Plasticizer

Plasticizers are admixtures that are added to concrete to increase the fluidity
or workability of a cement paste or concrete. It is also called as workability aids, that are
added to fresh or early stage concrete to change its workability characteristics. Plasticizers are
also called as water-reducers as they produce a concrete with the same workability at a lower
water/cement ratio. Plasticizers hence help to manufacture a concrete mix with high
durability with the same water content.

Concrete With and Without plasticizer

Action of Plasticizers in Concrete

Plasticizers have plasticizing action due to the
presence of polymer molecules present in it. These molecules when mixed with concrete
absorbs on the surface of the cement grains that would create a ionic group that points
outwards. This would finally give a negative charge to the cement particles.

These negatively charged cement particles cause mutual repulsion. This repulsion between
the particles breaks the flocs of particles in the water/cement system that would result in
entrapped air as shown in the figure below.
Other than the repulsion caused, these cement particles will be surrounded by sheath of
oriented water molecules which also prevent close approach of the cement grains. This
phenomenon is called as steric hindrance. This overall effect causes the greatest lubrication
and fluidity for the concrete paste. 

Classification of Plasticizers on Concrete

Based on the principle of working, plasticizers are classified as:
1. Hydrophilic
2. Hydrophobizing

1. Hydrophilic Plasticizers
Hydrophilic Plasticizers  is characterized by increased
wettability, the main function of which is to increase the plastic and flow characteristics of
the concrete.

2. Hydrophobizing Plasticizers
These type of plasticizer saturates the concrete mixture
with a large amount of air. Thus, it is possible to reduce the tension of moisture in the
solution and increase plastic characteristics of the concrete.

Advantages of Plasticizers in Concrete

The main advantages of using plasticizers are:
1. Improves workability of concrete without the addition of extra water.
2. Improves the strength of concrete without increasing the cement content.
3. Increase the strength characteristics of the finished concrete foundation by twenty five
percent.
4. Plasticizers make the compaction easy without the use of vibrators.
5. Improves flowability and good adhesion to the surface.
6. Concrete with high density is achieved using plasticizers.
7. Plasticizers reduce the moisture content in concrete, making it frost resistant and
prevents cracking.

Super Plasticizer
Superplasticizers (SPs), also known as high range water reducers, are
additives used in making high strength concrete. Plasticizers are chemical compounds that
enable the production of concrete with approximately 15% less water content.
Superplasticizers allow reduction in water content by 30% or more. These additives are
employed at the level of a few weight percent. Plasticizers and superplasticizers retard the
curing of concrete.
Generally, superplasticizer can be classified into such types: purified lignosulfonates,
carboxylate synthetic polymers, sulfonated synthetic polymers and synthetic polymers with
mixed functionality cementitious materials. SPs are used where well-dispersed particle
suspension is required to improve the flow characteristics (rheology) of suspensions such as
in concrete applications. Their addition to concrete or mortar allows the reduction of the
water to cement ratio without negatively affecting the workability of the mixture, and enables
the production of self-consolidating concrete and high performance concrete. They greatly
improve the performance of the hardening fresh paste. The strength of concrete increases
when the water to cement ratio decreases. The addition of SP in the truck during transit is a
fairly modern development within the industry. Admixtures added in transit through
automated slump management systems, such as Verifi,  allow concrete producers to maintain
slump until discharge without reducing concrete quality.

Types of Superplasticizer:

1.Sulphonated Melamine – Formaldehyde Condensates (SME):

Sulfonated melamine
formaldehyde condensates are often preferred superplasticizers in the precast industry
because they do not dim the cement setting.

2.Sulphonated Naphthalene Formaldehyde Condensates (SNF):

Sulphonated Naphthalene
Formaldehyde is a high range water reducer.

3.Modified Lignosulphonates (MLS):

Lignosulfonates or sulfonated lignins are water-

soluble anionic polyelectrolyte polymers, they are byproducts of wood pulp using sulfite
pulping.

