to the carbonation
resistance. Interestingly, when the slag replacement ratio was
increased from 15% to 30%, the carbonation depths would generally
decrease by up to 17.7%. With the further increase of slag replace-
ment ratio from 30% to 50%, the carbonation depths would gener-
ally increase by up to 38.6%, suggesting that the combined use g-
C2S and slag leads to a higher carbonation resistance that cannot be
achieved by their single use. Such phenomenon is probably caused
by the fact that the addition of an appropriate amount of g-C2S
would trigger the property of rapid surface hardening which would
be more pronounced in the presence of slag. Detailed explanations
are presented later in this section.
The above trend is also evidenced by the increase in CO2 capture
with the addition of a small amount of g-C2S beyond which there
might be a decrease in CO2 capture. Subsequently, the channels for
the further ingress of CO2 become blocked due to the formation of
more carbonation products. The highest carbonation depths of B20-
MC and C20-MC may also be explained by the hindered hydration
due to the presence of large amount of g-C2S in replacement of
cement. Moreover, the internal pH would approach neutral soon
after carbonation was initiated. From another perspective, the
lowest carbonation depths at the same replacement ratio of g-C2S
would generally occur to the mortar samples with 30% slag
replacement ratio, instead of the highest or the lowest ones.
10 Z.X. Chen et al. / Journal of Cleaner Production 262 (2020) 121385

Table 6
Carbonation depth results and percentage changes after carbonation for 28 days.

Samples Carbonation depth Percentage changes compared to C20-M Percentage changes due to the addition of g-C2S Percentage changes due to the addition of slag
(mm) (%) (%) (%)

3 7 28
days days days

A0-M 3.16 3.66 8.66 44.3 e e

A5-M 3.41 3.52 8.52 46.7 1.6 e
A10-M 3.29 3.53 8.71 43.5 0.6 e
A20-M 3.34 4.04 9.02 38.6 4.1 e
B0-M 3.55 3.90 8.20 52.5 e 5.3
B5-M 3.44 4.03 7.01 78.3 14.5 17.7
B10-M 3.22 4.00 7.50 66.7 8.5 13.9
B20-M 4.44 4.68 9.59 30.4 16.9 6.3
C0-M 3.88 4.26 10.01 24.9 e 22.1
C5-M 2.52 3.79 8.81 41.9 12.0 3.4
C10-M 3.40 4.03 10.52 18.8 5.1 20.8
C20-M 3.86 4.90 12.50 e 24.9 38.6

Overall, there exists an optimum combination of g-C2S and slag
that yields the lowest carbonation depth, from which certain
coupling effect between g-C2S and slag could be explored.
Compared with sample C20-M, the optimum combination of g-C2S
and slag brings about 78% decrease in carbonation depth, which is
indeed significant. To vividly illustrate the coupling effect, the
percentage changes in carbonation depth arising from the inclusion
of g-C2S and slag are plotted in Fig. 13(b). From the figure, it can be
seen that the coupling effect becomes more pronounced as the slag
content is adjusted into a suitable range. However, when the g-C2S
replacement ratio exceeds 10%, there is a high possibility that the
carbonation depth would increase, especially at an inadequate or
excessive slag content. Therefore, the replacement ratios of g-C2S
and SCM should be carefully controlled to exploit their coupling
effect in the development of carbonation immune cement-based
low carbon materials.
Possible mechanism behind these phenomena is elaborated
herein. To vividly illustrate the mechanism, a conceptual model, as
depicted in Fig. 14, is proposed with reference to previous research
(Ashraf and Olek, 2018a; Mu et al., 2018a). First, water transverses
the capillary pores and forms a thin film surrounding the g-C2S
particle, enabling the dissolution of gaseous CO2 into weakly acidic
H2CO3 solution. Second, the topotactic reaction of g-C2S particle
with H2CO3 leads to the precipitation of CaCO3, incurring the for-
mation of silica gel adhering to the surface of g-C2S particle.
