Colloids and Surfaces A: Physicochem. Eng.

Aspects 448 (2014) 119–129

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Synthesis, characterization and performance of a polycarboxylate

superplasticizer with amide structure
Xiao Liu a,∗ , Ziming Wang a , Jie Zhu a , Yunsheng Zheng b , Suping Cui a ,
Mingzhang Lan a , Huiqun Li a,c
a
College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China
b
State Key Laboratory of Solid Waste Reuse for Building Materials, Beijing 100041, China
c
Technology Department, 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

• Amide-PCE was synthesized success-

fully and the optimal conditions were
determined.
• The structure of amide-PCE and its
sufficient amidation reaction were
confirmed.
• Amide-PCE has better application
performance than the conventional
PCE in concrete.
• The dispersion mechanism of amide-
PCE in cement–water system was
illustrated.
• It can provide electrostatic repulsion,
steric hindrance, complex and lubri-
cation.

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

Article history: The amide-structural polycarboxylate superplasticizers (amide-PCEs) were synthesized by amidation
Received 24 July 2013 reaction between polyacrylic acid (PAA) and amino-terminated methoxy polyethylene glycol (amino-
Received in revised form 21 January 2014 PEG) under different conditions, and the effects of amide-PCE’s synthesis on amidation rate and flow
Accepted 10 February 2014
performance of cement paste were investigated. Fourier Transform Infrared Spectroscopy (FTIR), 1 H
Available online 18 February 2014
Nuclear Magnetic Resonance (1 H NMR), and molecular-weight measurements were used for structural
characterization, and the results confirmed ideal amide structure and sufficient amidation reaction.
Keywords:
Amide-PCE with the carboxyl–amino ratio of 4:1 exhibited the lowest surface tension, highest adsorption
Superplasticizer
Polycarboxylate
percentage, and the best paste fluidity results. Based on the above results, the dispersion and adsorp-
Amide structure tion mechanisms of amide-PCE in cement–water system were discussed. The application performances
Cement in concrete showed that amide-PCE had similar slump to that of conventional PCE, but also had bet-
Fluidity ter air-entraining ability, bubble retention and concrete frost-resistance than those of conventional
PCE. Depending on this amide structure and good performances, amide-PCE shows broad application
prospects.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction

