ACI MATERIALS JOURNAL
Synthesis and Properties of Amphoteric Superplasticizer
by Wenjuan Guo, Na Sun, Tao Yang, Meishan Pei, and Yingfei Wang
A series of amphoteric polycarboxylic acid-based superplasticizers
(APCs) was synthesized with different side chain lengths nEOfrom
seven to 56 and characterized by FTlR spectra. The dispersing
effectiveness of the APCs was assessed by the flow of paste. The
amount of superplasticizers adsorbed on the cement significantly
decreases with increasing side chain length nEO.The properties of
an anionic polycarboxylic acid-based superplasticizer (PCE) were
also tested to be compared with APCs. The adsorption amount of
APCs was larger than that of an anionic polycarboxylic acid-based
superplasticizer (PC). Zeta potential measurements using the elec-
troacoustic method indicate that the steric repulsion among the
cement particles carrying adsorbed polymer molecules is the main
force for dispersion.
INTRODUCTION
A superplasticizer (or high-range water reducer) is an
important chemical admixture widely used in concrete. I Its
function is to reduce the water-cement ratio (w/c) and enhance
the fluidity and fluidity-retaining performance of concrete.
Only a small amount of the chemical can greatly improve
the workability of concrete. A variety of superplasticizers
have been developed in recent years, such as sulfonated
naphthalene formaldehyde condensates (BNSs) and
sulfonated melamine formaldehyde condensates (PMSs).
Since the 1980s, a new generation of polycarboxylic acid-
based superplasticizers (PCs) has been used.2-7 They allow
for the achievement of excellent fluidity at a low wlc (as low
as 0.15) and provide slump retention over a prolonged period
of time.8 These chemicals are more effective than BNSs and
PMSS3-5because they can disperse cement particles, not only
by electrostatic repulsion, but also by steric hindrance.9-14
Until now, most superplasticizers have belonged to
anionic polymers. Amphoteric or cationic admixtures are
seldom reported. Many researchers 15,16have pointed out
that steric hindrance among the cement particles carrying
adsorbed polymer molecules is the main mechanism for
dispersion. Therefore, adsorbed amount is an important
parameter that greatly impacts the dispersing effectiveness
of a superplasticizer. Ordinary portland cement (OPC)
mainly consists of four minerals-namely, Ca3Si05 (C3S),
Ca2Si04 (C2S), Ca3A1206 (C.A), and C~A12Fe201O (C4A.F)
and gypsum.17-19 It was reported that the zeta potentials of
C3S and C2S were negative (-5 mY), while those of C3A
and C4A.F were positive (+5 to +10 mV).20 Therefore, the
adsorption capacity of the traditional anionic superplasticizer
was very limited. It can be inferred that adsorption saturation
would be improved by an amphoteric superplasticizer.
Anionic groups of an amphoteric superplasticizer can be
adsorbed on the surface of C3A and C~, while cationic
groups can be adsorbed on the surface of C3S and C2S.
In this paper, a series of amphoteric polycarboxylic
acid-based superplasticizers (APCs) was synthesized by
solution copolymerization from maleic anhydride (MA),
. TECHNICAL PAPER.
allyl polyethylene glycol (APEG) (with different side chain
lengths nEOfrom 7 to 56), and methacryloxyethyltrimethyl
ammonium chloride (DMC). The effect of the chemical
structure on the dispersing effectiveness of the APC was
assessed by the flow of paste. The adsorption amount
and zeta potential of APCs with different side chains
were investigated. The properties of a traditional anionic
polycarboxylic acid-based superplasticizer (PCE) reported in
the authors' previous study21was also tested to be compared
with the APe.
RESEARCH SIGNIFICANCE
A novel APC was prepared and the effect of the chemical
structure on its properties was investigated. The anionic
groups of the APC can be adsorbed on the positive surface of
cement particles, whereas cationic groups can be adsorbed
