Construction and Building Materials 233 (2020) 117181

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Construction and Building Materials

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

Effect of aliphatic-based superplasticizer on rheological performance of

cement paste plasticized by polycarboxylate superplasticizer
Baoguo Ma a, Huahui Qi a, Hongbo Tan a,⇑, Ying Su b, Xiangguo Li a, Xiaohai Liu a, Chunbao Li a, Ting Zhang a
a
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, Hubei, China
b
School of Civil Engineering, Hubei University of Technology, Wuhan 430068, Hubei, China

h i g h l i g h t s

Addition of AS in PCE system enhances bleeding and segregation resistance.

Competitive adsorption between AS and PCE occurs.

AS perturbs the adsorption ability of PCE.

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

Article history: Polycarboxylate superplasticizer (PCE) and aliphatic superplasticizer (AS) are widely used water-reducing
Received 19 April 2019 agent in concrete. In actual practice, the addition of AS has been developed as a common way to alleviate
Received in revised form 12 September the bleeding and segregation of concrete plasticized by PCE, while the main reason for this phenomenon is
2019
not clear. In this research, the effect of AS on dispersion of PCE was investigated. Adsorption behavior of AS
Accepted 6 October 2019
and PCE and conformation of these polymers in liquid phase were analyzed with total organic carbon
(TOC), conductivity, and dynamic light scattering (DLS). Finally, the experimental results were verified
by molecular dynamics simulation, and the dispersion model was proposed to better understand the
Keywords:
Polycarboxylate superplasticizer
mechanism behind. The results showed that the effects of AS on the rheological performance of cement
Aliphatic superplasticizer paste containing PCE was closely related to the added dosage, and it was observed that three stages were
Competitive adsorption divided according to the dosage of AS. The main reason was due to competitive adsorption between AS and
Plastic viscosity PCE. In addition, PCE molecules, which existed in the liquid phase due to competitive adsorption, would be
crosslinked through calcium ions in pore solution, leading to the increase in plastic viscosity of cement
paste despite with the decreased yield stress. These results explained why the addition of AS in PCE system
could enhance the resistance to bleeding and segregation. These results would offer usefully experience
for the application of multiple superplasticizer systems in practical engineering.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction
Generally, superplasticizer has been employed to promote the
workability of concrete under the same water/binder ratio or
enhance the strength under the same workability [1–6]. It has been
accepted as an indispensable component in high fluidity concrete
or high strength concrete. The development of superplasticizers
can be divided into three phases, and the typical products are lig-
nosulfonates, naphthalene or aliphatic superplasticizer (AS), and
polycarboxylate superplasticizers (PCE) [7–10]. PCE showed highly
efficient dispersion and excellent dispersion retention, which has
been deemed as the main development direction of superplasti-
⇑ Corresponding author.
E-mail address: thbwhut@whut.edu.cn (H. Tan).
cizer [11–15]. However, obvious defects had also been found in
actual engineering practice, such as bleeding and segregation,
and these significantly puzzle the practitioners and restrain the
use of PCE [16].
In the literatures, many attempts were done to resist bleeding
and segregation [17,18]. Addition of hydroxypropyl-methyl cellu-
lose ether (HPMC) and welan gum, known as viscosity-enhancing
agent (VEA), was reported to significantly enhance the bleeding
and segregation resistance [19,20]. One reason was that these
polymers increased the viscosity of the liquid phase, because a
three-dimensional network of thin filaments was formed. This pro-
vided good anti-bleeding property even in the case of high water/
cement ratio [21]. Other reason was reported that the competitive
adsorption would occur in adsorbing process of PCE and VEA,
thereby affecting the adsorption amount of PCE and finally increas-

https://doi.org/10.1016/j.conbuildmat.2019.117181
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
2 B. Ma et al. / Construction and Building Materials 233 (2020) 117181
ing the viscosity [22–25]. Additionally, in liquid phase, intermolec-
ular crosslink among PCE through Ca2+ also increased the viscosity
of liquid phase [26,27]. Consequently, three aspects were consid-
ered to promote the viscosity of cement paste plasticized by PCE:
the competitive adsorption between VEA and PCE, intermolecular
crosslink of PCE or VEA, and the viscosity-enhancing effect of
VEA. These previous researches allowed us to understand the
mechanism behind PCE-VEA system.
