Additive and Chemical Admixtures

 Additives/Mineral admixture are the chemical components

which are added to cement during manufacturing to give
new properties to it

 Admixtures are the chemical components that are added to

concrete mixtures during the mixing process to give new
properties
 Additives Admixtures
Added to the cement Add to the concrete
Add to during manufacturing Add to before or during the mixing

The additives are: Fly Ash, Silica-Fume, GGBFS,

Metakaolin, Rice husk ash, Coffee Hush Ash
 Additives/Mineral admixture
 Additives are chemical components that will be added to the cement
during its manufacturing to get new properties for cement.

 The raw materials used in the manufacturing of cement are lime,

silica, alumina and iron oxide.

 These materials are grounded into a fine powder and are mixed
followed by roasting.

 In order to obtain desired properties, various additives are added to

cement while manufacturing.
 Definition

Silica Fume Fly Ash

 Very fine non-crystalline silica  Fly ash is a group of materials
produced in electric arc furnaces that can vary significantly in
as a by product of the production composition.
of elemental silicon or alloys  It is residue left from burning
containing silicon. coal, which is collected on an
electrostatic precipitator or in a
 Grey colored powder similar to bag house.
Portland cement or some fly ash.
 It mixes with flue gases that
result when powdered coal is
used to produce electric power.
 Fly Ash standards:
 Class ” F “ is made from burning anthracite and/or bituminous
coal
 Class “ C “" is produced from lignite or sub bituminous coal. In
Canada, there is a further distinction.
 When the lime content is 8-20 percent, it is classified Cl, and
when it is higher, it is class C.

Coal Dry, Moisture Dry, volatile Heat

Carbon content before content(%) content(MJ/Kg)
Content(%) drying(%)
Anthracite 86-92 7-10 3-14 32-33
Bituminous 76-86 8-18 14-46 23-33
Sub-Bituminous 70-76 18-38 42-53 18-23
Lignite 65-70 35-55 53-63 17-18
Peat <60 75 63-69 15
 Advantages of Fly Ash :
In Fresh Concrete In Hardened Concrete

Fly Ash particles are spherical and in the same size Good quality fly ash generally improves workability or
range as Portland cement, a reduction in the at least produces the same workability with less water.
amount of water needed for mixing and placing The reduction in water leads to improved strength.
concrete can be obtained .
In precast concrete , this can be translated into Fly Ash resisting corrosion because it reacts with
better workability , resulting in sharp and Calcium Hydroxide.(tends to passivity of anodic
distinctive corners and edges with better surface current)
appearance , it also reduce permeability which is Also, it reduces permeability that help to protect the
leading cause of premature failure . concrete from Chloride penetration.
The use of Fly Ash can result in better workability A super plastizer combined with Fly Ash can be used
, pump ability ,Cohesiveness , finish, ultimate to make high-performance and high strength
strength and durability . concrete.
The fine particles in fly ash help to reduce bleeding Concrete containing fly ash generally performs better
and segregation . than plain concrete in drying shrinkage tests.
Cost of fly ash
Fly ash typically costs approximately 1/2 to 1/3 that of Portland cement as delivered,
assuming a suitable means of batching is already in place.
 Disadvantages of Fly Ash :
 Poor-quality fly ash can have a negative effect
on concrete (increase permeability ).
 Some concrete will set slowly when fly ash is
used.
 Though this might be perceived as a
disadvantage, it can actually be a benefit by
reducing thermal stress .
 Freeze-thaw durability may not be acceptable
with the use of fly ash in concrete.
 High-carbon fly ash materials tend to use more
water and darken the concrete as well.
Silica fume
Silica Fume ( ASTM C1240 ) :

•Minimum Silicon Dioxide of 85 %.

•Maximum Moisture content to 3 % .

•Maximum loss in ignition to 6 % .

 Comparison of chemical and physical Characteristics Fly Ash, Silica
Fume and Portland cement.
Property Portland Fly Ash Fly Ash Silica
Cement Class F Class C Fume
SiO2 % 21 52 35 85 to 97

CaO % 62 5 21 <1

Fineness as 370 420 420 15,000 to

surface area , 30,000
m2/Kg

Specific gravity 3.15 2.38 2.65 2.22

General use in Primary binder Cement Cement Property

Concrete replacement replacement enhancer

 Silica Fume is typically much more reactive, particularly at early ages ,

because of its higher silicon dioxide content and because of its very
small particle size .
 50 times finer than cement
 Reaction of Silica fume in Concrete :
 It is an ultrafine powder collected as a by-product of the
silicon and ferrosilicon alloy production.