However, it should be noted that a lower alkalinity of the solution,
as indicated by the lighter blueness, might be favourable to the
existence of H2CO3 and better functioning of water as catalyst in the
dynamic equilibrium process. As the silica gel becomes thick
enough, the carbonation reaction is gradually slowing down.
Eventually, a sandwich structure with non-carbonated g-C2S as
core, silica gel as intermediate layer and CaCO3 as shell forms.
Different from that in the hydration process, the water in the
carbonation process mainly acts as catalyst (Ashraf and Olek,
2018a). Owing to the rapid reaction, the carbonation products
may be enveloped with the adjacent ones and jointly contribute to
the rapid surface hardening.
Macroscopically, during the carbonation process of the samples,
an excessively high alkalinity would destroy the weak acid envi-
ronment provided by dissolved CO2 and be inconducive to the
formation of carbonation products for densified surface. An
appropriate amount of slag would be helpful in lowering the
alkalinity for better catalyst effect of water. Otherwise, a larger
amount of CO2 would be invaded through the surface that has not
been densified into a deeper area and eventually lead to a larger
carbonation depth. Above all, the inclusion of g-C2S in conjunction
with slag would offer certain coupling effect on carbonation
resistance. Moreover, there exists an optimum combination be-
tween g-C2S and slag for achieving the highest carbonation resis-
tance and the paste, mortar or concrete exhibiting such properties
could be viewed as carbonation immune cement-based low carbon
materials.
5. Conclusions
In this paper, to maximize the durability and minimize the
environmental impact, the possible coupling effect arising from the
combined use of g-C2S and slag was systematically investigated. On
one hand, g-C2S exhibits low hydraulic but high carbonation
reactivity. Compared to ordinary Portland cement, g-C2S generates
less CO2 and capture more CO2. On the other hand, the partial
replacement of cement by SCMs could lower down the cement
consumption but might render the concrete more vulnerable to
carbonation. Apart from the sustainability, the combined use of g-
C2S and slag has great potential to give rise to unprecedented
properties than their individual use and such potential has been
underestimated or ignored up to now. The inclusion of g-C2S might
counteract the negative effect brought by the addition of slag and
partially restore the carbonation resistance of cement-based ma-
terials. Meanwhile, the slag could provide appropriate environment
to facilitate the rapid surface hardening process that eventually
gives rise to carbonation immunity. To explore such mechanism,
the carbonation behaviors of 15%, 30% and 50% slag blended
cement-based materials incorporating 0%, 5%, 10% and 20% of g-C2S
were evaluated by XRD, FT-IR, TGA, MIP and carbonation depth
tests in this paper. Based on the above investigations, the following
conclusions could be drawn.
1. High purity synthetic g-C2S was manufactured and incorporated
into slag blended paste and mortar mixtures. Accelerated
carbonation of the samples under a relatively low CO2 concen-
tration of 5% shall emancipate the practical production from the
use of special equipment providing high CO2 concentration and
better enable the large-scale concrete production incorporating
g-C2S.
2. XRD and FT-IR analysis identified the formation of CaCO3 in
various polymorphs (calcite, aragonite, and vaterite) in the
cement paste after accelerated carbonation and vaterite as one
of the main carbonation products. The combined use of g-C2S
and slag gives rise to a larger increase in the amount of vaterite.
FT-IR revealed that accelerated carbonation is beneficial to g-C2S
 Z.X. Chen et al. / Journal of Cleaner Production 262 (2020) 121385
Fig. 12. Carbonation depths of slag blended mortar samples.
11
Fig. 13. Percentage change in carbonation depth due to addition of g-C2S and slag.
while detrimental to CeSeH gel as the carbonation of CeSeH
gel might lead to the formation of amorphous silicate gel.
