Construction and Building Materials 169 (2018) 452–461

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Construction and Building Materials

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

Synthesis, characterization and working mechanism of a novel

polycarboxylate superplasticizer for concrete possessing reduced
viscosity
Shanshan Qian a,b, Yan Yao a,c, Ziming Wang a, Suping Cui a, Xiao Liu a,⇑, Haidong Jiang b, Zhaolai Guo b,
Guanghong Lai a, Qian Xu a, Jianan Guan a
a
College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China
b
Jiangsu China Railway ARIT New Materials Co., Ltd, Nanjing 211505, China
c
China Building Materials Academy, Beijing 100024, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Synthesizes viscosity-reducing type

of PCE based on innovative molecular
design.
 Reduces viscosity and ensures
superior workability and rheological
performances.
 Calculates plastic viscosity via
mesomechanics process model
showing good correlation.
 Proposes working mechanism in
viewpoints of lubrication and release
of free water.
 Provides advanced viscosity-reducing
applications in high-grade fresh
concrete.

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

Article history: To solve the problem of high viscosity for fresh concrete especially high-grade concrete, a novel viscosity-
Received 14 August 2017 reducing type of polycarboxylate superplasticizer (PCE) was synthesized based on innovative design of
Received in revised form 25 December 2017 molecular structure, and also was characterized to confirm the designed molecular structure. The rheo-
Accepted 28 February 2018
logical performances of cement paste and fresh concrete containing synthesized PCE were probed, which
were analyzed by means of surface tension, adsorption behavior and zeta potential. The plastic viscosity
showed a good correlation with T50 and V-funnel time according to mesomechanics process model.
Keywords:
Moreover, the investigation of working mechanism interestingly showed that lowering molecular weight
Polycarboxylate superplasticizer
Viscosity reduction
and side chain length and introducing hydrophobic groups can achieve improved dispersion capacity and
Molecular design viscosity-reduction effectiveness. The aim of this study is to provide a promising avenue to synthesize
Fluidity PCE with superior workability and viscosity-reducing performance in fresh concrete. This new type of
Dispersion PCE can be used as a viscosity-reducing agent in concrete engineering.
Concrete Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction

In recent years, with the rapid development of the construction

⇑ Corresponding author. industry, modern buildings show the trends of high-rise, light
E-mail address: liux@bjut.edu.cn (X. Liu). weight and large span. Therefore, the high-grade concrete is

