Cement and Concrete Research 124 (2019) 105834

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Cement and Concrete Research

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

Recent advance of chemical admixtures in concrete T

a b,⁎ b a,b b
J. Liu , C. Yu , X. Shu , Q. Ran , Y. Yang
a
School of Material Science and Engineering, Southeast University, China
b
State Key Laboratory of High Performance Civil Engineering Materials, Sobute New Materials Co., Ltd., China

ARTICLE INFO ABSTRACT

Keywords: Recent advance on chemical admixtures and their influence on the concrete properties is summarized. The
Admixture conformational properties of PCE molecules both in solution and on the surface of cement have been studied by
Molecular structure computational simulations. Then the effect of molecular structure of PCE on the compatibility and rheological
Cracking resistance properties of cementitious materials is discussed. The research progress on admixtures to mitigate the shrinkage
C-S-H/PCE nanocomposites
and cracking risk of concrete is also introduced, including magnesia based expansive agent (MEA), super-
absorbent polymers (SAP), and a novel starch-based materials temperature rise inhibitor (TRI). Finally, the
development of C-S-H PCE nano composites and their effect on the early age hydration of cementitious materials
is reviewed. Advanced quantitative micro-analytical methods and computational modelling are helping us to
understand the action mechanism of chemical admixtures and leading to the performance based molecular and
microstructure design, which strongly promote the application of admixtures in high performance concrete.

1. Introduction relatively small size, the actual adsorption conformation of PCEs in

As an essential component of concrete, different types of chemical
admixtures have been widely applied to improve properties. Chemical
admixtures enable the manufacture and construction of high perfor-
mance ready-mix and also precast concretes [1,2]. This paper reviews
recent developments and research on chemical admixtures and their
applications, main focusing on polycarboxylate superplasticizers (PCE),
admixtures to improve the cracking resistance of concrete, and C-S-H/
PCE nanocomposites to increase the early strength. It aims to give some
new insights into the relationship between molecular structure or
chemical composition of admixtures and the macro behavior of con-
crete.
Since its invention in 1981, PCE has brought about numerous
technological advances for the modern concrete industry and also been
widely applied in the concrete construction. Taking China as an ex-
ample, in 2017 the consumption of PCE was 7.23 million tons, which
was about 77.6% of all water reducing admixtures used in that country.
PCE compositions and synthesis methods were reviewed in the last
ICCC Conference in Beijing 2015 [1]. Beside the continued develop-
ment of molecular structure, such as the introduction of phosphate
groups and new side chains, more researchers and engineers are ded-
icating to understand the action mechanism of PCE in cementitious
materials, and trying to establish the relationship between molecular
structure and its impact on the properties of fresh concrete. Owing its
cementitious materials is difficult to be determined in an empirical way.
Therefore, computational simulations have been introduced as a pow-
erful method to study the conformational behavior of PCEs in pore
solution and also the adsorption behavior on the mineral interface of
cement at the molecular and atomic level. These developments are
discussed in the first section of this paper. In addition, our under-
standing of the compatibility between admixtures and cementitious
materials is also reviewed. Then, an overview on the links between
chemical structure of PCE and rheology behavior of cementitious ma-
terials is presented.
Early age cracking caused by shrinkage may accelerate the ingress
of aqueous solutions and other mediums into concrete, leading to a
reduced durability of concrete. The risk of early age cracking increases
due to the increasing application of high-strength concrete or high-
performance concrete (HPC), which has a lower water to binder ratio
and a higher susceptibility to cracking [3]. In order to mitigate or even
eliminate the adverse impact caused by shrinkage and cracking, various
methods, including construction processes, curing technology, and
novel materials have been studied. In the second section, the research
progress of three different chemical admixtures to mitigate the
shrinkage and cracking risk of concrete is reviewed. First, the magnesia
based expansive agent (MEA), which may be applied to generate ex-
pansion and compensate the thermal shrinkage during the stage when
the temperature is dropping. Second, Superabsorbent polymers (SAP)

⁎
Corresponding author.
E-mail address: yucheng@cnjsjk.cn (C. Yu).

