CONCRETE TECHNOLOGY

TOPIC 1 ADMIXTURES IN
CONCRETE

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Admixtures

A material added to plastic concrete or

mortar, other than water, aggregates,
cement, and fibre to change one or more
properties of fresh or hardened concrete
(ASTM C494).
They are added in concrete by either
weighed or measured by volume as
recommended by the manufacturer.

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When to Use Admixture?

When the desired modification of properties

of fresh or hardened concrete cannot be
achieved by changes in the composition of
the mix proportion.

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Classification

Classified by chemical and functional

physical characteristics (Hewlett, 1978):
Air entrainers
Water reducers
Retarders
Hydration controller admixtures
Accelerators
Supplementary cementitious admixtures
Specialty admixtures

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Chemical Admixtures

1.
2.
3.

4.
5.

Chemical added in very small amount or

quantity to the mixture to develop special
properties in fresh or hardened concrete.
Accelerating admixture
Retarding admixture
Water-reducing/ high-range water-reducing
admixture
Air-entraining admixture
Others

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Reasons for Using Admixtures

Portland Cement Association (PCA) in USA

identifies 4 major reasons for using admixtures
(Kosmatka et al., 2002)
1. Reduce cost of concrete construction
2. Achieve certain properties in concrete more
effectively than by other means.
3. Ensure quality of concrete during the stages of
mixing, transporting, placing, and curing in adverse
weather conditions.
Overcome certain emergencies during concrete
operations.

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Accelerating Admixture

To accelerate the setting and early strength development of concrete,

particularly in cold weather applications.
Meet the requirement of ASTM D 98
E.g. Calcium Chloride (CaCl2)
The initial set time of 3 hours for a typical concrete reduced to 1.5 hours by
1% calcium chloride of the cement weight.
Adding 2% calcium chloride reduces the initial setting time to 1 hour.
Typical final setting times are 6 hours, 3 hours, and 2 hours for 0%, 1%,
and 2% calcium chloride.
Compressive strength at 3 days at least 25% higher than concrete without
admixture.
The amount of CaCl2 should be limited to 2% by weight of cement.
Excessive amounts of calcium chloride in concrete mix may result in rapid
stiffening, increase in drying shrinkage and creep of concrete and corrosion
of reinforcement.
CaCl2 is not recommended in hot weather concreting and for pre-stressed
concrete and may be ineffective at temperature below freeze before it
reaches the initial set.

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Reasons to use Accelerators

Reduce the amount of time before finishing

operations begin.
Reduce curing time.
Increase rate of strength gain
Plug leaks under hydraulic pressure
efficiently.

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The PCA recommends against using

calcium chloride under the following
conditions:

Concrete is pre-stressed.
Concrete contains embedded aluminum such as
conduits, especially if the aluminum is in conduct
with steel.
Concrete is subjected to alkali-aggregate reaction.
Concrete is in contact with water or soils containing
sulfates
Concrete is placed during hot weather.
Mass applications of concrete.

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ACI recommends the following limits to

water-soluble chloride ion content based
on percentage of cement
Member Type
Pre-stressed concrete

Chloride Ion Limit, %

0.06

Reinforced concrete
subjected to chloride in
service
Reinforced concrete
protected from moisture

0.15

Other reinforced concrete

0.30

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1.00

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Retarding Admixture

Some construction conditions require that the time between

mixing and placing or finishing the concrete be increased.
Added to concrete to delay its setting and hardening, especially
in hot weather applications (temperature greater than 320C).
Hot weather increases the rate of hardening which makes it
difficult to place and finish the plastic concrete.
Recommended in large structures and difficult situations such as
large piers and foundations, to delay the initial set as well as to
keep concrete workable throughout the entire placing period
(eliminate cold joint).
Sugar in any form is a retarder.
The use of retarder may reduce the strength at early age.
Because most retarders also act as water reducers, they are
frequently called water-reducing retarders.
Based on ASTM C 494, type B is simply a retarding admixture,
while type D is both retarding and water reducing, resulting in
concrete with greater compressive strength because of the lower
water-cement ratio.

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Retarding Admixture Cont.

