Chemical Admixtures

Sections 8.1, 8.2, 8.3 and 8.4 in

textbook
 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”.
 Historical development
• Romans – added blood or eggs to lime mortars for improved workability
• De Honnecourt in 1230 (Garrison, 1991) suggested impregnation of lime
concrete with linseed oil to make it impervious!
• Calcium chloride – 1873 in Germany
• Before WWII, Air entraining agents in USA (found accidentally!) –
polynaphthalene sulphonates used to disperse carbon black in concrete – led
to air entrainment and superior long term performance!
• 1950s/60s – high rise developments in Chicago saw the development of
water reducers; 1962 – ASTM C494 first released
• 1979 – First use of corrosion inhibitor; 1996 – SRA used
• Late 1980s – Advent of flowable concretes such as SCC paved the way for
development of new generation HRWRs
Mielenz 1984 paper
 Classification
• Water reducers
• Set-controlling chemicals Common characteristics of chemical
• Air entrainers admixtures:
• Specialty admixtures 1. Water soluble
- Viscosity modifiers 2. (Mostly) Organic
- Corrosion inhibitors Helpful to understand polymer
- Shrinkage reducing admixtures structure
- SBR latexes
- Others
• Specialty coatings including curing compounds (technically not
chemical admixtures!)
Polymer structures
 Water Reducers
•Normal (plasticizers)
•High-range (Superplasticizers)
 Broad classification
Water Reducers

Normal Mid-range High range

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

Up to 40% possible!
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
Effect of water reducers
 Normal water reducers
Lignosulphonate 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
- 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 ‘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 oleum 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
 Lignosulphonates
Product of bisulphite pulping of wood

Native lignin is water insoluble, but

introduction of sulphonic groups on
aliphatic chains makes it water soluble
Aitcin and Flatt, 2016
(sulphonation)

Avg MW 20000 – 30000 Na-LS more soluble than Ca-LS  better

dispersion; but more expensive
Can contain significant quantities of sugar,
causing retardation; but LS can be
retarding on its own also
 Polynaphthalene sulphonates
Also called Sulphonated Naphthalene
Formaldehyde Condensate (SNF)

α-substitution occurs at < 100 oC

Β more stable at > 150 oC
Rixom and Mailvaganam, 2003
Polycondensation with formaldehyde,
and neutralization with NaOH

Variable degree of polymerization

Basic naphthalene sulphonate molecule exhibited by different fractions of
Aitcin and Flatt, 2016
molecules; too small or too large
polymers not effective
 Polymelamine sulphonates

Aitcin and Flatt, 2016

Also called Sulphonated Melamine Formaldehyde Condensates (SMF)

Formaldehyde + Amino group of melamine under alkaline conditions,

followed by sulphonation, polycondensation, and neutralization

Some free formaldehyde may remain – could be hazardous

 Vinyl copolymers
Produced by radical copolymerisation 
large number of monomers are
compatible with this type of reaction
(sulphonate, carboxylate, phosphonate,
anionic functional groups, ether, amide
etc.) leading to multifunctionality

Principal precursor to polycarboxylate

ethers (PCE)
Aitcin and Flatt, 2016
 Comb shaped copolymers – including PCE
Main chain bearing carboxylic groups
(backbone is negatively charged – causes
surface adsorption)
Non-ionic side chains made of polyethers are
attached to main chain
Broad range of molecular structures possible,
Aitcin and Flatt, 2016 with multifunctionality

Produced by free radical copolymerisation of

monomer bearing carboxyl group and a
monomer bearing the side chain
Rixom and Mailvaganam, 2003
Paper by Marchon et al.
Dispersion effect
 References
• Science and Technology of Chemical Admixtures,
P C Aitcin and R J Flatt, Eds, Woodhead
Publishing, UK, 2016
• https://precast.org/2014/01/chemical-admixtures-
concrete-whats-next/
• Rixom R. and Mailvaganam N., Chemical
Admixtures for Concrete, 2003