Proceedings of International Conference on

Advances in Concrete and Construction, ICACC-2008

7-9 February, 2008, Hyderabad, India pp 981-994

A Review of the Influence of Water Reducing

Admixtures on the Hydration of Cement

Narayanan Neithalath,
Assistant Professor, Department of Civil and Environmental Engineering,
Clarkson University, Potsdam, NY 13699, USA.

E-mail: nneithal@clarkson.edu

Ravikumar, V.K
Cera-Chem Private Limited, 6, Park Street, Kilpauk, Chennai. India

E-mail: ravikumar@cerachemindia.com

Abstract

This paper is a condensed review of the influence of superplasticizers on the

hydration of cement. Significant amount of research is being carried out to
understand how superplasticizers influence the rate of hydration, formation of
hydration products, and its morphology. A brief review of thermodynamics and
kinetics of cement hydration can be found here, followed by details on specific
reactions that are modified by chemical admixtures. The physical and chemical
processes involved in adsorption of superplasticizer on the surface of cement
particles are also dealt with. The influence of superplasticizer on the initial
hydration period, dormant period and the acceleration period is covered with
emphasis on nucleation, ion complexation and crystal formation. Results from
limited literature on the morphology of hydration products in superplasticized
mixtures are also reported. A better understanding of the aspects relating to the
hydration rate and hydration products in the presence of superplasticizers will

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 A Review of the Influence of Water Reducing Admixtures on the Hydration of Cement

help in the formulation of specific admixtures for specific applications, and

ensure proper dosage of the admixture with respect to the intended results.

INTRODUCTION

The complexity of cement hydration reactions has been well

studied over the past several years. Cement hydration reactions are
complex not only due to compositional, morphological and
manufacturing variations, but also due to other possible variants
such as surface area, ambient conditions, and the presence of
chemical admixtures [1]. The latter is a significant parameter
considering the fact that chemical admixtures are an integral part
of any high performance concrete. Thus, understanding the
mechanisms underlying cement-admixture interactions and the
influence of admixture on cement hydration is key to developing
durable, strong and tough concrete. This is also a pre-requisite to
development of tailored admixtures for specific applications in
concrete.

A brief look at the influence of superplasticizers on the

thermodynamics and the chemistry of cement hydration and the
morphology of the hydrated products is presented here. The kinetic
and mechanistic aspect of cement hydration is reviewed that leads
into the specifics of superplasticizer interaction. The emphasis is
on the naphthalene sulfonate based superplasticizers whereas the
other types (melamine or carboxy acrylic acid based) are also dealt
with in passing.

Before discussing about the effects of superplasticizers on the

hydration reaction and the hydration products, it is essential to
review the thermodynamics and kinetics of cement hydration,
which will help in greater appreciation of the role of
superplasticizers in the system.

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 Proceedings of ICACC-2008, 7-9 February 2008, Hyderabad, India

CEMENT HYDRATION
The reaction of portland cement with water to form the hydration
products that impart strength and stability to concretes has been
studied for a long time. The major phases of portland cement
interact with water and with each other through various physical
and chemical processes.

Thermodynamics of hydration

The exothermic reaction of water with Portland cement results in

the formation of hydration products, finally yielding a dense and
stable matrix through a series of bonding reactions. The reactions
of cement minerals with water involve ionic release into solution,
reactions at the interface of the pore solution and the cement grain,
and solid-state reactions. The relative reactivity of different phases
is usually given as C3A>C3S>C2S≈C4AF, although absolute
reactivities vary considerably depending on the degree of metal ion
substitution in their phases and their crystal structure. It is well
known that the very early age behavior (up to 1 hour) of hydrating
cements is governed by the reactions of the aluminate phases,
particularly C3A and the setting and early strength behavior is
dependent on hydration of silicates, mostly C3S [2].

The high reactivity of the aluminate phase requires it to be

controlled and this is typically done using the presence of sulfate
ions (gypsum addition). The formation of mixed sulfoaluminate
products, i.e., ettringite (AFt) and monosulfoaluminate (AFm)
typically is responsible for this reaction control.

