CONCRETE TECHNOLOGY, UNIT-4.

04/26/2016

Module 1
ADMIXTURES
Definition
Admixtures are chemical/mineral substances (other than fine and coarse aggregates, cement, or
water), which are added just before or during the mixing stage of concrete to modify one or more
specific properties.
They can also be blended during the grinding stage of cement manufacturing.
Classification
Chemical Admixtures
1 General purpose admixtures
 Plasticizers
 Super plasticizers
 Retarders and retarding plasticizers
 Accelerators and accelerating plasticizers
 Air entraining Admixtures.
2 Special category Admixtures (This notes will not cover brief explanation of below mentioned
admixtures )
 Damp proofing and waterproofing admixtures
 Gas forming admixtures
 Air detraining admixtures
 Alkali aggregate Expansion inhibiting admixtures
 Grouting admixtures
 Corrosion inhibiting admixtures
 Bonding admixtures
 Fungicidal, germicidal, insecticidal Admixtures
 Colouring Admixtures

Mineral Admixtures
 Fly ash or Pulverised Fuel Ash (PFA).
 Silica Fume or Micro silica.
 Rice Husk Ash.
 Ground Granulated Blast Furnace Slag (GGBS).

 Admixtures for concrete, mortar or paste are inorganic or organic materials

 Chemical Admixtures can be added to the normal components of a mix not normally
exceeding 5% by mass of cement or cementitious materials.
 Cement can be replaced by mineral admixtures up to 30 to 40% as per IS codal provision.
 Admixtures interact with hydrating cement by physical, chemical or physicochemical
actions.
 They modify one or more properties of concrete, mortar or paste either in fresh or hardened
state.

MR.SHIVAKUMARA M J
ASST PROF, CMRIT 1
BENGALURU.
 CONCRETE TECHNOLOGY, UNIT-4. 04/26/2016

 Admixtures are usually very complex compounds chemically excepting a few.

Plasticizers :
The organic substances or combinations of organic and inorganic substances, which allow a
reduction in water content for the given workability, or give a higher workability at the same water
content, are termed as plasticizing admixtures.

These admixtures are used for following purposes:

1. To achieve a higher strength by decreasing the water cement ratio at the same workability
as an admixture free mix.
2. To achieve higher workability at same water content as admixture free mix.
3. To achieve the same workability by decreasing the cement content so as to reduce the heat
of hydration in mass concrete.
4. To increase the workability so as to ease placing in accessible locations
5. Water reduction more than 5% but less than 15%

The basic products constituting plasticizers are as follows:

(i) Anionic surfactants such as lignosulphonates and their modifications and derivatives,
salts of sulphonates hydrocarbons.
(ii) Nonionic surfactants, such as polyglycol esters, acid of hydroxylated carboxylic acids
and their modifications and derivatives.
(iii) Other products, such as carbohydrates etc.

Actions involved:
1. Dispersion:
Portland cement, being in fine state of division, will have a tendency to flocculate in wet concrete.
These flocculation entraps certain amount of water used in the mix and thereby all the water is not
freely available to fludify the mix.
When plasticizers are used, they get adsorbed on the cement particles. The adsorption of charged
polymer on the particles of cement creates particle to particle repulsive forces. Due to this repulsive
force cement particles will starts to move away from each other as a result cement particles are
deflocculated and dispersed. When cement particles are deflocculated, the water trapped inside the
flocs gets released which will increases workability.

2. Lubrication:
When cement particles get flocculated there will be interparticles friction between particle to
particle and floc to floc. But in the dispersed condition there is water in between the cement particle
and hence interparticle friction reduced.

3. Retardation:
A thin layer is formed over the cement particles protecting them from hydration and increasing the
setting time. Most normal plasticizers give some retardation, 30–90 minutes.

MR.SHIVAKUMARA M J
ASST PROF, CMRIT 2
BENGALURU.
 CONCRETE TECHNOLOGY, UNIT-4. 04/26/2016

Accelerating Admixtures (Accelerators):

An admixture which, when added to concrete, mortar, or grout, increases the rate of hydration of
hydraulic cement, shortens the time of set in concrete, or increases the rate of hardening or strength
development.

Accelerators may be used when concrete is to be placed at low temperatures, in the manufacture
of precast concrete (where a rapid removal of formwork is desirable), reduction of required period
of curing, earlier placement of structure in service.