on the negative surface. Therefore, for OPC, the adsorption
saturation of the APC was improved and the adsorption
amount was much higher than that of the PCE. The main
mechanism for dispersion of the APC was also investigated.
EXPERIMENTAL INVESTIGATION
Materials and methods
Polymer synthesis-DMC and four different APEG
ethers with side chain lengths of 7, 32, 45, and 56 ethylene
oxide units (nEO) were used for solution copolymerization
with MA. The copolymers were named APC-7, APC-32,
APC-45, and APC-56, respectively. The molar ratio of
the DMC, APEG ether, and MA was chosen as 0.6:1:3.
Potassium persulfate (KPS) was used as the initiator. The
initiator concentration was 4.0 wt. % of all the monomers.
For copolymer preparation, the MA and APEG ether were
added to the reaction vessel and heated to 348 K (l67F)
under stirring. A nitrogen blanket was applied. After
reaching 353 K (l76F), the initiator and DMC were added
to the mixture constantly for 1 hour. After further heating
the mixture for over 1.5 hours, the copolymer solutions were
neutralized by sodium hydroxide. The solid contents of the
copolymer solutions were 20 to 25% and the solution was
yellow. The chemical structures of the DMC and prepared
copolymers are shown in Fig. 1 and 2.
MA, KPS, sodium hydroxide (NaOH), DMC, and APEG
with 7, 32, 45, and 56 ethylene oxide units were used as
purchased. FTIR was used to confirm the chemical structure
of the monomers and APC.
ACI Materials Journal, V. 108, No.6, November-December 2011.
MS No. M-2010-222.R2 received February 16, 2011, and reviewed under Insutute
publication policies. Copyright 20 [1, American Concrete Institute. All rights
reserved, including the making of copies unless permission is obtained from the
copyright proprietors. Pertinent discussion including author's closure, if any, will be
published in the September-October 2012 ACI Materials Journal if the discussion is
received by June 1,2012.
Wenjuan Guo is a Lecturer in the School of Chemistry and Chemical Engineering at Table 1-ehemical components of ordinary portland
the University of Jinan. She received her PhD in physical chemistry from the School cement (OPC)
of Chemistry and Chemical Engineering at Shandong Ulliversity, Jillan, China, in
2007. Her research interests include the corrosion and inhibition of industrial metals Chemical components (%, by quality)
and alloys, self-assembled monolayers, chemically-modified electrodes, and electro-
Cement Si02 AI203 CaO F~03 MgO S03 Loss
chemical techniques.
OPC 19.95 4.71 60.58 2.90 1.41 - 1.24
Na Sun is a Master Candidate ill the School of Chemistly and Chemical Engineering
at the University of Jinan. She received her BEfrom the University of Jinan in 2007.
Table 2-Mineral components of ordinary portland
Tao Yang is a Master Calldidate ill the School of Chemistry alld Chemical Ellgi-
cement (OPC)
neering at the University of linon, linan, China. He received his BE from the Univer-
Mineral components (%, by quality)
sity of Jinan in 2009.
Cement C3S C2S C3A C.AF
Meishan Pei is a Professor of Polymer Chemistly ill the School of Chemistry alld
OPC 54.30 21.36 6.44 7.75
Chemical Engilleering at the University of Jillan. He received his PhD from the
Institute of Chemistry of the Chinese Academy of Science, Beijillg, China, in 2000.
His research interests include polymer-modified mortars, fiber-reinforced concretes,
Table 3-Physical properties of ordinary portland
and concrete admixtures. cement (OPC)
Physical
Yingfei Wang is a Senior Engineer at Engineering Technology Research Co. Ltd.
properties Specific surface Specific density
of China Communications Construction Fourth Harbor Engineering Co. Ltd. He
received his MEfrom the School of Materials Science and Engineering at the Wuhan 278.3 m2/kg (1358.6 ft2/1b) 2.94 g/cm3 (183.46 Ib/ft3)
University of Technology, Wuhan, China, in 1990.