With further research on the performance of superplasticizers
in liquid phase, all-atom molecular dynamics (MD) simulations
had been developed to study the properties of polymers [28–30].
For example, Qianping Ran studied the microscopic conformation
properties of three different kinds of PCE in the presence of Ca2+
and found that the complexation of Ca2+ with –COO- could change
the molecular conformation of PCE. And with the increase of car-
boxyl density, the effect of Ca2+ on the conformation of PCE was
reduced [31]. Through MD simulations, Molnar found that the dis-
tribution of the original sodium ion was affected by the interaction
between Ca2+ and chain of polyacrylic acid (PAA) [32]. Hongxia
Zhao gave the detailed information about the adsorption confor-
mation of PCE on the b-C2S (1 0 0) surface according to the MD
simulations results [33]. These studies showed that MD simula-
tions could be used as one method to reveal the dispersion mech-
anism of superplasticizers.
Recently, bleeding and segregation of concrete plasticized by
PCE could be obviously improved by adding AS. This meant that
PCE-AS system seemed to exhibit better performance than that
of single system of PCE. However, the mechanism behind seemed
not clear. Since PCE can only exert dispersion by adsorption on
cement particles, addition of AS most likely perturbed the adsorp-
tion of PCE, hence influencing the rheology of the cement paste. To
explain this phenomenon clearly, in this study, effect of AS on dis-
persion of PCE was investigated through mini slump in laboratory,
and the rheology performance of cement paste with AS and PCE
was also studied. According to the results of total organic carbon
test, the adsorption behavior of PCE and AS were discussed, and
the competitive adsorption between these two was also consid-
ered. The conformation of PCE and AS in the present of CH solution
was analyzed with conductivity and dynamic light scattering
(DLS), with intention to explain adsorption behavior; the experi-
mental results are verified by molecular dynamics simulation.
The dispersion model was finally proposed to reveal the mecha-
nism behind. These results would offer useful experience for the
application of multiple superplasticizer systems in actual practice.
2. Materials and test methods
2.1. Materials
2.1.1. Cement
The Portland cement used in this research met the require-
ments of Chinese standard GB 175–2007 and its chemical compo-
sitions (see Table 1) was gained with X-ray fluorescence
spectrometer (Axios advanced).
2.1.2. Superplasticizer
One commercially available PCE and AS were used in this study.
The chemical structure obtained from the suppliers was shown in
Fig. 1 and Fig. 2, and their basic properties were listed in Table 2.
Table 1
Chemical compositions of cement.
LOI SiO2 Al2O3
Cement wt% 3.82 24.08 4.72
2.2. Test methods
2.2.1. Fluidity
The fluidity test meeting the requirements of Chinese standard
GB/T 8077-2012 was carried out to investigate the effect of AS on
the dispersion ability of PCE. Cement and the solution contained AS
(0–0.40 wt%) and PCE (0.10 wt%) were mixed evenly with the same
water/cement ratio (0.29). The average of the maximum diameter
and width perpendicular obtained by a mini slump cone (with the
height of 60 mm, top diameter of 36 mm, and bottom diameter of
60 mm) was considered to be the fluidity value.