https://doi.org/10.1016/j.conbuildmat.2018.02.212
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
 S. Qian et al. / Construction and Building Materials 169 (2018) 452–461
gradually applied in some infrastructures due to its advantages of
high strength, high integrity and light weight [1–3]. However, to
reach high strength or ultra-high strength, the concrete should
be made by using a large quantity of cementitious materials and
employing low water-binder ratio, leading to high viscosity and
poor flowability for fresh concrete. This problem causes great diffi-
culties in practical construction especially in pumping construction
for ultra-high concrete, resulting in the frequent occurrence of
engineering accidents [4–8].
Polycarboxylate superplasticizer (PCE), an important type of
concrete admixture, has been widely applied in various engineer-
ing projects, which greatly promotes the concrete technology and
the building construction modernization. Consequently, there are
greater demands on the performances of concrete by the develop-
ments of building structures towards large scale and high function-
ality. As one important component of concrete, PCE shows strong
designability in molecular structure, and thus the high-
performance PCE can be obtained via adjusting and optimizing
the backbone length, side chain length and functional groups [9–
12]. Consequently, the researchers focus on the architecture design
of PCE macromolecule to specially solve some problems occurred
in concrete science and engineering.
At present, there are two main techniques employed to reduce
the viscosity of high-strength concrete, i.e., increasing the dosage
of superplasticizer and optimizing the size distribution of grain.
For the first technique, it can bring high construction cost, severe
retardation, bleeding and segregation of fresh concrete, leading
to some difficulties in building construction [13–16]. For the sec-
ond technique, there are many studies on this, whereas it cannot
thoroughly solve the practical problems [17–20] since good fluidity
of fresh concrete is mainly contributed by strong adsorption and
dispersive capacity of superplasticizer. Therefore, it has great sig-
nificance to develop a viscosity-reducing type of superplasticizer.
With the continuous development of concrete technology in
this field, researchers generally adopt a combination of conven-
tional PCE and viscosity modifying admixture (VMA) [21–24]
which essentially increases viscosity and thus thickens the mix
to prevent segregation [25–28]. VMA, as an important component,
have proved to be very effective in enhancing the cohesion (such as
water retention capacity of paste [29–31]) and rheological stability
of self-compacting concrete, underwater concrete [28,30,32–34]
and cement grout used for repairs, injection, embedding of anchors
and post-tensioning, and rock and oil-well grouting [35,36].
Recently, there has been a growing interest in the effects of VMA
content [21,37,38] and type [34,39–41] on the properties of mor-
tars and concretes. However, the negative effect of VMA was
proved in many literatures [24,42–44], such as increases yield
stress and plastic viscosity of cement-based grout [28,30,32,34];
only using conventional PCE will lead to severe segregation and
bleeding though it may reduce the viscosity of concrete to some
extent [45,46]. The question is why not design and synthesize a
novel PCE having a similar effect in this regard? Why not develop
a viscosity-reducing type of PCE from the viewpoints of molecular
architecture and surface-interface chemistry to control the viscos-
ity of concrete? There are few studies reported on these. Another
significance of this study is giving a guideline in reducing the vis-
cosity of concrete by specialized design and synthesis in molecular
Table 1
Chemical and mineral compositions of reference cement.
Cement SiO2 (%) Al2O3 (%)
Reference cement 22.91 4.29
Cement Loss (%) f-CaO(%)
Reference cement 1.48 0.63
453
structure of PCE, instead of blindly adjusting composition of con-
crete. Compared with previous work, herein we synthesized a
novel type of PCE possessing the function of reducing viscosity of
concrete through molecular design, which has more attractive
potentials in construction.
In this study, a viscosity-reducing type of PCE was synthesized
by using isopentenyl polyethylene polypropylene glycol (IPEPPG),
maleic anhydride (MA) and sodium methallyl sulfonate (SMAS)
as monomers. To evaluate the effects of the structural parameters,
the molecular weights of side chains and whole polymer were var-
ied. The synthetic products were characterized by 1H Nuclear Mag-
netic Resonance (1H NMR), Infrared Spectroscopy (IR) and Gel
Permeation Chromatography (GPC), respectively. The dispersion
capacities of PCEs to cement pastes and the rheological properties
of fresh concretes containing PCEs with different architectures
were probed; besides, the effects of structural parameters on the
viscosity-reducing capacity and interfacial adsorption behavior of
PCE were investigated through the measurements of surface ten-
sion, adsorption amount and zeta potential. Furthermore, the
working mechanism of viscosity-reducing type of PCE in the con-
crete system was summarized, and the relationship between work-
ability and viscosity for fresh concrete was investigated via
mesomechanics model. From these data, we hoped to gain an
insight into whether the novelly synthesized PCE according to
the molecular design would perform more effectively in the reduc-
tion of concrete viscosity. This research provides not only a new
direction for exploring novel viscosity-reducing type of PCE which
can improve the workability and rheological properties of fresh
concrete, but also a theoretical guidance for developing the work-
ing mechanism of PCE in the field of viscosity-reduction of
concrete.
2. Experimental
2.1. Materials
2.1.1. Chemicals
Maleic anhydrite (MA), sodium methallyl sulfonate (SMAS), hydrogen peroxide
(H2O2), sodium hydroxide (NaOH) and vitamin C (all 99% purity, purchased from
Sinopharm Chemical Reagent Co., Ltd, Shanghai, China), were used in the study
without further purification. Isopentenyl polyethylene polypropylene glycol
(IPEPPG, ethylene oxide (EO) unit/propylene oxide (PO) unit = 4:1) with the molec-
ular weights of 800, 1500 and 2900 identified as IPE12PP3G, IPE24PP6G and IPE48-
PP12G respectively, were received from Liaoning Kelong Fine Chemical Co., Ltd
(Liaoning, China).
2.1.2. Component materials of concrete
Reference cement P.I.42.5, a type of cement specially used for examining the
performances of concrete admixture, which quality was controlled according to
the standard method GB 8076-2008 [47] described in the National Standards of
China, was supplied by China Building Materials Research Institute (Beijing, China).