∗ Corresponding author. Tel.: +86 10 6739 6649; fax: +86 10 6739 6085. Superplasticizers are an important class of chemical admixture
E-mail addresses: liux@bjut.edu.cn, liulaugh@126.com (X. Liu). that can be added to concrete mixtures to improve workability of
http://dx.doi.org/10.1016/j.colsurfa.2014.02.022
0927-7757/© 2014 Elsevier B.V. All rights reserved.
120 X. Liu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 448 (2014) 119–129
concrete by dispersing agglomerated hydrating cement particles
present in the paste [1] and other applications [2–4]. Strength of
concrete is inversely proportional to the amount of water added or
water–cement ratio (w/c); however, if the amount of water is too
low, the concrete mixture can be unworkable and difficult to mix
and place. Therefore, the main function of a superplasticizer is to
enable a decrease in the w/c without losing fluidity of the cement
pastes, which results in higher strength and better durability of
concrete [5,6].
There are three generations of superplasticizers in concrete.
The first generation is commonly manufactured from lignosul-
fonates and the second generation from sulfonated naphthalene
formaldehyde or sulfonated melamine formaldehyde. In the 1980s,
polycarboxylate superplasticizers (PCEs) were introduced as the
third, new generation of concrete admixtures [7] and are still
developing. Because of its comb-type structure with poly(ethylene
glycol) (PEG) grafted side chains [8] and the associated steric inter-
particle repulsive forces [9], PCEs are effective at lower dosages,
and provides improved slump retention [10,11] than polyconden-
sates. Thus, nowadays PCEs have been introduced into the cement
systems replacing admixtures based on melamine and naphthalene
[12,13], and have attracted great research attention in recent years
[14–16].
Generally speaking, PCEs have a great diversity of chemical
structures and can mainly be classified as two categories. The
one is polyester-type PCE, made from ␻-methoxy poly(ethylene
glycol) methacrylate ester (MPEG-MA), either by aqueous free rad-
ical copolymerization [17] or by esterification/transesterification
reaction [18–21]. The other is polyether-type PCE, including ␣-
allyl-␻-methoxy or ␻-hydroxy poly(ethylene glycol) (APEG) ether
and maleic anhydride as key monomers via radical copolymer-
ization either in bulk or in aqueous solution [22], isoprenyl
oxy poly (ethylene glycol) macromonomers by copolymerization
with acrylic acid [23], and ␣-methallyl-␻-methoxy or ␻-hydroxy
poly(ethylene glycol) ether as macromonomer [24]. However, the
development of concrete technology needs more structure types
of PCE with better performance to meet the requirements in dif-
ferent projects. Only changing material ratio, chain length, initiator
concentration, or reaction conditions to achieve some performance
improvements [5,17,25–27] is not enough.
Amide/imide type PCE firstly was reported by Jeknavorian in
Grace [28,29] who obtained a copolymer formed by an acrylic poly-
mer with ammonia or an alkoxylated amine had higher imidization
degree and production cost. Hereafter, Vickers [30] synthesized
a PCE with at least one ester linkage and one amide linkage,
which had high water reduction and long shelf life. Peev [31]
reported a PCE comprising a water-soluble alkanolamines modi-
fied acrylic copolymer had both good flowability and high early
strength. Schober [32] described an acrylic polymer which com-
prised side chains connected to the backbone by ester, amide or
imide linkages. Danzinger [33] provided a polycarboxylic acid-
based cement dispersant containing a polyamide-polyamine in a
skeleton of a polymer, which had improved water reducing ability
and slump-flow retention but not in application due to its unavail-
able raw materials. Recently, PCE’s increased application promotes
the development of concrete technology, which in turn puts for-
ward higher requirements to its performance. Hence, exploring
new structural PCE with unique performance of concrete or cement
paste cannot be ignored, but there have been few studies on this.
The conventional PCEs produced by radical co-polymerization
are growing rapidly, whereas they have many shortcomings. For
the different monomers’ polymerization activities, it is difficult to
control the copolymer’s unit arrangement and molecular weight
of backbone. A part of copolymers with low molecular weight can
widen the molecular weight distribution and further weaken the
final performance. To overcome these difficulties, an amide-PEG
was synthesized by grafting reaction to form amide linkages. It
derives from the homopolymer with a constant molecular weight
and a narrow molecular weight distribution, and normally results
in a more statistically uniform distribution of PEGs attached onto
the polyacrylic acid backbone. This grafting approach thus is ben-
eficial to obtain a superior PCE-based dispersant which has broad
application prospects.
In this study, polycarboxylate superplasticizers with amide
structure (amide-PCEs) were synthesized by amidation reaction
between polyacrylic acid (PAA) and amino-terminated methoxy
polyethylene glycol (amino-PEG), and the optimal synthesis pro-
cess was determined. Influences of amide-PCEs with different
variable synthesis factors upon amidation rate and flow per-
formance of cement paste were described by the investigations
of catalyst dosage, water-carrying agent dosage, carboxyl–amino
ratio, amidation reaction temperature, and amidation reaction
time. In order to confirm its amide structure, amide-PCE was char-
acterized by Fourier Transform Infrared Spectroscopy (FTIR) and