Advantages of Superplasticizer:

1. Superplasticizers reduces the water content.

2. It reduces the cement content.

3. Also, increases the workability of concrete.

4. It reduces the permeability of concrete.

5. They are easy to placement.

6. Increased long terms.

7. It develops the early strength.

Disadvantages of Superplasticizer:

1. Slump loss are greater than conventional concrete.

2. Addition cost for admixture.

3. They increase air entrainment in concrete.

Uses of Superplasticizer:

 Superplasticizers disperses cement provides plastics with higher initial

strength than free concrete with the same W/C ratio.
 Set retards are adductors that cause delays in the setting time of wet concrete
mixes.
 Air entrances are added to solid forms millions of small non-coalescing air
bubbles, thus formed are deliberate ones are called perforated air.

2. It reduces
Retarders
Retarders for concrete are used to delay the initial setting time of the concrete upto
an hour. They are generally used in the hot weather condition to counter the rapid hardening
due to high temperature, thus allowing the time for mixing, transporting and placing.
Retarders also acts as water reducers. In this article we discuss about the mechanism of
retardation, types of retarders, effect of retarders on concrete properties and advantages.

Mechanism of retarders
 Adding a retarder, dissolved in the mixing water or sprayed on
the surface of the concrete, temporarily interrupts the hydration reactions, which creates a
longer dormant period. The mechanisms that appear depend on the combination of the type of
retarder and the type of cement. It’s also important to realize that the mechanisms of
retardation are temporary. After a predictable period, the effects of the mechanisms disappear
and the hydration continues. There are four different way in which the retardation process
happen in between retarder and cement. 

1. Adsorption
In this type on the surface of the cement particles, a retarding admixture is
adsorbed. This layer of retarding admixture creates a protective skin around the cement
particles. Due to this diffusion barrier the water molecules are hindered to reach the surface
of the unhydrated cement particles and the hydration is slowed down.The result is that there
is no considerable amount of hydration products to give rigidity to the cement paste so the
paste remains plastic for a longer period.

2. Nucleation
When water is added to the cement, calcium ions and hydroxyl ions are
released from the surface of the cement particles. When a critical value of the concentration
of those ions is reached, the hydration products C2S and CS start to crystallize. A retarding
admixture, which is incorporated into the cement, is adsorbed by the calcium hydroxide
nuclei, which prevents the growth of the calcium hydroxide nuclei until some level of
supersaturation.

3. Complexation
During the first few minutes, some kind of complexes with calcium
ions, released by the cement grains, are formed. The formation of those complexes causes an
increased solubility of the cement. During the hydration, in the presence of a retarding
admixture, an increased concentration of Ca2+, OH-, Si, Al and Fe will occur in the aqueous
phase of the cement paste. The accumulation of the calcium and hydroxyl ions in the solution
prevent the precipitation of those ions to form calcium hydroxide. In that way, hydration is
retarded.
4. Precipitation
Precipitation is nearly similar to adsorption but in the case of
precipitation some kind of insoluble derivatives of retarder are formed by a reaction with the
highly alkaline solution. Because of that, the pH of the solution rises over 12 after the first
few minutes of the contact between water and cement. The precipitation of protective
coatings of these insoluble derivatives around the cement particles suppresses the cement
hydration. The protective coating acts as a diffusion barrier so the water molecules can’t
make a good contact with the cement particles

Types of Retarders
Retarders are divided into 2 category depending on the nature of the retarders , they are:

1. Organic Retarders

 Lignosulphonates
 Hydroxycarboxylic acids and their salts
 Phosphonates
 Sugars
2. Inorganic or Chemical Retarders

 Phosphonates
 Borates
 Salts of Pb, Zn, Cu, As, Sb

Accelerators

Accelerating Admixture - an admixture that causes an increase in the rate of

hydration of the hydraulic cement and thus shortens the time of setting, increases the rate of
strength development, or both. Accelerating admixtures are added to concrete either to
increase the rate of early strength development or to shorten the time of setting, or both.
Chemical compositions of accelerators include some of inorganic compounds such as soluble
chlorides, carbonates, silicates, fluosilicates, and some organic compounds such as
triethanolamine.

