Super Plasticizer S

7/24/2014 Cement - Superplasticizer Compatibility
http://www.theconcreteportal.com/compat.html 1/12
This page describes the current level of knowledge worldwide about the issues of incompatibility between
cements and water reducing chemical admixtures. The definition, classification, and chemical
compositions of water reducing chemicals are discussed first, followed by their mechanism of action in
concrete. Test methods to evaluate effectiveness of plasticizers are also reviewed. Specific issues of
incompatibility are then addressed, namely, loss of workability, alteration of setting behaviour, reduced
rates of strength gain, and change in long term behaviour. The factors controlling the compatibility are
discussed next in detail, including the role of the chemistry (of cement and admixture), the presence of
other mineral and chemical admixtures, and the proportioning of concrete. Finally, a detailed insight
into the needs for further research is provided.
1. INTRODUCTION
Modern concretes almost always possess additives, either in the mineral form or chemical form.
Particularly, chemical admixtures such as water reducers and set controllers are invariably used to
enhance the properties of fresh and hardened concrete.
A Chemical Admixture is any chemical additive to the concrete mixture that enhances the properties of
concrete in the fresh or hardened state. This does not include paints or coatings. ACI 116R [2000] defines
the term admixture as a material other than water, aggregates, hydraulic cement, and fiber
reinforcement, used as an ingredient of concrete or mortar, and added to the batch immediately before
or during its mixing.
A number of types of chemical admixtures are used for concrete. The general purpose chemicals include
those that reduce the water demand for a given workability (called water reducers), those entraining
air in the concrete for providing resistance to freezing and thawing action (called air entrainers), and
those chemicals that control the setting time and strength gain rate of concrete (called accelerators and
retarders). Apart from these chemicals, there are others for special purposes namely, viscosity
modifying agents, shrinkage reducing chemicals, corrosion inhibiting admixtures, and alkali-silica
reaction mitigating admixtures.
Apart from the multitude of chemical admixtures, a number of different types and brands of cement are
also available in the market today. With the increasing number of types and brands of cement, as well as
variants of the water-reducing chemicals, there are issues that arise related to the compatibility between
these two ingredients of concrete. Most users apply a trial-and-error approach to these chemicals, often
resulting in an unfortunate negative experience and/or low cost-effectiveness, which produce a bias
against admixtures in general.
Common problems that arise as a result of incompatibility between cement and water reducers are:
rapid loss of workability, excessive quickening / retardation of setting, and low rates of strength gain.
Very often, there even exists incompatibility between a particular chemical and a certain batch of the
same otherwise compatible cement, indicating that the nature of the problem is complex, and needs
further understanding. Moreover, high performance concretes, which are in wide use today, almost
always incorporate a mineral admixture or filler such as silica fume, fly ash and limestone powder. This
further complicates the physico-chemical behaviour of the cement-based system since the mineral
admixtures play an important role in the evolution of the hydration reactions and the availability of free
water during the early ages of concrete.
2. WATER REDUCING CHEMICALS
A water reducing chemical, as the name implies, is used to reduce the water content of a concrete
mixture while maintaining a constant workability. The resultant effect of the reduced water content is
the increased strength and durability of concrete. However, water reducers may also be employed to
plasticize the concrete, i.e. make concrete flowable. In this case, the water content (or water to cement
ratio) is held constant, and the addition of the admixtures makes the concrete flow better, while the
compressive strength (which is a function of the water to cement ratio), is not affected. Another use of
water reducers is to lower the amount of cement (since water is proportionately reduced) without
affecting both strength and workability. This makes the concrete cheaper and environmentally friendly,
as less cement is consumed.
Water reducers are classified broadly into two categories: (1) Normal and (2) High range. The normal
water reducers are also called plasticizers, while the high range water reducers are called
superplasticizers. While the normal water reducers can reduce the water demand by 5 10%, the high
range water reducers can cause a reduction of 15 40%.
Water reducing chemicals are generally supplied as liquid formulations, with the active solids content in
the range of 30 40%. Normal water reducers are typically used at dosages of 0.3 0.5% liquid by
weight of cement. At higher dosages, there is a danger of excessive retardation, bleeding, and air
entrainment. High range water reducers do not have these problems and are capable of being used at
higher dosages of 0.7 1% (or more) liquid by weight of cement.