1 H Nuclear Magnetic Resonance (1 H NMR). The molecular char-
acteristics including molecular weight and its distribution were
measured by gel permeation chromatography (GPC). Also, the
effects of amide structure and grafting density on the properties
of amide-PCEs were examined and analyzed by assessing the paste
fluidity, surface tension and adsorption of a series of amide-PCEs
with different grafting densities. Both amide-PCE and conventional
PCE’s application performances in concrete including air content,
slump and slump flow, and frost-resistance were measured. Addi-
tionally, the dispersion and adsorption mechanisms of amide-PCE
in cement–water system were discussed.
2. Materials and measurements
2.1. Materials
Polyacrylic acid (PAA) with solid content of 49% and molecular
weight of 5000 was supplied by BASF (China) Co., Ltd (Shanghai,
China), and the amino-terminated methoxy polyethylene glycol
(amino-PEG) with molecular weight of 2000 was from Clariant
Chemicals (China) Ltd. (Shanghai, China). The conventional PCE
was liquid with a solid content of 42%. Toluene, sodium hydrox-
ide, concentrated sulfuric acid (98 wt%), and cyclohexane were of
analytical grade and purchased from Beijing Chemical Works (Bei-
jing, China). The p-toluene sulfonic acid and sulfamic acid were of
analytical grade and from Tianjin Guangfu Fine Chemical Research
Institute. Reference cement P. I. 42.5 and Liulihe cement P. O. 42.5
were supplied by China United Cement Qufu Co., Ltd (Qufu, China)
and Beijing Liulihe Cement Co., Ltd (Beijing, China), respectively.
The medium sand with a fineness module of 2.7 had a density of
2550 kg/m3 and a bulk density of 1460 kg/m3 , and the gravel with
a continuous grading of 5–20 mm had a density of 2630 kg/m3 and
a bulk density of 1540 kg/m3 . The chemical and mineral composi-
tions of cements are illustrated in Table 1.
2.2. Synthesis of amide-PCE
The amino-PEG, PAA, and catalyst were added in sequence to
a 500 mL four-neck round-bottom flask with a stirrer, a water
separator with a condenser, a thermometer and an intelligent
control temperature device by using the one-step process. The
temperature was slowly raised to 80 ◦ C by stirring and heating,
and then the water-carrying agent was added to the flask to ensure
the uttermost amidation reaction by continually removing the
produced water from reaction system to water separator. The
temperature was raised to 130–150 ◦ C and maintained for several
hours. After the reaction, the product was vacuumized to separate
 X. Liu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 448 (2014) 119–129
Table 1
Chemical and mineral compositions of cements.
Cement SiO2 (%) Al2 O3 (%)
Reference cement 22.93 4.29
Liulihe cement 21.47 4.73
Cement Loss (%) f-CaO (%)
Reference cement 1.48 0.64
Liulihe cement 1.53 0.54
the water-carrying agent to constant weight, followed by cooling
to room temperature. The final product is the amide-PCE. The
specimens used for the characterization and measurements were
subjected to several cycles of centrifugation and further purified
by repeated precipitation with acetone-methanol mix solvent.
The schematic diagram of the synthesis of amide-PCE by PAA and
amino-PEG is shown in Fig. 1.
2.3. Characterization of amide-PCE
2.3.1. Amidation rate
The product sample with a certain mass was conditioned by
repeated alternating treatments with 1 M HCl and 1 M NaOH with
a final step of adding 1 M NaOH. Thereafter, the mixture was placed
in a 250 mL conical flask, followed by adding 25 mL of anhydrous
ethanol and then 2 or 3 drops of 0.1 wt% phenolphthalein indica-
tors. After dissolved completely, this sample solution was titrated
by 0.1 M KOH standard solution until it appeared light pink for
30 s long, which was the titrating end-point. The consumed volume
of KOH standard solution for titration defined as V was recorded.
The amidation rate of amide-PCE was calculated according to the
equation
W = {N 1 − [m1 /40 + 0.1 V × (m1 + m2 )/m3 − N 3 ]}/N 2
where W was the amidation rate; m1 was the solute mass of sodium
hydroxide; m2 was the theoretical mass of product; m3 was the
mass of sample; N1 was the mole number of carboxyl groups of
PAA; N2 was the mole number of amino groups of amino-PEG; N3
was the mole number of p-toluene sulfonic acid.
2.3.2. FTIR analysis
The amidation product was purified via dissolution and pre-
cipitation for at least three times, and then dried in vacuum at
60 ◦ C for 24 h to constant weight. In characterizing the chemical
structure, the dried amide-PCE samples with a certain mass were
mixed with KBr and pressed into a disk. The FTIR spectrum of the
disk was recorded with a VERTEX 70 Fourier transform infrared
spectrometer (Bruker Co., Germany).
Fig. 1. Schematic diagram of the synthesis of amide-PCE.
121
Fe2 O3 (%) CaO (%) MgO (%) SO3 (%) Na2 O (%)
2.89 66.23 1.92 0.35 0.70
3.36 62.56 2.76 2.76 1.58
C3 S (%) C2 S (%) C3 A (%) C4 AF (%)
58.78 21.38 6.49 8.77
52.13 25.76 7.27 8.79
2.3.3. 1 H NMR
The amidation product was purified and dried in the same pro-
cess as FTIR analysis. 1 H NMR spectrum was obtained at room
temperature (25 ◦ C) with an ARX-400 spectrometer (Bruker Co.,
Germany) operating at frequencies of 400 MHz, and the chemical
shift values were expressed in d values (ppm) relative to tetram-
ethylsilane (TMS) as internal standard. Sample for 1 H NMR was
prepared by dissolving in the solvent, i.e., deuterated water (D2 O)
as internal reference.
2.3.4. Molecular weight and distribution
The number average molecular weight (Mn ), weight average
molecular weight (Mw ), and polydispersity index (PDI) of amide-
