ADMIXTURE

Admixtures
are chemical added to
ADMIXTURES
concrete, mortar or grout at the
time
of
mixing
to
modify
properties either in the wet state
or after mix has hardened
Can a be a single chemical or
blend
Usually in solutions with typically
35-40% active mineral compounds
Amount added is less than 5% of
cement (mostly < 2%)

Why Are They Used?

To modify properties of fresh & hardened
concrete
To ensure the quality of concrete during
mixing, transporting, placing & curing
To overcome certain unexpected
emergencies during concrete operations
(i. e. set retarders)
How Applied?
Most admixtures are supplied in a ready-to-use
form and added at plant or job site.
Pigments and pumping aids are batched by hand in
VERY small amounts for

MINERAL ADMIXTURE

Mineral Admixtures
Mineral admixtures are incorporated in concrete to:
Increase
the compressive strength, other
properties
mechanicaland durability.
Improve the rheological behaviour in the fresh state.
Correct deficiencies in the packing density
of
aggregates and/or increase the
the content
paste
increasing
the cement dosage (i.e., as a filler).
without
Decrease the heat of hydration.
Decrease
the environmental impact of concrete (i.e.,
by saving cement and/or utilising a waste product)

MINERAL ADMIXTURES:CLASSES
Cementitious
Natural cements
Hydraulic lime
Blast-furnace slag (GGBS)
Pozzolanic
Materials
of natural
such as crushed
origin
diatomites,
volcanic ashes and metakaolin
Fly ash
Microsilica or silica fume
Materials of low or negligible reactivity
Limestone, quartz or other rock dust
Bentonite
Hydrated lime

Supplementary Cementitious Materials

Pozzolanic Reaction
Amorphous + calcium hydroxide + water
hydrate
silica
S

CH

calcium silicate

CSH

Frequently, reactive alumina is also present in a pozzolan, which leads

to an analogous reaction to produce calcium aluminate hydrates.

CH

CAH

Calcium aluminate hydrates can react expansively with sulphate to

form ettringite.

Silica Fume ...

Very fine amorphous (noncrystalline) silica produced in electric arc
furnaces as a byproduct of the production of elemental silicon or
alloys containing silicon; also known as condensed silica fume or
microsilica.
Silica fume is a byproduct of producing silicon metal
or ferrosilicon alloys in an electric-arc furnace.
Has an amorphous SiO2 content > 85%.
Metals that produce silica fume:
Silicon metal - typically greater than 97% silicon
Ferrosilicon
alloys -ranging from 40 to
90%
alloyed with iron

Silica Fume: Physical properties

Particle size (typical)
Bulk density asproduced slurry
densified
Specific gravity
Surface area (BET)

<1m
130 to 430 kg/m3
1320 to 1440 kg/m3
480 to 720 kg/m3
2.2
13,000 to 30,000 m2/kg

Silica Fume: Effects in Concrete

Physical effect: Acts as a
micro-filler due to its small
particle size

Chemical effect: Has high

pozzolanicity

CONSEQUENCE OF SILICA FUME: FRESH

CONCRETE IS MORE COHESIVE

More strength gain

Increase fluidity
Makes concrete sticky
and cohesive
Often cause bleeding

Aggregate-paste interface
Transition Zone
In usual concrete, zone of
0.05 to 1 mm thickness
contains large crystals of
Ca(OH)2 and pores.
reason One
porosity offorthis the
zone is
higher
the
accumulation of bleed
water at the surface of
coarse aggregate particles.

Consequence in Hardened Concrete: Better aggregatepaste interface

The weakest zone in usual concrete is the Interfacial Transition Zone (ITZ)
between the hydrated cement paste (HCP) and the aggregate surface.
This zone is improved significantly by silica fume incorporation.

Fly
Ash:
Origin
ash precipitated from the exhaust gases of

It is the
coalfired power plants.

The particles are spherical and have high fineness.