Calcium chloride is the most effective accelerator and gives both set and hardening characteristics.
Calcium chloride is effective in accelerating the hydration of the calcium silicates, mainly C3S,
possibly by a slight change in the alkalinity of the pore water or as a catalyst in the reaction of
hydration. But it has one serious defect: the presence of chloride ions in the vicinity of steel
reinforcement or other embedded steel is highly conducive to corrosion. For this reason, it should
not be used in concrete where any steel will be embedded but may be used in plain unreinforced
concrete. Chloride-free accelerators are typically based on salts of nitrate, nitrite, formate and
thiocyanate. Hardening accelerators are often based on high range water reducers, sometimes
blended with one of these salts. Accelerating admixtures have a relatively limited effect and are
usually only cost effective in specific cases where very early strength is needed for, say, access
reasons. They find most use at low temperatures where concrete strength gain may be very slow
so that the relative benefit of the admixture becomes more apparent.

In summary, a hardening accelerator may be appropriate for strength gain up to 24 hours at low
temperature and up to 12 hours at ambient temperatures. Beyond these times, a high range water
reducer alone will usually be more cost-effective.

Accelerating Plasticizers
Certain ingredients are added to accelerate the strength development of concrete to plasticizers or
superplasticizers. Such accelerating superplasticizers, when added to concrete result in faster
development of strength. The accelerating materials added to plasticizers or superplasticizers are
triethenolamine chlorides, calcium nutrite, nitrates and fluosilcates etc.

Retarding Admixtures (Retarders):

The function of retarder is to delay or extend the setting and hardening time of cement paste in
concrete. These are helpful for concrete that has to be transported to long distance, and helpful in
placing the concrete at high temperatures.

When water is first added to cement there is a rapid initial hydration reaction, after which there is
little formation of further hydrates for typically 2–3 hours. The exact time depends mainly on the
cement type and the temperature. This is called the dormant period when the concrete is plastic
and can be placed. At the end of the dormant period, the hydration rate increases and a lot of
calcium silicate hydrate and calcium hydroxide is formed relatively quickly. This corresponds to
the setting time of the concrete. Retarding admixtures delay the end of the dormant period and the
start of setting and hardening. This is useful when used with plasticizers to give workability
retention.

MR.SHIVAKUMARA M J
ASST PROF, CMRIT 3
BENGALURU.
 CONCRETE TECHNOLOGY, UNIT-4. 04/26/2016

Retarders are useful in concreting in hot weather, when the normal setting time is shortened by the
higher temperature, and in preventing the formation of cold joints. In general they prolong the
setting and hardening time during which concrete can be transported, placed, and compacted.
They are also used in grouting oil wells. Oil wells are sometimes taken up to a depth of about 6000
meter deep where the temperature may be about 2000C.
Retarders are sometimes used to obtain exposed aggregate look in concrete look in concrete. The
retarder sprayed to the surface of the formwork, whereas the rest of the concrete gets hardened.
On removing the formwork after one day or so, the unhardened matrix can be just washed off by
a jet of water which will expose the aggregates.

Perhaps the most commonly known retarder is calcium sulphate (gypsum). It is interground to
retard the setting of cement. The appropriate amount of gypsum to be used must be determined
carefully for the given job. Use of gypsum for the purpose of retarding setting time is only
recommended when adequate inspection and control is available, otherwise, addition of excess
amount may cause undesirable expansion and indefinite delay in the setting of concrete.
In addition to gypsum there are number of other materials found to be suitable for this purpose.
They are: starches, cellulose products, sugars, acids or salts of acids. These chemicals may have
variable action on different types of cement when used in different quantities. Unless experience
has been had with a retarder, its use as an admixture should not be attempted without technical
advice. Any mistake made in this respect may have disastrous consequences.

Common sugar is one of the most effective retarding agents used as an admixture for delaying the
setting time of concrete without detrimental effect on the ultimate strength. Addition of excessive
amounts will cause indefinite delay in setting. At normal temperatures addition of sugar 0.05 to
0.10 per cent have little effect on the rate of hydration, but if the quantity is increased to 0.2 per
cent, hydration can be retarded to such an extent that final set may not take place for 72 hours or
more.

