Cement and Concrete Research 32 (2002) 1507 – 1513

Adsorption characteristics of superplasticizers on

cement component minerals
Kazuhiro Yoshiokaa,*, Ei-ichi Tazawab, Kenji Kawaib, Tomoyuki Enohatac
a
Tokuyama Research Laboratory, Tokuyama Corporation, Tokuyama City, Yamaguchi 745-8648, Japan
b
Department of Civil Engineering, Hiroshima University, Higashi-Hiroshima City, Hiroshima 739-8527, Japan
c
Kajima Corporation, Fukuoka City, Fukuoka 812-8513, Japan
Received 15 September 1998; accepted 12 March 2002

Abstract

Adsorption characteristics of various superplasticizers on portland cement component minerals were investigated. Adsorption isotherms
of various types of superplasticizers and z-potentials of cement component minerals at the maximum adsorption of the superplasticizers were
measured. The value of the adsorption isotherm was calculated from the amount of the superplasticizer adsorbed on a cement component
mineral in an equilibrated solution. The maximum amounts of adsorption and the adsorption isotherms varied with types of component
mineral and superplasticizer. For all types of superplasticizers, a larger amount of superplasticizer was adsorbed on C3A and C4AF than C3S
and C2S. However, the equilibrated concentration of each superplasticizer at the maximum adsorption was not influenced by types of
superplasticizer. Without superplasticizer, C3S and C2S had negative z-potential. On the contrary, C3A and C4AF had positive z-potential.
Therefore, accelerated coagulation of cement particles might occur due to their electrostatic potentials that are opposite each other. However,
all component minerals of cement had negative z-potential when they were mixed with any superplasticizer. Fluidity of fresh cement paste is
improved due to electrostatic repulsion acting between particles.
D 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Admixture; Adsorption; Dispersion; Cement; Cement paste

1. Introduction These dispersing mechanisms are also predicted from inter-

particle forces theoretically calculated from potential energy
Superplasticizer improves fluidity of concrete by dispers- [2 –5].
ing cement particles in paste. High-performance concrete It is reported that the type of superplasticizer and the
that includes the high-strength concrete and the high-fluidity mixing method varied the fluidity of cement paste [6– 8].
concrete can be produced with superplasticizer [1]. Sodium Portland cement mainly consists of four minerals, namely
salts of formaldehyde condenses of b-naphthalene sulfate Ca3SiO5, Ca2SiO4, Ca3Al2O6 and Ca4Al2Fe2O10, which are
(BNS) disperse cement particles by electrostatic repulsion abbreviated to C3S, C2S, C3A, C4AF and gypsum. For these
that results from the adsorption on cement surfaces. Poly- cement component minerals, superplasticizers are not
carboxylic acid (PC) with graft chains disperses cement expected to adsorb uniformly. Some component minerals
particles with the help of the steric hindrance effect that might adsorb much larger amount than the others.
results from the extension of their graft chains away from Therefore, it is important to understand how superplasti-
the surface of cement particles. Recently, a new type of cizers are adsorbed on each cement component mineral for
superplasticizer has been developed. This superplasticizer is controlling fluidity of cement paste and concrete. In this
contrived so as to activate both of the preceding two effects. paper, the adsorption characteristic of superplasticizers
(BNS, PC and the new type) was studied by measuring
adsorption isotherms to these component minerals. Further-
more, the relationship between the z-potential of each
* Corresponding author. Fax: +81-834-31-6662. cement component mineral and the fluidity of cement paste
E-mail address: [email protected] (K. Yoshioka). was investigated at a dosage of the maximum adsorption.