https://doi.org/10.1016/j.cemconres.2019.105834
Received 29 June 2019; Received in revised form 25 July 2019; Accepted 29 July 2019
Available online 15 August 2019
0008-8846/ © 2019 Published by Elsevier Ltd.
J. Liu, et al.
are used to reduce autogenous shrinkage. Finally, novel starch-based
materials so called temperature rise inhibitor (TRI) are introduced,
which can reduce the hydration heat of concrete without long term
negative effects on the strength development.
Recent progress in nanotechnology has brought technological in-
novation and industry transformation to the traditional cement in-
dustry. Synthetic C-S-H nano particles have attracted considerable sci-
entific interest in recent years and appear to be a promising and
realistic approach to efficiently improve the mechanical properties of
concrete, especially at early age. Therefore, in the third part, the pro-
gress of C-S-H/PCE nanocomposites is reviewed, including the pre-
paration, application and its mechanism of action on the hydration of
cement.
2. Research advances in polycarboxylate superplasticizer
2.1. Conformational properties of PCE by computational simulations
Recently, computational simulations at the molecular level have
attracted researchers' attention and have become a powerful tool to
study the conformational properties of polymer molecules in solution
and at liquid-solid interfaces at the microscopic level. The methods used
include first-principle calculations [4–6] and all-atom molecular dy-
namics (MD) simulations [7].
The binding of Ca2+ with different groups of superplasticizers, in-
cluding phosphonate, phosphate, carboxylate, sulfonic, sulfate and
hydroxyl, was investigated by DFT methods and it was found that the
binding strength of Ca2+ with those groups decreases in the order,
phosphonate > phosphate > carboxylate > sulfonate > sulfate >
alkoxide ≈ water [5]. An explicit solution for the adsorption of car-
boxylate, sulfonate, and phosphate on the calcite (1 0 4) surface was
studied by all-atom MD simulations and the adsorption strength of the
three small molecules on the calcite (1 0 4) surface in aqueous solution
decreases in the order phosphate > carboxylate > sulfonate [6]. The
binding strength of Ca2+ with the functional groups of PCEs obtained
by computational simulation could be correlated with experimental
data [8–10] . For practical applications of superplasticizers in cement
systems, polycarboxylate containing –COO– group are known to behave
better than the conventional cement dispersants containing -SO3-
group. The more recent generations of admixtures, containing phos-
phonates or phosphate groups, are promising candidates for further
improving the dispersing performance of conventional PCEs, or even
bringing appealing functions such as slump-retention and viscosity re-
duction. However, one should bear in mind that, there remain a larger
number of other design parameters including the number and the
density of the adsorbing groups, the side-chain length and grafting
density, etc. to guide the performance of superplasticizers. The ad-
sorption strength among the three types of functional groups follows
the same order as the binding strength with Ca2+ obtained from DFT
calculations; both results corroborate a similar rule-of-thumb estab-
lished by experiments. And those functional groups have the same
characteristics of the adsorption conformation, namely just two oxygen
atoms of two adjacent anchor groups adsorb on the calcium atoms on
the top layer of the crystal, as shown in Fig. 1.
Using all-atom MD simulations, the effects of counter-ion species,
such as Ca2+, solution pH, content of methyl groups, and hydrophobic
modifications on the conformational properties of PCE superplasticizers
in solution were explored and the adsorption conformations of hydro-
phobically-modified comb-shaped PCE superplasticizer were in-
vestigated. Counter-ion species, such as Ca2+, enable collapse or ag-
gregation of PCE due to the electrostatic interaction between the
counter-ion and charged groups of PCE [7] (as shown in Fig. 2), and
high solution pH results in the stretch of PCE due to the electrostatic
repulsion between the charged groups of PCE [11].
Methyl group substituted on the polymer backbone increase the
stiffness of polymer backbone, which resulted in a lower extent of
2
Cement and Concrete Research 124 (2019) 105834
conformation shrinkage in the pore solution and more carboxylic
groups could be exposed [12]. Hydrophobic modifications to the
backbone led to a more coiled PCE conformation, a lower adsorption
affinity and a smaller pervaded volume at the interface, as shown in
Fig. 3 [13–15]. Explicit solutions were calculated for the absorption on
a model surface of calcium silicate (C2S) of three different hydrophobic
modifying groups, namely, the ethyl group, the n-butyl group and the
phenyl group, decorated on the backbone(PCE2, PCE3 and PCE4),
along with a common PCE (PCE1). Compared to the hydrophobically
modified ones, the control (PCE1) possessed a larger in-plane radius but
a smaller adsorption layer thickness. The modified ones, PCE2, PCE3,
and PCE4, possessed similar in-plane radii. The trend of the dependence
of binding on the four PCE molecules was similar between vacuum and
solution-based simulations, and the order of binding stayed as
PCE1 > PCE3 > PCE4 > PCE2. These studies driven by experi-
mental work also carried during the product development have, in re-
turn, provided useful information for an improved understanding of
experimental phenomena.
The conformational properties of comb-like PCE studied by ato-
mistic MD simulations are rarely reported, especially the adsorption
behaviors at solid-liquid interfaces. Recently, Hirata et al. studied the
solution behavior and adsorbed conformations of three common PCE
molecules by atomistic MD simulations [16,17]. It showed the collapse
of PCE conformation in cement pore solution, PCE molecules initially
placed parallel/perpendicularly against the MgO surface gradually form
a train shaped or a loop and tail adsorption profile, respectively. The
molecular weights of the simulated comb-shaped PCE molecules in
their atomistic MD simulations were close to that used in mini slump
experiments, with explicit representation of water molecules and ions.
However, in this case, many atoms are included in the simulation sys-
tems and a great deal of calculations is needed to give reliable results.
Therefore, the polymer chains are much smaller than the realistic mo-
lecules and the simulation times are shorter. For this reason, the global
conformational properties cannot be accurately investigated by those
atomistic-level MD simulations. Theoretical models and coarse-grained
MD simulations for the conformations of comb copolymers in solution
and on surfaces would be useful to research the global conformation of
PCE [19–23]. However, the development of a special coarse-grained
model mapped on PCE and the comparison of the simulation results
with experiment have been seldom undertaken.
Those conformation results are valuable to understand, at the mi-
croscopic level, the properties of PCE in cement and for the computer-
aid design of new polymeric dispersant molecules with an improved
performance. Conformation properties of PCE in solution and at inter-
face are complex and any method is not omnipotent to solve all the
problems. A multi-level approach, starting from DFT calculations to
resolve atomic charges and detailed interactions between functional
groups of superplasticizers and the characteristic ions (e.g. Ca2+) in the
system, followed by atomistic MD simulations to resolve adsorbing
energy, local adsorbed conformations and water arrangements, and
maybe even further followed by coarse-grained MD simulations and
analytical theory of polymers at interfaces, would be beneficial to un-
derstand the working mechanisms of superplasticizers as well as other
chemical admixtures at the microscopic level and to the development of
computer-aided admixture design and optimization. Some microscopic
experimental techniques, such as dynamic and static light scattering,
small-angle neutron scattering atomic force microscope, can be per-
formed that together with simulation tools and analytical theory give
more insights into the PCEs conformation.
2.2. Compatibility between admixtures and cementitious materials
The compatibility of polycarboxylate superplasticizers with com-
ponents of concrete (cement, aggregate, supplementary cementitious
materials, SCMs) has been a big problem during application. So-called,
“incompatibility” of superplasticizers with these materials results in
J. Liu, et al. Cement and Concrete Research 124 (2019) 105834