Retarding Plasticizers
Instead of adding retarders separately, retarders are mixed with plasticizers or superplasticizers at
the time of commercial production. Such commercial brand is known as retarding plasticizers or
retarding superplasticizers. In the commercial formulation we have also retarding and slump
retaining version. Retarding plasticizers or superplasticizers are important category of admixtures
often used in the Ready mixed concrete industry for the purposes of retaining the slump loss,
during high temperature, long transportation, to avoid construction or cold joints, slip form
construction and regulation of heat of hydration.

Air Entrained Admixtures:

Air entrained concrete is made by mixing a small quantity of air entraining agent or by using air
entraining cement. These at entraining agents incorporate millions of non-coalescing air bubbles,
which will act as flexible ball bearings and will modify the properties of plastic concrete regarding
workability, segregation, bleeding and finishing quality of concrete. It also modifies the properties
of hardened concrete regarding its resistance to frost action and permeability.

The air voids present in concrete can be brought under two groups:

MR.SHIVAKUMARA M J
ASST PROF, CMRIT 4
BENGALURU.
 CONCRETE TECHNOLOGY, UNIT-4. 04/26/2016

(a) Entrained air (b) Entrapped air.

Entrained air is intentionally incorporated, minute spherical bubbles of size ranging from 5
microns to 80 microns distributed evenly in the entire mass of concrete. The entrapped air is the
voids present in the concrete due to insufficient compaction. Their size may range from 10 to 1000
microns or more and they are not uniformly distributed throughout the concrete mass.

Air entraining agents

The following types of air entraining agents are used for making air entrained concrete.
( a ) Natural wood resins
( b ) Animal and vegetable fats and oils, such as tallow, olive oil and their fatty acids such as stearic
and oleic acids.
( c ) Various wetting agents such as alkali salts or sulphated and sulphonated organic compounds.
( d ) Water soluble soaps of resin acids, and animal and vegetable fatty acids.
( e ) Miscellaneous materials such as the sodium salts of petroleum sulphonic acids, hydrogen
peroxide and aluminum powder, etc.

The Effect of Air Entrainment on the Properties of Concrete

Air entrainment will effect directly the following three properties of concrete:
(a) Increased resistance to freezing and thawing. (b) Improvement in workability (c) Reduction in
strength.
Incidentally air entrainment will also effect the properties of concrete in the following ways:
(a) Reduces the tendencies of segregation. (b) Reduces the bleeding and laitance. (c) Decreases
the permeability (d) Increases the resistance to chemical attack. (e) Permits reduction in sand
content. (f) Improves placeability, and early finishing. (g) Reduces the cement content, cost, and
heat of hydration. (h) Reduces the unit weight. (i) Permits reduction in water content. (j) Reduces
the alkali-aggregate rea4ion. (k) Reduces the modulus of elasticity.

Mineral Admixtures in Concrete

Types of Mineral Admixtures
Cementitious
These have cementing properties themselves. For example: Ground granulated blast furnace slag
(GGBFS)
Pozzolanic
A pozzolana is a material which, when combined with calcium hydroxide (lime), exhibits
cementitious properties. Pozzolanas are commonly used as an addition (the technical term is
"cement extender") to Portland cement concrete mixtures to increase the long-term strength and
other material properties of Portland cement concrete and in some cases reduce the material cost
of concrete. Examples are:

 Fly ash
 Silica Fume
 Rice Husk Ash
 Metakaolin

MR.SHIVAKUMARA M J
ASST PROF, CMRIT 5
BENGALURU.
 CONCRETE TECHNOLOGY, UNIT-4. 04/26/2016

Pozzolanic Action:
The additive act in three ways
Filler, Nucleating, Pozzolanic

1 Filler:
These additives/admixtures are finer than cement, so when added to concrete they occupy the small
pores previously left vacant.
2 Nucleating:
These fine particles accelerate the rate of hydration and precipitation starts.
3 Pozzolanic:
When cementing material reacts with water the following reaction take place:

C2S + H =CSH + CH

C3S + H =CSH + CH

CSH is responsible for strength while CH(Calcium hydroxide) is a soluble material reacts and
dissolves in water leaving behind pores. So when admixture is added

SiO3 or Al2O3+ CH = CSH

Thus, it reduces the amount of CH & increase CSH

Fly Ash:
The finely divided residue resulting from the combustion of ground or powdered coal. Fly ash is
generally captured from the chimneys of coal-fired power plants; it has POZZOLANIC properties,
and is sometimes blended with cement for this reason.

