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5.4.2 Superplasticizers
The use of superplasticizers (high-range water reducer) has become a quite common
practice. This class of water reducers was originally developed in Japan and Germany
in the early 1960s; it was introduced in the United States in the mid-1970s.
Superplasticizers are linear polymers containing sulfonic acid groups attached to the
polymer backbone at regular intervals. Most of the commercial formulations belong
to one of four families:
• Polycarboxylate derivatives
The sulfonic acid groups are responsible for neutralizing the surface charges on the
cement particles and causing dispersion, thus releasing the water tied up in the
cement particle agglomerations and thereafter reducing the viscosity of the paste
and concrete.
One problem associated with using a high-range water reducer in concrete is slump
loss. In a study of the behavior of fresh concrete containing conventional water
reducers and high-range water reducer, found that with time slump loss is very rapid
in spite of the fact that second-generation high-range water reducers are claimed
not to suffer as much from the slump loss phenomenon as the first-generation
conventional water reducers do. However, slump loss of flowing concrete was found
to be less severe, especially for newly developed admixtures based on copolymeric
formulations.
The slump loss problem can be overcome by adding the admixture to the concrete
just before the concrete is placed.
However, there are disadvantages to such a procedure. The dosage control, for
example, might not be adequate, and it requires ancillary equipment such as
truck-mounted admixture tanks and dispensers. Adding admixtures at the batch
plant, besides dosage control improvement, reduces wear of truck mixers and
lessens the tendency to add water onsite. New admixtures now being marketed can
be added at the batch plant and can hold the slump above 8 in. (204 mm) for more
than 2 hours.
Recommendations
1. Verification tests should be performed on liquid admixtures to confirm that the
material is the same as that which was approved. The identifying tests include
chloride and solids content, ph, and infrared spectrometry.
2. If transit mix trucks are used to mix high-slump concrete, it is recommended
that a 75 mm slump concrete be used at a full mixing capacity to ensure
uniform concrete properties.
3. If transit mix trucks are used to mix low w/c ratio concrete, it is recommended
that the load size be reduced to ½ to ⅔ of the mixing capacity to ensure
uniform concrete properties.
4. If freeze–thaw testing as described by ASTM C 666 indicates this to be a
problem, it is recommended that the air content be increased by 1.5%.
SCC has very high slump and flowability properties without segregation. It uses
specialty admixtures, which radically modify slump and flowability. Examples of such
admixtures are viscous modifiers and high-performance polycarboxylate polymers.
SCC is an improved version of HPC, with compressive and tensile strengths exceed-
ing those of normal concrete.
Benefits are:
• The voids and honeycombing seen in many traditional concrete mixes are
avoided.
• It can be used successfully in new construction projects with difficult
placement or finishing.
• It is effective for repairs of concrete honeycombing.
SCC for use in drilled shaft applications: When conventional concrete is used in
congested drilled shafts, coarse aggregates may bridge between reinforcing bars,
which may lead to segregation of the concrete between the inside and outside of
the reinforcing cage. SCC is feasible for use in congested drilled shaft applications.
Fig. 9.6. Isothermal calorimetry curves for a Type II/V cement/Class F fly ash blend
with (two different) and without an HRWR (Bentz, Ferraris, et al., 2013).
The above examples clearly indicate that calorimetry can be a useful tool in de-
veloping HVFA mixtures as it provides diagnostic information about the hydration
reactions occurring in the paste. As complete and useful as this measurement tech-
nique is, it cannot readily predict all the important early-age performance issues of
cement-fly ash mixtures such as false setting, early stiffening, etc. A more complete
picture of how these mixtures will perform will often require additional test meth-
ods, such as modified versions of the ASTM C359 Standard Test Method for Early
Stiffening of Hydraulic Cement (Mortar Method) (ASTM C359, 2013), a mini-slump
test (currently under ASTM ballot), and rheometer tests based on the guidance
provided in the ASTM C1749 Standard Guide for Measurement of the Rheological
Properties of Hydraulic Cementitious Paste Using a Rotational Rheometer and
elsewhere (ASTM C1749, 2012; Roberts & Taylor, 2007; Tanesi, Ardani, Meininger, &
Nicolaescu, 2012).
Other solutions include blends of pure PCEs. In these blends, the slump-keeper
polymers can be either copolymers having a high grafting degree (low amount
of charges on the backbone) or acrylic-based PCEs, of which the side chains can
undergo hydrolysis in alkaline pore solutions (Mäder et al., 2004).