PCE were determined at 30 ◦ C on a Waters PL-GPC50 (Waters
Instruments Co., USA) equipped with a differential refraction detec-
tor. The mobile phase consisted of a solution of 0.10 mol/L sodium
nitrate, and its flow rate was 0.5 mL/min. The standard sample was
polyethylene glycol with a concentration of 2 mg/mL and an injec-
tion volume of 50 ␮L.
2.3.5. Thermostability
The thermal behavior of the superplasticizers was performed
on a Netzschsta 449C thermo-analyzer instrument (Netzsch,
Germany) at a temperature range of 25–400 ◦ C, with a heating rate
of 10 ◦ C/min under the flow of argon gas.
2.4. Performance measurements
2.4.1. Surface tension of amide-PCE solution
The surface tension of the amide-PCE solution was measured
by a BZY-1 Surface or interface tension apparatus produced by
Shanghai Hengping Instrument Factory (Shanghai, China). The sam-
ple solution was obtained by dissolving amide-PCE in distilled
water so that its mass concentration was 5 wt%. After the heated
platinum plate cooled, it was submersed in the sample solution
and then the measured value was recorded.
2.4.2. Adsorption percentage of amide-PCE in cement
The amount of amide-PCE adsorption on cement particles was
evaluated using the depletion method [34]. The non-adsorbed
portion of polymer remaining in solution at equilibrium condition
was determined by analyzing the total organic carbon (TOC) con-
tent of the solution. In a typical experiment, 30 g of cement, 120 g
of deionized water, and the amount of amide-PCE to remain 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 produced by ShangHai Anting
Scientific Instrument Factory (Shanghai, China). The supernatant
was diluted 100 times with deionized water. The total organic car-
bon of the solution was determined on a Vario TOC cube instrument
(Elementar Analysensysteme GmbH, Germany).
The adsorption amount and adsorption percentage of amide-
PCE were calculated from the difference between the TOC content
of the polymer reference sample in the initial solution and that of
the supernatant of cement paste. The adsorption amount changes
with time were obtained by testing the amide-PCE adsorption for
122 X. Liu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 448 (2014) 119–129
Fig. 2. Fluidity of cement paste over time for amide-PCE with the catalyst of (a) concentrated sulfuric acid, (b) p-toluene sulfonic acid, and (c) sulfamic acid at different
dosages.
5 min, 30 min, 60 min, 90 min, and 120 min, respectively. Measure-
ments were generally repeated three times and the average was
reported as the adsorbed amount.
2.4.3. Fluidity of cement paste
The fluidity of fresh cement paste with amide-PCE was tested
according to the standard method GB/T8077-2000 [35] described
in the National Standards of People’s Republic of China. The effect of
the amide-PCE dosage (mass percentage) on the fluidity of cement
paste was studied at the same w/c of 0.29. Generally the dosage of
amide-PCE was 0.2 wt% of cement if there was no particular indica-
tion. To study the maintenance of fluidity efficiency, cement pastes
mixed with amide-PCE were examined every 60 min within a total
period of 120 min.
The fluidity of cement paste over time was measured using the
standard method. For each test of cement paste fluidity, the cement
paste mixture was poured into a truncated cone (60 mm height,
36 mm top diameter, 60 mm bottom diameter) on a glass plate,
and then the cone was vertically removed. After 30 s, the diameter
of paste was recorded as the fluidity of paste, and the resulting
spread of the paste was measured twice. The second measurement
was perpendicular to the first measurement, and the average was
calculated to yield the spread value.
2.4.4. Properties of concrete
Concrete was made by mixing water, binder (cement + fly
ash + slag), fine and coarse aggregate, and amide-PCE solution
Fig. 3. Fluidity of cement paste over time for amide-PCE with the water-carrying agent of (a) toluene, and (b) cyclohexane at different dosages.
(amide-PCE dissolved in part of mixing water and added with mix-
ing water). The workability of concrete for amide-PCE was indicated
by the slump and slump flow at 0 min and 1 h in a slump cone test
according to the standard GB/T50080-2002 [36]. In the preparation
of the concrete mixtures, the same powder dosage (cement + fly
ash + slag powder) and sand/coarse aggregate ratios were used. The
change of slump with time was then studied to evaluate the effect of
amide-PCE on the time dependent workability of concrete. The air
contents of fresh concrete at 0 min and 1 h were also determined
by a LC-615A/B Concrete air content analyzer (Sanyo Industries,
Ltd, Japan) according to the standard GB/T50080-2002 [36]. There-
after the concrete cubic specimens of 150 × 150 × 150 mm were
prepared, cured, and their compressive strengths were measured
by a YEW-2000 Computer control compression testing machine
produced by Beijing Lizhifang Science and Technology Develop-
ment Co., Ltd (Beijing, China), according to GB/T50081-2002 [37]
at the ages of 3, 7, and 28 days. The frost-resistance of concrete was
determined according to GB/T50082-2009 [38].
3. Results and discussion
3.1. Effect of catalyst and its dosage on cement fluidity
The amidation reaction rate is intensively influenced by the cat-
alyst and its dosage, and thus the fluidity of cement paste is also
affected. The strong acids including concentrated sulfuric acid, p-
toluene sulfonic acid and sulfamic acid were selected as catalyst.
 X. Liu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 448 (2014) 119–129 123

