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CONCRETE TECHNOLOGY
CHEMICAL ADMIXTURE

ADMIXTURES

Present day concrete often incorporates a fourth ingredient called admixtures in

addition to cement, aggregates and water. Admixtures are added to the concrete mix
immediately before or during mixing to modify one or more of the specific properties
of concrete in the fresh or hardened states. Often, instead of using a special cement, it
is possible to change same of the properties of the cement in hand by the use of a
suitable addition.

Admixture is defined as “a material other than water, aggregates, hydraulic cement,

and fiber reinforcement, used as an ingredient of a cementitious mixture to modify its
freshly mixed, setting, or hardened properties and that is added to the batch before or
during its mixing.”
The admixtures interact with the hydrating cementitious system by physical and
chemical actions, modifying one or more of the properties of concrete in the fresh
and/or hardened states.

Admixtures can be classified as i) Chemical ii) mineral.

The different types of chemical admixtures are as follows.

Accelerating admixtures.
Retarding admixtures.
Water reducing admixture
Air entraining admixtures.
Water proofing admixture

Some of the admixtures are often capable of modifying more than one property of
concrete for example, water reducing admixtures can also be set- retarders and air
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CHEMICAL ADMIXTURE

entraining admixtures increase the workability of the concrete mix, in addition to

providing air entrainment.

ACCELERATING ADMIXTURE

These are substances which when added to concrete increase the rate of hydration of
cement, shorten the setting time and increase the rate of strength development. The
chemicals that accelerate the hardening of concrete mixes include soluble chlorides,
carbonates, silicates etc.
The general action of accelerators is that they cause a more rapid dissolution of the
compounds of cement and hence facilitate more rapid hydration of these compounds.

Types of accelerating admixtures

Soluble inorganic salts—Studies have shown that a variety of soluble inorganic salts,
such as chlorides, bromides, fluorides, carbonates, thiocyanates, nitrites, nitrates,
thiosulfates, silicates, aluminates, and alkali hydroxides, decrease the setting time of
portland cement. Of these salts, calcium chloride is the most widely used because it
is the most cost-effective. Research by numerous investigators has shown that
inorganic accelerating admixtures act primarily by accelerating the hydration of
tricalcium silicate.
The most widely known accelerator is calcium chloride. Accelerating admixtures are
used when concrete is to be placed at low temperature or when urgent repair work is
to be done. CaCl2 is used up to 1.5% by mass of cement for plain and reinforced
concrete works in cold weather conditions.CaCl2 however, is not permitted to be used
in prestressed concrete because of its potential danger in augmenting stress corrosion.
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CHEMICAL ADMIXTURE

The action of calcium chloride is as follows

Reduces both initial and final setting time
Increases significantly the compressive strength in first 3 days.
Heat of hydration increases
Resistance to sulphate attack reduces
Alkali aggregate reaction aggravates
Bleeding reduces
Corrosion increases

It is important that calcium chloride be uniformly distributed throughout the mix and
this is best achieved by dissolving the admixture in the mixing water before it enters
the mixes.
In cases when the durability of concrete may be impaired by outside agencies the use
of CaCl2 may be inadvisable. For instance the resistance of cement to sulphate attack
is reduced by the addition of CaCl2 and the risk of an alkali- aggregate reaction, when
the aggregate is reactive is increased. CaCl2 has been found to raise the resistance of
concrete to erosion and abrasion.

Soluble organic compounds—The most common organic accelerating admixtures in

this class are triethanolamine and calcium formate. They are introduced into concrete
to provide noncorrosive acceleration. The effectiveness of calcium formate depends
on the tricalcium aluminate-to-sulfur trioxide ratio (C3A/SO3) of the cement. Cements
that are undersulfated (C3A/SO3 > 4.0) provide the best potential for calcium formate
to accelerate the early-age strength of concrete.
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Effects on hardened concrete

Time of setting—Initial and final setting times are reduced by an amount dependent
on the dosage of accelerator used, the temperature of the concrete, the ambient
temperature, and the characteristics of other materials used in the concrete.
Strength development—When calcium chloride is used, compressive strength may be
increased substantially at early ages; later strength may be reduced slightly. Because
accelerated strength development depends on accelerated hydration, heat of hydration
also develops faster, but there is no appreciable effect on total heat generation.
One of the major disadvantages of calcium chloride is that it induces corrosion of
metals embedded in concrete when in the presence of sufficient moisture and oxygen.
ACI 318 lists the chloride limits for concrete in new construction (Table 3.2) that
should be used to determine the maximum permissible water-soluble chloride-ion
content for concrete in various types of construction.