Retarding admixtures consists of both organic and

inorganic agents.
Organic retardants include unrefined calcium,
sodium, NH4, salts of lignosulfonic acids,
hydrocarboxylic acids, and carbohydrates.
Inorganic retardants include oxides of lead and zinc,
phosphates, magnesium salts, fluorates and
borates.
As an example of a retardant's effects on concrete
properties, lignosulfate acids and hydroxylated
carboxylic acids slow the initial setting time by at
least an hour and no more than three hours when
used at 65 to 100 degrees Fahrenheit.

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Reasons using Retarders

Offsetting the effect of hot weather

Allowing for unusual placement or long haul
distances.
Providing time for special finishes (e.g.,
exposed aggregate)

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Water-Reducing Admixture

One of Surfactants, also known as surface-active

chemical
To gain workability and maintain quality.
Used to reduce the quantity of mixing water required,
which increase the compressive strength, and to
produce concrete of desired consistency or high slump.
Can reduce water required by 12% or more.
Its effect is due to increased dispersion of cement
particles, causing a reduction in the viscosity of the
concrete
Increase mobility of the cement particles in the plastic
mix.

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Levels of Effectiveness

Conventional (low-range)
Mid-range
High range (Superplaticizer)

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Water Reducers Mechanism

Cement grains develop static electric charge on their surface

as a result of the cement grinding process.
Different charges attract to each other, causing the cement
grains to cluster or flocculate which in turn limits the workability.
The chemicals in the water-reducing admixtures reduce the static
attraction among cement particles.
The molecules of water-reducing admixtures have both positive
and negative charges at one end, and a single charge (usually
negative) on the other end.
These molecules are attracted by the charged surface of the
cement grains.
The water reducers neutralize the static attraction on the cement
surfaces. As a result, the clusters of cement grains are broken
apart.
Mutual repulsion of like charges pushes the cement grains apart,
achieving a better distribution of particles, more uniform
hydration, and a less-viscous paste.

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High-Range Water Reducer

Also called Superplasticizer (ASTM C494).

Superplasticizers are linear polymers containing sulfonic acid
groups (water-soluble organic polymers) attached to the polymer
backbone at regular intervals (Verbeck, 1968).
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 (Mindess and Young, 1981).
Superplasticizer is added in small dosage with mixing water
(typically 0.2% by weight of cement) to increase slump.
Flowing concrete- slump greater than 180mm
Dosage rate may vary from brand to brand for different types of
cement.

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High-Range Water Reducer Cont.

By using superplasticizer, it is possible to

have w/c ratio in the range of 0.3 to 0.45
which would be impossible otherwise.
Addition of superplasticizer increases cost by
5% BUT savings in labour can be as high as
33%.

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Families of Superplasticizers

1.

2.

3.
4.

Most of the commercial formulations belong

to one of four families:
Sulfonated melamine-formaldehyde
condensates (SMF)
Sulfonated naphthalene-formaldehyde
condensates (SNF) common used
Modified lignosulfonates (MLS)
Polycarboxylate derivatives

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Effect of Superplasticizer

Increase in workability
Increase in compressive strength
Eliminates segregation
Allow good dispersion of cement particles in
water

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Concrete With Superplasticizer

Has smooth surface

Much less likely to chip and spall
Has fewer plastic shrinkage cracks
Higher compressive strength (up to 70-80 MPa)
Less shrinkage
Low permeability
Less time to place and finish the concrete (stays
workable for 30 to 60 minutes)
An accelerating curing period because of rapid gain
in strength
Early removal of formwork

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Air-Entraining Admixture

Added to entrain air/ produce tiny air bubbles

in concrete to provide space for water to
expand upon freezing.
Air entrainment is a process by which a large
number of microscopic air bubbles are
dispersed throughout the concrete.
Diameter of bubbles in the range of 20 to
200m

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Air-Entraining Admixture

Air entrainers are usually liquid (ASTM C 260)

The agents enhance air entrainment by lowering the surface
tension of the mixing water.
Anionic (-) air entrainers are hydrophobic (water hating/ repelled
water).
The negative charge of the agent is attracted to the positive
charge of the cement particle.
The hydrophobic agent forms tough, elastic, air-filled bubbles.
Mixing disperses the air bubbles throughout the paste, and the
sand particles form a grid that holds the air bubbles in place.
Other types of air entrainers have differerent mechanisms but
produce similar results.

