Effect of Sulfate Ion on the Performance of Polycarboxylate Comb-Like Copolymers in Cement Suspensions

Effect of Sulfate Ion on the Performance of Polycarboxylate Comb-

Like Copolymers in Cement Suspensions
Qianping Ran1,2*, Min Qiao2, Yinhui Yu2, and Jiaping Liu1,2*
1
State Key Laboratory of High Performance Civil Engineering Materials, Jiangsu Research Institute of Building
Science, Nanjing, 210008, China
2
Jiangsu Bote New Materials Co. Ltd, Nanjing, 210008, China
Received: 27 April 2013, Accepted: 5 August 2013

SUMMARY
Polycarboxylate comb-like copolymer (PCE) is a kind of polyelectrolyte, which is easily affected by the ions
in cement suspensions. In this work, the effects of sulfate ion on the surface charge, adsorption and dispersion
in cement system with PCE as dispersant were investigated in detail. The addition of sulfate ion apparently
decreased the positive charge on the surface of cement particles. The sulfate ion reduced the adsorption and
dispersibility of PCE in cement suspensions, which was due to the competition between sulfate ions and PCE
in the adsorption behaviour on the surface of cement particles.

Keywords: Polycarboxylate comb-like copolymer; Sulfate ion; Cement; Adsorption; Dispersion

1. INTRODUCTION anionic polycarboxylate backbone and for comb-like copolymers to adsorb

Comb-like copolymers are new and
efficient types of cement dispersants
with a very flexible chemical
structure 1-5. It is easy to modify
and adapt their molecular structure
in order to maximize the targeted
properties and also meet specific
properties for different applications.
Thus they have attracted significant
attention and have been extensively
studied in the last 20 years1-7. These
comb-like copolymers are composed
of a polyelectrolyte backbone and
non-ionic polyethylene glycol (PEG)-
based “teeth” side chains grafted onto
the backbone at frequent intervals.
It is considered that, in comb-like
copolymers the carboxylate ions
in the backbone mainly act as the
driver of the adsorption because of
the electrostatic attraction between
Corresponding author: Qianping Ran, professor, E-mail: ranqianping@cnjsjk.cn; Fax: +8625
52704855: Phone: +8625 52700983. Jiaping Liu, Professor, E-mail: liujiaping@cnjsjk.cn;
Fax:+8625 52704855; Phone:+8625 83278598.
©
Smithers Information Ltd., 2014
cationic surface of cement particles,
meanwhile the hydrophilic PEG
side chains extend into the solution
and provide the steric repulsion,
which is the main driver for the
dispersion of cement particles5,6. The
polycarboxylate comb-like copolymer
(hereinafter called PCE) is a kind
of polyelectrolyte, which is easily
affected by the ions in the solution [8].
In the suspensions of cement, the type
and amount of the ions is complicated,
which will certainly affect the
interactions between polycarboxylate
comb-like copolymers and cement
particles. Among these ions, sulfate
ion (SO42-) is one of the most important
types of ions, because that negative
ion can be adsorbed onto the positive
surface of cement particles9. In this
case, the surface potential of cement
is reduced, which is disadvantageous
onto the cement particles 10. But
different types of cement have
different contents of sulfate ion, so
polycarboxylate comb-like copolymers
present poor adaptability for different
cements. To reveal the roles of the
relationship between sulfate ion
and polycarboxylate comb-like
copolymers, this study aims to
contribute to a precise understanding
of the impact of the sulfate ion on the
performance of polycarboxylate comb-
like copolymers. First, we synthesised
and characterized a series of PCE
with different charge densities and the
same length of side chain, as shown in
Figure 1. Then the effects of sulfate ion
on the surface charge, adsorption and
dispersion in cement system with PCE
as dispersant are investigated in detail.
2. MATERIALS AND
METHODS
2.1 Cement
An ordinary Portland cement (42.5,
Lafarge Cement Co., China) which