C3A + 3CSH2 + 26H C6AS3H32 (1)

2C3A + C6AS3H32 + 4H 3C4ASH12 (2)

Gypsum (Calcium sulfate) added to the clinker therefore is

sometimes viewed as the first chemical admixture used to control
the nature and properties of aluminate hydration products. The

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 A Review of the Influence of Water Reducing Admixtures on the Hydration of Cement

influence of addition of organic chemical admixtures on sulfates is

fairly significant.

Kinetics of cement hydration

As stated earlier, the process of cement hydration is a combination

of solution processes, interfacial phenomena and solid-state
reactions. A schematic representation of heat evolution from the
hydration of C3S and ordinary Portland cement are shown in
Figure 1. It identifies five different stages - (i) Initial hydration
process (0-15 minutes), (ii) Induction period or lag phase (15
minutes – 4 hours), (iii) Acceleration and set (4-8 hours), (iv)
Deceleration and hardening (8-24 hours), and (v) Steady state
(beyond 24 hours). It has been often reported that the stages which
are most influenced by superplasticizers are those occurring within
about 12 hours from the time cement particles come into contact
with water, which puts the first three stages into prominence. A
brief review of the physicochemical processes happening in the
initial 12 hours and the influence of superplasticizers is detailed
below.

I Initial hydration
process (~0-15
minutes)
II Induction period
(~15 minutes-4 hours)
III Acceleration and
set (~4 hours-8 hours)

Fig.1 Schematic cement hydration thermogram showing the distinct

stages in hydration process [3]

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 Proceedings of ICACC-2008, 7-9 February 2008, Hyderabad, India

Initial hydration process (~0-15 minutes)

+
The solution concentration of the ionic species including Na+, K ,
Ca2+ and OH- increases initially. Since silicate and aluminate ions
are soluble in highly alkaline solutions, their concentrations will
increase as the pH increases, but they remain lower than those of
Na+, K+, Ca2+, SO42- and OH-. A thin layer of intermediate
amorphous hydration products is formed, consisting largely of
aluminates [4]. Calcium sulfoaluminates nucleate and the growth
of hydration products proceed at a rate determined by the bulk
concentration of the solution species, the availability of water and
ionic species at the reaction sites. The presence of superplasticizers
can influence the nucleation process, the reaction rate and the
products of reaction.

Reactions during the induction period (~15 minutes-4 hours)

The aluminate phase reactions predominate during the initial

stages. Excessive nucleation of C-A-H (calcium aluminate hydrate)
products may occur (flash set) if sulfate concentration is too low,
or massive nucleation and growth of gypsum crystals (false set)
may occur if sulfate concentration is too high [5,6]. Increased
production of C-S-H will lead to an overlay onto the aluminate rich
gel layer, and increased osmotic and mechanical pressures develop
on the gel layer as hydration advances. Again, the interaction of
the admixture with any of the reactive species or its influence on
diffusion, nucleation and crystal growth can impact the behavior of
the cementitious system.

Acceleration and setting (~4-12 hours)

The rate of reaction increases rapidly in this stage. The energy of

the interactions between the growing particles of the system also
increases and the system is converted into a stiff matrix. The
hydrate protective layer is disrupted, and C-S-H (calcium silicate
hydrate) as well as CH (calcium hydroxide) grows and nucleates.

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 A Review of the Influence of Water Reducing Admixtures on the Hydration of Cement

This so-called “self-catalytic” behavior of cement hydration in the

acceleration stage may also be affected by chemical admixtures
[2].

FUNDAMENTALS OF SUPERPLASTICIZER-CEMENT
INTERACTION - ADSORPTION AND ITS SIGNIFICANCE

Before getting into the details of the influence of superplasticizers

on the hydration reaction of Portland cement systems, it is essential
to have a general overview on the physical processes that occur in
the system. Surface adsorption is one of the key factors that have a
significant effect on how superplasticized systems behave during
hydration reactions [3]. Amount of adsorption can be directly
linked to the workability of the superplasticized systems.