Lignosulphonate salts of sodium and calcium, hydroxycarboxylic acids (citric and gluconic acid) and
carbohydrates (corn syrup and dextrin) are examples of normal water reducers. The subject of interest
for this study, namely superplasticizers are generally chemicals of the type presented in Table 1. All the
superplasticizers are water soluble polymers. As for other polymers, the behaviour of superplasticizers is
also a function of the structure and the degree of polymerization.
Table 1. Superplasticizing chemicals [from Rixom and Maivaganam, 2003]
Class Origin
Structure (typical repeat
unit)
Relative
cost
Lignosulphonates
Derived from neutralization, precipitation, and
fermentation processes of the waste liquor
obtained during production of paper-making
pulp from wood
1
Sulphonated
melamine
formaldehyde
(SMF)
Manufactured by normal resinification of
melamine - formaldehyde
4
Sulphonated
naphthalene
formaldehyde
(SNF)
Produced from naphthalene by oleum or
SO
3
sulphonation; subsequent reaction with
formaldehyde leads to polymerization and the
sulphonic acid is neutralized with sodium
hydroxide or lime
2
Polycarboxylic
ether (PCE)
Free radical mechanism using peroxide
initiators is used for polymerization process in
these systems
4

Lignosulphonates are generally regarded as 1
st
generation superplasticizers, while the sulphonated
formaldehyde condensates are called 2
nd
generation, and the polycarboxylates and polyacrylates are
termed as 3
rd
generation superplasticizers. Currently, the most widely used superplasticizers are the
sulphonated formaldehyde condensates. However, the beneficial effects of polycarboxylates are ensuring
a gradual shift towards these chemicals.
In terms of costs, polycarboxylic ether and sulphonated melamine formaldehyde are almost equal (taken
on an effective solids basis), sulphonated naphthalene formaldehyde is about half the cost of the PCE,
while lignosulphonate is the cheapest (about of PCE). However, in terms of effectiveness to achieve a
specific workability of the concrete, the amount of PCE required is much lesser than SNF or
lignosulphonate. Thus, the overall cost of a normal plasticized concrete would not be affected based on
the choice of the chemical (with the exception of SMF, which are more expensive considering the desired
workability of concrete).
2.1 Characteristics of the different chemicals
Used at high dosages, lignosulphonates are capable of producing high range water reduction. However, a
major problem with the use of lignosulphonates as superplasticizers is the excessive retardation and air
entrainment in concrete. Modified lignosulphonates as superplasticizers lead to concrete with lesser
variation in properties.
Sulphonated salts of melamine formaldehyde condensates are good to achieve a high initial slump.
However, due to their poor slump retention characteristics, they are unsuitable for long haul
applications, and more particularly for ready mixed concrete. On the other hand, these admixtures are
excellent for precast concrete, where the concreting time is short. They are also suitable for cold climates.
However, SMFs are not widely used in India owing to the poor cost-competitiveness compared to SNF.
Sulphonated salts of naphthalene formaldehyde condensates possess all the necessary characteristics to
make them suitable for hot weather concreting. Mainly, these possess good slump retention
characteristics, enabling their use in ready mixed concrete where long hauls are common. Slump
retention characteristics are also improved by blending SNF with lignosulphonates, which is not possible
in the case of SMF. The cost of SNF is also low, making it the most used superplasticizer in India and
around the world. However, the maximum incompatibility issues arise with SNF, and these will be
discussed at length later in this report.
Polycarboxylates and acrylic copolymers are the most effective of all the chemicals. These can cause a
reduction in water content of as much as 40%. Thus, they are highly preferred to make high and ultra
high strength concrete, where the w/c may be as low as 0.20. Generally, these chemicals exhibit excellent
slump retention characteristics and do not cause any delay in the gain of strength of the concrete. The
downside of these admixtures is their high cost. However, as stated earlier, for the same category of
concrete (workability) PCEs can work at lower dosages than SNFs and lignosulphonates. Thus, the
overall cost of concrete is not affected. Only in the case of special concretes such as self compacting
concrete (SCC), the use of PCEs can substantially increase the concrete cost. It must be stated, though,
that making good quality SCC without these latest generation superplasticizers is almost impossible.
Limited experience with these chemicals indicates that they work well at low water to cement ratios, and
exhibit fewer compatibility problems compared to SNF.