3. TGA analysis showed that the CO2 capture increased by 16e31%
when the slag content was lowered down from 50% to 30%, and
that at the same slag content, the addition of g-C2S would
further increase the CO2 capture by 0.2e2.5%. In other words, an
optimum combination of g-C2S and slag exists such that g-C2S
would best contribute to the CO2 capture at an appropriate
amount of slag.
4. MIP analysis revealed that carbonation is remarkably effective in
refining the pore size, reducing the pore volume and providing
barriers to further ingress of CO2 and environmental attack. In
addition, there exists an optimum g-C2S and slag content for
achieving the lowest pore volume and the finest pore size. The
MIP results also revealed that the addition of g-C2S should be
accompanied by an accelerated carbonation process to avoid the
formation of increased pore volume.
5. An optimum combination of g-C2S and slag exists for achieving
the lowest carbonation depth, which is 5% g-C2S and 30% slag in
replacement of cement. At given slag content, the addition of g-
C2S would decrease the carbonation depth by up to 14.5%; while
at given g-C2S content, the addition of slag would decrease the
12 Z.X. Chen et al. / Journal of Cleaner Production 262 (2020) 121385
Fig. 14. Conceptual model for carbonation of g-C2S in presence of slag.
carbonation depth by up to 17.7%. Compared with the sample
C20-M, the optimum combination of g-C2S and slag brings
about 78% decrease in carbonation depth, which is indeed sig-
nificant. Hence, in practice, the replacement ratios of g-C2S and
slag should be carefully controlled to better exploit their
coupling effect on durability and sustainability.
6. A conceptual model is presented to elucidate the possible
mechanism behind the coupling effect. The addition of g-C2S
would more effectively trigger the property of rapid surface
hardening in the presence of slag while an excessively high g-
C2S content might induce negative effect. An appropriate
amount of slag would lower down the alkalinity of the mixture
for the better functioning of water as catalyst during the
carbonation of g-C2S.
Overall, the accelerated carbonation favored by the coupling
effect of g-C2S and slag was evidenced by the shallower carbon-
ation depth, finer pore size and reduced pore volume at an opti-
mum combination. The rapid surface hardening arising from the
accelerated carbonation would serve as a strong barrier to the
possible chloride and sulfate attack at early age and contribute to
improved durability at a later age. Such cement-based materials
may be defined as carbonation immune cement-based/concrete
(CIC) materials. It should be noted that the benefits of rapid sur-
face hardening would be more pronounced in strain-hardening
cementitious materials as fibres would refrain CIC from possible
crack localization (Chu et al., 2018; Chu et al., 2019; Chu and Kwan,
2019; Kwan and Chu, 2018; Li et al., 2018). Nevertheless, limitations
still exist in this research that a broader range of attributes,
including but not limited to mechanical strength, has not been
assessed and linked to the chemical and physical changes. Further
research is expected to explore the mechanisms behind the overall
materials properties of CIC and its potentials in prefabrication.
Declaration of competing interest
The authors declare no conflicts of interest.
CRediT authorship contribution statement
Z.X. Chen: Conceptualization, Investigation, Writing - original
draft. S.H. Chu: Conceptualization, Writing - original draft, Visual-
ization, Writing - review & editing. Y.S. Lee: Investigation, Data
curation. H.S. Lee: Conceptualization, Supervision, Funding
acquisition.
Acknowledgements
This research was partially supported by a grant
(19SCIPeB103706-05) from Construction Technology Research
Program funded by Ministry of Land, Infrastructure and Transport,
Government of South Korea. Necessary assistances provided by Mr.
S. Ishak and Mr. H. Cho during the experiments are appreciated.
References
Ashraf, W., 2016. Carbonation of cement-based materials: challenges and oppor-
tunities. Construct. Build. Mater. 120, 558e570.
Ashraf, W., 2018. Microstructure of chemically activated gamma-dicalcium silicate
paste. Construct. Build. Mater. 185, 617e627.
