Module 2 Chemical Admixtures

Admixtures in Concrete What is an admixture?

“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”.
NAJEEB M
Assistant Professor,
MEA Engineering College ,
Perinthalmann.

Courtesy: Dr. Elson John (M A College of Engineering, Kothamangalam) 1 3

Challenges in concrete
technology Admixture
• We need high quality concrete
• High quality  High strength & High Chemical Admixtures Mineral Admixtures
performance
• We can achieve this by using alternative and/or
unconventional materials
• However, there are serious compatibility issues
between various components within the
concrete

High quality concrete essentially contains

admixtures

4
2

Dept. of Civil Engineering, MEAEC 1

Module 2 Chemical Admixtures

Admixtures: Significance Chemical Admixtures: Significance

• Water-soluble materials that are added to concrete,
at dosages of less than 5% of the cement weight,
are generically called chemical admixtures.
• Chemical admixtures are now common and, in
many cases, essential components of high-quality
concrete.
• About 90-95% of the concrete produced in several
countries incorporates some type of admixture.
• Admixtures have led to the development of several
high performance concretes; e.g., High-Strength
5 Concrete and Self-Compacting Concrete. 7
Aïtcin

Correct Use of Admixtures

• It is important to know the effect of the

admixture on concrete properties, both those
for which it has been designed and those in
which it can interfere, as well its secondary
Chemical admixtures effects.

• Know the specifications and recommendations

of the supplier.

6 8

Dept. of Civil Engineering, MEAEC 2

Module 2
Factors that Affect the Action of the
Chemical Admixture
• Dosage and addition procedures
• Characteristics of the cement and
aggregates
• Environmental conditions (temperature)
The dosage of the admixtures
should be prescribed and
controlled rigorously. 9 11
Admixture Selection by Application
• Chemical resistant concrete
• Concrete should have low permeability, well
compacted and good quality top layer (dense, free
from bleed water).
• Plasticizer/water reducer will help limit w/c
• Water-resisting admixture with hydrophobic properties
may help liquid penetration at the surface
• Cold weather concreting
• Low temperatures cause slow setting, loss of moisture
and delayed strength gain.
• Accelerating admixtures counter these effects.
10
Dept. of Civil Engineering, MEAEC
Chemical Admixtures
Admixture Selection by Application
• Coloured concrete
• Pigments are added to concrete to change its colour.
They are usually fine powders that have to be
dispersed properly.
• Plasticizing admixtures help the dispersion.
• Efflorescence is more noticeable in coloured concrete.
So, permeability-reducing admixtures help.
• Congested reinforcement
• Difficult to ensure compactness of concrete
• Superplasticizers increase the workability and flow.
• Consequent reduction of w/c provides a denser cover.
Admixture Selection by Application
• Early removal of formwork
• Rapid strength gain is needed.
• Superplasticizers can be used to decrease w/c leading
to higher early strength.
• Accelerators may be necessary, especially in colder
climates.
• Fibre reinforced concrete
• The incorporation of fibres reduces workability.
• Superplasticizers help recover the workability.
12
3
Module 2
Admixture Selection by Application
• Flooring concrete
• Concrete floors require mix to be easy to place, not
bleed, predictable setting and minimal shrinkage.
• Plasticizers should be non-retarding.
• Accelerators may be necessary, especially in colder
climates.
• Shrinkage reducing admixtures are expensive but
helpful.
• High strength concrete
• Superplasticizers essential to overcome cohesiveness
due to low w/c and high binder content.
13
Admixture Selection by Application
• Hot-weather concreting
• High temperatures lead to rapid workability loss and
quick setting.
• Retarding and plasticizing admixtures help.
• Marine concrete
• Superplasticizers essential to limit permeability.
• Corrosion inhibiting admixtures increase the corrosion
threshold of the steel.
• Abrasion resistance can be increased by using higher
strength superplasticized concrete.
14
Dept. of Civil Engineering, MEAEC
Chemical Admixtures
Admixture Selection by Application
• Pumped concrete
• Plasticizing admixtures can reduce pump pressures in
concretes with high cement content.
• Pumping aids increase the cohesion in the concrete
and prevent segregation.
• Slipformed concrete
• Needs continuous filling of formwork that is moved at a
consistent rate.
• Vertically slipforming needs concrete with high
strength, which can be achieved with superplasticizers.
Retarders may be needed to avoid cold joints.
• Horizontal slipforming is fast; the concrete is only a few
minutes old when it emerges from the form. Should
have cohesiveness and rapid strength gain. 15
Admixture Selection by Application
• Shotcrete
• Plasticizing admixtures are used to get high strength
and flow.
• Set-accelerating admixture is added at the nozzle to so
that the concrete sets rapidly as it hits the substrate.
• Architectural concrete
• Needs good surface finish. So concrete should be
cohesive, dense, easy to compact and not bleed.
• Concrete needs to have high early strength so that it is
not damaged during formwork removal.
16
4
Module 2 Chemical Admixtures

