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 116R 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
-SBR latexes
-Others
Water Reducers

•Normal (plasticizers)
•High-range (Superplasticizers)
 Broad classification

Water
Reducers

Normal High range

Mid-range
5-8% water 8-15 % water 15-25% water
reduction reduction 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
Basic Chemistry

Water reducers belong to the ‘dispersants’ family.

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

Ligno sulphonate salts (Sodium salts of sulphonated lignin)

Hydroxycarboxylic acids –Citric, gluconic acid

Carbohydrates –Corn syrup, dextrin

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
-Sulphonatedmelamine formaldehyde (SMF)
-Sulphonated naphthalene formaldehyde (SNF)

3rd generation:- Polycarboxylates-Polyacrylates-

Monovinylalcohols

Typical dosage: 0.7 –1.0% by weight of cement. Also

called ‘Superplasticisers’
 Water-reducing polymers

Lignosulphonates-derived from neutralization, precipitation,

and fermentation processes of the waste liquor obtained
during production of paper-making pulp from wood

• Poly-naphthalene formaldehyde condensates -produced

from naphthalene by oleumn or SO3 sulphonation;
subsequent reaction with formaldehyde leads to
polymerization and the sulphonic acid is neutralized with
sodium hydroxide or lime

•Sulphonated melamine formaldehyde condensates -

Manufactured by normal resinification of melamine -
formaldehyde

•Poly-carboxylates-free radical mechanism using peroxide

initiators is used for polymerization process in these systems.
 2 primary mechanisms of action

Lowering of Zeta Potential (leading to electrostatic

repulsion) Substances with functional groups-

-Lignosulfonates
-Sulfonated condensate of naphthalene formaldehyde
-Sulfonated condensate of melamine formaldehyde
-Sugar refined lignosulfonates
Steric hindrance
Polymers with backbone and graft chains

- Polycarboxylate ester
- Carboxylic acrylic acid with acrylic ester
- Cross linked acrylic polymer
 Types and properties of plasticizers

a) Unrefined lignosulfonates
b) Melamine formaldehyde
c) Naphthalene formaldehyde
d) Polycarboxylate esters and acrylic copolymers
 Unrefined Lignosulfonates

Wide variation in properties

Large molecular weight
Sugar content causes retardation
May entrain air
Inconsistent performance
 Melamine Formaldehyde

• No slump retention
• Suitable for cold weather
• Suitable for precast concrete
• Unsuitable for ready mix concrete (long hauls)
• Unfavorable costs
• Not widely used in India
 Naphthalene Formaldehyde

Good slump retention

Can be blended with lignosulfonate
Suitable for hot tropical climates
Favourable cost

Downside:
Not compatible with PC admixtures
Problems in concretes with low w/c ratios
 Superplasticizers based on
graft chain copolymers

•Works in low w/c ratio systems

•Good slump retention
•No compatibility problems
•Dilution with modified lignosulfonate is possible
•Cannot be diluted with naphthalene formaldehyde
•Limited experience
•Expensive
 Modified Lignosulfonates

Sugars removed by fermentation

Low molecular wt matter removed by ultra-

centrifuging (less entrained air)

Modified lignosulfonates used as superplasticers

Suitable for blending with SNF and PCE admixtures

 Relative Costs

Type Cost of dry Cost of

Concentration
polymer Solution

Acrylic Polymer 100 30% 30

Melamine 80 40% 32

Naphthalene 40 40% 16

Modified Ligno 20 40% 8

 Comparison of plasticizers
Unrefined ligno: Inconsistent performance, large
doses not possible

Melamine formaldehyde: Not suitable for tropics,

expensive

Naphthalene formaldehyde: Suitable for tropics,

cost effective

Acrylic copolymers: Suitable for tropics, low w/c

systems, expensive

Modified ligno: Suitable as superplasticizers

 Range of action
The 1st generation HRWRs need a slump of around 75 mm
for action (~0.45 w/c). The slump is increased up to 150 –
200 mm.

The 2nd generation admixtures can work at reasonably low

slumps (25 –50 mm, corresponding to w/c of 0.35 –0.40) to
increase the slump to ~ 250 mm.