2.2 Mechanism of action of water reducers
Water-reducing chemicals belong to a group of chemicals known as dispersants. The action of the
dispersant is to prevent the flocculation of fine particles of cement. These dispersants are basically
surface-active chemicals consisting of long-chain organic molecules, having a polar hydrophilic group
(water-attracting, such as -COO
-
, -SO
3
-
, -NH
4
+
) attached to a non-polar hydrophobic organic chain
(water-repelling) with some polar groups (-OH). The polar groups in the chain get adsorbed on the
surface of the cement grains, and the hydrophobic end with the polar hydrophilic groups at the tip
project outwards from the cement grain. The hydrophilic tip is able to reduce the surface tension of
water, and the adsorbed polymer keeps the cement particles apart by electrostatic repulsion (The
grinding of cement results in the ground particles having a surface charge (zeta potential). The
adsorption of the admixture leads to a decrease of the zeta potential, and eventually causes like charges
(negative) on the cement particles). With the progress of hydration, the electrostatic charge diminishes
and flocculation of the hydrating product occurs.
Lignosulphonates (normal, and sugar-refined), SMF, and SNF based superplasticizers work on the
mechanism of lowering zeta potential that leads to electrostatic repulsion. On the other hand, polymers
with backbone and graft chains, such as PCEs, acrylic esters, and cross-linked acrylic polymers, cause
dispersion of cement grains by steric hindrance [Uchikawa et al., 1997]. This phenomenon relates to the
separation of the admixture molecules from each other due to the bulky side chains. Steric hindrance is a
more effective mechanism than electrostatic repulsion. The side chains, primarily of polyethylene oxide
extending on the surface of cement particles, migrate in water and the cement particles are dispersed by
the steric hindrance of the side chains.
Figure 1. Mechanism of electrostatic repulsion (top) and steric hindrance (bottom)
Electrostatic repulsion depends on the composition of the solution phase and the adsorbed amount of the
SP (greater the adsorption, better the repulsion) [Nakajima and Yamada, 2004]. On the other hand,
steric repulsion depends on the length of main chain, length and number of side chains [Sugiyama et al.,
2003].
In the case of PCE based admixtures, for fluidity retention, the main chain should be short, with large
numbers of long side chains [Sugiyama et al., 2003]. Because of the steric repulsion mechanism, PCEs are
generally more effective than the sulphonate based admixtures, and generally do not experience much
problems at low water to cement ratios. However, they are more sensitive to overdosing, and can lead to
problems like excessive air entrainment and retardation.
Additional mechanisms of SP action include dispersion of cement particles by reduction in surface
tension of mixing water and a decrease in frictional resistance because of the line-up of linear polymers
along the concrete flow direction and lubrication properties produced by low molecular weight polymers
[Uchikawa et al., 1995].
Apart from affecting the early age physical properties of concrete, SPs can also cause some changes in
the morphology of hydration products. Size of portlandite crystals decreases with addition of admixtures
[Grabiec, 1999]. Ettringite in the presence of SPs (at high dosage) crystallizes in small and massive
clusters rather than the conventional needle shape [Hanna et al., 2000; Prince et al., 2002]. In general,
SPs improve rheological properties by yielding smaller hydrate particles and preventing hydration
products from bridging neighbouring cement particles. There is also a difference in porosity and pore
size distribution of superplasticized concrete compared to normal concrete. Higher numbers of smaller
pores are produced in superplasticized mixtures, which could have an influence on the degree of
shrinkage.
While the mechanism of action of water-reducing chemicals is reasonably well-established, there still
exist gaps in the comprehension of why occasionally these chemicals do not work as intended. This is
because the problem of cement-superplasticizer compatibility has many dimensions to it. On the one
hand, there is the composition of the water reducer, as discussed above. On the other end of the spectrum
is the composition of cement, particularly the relative proportions of C
3
A, alkalis and C
3
S in the cement.
In addition, the type of gypsum available (gypsum, hemihydrate, or anhydrite) has an important role to
play. The fineness of cement could also affect its compatibility with a particular admixture. Each of these
factors influences the phenomenology of cement-water reducer interaction. This aspect is discussed in the
next section.