Types of Chemical Admixtures Types of Chemical Admixtures

• Admixtures that mainly affect the fresh state Special purpose admixtures:
• Water-reducing agents • Shrinkage-reducing admixtures
• Superplasticizers
• Alkali-aggregate expansion-reducing admixtures
Reduce the amount of water needed for increasing
the workability or yield higher workability without • Corrosion inhibitors
any change in the water content. • Viscosity-modifying, Antiwashout or Pumping-aid
admixtures
• Admixtures that mainly affect the setting stage • Surface retarders
• Set-accelerators • Fungicides
• Set-retarders • Damp-proofers or water-repellents
Reduce/increase the initial rate of reaction
between cement and water. This causes a • Multi-functional admixtures
reduction/increase in the time taken by mortars
and concrete to pass from the plastic to solid state.
17 19

Types of Chemical Admixtures Admixtures in Use

• Admixtures that mainly affect the hardening state
• Hardening accelerators
Accelerate the development of early strength.
• Admixtures that mainly affect the hardened state
• Air-entraining agents
Cause the formation of uniformly distributed
microscopic bubbles of air in the concrete or mortar.
These bubbles remain after hardening and lead to
higher freeze-thaw resistance.
18
• Admixtures should comply with National
Standards
• Dosage and type of admixture should conform
with design specifications and codes
• Admixtures dispensers should be
• Accurate, calibrated
• Ensure complete dosage is delivered to concrete
• Time of addition should be fixed (never added to
dry material)
• Redosing should be supervised
• Health, safety and environmental aspects
should be considered 20

Dept. of Civil Engineering, MEAEC 5

Module 2 Chemical Admixtures

Ligosulfonates

• Lignin makes up 20% of the composition of wood.

WATER-REDUCERS OR • During paper-making, products of lignin are
PLASTICIZERS obtained as by-products.

• After processing, lignosulfonates are produced.

Mechanisms of action
• Commercial lignosulfonates used in admixtures
and effects are mainly calcium or sodium based with sugar
contents of 1-30%.

21 23

Water Reducers Ligosulfonates

• Admixture that reduces the water content of a • Lignosulfonates incorporate air into the concrete.
mortar or concrete for a given workability. Usually
has a secondary effect of retarding the setting of • The lignosulfonate molecule and the sugars
the concrete. present have a retarding effect on the hydration of
cement.
• Mainly based on pure or modified lignosulfonic
acids and their salts, hydroxycarboxylic acid and • Secondary materials are added to the
hydroxylated polymers. lignosulfonates to decrease/increase air
entrainment, to compensate retardation and to
• Lignosulfonates have been used since the 1930s accelerate setting.
in concrete.

22 24

Dept. of Civil Engineering, MEAEC 6

Module 2 Chemical Admixtures

Effect of Water-Reducing Admixtures

• When the admixture is added to the concrete mix,
a part of it is adsorbed by the cement and the
hydration products, with the initial hydration
products having the higher adsorption capacity. SUPERPLASTICIZERS
• There is a modification of the normal process of
ettringite formation and a delay in the C3S Mechanisms of action,
hydration.
dosage and use
• The final hydration products are not significantly
affected by the presence of the admixture.
However, the morphologies of the C-S-H gel and
Ca(OH)2 are sometimes modified.
25 27

Effect of Water-Reducing Admixtures History of Superplasticizers

• Workability increases with the incorporation of the
water-reducing admixture.
• Reduction in w/c depends on the slump value; the
w/c reduction can be 5-8% at slump of 50 mm
and 12-15% at slump of 150 mm. Effectiveness
decreases with an increase in the C3A or alkali
content.
• Initial setting time of cement can be extended by
several hours, depending on the dosage.
• 1930: Use of a napthalene for dispersing
coloring agent in concrete (USA).
• 1960s: Naphthalene/Melamine based
superplasticizers introduced:
• To reduce the w/c - Japan (Hattori):
ß-naphthalene sulphonate
• To improve workability without increasing the w/c
- Germany (Einesburger): melamine sulphonate

• Drying shrinkage and creep seem to increase with • Present: Synthesis of new and more efficient
water-reducing admixture addition. copolymer formulations.
26 28

Dept. of Civil Engineering, MEAEC 7

Module 2 Chemical Admixtures

Usage of Superplasticizers Consequences of Superplasticizer Usage

Constant w/c: Increase Constant workability: • Reduces placing and compaction time, leading
in the workability Lower w/c
to lower construction costs.