0008-8846/02/$ – see front matter D 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 8 - 8 8 4 6 ( 0 2 ) 0 0 7 8 2 - 2
1508 K. Yoshioka et al. / Cement and Concrete Research 32 (2002) 1507–1513

2. Experimental methods

2.1. Materials

Commercial ordinary portland cement was used, and

cement component minerals were synthesized in labor-
atory. Tricalcium silicate (C3S), dicalcium silicate (C2S),
tricalcium aluminate (C3A) and tetracalcium ferroaluminate
(C 4AF) were used. The composition of these com-
ponent minerals was Ca105Mg2Al(AlSi35)O180, Ca85M-
gAl2Fe(Na0.5K0.5)(Al3Si42)O180, Ca3Al2O6 and Ca4Al2-
Fe2O10, respectively. These samples were synthesized by
rapid cooling after reacting raw materials at 1550, 1450,
1350 and 1350 C, respectively, and mineralogical com-
ponents of these materials were identified with an X-ray
diffractometer.
Four types of commercial superplasticizers used in this
study are shown in Table 1, together with their dispersing
mechanisms and solid contents. The presumed chemical
structure of the main component in each superplasticizer
is also shown in Fig. 1. All cement component minerals
were pulverized in a mortar by hands just before each
experiment.

2.2. Measurements

2.2.1. Fluidity of cement paste

Fig. 1. Chemical structure of main component in each superplasticizer.
Cement paste was prepared with a water/cement ratio of
0.26. A certain amount of superplasticizer was added to
mixing water in advance. A flow cone specified in JIS
R5201 was filled with a sample. After the cone was other cases. In the latter case, the wavelength of 500 nm
removed from the sample, the maximum diameter of the was used for quantitative analysis. In this study, it was
spread sample and the maximum width perpendicular to that confirmed that the calibration curves were not influenced
diameter were measured. The average of these two values by OH concentration in cement paste. This OH
was defined as the flow value. concentration would be varied with the kind of cement
component mineral and the water/cement ratio.
2.2.2. Adsorption measurements Ten grams of solution containing various amount of
The mass of superplasticizers adsorbed on a cement superplasticizer and 0.5 g of each component mineral of
component mineral was measured with a TOC in case of cement were mixed by a magnetic stirrer for 10 min. In this
C and an ultraviolet and visible spectrophotometer in the study, the water/component mineral ratio was 2000%. The
paste sample was filtrated with a 0.22-mm membrane filter
using a suction pump. The concentration of the superplasti-
cizer remaining in the resultant solution was measured. The
amount of superplasticizer adsorbed on the component
Table 1 mineral was calculated from the difference between the
Classification of superplasticizer
amount of the superplasticizer in liquid before and after
Repulsion mechanism Solid mixing. The equilibrated concentration of adsorption was
Steric content determined by this concentration of superplasticizer after
Electrostatic hindrance Symbol Type Composition (wt.%) mixing. These concentrations were represented as weight
2 – MT BNS Maleic acid 42.0 percent of solids in the superplasticizer. The adsorption
derivatives isotherms were drawn with the value of adsorption and
6 6 C Polysulfonic Methacrylic 28.3
acid acid
the equilibrated concentration. In addition, the amount of
– 6 HP PC Ether chain 27.0 superplasticizers adsorbed on C3A and C4AF in saturated
– 2 MH PC Long 25.0 gypsum solution was measured. The saturated gypsum
ether chain solution was prepared with CaSO4
2H2O of qualified
C is a new type of superplasticizer. reagent. All operations were made at 20 C.
 K. Yoshioka et al. / Cement and Concrete Research 32 (2002) 1507–1513 1509

3. Results and discussions

3.1. Fluidity of cement paste

Flow values of cement pastes as a function of solid

concentrations of superplasticizer are shown in Fig. 2. The
value of paste flow increases with the increased concentra-
tion. The increment varied with the types of superplasticizer.
The paste flow value increases with much smaller dosage of
MH than that of the other superplasticizers. The paste mixed
with MH at a dosage of 0.4 wt.% was segregated into
cement and solution. In the cases of MT and C, the paste
flow value increases gently with the increased dosage of
Fig. 2. Flow curve for cement paste.
superplasticizer. Then, the value reached to a constant value
for more than 2 wt.% of their dosage.