of a superplasticizer increases with an increasing

Cement-OPC 42,5 was used for the test. The composition
of the pure cement and its physical properties are shown in
Tables 1 through 3.
Flow of paste-The slump test, according to GB8076 from
the Standardization Administration of the People's Republic
of China, was used to determine the paste flow. The test was
carried out as follows: the fresh cement paste with an APC
was prepared with a wlc of 0.35. The APC was added into
the mixing water at a dosage of 0.3% (weight percent of solid
content to cement; the same_as. in the following). Cement
with a weight of 200 g (7.055 oz) and 0.6 g (0.021 oz)
APCs were added and agitated for 1 minute at low speed,
remained for 1 minute without being stirred, and then were
stirred again for 2 minutes at high speed. The cement paste
was then immediately poured into a minislump cone 60 mm
(2.364 in.) tall, 36 mm (1.4184 in.) in top diameter, and 60 mm
(2.364 in.) in bottom diameter onto a glass plate and the cone
was vertically removed. The resulting spread of the paste
was measured three times.
Adsorption-The adsorption amount is an important
index that greatly impacts the dispersing effectiveness of
superplasticizers. In general, the dispersing effectiveness
adsorption amount.22 The adsorption amount of the APC
on cement was measured according to the depletion
method.2 The concentration of both the initial APC solution
and the unadsorbed APC (existing in the liquid phase of
cement paste after adsorption) were measured by a total
organic carbon analyzer (TOC). The adsorption amount was
calculated from the difference between the concentrations
of the polymer in the initial solution and the liquid phase of
cement paste (with an APC dosage of 0.3% and a wlc of 0.5)
after APC adsorption for 30,60,90, and 120 minutes, which
was obtained by centrifugal separation for 8 minutes. The
measurements were repeated three times and the average
values were obtained.
Zeta potential-The zeta potential measurement of
cement paste is an effective method to investigate the
dispersing mechanism. IS The zeta potentials of cement
with different dosages of superplasticizers were measured
by an electroacoustic spectrometer. The cement and the
solution containing the superplasticizer were mixed by
hand for 5 minutes. The mixture was determined at a wlc of
SOil and a polymer-cement ratio (PIC) of 0.35.
Instruments
The structures of the monomers and copolymers were
confirmed by FTIR spectrometer. The range of the spectrometer
is 7800 to 350 cm-l (3073.2 to 137.9 in.-1). The resolution is
0.5 cm-l (0.197 in.-I) and the signal-to-noise ratio (SNR) is
180,000:1. The cement paste was stirred with a cement paste
mixer 600 mm (23.64 in.) long, 320 mm (12.61 in.) wide,
and 660 mm (26.00 in.) tall. The width of the mixing blade
is 135 mm (5.32-in.). The low speed is l40 5 rpmand the high
speed is 285 5 rpm. The adsorption amount was measured by
a TOe. The range of measurement is 0 to 1% and min period
of measurement is 4 minutes. An electroacoustic spectrometer
was used for measuring the zeta potentials. The resolution of
the spectrometer is 4 pixels/l1m (101,600 pixels/in.) and the
range is 0.5 to 20 11m(0.000019 to 0.00078 in.). The proper
range of the pH is 2.0 to 12.0.
EXPERIMENTAL RESULTS AND DISCUSSION
Polymer synthesis and chemical structure of APC
The superplasticizers were prepared and the chemical
structures of the monomers and APC are shown in Fig. 3.
 ~4
Q)B2
~80

i]78
E76
en
~74
f-72

70

68

'1000 3500 3000 2500 2000 150~ 1000 500 4000350030002500200015001000 500
\l\Gve numb er(i n- ) Wavenumber in-1)

~60
~
ID50
u
c:
ro'1O
t:l

~30
c:
ro
f'= 20
10
437

4000350030002500 2000 150~ 1000 500 '1000350030002500200015091000 500

Wavenumber(in- ) VVavenumber(in- )