 The main field of application is as pozzolanic material for

high performance concrete

 The benefit seen from adding Silica Fume are the result of
changes to the microstructure of the concrete
Physical and chemical contribution of Silica fume
Physical Contribution :
 Adding Silica Fume brings millions and millions of very small
particles to concrete mixture.
 Just like fine aggregates fills in the spaces between coarse aggregate
particles, Silica Fume fills in the spaces between cement grains.
 This phenomenon is frequently referred to as particle packing or
micro-filling .
 Even if Silica Fume didn’t react chemically, the micro-filler effect
would bring about significant improvement in the nature of the
concrete .
 Chemical Contribution of silica fume :
 It is a very high amorphous silicon dioxide content because of that
silica fume is a very reactive Pozzolanic material in concrete.
 As the Portland Cement in concrete begins to react chemically it
releases Calcium hydroxide.
 The Silica Fume reacts with this Calcium hydroxide to form
additional binder material called Calcium Silicate hydrate , which is
very similar to the Calcium hydrate formed from the Portland cement
 It is largely this additional binder that gives silica-fume concrete its
improved hardened properties.
 Metakaolin
 Is anhydrous calcined form of the clay mineral
kaolinite.
 Minerals that are rich in kaolinite are known as china
clay or kaolin, traditionally used in the manufacture
of porcelain.
 The particle size of metakaolin is smaller than
cement particles, but not as fine as silica fume.
 Kaolin [Al2Si2O5(OH)4] calcined (heated to 770 oc), bonded water
evaporates

Al2O3.2SiO2.2H2O Al2O3.2SiO2.2(1-α)H2O + 2 α H20

Kaolinite Metakaolin

α is coefficient of dehydration

 Metakaolin = a pozzolan -a silicate-based material that consumes

calcium hydroxide (lime) to produce additional calcium silicate
hydrate, the material responsible for holding concrete together.

 Consuming lime increases the strength and density of concrete,

decreases efflorescence; virtually eliminates alkali-silica reaction.
 What is a chemical admixture?
 Any chemical additive to the concrete mixture that
enhances the properties of concrete in the fresh or
hardened state
 Does not typically include paints and protective coatings
(for steel or concrete)
 ACI defines the term admixture as "a material other than
water, aggregates, hydraulic cement, and fiber
reinforcement, used as an ingredient of concrete or mortar,
and added to the batch immediately before or during its
mixing.“
 Classification
 Water reducers
 Set-controlling chemicals
 Air entrainers
 Specialty admixtures
- Viscosity modifiers
- Corrosion inhibitors
- Shrinkage reducing admixtures
1. Water Reducers

• Normal (plasticizers)
• High-range (Super plasticizers)
 Broad classification
Water Reducers

Normal Mid-range High range

5 - 8% water reduction 8 - 15% water reduction 15 - 25% water reduction

Water reduction
 For a given workability, the water demand is reduced, thus resulting
in higher strength and durability.
 For a given w/c and strength, workability can be increased.
 For a given w/c, strength and workability, the quantity of cement
can be reduced
 The chemistry
 Water reducers belong to the ‘dispersants’ family (like the detergents
and soaps used for washing)
 Dispersants are long-chain organic molecules have polar (hydrophilic)
and non-polar (hydrophobic) groups; these get adsorbed on the
cement particles
 Cement particles are dispersed by electrostatic repulsion
 Upon hydration, electrostatic charge diminishes and flocculation
occurs
 Normal water reducers

 The dosage of normal WRs is 0.3 – 0.5 % by weight of

cement.
 At higher dosages, there is danger of excessive retardation
and bleeding.
 Also, returns diminish, and excessive air entrainment can
occur.
 High-range water reducers
 1st generation: Lignosulphonates at high dosages
 2nd generation: Polysulphonates
 - Sulphonated melamine formaldehyde (SMF)
 - Sulphonated naphthalene formaldehyde (SNF)
 3rd generation:
 - Polycarboxylates
 - Polyacrylates
 - Monovinyl alcohols
 Typical dosage: 0.7 – 1.0% by weight of cement.
Also called ‘Super plasticisers’
Action of Superplasticizers
 Surface adsorption