Abstract
Accelerators for normal concrete play an important role in some engineering
constructions. This paper reviews different types of accelerators and discusses their effects on
hydration, microstructure and properties of cement-based materials. Generally, calcium and
alkali chlorides are the main kinds of chloride-based accelerators, while nitrates, nitrites,
thiocyanates, formates and alkanolamines are the chemicals commonly used in non-chloride
accelerators. Acceleration of tricalcium oxy silicate (C3S) hydration and
corresponding calcium silicate hydrate (C–S–H) formation is regarded as the main reason for
rapid setting and/or hardening according to existing researches. Although some accelerators
present anti-freezing or corrosion inhibiting properties, most of them have negative effects on
the durability of concrete and high dosages of accelerators are particularly harmful for
durability. Incorporation of supplementary cementitious materials and/or chemical
admixtures presents a feasible approach to overcome these negative effects. This review also
gives some perspectives for future development in the field of accelerators for normal
concrete.

Introduction
Accelerators, both for normal concrete and for shotcrete, are widely used in
modern construction because they can shorten the setting time and/or increase the early
strength [[1], [2], [3]]. Different from those for shotcrete to reduce the setting time as much
as possible [4], accelerators for normal concrete have minimum requirement on the setting
time to ensure sufficient time for concreting, which should not be less than 30 min according
to the European norm EN 934-2: 2009+A1: 2012 [5].

Depending on their specific effect, accelerators for normal concrete can be divided into
setting and hardening types. Setting accelerators decrease the time of cement-based materials
from plastic to rigid state. Whereas hardening accelerators boost early strength of cement-
based materials. In actual applications, setting accelerators contribute to earlier finishing of
surfaces and are more effective in sealing against hydraulic pressure, while hardening
accelerators contribute to earlier removal of forms, reduction of the required period of curing
and protection, earlier placement in service of a structure or a repair and partial or complete
compensation for the effects of low temperatures on strength development [6]. It is
noteworthy that some accelerators can accelerate both setting and hardening. Based on their
chemical composition, accelerators for normal concrete can be divided into chloride and non-
chloride types [7,8]. Although chloride-based accelerators can effectively accelerate the
setting and hardening of Portland cement, they are limited because their application is not
recommended in steel reinforced concrete due to the potential steel corrosion concerns [8].
Thus, non-chloride accelerators are still widely used in normal concrete, despite of their
relatively high costs. This paper presents the chemical composition of accelerators available
for normal concrete. Their effects on hydration, microstructure and properties of cement-
based materials are discussed and analyzed. Some insights into further research and
application of accelerators are also proposed.
Chemistry of accelerators

Calcium and alkali chlorides are the main types of chloride-based accelerators, while nitrates,
nitrites, thiocyanates, formates and alkanolamines are commonly used non-chloride
accelerators, as listed in Table 1. Most accelerators are in liquid form and normally present
combinations of several chemicals. Some typical formulations of commercial accelerators are
summarized in Table 1. Specific combinations to obtain better acceleration efficiency are
worth noting, such as the blend of calcium.

Effect of chloride-based accelerators on cement hydration

With respect to heat

evolution, calcium chloride has been observed to advance the peak corresponding to the
maximum heat liberation from 8 h to 3 h as calcium chloride dosage increased from 0% to
2% [17]. Chen et al. [27] reported that calcium chloride enhances both the main hydration
peak and the exothermic shoulder of Portland cement, as is shown in Fig. 1. They attributed
the increased cement hydration to accelerated dissolution of C3S in pore solution. It was also
found that calcium.

Effect of chloride-based accelerators on pore structure development

The porosity of
cement paste increases with increasing dosage of calcium chloride (0, 1, 2 and 3.5%),
especially the formation of micropore (10–50 Å) is promoted [43]. Ramachadran [17]
concluded that the increasing porosity could be attributed to the much denser structure of
hydration products. However, an opposite result on the total porosity of Portland cement
pastes admixed with 0.25, 0.50, 0.75% of calcium chloride was reported at 31.18, 30.64 and
30.42%, respectively [44].