The wide absorption band of approximately 3434 cm-1

(1353 in.-1) assigned to the hydroxyl groups was closely
observed in the FrIR spectrum of the APC. The characteristic E
absorption bands for the monomers were found in the orE 200
FrIR spectra (Fig. 3(a), (b), and (c. For instance, inOJ -"-APC]
-o-APC-32
the strong C = C stretch (1717 cm-1 [676 in.-1])-the
0.. 150
-A-APC45
'0 -o-APC-56
characteristic ethilenic peak-obviously appeared in the ;: -"-PCE
.Q 100
U. -oil-Plain
spectra of the monomers, whereas the absorption peaks of '"------"i ---------"i _

approximately 1600 to 1870 cm-1 (630 to 737 in.-1) were 50+---~~~~-~~~~r---~-

20 40 60 80 100 120
not found in the FrIR spectrum of the APC (Fig. 3(d. This
Elapsed time(min)
indicated that the monomers were polymerized to become
the target product and that the product did not contain
double bonds.
'29
Flow of paste ~8
inOJ
The flow test of the cement paste was introduced for 0..
7 ---APC]
--APC32
assessing the dispersing effectiveness of APCs. The 'C 6 -A- APC-45
- __ APC56
result is shown in Fig. 4. All the prepared amphoteric ~ 5
u::: -"- PCE
superplasticizers show high efficient dispersing and good 4
-.-Plain _..
flow retention. The copolymer with a short side chain (nEO "'__ ~ __ ------"i

= 7) is particularly effective. It was observed that the initial o 20 40 60 80 100120

flow of paste decreased with the increase of the side chain
length but still showed perfect flow retention. Similar results
were reportedl5 that a shorter PEa side chain gave more
fluidity at the same dosage. The dispersing effectiveness and
flow retention of APCs are better than PCEs.
Adsorption
The adsorption amounts of APCs and PCEs on ope
42.5 were determined. Table 4 illustrates the adsorption
amounts of four amphoteric superplasticizers with side
Elapsed time(min)
Fig. 4-Effects of side chain length on initial paste flow and
flow retention.
chain lengths of nEO= 7, 32, 45, and 56. An anionic PCE was
also tested to be compared with the APe.
It can be seen from Table 4 that the adsorption amounts of
the APCs increased with time and that the point of adsorption
saturation was much higher than that of the anionic PCE. The
 Adsorption, mg (oz)
Time, minutes PCE APC-7 APC-32 APCA5 APC-56
5 0.937 (3.30 x 10-4) 2.002 (7.60 x 10-4) 1.024 (3.62 x 10-4) 1.05 (3.70 x 10-4) 1.007 (3.55 x 10-4)
30 1.595 (5.62 x 10-4) 2.087 (7.36 x 10-4) 2.027 (7.15 x 10-4) 2.032 (7.17 x 10-4) 2.015 (7.1 J x 10-4)
60 1.732 (6.11 x 10-4) 2.087 (7.36 x 10-4) 2.080 (7.33 x 10-4) 2.077 (7.32 x 10-4) 2.078 (7.33 x 10-4)
120 1.668 (5.88 x 10-4) 2.087 (7.36 x 10-4) 2.086 (7.36 x 10-4) 2.078 (7.33 x 10-4) 2.073 (7.31 x 10-4)

- - It is also shown in Table 4 that the adsorption amounts

- -
decreased slightly with the increase of the side chain length.
+
~ Similar results on adsorption amounts were reported by Sakai
et al.Z6 and Plank and Sachsenhauser.15 Sakai et al.Z6 proposed
that the decline of the saturated amount of adsorbed polymer
observed with the increasing side chain length might be

e
~e_ attributed to a change in the conformation of adsorbed
comb-polymers. Plank and Sachsenhauser15 considered that
copolymers with short side chains adsorb flat in a high amount
and form a densely packed polymer film, whereas the adsorbed
amount of copolymers with long side chains is smaller because
the steric effect of their side chains prevents a dense packing of
molecules on the surface of the cement particles.
. --