2.2.2. Rheological measurements
The samples used for rheological measurements were prepared
at a water-cement ratio of 0.29. The added amount of PCE was
reduced compared with that in fluidity test for the purpose of
keeping the yield stress within the measurement range of the
instrument and the added amount of AS remained the same. The
slurry of the reference structural state was obtained by 30 s pre-
sheared at a shear rate of 120 s1. After pre-sheared, the shear rate
was increased from 0 to 100 s1, then back to 0 s1, using 120 s and
60 s respectively. Analysis yield stress and plastic viscosity using
Bingham fluid model.
2.2.3. Adsorption behavior
Total organic carbon analyzer (TOC, Liquid TOC II, Germany)
was used to analyze the adsorption behavior of plasticizer. The car-
bon content of AS or PCE at different concentrations was obtained
and the relationship between concentration and carbon content
was plotted, as shown in Fig. 3. According to these results and
the measured carbon content, the concentration of plasticizer
could be calculated.
2.2.3.1. Adsorption amount. The adsorption amount of single sys-
tem was measured at the determined liquid/cement ration
(20:1). The mixture was thoroughly stirred for 5 min, and then
centrifuged at 3000 r/min to obtain upper supernatant. Through
the results shown in Fig. 3 and the carbon content in the super-
natant, the residual concentration of PCE or AS could be obtained.
The amount of PCE or AS adsorbed on cement could be calculated
according to Eq. (1).
Adsorption amount ðmg=g  cementÞ ¼ VðC0  CÞ=m ð1Þ
where V: liquid volume;C0: initial concentration of PCE before
adsorption, g/L;C: residual concentration after adsorption, g/L;m:
mass of the cement, g.
2.2.3.2. Competitive adsorption between AS and PCE. Both AS and
PCE contain carbon which can be detected by TOC, the adsorption
amount of AS or PCE cannot be obtained accurately in PCE-AS sys-
tem. However, whether the competitive adsorption took place can
be speculated as followed [34–36]:
Two mixed systems containing different amount of AS and PCE
were disigned. In the system 1, AS was determined to be 0.4 g/L
and the concentration of PCE increased from 0.2 g/L to 2.4 g/L. In
contrast, the concentration of PCE was fixed at 0.4 g/L and the con-
centration of AS increased from 0.2 g/L to 2.4 g/L in system 2. The
solution (20.0 g) was mixed evenly with cement and processed
with the same steps as above. The carbon content in the upper
supernatant of the mixed system was taken as the actual value
Fe2O3 SO3 CaO MgO K2O Na2O
2.46 2.31 58.24 1.95 1.02 0.27
 B. Ma et al. / Construction and Building Materials 233 (2020) 117181
Fig. 1. Molecular structure diagram of Polycarboxylate superplasticizer.
Fig. 2. Molecular structure diagram of aliphatic superplasticizer.
and compared with the summation of carbon contained in the
supernatant (seen as predictive value) obtained from the single
system. If PCE or AS won’t hinder each other’s adsorption, the
actual value will be theoretically equal to the predictive value. If
the actual value is greater than the predictive value, it indicates
that PCE or AS will affect each other’s adsorption, that is, compet-
itive adsorption occurs.
2.2.4. Conductivity measurement
The electrical conductivity meter (Seven Compact S230,
Switzerland) was performed to test the conductivity of PCE solu-
tion (10 g/L) and AS solution (0.5 g/L) at different calcium concen-
tration. Calcium concentration was changed by adding CH solution
(0.5 g/L). The increasing trend of conductivity different from that in
aqueous solution indicated that calcium ions react with PCE or AS
in solution.
2.2.5. Conformation of PCE and AS in solution
The conformational dimensions of these polymers, AS, PCE, and
PCE-AS, were tested and compared to the conformational size in
the presence of CH. All polymer solutions used for testing were
prepared in advance according to the following concentrations:
PCE solution (0.30%), AS solution (0.30%) and PCE-AS solution
(0.30% PCE and 0.30% AS). CH solution prepared at a concentration
of 0.01%.