Ashraf, W., Olek, J., 2016. Carbonation behavior of hydraulic and non-hydraulic
calcium silicates: potential of utilizing low-lime calcium silicates in cement-
based materials. J. Mater. Sci. 51 (13), 6173e6191.
Ashraf, W., Olek, J., 2018a. Carbonation activated binders from pure calcium sili-
cates: reaction kinetics and performance controlling factors. Cement Concr.
Compos. 93, 85e98.
Ashraf, W., Olek, J., 2018b. Elucidating the accelerated carbonation products of
calcium silicates using multi-technique approach. J. CO2 Util. 23, 61e74.
Bentz, D.P., Ardani, A., Barrett, T., Jones, S.Z., Lootens, D., Peltz, M.A., Sato, T.,
Stutzman, P.E., Tanesi, J., Weiss, W.J., 2015. Multi-scale investigation of the
performance of limestone in concrete. Construct. Build. Mater. 75, 1e10.
Bernal, S.A., Provis, J.L., Walkley, B., San Nicolas, R., Gehman, J.D., Brice, D.G.,
Kilcullen, A.R., Duxson, P., van Deventer, J.S.J., 2013. Gel nanostructure in alkali-
activated binders based on slag and fly ash, and effects of accelerated carbon-
ation. Cement Concr. Res. 53, 127e144.
Borges, P.H.R., Costa, J.O., Milestone, N.B., Lynsdale, C.J., Streatfield, R.E., 2010.
Carbonation of CH and CeSeH in composite cement pastes containing high
amounts of BFS. Cement Concr. Res. 40 (2), 284e292.
Burciaga-Díaz, O., Escalante-García, J.I., Rigaud, M., 2013. Structure, mechanisms of
reaction, and strength of an alkali-activated blast-furnace slag. J. Am. Ceram.
Soc. 96 (12), 3939e3948.
Chang, J., Fang, Y., Shang, X., 2016. The role of b-C2S and g-C2S in carbon capture and
strength development. Mater. Struct. 49 (10), 4417e4424.
Choi, H., Inoue, M., Sengoku, R., 2018. Change in crystal polymorphism of CaCO3
generated in cementitious material under various pH conditions. Construct.
Build. Mater. 188, 1e8.
Chu, S.H., 2019. Effect of paste volume on fresh and hardened properties of con-
crete. Construct. Build. Mater. 218, 284e294.
Chu, S.H., Jiang, Y., Kwan, A.K.H., 2019. Effect of rigid fibres on aggregate packing.
Construct. Build. Mater. 224, 326e335.
Chu, S.H., Kwan, A.K.H., 2019a. Co-addition of metakaolin and silica fume in mortar:
effects and advantages. Construct. Build. Mater. 197, 716e724.
Chu, S.H., Kwan, A.K.H., 2019b. Mixture design of self-levelling ultra-high perfor-
mance FRC. Construct. Build. Mater. 228, 116761.
Chu, S.H., Kwan, A.K.H., 2019. A new bond model for reinforcing bars in steel fibre
reinforced concrete. Cement Concr. Compos. 104, 103405.
Chu, S.H., Li, L.G., Kwan, A.K.H., 2018. Fibre factors governing the fresh and hardened
properties of steel FRC. Construct. Build. Mater. 186, 1228e1238.
Diaz-Loya, I., Juenger, M., Seraj, S., Minkara, R., 2019. Extending supplementary
cementitious material resources: reclaimed and remediated fly ash and natural
pozzolans. Cement Concr. Compos. 101, 44e51.
Dong, H., Gao, P., Ye, G., 2017. Characterization and comparison of capillary pore
 Z.X. Chen et al. / Journal of Cleaner Production 262 (2020) 121385
structures of digital cement pastes. Mater. Struct. 50 (2), 154.
Elhoweris, A., Galan, I., Glasser, F.P., 2018. Stabilisation of a0 dicalcium silicate in
calcium sulfoaluminate clinker. Adv. Cement Res. 1e13.