 Inhibition of reactive sites

 Action of Super plasticizers
Surface Adsorption
 Negative charges on surface of fine powders

 Surface adsorption increases with molecular weight

 Calcium ions promote surface adsorption

 Inhibition of Reactive Sites
 Some low molecular wt organic materials cover
reactive sites and inhibit reactions
 Examples: Starch, Glucose
 Reactive sites may be inhibited by low molecular wt
fractions
 This leads to excessive retardation
Sequence of addition of WRs
 Generally, water reducers are added along with the mix
water to the concrete mixture.
 In the case of super plasticizers, it may be
advantageous to add it to the mix in two, or even
three, operations, since the slump loss is rapid
2. Set-controlling chemicals

• Accelerators
• Retarders
 Applications
 Accelerators
- Earlier finishing of slabs
- Increase early age strength
- Early removal of formwork
- Cold-weather concreting
 Retarders
- Hot-weather concreting
- ‘Long-haul’ applications
- Workable for longer time
 Common issues with set-controllers
 Essential to pay particular attention to dosage
 Same chemical may behave as accelerator or retarder
depending on concentration
 Admixtures should be added soon after cement and water
come into contact
3. Air-entraining agents
 Improve workability
 Reduce segregation and bleeding
 Mainly – Protect against damage due to freezing and
thawing cycles
 Problem – reduced strength due to increased porosity
 The chemistry
 Air-entraining agents are also surface-active chemicals.
 Unlike the water-reducing surfactants, the hydrocarbon
chain does not have any polar groups, and is entirely
hydrophobic.
 Mode of action
 Air bubbles are generated during the agitation and mixing of the
concrete.
 The air-entraining agents simply help to stabilize these bubbles by
altering the surface tension of water.
 Some common chemicals used as air entrainers are fatty acids,
synthetics like dodecyl benzene sulfonate etc.
 Air entrainers are added to the concrete mixture either early in the
process with the sand and coarse aggregate or after the cement has
been added along with some of the mix water.
 Air entraining chemicals should never be mixed with any other
chemical additives.
Small and stable air bubbles required
Air void parameters – total entrained
air, and distance between voids (not
more than 200 micron)
 4. Specialty admixtures
Viscosity modifying agents (VMAs)
Applications
 To provide stability to extremely flowable concrete
(which maybe prone to segregation)
 To prevent the wash-out of concrete in underwater
applications
 In this case the VMA is also called ‘Anti-washout
admixture’
 VMA – Mechanism of action
 Adsorption: Long-chain polymer molecules adhere to the
periphery of water molecules, thus adsorbing and fixing
part of the mix water and thereby expanding; this causes
an increase in the viscosity.
 Association: Molecules in adjacent polymer chains develop
attractive forces, thus further blocking the motion of water
by forming a viscous gel.
 The dosage of VMA is generally 0.03 – 0.08% by weight of
cement.
 Shrinkage reducing admixtures
 SRM contain chemicals such as polyoxyalkylene that reduce
the surface tension of water in the capillaries, thus reducing the
tensile stresses on drying.

 These admixtures are typically used at a high dosage – about 2

– 4% by weight of cement.
 Corrosion inhibitors

Also, specialty admixtures

Process of corrosion
 Use of corrosion inhibitors
 Mechanisms of action
· Oxidizing or non-oxidizing passivators of steel
· Oxygen scavengers
· Film forming compounds (adsorption)
· Cathodic effects: paste can be made hydrophobic
Some typical corrosion inhibitors are:
 Inorganic: Calcium nitrite

 Organic: Amines, esters

 These compounds are usually added at high dosages, ~ 2% by weight of cement

 very expensive!!!
 The amines coat the steel and provide a film on the steel surface, while the esters
make the paste hydrophobic and reduce the availability of water for the cathodic
reaction.
 Cost of chemical admixtures
 Use of admixtures generally tends to drive up the cost
 Air entrainers are typically cheap, so are conventional
water reducers;
 but SPs, especially the new generation, can increase
costs substantially