2.2.6. Simulation method
Molecular dynamics (MD) simulations were carried out using
Condensed-phase Optimized Molecular Potentials for Atomistic
Simulation Studies (COMPASS Ⅱ) force field in Material Studio 8.0
package. In this model, each atom exists solely without valence
bond. The ionic bond, a strong attractive force, between opposite
charged atoms and the repelling effect of van der Waals terms
Table 2
The basic performance of PCE and AS.
Cl- Alkali content (%)
PCE 0.03 3.85
AS 0.01 6 16
3
Fig. 3. Relationship between carbon content and concentration of PCE or AS.
jointly decided the distance between opposite charged atoms.
Using COMPASS Ⅱ force field to describe water molecules, sodium
gluconate molecules and polymers [29]. The polymers model used
in the simulations shared similar structure to that used in industry,
as shown in Fig. 1, but it is relatively small [31].
Using Smart Minimizer method to fully optimize every initial
model. Then, the NPT ensemble was used to obtain the stable den-
sity for 2000 ps with constant number of atoms, pressure (0.0001
Gpa), temperature (298 K). Lastly, an extra 3000 ps NVT dynamics
was performed under the same condition of the number of atoms
(N), the system volume (V) and the temperature (T). During the
running process of 3000 ps, the system was further balanced by
the first 2000 ps trajectories and the data obtained in the last
1000 ps trajectories was used for investigation. Non-bond interac-
tions were calculated by the methods of atom-based summation
and particle–particle particles-mesh (PPPM) summation respec-
tively, with a cutoff radius of 12.5 Å [31,37–39].
3. Results and discussion
3.1. Rheology of cement paste plasticized by AS and PCE
3.1.1. Mini slump
With different added amount of AS, the fluidity of the paste
plasticized by PCE was firstly reduced and then kept nearly con-
stant, and thereafter increased, as shown in Fig. 4. Specifically,
the dosage of AS less than 0.08% declined the fluidity, while the
dosage ranged from 0.08 to 0.15% almost exhibited no effect on
the fluidity; further increase in dosage significantly increased the
fluidity. These results illustrated that addition of AS obviously
affected the fluidity of the paste plasticized by PCE, implying that
AS influenced the dispersion of PCE system and the influence most
likely depended on AS dose. Interestingly, with addition of 0.08–
0.15% AS, neither PCE nor AS seemed effective to plasticize the
paste.
As reported in the literatures, PCE exerted dispersion in cement
paste by the steric hindrance, and this could not be done if PCE
existed in liquid phase [34,40–42]. Generally, more amounts of
PCE adsorbing onto the surface resulted in stronger dispersion abil-
Water reducing ration (%) PH value Solid content (%)
29.1 6.8 40
12.5 28
4 B. Ma et al. / Construction and Building Materials 233 (2020) 117181
Fig. 4. Fluidity of the cement paste containing 0.10% PCE with different dosage of
AS.
ity. According to this theory, it was deduced that the decline (i.e.
with dosage of AS from 0 to 0.08%) was because AS hindered the
adsorption of PCE. Furthermore, AS, as one of the commonly used
superplasticizers in actual practice, could also exert excellent dis-
persion in cement suspension by electrostatic repulsion which
was provided by the adsorption of polymers on cement particles.
In PCE-AS system, competitive adsorption inevitably took place
between PCE and AS because both two had the ability to adsorb
on the cement.
Despite the fact that PCE hindered the adsorption behavior of
AS, adsorption of AS would inevitably happen. Electrostatic repul-
sion would offer enough dispersion force to plasticize the cement
paste once the dosage of AS exceeded the threshold. This could
be used to explain why the fluidity increased with the dosage of
AS more than 0.15%. Furthermore, with 0.08–0.15% dosage of AS,
most of PCE was probably presented in the liquid phase, with little
steric hindrance, because of the competitive adsorption. AS became
the main plasticizer on the surface of cement particles, but could
not provide sufficient electrostatic repulsion to plasticize the paste.