The dosage of catalyst is the mass percentage of total reactants.

The relationship between the cement paste fluidity and the dosages
(from 2.0 wt% to 4.0 wt%) of catalysts is shown in Fig. 2.
For the concentrated sulfuric acid as catalyst, cement paste
remained flow state within 120 min only at the dosage of 2.5 wt%.
This is possibly owing to its strong oxidation and more side reac-
tions at high temperature, leading to carbonization and black
product. The sulfamic acid was better, and the p-toluene sulfonic
acid was the best than concentrated sulfuric acid as catalyst. Fluid-
ity and its retention gradually increased with increasing the dosage
of p-toluene sulfonic acid from 2.0 wt% to 4.0 wt%. When the dosage
of p-toluene sulfonic acid was greater than 3.0 wt%, it can achieve
the initial paste fluidity of 252 mm and good fluidity retention. The
same initial fluidity and better fluidity retention were obtained
for the dosage of 3.5 wt% compared with the dosage of 4.0 wt%.
This may be caused by a little excess catalyst leading to decrease
of the effective components in amidation product. Therefore, the Fig. 4. Fluidity of cement paste over time and amidation rate for amide-PCE syn-
p-toluene sulfonic acid at the dosage of 3.5 wt% was used for ami- thesized by different carboxyl–amino ratios.
dation reaction.