Fig. 1. The complexes of three monomers (carboxylate, sulfonate, and phosphate) with Ca2+ optimized at the B3LYP/6-311+G(d,p) level of theory and the last
snapshots for the three monomers adsorbed on the calcite (1 0 4) surface simulated by all-atom MD simulations.

unfavorable performance of cementitious material, including low initial
slump, bleeding and segregation, rapid slump loss, flash set, and set
retardation [24–28]. As indicated by many other reports [29,30], the
rheological property was determined by the interaction (especially the
colloidal interaction) between solid particles and also the intrinsic
property of these particles. The enhancement of the interaction, either
through the bridging of particles by hydration products (e.g. CSH nu-
cleation), or the formation of stronger particle network [31], would
reduce the workability (increase of yield stress, thixotropy), and finally
cause the hardening of the cementitious material. In the presence of
superplasticizers, the surfaces with polymer adsorbed would keep
particle away from each other through steric repulsion. The de-
flocculation process [32] released large amount of water decreasing the
effective solid volume fraction and thereby improve the workability.
The distribution of polymer molecules and the interaction with particles
would greatly affect the workability of cementitious material.
The mix proportion, temperature, crystal structure of the mineral
phase, the fineness, and the extent of prehydration [33] influenced the
hydration process and thereby the performance of superplasticizers.
Rapid hydration would always cause a lot of workability problems.
Cement of finer particle size distribution require higher amount of
water to achieve the same consistency. While, the admixture might be
more effective for the fresh state property of mixture with cement of
higher fineness can be improved by adding high range water-reducing
admixtures [34]. This seems to be caused from the higher adsorption of
the admixture on finer cement grains than on the coarser particles.
At the early stage, especially the very beginning, the most pro-
nounced effect comes from the really rapid hydration of C3A.
Additionally, the negatively-charged polymer molecules exhibited the
highest affinity toward the positively-charged surface of C3A and the
hydration product (calcium sulphoaluminate phase) [35]. In this re-
gard, the compatibility problem should primarily come from the in-
teraction of polymer molecule with the hydration process [36]. Dif-
ferent hydration products (e.g. rod-like ettringite and plate-like Ca
(OH)2 particles) formed and increased the volume fraction of solid
particle and reduced the packing density, which enhanced the particle
network.
Marchon showed that for the first time that once the ettringite
surface is fully covered by the PCE, PCE adsorbs onto the reactive sites
of C3S, inhibiting its dissolution and leading to the observed delay of
C3S hydration (Fig. 4) [37]. The surface area increases and the polymer
surface coverage is reduced [37,38], inducing the concomitant decrease