The particle sizes are between less than 1 m and 100 m.
The Blaine specific surface is usually between 250 and 600
m2/kg.

Fly Ash: Origin

Common fly ash derived from bituminous coal, is
mainly
siliceous (ASTM Class F).
Sub-bituminous coal and lignite result in high-lime fly ash
(ASTM Class C).
Class F fly ash is pozzolanic, has a combined silica,
alumina and ferric oxide content of at least 70%, a
maximum SO3 content of 5% and maximum loss on ignition
of 6%. The fineness, carbon content and colour varies from
plant to plant.
Class C fly ash may have a lime content as high as 24%. It
has some cementitious properties. The carbon content is
low, the fineness is high and the colour is light.

Influence of Fly Ash on Fresh

Concrete
The setting time is increased.
Workability and flow of concrete are increased due to the
spherical shape of the fly ash particles, which has a ballbearing effect. Therefore, the paste demand decreases.
Bleeding and segregation are usually reduced for wellproportioned fly ash concrete.

Influence of Fly Ash on Hardened Concrete

Pozzolanic activity is proportional to the amount of
particles
under 10 m in diameter.
Strength gain of fly ash concrete is slower than normal
concrete. Ultimate strengths are reached much after 28 days.
This leads to lower thermal cracking.
Creep and shrinkage of fly ash concrete are typically lower
than normal concrete because of the lower amount of paste in
the concrete.
Resistance against corrosion, alkali aggregate reaction and
sulphate attack is increased due to a less permeable and
porous microstructure and reduced portland cement content.

Ground Granulated Blast-Furnace Slag

(GGBS)
Blast furnace slag is a by-product of the extraction of
pig
iron from iron ore.
Coke and limestone are added as fluxes inside the blast
furnace. The impurities in iron ore combine with the lime
and rise up to the surface of the blast furnace as slag, while
the heavier molten iron stays at the bottom.
The slag is subsequently granulated and can be ground
later to the desired fineness (usually greater than 350
m2/kg).

GGBS: Structure and Action

When quenched from its molten state, granulated slag
remain in a meta-stable amorphous state, which gives it
hydraulic qualities. (Slow air-cooled slag is hydraulically
inert.)
Quenched slag is a glass containing CaO, SiO2 and Al2O3.
It is reactive, forming an aluminum-substituted C-S-H:
CSA + H CSH
The hydraulicity of slag is activated by calcium
hydroxide in
concrete.

INFLUENCE OF GGBS ON FRESH

CONCRETE
Workability is improved.
Bleeding and segregation are usually
reduced.
Some early slump loss.
The setting time is increased.

Influence of GGBS on Hardened Concrete

The
microstructure is denser because
less lime
is
produced.
Heat development is lowered.
Higher long-term strength gain, especially when the GGBS has a
high fineness.
Resistance
against corrosion is increased due to a
less
permeable and porous microstructure.
Resistance
to sulphate attack is improved due to
lower calcium hydroxide content
Alkali aggregate reactivity is lowered due to the reduction in the
alkali mobility by the lower permeability.

Chemical Admixtures: Significance

Water-soluble materials that are added to concrete,
at dosages of less than 40-60% of the cement
weight, are generically called chemical admixtures.
Chemical admixtures are now common and, in
many cases, essential components of high-quality
concrete.
About 90-95% of the concrete produced in several
countries incorporates some type of admixture.
Chemical Admixtures have led to the development
of several
high performance concretes; e.g.,
shortcrete and Self-Compacting Concrete.

Factors that Affect the Action of the

Chemical Admixture

Dosage and addition procedures

Characteristics of the cement
and aggregates
Environmental conditions
(temperature)
The dosage of the admixtures should
be prescribed and controlled rigorously.