Physical processes in adsorption

Organic molecules with charged groups like SO3- (as in

naphthalene sulfonates) or COO- (as in carboxy acrylic esters) can
interact with the cement particle surface through electrostatic
forces (surface charges of the particle and ionic groups of the
admixture molecule). This phenomenon of surface adsorption
occurs mostly on the hydrating phases (those phases in reaction
with water) rather than the unhydrated phases. It has been proved
that for sulfonated naphthalene superplasticizers, a small
adsorption occurs at the surface initially, and further adsorption is
due to increased dispersion and hydration. When superplasticizer is
added with mixing water, the C3A-gypsum mixture rigidly attaches
to the admixture molecule, leaving little for dispersion of silicate
phases [7]. Delayed addition of admixture, thus overcomes this
problem, by reducing the adsorption capacity of the aluminates and
the sulfates. The C3A/SO3 ratio of the cement thus influences the
adsorption behavior. It has also been indicated that the adsorption
behavior is dependent on the C3S/C2S and C3A/C4AF ratios. It is
also observed that low-alkali cements tend to adsorb less
superplasticizer than the high alkali ones. This is an important
aspect to consider while arriving at superplasticizer dosage for
various cements.

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 Proceedings of ICACC-2008, 7-9 February 2008, Hyderabad, India

Chemical processes in adsorption

The organic molecules are chemically adsorbed at the highly

reactive sites on the surface of the cement particle. Sulfates, SO42-,
as explained earlier, reacts preferentially with the aluminate phase
in a cement particle (highly reactive site), competing with
sulfonate group in the superplasticizer [2]. This is shown
schematically in Figure 2. If the admixture has a dominant
carboxyl group, it can help solubilize the ionic species through
association or complexation, as shown in Figure 3.

C3A site on the

cement particle

SO42- (from gypsum)

Sulfonate group from the

superplasticizer

Fig.2 Preferential adsorption of organic molecules on specific sites (selective

blocking of reactive surface sites)

COO-

Fig.3 Complexation and solubilization of ionic species

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 A Review of the Influence of Water Reducing Admixtures on the Hydration of Cement

Complexation reactions can either accelerate the dissolution

processes or can delay the precipitation of insoluble hydrates like
C-S-H and CH. The presence of organic molecules at the interface
of the hydrating solid and the pore solution can inhibit nucleation
and growth of the hydration products. The growth of hydration
products in the presence of adsorbed admixtures may result in
structural alteration or morphological changes in the hydration
products. Thus, the adsorption process can be seen to be of
extreme significance and dictates the behavior of the material.

HYDRATION IN SUPERPLASTICIZED CEMENTITIOUS

SYSTEMS

Reactions in the first stage

The adsorption of naphthalene sulfonates occurs preferentially on

to the aluminate phases. The amount adsorbed depends on the
alkali content of the cements – with increasing alkali contents, the
adsorption is reduced. It is generally agreed that superplasticizers
retard the hydration of C3A [8-10]. Conduction calorimetric curves
of C3A hydration give ample evidence of this, as shown in Figure 4
[3]. A significant reduction in heat of hydration is observed at very
early ages. There is divided opinion on the kinetics of the
hydration of C3A + gypsum in the presence of superplasticizers.
All three possibilities – acceleration, retardation and no effect have
been reported. In general, it is found that superplasticizers retard
the conversion of ettringite to monosulfate, probably due to the
adsorption of superplasticizer on the hydrating C3A surface. It has
also been stated that low molecular weight admixtures are more
effective than high molecular weight ones at the same solution
concentration. This is a crucial aspect in the design of the
superplasticizer molecule for effectiveness.