Accordingly, it seemed no obvious plasticizing effect in PCE-AS sys-
tem. In addition, with the dosage of AS less than 0.08%, the main
dispersion force was steric hindrance provided by PCE, in spite of
AS would disturb the adsorption of PCE.
In PCE-AS system, if PCE were predominated, the dispersion
force would be offered by the steric hindrance; if AS were predom-
inated, the electrostatic repulsion would provide the main disper-
sion force. With the dosage of AS less than 0.08%, steric hindrance
offered by PCE should exert main dispersion force; with the dosage
ranged from 0.08 to 0.15%, these two aspects reached a balance;
with dosage more than 0.15%, the electrostatic repulsion should
be dominated. It is noted that two kinds of dispersion force can
be efficiently conducted with the precondition of adsorbing on
cement. Based on this, more detail about adsorption behavior
should be further considered.
3.1.2. Rheological performance
Rheology of the cement pastes with PCE-AS were also investi-
gated. In Fig. 5, black and red curves are used to show the variation
of yield stress and plastic viscosity of cement slurry with the addi-
tion of AS, in order to better understand the effect of AS on rheolog-
ical performance. As shown, the yield stress was increased firstly
and then kept constant, and thereafter reduced. This result illus-
trated that plasticizing effect of PCE-AS system was reduced firstly
and then kept constant, and thereafter increased, same as the flu-
idity results. Furthermore, the plastic viscosity was slightly
increased, when the dosage was no more than 0.15%, as shown
Fig. 5. Effect of AS on the rheology of the cement paste plasticized by PCE.
in Fig. 5. It was noticed that with the dosage more than 0.24%,
the addition of AS increased the viscosity in spite of the decline
in yield stress, which was of great interest. Theoretically, the trend
of plastic viscosity should coincide with yield stress in most cases,
and the plastic viscosity was expected to increase firstly and then
decrease. When the dosage of AS less than 0.24%, an increase con-
sistent with expectation was found. However, when the dosage of
AS was more than 0.24%, the plastic viscosity increased rather than
decreased with the decreased yield stress. The possible reason for
this abnormal phenomenon of plastic viscosity was related to the
interactions among superplasticizers, cement particles, and ions
in liquid phase [43–45]. More evidence will be provided in the fol-
lowing text.
Based on fluidity and rheology results mentioned above, one
conclusion could be drawn that the presence of AS would obvi-
ously influence the dispersion ability of PCE; even though the yield
stress was reduced obviously, the plastic viscosity of the paste
showed a little increase with the dosage of AS more than 0.15%.
3.2. Adsorption behavior
As adsorption was accepted as the precondition of superplasti-
cizer to offer dispersion force, adsorption behavior of PCE and AS
was investigated by TOC and the mutual influence between these
two was also discussed.
Fig. 6 showed adsorption amount of single system on cement
particles. As shown, the adsorption amount of AS and PCE
increased gradually with the increase of dosage, and this result
agreed with the results in literatures [46–48]. With the same
dosage, higher adsorption amount of AS than PCE was observed,
indicating that the adsorption capacity of AS was stronger than
that of PCE.
One reason for adsorption of AS on cement particles was the
reaction between -SO-3 and Ca2+ [40,49], and the reaction between
–COO- and Ca2+ was accepted as one of mechanisms behind
adsorption of PCE. In PCE-AS system, since both –COO- and -SO-3
could react with Ca2+, the competitive adsorption would most
likely happen between AS and PCE.
In order to confirm the competitive adsorption between AS and
PCE, TOC measurement was employed. The total carbon content in
upper supernatant could be detected by the TOC instrument, while
the carbon attribution could not be distinguished. In this section,
AS-PCE solutions with different concentration were designed, and
the total carbon content in upper supernatant after adsorption,
which were tested by TOC, was discussed, with intention to verify
the competitive adsorption. It was noted that in AS-PCE system,
one component content was fixed, and the other was altered.