3.2. Adsorption isotherm

2.3. z-potential measurement
The adsorption isotherms on each component mineral
The component sample and the solution containing the of cement are shown in Figs. 3 –6, respectively, for MT,
superplasticizer were mixed by hands for 5 min. The C, HP and MH. The value of maximum adsorption and
concentration of the superplasticizer in this solution was the equilibrated concentration of superplasticizer corres-
the maximum concentration of adsorption. The samples for ponding to the maximum adsorption are presented in
z-potential measurement were prepared by diluting the Table 2. The shape of adsorption isotherm varied with
above paste with deionized water up to 1500 times and the type of superplasticizers. The value of adsorption of
mixed for 3 min. A z-potential meter using electrophoresis MT and C increased gradually with the increase of the
of a colloid particle (made by Rank Brothers) was used for equilibrated concentration of superplasticizer and then the
the z-potential measurements of each component particle. value approached to a constant value. These adsorption
In addition, for C3A and C4AF particles, their z-potential isotherms showed a typical Langmuir curve. The value of
in saturated gypsum solution was also measured. maximum adsorption varied with the type of superplasti-

Fig. 3. The adsorption isotherms on each component of cement for MT.

1510 K. Yoshioka et al. / Cement and Concrete Research 32 (2002) 1507–1513

Fig. 4. The adsorption isotherms on each component of cement for C.

cizer used. This value of HP and MH was larger than value. It was reported by Kawai et al. [8] that the adsorption
that of the others. isotherm of a polycarboxylic-type superplasticizer on each
It was reported that the maximum value of adsorption of component minerals showed a similar behavior.
the polycarboxylic-type superplasticizer was approximately With regarded to this observation, the following reasons
1 mg/1 g of cement, in which using a lower water/cement could be considered. Micelles of the superplasticizer might
ratio than the ratio in this study [7]. The maximum values of be formed due to higher concentration of the superplasti-
adsorption in this study were larger than that reported in the cizer in solution and higher water/component minerals ratio
previous studies. in this study. The adsorption behaviors observed for HP and
The value of adsorption of HP and MH increased by two MH in this study might be explained by the same mech-
steps with increasing equilibrated concentration of super- anism. There is an opinion, however, that some of the
plasticizer and decreased again after reaching a maximum adsorbed superplasticizer might have separated from par-

Fig. 5. The adsorption isotherms on each component of cement for HP.

 K. Yoshioka et al. / Cement and Concrete Research 32 (2002) 1507–1513 1511

Fig. 6. The adsorption isotherms on each component of cement for MH.

ticles during filtering process [8]. Therefore, the value of imum value for MT in gypsum-saturated water decreased to
adsorption in this study was the value of ‘‘apparent’’ 1/5 of that in deionized water. It was reported that (a) some
adsorption in the strict sense of the word. type of superplasticizer was adsorbed on the specific com-
The maximum value of adsorption varied with minera- ponent mineral more than on the others and (b) the value of
logical compositions of cement particles and the type of adsorption of superplasticizer decreased when sulfate ion
superplasticizer. Compared with calcium silicate particles, was supplied from gypsum to a higher concentration [9–
C3A and C4AF adsorbed much more superplasticizer. The 12]. These experimental behaviors reported were in good
ratio of the maximum value of adsorption on C3A to that on agreement with the results of this study.
C3S is shown in Table 3. A larger amount of the super- The equilibrated concentration of superplasticizer varied
plasticizer MT was adsorbed on C3A and C4A in particular, with the type of superplasticizer when adsorption was
while the superplasticizer C was adsorbed on all component saturated. On the contrary, the concentration was not
minerals without great difference. changed with the type of mineralogical composition of
The shape of adsorption isotherm in deionized water cement. The equilibrated concentrations of superplasticizer
resembled with that in gypsum-saturated water for all types were the same regardless of the presence of gypsum in
of superplasticizers. The maximum value of adsorption of solution. The reason might be presumed that the cement
superplasticizer in saturated gypsum water, however, was particles have some site, which could combine with the
smaller than that in deionized water. Especially, the max- superplasticizer, and the number of the sites were changed
with the type of component mineral. The site might
decrease with increasing concentration of SO42 supplied
Table 2
The maximum (apparent) adsorption on cement composition (upper in cell)
from gypsum. On the contrary, the adsorption equilibrium
and equilibrated concentration of superplasticizer in solution (lower in cell)
Maximum (apparent) adsorption (mg/g)
equilibrated concentration (wt.%)
Mineralogical Type Table 3
composition of water MT C HP MH The ratio of maximum value of (apparent) adsorption on C3A to that of C3S
C3S Deionized 19 35 70 90 and the ratio in deionized water to that in gypsum saturated water
water 1.5 0.13 0.9 6.0 Ratio of maximum value
C2S Deionized 21 36 55 138 of (apparent) adsorption ( – )
Mineralogical Type of
water 1.0 0.11 0.6 7.0
composition water MT C HP MH
C3A Deionized 225 61 425 692
water 1.1 0.12 1.0 5.0 C3A/C3S Deionized water 11.8 1.7 6.1 7.7
Gypsum 150 48 330 490 C3A Deionized water/ 1.5 1.3 1.3 1.4
saturated 0.9 0.15 0.8 4.0 gypsum-saturated
C4AF Deionized 220 68 320 600 water
water 1.1 0.12 1.3 6.0 C4AF Deionized water/ 4.9 1.7 1.6 1.7
Gypsum 45 41 200 350 gypsum-saturated
saturated 1.0 0.15 1.4 4.9 water
1512 K. Yoshioka et al. / Cement and Concrete Research 32 (2002) 1507–1513