Quick-setting admixtures—Quick-setting admixtures are used to produce quick-

setting mortar or concrete suitable for shotcreting and sealing leaks against
hydrostatic pressure. These admixtures are believed to act by promoting the flash
setting of tricalcium aluminate. Ferric salts, sodium fluoride, aluminum chloride,
sodium aluminate, and potassium carbonate are reported to produce quick-setting
mortars, but many proprietary formulations are mixtures of accelerating admixtures.
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CHEMICAL ADMIXTURE

Quick-setting admixtures for shotcrete, employed extensively in both the dry and wet
processes, are a specific class of quick-setting admixtures, traditionally based on
soluble aluminates, carbonates, and silicates. These materials are caustic,
hazardous, and require special handling; refer to material safety data sheets from the
manufacturer. Newer, neutral-pH, chloride-free proprietary admixtures, based on
specific sugar-acid compounds, are available to overcome these deficiencies.
Generally, the wet-process shotcrete mixture quickly stiffens and reaches a rapid
initial set, with final set occurring. The early stiffening imparted by the accelerator,
however, aids in vertical and overhead placement. Using dry-process shotcrete and a
compatible cement and accelerator, an initial setting time of less than 1 min and a
final setting time of less than 4 min can be attained. The rate of strength gain can
be greatly accelerated using quicksetting admixtures in dry-process shotcrete.
Strength in excess of 21 MPa (3000 psi) in 8 h is typical for a noncaustic accelerator
and 14 MPa (2000 psi) is typical for a conventional caustic accelerator.
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RETARDING ADMIXTURES

A delay in the setting of concrete is achieved by the use of retarding admixtures.

Retarders slow down the rate of initial hydration of cement either by forming a thin
coating on the cement particles and thus delay their dissolution in and reaction with
water or by increasing the intra molecular distance of the reacting silicates and
alluminates from water molecules by forming certain transient compounds in the
system. But these actions are not permanent and as silicates and alluminates are
formed, the influence of the retarder diminishes and the hydration process becomes
normal.

Retarding action is exhibited by sugar, carbohydrate derivatives, soluble zinc salts,

soluble borates etc. Retarding admixtures are used in hot weather when normal setting
time of cement gets reduced due to high temperature. Set retarders are used in
preventing the formation of cold joints between successive lifts. A small quantity of
sugar (about 0.05 percent by mass of cement) delays the setting time of concrete by
about 4 hours.

Great care is necessary in using retarders as in incorrect quantities they can totally
inhibit the setting and hardening of concrete. The exact effects of sugar depend
greatly on the chemical composition of cement. For this reason, the performance of
sugar and indeed of any retarder, should be determined by trial mixes with the actual
cement which is to be used in construction. A large quantity of sugar, say 0.2 to 1
percent of the weight of cement will virtually prevent the setting of cement.
Retarders tend to increase the plastic shrinkage because the plastic stage is
extended.
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CHEMICAL ADMIXTURE

WATER REDUCING ADMIXTURES - PLASTICIZERS AND SUPER

PLASTICIZERS

The principal characteristic of water reducing and high range water reducing
admixtures is to cause higher flowability of a given concrete. The higher flowability
will enable one or more of the following.
Concrete can be placed at a faster rate and as such greater productivity can be
obtained from concrete equipment such as mixers, vibrators, hoists, buckets etc.
The higher flowability can be used to economise on cement through reducing the
water content of the mix and retaining the specified water cement ratio. Usually
the cost of cement saved will be higher than the cost WR or HWR admixtures.
The higher flowability can be used to reduce the water-cement ratio through
reducing the water content of the mix and retaining the cement content. This
results in enhanced strength and a more durable concrete.
Concrete can be placed without vibration in relatively poorly accessible locations
such as deep piles, well foundation, highly reinforcement congested sections as self
compacting concrete i.e. concrete compacted by its own weight.