 B. Ma et al. / Construction and Building Materials 233 (2020) 117181
Fig. 6. Adsorption amount of PCE and AS in cement suspension.
These results were marked as the actual results. Based on hypoth-
esis of no competitive adsorption, these results were also calcu-
lated from the results shown in Fig. 6, which were seen as the
predictive results. Fig. 7 illustrated the comparison of actual results
and predictive results. Obviously, the actual results were higher
than the predictive results, indicating that PCE or AS will affect
each other’s adsorption, that is, competitive adsorption occurs.
Fig. 7(a) showed the effect of added dosage of PCE on residual
carbon content of PCE-AS system (AS = 0.4 g/L). AS shown in the
figure, the actual value results were slightly higher than the predic-
tive results, indicating that PCE could only slightly hinder the
adsorption of AS. Fig. 7(b) showed the effect of added dosage of
AS on residual carbon content of PCE-AS system (PCE = 0.4 g/L).
The results were very different from that in Fig. 7(a). The gap
between predictive results and actual value results was increased
with the increasing added amount of AS. This implied that addition
of AS could obviously hinder the adsorption of PCE.
One conclusion could be made that adsorption capacity of AS
was stronger than that of PCE, and the addition of AS could obvi-
ously influence the adsorption of PCE. In PCE-AS system, AS could
affect the adsorption capacity of PCE.
3.3. Interaction between superplasticizer and Ca2+
3.3.1. Conductivity
Previous studies showed that the carboxyl groups or sulfonate
groups could react with Ca2+. This was one of the reasons why
polymers, such as PCE and acrylic emulsion, could adsorb onto
the surface of cement particles [35,50,51]. Theoretically, the
Fig. 7. Competitive adsorption between PCE and AS.
5
reaction with Ca2+ led to a decrease in conductivity of the solution.
The conductivity of PCE and AS solution with increasing addition of
CH was investigated [52–54], as shown in Fig. 8 and Fig. 9, with
intention to verify the reaction between CH and PCE/AS. From
Fig. 8, the increase in added amount of CH (0.50 g/L) firstly reduced
the conductivity of PCE (10 g/L) and then increased it, with an obvi-
ous inflection point. The reduced stage implied the reaction
between PCE and CH (i.e. forming complex), consuming ions in
solution [53,55], and the increase stage caused by the added CH
solution which brought a large amount of Ca2+ and OH– to con-
tribute the conductivity. However, Fig. 9 showed a different phe-
nomenon from Fig. 8, and no inflection point was found with the
increasing added amount of CH. As reported in the literatures, elec-
trostatic attraction rather than complexation happened between
SO-3 and Ca2+ [27,56–58]. In that case, the increasingly added
dosage of CH solution, with Ca2+ and OH–, increased the conductiv-
ity of AS solution, sharing the same increasing tendency as the
deionized water; but it was noticed that the value of conductivity
was lower than that of the deionized water, which was caused by
the electrostatic attraction between SO-3 and Ca2+.
3.3.2. Conformation of AS/PCE in the presence and absence of CH
Conformation of PCE, AS and PCE-AS in liquid phase with and
without CH were studied by DLS measurement. As shown in
Fig. 10(a), conformation size of AS was 10–40 nm, and the presence
of CH increased it to 50–90 nm. This increase was due to the reac-
tion between Ca2+ and -SO-3 by electrostatic attraction [49,59]; one
Ca2+ connected two -SO-3, resulting in increase in conformation
size. As we can see from Fig. 10(b), the conformation size for PCE
was 7–15 nm, and the presence of CH increased it to 820–
1500 nm. This increase was due to the complexation between
Ca2+ and –COO- [60,61]; one Ca2+ connected more than two –
COO-, and the crosslink structure of PCE was produced, leading to
increase in conformation size [35,62]. This result also indicated dif-
ference in reaction between AS-CH and PCE-CH
Furthermore, in PCE-AS-CH system, theoretically, if the addition
of AS had no effect on the conformation of PCE-CH, PCE-CH, with
conformation size ranged from 820 to 1500 nm, would be
observed. However, the conformation size of PCE-AS-CH was
340–615 nm, as shown in Fig. 10(b), in inconsistency with theoret-
ical assumptions. It could be inferred that AS influenced the confor-
mation of PCE-CH system. This influence was most likely due to the
reaction between -SO-3 with Ca2+, which was further proved by
molecular dynamics simulation.