Admixture dosage
Admixtures should comply with National
Standards
Dosage and type of admixture should
conform
with design specifications and codes
Admixtures dispensers should be
Accurate, calibrated
Ensure complete dosage is delivered to
concrete

Time of addition should be fixed (never

added to
dry material)
Redosing should be supervised
Health, safety and environmental

Types of Chemical Admixtures

Admixtures that mainly affect the fresh state
Water-reducing agents
Superplasticizers
Reduce the amount of water needed for increasing
the workability or yield higher workability without
any change in the water content.

Admixtures that mainly affect the setting stage

Set-accelerators
Set-retarders

Reduce/increase the initial rate of reaction

between
and water. This causes a
cement
reduction/increase in the time taken by
mortars and concrete to pass from the plastic to
solid state.

 Admixtures that mainly affect the hardening state

Hardening accelerators
Accelerate the development of early strength.

Admixtures that mainly affect the hardened state

Air-entraining agents
Cause the formation of uniformly distributed
microscopic bubbles of air in the concrete or mortar.
These bubbles remain after hardening and lead to
higher freeze-thaw resistance.

Admixture by action
Water reducer and plasticizer
Superplasticizer
Set retarder
Set accelerator
Air entertaining agent
Water repelling admixture
Viscosity modifier
Corrosion resistant admixture
Cold whether admixture
Shrinkage reducer

Water Reducers
Admixture that reduces the water content of a
mortar or concrete for a given workability. Usually
has a secondary effect of retarding the setting of
the concrete.

Mainly based on pure or modified lignosulfonic

acids and their salts, hydroxycarboxylic acid and
hydroxylated polymers.

Lignosulfonates have been used since the 1930s

in concrete.

Ligosulfonates
Lignin makes up 20% of the composition of wood.
During paper-making, products of lignin are
obtained as by-products.

After processing, lignosulfonates are produced.

Commercial lignosulfonates used in admixtures
are mainly calcium or sodium based with sugar
contents of 1-30%.

Action of Water-Reducing Admixtures

When the admixture is added to the concrete mix,
a part of it is adsorbed by the cement and the
hydration products, with the initial hydration
products having the higher adsorption capacity.

There is a modification of the normal process of

ettringite formation and a delay in the C3S
hydration.

The final hydration products are not significantly

affected by the presence of the admixture.

However, the morphologies of the C-S-H gel and
Ca(OH)2 are sometimes modified.

Effect of Water-Reducing
Admixtures
Workability increases with the incorporation of the
water-reducing admixture.

Reduction in w/c
Initial setting time of cement can be extended by
several hours, depending on the dosage.

Drying shrinkage and creep seem to increase with

water-reducing admixture addition.

Superplasticizer

MECHANISMS OF ACTION, DOSAGE

AND USE
Constant w/c:
Increase
in the workability

Constant workability:
Lower w/c

same workability
No
admixture

MLS

SMF

LOWER WATER CONTENT

Usage of
Superplasticizers

Lower w/c

SC

Mechanisms of Action
Types of interaction between cement
particles and the superplasticizer
PHYSICAL

CHEMICAL

Adsorption and
generation of
repulsive forces
between cement
particles

Chemisorption,
formation of
admixture-Ca2+
complexes and
interaction with the
hydration
reactions

Chemical Formulation
Surfactants soluble in water, with different
functional groups:

Sulphonate (SO3-)

Modified Lignosulphonates (MLS)

Salts of naphthalene sulphonate and
formaldehyde condensates (SNF)
Salts of melamine sulphonate and
formaldehyde condensates
(SMF)
Comb-type polymers

Carboxylate (COO-),
Hydroxide (OH-) or
Phosphonate (PO3-)

Hydrophobic group
Hydrophilic group

Superplasticizer Action
Flocculation in the absence
of superplasticizer
Water

Cement
particle

Entrapped
water

Effect of the superplasticizer

Water

Cement
particle

Consequences of Superplasticizer Usage

Reduces placing and compaction time, leading
to lower construction costs.

Facilitates the casting of elements with

complex shapes and dense reinforcement.

Improves

surface finish of the concrete

the
elements.
Leads to superior strength and durability
with
lower cement contents.