Fig. 2. Equilibrium conformations of three kinds of P(AA-co-MAPEG) chains in Ca2+ solution (the yellow and the blue chains are two different backbones, the red
atoms are the O of the –COO-, the grey chains are the side chains, the green ions are Ca2+, and grayish molecules are water molecules, all the hydrogen atoms in
polymers are omitted for clarity). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

3
J. Liu, et al. Cement and Concrete Research 124 (2019) 105834

Fig. 3. Representative conformations of four PCE chains adsorbed on the C2S (1 0 0) surface in solution-based simulations. The color coding is as follows. For the C2S
surface, calcium (green), oxygen (red), silicon (orange). For the PCEs, side chains (blue), carbon atoms of backbone (yellow), oxygen atoms of backbone (red),
functional groups (purplish red). For the solution environment, oxygen (red), sodium counterions (purple). All the hydrogen atoms were omitted for clarity [15]. (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Fig. 4. Hydration delay in case of direct addition.

Reproduced from [37,66].

4
J. Liu, et al.
of average particle separation distance and slump loss. The hydration
rate, size, amount, morphology and the surface property of the hydra-
tion products greatly affected the workability. The amount of C3A [39]
and sulfate [40–42] are the initial two significant parameters. High C3A
content resulted in high yield stress, apparent viscosity, poor slump
retention, yet high early-age strength [39]. High superplasticizer do-
sage was required to achieve the same flow. Low alkalisulfate to C3A
ratio (lower than 1.3) would induce complicated hydration products of
C3A [40]. The chemisorption of superplasticizer (e.g. intercalation)
would enhance the consumption and raise the dosage. The chemi-
sorption could be reduced by increase the ratio to ~2, while the pre-
dominant hydration product is ettringite. It should be noted that
gypsum are always applied in cement to modify (slow down) the hy-
dration process of C3A. Indeed hemihydrates dissolved more rapid than
anhydrous and dihydrate gypsum. A lot of papers reported the effect of
type and amount of gypsum [42,43]. Large amount of gypsum reduced
the density of cement, increase the water amount, and delayed the
setting time until an optimum content [41]. Hemihydrate induced high
hydration rate in the early stage. More ettringite and calcium mono-
sulfoaluminate formed and promoted the increase of early compressive
strength. The PCE compatibility with cement with dihydrate was better,
resulting in better fresh state and rheological properties of cementitious
mixtures [43].
Considering the superplasticizers of different adsorption affinity
toward surface of different mineral phases and hydration products, the
influences on the hydration process and the formation of ettringite is
different from each other [44]. PCE slightly slow down the formation of
ettringite, yet greatly increased the total surface area [45]. PCE of high
charge density would promote the formation of ettringite particles of
high aspect ratio and much smaller size (~102 nm compared with
several micrometers in the absence of PCE). The effect became more
obvious at high PCE dosage [46,47], probably due to the dense covering
of the lateral crystal surface. This should reduce the workability.
It should be noted that the hydration process and the adsorption
occurred in a certain time period. The mixing procedure and the ad-
sorption kinetics of PCE superplasticizers also affected the workability.
The delayed addition procedure, which incorporates superplasticizers
slightly later (~minutes) than the initial mixing, could greatly reduce
the PCE consumption during the early hydration stage (e.g. formation
of organo-mineral phase), especially for the cement with low alkali-
sulfate to C3A ratio [40]. The continuous adsorption of PCE molecule
onto the particle surface would compensate the slump loss induced by
the hydration. Indeed PCE containing small ester group has therefore
been developed for slump retention. The hydrolysis of the ester bond
could give a higher charge on the PCE molecule and promote adsorp-
tion [48,49]. If the cement paste, mortar, or concrete is mixed for a
relatively short time period, the amount of PCE adsorbed might not be
sufficient to provide proper workability. Excess of PCE would be re-
quired for the initial flow, which might result in bleeding or segregation
at later stage (e.g. minutes or hours). On the other hand, a PCE which
rapidly reaches the adsorption equilibrium might lead to more rapid
slump loss. It seems that PCE of high adsorption affinity (high backbone
stiffness [50], high charge density, low content of hydrophobic groups
[51]) would reach the equilibrium earlier.
Due to the different adsorption affinity toward different surfaces,
the compatibility of PCE with a mixed binder or powder system (with
SCMs or inert powder, e.g. stone powder) should primarily depend on