Its chemical and mineral compositions determined respectively by X-ray Fluores-
cence (XRF) and X-ray diffraction (XRD) using Rietveld refinement method are illus-
trated in Table 1. The medium sand with a fineness modulus of 2.7 had a density of
2550 kg/m3 and a bulk density of 1460 kg/m3. The gravel with a continuous grading
of 5–20 mm (wherein 40% of 5–10 mm and 60% of 10–20 mm; content of elongated
and flaky particles 5%; voidage 40%; clay content 0.5%) had a density of 2630
kg/m3 and a bulk density of 1540 kg/m3. Tackifier (hydroxypropyl methyl cellulose
MHPC500PF) as a role of viscosity modifying agent (VMA) (residue 1%) was com-
mercially available from Shanghai Greenchem Trading Co., Ltd (Shanghai, China).
Deionized water was used throughout the experiment.
Fe2O3 (%) CaO (%) MgO (%) SO3 (%) Na2O (%)
2.89 66.23 1.93 0.34 0.71
C3S (%) C2S (%) C3A (%) C4AF (%)
58.68 21.48 6.49 8.79
454 S. Qian et al. / Construction and Building Materials 169 (2018) 452–461
2.2. Synthesis
IPEPPG was mixed with distilled water in a four-neck round-bottom flask which
was placed in a constant temperature bath with a stirrer, and then MA, SMAS and
H2O2 were added in sequence, followed by heating to 65 °C with stirring for 15 min.
Thereafter, vitamin C aqueous solution at a concentration of 0.4% was dropwise
added to the flask within 4 h, and then retained stirring at 70 °C for 1 h (SMAS:
H2O2:Vitamin C:IPEPPG = 0.03:0.32:0.02:1). After the reaction was completed, the
polymer solution was neutralized by NaOH aqueous solution at a concentration
of 30% to adjust pH value to 7 ± 1 followed by cooling to room temperature, thus
yielding the final product (solid content: 40 wt%). The structural sketch of the syn-
thesis of viscosity-reducing type of PCE is represented in Fig. 1. The PCE polymers
designated as P(MAa-IPE4mPPmG)n, whereby ‘‘a” presents the molar ratio of MA to
IPE4mPPmG; ‘‘m” presents the polymerization degree of PO unit, which can be calcu-
lated from the molecular weight of IPE4mPPmG; ‘‘n” presents the polymerization
degree of MAa-IPE4mPPmG unit (SMAS is ignored due to its too low amount), which
also can be calculated from the measured molecular weight of polymer, ‘‘a” value,
and molecular weights of MA and IPE4mPPmG.
2.3. Characterizations and measurements of PCEs
The PCE specimens used for all the characterizations and measurements were
placed in a dialysis bag (MWCO 5000), in which the water was changed every 4–
6 h for lasting 3 days to remove the unconverted reactants, and then were dried
in vacuum overnight at 60 °C to a constant weight.
2.3.1. IR analysis
The PCE specimen with a fixed mass was mixed with KBr and pressed into a
disk, which was scanned by a VERTEX 70 Fourier transform infrared spectrometer
(Bruker Co., Germany) at 25 °C to record the IR spectrum.
2.3.2. 1H NMR analysis
The 1H NMR spectrum of PCE specimen was recorded on an ARX-400 spectrom-
eter (Bruker Co., Germany) operating at a frequency of 400 MHz, and the chemical
shift values were expressed in d values (ppm) relative to tetramethylsilane (TMS) as
an internal standard. Sample for 1H NMR was prepared by dissolving in the solvent,
i.e., deuterated water (D2O) as internal reference.
2.3.3. GPC
The number average molecular weight (Mn), weight average molecular weight
(Mw) and polydispersity index (PDI) of PCE specimens were determined on a Waters
1515 GPC (Waters Co., United States). The mobile phase was 0.1 mol/L NaNO3 aque-
ous solution, with an injection volume of 100 mL and a flow rate of 1 mL/min.
Fig. 1. Structural sketch of the synthesis of viscosity-reducing type of PCE.
2.3.4. Surface tension
The surface tension of PCE solution was conducted on an OCA40 Micro surface
contact angle tester (Dataphysics Co., Germany), with the measurement range of
0.01–2000 mN/m and measurement accuracy of ±0.01mN/m. The measurements
were generally repeated three times and the average was calculated to yield the
final value.
2.3.5. Adsorption on cement
The adsorption amounts of PCEs on the surfaces of cement particles were eval-
uated according to the reported method [48]. The non-adsorbed portion of polymer
remaining in solution at equilibrium condition was determined by analyzing the
total organic carbon (TOC) content of the solution. In a typical experiment, 30 g
of cement, 120 g of deionized water and the PCE to be tested (remaining the same
concentration as in cement paste) were filled into a 50 mL centrifuge tube and then
centrifuged for 5 min at 6000 rpm in a TGL-16C High speed bench centrifuge pro-
duced by Shanghai Anting Scientific Instrument Factory (Shanghai, China). The
supernatant was diluted with deionized water. The TOC content of the solution
was determined on a TOC-II total organic carbon analyzer (Elementar Analysensys-
teme GmbH, Germany). To obtain the carbon content in the PCE solutions, the same
PCE solutions without addition of cement were taken and measured in the same
manner. From the difference between the TOC content of the PCE reference sample
and that of the supernatant, the adsorption amount of PCE was calculated. Measure-
ments were generally repeated three times and the average was recorded as the
adsorption amount.
2.3.6. Zeta potential
The zeta potentials of cement pastes containing PCEs at PCE dosages of 0%, 0.2%,
0.4%, 0.6%, 0.8% and 1.0% by weight of cement (bwoc) respectively were determined
on a Malvern Zetasizer Nano ZS90 zeta potential analyzer (Malvern Instruments
Ltd., UK) at 25 °C. In a typical experiment, dilute cement slurries were prepared
by placing 0.5 g of reference cement in PCE aqueous solution with a W/C of 0.5.
All of the suspensions were mixed for 5 min before testing the supernatants. Mea-
surements were generally repeated three times and the mean value was reported as
the zeta potential.
2.3.7. Performances of the polymers in cement
The fluidities and fluidity retentions of cement pastes containing PCEs were
examined according to the standard method GB/T 8077-2012 [49] described in
the National Standards of China. Generally, the PCE solution was added to the mix-
ing water, and the amount of water contained in the PCE solution was subtracted
from the amount of mixing water required for a water-cement ratio (W/C) of
0.29. The viscosity of cement paste containing PCE at a W/C of 0.29 was measured
by a LVDV-S rheometer (Ametek Brookfield, United States).
2.3.8. Performances of the polymers in concrete
The slump flow, time to flow a diameter of 50 cm (T50) and V-funnel time of
fresh concretes containing PCEs were measured according to the standard method
CECS203-2006 [50] described in the Engineering Construction Standards of China.
The viscosity of concrete containing PCE was measured by an IBB rheometer (IBB
 S. Qian et al. / Construction and Building Materials 169 (2018) 452–461 455