Decrease in the entrapped air and water contents of the

fresh paste leads to lower porosity and crystallinity of the
hydrated cement paste

Unhydrated
cement grains

Consequence of
Superplasticizer
Action
Water

Atcin

w/c =
0.65

w/c =
0.25

Applications where a
Superplasticizer is Essential

Fluid/Flowing/Pumpable concrete
Shotcrete
Self-compacting concrete
High-strength concrete
High-durability concrete
Concrete with low shrinkage and creep

Common high-range water reducers (or Superplasticizers):

1st generation: Lignosulphonates at high dosages
2nd generation:
Polysulphonates
- Sulphonated melamine formaldehyde (SMF)
- Sulphonated naphthalene formaldehyde (SNF)
3rd generation:
- Polycarboxylates
- Polyacrylates
- Monovinyl alcohols

SET-RETARDERS

Effect of Set-Retarding Admixtures

When a retarder is added to cement-water
system, physical
adsorption and
reactions generally
chemical occur with the C3A and C3S.
The result is the retardation of setting of the
cement and hardening of the concrete.

The initial and final setting times are increased.

Workability is maintained longer.
Heat of hydration and

concretes
are lesser at early ages.
temperature

rise of

Effect of Set-Retarding Admixtures in hardened

concrete
When there is plasticizing effect in addition to
retardation, strength increases as water content is
consequently reduced.

Set retardation

generally leads to slower

formation of more ordered, smaller and denser
hydration products. This results in higher longterm strength.

Due to the extended plastic stage, the concrete

should be protected against shrinkage and cured
longer.

SET-ACCELERATORS
&
HARDENING-ACCELERATORS

Types of Accelerators
Chloride-based
Calcium chloride (CaCl2) is the most common
accelerator. Has been used since 1885.

Non-chloride accelerators
Calcium formate, triethanolamine, calcium
nitrate, etc.

Effect of Accelerators
The rates of hydration of C3A and/or C3S are generally
increased.

Calcium chloride decreases the dormant period of C3S,

accelerates the hydration of C2S, and the reaction
between C3A and gypsum. It may also combine with C3A
and gypsum.
Calcium
formate increases the
rate of C3S.
However,
hydration it is not as effective as calcium chloride.

Triethanolamine

accelerates the hydration C3A, and

of
retardsearly
the hydration
of C3S and
Higher
strength results
fromCthe
2S. increased amount of
hydration products.

Advantage and Disadvantage

Primary application is in cold-weather concreting.
For improving the bonding of shotcrete to the base or
previously-placed layers.
Used for obtaining higher early-age strengths.
increase the corrosion
reduce the resistance against sulphate attack

Can cause stains on the concrete surface due

to efflorescence
reduce the long-term strength

AIR ENTRAINING
AGENTS

Freezing and Thawing of Concrete

When the temperature of concrete drops to below 0C, the
water does not all freeze immediately.
Water in smaller pores will need a lower temperature to freeze
(e.g., water in 10 nm pores will not freeze until - 5C, and
pores of 3.5 nm will not freeze until - 20C; gel water will not
freeze until -78C).
As the water freezes, it dilates and compresses the remaining
water. The pressure is relieved if the water diffuses to open
voids. If no voids are available near enough, the pressure may
build up and cause rupture.
In air-entrained concrete, the bubbles relieve the pressure and
prevent damage from occurring.

A surfactant used to produce air bubbles and disperse

them throughout the cement paste.

Air entraining surfactant

Effect of Air
Entraining
Admixtures
Mehta and Monteiro

Freezing and Thawing

of Concrete
Mehta and Monteiro

Applications of Air Entraining Agents

Protection against the damage produced in
the concrete by freeze-thaw.
Reduction of bleeding and improvement of
the uniformity of the concrete, as well as
the workability and consistency.
Lowering the density of concrete.