3. CEMENT SUPERPLASTICIZER INCOMPATIBILITY
3.1 What is incompatibility?
The term incompatibility refers to the adverse effect on performance when a specific combination of
cement and superplasticizer is used. Common problems include flash setting, delayed setting, rapid
slump loss, improper strength gain, inordinate cracking etc. These issues in turn affect the hardened
properties of concrete, primarily strength and durability.
The use of superplasticizers has become very common in India. There has also been a proliferation in the
number of brands of cement, and in the types of cement available. It is very difficult to ensure that an
admixture that produces all the desired effects with cement A would do the same with cement B. Users,
who are unaware of compatibility issues, often suffer when the supply of cement and/or admixture is
changed midway through a project. Problems arising out of compatibility issues are often mistaken for
problems with concrete mixture design, because of the lack of information about the subject amongst
practicing engineers. Admixture manufacturers try to overcome the problem by formulating project-
specific chemicals. Obviously, this is only a short term solution. For a more comprehensive approach, a
thorough understanding of the causes and remedies of incompatibility is necessary.
Leading researchers have recognized the need to review the acceptance standards for both cements and
superplasticizers since the incompatibility problems are expected to grow with further and more
extensive use of high performance concrete [Tagnit-Hamou et al., 1992], and also with the number of
cements and chemicals available in the market.
Incompatibility could also arise as a result of the use of additional mineral additives, or while using
multiple chemicals [Bedard and Mailvaganam, 2006]. However, in order to keep the discussion focused,
this paper is restricted to the analysis of incompatibilities resulting from the cement and SP alone.
3.2 Factors affecting compatibility
Interaction problems are caused by the effect of the admixtures on the hydration reaction of cement and
due to adsorption of the admixture to the cement particles. These are different from problems in fresh
concrete that are caused due to poor material selection. For example, overdosing of the SP might lead to
segregation (since paste viscosity and yield stress get highly reduced) and retardation of setting with any
cement this is a problem of poor design. However, compatibility problems arise even when the material
selection and design is supposedly proper.
Compatibility between cements and superplasticizers is affected by a combination of reasons, including
cement composition, admixture type and dosage, concrete mixture proportions etc. Atcin [1998]
describes the complicated nature of the interaction using the schematic diagram shown in Figure 2. The
influence of cement composition encompasses a wide variety of issues, which are discussed below.
Figure 2. Complexity of the superplasticized cement paste system (based on Atcin [1998])
3.2.1 Cement composition and fineness
Cement is composed of four major compounds, namely, C
3
S (tricalcium silicate), C
2
S (dicalcium
silicate), C
3
A (tricalcium aluminate), and C
4
AF (tetracalcium aluminoferrite). In addition, a number of
minor oxides, such as alkali oxides (K
2
O and Na
2
O), MgO, and SO
3
which is contributed by gypsum,
which is added in the final stages of cement manufacture as a set regulator. Because of the final grinding
operation, the particles of cement are charged (the surface charge is measured as the Zeta potential).
While C
3
S and C
2
S possess a negative zeta potential, C
3
A and C
4
AF particles are positively charged.
Role of C
3
A
The C
3
A content, or more specifically, the C
3
A to SO
3
ratio has a profound effect on the early age
behaviour of cement paste. In a normal hydration process of OPC, the amount of C
3
A is such that the
end product of aluminate hydration is monosulphate (AF
m
). However, in low C
3
A cement (sulphate
resistant) ettringite remains after the initial hydration.
When the C
3
A to SO
3
ratio is very high (or when SO
3
is not easily available in solution), flash setting
occurs due to rapid hydration of C
3
A. In the case of low C
3
A to SO
3
ratio, there is a high possibility of
false setting (conversion of calcium sulphate forms to gypsum).
When the C
3
A content of cement is high, and the sulphate availability is low, superplasticized concretes
experience high rates of slump loss (this aspect is discussed further in the next section). Cements having
moderate to high C
3
A contents (~ 9%) showed increased slump loss over that of control concrete
[Perenchio, 1979]. On the other hand, when there is less C
3
A available, SPs would tend to get adsorbed in
higher amounts on C
3
S and C
2
S, resulting in a reduction in the rate of strength development [Roberts,
1995]. The use of special Portland cement containing less than 10% of interstitial phase (3.6% C
3
A and
6.9% C
4
AF) was reported to be very economical in terms of SP dosage to make fluid high performance
concrete at low water/binder ratio.