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 Proceedings of ICACC-2008, 7-9 February 2008, Hyderabad, India

4
No superplasticizer
3
Cal/g/min

1
2% sulfonate based
superplasticizer

0
0 1 2 3
Time in minutes

Fig.4 Conduction calorimetric curves for C3A hydration

Reactions during the induction period

Beyond the rapid initial adsorption, which is to saturate the most

reactive phases, the admixture uptake by the hydrating cement
continues at a reduced rate. Continued adsorption takes place,
mainly due to the growth of the hydrate particles. The hydration of
the C3S phase is retarded. This can be observed from the
thermogram shown in Figure 5. The rate of the hydration process is
substantially reduced in the presence of a naphthalene sulfonate
admixture. The low heat output suggests that very limited amounts
of new hydrates are formed during the dormant period. The
consumption of admixture in this stage is by adsorption into the
nucleating hydrating phases.

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 A Review of the Influence of Water Reducing Admixtures on the Hydration of Cement

5
No
5
l i i
Temperature (degrees 4

3
2% sulfonate
3
based

0 2 4 6 8 1
Time
(h )
Fig.5 Hydration thermogram of OPC paste with and without superplasticizer [3]

Reactions during the acceleration period

The onset of acceleration is substantially postponed as a result of

the interactions occurring in the first two phases. The effects of
admixture in this stage is really because of the delay experienced
in the previous stages since there remains only low quantities of
free organic groups, which is insufficient to control the massive
nucleation-reaction-precipitation reactions triggered when the
initial hydrate layers (protective layers) are disrupted. A
conduction calorimetric curve of Portland cement hydrated in the
presence of a naphthalene sulfonate superplasticizer is shown in
Figure 6.

The estimation of calcium hydroxide formed at different times can

also provide information on the effect of superplasticizers on
cement hydration. The early formation of CH is markedly reduced,
but after around 3 days, there is no significant effect. The relative
retardation effect of superplasticizers depends on the fineness of
cement also. It has been proved that for fine cements rich in alkali

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 Proceedings of ICACC-2008, 7-9 February 2008, Hyderabad, India

and sulfate, there is no significant retardation whereas the coarser

cements liberate less amounts of heat and is retarded [2,3].

0%
3
1%
Cal/g/h

2%

2
4%

0
0 5 1 1
Time, in hours

Fig.6 Conduction calorimetric curves of potland cement hydrated in the

presence of a sulfonated formaldehyde superplasticizer [3]

MORPHOLOGY OF THE HARDENED PASTE

Not many reported literature discuss in great detail, the salient

features of microstructure of cementitious systems incorporating
superplasticizers as compared to those without them. Studies on
the hydration of C3A-gypsum system [11] has shown that large
fibrous ettringite bundles are formed in the absence of a sulfonate
superplasticizer whereas the ettringite is more needlelike in the
presence of a superplasticizer. The former type may lead to
enhanced interlocking and loss of workability whereas the latter
type results in the mixture being workable for a longer duration.
This is one of the significant factors that help superplasticized
mixtures retain workability for longer durations. Similar

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 A Review of the Influence of Water Reducing Admixtures on the Hydration of Cement

observations were also made by Prince et al. [6] where they

reported small and massive clusters of ettringite in an amorphous
background. It is conceivable that superplasticizers are
progressively consumed within this amorphous phase. The usual
ettringite crystals start to grow once all the superplasticizer
molecules are consumed [6]. Thus, the presence of superplasticizer
results in a definite modification of ettringite morphology.

Some studies also point to the influence of superplasticizer on the

morphology of calcium hydroxide phase. Pseudo-hexagonal
prismatic morphology of CH crystals are reported in the absence of
sulfonate superplasticizers, but in their presence, the CH crystals
were very thin and irregular and consisted of numerous stacked
platelets [3].