PLASTICIZERS
They belong to following two main groups
a) Ligno sulphonic acids and their salts
b) Hydroxylated acids and their salts
Ordinary water reducing plasticizers enable up to 15 percent of water reduction.

PHYSICAL INTERACTION
Fine cement particles, being very small, lump together and flocculate when water is
added to concrete. This ionic attraction between the particles trap considerable
volume of water and hence water required for workability of concrete mix is not fully
utilized. Plasticizers are principally surface active (surfactants). They induce a
negative charge on the individual cement particles such that the fine cement particles
are dispersed due to inter particle repulsion. Negative charges are induced on the fine
cement particles causing flocs to disperse and release the entrapped water. Water
reducing admixtures or plasticizers, therefore, help to increase the flow of the
concrete mix considerably.
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CONCRETE TECHNOLOGY
CHEMICAL ADMIXTURE

SUPER PLASTICIZERS (HIGH RANGE WATER REDUCERS)

These are a modern type of water reducing admixtures much more effective than
other water reducing admixtures. Chemically they are sulphonated melamine formal-
dehyde condensates and sulphonated naphthalene formal-dehyde condensates.

Super plasticizers can reduce the water content for a given workability by 25 to 35
percent. The plasticizing action of super plasticizers is of short duration; after some
30 to 90 minutes the workability returns to normal. The dispersing action is mainly
promoted by the sulphonic acid being adsorbed on the surface of cement particles,
causing them to become negatively charged and thus mutually repulsive (electro static
repulsion). This increases the workability at a given water-cement ratio. The resulting
flowing concrete is cohesive and not subject to be excessive bleeding or segregation.
The sulphonated melamine based plasticizers are generally preferable if ambient
temperatures are low, while sulphonated naphthalene based plasticizers are preferable
in high ambient temperatures due to their good workability retention quality.
Polycarboxylate admixtures are high performance plasticizers which also help in
slump (workability) retention for a longer period.

DOSAGE

Optimal dosage of superplasticiser is important. Dosage beyond the optimal dosage

may be detrimental and can cause segregation or excessive retardation which can be
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CHEMICAL ADMIXTURE

harmful to concrete. The dosage optimization can be done by using Marsh Cone
apparatus or using mini-slump test or by the flow table methods described in ASTM
C 109.
The Marsh Cone method
The principle of the method consists in preparing a grout and measuring how long it takes
for a certain volume of the grout to flow through a funnel having a given diameter.
This is a standard plastic cone used by the petroleum industry to measure the flow time of
drilling muds. Its total capacity is 1.2 litre. A schematic of this cone is presented below.

150mm.

2 mm. Sieve

Capacity 1.2L
350mm.
50mm.

O.D.=5mm

The amount of water, cement and super-plasticizer needed to prepare 1.2 litre of grout is
calculated. Usually the test is preformed at a water / cement or water/ binder ratio of 0.35
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CHEMICAL ADMIXTURE

in order to test the cement and super-plasticizer under condition similar to those of the
paste of a high-performance concrete.

The sample preparation comprises the following steps :

 Weighing of the water and super-plasticizer in the container where the mixing
will be done.
 Starting the mixer while introducing progressively the amount of cement within 1
minute and 30 seconds
 Stopping the mixing for 15 seconds in order to clean with a spatula the cement
glued to the container
 Mixing for 60 seconds
 Measuring the temperature.
 Measuring the time it takes to fill a 1liter beaker with the grout
 Measuring at different time intervals the flow time up to 60 or 90 minutes. Each
time the temperature of the grout is measured.
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Saturation point

When the flow time is measured with different super-plasticizer dosages expressed as a
percentage of the solids contained in the super-plasticizer to the cement mass at a
given time, a curve like that presented in Figure is obtained.