Table 2
Mix proportion of self-compacting concrete.

Sample Cement (kg/m3) Sand (kg/m3) Gravel (kg/m3) Water (kg/m3) VMA (kg/m3) Air entraining agent (kg/m3) PCE (kg/m3)
Blank 520 826 894 165 1.04 0.052 0
1 520 826 894 165 1.04 0.052 3.12
2 520 826 894 165 1.04 0.052 4.16
3 520 826 894 165 1.04 0.052 5.20
4 520 826 894 165 1.04 0.052 6.24

Rheology Inc., Canada). The mix proportion of self-compacting concrete used in this
test is shown in Table 2. The PCE (solid content: 20 wt%) dosage was 0%, 0.6%, 0.8%,
1.0% and 1.2% bwoc respectively.
3. Results and discussion
3.1.3. 1H NMR analysis
Fig. 4 shows the 1H NMR spectra of the synthesized PCEs, which
were analyzed by the reported literatures [51–54].
From Fig. 4(a), a large peak at 3.5–3.8 ppm corresponds to the H
atoms from polyoxyethylene oxide and polypropylene oxide on the
side chains of PCE, which are distinctly higher than other peaks due

3.1. Structural analysis of synthesized polymer

3.1.1. Molecular weight analysis

To investigate the effects of structural parameters on the
viscosity-reducing performance of concrete, the PCEs with differ-
ent structures were obtained through changing monomer ratio
and side chain length. Two routes were designed as follows: (1)
same side chain length but different monomer ratio, namely P
(MA3.5-IPE12PP3G)5, P(MA4-IPE12PP3G)9 and P(MA4.5-IPE12PP3G)12;
(2) same monomer ratio but different side chain length, namely
P(MA4-IPE12PP3G)9, P(MA4-IPE24PP6G)9 and P(MA4-IPE48PP12G)9.
The molecular properties are shown in Table 3 and Fig. 2.
In Table 3, the measured values of molecular weight are essen-
tially in agreement with the calculated results from their molecu-
lar formulas, showing a good synthetic efficiency for these
polymers. Such PDI values for these samples are slightly higher
than 1.00, indicating a fairly narrow molecular weight distribution.
Furthermore, the PDI value of Sample A is significantly lower than
those of other samples, which is also presented as a narrower peak Fig. 2. GPC spectra of the synthesized PCEs.
in Fig. 2. Also, the conversion rates for the monomers of >90% were
accomplished, which confirms high turnover rate and formation of
quite uniform polymers.

3.1.2. IR analysis
Fig. 3 shows the IR spectra of the synthesized viscosity-reducing
type of PCEs, which were analyzed according to reported litera-
tures [51–53].
For the synthesized PCEs in Fig. 3, the vibration peaks for ACH3
groups from polypropylene oxide on the side chains of PCE appear
at 1385 cm 1; the symmetric and stretching vibration peaks for
ACH2ACH2AOA from polyoxyethylene oxide and polypropylene
oxide on the side chains of PCE appear at 1105 cm 1 and 2880
cm 1, respectively. Besides, the symmetric vibration peaks for
AC@O bonds from MA units appear at around 1636 cm 1 and
1470 cm 1, and the stretching vibration peak for ASO3 groups from
SMAS units appear at around 1348 cm 1. All of the results thus
show the occurrence of polymerization process and the existence
of various characteristic functional groups including sulfo, car-
Fig. 3. IR spectra of the synthesized viscosity-reducing type of PCEs.
boxyl, methyl, ether groups for the polymerization product.

Table 3
Molecular properties of the synthesized PCEs.

Sample Monomer ratio (MA:IPE4mPPmG) PCE Mn (g/mol) Mw (g/mol) PDI

A 3.5:1 P(MA3.5-IPE12PP3G)5 5500 6800 1.29
B 4:1 P(MA4-IPE12PP3G)9 10,600 15,200 1.43
C 4.5:1 P(MA4.5-IPE12PP3G)12 15,200 21,100 1.42
D 4:1 P(MA4-IPE24PP6G)9 17,000 23,970 1.45
E 4:1 P(MA4-IPE48PP12G)9 30,100 41,800 1.47
456 S. Qian et al. / Construction and Building Materials 169 (2018) 452–461
Fig. 4. 1H NMR spectra of the synthesized PCEs (a) and IPEPPG (b).
to the great proportion; besides, peaks for both H atoms linked to
ASO3 groups and H atoms of methyls of polypropylene oxide also
appear around 3.6 ppm, which partially overlap with the above
large peak. Also from Fig. 4(a), peaks around 0.8 ppm and around
2.3 ppm correspond to the H atoms of methyl linked to backbone
and the H atoms of methylenes in backbone, respectively. Fig. 4
(b) shows the 1H NMR spectrum of macromonomer IPEPPG, show-
ing a peak corresponding to H atoms of vinyl groups at 4.0 ppm;
however, there is no peak found at 4.0 ppm in Fig. 4(a), confirming
the occurrence of polymerization process. These characteristic H
atoms are correspondingly marked in the schematic structure dia-
gram displayed in Fig. 4. Such results verify the introduction of
characteristic groups into the macromolecules, which are in accor-
dance with our expected structure.
3.2. Physico-chemical characterizations of synthesized PCE
3.2.1. Surface tension
The surface tension results of PCE solutions at the different con-
centrations are shown in Fig. 5.
From Fig. 5, when the concentration of PCE solution increases,
the surface tension of PCE solution correspondingly decreases, all
of which are significantly lower than that at a concentration of
0% (72.47 mN/m). This is because the introduced hydrophobic PO
units in the side chains change the HLB value of superplasticizer.
As this trend, when the concentration of P(MA4-IPE12PP3G)9 solu-
Fig. 5. Surface tension of PCE solution as a function of PCE concentration.
tion which presents the largest decline in surface tension is 10%,
the surface tension of solution declines to be as low as 31.78
mN/m, indicating that the molecular structure of synthesized PCE
has a significant influence on the decreasing degree of surface ten-
sion and further the dispersion capacity to cement particles.
Also from Fig. 5, with the increase of concentration of PCE
solution, the order of decline degree in surface tension is
P(MA4-IPE12PP3G)9 > P(MA4.5-IPE12PP3G)12 > P(MA3.5-IPE12PP3G)5 >
P(MA4-IPE24PP6G)9 > P(MA4-IPE48PP12G)9. Since P(MA4-IPE12PP3G)9
possessing short side chains and low molecular weight shows weak
steric hindrance effect, the hydrophobic association is strengthened
to form the aggregation in solution [55] which presents aggregated
hydrophobic groups with hydrophilic groups inside, manifesting
as the most significant decline in surface tension with the increase
of concentration of PCE solution. As for P(MA4.5-IPE12PP3G)12
possessing the longest backbone, the hydrogen bonds between H
atoms of carboxyls in backbone and O atoms in side chains are easily
formed to increase the intermolecular interaction and aggregation,
thus leading to an increase of surface tension. As for
P(MA4-IPE48PP12G)9 possessing the longest side chain length, the
steric hinderance effect provided by IPE48PP12G is far stronger than
that of IPE24PP6G and IPE12PP3G, thus showing the slightest and
the slowest decline in surface tension with the increase of concentra-
tion of PCE solution.
Under the same monomer ratio, the order of decline amplitude
in surface tension is P(MA4-IPE12PP3G)9 > P(MA4-IPE24PP6G)9 > P
(MA4-IPE48PP12G)9, indicating that the side chain length of PCE is
inversely proportional to the decline amplitude in surface tension.
This is caused by the relevance between long side chain length and
strong hydrophilicity for PCE macromolecules. Therefore, adding
our synthesized viscosity-reducing type of PCE possessing low sur-
face tension can effectively lower the solid-liquid interfacial energy
in the cement-water system, but also easily form a large number of
micro-bubbles in fresh concrete to separate cement particles,
which is helpful to dispersing cement particles with a good
retention.
Interestingly, the surface tension results for the synthesized
PCEs are basically consistent with the fluidity results of cement
pastes containing synthesized PCEs. This signifies that low surface
tension can contribute to great flow properties of cement paste. To
be specific, the lower surface tension it has, the lower gas-liquid
interfacial energy it exhibits; thus, when the adsorption of synthe-
sized viscosity-reducing type of PCE occurs at the interfaces, many
uniform and stable bubbles are formed due to the negatively
 S. Qian et al. / Construction and Building Materials 169 (2018) 452–461 457