the distribution on different surfaces, that is to say, the consumption by
different particles. The surface coverage (amount of surface-attached
side chains, proportional to the mass of PCE adsorbed [9]) on different
particles together with the size distribution (morphology) of particles
determine the packing state and therefore the workability of the ma-
terial. PCE strongly adsorbs onto positively-charged surfaces, which
could be weakened by the screening effect of counter-ions. The PCE
suitable for an alkali-activated binder system might be PCE of high
adsorption affinity, to reduce the competitive adsorption from anions
5
Cement and Concrete Research 124 (2019) 105834
[52]. The adsorption onto negatively-charged surfaces has been a pro-
blem. The Ca2+-coordination capacity is believed to account for at-
tachment on negatively-charged surface [8]. One possible solution
might be a positively-charged PCE [53]. It is worth noting that, due to
the excellent Ca2+ capacity and adsorption affinity, PCE with phos-
phate group or phosphonate group exhibited good performance in a
high ionic environment [54–58] . The compatibility was believed to be
very good in different systems [59]. For a system with particles of
layered structure and swelling ability (e.g. clay particles), PCE is greatly
consumed, and both the initial workability of the cementitious system
and slump retention would be reduced [60–62]. PCE of 4-hydroxy butyl
vinyl ether unit might be more effective in such a system [63]. Some
other examples include PCE with slight content of sulfate [64] and
lignopolymer superplasticizers [65]. The authors reasoned that im-
proving the surface coverage of PCE toward all the surfaces should be
useful for the improvement of workability of different binder systems.
2.3. The influence of chemical structure of PCE on the rheology behavior of
cementitious materials
Yield stress is associated with a network of rigid particles that must
deform and fail before flow can occur, which is determined by strength
of the network structure. For a cement paste, yield stress originates
from colloidal and contact interactions between particles and depends
on the volume fraction and nature of the solid particles. The yield stress
of cement paste is closely related to the dispersion of PCEs [67]. Once
adsorbed on the cement particles, PCEs disperse cement particles
through steric hindrance effect, thus reducing attractive interparticle
force and releasing water trapped in the agglomerated cement particles
[68,69]. At the high ionic strength of the cement pore solution, elec-
trostatic repulsion is screened and the working mechanism of PCEs in
cementitious systems is only due to steric hindrance [70,71]. Generally,
the dispersing ability of PCEs comes from the non-adsorbing side chains
[67,72,73], which are responsible for the steric hindrance effect. The
higher the PCE surface coverage on cement particles, the lower is the
yield stress of the cement paste. The effects of PCEs on rheological
properties of cement paste is also related to their structure i.e. number
of ionic groups, length of the side chains, length of the backbone or
grafting degree. It has been clearly shown in Fig. 5 that it is the ad-
sorbed polymer that controls the reduction of the yield stress [9]. The
structure of the PCEs determines its adsorption and the amount of
polymer adsorbed (independently of the structure) leads to a decrease
of the yield stress. In addition to experimental studies, Flatt and Bowen
Fig. 5. Evolution of the yield stress as a function of the mass of carboxylate
superplasticizers adsorbed. The line represents the best linear fit “log(yield
stress) vs. mass adsorbed for all PCE”, from [9].
J. Liu, et al.
developed a yield stress of a suspension called Yodel [74], which con-
sidered that yield stress was mainly dominated by the interparticle
forces and the number of interacting particles through volume fractions
of solids and particle size. This principle analysis of yield stress can help
to explain the effect of molecular structure of PCEs.
In general, the addition of PCEs reduces both yield stress and visc-
osity [75–77]. For pastes with the same yield stress, the viscosity may
be different. Liu [78] showed that apparent viscosity increased with the
increased PCE dosage for pastes with low w/c. Apparent viscosity is
defined as the ratio between instantaneous shear stress and shear rate,
which results from a complex interplay between hydrodynamic, col-
loidal and contact forces involved in the motion of the suspended ce-
ment grains. From its origin, apparent viscosity is thought to consist of
two parts. One part comes from the energy required to destroy the
colloidal interaction network between cement particles, and the other is
the energy dissipation to overcome the hydrodynamic force during
shearing and particle inertia. It depends on the shear rate between
particles and the viscosity of the continuous phase. At consistent shear
intensity, the shear rate is reversely correlated with the distance be-