Fly ash includes substantial amounts of silicon dioxide (SiO2) (both amorphous and crystalline)
and calcium oxide (CaO). Toxic constituents include arsenic, beryllium, boron, cadmium,
chromium, cobalt, lead, manganese, mercury, molybdenum, selenium, strontium, thallium, and
vanadium.

Fly ash is the most common artificial pozzolana, the fly ash particles are spherical and have very
high fineness : the vast majority of particles have a diameter between less than 1 micrometer to
100 micrometer, and the specific surface of flyash is usually between 250 to 600m2/kg. The high
specific surface means the material is readily available for reaction with calcium hydroxide.

Addition of flyash in concrete helps to improve many properties of concrete in fresh and hardened
state of concrete. In fresh state of concrete addition of flyash leads to production of a fatty mix
which helps in improving workability, reducing segregation and bleeding. Secondary hydration
caused by flyash produces more amount of CSH gel and reduces soluble Calcium hydroxide in
concrete which will improves strength of the concrete in later ages and reduces permeability of
concrete which leads to inhibiting alkali-aggregate reaction, and enhancement of sulfate resistance.
In addition use of flyash leads reduced heat evolution during the process of hydration.

MR.SHIVAKUMARA M J
ASST PROF, CMRIT 6
BENGALURU.
 CONCRETE TECHNOLOGY, UNIT-4. 04/26/2016

Class F Fly Ash:

The burning of harder, older anthracite and bituminous coal typically produces Class F fly ash.
This fly ash is pozzolanic in nature, and contains less than 5% lime (CaO). The glassy silica and
alumina of Class F fly ash requires a cementing agent, such as Portland cement, quicklime, or
hydrated lime, with the presence of water in order to react and produce cementitious compounds.

Class C Fly Ash:

Fly ash produced from the burning of lignite or subbituminous coal, in addition to having
pozzolanic properties, also has some self-cementing properties. In the presence of water, Class C
fly ash will harden and gain strength over time. Class C fly ash generally contains more than 10%
lime (CaO). Unlike Class F, self-cementing Class C fly ash does not require an activator. Alkali
and sulfate (SO4) contents are generally higher in Class C fly ashes.

Silica Fume
Siica fume, also referred to as microslica or condensed silica fume, is another material that is used
as an artificial pozzolaric admixture. It is a product resulting from reduction of high purity quartz
with coal in an electric arc furnace in the manufacture of silicon or ferrosilicon alloy. Silica fume
rises as an oxidised vapour. Condensed silica fume is essentially silicon dioxide (more than 90%)
in noncrystalline form. Since it is an airborne material like fly ash, it has spherical shape. It is
extremely fine with particle size less than 1 micron and with an average diameter of about 0.1
micron, about 100 times smaller than average cement particles. Silica fume has specific surface
area of about 20,000 m2/kg, Because of its extreme fineness and high silica content, Silica Fume
is a highly effective pozzolanic material.

Pozzolanic Action. Microsilica is much more reactive than fly ash or any other natural pozzolana.
Most research workers agree that the C - S - H formed by the reaction between microsilica and
Ca(OH)2 appears dense and amorphous.s.

Influence on Fresh Concrete

Water demand increases in proportion to the amount of microsilica added. The addition of
microsilica will lead to lower slump but more cohesive mix. The microsilica make the fresh
concrete sticky in nature and hard to handle. It was also found that there was large reduction in
bleeding and concrete with microsilica could be handled and transported without segregation. It is
reported that concrete containing microsilica is vulnerable to plastic shrinkage cracking and,
therefore, sheet or mat curing should be considered. Microsilica concrete produces more heat of
hydration at the initial stage of hydration, however the total generation of heat will be less than
that of reference concrete.

Influence on Hardened Concrete: Concrete containing microsilica showed outstanding

characteristics in the development of strength. It has been also found out that modulus of elasticity
of microsilica concrete is less than that of concrete without microsilica at the same level of
compressive strength. As regards, the improvement in durability aspects many published reports,
of this investigation carried out, indicate improvement in durability of concrete with microsiica.