Falikman, V., Realfonzo, R., Coppola, L., Ha jek, P., Riva, P., 2018. SP-326: durability
and sustainability of concrete structures (DSCS-2018). ACI Spec. Publ. 326, 1192.
N.A. Garrault, S., 2001. Hydrated layer formation on tricalcium and dicalcium sili-
cate surfaces experimental study and numerical simulations Langmuir 17,
8131e8138.
Gartner, E., Hirao, H., 2015. A review of alternative approaches to the reduction of
CO2 emissions associated with the manufacture of the binder phase in concrete.
Cement Concr. Res. 78, 126e142.
Ghouleh, Z., Guthrie, R.I.L., Shao, Y., 2015. High-strength KOBM steel slag binder
activated by carbonation. Construct. Build. Mater. 99, 175e183.
Gruyaert, E., Van den Heede, P., De Belie, N., 2013. Carbonation of slag concrete:
effect of the cement replacement level and curing on the carbonation coeffi-
cient e effect of carbonation on the pore structure. Cement Concr. Compos. 35
(1), 39e48.
Guan, X., Liu, S., Feng, C., Qiu, M., 2016. The hardening behavior of g-C2S binder
using accelerated carbonation. Construct. Build. Mater. 114, 204e207.
Higuchi, T., Morioka, M., Yoshioka, I., Yokozeki, K., 2014. Development of a new
ecological concrete with CO2 emissions below zero. Construct. Build. Mater. 67,
338e343.
Humbert, P.S., Castro-Gomes, J., 2019. CO2 activated steel slag-based materials: a
review. J. Clean. Prod. 208, 448e457.
Jiang, Y., Ling, T.C., Shi, C.J., Pan, S.Y., 2018. Characteristics of steel slags and their use
in cement and concreteda review. Resour. Conserv. Recycl. 136, 187e197.
Kim, G., Kim, J.-Y., Kurtis, K.E., Jacobs, L.J., Le Pape, Y., Guimaraes, M., 2014. Quan-
titative evaluation of carbonation in concrete using nonlinear ultrasound.
Mater. Struct. 49 (1e2), 399e409.
Kriskova, L., Pontikes, Y., Zhang, F., Cizer, O., € Jones, P.T., Van Balen, K., Blanpain, B.,
2014. Influence of mechanical and chemical activation on the hydraulic prop-
erties of gamma dicalcium silicate. Cement Concr. Res. 55, 59e68.
Kwan, A.K.H., Chu, S.H., 2018. Direct tension behaviour of steel fibre reinforced
concrete measured by a new test method. Eng. Struct. 176, 324e336.
Li, L.G., Chu, S.H., Zeng, K.L., Zhu, J., Kwan, A.K.H., 2018. Roles of water film thickness
and fibre factor in workability of polypropylene fibre reinforced mortar. Cement
Concr. Compos. 93, 196e204.
Liu, J., Qiu, Q., Chen, X., Xing, F., Han, N., He, Y., Ma, Y., 2017. Understanding the
interacted mechanism between carbonation and chloride aerosol attack in or-
dinary Portland cement concrete. Cement Concr. Res. 95, 217e225.
Lu, B., Shi, C., Hou, G., 2018. Strength and microstructure of CO2 cured low-calcium
clinker. Construct. Build. Mater. 188, 417e423.
Mabudo, G.M., Lee, S., Kang, S., Song, M., 2016. Physical properties and carbon di-
oxide capture of synthetic gamma-C2S cement composites in the early days of
curing. Mag. Concr. Res. 68 (21), 1079e1084.
Miller, S.A., Myers, R.J., 2020. Environmental impacts of alternative cement binders.
Environ. Sci. Technol. 54 (2), 677e686.