tween cement particles. Roussel [32] believed that the increasing PCE
dosage would increase the apparent viscosity of a cement paste at a
high shear rate, and he suggested that the residual difference between
polymers in the final macroscopic viscosity come from the pronounced
increase in the local viscosity of interstitial fluid between neighbouring
particles.
3. Novel chemical admixtures to improve the cracking resistance
of concrete
3.1. Temperature rise inhibitor and its mechanism on hydration
Polysaccharides have been used to synthesize environment-friendly
water-retaining agent or viscosity modifying admixtures [79]. These
polymers such as cellulose and starch could be used as water retention
agent or set-retarding agents, thus modifying cement hydration. Re-
cently, A novel admixture prepared by acid hydrolysis of corn starch
has been specially designed to solve the thermal cracking issue by
controlling the exothermic process of cement hydration [80]. This
starch based chemical admixture so called temperature rise inhibitor,
flattens the main hydration peak to without delaying the induction
period for too long. As shown in Fig. 6. regarding the cumulative heat,
TRI can be used to control the heat release during the hardening process
to any desired level and as a result, reduces the temperature gradients
in the structure [80,81]. It was found that the dissolution of TRI is very
limited so that molecules are only available in small quantity over the
first few hours. Nevertheless, the TRI molecules are rapidly absorbed
3.0
(a)
2
2.5
Heat flow (mW/g OPC)
1
2.0
0
1.5
0 3
1.0
0.5
0.0
0 48 96 144 192
Time (h)
Fig. 6. Calorimetry curves of the cement pastes in the presence of TRI: (a) heat flow, (b) cumulative heat. By increasing the dosage of TRI, the maximum heat flow is
proportionally reduced and a broad second peak appears. The final cumulative heat is not affected [82].
Cement and Concrete Research 124 (2019) 105834
once dissolved, and will have a continuous effect on the hydration ki-
netics. TRI has little influence on the dissolution kinetics of cement,
while both experimental observations and modelling results strongly
indicate TRI continuously inhibits the nucleation of C-S-H to restructure
the main hydration peak [81,82]. Moreover, Zhang [83] found rheo-
logical property was determined by the interaction that TRI could also
significantly reduce the autogenous shrinkage of cement paste. This
phenomenon is not attributed to the reduction of capillary pressure
since the surface tension of pore solution is maintained at a constant
value. The mechanism still remains controversial. However, as a newly
developed chemical admixture, more research progress on the me-
chanism and application in the field are expected in the near future.
3.2. MgO based expansive agent
The compensation of thermal shrinkage with the delayed expansion
of slow hydrating MgO has proven effective in preventing the thermal
cracking of mass concrete, such as dams, diversion tunnels, and also
jointed reinforced concrete pavement in China [84–86]. MgO expansive
agent is typically calcined from magnesite at high temperature. The
calcination conditions affect the microstructure and hydration re-
activity of MgO, and thereby the expansion properties in concrete. MgO
based expansive agent has many advantages, including chemically
stable hydration products, relatively low water requirement, and in
particular adjustable expansion properties [86,87]. Recent research has
confirmed that the expansion property of the MgO is more sensitive to
the temperature compared to other types of expansive agent [88,89].
The curing temperature influences its hydration rate and hence the
corresponding expansion. Yan [85,90,91] proposed a new evaluation
method for the reactivity of MgO expansive agents, and found that the
expansion effect of MgO expansive agent lags behind its hydration in
cementitious materials, as shown in Fig. 7. Therefore, in order to well
compensate for the shrinkage of concrete and avoid the corresponding
shrinkage cracking, it is vital to make sure the expansion process pro-
duced by the expansive agent matches well with the shrinkage process
of concrete. Therefore, a suitable type of MgO expansive agent with
proper hydration reactivity and addition dosage should be used in a
specific concrete considering its shrinkage process in real structure.
3.3. Superabsorbent polymers
Superabsorbent polymers (SAP) are another most commonly used
internal curing agent [92,93]. SAP exhibit superior desorption capacity
compared to other candidate internal curing materials [92,94–97], SAP
are usually employed as a dry concrete admixture and take up water
during the mixing process. The use of SAP permits moreover free design
350
(b)
280
Heat (J/g OPC)
210
6
REF
140 0.025%_S
0.050%_S
0.075%_S
70 0.100%_S
0.125%_S
0.150%_S
0
240 288 0 48 96 144 192 240 288
Time (h)
6
J. Liu, et al. Cement and Concrete Research 124 (2019) 105834