of each site was not influenced by the presence of gypsum Derjaguin – Landau – Verway – Overbeek (DLVO) theory,
in solution. the z-potential of cement must be less than 15 or less
than 25 mV for stable dispersion, with some discrepancy
3.3. z-potential depending on the authors [13 –15]. According to this theory,
C3S, which composes approximately 60% of cement, could
z-potentials of each mineralogical composition of cement not be stably dispersed because the absolute value of its
in a solution with and without superplasticizer are shown in charge is less than 10 mV. In fact, the paste with MT showed
Fig. 7. For C3A and C4AF particles, their z-potential in higher fluidity than that without superplasticizer. This
gypsum-saturated water is also shown in Fig. 7. Without means that we cannot explain this improvement in fluidity
superplasticizer, the z-potentials of C3S and C2S were only by electric repulsion. It was observed that superplasti-
negative ( 5 mV). However, those of C3A and C4AF were cizer made all component particles into electrostatically
positive from + 5 to + 10 mV. Therefore, accelerated homoparticles, thereby significantly improving the fluidity
coagulation of cement particles in a plain paste might occur of paste immediately after mixing. It was reported that the
due to their electrostatic potentials that are opposite each superplasticizers MH and HP dispersed cement particles
other. mainly by steric hindrance effect [1]. It has been shown,
With superplasticizer, z-potentials of component miner- however, that component particles are charged into a homo-
als varied with the type of superplasticizer. The z-potential system even with these superplasticizers.
of C3S with superplasticizers was approximately 10 mV For any superplasticizer, the z-potential increases with
immediately after mixing. The others were approximately time elapsed. Especially, the z-potential of C3S with MT
15 mV. With superplasticizer, all component minerals and that of C4AF with C increased remarkably. It is
were negative in their potential. With the aid of the known that the flow value of paste with MT greatly

Fig. 7. The z-potentials of each mineralogical composition of cement in a solution with and without superplasticizer.
 K. Yoshioka et al. / Cement and Concrete Research 32 (2002) 1507–1513 1513