Mo, L., Zhang, F., Panesar, D.K., Deng, M., 2017. Development of low-carbon
cementitious materials via carbonating Portland cementefly ashemagnesia
blends under various curing scenarios: a comparative study. J. Clean. Prod. 163,
252e261.
Moon, E.-J., Choi, Y.C., 2019. Carbon dioxide fixation via accelerated carbonation of
cement-based materials: potential for construction materials applications.
Construct. Build. Mater. 199, 676e687.
Morandeau, A., Thie ry, M., Dangla, P., 2014. Investigation of the carbonation
mechanism of CH and C-S-H in terms of kinetics, microstructure changes and
moisture properties. Cement Concr. Res. 56, 153e170.
Morioka, M., Yamamoto, K., Torichigai, T., Yokozeki, K., 2010. Manufacturing of g-C2S
used by industrial raw material and its evaluation of CO2 emission. Cem. Sci.
Concr. Technol. 64, 29e34.
Mu, Y., Liu, Z., Wang, F., 2019. Comparative study on the carbonation-activated
calcium silicates as sustainable binders: reactivity, mechanical performance,
and microstructure. ACS Sustain. Chem. Eng. 7 (7), 7058e7070.
Mu, Y., Liu, Z., Wang, F., Huang, X., 2018a. Carbonation characteristics of g-dicalcium
silicate for low-carbon building material. Construct. Build. Mater. 177, 322e331.
Mu, Y., Liu, Z., Wang, F., Huang, X., 2018b. Effect of barium doping on carbonation
behavior of g-C2S. J. CO2 Util. 27, 405e413.
Na, S., Kang, S., Lee, S., Song, M., 2015. Gamma-C2S synthesis from fly ash of fluidize-
bed boiler for CO2 capture. Acta Phys. Pol., A 127 (4), 1282e1285.
€
Ozbay, E., Erdemir, M., Durmuş, H.I., _ 2016. Utilization and efficiency of ground
granulated blast furnace slag on concrete properties e a review. Construct.
Build. Mater. 105, 423e434.
13
Pan, X., Shi, C., Hu, X., Ou, Z., 2017. Effects of CO2 surface treatment on strength and
permeability of one-day-aged cement mortar. Construct. Build. Mater. 154,
1087e1095.
Parrott, L.J., 1990. Damage caused by carbonation of reinforced concrete. Mater.
Struct. 23 (3), 230e234.
Phung, Q.T., Maes, N., Jacques, D., Bruneel, E., Van Driessche, I., Ye, G., De
Schutter, G., 2015. Effect of limestone fillers on microstructure and permeability
due to carbonation of cement pastes under controlled CO2 pressure conditions.
Construct. Build. Mater. 82, 376e390.
Rashad, A.M., 2018. An overview on rheology, mechanical properties and durability
of high-volume slag used as a cement replacement in paste, mortar and con-
crete. Construct. Build. Mater. 187, 89e117.
Saito, T., Sakai, E., Morioka, M., Daimon, M., 2007. Carbonation reaction of Calcium
silicate hydrates by hydrothermal synthesis at 150 C in OPC-g-Ca2SiO4-a-
Quartz. J. Adv. Concr. Technol. 5 (3), 333e341.
Saito, T., Sakai, E., Morioka, M., Otsuki, N., 2010. Carbonation of g-Ca2SiO4 and the
mechanism of vaterite formation. J. Adv. Concr. Technol. 8 (3), 273e280.
Salman, M., Cizer, O., Pontikes, Y., Snellings, R., Vandewalle, L., Blanpain, B., Van
Balen, K., 2015. Cementitious binders from activated stainless steel refining slag
and the effect of alkali solutions. J. Hazard Mater. 286, 211e219.
Salman, M., Cizer, O.,€ Pontikes, Y., Vandewalle, L., Blanpain, B., Van Balen, K., 2014.
Effect of curing temperatures on the alkali activation of crystalline continuous
casting stainless steel slag. Construct. Build. Mater. 71, 308e316.