charged liquid film caused by the cooperation of carboxyl groups

and side chains in the macromolecule. As a result, the electrostatic
repulsion generated from bubble-bubble and bubble-cement
forces cement particles to well disperse in the system, presenting
a good fluidity of cement paste.

3.2.2. Adsorption behavior on cement

To quantify the interaction between the synthesized PCEs and
cement particles, the absorption behavior of viscosity-reducing
type of PCE with various dosages on cement particles was investi-
gated. The resulting adsorption amount curves are shown in Fig. 6.
From Fig. 6, the adsorption amounts for all the PCE samples
increase sharply (PCE dosage < 4 mg/g) then slightly (PCE dosage
> 4 mg/g). This is a result of competition between the weakened
adsorption caused by the generated hydration products and the
continuous adsorption caused by the unabsorbed PCE in pore solu-
tion [56]. The curves displayed in Fig. 6 shows that the order of
adsorption amount at high PCE dosage is P(MA4-IPE12PP3G)9 > P
(MA3.5-IPE12PP3G)5 > P(MA4.5-IPE12PP3G)12 > P(MA4-IPE24PP6G)9 >
P(MA4-IPE48PP12G)9, signifying that the adsorption behavior of the
synthesized viscosity-reducing type of PCE is related to its molec-
ular weight, monomer ratio and side chain length. Compared with
P(MA3.5-IPE12PP3G)5, P(MA4-IPE12PP3G)9 possessing longer back-
bone and more polar groups exhibits lower side chain density, so
that the macromolecules are more flexible to show more absorb-
able polar points, leading to a high probability of absorption at
interface. The adsorption capacity of P(MA4.5-IPE12PP3G)12 possess-
ing the longest backbone is not so high, possibly because too long
macromolecular chains are apt to intertwine to wrap the polar
groups and further lessen the absorbable points. The adsorption
amounts of P(MA4-IPE24PP6G)9 and P(MA4-IPE48PP12G)9 are low,
which is also determined by their molecular structure characteris-
tics especially for side chains. Compared with IPE24PP6G, IPE48PP12-
G contains more ether bonds, and thus its O atoms are apt to
associate with water molecules to form hydrogen bonds, resulting
in a thicker water film and stronger steric hindrance effect, which
can shield the polar groups and further lower the adsorption
capacity. This viewpoint also can be used to explain the order of
adsorption amount of PCEs under the same monomer ratio, namely
P(MA4-IPE12PP3G)9 > P(MA4-IPE24PP6G)9 > P(MA4-IPE48PP12G)9.
It is also worth recalling that the trend of adsorption amount of
PCEs basically corresponds to that of paste fluidity data mentioned
above, which is also quite agrees with other investigation reported
by Pourchet [57] pointing out that the dispersion effect of PCE is
well correlated to the amount of adsorbed polymer and can be
interpreted in terms of surface coverage.
Fig. 7. Zeta potential of cement paste as a function of PCE dosage.
3.2.3. Zeta potential
To further probe the electrostatic characteristic, the zeta poten-
tial of cement paste containing synthesized viscosity-reducing
type of PCE was measured. The zeta potential results with varied
PCE dosages from 0% to 1% bwoc are shown in Fig. 7.
From Fig. 7, the zeta potential of cement paste initially exhibits
positive value but then changes to negative value when adding the
synthesized PCE, owing to the adsorption of anionic groups of the
synthesized PCE on the surfaces of cement particles. With the PCE
dosage increases, all of the absolute values of zeta potential slightly
increase, since the adsorbed anionic groups of PCE on the surfaces
of cement particles can replace a part of high-valent anions such as
SO24 , which is an unequal ion exchange existing the competitive
adsorption [58–60].
Also from Fig. 7, the order of zeta potentials (absolute value) of
cement pastes containing synthesized PCEs in the measured range
of dosages is P(MA4-IPE12PP3G)9 ( 26.507 mV) > P(MA3.5-IPE12PP3G)5
( 23.194 mV) > P(MA4.5-IPE12PP3G)12 ( 18.463 mV) > P(MA4-
IPE24PP6G)9 ( 12.257 mV) > P(MA4-IPE48PP12G)9 ( 5.997 mV),
presenting the same trend as the adsorption behavior on cement
particles. This implies a good correlation between zeta potential
and adsorption amount. As for P(MA4-IPE12PP3G)9, high absolute
value of zeta potential signifies high intensity of anionic charge pro-
vided by the added PCE, further illustrates the high adsorption
amount on cement particles. Consequently, the electrostatic repul-
sion between cement particles increases so that it makes the free
water from cement aggregates released, manifesting as an increased
dispersion capacity to cement for the synthesized viscosity-reducing
type of PCE, which is in line with the above-mentioned fluidity data.