decreases with time, corresponding to ‘‘the slump-loss of hashi of Lion and Akihiro Hori of Denki Kagaku Kogyo
concrete.’’ It was explained that the paste flow decreased K.K. are greatly acknowledged. The authors would like to
due to the increase in the z-potential [14]. In this study, express deep appreciation to Lion and Denki Kagaku Kogyo
z-potential of MT-adsorbed C3S particles has changed K.K. for supplying the new type of superplasticizer and
from 12 mV at 10 min after mixing to 5 mV after mineralogical compositions of portland cement (C3A and
70 min. This increase in z-potentials of C3S particle C4AF), respectively.
could be the main cause of ‘‘the slump-loss of concrete,’’
because the z-potential of the other mineralogical com-
positions remained almost unchanged.
References
The maximum adsorption of C3A and C4AF decreased
significantly in saturated gypsum solution, but the z-poten- [1] M. Kinoshita, Recent development of new chemical admixtures,
tial of C3A and C4AF was not varied with and without Kagakukogyo 49 (5) (1998) 383 – 391 (in Japanese).
gypsum. Therefore, the adsorbed amount of adsorption of [2] T. Nawa, H. Eguchi, Effect of types of calcium sulfate on fluidity
superplasticizer on C3A and C4AF did not have direct of cement paste, Cement-gizyutu-nempou 41 (1987) 46 – 49 (in
influence on the z-potential of these particles at the max- Japanese).
[3] K. Hattori, K. Izumi, A rheological expression of coagulation rate
imum adsorption.
theory, J. Dispers. Sci. Technol. 3 (2) (1992) 129.
[4] K. Yoshioka, E. Sakai, M. Daimon, A. Kitahara, Role of steric hin-
drance in the performance of superplasticizers for concrete, J. Am.
4. Conclusions Ceram. Soc. 80 (10) (1997) 2667 – 2671.
[5] T. Nawa, Doctoral Dissertation, Tokyo Institute of Technology, 1992
(in Japanese).
Adsorption characteristics of various types of superplas-
[6] E. Tazawa, B. Mtasiwa, M. Takahashi, Effect of types of superplasti-
ticizers on mineralogical compositions of portland cement cizers and mixing methods on the properties of cementitious systems,
were investigated. As a result, the following conclusions Proceedings Fifth CANMET/ACI International Conference Rome,
were obtained. Superplasticizers and Other Chemical Admixtures in Concrete (1997)
637 – 656.
[7] A. Ohta, T. Sugiyama, Y. Tanaka, Fluidizing mechanism and applica-
1. A larger amount of superplasticizers was adsorbed on
tion of polycarboxlate-based superplasticizers, Proceedings Fifth
C3A and C4AF particles than on C3S and C2S for all CANMET/ACI International Conference Rome, Superplasticizers
types of superplasticizers. However, the equilibrated and Other Chemical Admixtures in Concrete (1997) 359 – 378.
concentration of superplasticizer was much the same [8] K. Kawai, R.M. Capito, M. Kajitani, E. Tazawa, H.M. Jennings, to be
value at the maximum adsorption. submitted.
[9] H. Uchikawa, D. Sawaki, S. Hanehara, Influence of kind and
2. Without superplasticizer, C3S and C2S had negative z-
added timing of organic admixture on the composition, structure
potential. On the contrary, C3A and C4AF had positive and property of fresh cement paste, Cem. Concr. Res. 25 (2)
z-potential. Therefore, accelerated coagulation of (1995) 353 – 364.
cement particles in a plain paste might occur due to [10] C. Wu, M. Tezuka, M. Imai, N. Horikoshi, The effect of type of
this opposite charge in particles. cement and superplasticizer on high-plasticity mortar, Proc. Jpn.
Concr. Inst. 18 (1) (1996) 57 – 62 (in Japanese).
3. All mineralogical components of cement showed nega-
[11] H. Uchikawa, S. Hamehara, D. Sawaki, T. Shirasaki, Interaction be-
tive z-potential when they are dispersed in a solution tween cement and organic admixture at early age, Concr. Res. Tech-
with superplasticizer. Therefore, it is expected that flu- nol., Jpn. Concr. Inst. 4 (1) (1993) 91 – 102 (in Japanese).
idity of cement paste in early age is improved by [12] T. Nawa, M. Ohkubo, H. Eguchi, The fluidity of belite rich cement for
hindering accelerated coagulation described in the above. highly flowable concrete, Proceedings of the JSCE Symposium on
Self-Compacting Concrete, (1996) 37 – 42 (in Japanese).
[13] H. Uchikawa, Material design of high strength concrete, Gypsum and
lime 242 (1993) 2 – 15 (in Japanese).
Acknowledgments [14] K. Hattori, Mechanism of slump loss and its control, J. Soc. Mater.
Sci. 29 (1980) 240 (in Japanese).
[15] M. Yang, C.M. Neubauer, H.M. Jennings, Interparticle potential and
Valuable advice of Professor Asuo Yonekura, Miss sedimentation behavior of cement suspensions, Adv. Cem. Based
Motoko Yoshida of Hiroshima University, Masatosi Taka- Mater. 5 (1997) 1 – 7.