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Advantages of Air-Entraining Admixtures

It causes the disruption of the continuity of

capillary pores result in reduction in
permeability and reduces internal stresses
caused by expansion of the pore water on
freezing.
Foaming agents are added in small amount
(typically about 0.05% by weight of cement)
during mixing and can be used to entrain 3 to
10% air.

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Advantages of Air-Entraining Admixtures

Cont.
The use of air-entraining admixture can:
- Improved workability
- Reduce bleeding
- Reduce segregation
- Shrinkage-compensated (e.g. aluminium
powders)
However:
- Lower compressive strength
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Variety of Air-Entraining Materials

Salts of wood resins (Vinsol resin)

Synthetic detergents
Salts of sulfonated lignin (by-product of paper
production).
Salts of petroleum acids
Salts of proteinaceous material
Fatty and resinous acids
Alkylbenzene sulfonates
Salts of sulfonated hydrocarbons.

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Chemical Admixture
Description

Applications

Water-reducing Admixture

To get dense concrete, to improve

workability

Retarding admixture

To delay setting and hardening,

hot weather concreting, large
structures

Accelerating admixture

To accelerate setting and early

strength development, cold
weather concreting

Air-entraining admixture

To improve durability and

workability

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Mineral Admixtures

Are natural pozzolanic materials or industrial

by-products that are used in concrete to
replace part of cement
It is known as supplementary cementing
material
Are generally added in relatively large
quantities in comparison with chemical
admixtures
Contains reactive silica (SiO2) /amorphous
silica

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Reactive
Silica
Rocks
and
Minerals
ROCKS
Reactive Minerals
Arenite

Tridymite

Arkose
Shale

Cristobalite
Volcanic glass

Sandstone

Cryptocrysalline (or
microcrystalline) quartz
Strained quartz

Limestone
Chert
Flint
Quartzite
Quartz-arenite
Gneiss
Argillite
Granite
Greywacke
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Siltstone

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Silica Crystals

Tetrahedral coordination of silica (SiO2), the basic building block of the most ideal glass former.

Crystal structureTetrahedral coordination

of silica (SiO2), the basic
building block of the most
ideal glass former.

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The amorphous structure of

glassy silica (SiO2) in twodimensions. No long-range
order is present; however
there is local ordering with
respect to the tetrahedral
arrangement of oxygen (O)
atoms around the silicon
(Si) atoms. Note that a
fourth oxygen atom is
bonded to each silicon
atom, either behind the
plane of the screen or in
front of it; these atoms are
omitted for clarity.

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The Effect of pH on Silica

Solubility.

The pore solution pH influences the solubility of silica. The higher the pH
(the more OH-), the more likely silica will dissolve.

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Blended Cement- Green Materials

(Environmental-friendly)

Portland cement consists of 95% cement

clinker (carbon dioxide emissions through
manufacturing process) and 5% gypsum.
To reduce CO2 emissions, produce blended
cement = OPC + pozzolans/ mineral
admixtures (industrial wastes or by- products)
Green technology- reduce, reuse and
recycle the wastes (industrial ecology), so
reduce the environmental impact.

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Pozzolans

Are siliceous or siliceous and aluminous

materials which in themselves possess little
or no cementitious property
BUT in finely divided form and in the
presence of moisture, these materials can
react with calcium hydroxide of cement at
ordinary temperature to form compounds of
cementitious properties
This reaction is called POZZOLANIC
REACTION

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Pozzolanic Activity

The Pozzolanic reaction primarily occurs between

amorphous siliceous materials (namely, pozzolan
and pozzolana, a finely divided volcanic ash, rich in
Obsidian/ igneous rock, a mineral glass commonly
found in lava (molten rock expelled by a
volcano) ) and slaked lime (calcium hydroxide) to
form calcium silicate hydrates
At the basis of the Pozzolanic reaction stands a
simple acid-base reaction between calcium
hydroxide, also known as Portlandite, or (Ca(OH)2),
and silicic acid (H4SiO4, or Si(OH)4).