The 3rdgeneration HRWRs, on the other hand, can even be

used with no slump concrete (0.29 –0.31 w/c), and the
slump is increased to more than 250 mm.

Concrete possessing slump above 225 –250 mm is called

‘rheoplastic’.
 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, since the slump

loss is rapid, it may be advantageous to add it to the
mix in two, or even three, operations.
 Set-controlling chemicals

•Accelerators
•Retarders
• Accelerators
- Earlier finishing of slabs
- Increase early age strength
- Early removal of forms
-Cold-weather concreting

• Retarders

- Hot-weather concreting
-‘Long-haul’ applications
- Workable for longer time
 Basic admixture chemistry

Set-controllers are organic or inorganic chemicals

that interfere with the hydration process of the
cement

•The rate of dissolution of cement compounds, that is

necessary for hydration to occur, is either speeded
up or slowed, depending on the chemical
 Accelerating chemicals

Organic
Non-Chloride
Accelerators Inorganic
Chloride
Chloride accelerators: CaCl2, NaCl

Non-chloride accelerators

Inorganic: Nitrates and nitrites of Ca and Na,

thiocyanates, thiosulphates, and carbonates of Ca
and Na.

Organic: Amines (triethanolamine –TEA,

diethanolamine –DEA), carboxylic acids (Ca salts of
formic and acetic acid), formaldehyde.
 Retarding chemicals

Retarders

Extended
Organic Inorganic
Set
Organic retarders: Lignosulphonates,
hydroxycarboxylicacids (citric, gluconic), carbohydrates
(corn syrup, dextrin). These are the same chemicals as
normal water reducers.

Inorganic retarders: Borates, phosphates, Zn and Cu

compounds. These are not generally used because of their
high costs and low solubility.

Extended set admixtures: Phosphonates and other

phosphorus containing organic acids and salts, gluconic
acid, etc. These admixtures are used for the following
purposes:
 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
 Air-entraining agents

Applications
• Protect against damage due to freezing and
thawing cycles

•Side effects:
1.Improve workability
2.Reduce segregation and bleeding
3.Reduce strength due to increased porosity
 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 neutralized

vinsol resin, derivatized pine rosin, and fatty acids (palmitic and
stearic acid), and synthetics like dodecyl benzene sulfonate.

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.
 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’
 Some VMAs

Biopolymers and synthetics:

• Xanthan gum
• Diutan gum
• Alginates
• Hydroxy propyl methyl cellulose
• Hydroxy propyl starch

Used as thickeners in fluid concretes

 VMA –Mechanism of action

VMAs are long-chain water soluble polysaccharides (Cellulose ether

derivatives and microbial source polysaccharides, such as Welan gum)
that enhance the water retention capacity of the paste.

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.

Intertwining: At low shear rates, polymer chains intertwine and entangle,

causing an increase in the viscosity

The dosage of VMA is generally 0.03 –0.08% by weight of cement.

 Shrinkage reducing admixtures

•Shrinkage reducing admixtures contain chemicals such

as polyoxyalkylene alkyl ether 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
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, alkanolamines

These compounds are usually added at high dosages, ~ 2% by

weight of cement and hence very expensive!!!

Some commercially available admixtures are two-part products,

such as those containing amines and esters. 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.
 Styrene-butadiene latexes

Combination of styrene and butadiene

• Solids content of latex ~ 40 –50%

• Polymer film forms along with the hydrating

cement, resulting in a monolithic matrix

• Causes improved paste-aggregate bond,

resistance to crack propagation, and water
tightness of concrete
 Other specialty admixtures
Antifreeze compounds: These lower the freezing point of
water. For example, NH4OH, calcium and sodium nitrates
and nitrites, CaCl2, K2CO3, glycols, etc.

Waterproofing admixtures: These are organic compounds

that adsorb on the pore walls and make them hydrophobic.
Thus, once the concrete becomes dry, it is difficult to re-wet
it. For example, oleic acid, emulsions of waxy materials, Ca
and Al stearate.

Alkali-silica reaction mitigating admixtures: Compounds of

active alkalis such as Lithium (e.g. Li OH, Li2NO3, etc.),
which bind the reactive silica to form non-expansive
compounds. The cost of these admixtures, however, is
prohibitive.