Salvoldi, B.G., Beushausen, H., Alexander, M.G., 2015. Oxygen permeability of con-
crete and its relation to carbonation. Construct. Build. Mater. 85, 30e37.
Sanna, A., Uibu, M., Caramanna, G., Kuusik, R., Maroto-Valer, M.M., 2014. A review of
mineral carbonation technologies to sequester CO2. Chem. Soc. Rev. 43 (23),
8049e8080.
Saphouvong, K., Saito, T., Otsuki, N., Yumoto, T., 2012. Corrosion of steel bars in
autoclaved concrete pile containing g-2CaO$SiO2 with an accelerated carbon-
ation. J. Soc. Mater. Sci. 61 (3), 299e307.


Savija, B., Lukovic, M., 2016. Carbonation of cement paste: understanding, chal-
lenges, and opportunities. Construct. Build. Mater. 117, 285e301.
Schmidt, W., Alexander, M., John, V., 2018. Education for sustainable use of cement
based materials. Cement Concr. Res. 114, 103e114.
Shah, V., Bishnoi, S., 2018. Carbonation resistance of cements containing supple-
mentary cementitious materials and its relation to various parameters of con-
crete. Construct. Build. Mater. 178, 219e232.
Shi, C., Hu, S., 2003. Cementitious properties of ladle slag fines under autoclave
curing conditions. Cement Concr. Res. 33 (11), 1851e1856.
Shi, C., Liu, M., He, P., Ou, Z., 2012. Factors affecting kinetics of CO2 curing of con-
crete. J. Sustain. Cem. Based Mater. 1 (1e2), 24e33.
Shi, C.J., 2002. Characteristics and cementitious properties of ladle slag fines from
steel production. Cement Concr. Res. 32, 459e462.
Shi, C.J., 2004. Steel slagdits production, processing, characteristics. J. Mater. Civ.
Eng. 16 (3), 230e236.
Sung, M.-J., Cho, H.-K., Lee, H.-S., 2015. Properties of cement paste containing high
volume g-C2S and MgO subjected to CO2 curing. J. Korea. Inst. Build. Constr. 15
(3), 281e289.
Wang, X.-Y., Lee, H.-S., 2019. Effect of global warming on the proportional design of
low CO2 slag-blended concrete. Construct. Build. Mater. 225, 1140e1151.
Wang, X., Ni, W., Li, J., Zhang, S., Hitch, M., Pascual, R., 2019. Carbonation of steel slag
and gypsum for building materials and associated reaction mechanisms.
Cement Concr. Res. 125, 105893.
Wu, B., Ye, G., 2017. Development of porosity of cement paste blended with sup-
plementary cementitious materials after carbonation. Construct. Build. Mater.
145, 52e61.
Xuan, D., Zhan, B., Poon, C.S., 2016. Development of a new generation of eco-friendly
concrete blocks by accelerated mineral carbonation. J. Clean. Prod. 133,
1235e1241.
Yang, Y., Zhan, B., Wang, J., Zhang, Y., 2020. Nondestructive assessment of the
compressive strength of concrete with high volume slag. Mater. Char. 162,
110223.
Yip, C.K., Lukey, G.C., van Deventer, J.S.J., 2005. The coexistence of geopolymeric gel
and calcium silicate hydrate at the early stage of alkaline activation. Cement
Concr. Res. 35 (9), 1688e1697.
Zhou, X., Mu, Y., Liu, Z., Wang, F., 2018. Fabrication and characterization of a novel
carbonated 0-3 piezoelectric g-C2S composite. Ceram. Int. 44 (11),
13426e13429.
Zou, F., Hu, C., Wang, F., Ruan, Y., Hu, S., 2020. Enhancement of early-age strength of
the high content fly ash blended cement paste by sodium sulfate and CeSeH
seeds towards a greener binder. J. Clean. Prod. 244, 118566.