Role of Calcium Sulphates
In the early stages of cement hydration, the reactions that dominate are the reaction of C
3
S with water to
produce CSH and calcium hydroxide, and the reaction of C
3
A with gypsum to produce ettringite (that
later converts to monosulphoaluminate in ordinary Portland cement paste). It is during this period that
the interaction of the SP with cement occurs. SP molecules with sulphonate functional groups have an
affinity for the aluminates, which are positively charged. As a result, they compete with the sulphate
released from gypsum for the aluminate reaction sites [Ramachandran, 2002; Jolicoeur and Simard,
1998, Jolicoeur et al., 1994]. When the solubility of the calcium sulphate is low, the SP molecules tend to
get adsorbed first on the aluminate compounds, thus preventing the normal setting reaction involving the
formation of ettringite. Based on the raw material for calcium sulphate and on the temperatures attained
during the final grinding process, the calcium sulphate present in OPC can be a mixture of dihydrate
(gypsum), hemihydrate, or anhydrite. In order to prevent the SP molecules from interfering with the
aluminate hydration, it is imperative that the SO
3
becomes available in solution as early as possible.
Thus, the solubility of the calcium sulphate is important. While hemihydrate and synthetic anhydrite
possess greater solubility than gypsum, natural anhydrite is very slowly soluble. The presence of natural
anhydrite has always been found in systems presenting compatibility problems. It must be also noted
that the solubility of sulphates would decrease in the presence of SPs with sulphonate functional groups,
thus affecting the normal setting process of the cement [Hanna et al., 2000]. In order to avoid such
problems, cements usually contain sufficient amounts of quickly soluble alkali sulphates. However,
alkalis themselves affect compatibility in a number of ways, as discussed below.
Role of Alkalis
Alkalis in cement are essential from the point of view of accelerating C
3
S hydration. However, excess
alkalis could have adverse effects, one of them being the alkali aggregate reaction. Hence, there is
typically a strict control on the alkali limits. The use of cements high in alkali causes workability
problems in concrete without any admixtures, but cements low in alkali are known to result in poor
rheology of the concrete in concretes using sulphonate based admixtures [Jiang et al., 1999]. This is again
interconnected with the availability of soluble sulphates, discussed in the previous section. The problem
with low alkali cements can be overcome by adding an optimum amount of soluble alkalis, primarily in
the metasilicate or sulphate forms [Li et al., 2003]. Jiang et al. [1999] found that 0.4 0.5% soluble alkali
content was optimum to maximize fluidity and reduce fluidity loss of the concrete. Higher alkali contents
promote the solubility of sulphate ions and decreases the loss of fluidity with SNF [Dodson and Hayden,
1989; Chandra and Bjornstrom, 2002]. However, there are also negative effects in the presence of high
amount of alkalis when using an alkali sulphate rather than calcium sulphate, it is difficult for ettringite
to crystallize so that rapid stiffening is experienced [Prince et al., 2002].
Alkalis in the form of K
2
O increase reactivity of C
3
A whereas Na
2
O reduces the reactivity of C
3
A
[Spiratos et al., 2003]. Also, efflorescence problems are observed when naphthalene and melamine based
superplasticizers are used with cements having high alkali oxide content (Na
2
O + K
2
O > 0.75%).
Influence of Fineness
The finer the cement, the higher the specific surface area, and consequently, the water demand for a
given workability is also expected to be higher. In cases where SPs are used, the amount of SP required
for certain workability would be higher for a finer cement [Jolicoeur et al., 1994]. The amount of SP
adsorbed would also depend on the fineness, with finer cements causing more SP adsorption.
3.2.2 Admixture type and dosage
The type and dosage of admixture have major effects on the cement admixture compatibility issues. In
the previous section, the affinity of SPs with sulphonate groups for the aluminate compounds in cement
has already been described.
It is also well known that almost all SPs increase the length of the dormant period and slow down the
hydration process [Jolicoeur and Simard, 1998]. Primarily, SPs cause the slowing down of the dissolution
of Ca
2+
and inhibit ettringite crystallisation [Ramachandran, 2002; Prince et al., 2002].
Adsorption effects
The adsorption of the admixture on the surface of cement particles leads to a reduction of the chemical in
solution. Thus when adsorption levels are higher, more admixture is required to obtain a given fluidity.