10.1 Introduction
The working mechanisms of numerous chemical admixtures involve the adsorption
of water-soluble compounds at a solid–liquid interface. This is particularly the case
for water reducers and high-range water reducers, to which most of this chapter is
dedicated. Moreover, this process also concerns retarders. Additionally, adsorption
of rather water-insoluble compounds and/or substances with a high affinity to
surfaces is exploited in air-entraining and shrinkage-reducing admixtures, where
surface active agents (surfactants) are used to specifically alter properties of the
liquid–vapor interface of concrete. Despite having high affinity to liquid–air inter-
faces, these surfactants may, however, also adsorb onto the solid–liquid interface or
self-associate into micelles or liquid crystals. This makes the description of surfactant
adsorption a delicate task, as discussed in Section 10.4.3 for the solid–liquid interface
and in Section 10.7 for the liquid–air interface.
If we consider a given dispersant, its impact on fluidity increases with dosage, pro-
vided that the admixture continues to adsorb on the surface of the solid particles to
disperse (Section 10.2). In fact, it is especially the adsorbed fraction of the dispersant
that is responsible for the effect on fluidity, as explained in Chapter 11 (Gelardi and
Flatt, 2016). Depending on the admixture type and its dosage, there may or may
not be an equilibrium established between the fraction of admixtures adsorbed and
those remaining in solution. The nature of this relationship is most often reported
in the form of adsorption isotherms, which are covered in Section 10.3.
In addition to the nature of the surface, this relation is profoundly affected by the
chemical nature of the dispersant. Although it is difficult to establish general
relationships owing to the variety of chemical compositions and structures available,
we outline some general chemical features of dispersants that affect their adsorption
in Section 10.4.
Molecules with a low affinity to the surface may desorb if the conditions are changed
(Section 10.5). This may be by replacing the solution with water (Platel, 2005, 2009)
or by modifying the ionic composition of the solution by increasing the sulfate or
hydroxyl ions concentrations (Yamada et al., 2001; Marchon et al., 2013). Admixtures
may therefore be subject to competitive adsorption, which can reduce their perfor-
mance as discussed in Section 10.5.2.
Other factors that reduce the performance of admixtures can involve an apparent
increase rather than reduction in adsorption (Section 10.6). Most of these are
due to artifacts linked to the standard way of solution depletion used to measure
adsorption. Indeed, in this approach, adsorption is determined by measuring the
difference between the amount of admixture added and its fraction remaining in
solution after a given time. However, if admixtures are consumed by precipitation
(Section 10.6.1) or intercalation (Section 10.6.2), their apparent adsorption increases.
The amount of admixture adsorbed and acting as dispersant may either increase,
remain equal, or even decrease. The latter situation happens if the admixtures are
more effectively precipitated or intercalated, so that the surface coverage of particles
to be dispersed decreases. A similar situation may occur if the admixtures modify
the process of nucleation and growth of aluminates, causing an increase in the
solid–liquid interfacial area (Section 10.6.3).
The above issues concerning the interpretation of adsorption data are tightly linked
to experimental procedures. For this reason, we include at the end of this chapter
an extensive section about experimental aspects (Section 10.8).
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Polynaphthalene sulfonates
Polynaphthalene sulfonates (PNS) are naphthalene sulfonic acid formaldehyde con-
densates. The dispersing ability of PNS is higher than that of lignosulfonates and
therefore higher water reduction is possible. PNS can be called ‘high range water
reducers’ or superplasticizers. First introduced into the admixture market in the
1960s they are widely used nowadays.
The polycondensates are produced in two steps as shown in Fig. 7.2. First naph-
thalene is sulfonated with sulfuric acid to give P-naphthalene sulfonic acid. In the
following condensation reaction with formaldehyde in aqueous medium the linear,
anionic polymer is formed. The molecular weight of these polymers is dependent
on the reaction time and can be thus regulated (Pieh, 1987).
7.2. Reaction scheme for production of PNS (Pieh, 1987).
PNS are mostly linear anionic polymers that are commercially available as sodium
or calcium salts. They are sold as aqueous solutions with 20–45% solids or as brown
powder. The sodium salts may still contain remarkable amounts of residual sodium
sulfate from the production, whereas the amount of sulfate in the calcium salts is
usually lower due to the poor solubility of gypsum which precipitates and can be
removed form the solution.
PNS dispersants have relatively low molecular weights. Their dispersing ability
starts with about five repeating units with a maximum dispersing power at higher
molecular weights between 1000 and 20 000 (Pieh, 1987; Aitcin et al., 2001). The
optimal molecular weight of PNS dispersants is, however, dependent on the type
of the cement. High molecular weight PNS are more effective in fluidizing pastes
made with cements with a high alkali content. However, the molecular weight has
little effect in fluidizing pastes made from a low alkali cement. Differences in the
molecular weight of PNS do not appear to significantly affect cement hydration
(Kim et al., 1999).