shrinkage with internal curing water to be absorbed by the SAP and

based on the measured absorption capacity of the SAP [110].

4. C-S-H/PCE nanocomposites

Calcium silicate hydrates (C-S-H) are the principal hydration pro-

ducts (approximately 50% by mass) and primary binding phases in
hydrated Portland cement [112]. Following laboratory studies [113], C-
S-H based materials are now being developed commercially to accel-
erate hydration [114]. Owens et al. [115] reported an increase in early
strength development with 2 wt% C-S-H addition, where both the initial
and final setting times decreased by approximately 50%. Thomas et al.
[113] studied the early hydration kinetics by partially replacing Port-
land cement and pure C3S with pure C-S-H at different weight per-
centages. The addition of C-S-H was found to accelerate the main hy-
dration rate peak times and increase the amount of hydration by
seeding the hydration process [116]. The extent of nucleation and ac-
Fig. 7. Relationship between expansion rate and MgO content. celeration often depends on the surface area of the added fine particles
Reproduced from [90]. [117], the minor acceleration effect may be due to a lowed surface area
caused by agglomeration of C-S-H particles, which do not retain in their
original size during synthesis.
of the shape and size of the formed voids [92].
Recently, several organic-inorganic or pure inorganic nanocompo-
SAP particles are polymer hydrogels composed of polyelectrolyte
sites have been introduced for the purpose of improving the dispersion
chains which are covalently crosslinked to form a three-dimensional
of nanoparticles in cement-based materials [118–120]. The use of a
polymer network [98]. Driven by osmotic pressure and water affinity,
dispersant, especially a superplasticizer, is a good solution to improve
dry SAP particles swell when in contact with water (or aqueous solu-
the dispersion property of nanoparticles in cement-based materials for
tions) [99]. Osmotic pressure results from the formation of a chemical
solving the problem of agglomeration [121–124]. The size of the C-S-H
potential gradient in the system due to the relatively high concentration
particles can be controlled to nanoscale by selecting suitable molecular
of ions within the network of the SAP compared to the external en-
structure, synthesize conditions and also the concentration of PCEs
vironment [100]. The most common SAPs used as internal curing
[125,126]. Because of the layered silicate structure in C-S-H, C-S-H/
agents in concrete are covalently cross-linked copolymers of acrylic
polymer nanocomposites are excellent candidates for the manipulation
acid and acrylamide. They are chemically stable and able to swell in the
and control of properties through the intercalation of organic molecules
strongly alkaline cement pore solution [101]. The carboxylic acid
[127,128]. Sun [129] found that it is possible to control the average
groups of the acrylic acid monomer will deprotonate at pH > 5 (par-
size of the C-S-H/PCE nanocomposites by controlling the initial volume
tially neutralized acrylic acid sometimes is directly used for synthesis),
of the PCE solution, and the addition of synthetic C-S-H/PCE nano-
whereas the amide groups of the acrylamide monomer are partially
composites can accelerate early hydration, optimize the pore structure
hydrolyzed to form anionic carboxylic groups along the polymer chain
and improve the early compressive strength of cement significantly
when the pH is higher than about 12 [102]. During the hydration
even at small dosage. Plank concluded that PCE polymers produced
process of cement, multiple ions are released into the pore solution,
smaller particle sizes for C-S-H/PCE nanocomposites than C-S-H. The
such as K+, Na+, Ca2+, SO42− and OH– [102,103]. The swelling of SAP
nanocomposites can contribute to significant increases in the early
in pore solution is substantially lower compared to deionized water
compressive/flexural strength of the mortar [126,130]. C-S-H–PCE
[104,105]. Lower absorption in cement filtrate compared to a 0.1 M
nanocomposite not only accelerates the hydration of the silicate phases
NaOH solution with similar pH (~12) was observed in. This phenom-
present in the clinker, but also promotes the pozzolanic reaction of the
enon, commonly observed in the swelling of ionic hydrogels, is often
fly ash, slag and calcined clay substantially [130,131]. The addition of
attributed to a charge screening effect of the additional cations [98].
nanocomposites shows an earlier and more pronounced consumption of
This screening reduces the electrostatic repulsion and leads to a de-
portlandite since the on-set of pozzolanic reaction. However, the un-
creased osmotic pressure between the hydrogel network and the ex-
derlying mechanism remains unknown. More microstructure level stu-
ternal solution [106]. Besides, the presence of Ca2+ ions in the pore
dies show that in the absence of PCEs following a non-classical nu-
solution has a strong impact on the absorption kinetics of the SAP in
cleation mechanism C-S-H initially precipitates as metastable, globular
relation to the anionic group density of the SAP. Ca2+ will in fact
nanoparticles which within less than 1 h convert to the characteristic
complex with carboxylate groups from the molecular chains of the SAP,
nanofoils of early C-S-H, (Fig. 8) [132,133].
forming additional crosslinks which restrain the movement of the
More detailed studies are needed to reveal the effects of the
chains in the polymer [100,102,103]. The absorption of SAP particles in
synthesis conditions on the size of C-S-H/PCE nanocomposites.
cement paste, mortar or concrete is even smaller than in artificial pore
Moreover, further research should be carried out into the effect of
solution, likely because of the resistance to swelling exerted by the
synthetic C-S-H/PCE nanocomposites on the long term properties of
surrounding material [105] or due to the mixing process. According to
cementitious materials. Also, the most probable application for C-S-H/
Snoeck et al., SAPs with high absorption and large particle size are not
PCE nanocomposites would be prefabricated concrete and construction
ideal for mitigating autogenous shrinkage [107].
in winter with a relatively low temperature, to improve the early age
SAPs can efficiently reduce the autogenous shrinkage according to
strength of concrete. Therefore, the effect and mechanism of nano-
many laboratory testing results, however, it will also bring negative
composites under different temperature would be also necessary in the
impacts on the other properties of concrete, mainly mechanical prop-
future.
erties and workability [108–110]. Therefore, it is essential to set up a
procedure for designing mix composition based on finding a trade-off
5. Conclusion
between mitigation of autogenous shrinkage and possible negative ef-
fects on concrete properties [93,110,111]. Furthermore, a theoretical
Recent advances of chemical admixtures and their influence on the
guideline is provided based on compensating the volume of chemical
concrete properties are summarized.