3.2. Effect of water-carrying agent and its dosage on cement

achieved as a result of the low grafting density of side chain. On
fluidity
the contrary, at a carboxyl–amino ratio of 2:1, the structure with
a thicker grafting side chain might be formed difficultly because
The amidation reaction is a reversible reaction, and its amida-
of the steric hindrance, and thus a part of unreacted amino-PEG
tion rate depends on the amount of water produced during the
lowered the effective components and led to poor fluidity results,
reaction and the promptness of its remove from the reaction sys-
which was in accordance with its low amidation rate. Therefore,
tem. In order to achieve the utmost forward reaction, the toluene
the carboxyl–amino ratio was set at 4:1.
and cyclohexane were chosen as water-carrying agents. The dosage
of water-carrying agent is the mass percentage of total reactants.
3.4. Effect of amidation reaction temperature on cement fluidity
The relationship between the cement paste fluidity and the dosages
(from 10 wt% to 25 wt%) of water-carrying agents is shown in Fig. 3.
The lower amidation reaction temperature leads to decrease
For toluene in Fig. 3(a), no fluidity was observed at the toluene
of reaction rate, and the higher amidation reaction temperature
dosage of 10 wt%, indicating the low water-carrying ability which
leads to excessive oxidation of reactants. In this reaction system,
was probably due to the insufficient water-carrying agent. The flu-
the water initially produced during the reaction was observed at
idities were approximate when the toluene dosages were 15 wt%,
128 ◦ C from the water separator, and thus 130 ◦ C, 135 ◦ C, 140 ◦ C,
20 wt% and 25 wt%. In consideration of preparation cost, the toluene
145 ◦ C and 150 ◦ C were selected as amidation reaction tempera-
dosage was determined to 15 wt%. For cyclohexane in Fig. 3(b), flu-
ture to be investigated. The relationship between the cement paste
idities at the cyclohexane dosages of 10 wt% and 15 wt% were a
fluidity and the amidation reaction temperature is shown in Fig. 5.
little higher than those at the dosages of 20 wt% and 25 wt%. As
From Fig. 5, the initial fluidity of cement paste mixed with
a whole, fluidities for cyclohexane as water-carrying agent were
amide-PCE synthesized above 130 ◦ C was in the range of 285 mm
lower than those for toluene, possibly because of the difference
to 300 mm, but the cement paste mixed with amide-PCE synthe-
between their water-carrying abilities and azeotropic points with
sized at 135 ◦ C exhibited the best fluidity retention and the highest
water. Thus, toluene was designated as water-carrying agent and
amidation rate. Thus the amidation reaction temperature was fixed
its dosage was 15 wt%.
at 135 ◦ C. When the amidation reaction temperature was as low as
130 ◦ C, the amidation rate was the lowest and the poor fluidity was
3.3. Effect of carboxyl–amino ratio on cement fluidity
observed. When the amidation reaction temperature was as high
The molar ratio of PAA to amino-PEG, i.e., carboxyl–amino
ratio, is an important factor for the amidation reaction. It deter-
mines the grafting density of side chain for the amide-PCE. The
carboxyl–amino ratio should be more than 1:1, or there will be
plenty of free amino-PEG which cannot participant in amida-
tion reaction. Actually, if the carboxyl–amino ratio is 1:1, the
whole amide-structure with all carboxyl groups amidated by amino
groups is unable to be formed because of the steric hindrance.
Fig. 4 shows the fluidity of cement paste over time and amida-
tion rate for amide-PCE synthesized by different carboxyl–amino
ratios. The initial fluidity and fluidity retention of cement paste
mixed with amide-PCE synthesized at the carboxyl–amino ratio of
4:1 were the most excellent, as opposed to that of 2:1. This indi-
cates that the proper grafting density of side chain is beneficial to
fully exerting the effects of electrostatic repulsion and steric hin-
drance of the comb-structural PCE, leading to the improved fluidity
of cement paste.
At the carboxyl–amino ratio of 5:1, the repulsion effect of side Fig. 5. Fluidity of cement paste over time and amidation rate for amide-PCE syn-
chain of PCE adsorbed on the cement particles might not be fully thesized at different amidation reaction temperatures.
124 X. Liu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 448 (2014) 119–129

Fig. 6. TG curves for amide-PCE synthesized at different amidation reaction tem- Fig. 7. Fluidity of cement paste over time for amide-PCE synthesized for different
peratures. amidation reaction times.

reaction time. In consideration of energy saving and high efficiency,

as 150 ◦ C, the fluidity retention was poor, which was possibly due
to partial cleavage of ether bonds of amino-PEG at high tempera-
ture, and the shortened side chain cannot effectively improve the
dispersion of cement particles. With the hydration of cement, the
steric hindrance effect was weakened distinctly, manifested as the
great fluidity loss over time.
The thermostability of amide-PCEs synthesized at different ami-
dation reaction temperatures is shown in Fig. 6. Prior to the thermal
analysis measurement, the samples were dried thoroughly by vac-
uum oven.
From Fig. 6, there is a significant weight loss occurred at tem-
perature range of 200–300 ◦ C. An unapparent weight loss ranged
from room temperature to around 200–240 ◦ C was about 10% mass
losses, which can be ascribed to the decomposition of the small
molecules of short chain. For amide-PCE synthesized at 130 ◦ C, the
temperature of 5 wt% weight loss is about 164 ◦ C, but for amide-
PCE synthesized at 135 ◦ C that is about 214 ◦ C. This result indicates
that the amide-PCE synthesized at 135 ◦ C has good thermal sta-
bility, which is proportional to the results of amidation rate. The
main reason is that the sample synthesized at inappropriate amida-
tion reaction temperature with low amidation rate contains many
unreacted macromonomers, which causes the decrease of decom-
position temperature; on the contrary, the sample synthesized at
the appropriate amidation reaction temperature with high ami-
dation rate contains a great number of macromolecular chains
with homogeneous structures, which have similar ability of ther-
mal motion and causes the increase of decomposition temperature.
This result is in agreement with the effect of amidation reaction
temperature on cement fluidity.
the amidation reaction time was 4 h.
3.6. FTIR analysis
The amide-PCE was synthesized as the optimum conditions con-
cluded above, and its FTIR spectrum is shown in Fig. 8. Peaks at
3031.98 cm−1 to 2667.44 cm−1 and 1502.49 cm−1 to 1328.90 cm−1
were stretching vibration peak and deformation vibration peak
of –CH3 and –CH2 , respectively. Peaks at 1253.68 cm−1 and at
1209.32 cm−1 to 1053.09 cm−1 corresponded to C–C bonds in the
main chain and ether bonds in the side chain of amide-PCE, respec-
tively.
Also from Fig. 8, peak at 1732.00 cm−1 was stretching vibra-
tion peak of –COOH derived from unreacted carboxyl groups in the
main chain of amide-PCE. Peaks at 3517.05 cm−1 , 1662.57 cm−1 ,
1542.99 cm−1 , 1296.11 cm−1 and 680.84 cm−1 were stretching
vibration peak of –N–H–, stretching vibration peak of –C=O, in-
plane bending vibration peak of –N–H–, stretching vibration peak
of –C–N– and out-plane bending vibration peak of –N–H– in the
amide structure of amide-PCE, respectively. It is worth mentioning
that the imide structure may not be formed, for no characteris-
tic peaks of imide group in Fig. 8, which stretching vibration peak,
in-plane bending vibration peak and out-plane bending vibration
peak were generally around 1780 cm−1 , 1380 cm−1 and 720 cm−1 ,
respectively. Based on the above analysis, the product certainly had
the amide structure.