CORROSION-INHIBITING
ADMIXTURES

Action of the Corrosion Inhibitor

Provides a second line of defence to prevent the corrosion
of the steel reinforcement in concrete, augmenting the
protection provided by the alkaline nature of the concrete.
The most common corrosion inhibitors are nitrite-based
compounds (e.g., calcium nitrite). They act by interfering
with the corrosion reaction through the formation of a
protective ferric oxide layer on the steel and/or reducing
access to the steel (less chemisorption and dissolution).

Rixom and Mailvaganam

DAMP-PROOFERS
WATER-REPELLING
ADMIXTURES

Action of the Damp-proofer

Provides
a thin hydrophobic layer within the pores
and voids, and on the surface of the concrete by:
Reaction with the cement hydration products,
Coalescence from emulsion form, or
Incorporation in a very finely divided form.
Those that react with the hydration products are based on
liquid fatty acids, such as stearic acid and butyl stearate.
Those
that coalesce on contact with the
hydration products are fine wax emulsions.
Those
that are fine hydrophobic materials are based
on
calcium and aluminium stearates.
Rixom and Mailvaganam

VISCOSITY-ENHANCING
AGENTS
VISCOSITY-MODIFYING
AGENTS

Action of the Viscosity Modifying Agent

Induces cohesion but does not inhibit the flow significantly.
Its flow behavior is pseudoplastic (i.e., has a decreasing
viscosity with higher shear rate).
The cohesion increases due to:
The increase in the viscosity of water (water-soluble
organic polymers such as Welan gum, starch,
cellulose ethers and polyacrylamide), or
Higher interparticle attraction after the admixture is
adsorbed on the cement particles (organic watersoluble flocculants such as styrene copolymers)

Rixom and Mailvaganam

Action of the Viscosity Modifying Agent

Underwater test

Nagataki

Applications of Viscosity-Modifying Agents

Underwater concrete
Facilitates

sufficient mobility of the

concrete
under water with little loss of cement.

Self-compacting concrete
Leads to high flowability with no segregation.

Grouting
Eliminates

the migration of water from the

grout due to the differential pressure.
Helps maintain the cement particles in
suspension once injection ceases.

COLD WEATHER
ADMIXTURE SYSTEMS

Action of Cold Weather Admixture

Systems (CWAS)
CWAS can be developed from existing admixtures for
concretes to be placed at temperatures down to -5 C.
They help protect the concrete against freezing and
maintain productivity.
Generally, setting time doubles for each 10 C drop in
temperature. However, the CWAS should not allow the set
retardation to occur. Also, the water in the concrete should
not be allowed to freeze.
CWAS can consist of accelerating admixtures, corrosion
inhibitors and water-reducing admixtures. The
accelerating admixtures and corrosion inhibitors tend to
depress the freezing point of the concrete.

SHRINKAGE-REDUCING
ADMIXTURES

Shrinkage Mechanisms
Plastic shrinkage: Due to the loss of water in the
plastic state due to evaporation.

Autogenous shrinkage: Chemical shrinkage (lower

volume of hydrates than cement and water) + Selfdesiccation (reduction in the pore water due to
hydration).

Thermal contraction (or thermal shrinkage): Due to the

decrease in temperature after setting.

Drying shrinkage: Due to the loss of water to the

environment in the hardened state.

Carbonation

shrinkage: Volume reduction due to

the
reaction of hydrated cement paste with CO2 in the
presence of moisture.

Drying

Autogenous

Thermal
(contraction)

Plastic

Carbonation

Shrinkage
hours

days

weeks

Time
months

years

Shrinkage Reducing Admixture (SRA)

First used in Japan, in the 1980s.
It acts by reducing the surface tension of the
evaporable water in the pores.
Leads to lower capillary stresses during
drying.
Cement particle

Water

 To satisfy the growing demands of the society

and the construction sector.

To

provide better stability under

certain environmental conditions.

To

increase the productivity/efficiency

during fabrication, transport and placing.
The capacity of traditional materials to satisfy
these demands is limited.

END