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Pozzolanic Reaction

Hydration process:
cement + H2O
C-S-H gel + Ca(OH)2
Pozzolanic reaction:
Ca(OH)2 + H4SiO4 > Ca2+ + H2SiO42- + 2
H2O > CaH2SiO4 2 H2O (Calcium

Silicate Hydrate gel)

or summarized in abbreviated notation of

cement chemists:
SiO2 + Ca(OH)2
C-S-H gel

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Pozzolanic Reaction

The ratio Ca/Si, or C/S, and the number of water molecules can vary
and the here above-mentioned stoichiometry (the calculation of
quantitative (measurable) relationships of the reactants and
products in a balanced chemical reaction) may differ.
As the density of CSH is lower than that of Portlandite and pure
silica, a consequence of this reaction is a swelling of the reaction
products.
This reaction may also occur with time in concrete between alkaline
cement pore water and poorly-crystalline silica aggregates (ASR).
This delayed process is also known as alkali-silica reaction (ASR),
or alkali-aggregate reaction (AAR), and may be very damageable to
concrete structures because the resulting volumetric expansion is
also responsible for spalling and decrease of the concrete strength.

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Example of Pozzolans

Ground Granulated Blast Furnace slag

(GGBFS)
Pulverised Fuel Ash (PFA)
Silica Fume (SF)
Rice Husk Ash (RHA)
Palm Oil Fuel Ash (POFA)

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Method of Replacement

Replacing part of the cement content (by

weight of cement)
Can be added during mixing process or grind
together with cement (pozzolan cement)

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Effect of Pozzolanic Admixtures

Lower early strength

Lower heat of hydration
Higher ultimate strength
Less permeable
Reduce cost
Increase workability

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Slag (ASTM C 989)

Is a non metallic product, consisting essentially of

silicates and aluminates of calcium bases
Not only pozzolanic but also cementitious
It is develop in a molten condition simultaneously
with iron in a blast furnace
Is the glassy (amorphous, non crystalline solid)
granular material formed when molten blast furnace
slag in rapidly chilled as by immersion in water.
The granular material is then ground to less than 45
microns.
Specific gravity in the range of 2.85 to 2.95
Amount replacement: From 20% up to 80%
Level of reactivity- Grade 80, 100, or 120

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Ground granulated blast furnace slag

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Fly Ash

Is a by-product of burning powdered coal in electric generating

power plant
Generally finer than Portland cement and consists mainly of small
spheres of glass involving silica, alumina, and ferric oxide
Particles diameters range from 1m to more than 0.1mm, with an
average of 0.015mm to 0.02mm, and are 70% to 90% smaller than
0.045mm/ 45m.
Primarily a silica glass composed of silica (SiO2), alumina (Al2O3),
iron oxide (Fe2O3), and lime (CaO)
Amount of replacement: 20 to 70%
Spherical shape of fly ash increases workability.
Fly ash extends the hydration process, allowing a greater strength
development and reduced porosity.
20% replacement- smaller pore size distribution, lower heat of
hydration decelerate early strength, but extended reaction permits a
continuous gaining of strength.

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Classification of Fly Ash (ASTM C 618)

Three types:
Class N Fly Ash- Raw or calcined natural pozzolans,
including diatomaceous earths, opaline cherts and
shales, ruffs and volcanic ashes or pumicites, and
some calcined clays and shales.
Class F Fly Ash- low calcium fly ash (5-10% CaO).
Has no cementitious properties but can react with
calcium hydroxide (pozzolan properties)
Class C Fly ash high-calcium fly ash (15 to 30%
CaO). Has cementitious properties in addition to
pozzolanic properties

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Pulverised Fuel Ash (PFA) powder

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Silica Fume (ASTM C 1240)

Is a by-product of the electric arc furnaces in the

silicon metal and ferrosilicon alloy industries
Consist of amorphous/ non-crystalline silica (85 to
90% silicon oxide)
Very fine particles less than 0.1m (100 times
finer than cement)
Highly pozzolanic and very reactive
Is available in wet or dry forms.
Amount replacement: 10 to 20%
Produce high strength concrete (15,000 psi), reduce
concrete corrosion induced by deicing or marine
salts, highly resistant to penetration by chloride ions.

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Silica Fume
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Rice Husk Ash

Is an agricultural fly ash which is obtained

from burning and grinding of rice husk
Contains reactive silica
Amount replacement: 10 to 30%

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Bottom RHA from

fix grate boiler

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RHA from circulating

fluidised bed boiler

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Palm Oil Fuel Ash

Obtained from the burning of palm oil clinker

Amount replacement: 10 to 30%

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UTILIZATION OF PALM OIL

FUEL ASH (POFA) IN CONCRETE

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Natural Pozzolans

A pozzolan is a siliceous and aluminous materials,

possesses little or no cementitious value.
In finely divided form and in the presence of moisture,
react chemically with calcium hydroxide at ordinary
temperature to form compounds possessing
cementitious properties.
Natural occurring pozzolan, e.g. volcanic ash,
combined with burned lime, were used about 2000 years
ago.
Up to 15% of the weight of Portland cement is hydrated
lime.
Adding a pozzolan to Portland cement generates an
opportunity to convert this free lime to a cementitious
material.