SUMMARY

From the foregoing discussion, it can be summarized that the

presence of superplasticizers has a significant influence on the
hydration kinetics of cement hydration. The phenomenon of
surface adsorption plays a crucial role in how superplasticizers
alter the hydration kinetics, and that depends to a large extent on
the surface chemistry of the cement grains. The nucleation process
of hydrates can be altered by the presence of superplasticizers. The
reaction rate and the products of reaction are also dependent on the
presence of chemical agents. The diffusion process of reactive
ionic species in the pore solution is affected by chemical
admixtures. This in turn, dictates the nucleation and crystal growth
processes and subsequently the formation of final products of
hydration. The disruption of protective hydrate layer – the “self-
catalytic” behavior may also be influenced by superplasticizers.

REFERENCES

1. Kreppelt, F, Weibel, M, Zampini, D, Romer, M. Influence of

solution chemistry on the hydration of polished clinker surfaces
– a study of different polycarboxylic acid-based admixtures.
Cement and Concrete Research, Vol.32, 2002, pp 187-198

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 Proceedings of ICACC-2008, 7-9 February 2008, Hyderabad, India

2. Jolicoeur, C and Simard, M.A. Chemical admixture-cement

interactions: phenomenology and physico-chemical concepts.
Cement and Concrete Composites, Vol.20, 1998, pp 87-101

3. Ramachandran, V S and Malhotra V M. Superplasticizers. In

Concrete Admixtures Handbook – Properties, Science and
Technology, 2nd ed. Edited by V S Ramachandran. Noyes
Publications, New Jersey, 1995

4. Lea, F M. The Chemistry of Cement and Concrete, 3rd ed.

Edward Arnold Ltd., London, 1970

5. Gaidis, J M and Gartner, E M. Hydration Mechanisms II. In

Material Science of Concrete II, Edited by J.Skalny and S.
Mindess. The American Ceramic Society Inc, OH, 1991, pp 9-
39

6. Prince, W, Edwards-Lajnef, M, Aitcin, P C. Interaction

between ettringite and a polynaphthalene sulfonate
superplasticizer in a cementitious paste. Cement and Concrete
Research, Vol. 32, 2002, pp 79-85

7. Flatt, R J and Houst, F Y. A simplified view on chemical

effects perturbing the action f superplasticizers. Cement and
Concrete Research, Vol. 31, 2001, pp 1169-1176

8. Bonen, D and Sarkar, S L. The superplasticizer adsorption

capacity of cement pastes, pore solution composition and
parameters affecting flow loss. Cement and Concrete Research,
Vol. 25, 1995, pp 1423-1434

9. Hanehara, S and Yamada, K. Interaction between cement and

chemical admixture from the point of cement hydration,
absorption behavior of admixture and paste rheology. Cement
and Concrete Research, Vol. 29, 1999, pp 1159-1165

10. Chandra, S and Bjornstrom, J. Influence of superplasticizer

type and dosage on the slump loss of Portland cement mortars

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– Part II. Cement and Concrete Research, Vol. 32, 2002, pp

1613-1619

11. Sakai, E, Raina, K, Asaga, K, Goto, S, Kondo, R. Influence of

sodium aromatic sulfonates on the hydration of tricalcium
aluminate with or without gypsum. Cement and Concrete
Research, Vol. 10, 1980, pp 311-319

NOTATIONS
Some of the common cement chemistry notations that have been
used in this paper are shown below:

C: Calcium oxide (CaO)

S: Silicon dioxide (SiO2)
A: Aluminum oxide (Al2O3)
S: Sulfate (SO3)
H: Water (H2O)
C3S: Tricalcium silicate (3 CaO. SiO2)
C3A: Tricalcium aluminate (3 CaO. Al2O3)
C2S: Dicalcium silicate (2 CaO. SiO2)
C4AF: Tetracalcium aluminoferrite (4 CaO. Al2O3. Fe2O3)
CSH2: Gypsum (CaSO4. 2H2O)
C6AS3H32: Ettringite (Aft)
C4ASH12: Monosulfoaluminate (AFm)
C-S-H: Calcium silicate hydrate
C-A-H: Calcium aluminate hydrate
CH: Calcium hydroxide

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