Polymers & Polymer Composites, Vol. 22, No. 6, 2014 527

 Qianping Ran, Min Qiao, Yinhui Yu, and Jiaping Liu

meets the requirements of GB8076
standard was used in this study. The
cement composition was determined
by x-ray fluorescence and Bogue
analysis. The particle size analysis
using a Helos-Sucell Laser particle size
Figure 1. the illustration of the chemical structure of comb-like copolymers with
different charge densities
analyzer (SYMPATEC Instruments,
German) showed the average mean
particle size was about 25 μm. The
BET surface area was 0.8424 m2.g-1.
The characteristics and composition of
the sample are given in Table 1.
2.2 Comb-like Copolymer
Dispersants
The comb-like polymers dispersant
(PCE) composed of sodium polyacrylate
backbone and uncharged polyethylene
glycol (PEG) teeth as shown in Figure 1
were prepared in our laboratory. Details
of the preparation procedure and
characterization methods are described
elsewhere4,7. In this study, a series of
comb-like copolymers with different
charge densities have been chosen
and tested. The composition of PCE
has been estimated classically by
1
H-NMR spectroscopy. The molecular
weight of PCE was determined using
a Wyatt Technology miniDAWN®
static three-angle laser light scattering
detector (MALLS) equipped with
TSK-GELSW (TOSOH) columns.
The used PCE architectures and their
molecular characteristics are listed
in Table 2. All the PCE were used as
sodium salts.

2.3 Zeta Potential

Measurements
Zeta Potential of cement suspensions
was tested in 0.01 mol/L KCl solution
as background. 1 wt.% cement
suspensions were prepared by adding
1 part of cement powders to 99 parts
Table 1. Phase composition and physical properties of the cement of 0.01 mol/L KCl solution. The
Phase composition/% Percent volume diameters/ BET The content prepared cement suspensions had
μm surface of SO3/ a pH value in range of 12.5~12.8.
C3S C2S C3A C4AF d10 d50 d90 VMD area/m2.g-1 mass%
The sodium sulfate is added to the
52.17 21.16 7.49 8.21 3.74 19.82 52.05 25.04 0.8424 0.485 suspensions. Then Zeta Potential of
Here, C3S, C2S, C3A and C4AF represent dicalcium silicate, tricalcium aluminate, cement suspensions is determined at
tricalcium silicate and tetracalcium aluminate ferrite, respectively. d10, d50 and d90 20±2 °C using a Colloidal Dynamics
represent the particle size below which the volume percent is 10%, 50% and 90% electroacoustic-based Zeta Probe
respectively. VMD is the average mean particle size analyzer (USA).

2.4 Adsorption Measurements

Table 2. Molecular characteristics of comb copolymer dispersants (4,7)
Molar composition /% Mn a Mw b μmol COO-/ g
The amounts of PCE comb-like
polymer copolymers adsorbed were determined
x y
by means of a total organic carbon
PCE1 67 33 23600 33490 1400 analyzer, Multi N/C3100 (Analytikjene
PCE2 76 24 24510 33680 2100 AG, Germany). 20 g of solution
PCE3 81 19 24730 33980 2800 containing various amount of PCE
and 10 g of cement were mixed by a
PCE4 86 14 25050 34270 3500
magnetic stirrer for 5 minutes at 20 °C.
a
Mn =number average molecular weight, Mw =weight average molecular weight,
b
The sample solution was separated by
c
DPw is the degree of polymerization which is calculated according to Mw
a suction filter. The aqueous phase was