Zeta potential
The dispersing effectiveness of cement is generally
produced by electrostatic and steric repulsion among the
cement particles. Many researchers 10 have reported, however,
that the absolute value of the zeta potential of cement
particles adsorbing a PC is smaller than that of a conventional
naphthalene-based superplasticizer. Plankzz pointed out
that if the zeta potential changes only slightly during the
superplasticizer addition, steric repulsion among the cement
particles carrying adsorbed polymer molecules is the main
mechanism for dispersion.
The results of the zeta potential measurements are shown
in Fig. 6. It can be seen from Fig. 6 that the zeta potential
>0 of cement particles is negative and that the absolute value of
S the zeta potential of cement particles slightly decreases with
Iii -1
an increase of the dosages. A similar result is reported in
~ Reference 20: all mineralogical components of the cement
2 -2
o
a. showed negative zeta potential when they were dispersed in
(Ll -3 a solution with superplasticizer. A strong decline of the zeta
Iii potential to more negative values indicates that electrostatic
N -4
repulsion is the main mechanism for dispersion. They become
-5 +--~--,--~---.----.---.--~----; more negatively charged due to adsorbed superplasticizer
00 01 0.2 0.3 0.4
molecules.zz Therefore, steric repulsion was found to be the
Superplasticizer dosages(wt. %) key factor for dispersion for this kind of APC.
Figure 6 also illustrates the effect of side chain length
Fig. 6-Effect of side chain length and dosages on zeta on zeta potential. The absolute value of the zeta potential
potential of APes. of cement particles increases with the increase of the side
chain length. The explanation for this phenomenon is that
mechanism for adsorption is shown in Fig. 5. This is because the adsorption amount of superplasticizers with short-side. .._.
OPC 42.5 mainly consists of four minerals-C3S, CzS, C3A, chains is larger than that of superplasticizers with long
and C,J,F-and gypsum. The particles of C3S and CzS exhibit side chains. For superplasticizers with short side chains,
negative surfaces, whereas C3A and c4AF exhibit positive molecules can be expected to be adsorbed on the cement
surfaces.Z3-Z5 The molecular model of the APC is shown in surface to form a densely packed thin polymer film; hence,
Fig. 5(a). The APC contains both anionic and cationic groups. cement particles exhibiting a positive or negative surface are
The anionic groups of the APC can be adsorbed on the surface covered by polymers. Consequently, the absolute value of
of C3A and c4AF, and the cationic groups can be adsorbed the zeta potential of the cement particles decreases.
on the surface of C3S and CzS, as shown in Fig. 5(b). The
adsorption was improved compared with the traditional CONCLUSIONS
anionic superplasticizer. Stene repulsion among the cement In this paper, a series of APCs was synthesized with
particles covered with polymer molecules caused the cement different side chain lengths of nEQranging from 7 to 56. The
to have better dispersion, as shown in Fig. 5(c). flow tests of cement paste illustrate that the initial flow of
paste decreases with the increase of the side chain length and
that the dispersing effectiveness and flow retention of APCs
are better than those of PCEs. The adsorption amounts of
APCs are much larger than that of anionic PCEs. Anionic
groups of superplasticizer molecules are adsorbed on the
surface of C3A and C4AF and cationic groups are adsorbed
on the surface of C3S and CzS. The adsorption amounts
decrease with the increase of side chain length because
copolymers with short side chains adsorb flat in a high
amount and form a densely packed polymer film. The zeta
potential measurements indicate that steric repulsion among
the cement particles carrying adsorbed polymer molecules is
the main force for dispersion.
ACKNOWLEDGMENTS
This project was financially supported by the National Natural Science
Foundation of China (Grant 50872042), the Natural Science Foundation of
Shandong Province (Grant Y2008B61), and the Science and Technology
Development Project of Shandong Province (Grant 2008GG I 003024).
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