7
J. Liu, et al.
Fig. 8. TEM images of C-S-H precipitated from Ca(NO3)2 and Na2SiO3 solutions after 15 min, 45 min and 60 min of crystallization. Magnifications: 60 k, 30 k and 80 k
[132,133].
In the area of PCEs, apart from the chemical structure and synthesis
methods, more research has been devoted to understand the action
mechanism of PCE in the cementitious materials, and to establish the
relationship between molecular structure and its impact on the prop-
erties of fresh concrete. Computational simulations were introduced as
a powerful method to study the conformational behavior of PCE in pore
solution and the also the adsorption behavior on the mineral interface
of cement at the molecular and atomic level. Owing to the progress in
terms of cement hydration and interaction between molecule and mi-
neral surface, we come to a better understanding on the compatibility
between admixtures and cementitious materials. Also, the linkage be-
tween chemical structure of PCE and rheology behavior of cementitious
materials is starting to be established with the help of advanced ana-
lytical equipment and computational modelling.
The research progress of three different chemical admixtures to
mitigate the shrinkage and cracking risk of concrete is reviewed in the
second part. The magnesia based expansive agent (MEA), owing to its
advantages compared with other type expansive agents, can be effec-
tively applied to compensate the thermal shrinkage at later stage. For
SAP, based on a clear view of its mechanism and performance, a pro-
cedure for designing mix composition is based on finding a trade-off
between mitigation of autogenous shrinkage and possible negative ef-
fects on concrete properties. Finally, a novel starch-based materials
temperature rise inhibitor (TRI) was introduced, which could effec-
tively reduce the hydration heat of concrete without bringing negative
effect on the strength development. More research is needed to un-
derstand its mechanism and performance in field construction.
Finally, as a newly proposed materials in last ICCC conference, the
recent research progress of C-S-H/PCE nanocomposites is reviewed,
including the preparation, application and its action mechanism on the
hydration of cement. It has been confirmed that C-S-H/PCE nano-
composites can efficiently improve the mechanical properties of con-
crete, especially at early age. However, more detailed studies are
needed to reveal the effects of the synthetic conditions on the size of C-
S-H/PCE nanocomposites, and also understand its effect on the long
term properties of cementitious materials.
Acknowledgements
The financial support from the National Key Research and
Development Program of China (Grant No. 2017YFB0310002) and
Scientific Research and Development Program of China Railway
(P2018G004) is acknowledged.
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