528 Polymers & Polymer Composites, Vol. 22, No. 6, 2014

 Effect of Sulfate Ion on the Performance of Polycarboxylate Comb-Like Copolymers in Cement Suspensions

separated by centrifuging at 13,000 rpm surface of cement particles due to But it is interesting that the PCE with
for 5 minutes. The supernatant was electrostatic attraction. The zeta higher contents of carboxyl suffered
immediately decanted and dilute with potential data indicated that the less decrease in adsorption with the
deionized water for TOC. Several addition of sulfate ion could influence addition of sulfate ion (the sequence
aliquots of each sample were measured. the surface charge of cement particles, of PCE in content of carboxyl:
The difference in the concentration so a series of experiments was held PCE1<PCE2<PCE3<PCE4). So it
before and after contact with the cement to reveal the effect of sulfate ion on could be considered that sulfate ion and
was assumed to be adsorbed polymer. the adsorption of PCE as shown in PCE are competitive in the adsorption
Figure 3. It could be clearly seen that process, as shown in Figure 4. On
the adsorption ratio of PCE decreased the surface of cement particle, the Ca
2.5 Dispersion Behaviour
as the addition of sulfate ion increased. ions give the surface a positive charge.
Cement pastes were mixed at 20 °C and
at water to cement ratio (w/c) =0.23,
using a Hobart mixer. First, PCE and Figure 2. Zeta potential curve of cement suspensions with different additions of
water were weighed into a bowl. Then sulfate ion
300 g of cement was added and mixed
for 1 min at low speed and a further
2 min at high speed. The amount of PCE
added was expressed as a percentage
of dry solid with respect to the mass
of cement. The cement paste was used
to measure fluidity and rheological
behaviour at the same time. The fluidity
of cement paste was evaluated by a
flow test. The paste flow was measured
at 20 °C by pullout spread of cement
paste from a cone (upper inner diameter
36 mm, lower inner diameter 60 mm
and height 60 mm), in accordance with
GB8076-2008.

3. RESULTS AND
DISCUSSION
3.1 Zeta Potential Test
Figure 3. Influence of SO42- concentration on the adsorption of PCE onto cement
As shown in Figure 2, after adding
particles
sulfate ion, the potential of the
cement particle surfaces decreased
rapidly from 1.2 mV to 0 when the
content of sulfate ion was increased
to 160 mmol/L. When increasing
the content of sulfate ion to more
than 160 mmol/L, the potential of
particle surface reversed to become
negative. The results indicated that
adsorption of sulfate ion on the surface
of cement particles had place, and the
surface charge of cement particles had
therefore been influenced, which is also
proven by L. Divet11.