3.3. Performances of synthesized product in cement paste and concrete

3.3.1. Dispersion capacity in cement paste

The fluidities at 0 h, 0.5 h and 1 h of cement pastes containing
synthesized PCEs at a dosage of 0.18% bwoc were determined to
probe the dispersing capacity, as shown in Table 4.

Table 4
Fluidities of cement pastes containing different PCEs.

Sample PCE Fluidity (mm)

Initial 0.5 h 1h
A P(MA3.5-IPE12PP3G)5 203 185 163
B P(MA4-IPE12PP3G)9 230 205 198
C P(MA4.5-IPE12PP3G)12 222 171 148
D P(MA4-IPE24PP6G)9 220 190 178
E P(MA4-IPE48PP12G)9 205 170 139
Fig. 6. Adsorption amount of PCE on cement as a function of PCE dosage.
458 S. Qian et al. / Construction and Building Materials 169 (2018) 452–461

From Table 4, under the same monomer ratio, the order of dis-
persion capacity in cement paste is Sample B > Sample D > Sample
E, indicating that decreasing side chain length is effective to con-
tribute good initial fluidity and fluidity retention of cement pastes.
This is possibly because the thickness of water film formed on the
surfaces of cement particles tends to thin with the decrease of side
chain length, leading to the release of free water which can con-
tribute to the fluidity performances; besides, if the side chain
length is too long, the entanglement of molecular chains will
increase the flow resistance and the apparent viscosity, leading
to poor paste fluidity. Also from Table 4, under the same side chain
length (for Sample A, B and C), the best paste fluidity and fluidity
retention are obtained at the MA/IPEPPG monomer ratio of 4:1.
This is possibly because the proportion of side chains which can
provide steric hindrance is correspondingly decreased when the
MA/IPEPPG monomer ratio is too high, thus lowering the disper-
sion effect; besides, too low MA/IPEPPG monomer ratio is apt to
entangle such side chains, causing high viscosity and poor fluidity
for cement paste. These results show that the synthesized PCE with
proper monomer ratio and side chain length can exhibit high
working efficiency, verifying the contribution of regulating struc-
tural parameters to the improvement in flow performances of
cement paste [61].
design. For one thing, many hydrophobic groups were introduced
into the side chains of PCE macromolecules, i.e., a part of EO units
were replaced by PO units which were in essence the introduction
of methyls into EO units, to lower the Hydrophile-Lipophile Bal-
ance (HLB) value, thus causing the decrease of interaction between
PCE and water and the release of some free water. For another, the
molecular weight of the synthesized P(MA4-IPE12PP3G)9 (Sample B)
is only 1/3 of that of conventional PCE, and thus its molecular
chains stretch with freedom in water more easily, which con-
tributes to rapid absorption and dispersion, showing high fluidity
and low viscosity. This signifies that changing molecular weight
as our design is helpful to improve molecular effectiveness and
application performances. It is also worth noting that when we
design the molecular structure of viscosity-reducing type of PCE,
many structural parameters such as molecular weight, side chain
length and side chain density should be considered to achieve a
balance between viscosity reduction and fluidity enhancement,
and it is inadvisable to extremely lower the HLB value, which will
cause difficulties in dissolution or fluidization. Overall, the synthe-
sized viscosity-reducing type of PCE has a potential application in
concrete engineering requiring low viscosity and high flowability.
3.4. Working mechanism of viscosity-reducing type of PCE