Not all cements are compatible with all PNS. This is a serious problem for concrete
production. PNS dispersants usually greatly increase the fluidity of fresh concrete.
However, the dispersing effect can be of short duration and can result in a rapid
slump loss depending on the particular combination of cement and PNS used.
Because of these incompatibility problems, the mode of action and behaviour of
PNS in different cements or concretes have been extensively studied.
Soluble alkalis were shown to increase the fluidity and the duration of the fluidity of
a cement paste superplasticized with PNS (Jiang et al., 1999). This effect is explained
by the fact that alkalis increase the concentration of sulfate ions, which in turn
reduce the adsorption of PNS on aluminate phases causing more PNS to remain
in the solution (Kim et al., 2000; Aitcin et al., 2001). This is congruent with the
findings that the incompatibility is related to the type and amount of gypsum in the
cements (Nakajima and Yamada, 2004). More detailed explanations on the influence
of soluble alkalis and sulfates on the performance of superplasticizers are given later.
9.2.1 Introduction
In this section the chemistry of the main types of superplasticizers (SPs), also called
high-range water-reducing admixtures, is presented.
The first part is dedicated to natural polymers, which are rather plasticizers or
mid-range water-reducing admixtures. The use of such dispersants dates back to
the 1930s. Although the performance of natural polymers is limited compared to
synthetic ones, it is worth mentioning them as they are still widely used in the
concrete industry–mainly because of their low cost of production.
Next, synthetic linear polymers are described. This category includes some of
the most commonly used SPs, such as polynaphthalene sulphonates (PNS), poly-
melamine sulphonates (PMS) and vinyl copolymers. The higher dispersing ability
of these compounds qualifies them as true SPs or high-range water reducers (in
contrast to lignosulphonates or other low- or mid-range water reducers). They
were introduced during the 1960s and are generally referred to as electrostatic
dispersants, although some show predominant steric effects. They made it possible
to develop high-performance concrete as a reliable form now used in numerous
structures. The practical use of SPs is dealt with in Chapter 16 (Nkinamubanzi et al.,
2016).
3.4 Conclusions
The knowledge of movements and cracking processes presented in this chapter has
been developed from theories, research and technical field data published over many
years for conventional types of concrete, namely low-strength mixes using natural
aggregates. Although the principles are not expected to change, in the future design
methods given in Codes of Practice will be continuously amended to account for the
use of more sophisticated concreting materials, such as high performance concrete,
which refers to both high durability (low permeability) and/or high strength concrete.
In some cases, the high strength is required to design smaller concrete elements or
low deflections through a corresponding high modulus of elasticity, low creep and
low shrinkage. Such concrete tends to be more brittle and prone to cracking so that
ductility needs to added, say, in the form of fibre reinforcement. High performance
is achieved by the combined use of chemical and mineral admixtures: high range
water-reducers (superplasticisers) and fine cement replacement materials to replace
part of cement, e.g. silica fume.
On the other hand, admixtures designed to reduce shrinkage, creep and the risk
of cracking are likely to be used more frequently in conjunction with, say, super-
plasticisers to offset any reduction in strength. Little is known about the long-term
behaviour of concretes made with cocktails of different admixtures and the pos-
sible interactions between supplementary cementing materials (or mineral admix-
tures) and multi-functional chemical admixtures need to be assessed. Advanced
methodologies may have to be developed for evaluating the early age cracking
characteristics of some of the newer formulations being considered for use in high
strength applications and repair situations (Bentur and Kovler, 2003). The increased
usage of recycled concrete and other waste materials to replace or augment natural
aggregates in concrete has also to be considered in the context of prediction models
and design documents.
It should be emphasised that it has been only possible to present brief details
of movements and cracking processes experienced by concrete in this chapter,
there being a huge amount of research and technical literature available. From the
references given in Section 3.5, further background information is recommended
as follows:
• Movements in plain and reinforced concrete: Illston et al., 1979; Mindess and
Young, 1981; Neville et al., 1983; Bazant, 1988; Gilbert, 1988; Neville, 1995;
Neville and Brooks, 2002.
• Non-structural cracking: Harrison, 1981; Concrete Society, 1992; ACI 224R-90,
1996.
• Fracture mechanics: Mindess and Young, 1981; ACI SP-118, 1989; ACI Com-
mittee 446, 1991; Karihaloo BI, 1995; Shah et al., 1995.