3.2 Adsorption Behaviour

The negatively charged PCE molecule
is easy to adsorb on the positive

Polymers & Polymer Composites, Vol. 22, No. 6, 2014 529

 Qianping Ran, Min Qiao, Yinhui Yu, and Jiaping Liu
Figure 4. The competition between SO42- and PCE in the process of adsorption
on the surface of cement particles
Figure 5. Influence of SO42- concentration on dispersion of cement pastes
containing PCE dispersant (the dosage of PCE was 0.2% of the weight of cement)
When added to the suspensions, SO42-
anions have strong ionic bonding with
Ca2+, which makes the sulfate ions more
easily adsorbed; hence the adsorption
of PCE is suppressed. When the charge
density of PCE is low, the driving force
for adsorption is weak, which means
that in the competitive adsorption
process sulfate ion could easily
displace the PCE. So the adsorption
ratio of PCE1 decreases rapidly when
the amount of added sulfate ion is
enhanced. When the charge density
of PCE is high, the drive force for
adsorption is strong, which meant that
in the competitive adsorption process
PCE is able to defeat sulfate ion. So
the adsorption ratio of PCE1 had no
530
distinct changes when the amount of
added sulfate ion is enhanced.
3.3 Dispersion Behaviour
It is considered that the dispersibility
of comb-like copolymers is dependent
on the adsorption and steric repulsion.
Comb-like copolymers with higher
adsorption activity and stronger
steric repulsion would have better
dispersibility. The dispersion behaviour
of PCE in cement paste is shown in
Figure 5. Because of the same length
of side chain, the 4 PCEs would
have similar steric repulsion. So the
adsorption will play an important
role for the dispersion. As shown
Polymers & Polymer Composites, Vol. 22, No. 6, 2014
in Figure 4, the PCE with higher
content of carboxyl had less decrease
in dispersion when enhancing the
addition of sulfate ion (The sequence
of PCE in content of carboxyl:
PCE1<PCE2<PCE3<PCE4), which
was consistent with the result of
adsorption behaviour.
4. Conclusions
Polycarboxylate comb-like copolymer
(PCE) is a kind of polyelectrolyte,
which is easily affected by the ions
in the ambient solution. Among
these ions, sulfate (SO42-) is the most
important type of ion. It has been
found that the addition of sulfate ion
can decrease the positive charge on
the surface of cement particles. The
sulfate ion reduced the adsorption
and dispersibility of PCE in cement
suspensions. But increasing the charge
density in copolymers can weaken the
influence of sulfate ion. It is considered
that the dispersibility of PCE depends
on both of the adsorption and steric
repulsion. In this paper, it was shown
that the molecular structure of PCE
could be optimized to weaken the
influence of sulfate ions in cement
suspensions. PCE with high charge
density was less sensitive to the sulfate
ions in cement suspensions.
Acknowledgments
This study is financially supported
by National Basic Research Program
of China (973 Program) (Grant No.
2009CB623205) and National Fund for
Natural Sciences (Grant No. 51278132).
References
1. Yoshioka K., Sakai E., Daimon
M., and Kitahara A., Role of Steric
Hindrance in the Performance of
Superplasticizers for Concrete. J.
Am. Ceram. Soc. 80 (1997) 2667-
2671.
2. Yamada K., Hanehara S., and Honma
K., Effect of the chemical structure
on the properties of polycarboxylate
type superplasticizers, Cement
Concrete Res., 30 (2000) 197-207.
 Effect of Sulfate Ion on the Performance of Polycarboxylate Comb-Like Copolymers in Cement Suspensions
3. Yoshioka K., Tazawa E., Kawai
K., and Enohata T., Adsorption
characteristics of superplasticizers on
cement component minerals, Cement
Concrete Res., 32 (2002) 1507-1513.
4. Ran Q.P. and Somasundaran P.,
Miao C.W., Liu J.P., Wu S.S., Shen
J., Adsorption Mechanism of Comb
Polymer Dispersants at the Cement/
Water Interface, J. Disper. Sci.
Technol., 31 (2010) 790-798.
5. Plank J., Vlad D., Brandl A., and
Chatziagorastou P., Colloidal
chemistry examination of the
steric effect of polycarboxylate
superplasticizers. Cement Int., 3
(2005) 101-110.
Polymers & Polymer Composites, Vol. 22, No. 6, 2014
6. Uchikawa H., Hanehara S., and
Sawaki D., The role of steric
repulsive force in the dispersion
of cement particles in fresh paste
prepared with organic admixture.
Cement Concrete Res., 27 (1997) 37-
50.
7. Ran Q.P., Somasundaran P., Miao
C.W., Liu J.P., Wu S.S., and Shen J.,
Effect of the length of the side chains
of comb-like copolymer dispersants
on dispersion and rheological
properties of concentrated cement
suspensions, J. Colloid Interf. Sci.,
336 (2009) 624-633.
8. Solis F. and Cruz M.O., Collapse
of flexible polyelectrolytes in
multivalent salt solutions. J. Chem.
Phys., 112(4) (2000) 2030-2035.
9. Veiga K.K. and Gastaldini A.L.G.,
Sulfate attack on a white Portland
cement with activated slag. Constr.
Build. Mater., 34 (2012) 494-503.
10. Yamada K., Ogama S., and Hanehara
S., Controlling of the adsorption and
dispersing force of polycarboxylate-
type superplasticizer by sulfate ion
concentration in aqueous phase.
Cem. Concr. Res., 31 (2001) 375-
383.
11. Divet L. and Randriambololona R.,
Delayed ettringite formation: the
effect of temperature and basicity on
the interaction of sulphate and C-S-H
phase. Cem. Concr. Res., 28(3)
(1998) 357-363.
531
 Qianping Ran, Min Qiao, Yinhui Yu, and Jiaping Liu

532 Polymers & Polymer Composites, Vol. 22, No. 6, 2014