This curve is composed of two lines having different slopes. The intersection of these two
lines corresponds to what is called the “saturation point”. This is the point at which, in the
experimental conditions used for the measurement of the flow time, any increase in the
dosage of the super-plasticizer has no effect on the rheology of the grout. The super-
plasticizer dosage corresponding to this point is called the saturation dosage, and the
flow time, the flow time for the saturation dosage. It has been found from experience that
it is convenient to adjust the water / binder ratio of the grout so that the 5 minute Marsh
cone flow time is between 60 and 90 seconds.
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CHEMICAL ADMIXTURE

From a practical point of view, when using the Marsh cone testing method to study the
rheological compatibility of a given cement and a given super-plasticizer, it is suggested
proceeding in the following way :

 A 0.35 water / binder ratio grout is made using a super- plasticizer dosage that
corresponds to a solid content of around 1% of the cement mass.
 If the measured flow time with a Marsh cone with a 5mm opening is between 60
and90 seconds, the 0.35 water / binder ratio is selected to pursue the study of the
variation of the flowing time as a function of the super-plasticizer dosage. The
concentration of the super-plasticizer can then be increased and decreased by
0.2% in steps from the initial 1% value.
 If the flow time is greater than 90 seconds, another test should be made, this time
using a water / binder ratio of 0.40, and again a 1% dosage of super-plasticizer. If
the flow time is between 60 and 90 seconds, the experiment is pursued at a water /
binder ration of 0.40, as in the previous case.
 It the Marsh cone flow time is still greater than 100 seconds at a water / binder
ratio of 0.40, it is better to use another super-plasticizer, or if all the available
super-plasticizer behave the same with that particular cement, it is better to select
another cement.

Figure 7.11(a) represents the case of a fully compatible combination of cement and
superplasticizer dosage at the point of saturation is low (around 1.0%) and the 60
minute curve is close to the 5 minute one. Thus the increased flow time is maintained
for 1 hour.
Figure 7.11(b), on the other hand, represents a case of incompatibility: the
superplasticizer dosage at the less well-defined saturation point is quite high and the
60 minute curve is much higher than the 5 minute curve. Sometimes, when the
incompatibility is more pronounced, the grout stops flowing very rapidly, possibly as
early as 15 minutes after the beginning of mixing.
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CHEMICAL ADMIXTURE

Figure 7.11(c) and 7.11(d) represent intermediate cases. In Figure 7.11(c), the 5
minute curve is similar to the 5 minute curve in Figure 7.11(a) but the 60 minute
curve is similar to the 60 minute curve in Figure 7.11(b). In Figure 7.11(b) and the 60
minute curve has a position relative to the 5 minute curve similar to the situation in
Figure 7.11(a).
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CHEMICAL ADMIXTURE

Plasticizers and super plasticizers

Specific gravity of the superplasticizer, Gsup = (Mliq / Vliq)
Mliq is measured in grammes, Vliq in cubic centimeters.

Solid content s of the superplasticizer is

s = (Msol / Mliq)* 100
Msol = (s * Mliq) /100 = ( s * Gsup* Vliq) / 100

EX. 6 litres of a melamine superplasticizer having a specific gravity of 1.1 and a solid
content of 22% contain 0.22 x 1.1 x6 = 1.45 kg of solids.

Mass of water contained in a certain volume of superplasticizer

When adding sevaral liters of liquid superplasticizers it is necessary to take into account
the amount of water added within the concrete in order to be able to calculate the exact
water binder ratio.
Mliq = Mw + Msol
Mw = Mliq - Msol
We know, Mliq = (Msol * 100)/s
Mw = (Msol * 100)/s – Msol
= Msol ( (100-s)/s )
= ( s * Gsup* Vliq) / 100 * (100-s)/s
Vw = Vliq * Gsup * (100-s)/100

EX. 8.25 liters of naphthalene superplasticizer with a specific gravity of 1.21 and a solid
content of 40% have been used in a concrete in order to obtain the desired slump. What is
the volume of water that is added to the concrete when using the solution of commercial
superplasticizer.
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CHEMICAL ADMIXTURE

Vw = Vliq * Gsup * (100-s)/100

= 8.25 * 1.21 * (100 – 40)/100
= 6.00 lit / m3

If d percent is the dosage of the solids of a superplasticizer suggested by a manufacturer

to obtain a desirable slump in a concrete containing mass C of cementitious material, the
volume of liquid superplasticizer, Vliq having a specific gravity Gsup and a solid content
s can be calculated as follows.
Msol = C x d / 100
We know that Msol = (s * Mliq) /100