3.5. Effect of amidation reaction time on cement fluidity

From the water separator, the weight of produced water kept

almost unchanged after about three and a half hours. Consequently,
the amidation reaction times of 4 h, 5 h and 6 h were chosen to
be investigated. The fluidity of cement paste over time for amide-
PCE synthesized for different amidation reaction times is shown in
Fig. 7.
With the increase of amidation reaction time, no distinct
changes were observed among each other, whether for the ini-
tial fluidity or for the fluidity retention. The larger version of Fig. 7
showed the differences of initial fluidity, fluidity at 1 h, and fluid-
ity at 2 h were about 2.3%, 5.6%, and 8.8%, respectively. Hence, it is
concluded that there is no significant effect of amidation reaction
time on cement paste fluidity, which cannot increase by prolonging Fig. 8. FTIR spectrum of amide-PCE.
 X. Liu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 448 (2014) 119–129
Fig. 9.
3.7. 1H NMR analysis
Fig. 9 shows the 1 H NMR spectrum of newly synthesized amide-
PCE, and this spectrum was analyzed by means of the reported
references [3,39].
In the main chain, –CH2 , –CH connected carboxyl group and –CH
connected side chain gave signals at ı = 1.119 ppm, 1.240 ppm and
2.354 ppm, respectively. In the side chain, –CH3 at the chain end
and –CH3 in polypropylene oxide gave signals at ı = 3.331 ppm and
3.45 ppm to 3.55 ppm, respectively. The strong peak at 3.60 ppm
to 3.75 ppm corresponded to –CH2 CH2 – in polyethylene oxide and
–CH2 CH– in polypropylene oxide, for the side chain contained more
about 40 units of ethylene oxide (EO) or propylene oxide (PO).
Besides, peaks at 4.70 ppm and 7.309 ppm to 7.649 ppm corre-
sponded to D2 O used for dissolving sample and a small amount
of residual p-toluene sulfonic acid, respectively. The above results
confirmed the amide structure of synthetic product, which were in
accordance with FTIR analysis.
3.8. Molecular weight of amide-PCE
Molecular weight and its distribution of newly synthesized
amide-PCE are shown in Table 2 and Fig. 10. According to PAA
molecular weight of 5000, there were about 70 (5000/72≈70)
acrylic acid units, and about 18 (70/4≈18) units amidated with
Table 2
Molecular weight and its distribution of amide-PCE.
Superplasticizer Mn (g/mol) Mw (g/mol) Mz (g/mol)
Amide-PCE 46,889 53,847 61,320
125
1
H NMR spectrum of amide-PCE.
amino-PEG due to carboxyl–amino ratio of 4:1. Thus the estimated
Mn of amide-PCE was about 41,000 (5000 + 18 × 2000 = 41,000),
which slightly deviated from the tested value of 46,889 in Table 2.
The conclusion that the expected amidation product was almost
synthesized can be drawn from above calculation.
In Fig. 10, except for a negative peak corresponded to solvent,
there was only one positive peak corresponded to synthesized
amide-PCE, indicating few unreacted reactants and high amidation
rate. Furthermore, the narrow peak shape in Fig. 10 was consistent
with low PDI value in Table 2, indicated few low-molecular-weight
product and similar molecular weight of each macromolecule. The
above analysis showed that sufficient amidation reaction and ideal
amide structure were achieved.
PDI
1.14839
Fig. 10. Molecular weight and its distribution of amide-PCE.
126 X. Liu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 448 (2014) 119–129
Fig. 11. Surface tensions of amide-PCE solutions.
3.9. Surface tension of amide-PCE solution
The surface tension of amide-PCE was measured due to its pos-
sible influence on the dispersion of cement particles. The surface
tensions of conventional PCE, amide-PCE-3:1, amide-PCE-4:1 and
amide-PCE-5:1 synthesized at the carboxyl–amino ratio of 3:1, 4:1
and 5:1, respectively, were assessed, and the results are shown in
Fig. 11.
In Fig. 11, the surface tension values of amide-PCEs were all
in the range of 40–50 mN/m, which was lower than that of con-
ventional PCE (60.3 mN/m) as well as pure water (72–75 mN/m).
This shows that adding amide-PCE can significantly decrease the
surface tension which is probably attributed to the amide struc-
ture, but also shows that its high surface activity is beneficial to
wetting–permeation–adsorption on the surfaces of cement par-
ticles and foaming on the gas–liquid interfaces. Accordingly, one
reason of cement paste for amide-PCE with good dispersion and
fluidity is likely that the lowering surface tension can increase air
content, which can increase flow by bubbles’ smooth surface as ball
effect.
Also from Fig. 11, the surface tension reduced to a minimum
(43.4 mN/m) at the carboxyl–amino ratio of 4:1, indicating that the
adsorption and arrangement of macromolecule on the surfaces of
cement particles can be effectively improved at this ratio. This may
be related to the good flow properties at this ratio, correspond-
ing to the strong adsorption and dispersion to cement particles
and then exhibiting the strong orientation on both gas–liquid and
solid–liquid interfaces. The correlation between good flow proper-
ties and low surface tension for the sample at the carboxyl–amino
ratio of 4:1 showed that the hydrophilic groups of amide-PCE with
low surface tension easily adsorbed on the surfaces of hydrophilic
cement particles and then its hydrophobic groups around the
cement particles repelled each other to achieve good flow prop-
erties, and moreover, the possible reason of good paste fluidity
retention for amide-PCE-4:1 with low surface tension was that
the energy changed by hydration cannot overcome amide-PCE’s
adsorption energy.
3.10. Adsorption of amide-PCE on cement particles
Approximately half of element in the whole amide-PCE
molecule was organic carbon, and thus the adsorption amount
can be calculated by the difference between the concentration
of organic carbon in the filtrate before adsorption and that after
adsorption, and the adsorption percentage was the ratio of adsorp-
tion amount at a certain time to initial adsorption amount. The
adsorption percentages of amide-PCE-3:1, amide-PCE-4:1 and
amide-PCE-5:1 on the cement particle surfaces over time is shown
Fig. 12. Adsorption percentages of amide-PCEs over time.
in Fig. 12. All of amide-PCEs exhibited the rapid adsorption on the
surfaces of cement particles within 5 min, and subsequently the
adsorption became stable with slight fluctuation. This is a result of
competition between weakened adsorption caused by generated
hydration products and continuous adsorption caused by unab-
sorbed amide-PCE in pore solution.
Also from Fig. 12, the absorption percentage of amide-PCE-4:1
was highest and corresponded to the same fluidity phenomena,
indicating that amide-PCEs’ adsorption characteristics are related
to their dispersing efficiency. Yamada et al. [25] investigated the
effects of PCE’s chemical structure on the adsorption behavior, and
the results showed that polymers with longer side chains, shorter
main chain length, and higher contents of sulfonic groups exhib-
ited the higher dispersing power per adsorption amount. Thus
amide-PCE’s adsorption characteristics can only be considered to be
associated with its chemical structure including functional groups,
grafting density of side chain, main chain length, and charge den-
sity.
As for amide-PCEs’ chemical structures with the same main
chain length, amide-PCE-3:1 has the greatest grafting density of
side chain as well as the fewest carboxyl groups, as opposed to
those of amide-PCE-5:1. The lowest initial adsorption percentage
of amide-PCE-3:1 was caused by its fewest carboxyl groups adsorb-
ing on the surfaces of cement particles, and its low equilibrium
adsorption percentage was caused by entanglement among lots of
side chains. Amide-PCE-5:1 with the most adsorption sites exhib-
ited a high initial adsorption percentage, but its decreased steric
effect owing to the fewest side chains led to the low equilibrium
adsorption percentage. Only amide-PCE-4:1 with the moderate
adsorption site and grafting density of side chain exhibited the
highest adsorption percentage, probably because the unabsorbed
macromolecules in pore solution continuously adsorbed on the sur-
faces of cement particles during the hydration process. This was
able to inhibit the side effect of hydration products on amide-PCE’s
adsorption, and thus showed the best fluidity retention of cement
paste.
3.11. Application performance of amide-PCE in concrete