Organic admixtures (essentially, all superplasticizers!) form organo mineral compounds with C
3
S and
slow down the precipitation and growth of C-S-H and C-H [Jolicoeur, 1998; Flatt and Houst, 2001]. The
formation of these organo-mineral phases reduces the amount of SP available in solution, leading to
slump loss.
The surface adsorption of the admixture increases with the molecular weight of the polymer, and the
presence of calcium ions promotes this adsorption. This seems to indicate that the manufacturing process
can largely dictate the performance of the chemical. It is desirable to use polymers with large fractions of
high molecular weight chains. However, this requires a strict control on the process.
Molecular weight of polymer
In the case of the lignosulphonates [Rixom and Mailvaganam, 1999; Mollah et al., 1995], the presence of
low molecular weight ingredients is known to cause excessive air entrainment leading to loss of strength.
In addition, the high sugar content of these admixtures could cause unnecessary retardation, especially at
high dosages. A further unpredictability might arise depending on whether the chemical is a sodium salt
or a calcium salt. Reports from the industry indicate that neither type of chemical is compatible with all
cements. In order to be effective, lignosulphonates should be modified the sugars should be removed by
fermentation, and low molecular weight matter should be removed by centrifuging. Lignosulphonate
admixtures produce a complex salt with Ca
2+
, thus decreasing the Ca2+ concentration in the liquid
phase, resulting in a delay in the hydration of alite, and causing set retardation.
SNF based admixtures are most prone to rapid loss of workability, particularly at low water to cement
ratios, which are the norm for most special concretes today. Another common problem with SNF
admixtures is excessive retardation, which may be caused because of the blending of these chemicals with
lignosulphonates in commercial formulations. Similar to lignosulphonates, the presence of moderate to
high molecular weight chain fractions leads to a better performance for SNF admixtures. The low
molecular weight fractions cause excessive retardation by covering reactive sites on the cement surface
and inhibiting reactions. Another factor affecting SNF effectiveness is the location of the sulphonate (-
HSO
3
) group in the naphthalene structure. It is well accepted that the presence of the sulphonate group
in the -position leads to a high polymer charge and better electrostatic repulsion.
Compared to lignosulphonates, the adsorption of SNF depends more on the type of cement, thus
necessitating its addition in higher quantities [Uchikawa et al., 2002]. Chandra and Bjornstrom [2002]
found that slump loss is lower for mortars with lignosulphonates than with SMF or SNF, since
lignosulphonates do not get adsorbed to the same degree as SNF/SMF.
Time of addition of the SP
Delayed addition is proposed as a means of retaining fluidity in the case of SMF and SNF based
admixtures [Uchikawa et al., 1992; Aiad et al., 2002]. The amount of admixture adsorbed reduces when
cement hydrates; in other words, adsorption is greater on unhydrated compounds compared to the
hydrated phases [Flatt et al., 1998]. As a result, when a delayed addition is done, there is more admixture
available in the solution to maintain the fluidity. According to Aiad [2003], the optimum delaying time of
the admixture is 10 15 min, and this time does not depend on the cement and SP type. Delayed addition
has been shown to result in lesser participation of the polymer in the formation of the organo-mineral
phase [Flatt and Houst, 2001].
Uchikawa et al. [1995] linked the improvement in fluidity of concretes with later addition of SPs to the
increased availability of the admixture in solution. They also found that SNF based chemicals were more
sensitive to delayed addition compared to PCE and linosulphonates.
Studies at IIT Madras
The role of the type of superplasticizer on fresh concrete properties was investigated taking into account
following factors: type of superplasticizer (Sulphonated melamine-formaldehyde condensate (SMF),
Sulphonated naphthalene-formaldehyde condensate (SNF), Lignosulfonate (LS), and Polycarboxylic
Ether (PCE)), superplasticizer dosage, water to cement ratio, and cement properties.
The results show that the slump retention characteristics and flowability of concrete are affected by a
complex interplay of the chemistry of cement and superplasticizer. The PCE based superplasticizer is
more compatible with all the cements used in this study compared to other three SPs. The saturation
dosages obtained can be ranked as PCE < SMF < SNF < LS. The effect of C
3
A, C
3
A/SO
3
and alkali
contents on slump retention of concrete varied with the type of superplasticizer used. The slump
retention potential of concrete can be ranked in the order PCE > SMF > SNF > LS.