3.3.2.1. Molecular dynamics simulation. In the literatures, the con-
formational behavior of PCE in the solution of Ca2+ can be obtained
by molecular dynamics simulation [31–33]. In this study, the effect
6 B. Ma et al. / Construction and Building Materials 233 (2020) 117181
Fig. 8. Conductivity of PCE (10 g/L) solution with CH (0.5 g/L).
Fig. 9. Conductivity of AS solution with CH (0.5 g/L).
of AS on the combination between PCE and Ca2+ was discussed
through molecular dynamic simulation. In a system of atoms, the
radial distribution function (RDF) obtained through analyzing sim-
ulation results was accepted as an important parameter to charac-
terize the position of two-body correlations [63]. The shortest
distance between atom A and atom B can be obtained from the
position of the first peak. In addition, the probability density of
finding atom B around atom A within the r distance can be
obtained from the height of the peak. The RDF (gA-B(r)) can be
obtained as follow:
P Based on the above results, one conclusion was drawn that PCE
hV i–j dðr  jr Ai  r Bi jÞ
g AB ðrÞ ¼
ðNA N B  NAB Þ4pr 2 dr
Fig. 10. (a). Size distribution of PCE and AS in solution, (b). Size distribution of PCE, AS and CH in solution.
Fig. 11. Typical plots of the temperature and potential energy versus the simulation
time.
where A: atom A; B: atom B; V: the system volume; NA: particles of
atom A; NB particles of atom B; NAB particles belonging to atom A
and atom B simultaneously; rAi: the position of particle i of atom
A; rBj: the position of particle i of atom B.
Fig. 11 showed the typical temperature and energy fluctuation
curve in the MD simulation of PCE and PCE-AS system for the last
1000 ps. Generally, when the temperature and energy fluctuated
around the constant average, the systems reached equilibrium
[64]. From Fig. 11, fluctuation around the constant average indi-
cated the system had reached equilibrium, showing that the results
of the simulation were reliable. Fig. 12 showed a typical sketch that
reflects the interaction between Ca2+ and –COO–. In order to better
show the complexation between calcium ions and –COO– the side
chains are omitted. It could be seen that the distance between oxy-
gen and Ca2+ ranged from 1.998 to 2.117 Å. As shown in Fig. 13, the
first peak appeared at approximately 2.0 Å, which was consistent
with the results of previous studies [65]. It was reported that –
COO– in PCE was the main groups reacting with Ca2+, and the
RDF value of Ca2+ and oxygen in –COO– (i.e. gO-Ca(r)) reflected the
possibility of formation of –COO-Ca- complexation [29,31]. If AS
could obviously alter this value, the impact of AS on conformation
of PCE in the presence of CH would be confirmed. In Fig. 13, the
presence of AS reduced the peak value of the first peak obviously.
This indicated that the incorporation of AS perturbed the complex-
ation between Ca2+ and –COO–. Most likely, AS was reacted with
Ca2+ by electrostatic attraction to detach the complexes, as shown
in Fig. 14.
and AS were reacted with Ca2+ by complexation and electrostatic
attraction, respectively. By contrast, the electrostatic attraction
 B. Ma et al. / Construction and Building Materials 233 (2020) 117181
Fig. 12. The representative interaction between Ca2+ with oxygen atoms of –COO-
Fig. 13. The RDF of Ca2+ and oxygen atoms of –COO- for PCE system and PCE-AS
system.