3.3.2. Rheological properties of fresh concrete
The rheological properties of fresh concretes containing synthe-
sized PCEs (prepared according to Table 2) were tested, as illus-
trated in Table 5.
From Table 5, the blank sample doesn’t show any rheological
properties, due to less contribution from other raw materials to
flowability; when the dosage of PCE is 0.6%–1.0%, the rheological
properties of concrete containing synthesized PCE increase greatly,
and then increase slowly with the occurrence of some segregation
when the dosage of PCE exceeds 1.0%. This trend presents in all of
the PCE samples. According to the above results, the dosage of syn-
thesized viscosity-reducing type of PCE is determined as 1.0%
bwoc. Also from Table 5, the order of rheological properties is Sam-
ple B > Sample D > Sample E under the same monomer ratio, and
besides, the best rheological properties can be achieved at the
MA/IPEPPG monomer ratio of 4:1 under the same side chain
length, which are well consistent with the results of cement paste.
The synthesized PCE provides good flow properties and low viscos-
ity for concrete, which can be attributed to its own structure as our
3.4.1. Effect on viscosity of mortar and concrete
To evaluate the working effect of synthesized viscosity-
reducing type of PCE, the viscosities of cement paste (gC1), mortar
(gC2) and concrete (gC3 and gCM) were determined. The gC1 and
gCM were the measured values, and the gC2 and gC3 were calcu-
lated from the tested gC1 value according to mesomechanics pro-
cess model, which is described in detail in the literatures [62–
64]. P(MA4-IPE12PP3G)9 (sample B) was selected in this experiment
with the dosages of 0%, 0.6%, 0.8%, 1.0% and 1.2% bwoc. The mix
proportion of concrete used in this test is shown in Table 2, and
the viscosity results are shown in Table 6.
From Table 6, the blank sample exhibit far higher viscosity than
other samples containing PCE, thus reflecting an important role of
this synthesized PCE in viscosity reduction in each cement-based
system. For the samples containing PCE, it can be observed that
gC1, gC2, gC3 and gCM significantly decrease with the increase of
PCE dosage under a fixed W/C. Interestingly, the calculated gC3 val-
ues are highly closed to the measured gCM values, and the higher
the PCE dosage, the better the fitness; with the increase of PCE

Table 5
Rheological properties of concrete mixtures containing different PCEs.