Therefore, (s * Mliq) /100= C x d / 100

(S* Gsup* Vliq) = C x d
Vliq = (c*d)/(s* Gsup)
If C is the total mass of the cementitious materials used in a particular mix and if d
percent is the suggested doseage of solid particles, then the mass Msol of solids needed as
Msol = C x d / 100
The volume of liquid superplasticizer needed to have Msol of solid particles is calculated
as follows.
Vliq = (Msol * 100)/(s* Gsup)
Volume of solid particles contained in Vliq
Vsol = V liq - Vw
= V liq - Vliq * Gsup * (100-s)/100
= V liq (1 - Gsup * (100-s)/100)
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AIR ENTRAINING ADMIXTURES

These admixtures cause air to be incorporated in the form of minute bubbles in the
concrete during mixing, usually to increase workability and resistance to freezing and
thawing. They control the amount of air in fresh concrete and disperse properly sized
air bubbles throughout the concrete. The presence of entrained air is also beneficial in
reducing bleeding.

The origins of an entraining admixture are as follow.

a) Natural wood resins containing abietic acid salts.
b) Animal or vegetable fats and oils.
c) Various wetting agents, such as alkali salts of sulphated and sulphonated
organic compound.
d) Water soluble soaps of resin acids and animal or vegetable fatty acids.
e) Hydrogen peroxide, aluminum powder etc.

Air entrained concrete is made by mixing small quantity of air entraining agents. This
air-entraining agents produces numerous tiny non-coalescing air bubbles which are
distributed throughout the body of concrete. These bubbles act almost like flexible
ball bearings. It improves workability, reduces the tendency for segregation and
bleeding. During freeze cycles, the pressure exerted by the expanded volume of ice is
taken up by the air bubbles acting like tiny springs and during the thaw cycles these
bubbles revert to their thin size.

WATER PROOFING ADMIXTURES

Damp proofing or water proofing agents alter the concrete surface layer such that it is
rendered water repellant. This water repelling capacity is effective only when the
pressure which is forcing the water to enter into the concrete is small, e.g., wind
driven rain, capillary suction. But under high hydrostatic pressures, this will not be
sufficient and water will permeate unless the capillary diameters are small and are
segmented. This state will be possible only when the water cement ratio of the cement
paste system is low and the concrete is fully compacted without voids.

Influence of water proofing agents on properties of concrete are

 Bleeding is reduced
 No effect on setting time
 No significant effect on strength development
 Durability enhanced
Admixtures of this type are based on liquid fatty acids, stearic acid, oleic acid, capric
acid etc.
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DIFFERENT PURPOSES OF USING CHEMICAL ADMIXTURES

The reasons for the use of admixtures are outlined by the following functions
that they perform:

• Increase workability without increasing water content or decrease the water

content at the same workability;
• Retard or accelerate time of initial setting;
• Reduce or prevent shrinkage or create slight expansion;
• Modify the rate or capacity for bleeding;
• Reduce segregation;
• Improve flowability and pumpability;
• Reduce rate of slump loss;
• Retard or reduce heat evolution during early hardening;
• Accelerate the rate of strength development at early ages;
• Increase strength (compressive, tensile, or flexural);
• Increase durability or resistance to severe conditions of exposure, including
application of deicing salts and other chemicals;
• Decrease permeability of concrete;
• Control expansion caused by the reaction of alkalies with potentially reactive
aggregate constituents;
• Increase bond of concrete to steel reinforcement;
• Increase bond between existing and new concrete;
• Improve impact and abrasion resistance;
• Inhibit corrosion of embedded metal
• Produce colored concrete or mortar.
 Damp proofing
 Enhance resistance to acidic and sulphate solutions
 Increase resistance to freeze and thaw

Admixtures have facilitated many new technologies in the transportation, placement

and compaction of concrete because of which it is now possible to place very large
pours without construction joints, transport concrete to great heights, carry it over
long distances. Development of self compacting concrete and ready mixed concrete
are also possible due to admixtures.

These admixtures are used to significantly increase slump without adding more water
or to substantially reduce water content without a loss in slump. Often referred to as a
superplasticizer, this material is properly categorized as a high-range water-reducing
admixture (HRWRA)