Concrete was used for measuring the application performance
of amide-PCE. The designed concrete should have the least initial
slump of 200 mm and slump flow of 500 mm with 28-day com-
pressive strength of 30 MPa. Besides, the designed concrete cannot
have any bleeding or segregation occurred. The mix proportion
of concrete with amide-PCE-4:1 or conventional PCE is listed as
follows. Cement:fly ash:slag:water = 222:98:55:175 (kg/m3 ), with
a concrete volume of 10 L and a sand/coarse aggregate ratio of
 X. Liu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 448 (2014) 119–129
Table 3
Application performances of PCEs in concrete.
Sample Slump (mm) Slump flow (mm)
Initial 1h Initial 1h
PCE 230 210 540 430
Amide-PCE-4:1 225 210 570 405
45%. The dosages of PCE and sodium gluconate were 0.2% and
1%, respectively. The results of PCEs’ application performances in
concrete are shown in Table 3.
From Table 3, the fresh concretes mixed with amide-PCE or
conventional PCE both exhibited the good slump and slump reten-
tion at the same dosage, and furthermore, these similar results
indicated the comparable dispersion between amide-PCE and con-
ventional PCE. The air content of fresh concrete with amide-PCE
was higher than that of conventional PCE, which was consistent
with the testing result of surface tension. This was likely caused by
amide-PCE’s amide structure lowering the surface tension of con-
crete pore solution in which great deals of bubbles were emerged.
Generally speaking, the air content loss of fresh concrete increased
over time, but there was almost no loss within an hour for concrete
with amide-PCE, indicating good bubble retention. In terms of its
molecular structure, the surface tension of PO unit, which is bene-
ficial to forming plenty of stable bubbles, is lower than that of EO
unit.
Also from Table 3, the compressive strengths both grew steadily
with increasing the ages, and reached nearly 30 MPa at 7 days
as well as above 45 MPa at 28 days. The hardened concrete for
amide-PCE exhibited the lower compressive strength. One of the
reasons was the higher air content, which affected the compact-
ness of concrete to decrease its strength. From the results of
concrete frost-resistance, the dynamic modulus values of concrete
with amide-PCE were all higher than those with conventional PCE
at the same freezing–thawing cycles, manifesting the good frost-
resistance property. This result is also likely linked to its high air
content of concrete.
3.12. Dispersion and adsorption mechanisms of amide-PCE
The dispersion effect of amide-PCE is largely dependent on the
amide-PCE’s adsorption on cement particles. The dispersion and
adsorption mechanisms of amide-PCE were discussed based on
the current theories and measured structure-properties results.
The mechanisms for amide-PCE in cement–water system mainly
included electrostatic repulsion, steric hindrance, complex, and
Fig. 13. Schematic diagram of dispersion and adsorption mechanisms of amide-PCE.
127
Air content (%) Compressive strength (MPa) Dynamic modulus at different
freezing–thawing cycles (%)
Initial 1h 3d 7d 28 d 0 4 8 12
4.2 3.7 17.9 29.8 52.4 100.0 93.9 85.0 77.1
5.5 5.4 16.8 27.2 45.8 100.0 94.8 89.2 81.2
lubrication [20,40,41]. A schematic diagram of dispersion and
adsorption mechanisms of amide-PCE on the surfaces of cement
particles is shown in Fig. 13.
As for electrostatic repulsion, when amide-PCE adsorbed on
the surfaces of cement particles, according to the theory of
PCE’s electrostatic repulsion [42,43], electrostatic repulsion [44,45]
occurred among identical charged cement particles caused by
hydrophilic groups’ hydrolysis, leading to the stable suspension
and good dispersion for cement particles in cement–water sys-
tem. From the results in this study, the synthesized amide-PCE
as a surfactant lowered the surface tension and in addition
produced the electrostatic repulsion, which was confirmed in
Section 3.9. Too high or too low carboxyl–amino ratio can
unbalance the hydrophilic–hydrophobic ratio, but only an appro-
priate carboxyl–amino ratio can achieve low surface tension and
stable electrostatic repulsion to improve cement particles’ disper-
sion.
As for steric hindrance, amide-PCEs’ main chains adsorbed on
the surfaces of cement particles, and their side chains stretched
in aqueous phase to form a thick adsorbed layer. Then the
cement particles repelled each other and the good dispersion
was achieved by this steric hindrance effect [46]. Besides from
other reports [47,48], the strong hydrogen bonds can be formed
between amide and polyether chains to strengthen the steric
hindrance effect. From the results in this study, the comblike
amide-PCE’s carboxyl groups were the adsorption sites and grafted
PEGs still extended as adsorbed layer to form steric repellent
even during hydration. The constant backbone length (M = 5000)
implied the reduced adsorption sites if too low carboxyl–amino
ratio, or incomplete adsorbed layer if too low carboxyl–amino
ratio, and an adsorption sites-layer balance only if an appro-
priate carboxyl–amino ratio, which was confirmed in Section
3.3.
As for complex, the concentration of calcium ion released during
the hydration decreased by forming the complexes with carboxyl
groups [49] of amide-PCE and forming the ligands with nitrogen
atoms in amide structure [50]. From the results in this study, these
two effects lowered the concentration of Ca2+ and delayed the
128 X. Liu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 448 (2014) 119–129
production of calcium hydroxide and C–S–H gel, which exhibited
the good fluidity retention and was confirmed in Sections 3.1–3.5.
As for lubrication, p–␲ conjugated system formed between car-
bonyl group and lone-pair electrons of nitrogen atom in amide
structure led to the decreased electron density, and in addition, the
hydrogen atom was easily decomposed into proton to show acidity
by the enhanced polarity of –NH– bond. Thus the good interaction
between acidic amide-PCE and alkaline cement system contributed
to amide-PCE solution’s wetting-permeation-adsorption on the
surfaces of cement particles and lubrication among the aggregate
particles. Moreover according to Kim’s research [51], a water film
with a certain strength formed on the surfaces of particles can break
the flocculated cement particles and improve the flow properties.
Thus, an appropriate carboxyl–amino ratio (4:1) can optimize the
contribution of amide-PCE’s carboxyl and amide groups to lubrica-
tion, which was in accordance with the results in Section 3.3.
4. Conclusions
With PAA and amino-PEG used as reactants, p-toluene sulfonic
acid as catalyst at a dosage of 3.5 wt%, and toluene as water-carrying
agent at a dosage of 15 wt%, the amide-PCE with the highest ami-
dation rate and best flow properties was synthesized at 135 ◦ C for
4 h at a carboxyl–amino ratio of 4:1.
FTIR and 1 H NMR measurements confirmed the amide structure
of synthesized product, and the test results of molecular weight
showed that the sufficient amidation reaction and ideal amide
structure were achieved.
Amide-PCE can distinctly lower the surface tension of its
solution, but also rapidly adsorb on the surfaces of cement par-
ticles. Furthermore, amide-PCE at the carboxyl–amino ratio of 4:1
exhibited the lowest surface tension and the highest adsorption
percentage, which were in accordance with its paste fluidity results.
The concrete slump of amide-PCE was similar to that of conven-
tional PCE, and the air-entraining ability, bubble retention and
concrete frost-resistance of amide-PCE were better than those of
conventional PCE.
Amide-PCE adsorbed on the surfaces of cement particles maybe
promoted the formation of the strong hydrogen bonds between
amide and polyether chains to strengthen the steric hindrance
effect, but also was likely to delay the hydration products by inter-
acting with calcium ion to achieve the fluidity improvement of
cement paste.
Acknowledgments
This research program was funded by the National Natural Sci-
ence Foundation of China (Grant 51208012) and Research Fund
of New Teachers for the Doctoral Program of Higher Education
of China (Grant number: 3c009011201301). The authors are also
grateful to the College of Materials Science and Engineering of BJUT.
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