3.2.3 Other issues affecting compatibility
The w/c of concrete seems to affect the performance of SPs. As already stated, SNF admixtures are more
prone to slump loss problems at low w/c, as compared to the PCEs. Collepardi [1998] feels that the lower
w/c in superplasticized concrete and the resulting lower interparticle separation of the cement particles
makes it more sensitive to loss of water by evaporation or reaction with cement during transportation of
the concrete. In general, most compatibility problems only exist at low w/c.
Added to the cement-water reducer interactions, the effect of an inert component on the workability
could be significant (for example, when there is some interaction between a superplasticizer and the fines
of the sand being used leading to a high loss of workability during transportation), and early-age
cracking increases even when the concrete is of better quality (which can occur when fillers absorb the
bleed water, causing higher plastic shrinkage, or when a high paste content causes excessive thermal
shrinkage). The fines content in river sand affects the performance of SPs [Papayianni et al., 2005].
The placing of concrete at high ambient temperatures adds a new dimension to the problem of
incompatibility. Low temperature has been reported to decrease fluidity. This decrease in workability at
low temperature cannot be compensated with SP [Gettu et al., 1997]. On the other hand, high
temperatures increase SP adsorption which increases fluidity [Greisser, 2002]. Conversely, temperature
increase causes increase in reactivity of C
3
A which causes higher ettringite contents with fine
morphology in the presence of SP [Greisser, 2002 ; Spiratos et al., 2003], thus causing a higher rate of
slump loss. The influence of temperature on cement SP interaction is closely associated with the cement
composition [Charles, 2008]. Concrete placement temperatures exceeding 40
o
C are routinely
encountered in practice, which exacerbates the sensitivity of the cement superplasticizer combination.
In this study, the influence of temperature on the properties of fresh cement pastes containing various
cements and superplasticizers was investigated. The variation in the flowability with time of normal
Portland cement pastes with different superplasticizers (PCE and SNF) were studied at various
temperatures (25, 35 and 45 oC) using Marsh Cone test, and the setting times of the pastes were also
measured. Cement having low C
3
A to SO
3
ratio was found to be more sensitive to temperature variations
in fluidity retention characteristics than cements having higher C
3
A to SO
3
ratio. Also, cement having
higher Equivalent Alkali content was more sensitive to temperature variations.
On an India-specific note, cement standards in our country are not very stringent, and enable
manufacturers to adjust their product in many different ways. For example, while the minimum fineness
is specified for different grades of cement, there is no control on the maximum. Thus, a manufacturer
could use the same composition and grind cement to different finenesses, and still have the same end
product. Such a situation might lead to incompatibility issues. Additionally, the requirements of chemical
composition are also not stringent, and large ranges are acceptable. This could result in significant
variability in the cement properties, even from the same manufacturing plant. From the viewpoint of use
of water reducers, there is insufficient knowledge among users regarding the limitations of different
types of chemicals.
4. SUMMARY
Cement superplasticizer interaction in concrete is a complex blend of chemical and physical
mechanisms that are interdependent. The complicated nature of the problem prevents the development
of simple solutions to address the field related issues of application of superplasticizers.
Studies on cement-water reducer interactions in India have been limited to the workability evaluation of
concretes containing these chemicals, in specific regions where rapid slump loss has been observed in
concreting operations. There have not been any investigations to understand the physico-chemical nature
of this interaction. Thus, the results from these studies are not broad-based, i.e. they apply to a small
group of cements and/or chemical admixtures. There is a distinct need for the characterization of Indian
cement and admixture properties, in order to understand the nature of their interactions. Moreover, the
wide range of cements used, varying transportation durations and climatic conditions necessitate a
fundamental study that explains the mechanisms of interaction and helps establish methods for
identifying incompatibility in practical situations.
In addition, simple methodologies are required to be able to identify systems prone to undesirable effects
due to such interactions and to further understand the fundamental nature of admixture behaviour in
cement-based systems. The understanding of these interactions should be both at the applications scale
(for example, studying flowability and retention of workability in pastes and concretes), as well as at the
micromolecular scale, where some insight can be obtained into the physico-chemical interactions between
cement particles and water reducer molecules.
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