MR.SHIVAKUMARA M J
ASST PROF, CMRIT 7
BENGALURU.
 CONCRETE TECHNOLOGY, UNIT-4. 04/26/2016

Silica fume offers better resistance against for alkali-aggregate reaction, Sulphate attack and
chloride attack, but vulnerable to frost action.

Curing: Curing is probably the most important aspect of microsilica concrete as the material
undergoes virtually zero bleeding. If the rate of evaporation from the surface is faster than the rate
of migration of water from interior to the surface plastic shrinkage takes place. In the absence of
bleeding and slow movement of water from interior to the surface, early curing by way of
membrane curing is essential.

Rice Husk Ash:

Rice husks are natural a natural waste product. Rice husk have very high silica content, and slow
firing at a temperature of 500 to 7000C results in an amorphous materials with a porous structure.
Thus the specific surface can be as high as 50000m2/kg, even though the particle size is large :10
to 75 micrometer. The rice husk ash particles have complex shapes, reflecting their plant origins
and they therefore have high water demand unless interground with clinker so as to breakdown the
porous structure.

Rice husk ash is reported to contribute to the strength of concrete already 1 to 3 days. However, to
achieve adequate workability, as well as high strength, the use of superplasticizers may be
necessary, this negates the economic benefits of the use of rice husk ash in less affluent areas of
the world where collection of the husks for processing may also present problems. The use of rice
husk ash can lead to increased shrinkage.

Ground Granulated Blast Furnace Slag (GGBFS)

Ground granulated blast-furnace slag is the granular material formed when molten iron blast
furnace slag (a by-product of iron and steel making) is rapidly chilled (quenched) by immersion in
water. It is a granular product, highly cementitious in nature and, ground to cement fineness,
hydrates like Portland cement.

(Blast-Furnace Slag: A by-product of steel manufacture which is sometimes used as a substitute

for Portland cement. In steel industry when iron ore is molted, then in the molted state all the
impurities come at its surface which are removed called slag. It consists mainly of the silicates and
aluminosilicates of calcium, which are formed in the blast furnace in molten form simultaneously
with the metallic iron. Blast furnace slag is blended with Portland cement clinker to form
PORTLAND BLASTFURNACE SLAG CEMENT). GGBFS is used to make durable concrete
structures in combination with ordinary Portland cement and/or other pozzolanic materials.
GGBFS has been widely used in Europe, and increasingly in the United States and in Asia
(particularly in Japan and Singapore) for its superiority in concrete durability, extending the
lifespan of buildings from fifty years to a hundred years.

Concrete made with GGBFS cement sets more slowly than concrete made with ordinary Portland
cement, depending on the amount of GGBFS in the cementitious material, but also continues to
gain strength over a longer period in production conditions. This results in lower heat of
hydration and lower temperature rises, and makes avoiding cold joints easier, but may also
affect construction schedules where quick setting is required.

MR.SHIVAKUMARA M J
ASST PROF, CMRIT 8
BENGALURU.
 CONCRETE TECHNOLOGY, UNIT-4. 04/26/2016

Use of GGBFS significantly reduces the risk of damages caused by alkali-silica reaction (ASR),
provides higher resistance to chloride ingress, reducing the risk of reinforcement corrosion, and
provides higher resistance to attacks by sulfate and other chemicals.

Benefits:

1. Durability
1. GGBFS cement is routinely specified in concrete to provide protection against both
sulphate attack and chloride attack
2. GGBFS is also routinely used to limit the temperature rise in large concrete pours.
The more gradual hydration of GGBFS cement generates both lower peak and less
total overall heat than Portland cement.
2. Appearance
1. In contrast to the stony grey of concrete made with Portland cement, the near-white
color of GGBFS cement permits architects to achieve a lighter colour for exposed
fair-faced concrete finishes, at no extra cost.
3. Strength
1. Concrete containing GGBFS cement has a higher ultimate strength than concrete
made with Portland cement. It has a higher proportion of the strength-enhancing
calcium silicate hydrates (CSH) than concrete made with Portland cement only, and
a reduced content of free lime, which does not contribute to concrete strength.
Concrete made with GGBFS continues to gain strength over time, and has been
shown to double its 28 day strength over periods of 10 to 12 years.

MR.SHIVAKUMARA M J
ASST PROF, CMRIT 9
BENGALURU.