Sample PCE Dosage (%) V-funnel time (s) T50 time (s) Slump flow (mm) Segregation
Blank – 0 – – – No
A1 P(MA3.5-IPE12PP3G)5 0.6 17 – 360 No
A2 P(MA3.5-IPE12PP3G)5 0.8 13 12 540 No
A3 P(MA3.5-IPE12PP3G)5 1.0 11 11 580 No
A4 P(MA3.5-IPE12PP3G)5 1.2 10 9 600 No
B1 P(MA4-IPE12PP3G)9 0.6 9 10 610 No
B2 P(MA4-IPE12PP3G)9 0.8 8.2 8 650 No
B3 P(MA4-IPE12PP3G)9 1.0 6.5 3.8 700 No
B4 P(MA4-IPE12PP3G)9 1.2 7.6 3.5 720 Yes
C1 P(MA4.5-IPE12PP3G)12 0.6 10 8.6 610 No
C2 P(MA4.5-IPE12PP3G)12 0.8 8.5 7.7 630 No
C3 P(MA4.5-IPE12PP3G)12 1.0 7 6.9 650 No
C4 P(MA4.5-IPE12PP3G)12 1.2 7.8 5.4 670 No
D1 P(MA4-IPE24PP6G)9 0.6 10 8 600 No
D2 P(MA4-IPE24PP6G)9 0.8 9 6.5 640 No
D3 P(MA4-IPE24PP6G)9 1.0 8.9 5.2 660 No
D4 P(MA4-IPE24PP6G)9 1.2 7.6 4.7 680 Yes
E1 P(MA4-IPE48PP12G)9 0.6 16 13 540 No
E2 P(MA4-IPE48PP12G)9 0.8 13 10 570 No
E3 P(MA4-IPE48PP12G)9 1.0 10 8.6 610 No
E4 P(MA4-IPE48PP12G)9 1.2 8.6 7.5 630 No
 S. Qian et al. / Construction and Building Materials 169 (2018) 452–461
Table 6
Viscosities of cement paste, mortar and concrete containing synthesized PCE.
Sample Dosage (%) gC1 (Pa
s)
Blank 0 12.86
1 0.6 4.05
2 0.8 3.27
3 1.0 2.58
4 1.2 2.33
dosage from 0.6% to 1.2%, the reduction amplitudes of viscosity of
cement paste, mortar and concrete, namely 42.47%, 45.17%, 46.23%
and 43.7% respectively, are almost the same, signifying that the
synthesized viscosity-reducing type of PCE presents stable working
effectiveness in different systems. The reduction of viscosity slows
down when the PCE dosage is high, mainly because the bleeding or
segregation was apt to occur at high dosage of PCE. Compared with
the existing conventional PCE in previous report [65,66], our vis-
cosity results are lower, thus showing some advantages for this
novel viscosity-reducing type of PCE. These results allow to con-
clude that the reduction of viscosity is ascribed to strong adsorp-
tion and dispersion capacities of the synthesized viscosity-
reducing type of PCE, and consequently, the flocculation of cement
particles is broken to release the constrained water due to the
improved electrostatic repulsion between cement particles.
Besides, the introduced hydrophobic groups of PCE are beneficial
to weaken its combination with water and improve the utilization
efficiency of water; moreover, low molecular weight of viscosity-
reducing type of PCE contributes to high molecular freedom and
low surface tension, thus significantly improving the wettability
of the whole system.
3.4.2. Relationship between viscosity and workability
In practical engineer application, it is inappropriate to reflect
the workability and viscosity characteristics of high-grade concrete
only by either T50 time or V-funnel time. For example, when the
viscosity is too low, T50 time is short whereas V-funnel time is
long, since the segregation makes coarse aggregates sink to block
the outlet; when the viscosity is too high, T50 time is long but also
V-funnel time is too long [14,67,68]. Therefore, both T50 time and
V-funnel time are employed in this study to better evaluate the
workability of high-grade concrete. The results of plastic viscosity
of concrete are calculated based on the data displayed in Tables 5
and 6 according to mesomechanics process model, and further the
fitting curves and equations concerning plastic viscosity with T50
time and V-funnel time respectively were obtained, as shown in
Fig. 8.
Fig. 8. Correlation between plastic viscosity and (a) T50 time (b) V-funnel time.
459
gC2 (Pa
s) gC3 (Pa
s) gCM (Pa
s)
59.31 271.54 301.22
20.92 97.19 89.36
16.60 76.67 79.83
12.89 59.12 62.21
11.47 52.27 50.31
From Fig. 8, with the increase of plastic viscosity of fresh con-
crete, the T50 time and V-funnel time correspondingly increase,
presenting a good correlation with the correlation coefficients of
0.9779 and 0.9578 respectively. This result implies that the T50
time and V-funnel time are applicable to reflect the viscosity char-
acteristics of fresh concrete.
3.4.3. Viscosity-reducing mechanism of the synthesized PCE
The viscosity of slurry depends not on the solid cement particles
but on the water film on the surfaces of cement particles, which
thickness is determined by the water amounts from initial addition
and flocculation. The amount of initially added water is generally
too low in high-grade concrete, and thus the reduction of viscosity
mainly relies on the released water from flocculation of cement
particles by means of strong adsorption-dispersion and reduced
combination with water for PCE. Since the viscosity and strength
of high-grade concrete are greatly influenced by the water-binder
ratio which cannot be optionally changed, it is necessary to fully
perform the functions of viscosity-reducing type of PCE to achieve
the reduction of concrete viscosity. Based on the current theories
and our test results in this study, the deductive mechanism of
viscosity-reduction is illustrated in Fig. 9.
As is shown in Fig. 9, the detailed mechanism of the synthesized
viscosity-reducing type of PCE is described as follows. (1) The
molecular weight of viscosity-reducing type of PCE is only 1/3 of
that of conventional PCE. Thus, the viscosity-reducing type of PCE
exhibits higher molecular freedom in pore solution to stretch its
molecular chains, bringing about great adsorption on the surfaces
of cement particles in a short time and further rapid dispersion
to cement particles. That is to say, other than high molecular
weight and strong steric hindrance for the conventional PCE, low
molecular weight and short side chain of viscosity-reducing type
of PCE are helpful to its dense adsorption on the surfaces of cement
particles. (2) Through introducing some hydrophobic methyl
groups into side chains, the surface tension of viscosity-reducing
type of PCE is lower than that of conventional PCE, resulting in
the reduced solid-liquid interfacial energy which helps to achieve
460 S. Qian et al. / Construction and Building Materials 169 (2018) 452–461
Fig. 9. Schematic diagram of mechanism of viscosity-reducing type of PCE.
stable adsorption and dispersion. (3) The side chain length of
viscosity-reducing type of PCE is 1/2 shorter than that of conven-
tional PCE, and thus the thickness of formed water film in concrete
system shall correspondingly reduce to a half so as to release more
free water to achieve the reduction of concrete viscosity. (4) Lower
molecular weight of the viscosity-reducing type of PCE also causes
fewer amounts of hydroxyl and carboxyl groups and thus fewer
generated hydrogen bonds, leading to the release of more free
water. (5) The thickness of water film coated on the surfaces of
cement particles for viscosity-reducing type of PCE is lower due
to its lower molecular weight and shorter side chains. Conse-
quently, the whole coated cement particles are easy to move flex-
ibly to exert the lubrication of such water film which can
effectively reduce the friction resistance between cement particles,
contributing to the further reduction of concrete viscosity.
4. Conclusions
A series of new viscosity-reducing type of PCEs with different
side chain densities and side chain lengths were successfully syn-
thesized as our design. The acquisition of expected molecular
structures of polymer with high conversion rate and uniform prod-
ucts are confirmed.
The synthesized P(MA4-IPE12PP3G)9 exhibits the highest
adsorption amount, the lowest solution surface tension and the
highest zeta potential (absolute value) of cement paste, which
are correlated with its superior dispersion capacity to cement par-
ticles. This trend also occurs in the fluidity of cement paste and
rheological properties of fresh concrete. The viscosities decrease
by more than 40% with the increase of PCE dosage from 0.6% to
1.2%. The calculated fitting results according to mesomechanics
process model show a good correlation of plastic viscosity with
T50 time and V-funnel time.
The working mechanism is that, this novel PCE with relatively
low molecular weight and short side chain presents thin water film
on the surfaces of cement particles and highly stretched molecular
freedom in pore solution, thus resulting in an effective reduction in
friction resistance between cement particles. Moreover, introduc-
ing a part of hydrophobic groups into side chains of PCE can lower
solid-liquid interfacial energy and improve electrostatic repulsion
to achieve good fluidity properties and to lessen the combination
with water.
The purpose of this study is to innovatively offer a promising
approach to effectively improve the dispersion effect and
viscosity-reducing performances based on our novel molecular
design. This is the first report on the contribution of altering molec-
ular parameters or introducing modified groups to the viscosity-
reducing effectiveness of PCE in fresh concrete, giving a useful
insight into the working mechanism of viscosity-reducing type of
PCE. The extra interest of this study lies in providing a general idea
for obtaining a viscosity-reducing type of PCE with great potential
applications in concrete engineering.
Acknowledgments
The authors express our sincere appreciation to the National Natu-
ral Science Foundation of China (Grant number: 51578025), Beijing
Natural Science Foundation (Grant number: 2162007), Funding
Program for High-Caliber Talents of Beijing Municipal Institutions
(Grant number: CIT&TCD201804008) and Rixin Talent Develop-
ment Project of Beijing University of Technology (Grant number:
2015-RX-L09) for supporting and financing this research work.
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