Fig. 14. Addition of AS into the PCE solution in the presence of Ca2+.
7
between -SO-3 and Ca2+ was stronger than complexation between –
COO- and Ca2+. In cement slurry, addition of AS would preferen-
tially combine with Ca2+, thereby perturbing the adsorption ability
of PCE and altering the conformation of PCE in liquid phase.
3.4. Dispersion model
It was confirmed that the influence of AS on the fluidity of
cement system containing PCE was decided by the amount of AS.
With the increasing dosage of AS, three stages were observed, as
shown in Fig. 15.
At stage I, with a small amount of AS, the fluidity of the slurry
was reduced with the increasing added amount of AS. The reason
was revealed: because of competitive adsorption, the presence of
AS hindered the adsorption of PCE. Despite this, most of PCE was
still present on cement, and the main dispersion force was steric
hindrance offered by PCE, as show in Fig. 16. In this stage, AS acted
as negative role in dispersing cement particles. Furthermore, at
stage II, invalidation of both PCE and AS was observed. One precon-
dition to offer dispersion was there were enough amounts of poly-
mers adsorbing on cement. However, at this stage, because of
competitive adsorption, adsorption amount of both AS and PCE
was not enough to provide dispersion force, which meant that nei-
ther steric hindrance offered by PCE nor electrostatic repulsion
provided by AS showed obviously contribution to dispersion. Addi-
tionally, at stage III, with a large amount of AS added, adsorption of
AS on cement was enough for providing electrostatic repulsion to
plasticize the paste. Meanwhile, most of PCE were present in the
liquid phase due to competitive adsorption rather than on the sur-
face of cement particles.
Fig. 15. Effect of AS on fluidity of cement paste plasticized by PCE.
8 B. Ma et al. / Construction and Building Materials 233 (2020) 117181
Fig. 16. Schematic illustration of Competitive adsorption between AS and PCE.
The reason why AS could increase viscosity of cement paste
containing PCE was revealed as follows:
Because of competitive adsorption, the amount of PCE pre-
sented in liquid phase increased, and these PCEs were combined
with each other by complexation between Ca2+ and –COO-. One
Ca2+ could react with different carboxylates from different PCE
molecules, creating crosslinks among PCEs, resulting in obvious
increase in molecular weight of PCE, as shown in Fig. 16; this
was also illustrated from the DLS results in Fig. 10(b). These cross-
links increased the viscosity of liquid phase, showing the increase
in viscosity. These two aspects revealed the reason why the syner-
gistic use of AS and PCE could improve the bleeding and segrega-
tion resistance in actual practice.
4. Conclusion
(1) In cement paste containing PCE, with the increasing dosage
of AS, the fluidity of the cement paste firstly decreased and
then kept nearly constant, and thereafter increased. The
decrease was attributed to the reduced adsorption amount
of PCE caused by competitive adsorption; the constant stage
indicated that neither PCE nor AS could offer effective dis-
persion, because the amount of PCE or AS adsorbing on
cement was not enough to provide steric hindrance or elec-
trostatic repulsion. The increase was ascribed to the
increased electrostatic repulsion offered by the increased
adsorption amount of AS.
(2) Competitive adsorption between AS and PCE happened.
Because of the adsorption capacity of AS stronger than
PCE, calcium ion on the surface of cement particles would
be occupied by AS; these PCE molecules in the liquid phase
would be crosslinked through calcium ions in pore solution,
resulting in an increase in the viscosity of liquid phase. On
the other hand, because of competitive adsorption, effective
adsorption of superplasticizer was reduced, resulting in the
decrease in yield stress of the paste, which would also
increase the viscosity. These two aspects could be used to
explain the enhancement of bleeding and segregation
resistance.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgment
Financial support from National Natural Science Foundation of
China (51772227, 51572207) is gratefully acknowledged.
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