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Fiber for Concrete

To control plastic shrinkage cracking and drying

shrinkage cracking.
They also lower the permeability of concrete and
thus reduce bleeding of water.
Some types of fibers produce greater impact,
abrasion and shatter resistance in concrete.
Generally fibers do not increase the flexural strength
of concrete, so it can not replace moment resisting
or structural steel reinforcement. Some fibers reduce
the strength of concrete.
E.g. of fibers: steel, plastic, glass and natural
materials

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Fiber for Concrete Cont.

The shape of fibers described by the aspect

ratio, length/diameter. E.g. steel fiber,
diameters from 0.25mm to 0.9mm with
aspect ratio 30 to 150mm.
Addition of fibers reduced workability of
concrete, so, limited to maximum 2% by
volume of the mix.
Fiber reinforced concrete successfully used
for floor slabs, pavements, slope stabilization,
and tunnel linings.

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Benefits of Polyproplene [CH3]n Fiber

Improve mix cohesion, improving pumpability over

long distances
Improve freeze-thaw resistance
Improve resistance to explosive spalling in case of a
severe fire
Improve impact resistance
Increase resistance to plastic

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Factors Affecting the Suitability and

Performance of Admixture in Concrete

Type of cement
Mix proportions and method of mixing
Temperature and time when the admixture is
added into the mix
Chemical composition of the admixture

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Monitoring and Precaution

Selection of material
Trial mix
Short-term and long-term effect
Eliminate over-dosing on site
Manufacturers advice

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Special Admixtures- Water Proofing

Admixture (WPA)

Concrete absorbs water because surface

tension in capillary pores in the hydrated
cement paste pulls in water by capillary
suction.
WPA aim at preventing this penetration of
water into concrete (make concrete
hydrophobic)
WPA react with calcium hydroxide, e.g.
stearic acid, vegetable or animal fats to make
concrete hydrophobic.

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Special Admixtures- Water Proofing

Admixture (WPA)

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Other WPA, e.g. very fine material containing

calcium stearate or hydrocarbon resins or coal tar
pitches which produce hydrophobic surfaces.
Side effect: improve workability due to finely divided
wax or bituminous emulsions, which entrain some
air. Also improve cohesion of concrete but may
result in sticky mix.
Vital to ascertain WPA contains no chlorides.
Water proof membranes are emulsion-based
bitumen coatings, possibly with rubber latex, which
produce a tough film with some degree of elasticity.
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Special Admixtures- Anti Bacterial Agent

(ACI 212.3R-91)

Bacteria/ fungi, or insects mechanisms are: releasing corrosive

chemicals through metabolic action, and creation of an
environment which promotes corrosion of steel. Staining of the
surface can also result.
Mineral or organic acid (from bacteria) + cement paste (alkaline)
= neutralize, extra acids destroy concrete.
Agent toxic apply on concrete surface to the attacking
organisms: anti-bacterial, fungicidal, or intersecticidal.
Copper sulfate and pentachlorophenol- control the growth of
algae or lichen on hardened concrete BUT their effectiveness is
lost with time.
Admixtures which may prove toxic should not be used.

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References

Malhotra, V. M. 1989. Superplasticizers: A global

review with emphasis on durability and innovative
concrete. In ACI SP-119: Superplasticizers and
other chemical admixtures in concrete, ed. V. M.
Malhotra, 1-19. Detroit: American Concrete Institute.
Malhotra, V. M., ed. 1989. ACI SP-119:
Superplasticizers and other chemical admixtures in
concrete. Detroit: American Concrete Institute.
Mielenz, R. 1984. History of chemical admixtures for
concrete. Concrete International: Design and
Construction 6 (4):40-54 (April).
Mindess, S., and J. F. Young. 1981. Concrete.
Englewood Cliffs, N.J.: Prentice-Hall, Inc.

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