• Facilitates the casting of elements with

complex shapes and dense reinforcement.
same workability
No MLS SMF SC
admixture

LOWER WATER CONTENT

• Improves the surface finish of the concrete
elements.

• Leads to superior strength and durability with

Lower w/c
29 lower cement contents. 31

Superplasticizer Action Consequence of Superplasticizer Action

Decrease in the entrapped air and water contents of the
Flocculation in the absence
Effect of the superplasticizer fresh paste leads to lower porosity and crystallinity of the
of superplasticizer
hydrated cement paste
Water Cement
Water Cement particle
particle

Unhydrated
cement grains

Entrapped Water
water

Aïtcin w/c = 0.65 w/c = 0.25

30 32

Dept. of Civil Engineering, MEAEC 8

Module 2 Chemical Admixtures

Applications where a
Mechanisms of Action
Superplasticizer is Essential
Types of interaction between cement
• Fluid/Flowing/Pumpable concrete particles and the superplasticizer
• Shotcrete
• Self-compacting concrete PHYSICAL CHEMICAL
Adsorption and Chemisorption,
• High-strength concrete generation of formation of
• High-durability concrete repulsive forces admixture-Ca2+
between cement complexes and
• Concrete with low shrinkage and creep particles interaction with the
hydration reactions
33 35

Chemical Formulation MECHANISMS: Physical Interactions

Surfactants soluble in water, with different 1. FORMATION OF AN ADSORBED LAYER ON

functional groups: THE CEMENT PARTICLES.
• Modified Lignosulphonates (MLS)
• Salts of naphthalene sulphonate and
formaldehyde condensates (SNF) 2. GENERATION OF REPULSIVE FORCES
• Sulphonate (SO3-) • Salts of melamine sulphonate and BETWEEN CEMENT PARTICLES:
formaldehyde condensates (SMF)
DEFLOCCULATION. - - - - - -
- -
• Comb-type polymers - -
• Electrostatic Repulsion -
- -
- - - - -
(SNF & SMF)
• Carboxylate (COO-),
• Hydroxide (OH-) or • Steric hindrance due to the
• Phosphonate (PO3-) Hydrophobic group lateral chains of the
Hydrophilic group 34 comb-type polymers 36

Dept. of Civil Engineering, MEAEC 9

Module 2 Chemical Admixtures

MECHANISMS: Chemical Interactions

 Chemisorption
 Change in chemical composition as a function of
the thickness of the adsorbed layer.
SET-RETARDERS
 Formation of complexes between the
superplasticizer and calcium ions
 Reduces the concentration of Ca2+ in the aqueous
solution, retarding the setting of cement.

 Interaction with the chemical reaction sites

 Blocks reactive sites, inhibiting the chemical
reactions between the cement and water. 37 39

Factors that Affect the Saturation Point Effect of Set-Retarding Admixtures

• When a retarder is added to cement-water
• Type of superplasticizer system, physical adsorption and chemical
reactions generally occur with the C3A and C3S.
• Type of cement The result is the retardation of setting of the
• Water/cement ratio cement and hardening of the concrete.

• Presence of mineral admixtures • The initial and final setting times are increased.
• Mixing sequence
• Temperature • Workability is maintained longer.

• Heat of hydration and temperature rise of

38
concretes are lesser at early ages. 40

Dept. of Civil Engineering, MEAEC 10

Module 2 Chemical Admixtures

Effect of Set-Retarding Admixtures

• When there is plasticizing effect in addition to

retardation, strength increases as water content is SET-ACCELERATORS
consequently reduced.
&
• Set retardation generally leads to slower HARDENING-ACCELERATORS
formation of more ordered, smaller and denser
hydration products. This results in higher long-
term strength.

• Due to the extended plastic stage, the concrete

should be protected against shrinkage and cured
longer.
41 43

Application of Set-Retarding Admixtures Types of Accelerators

• Primary application is in hot-weather concreting. • Chloride-based

• Calcium chloride (CaCl2) is the most common
• Used in mass concrete to permit the control of the accelerator. Has been used since 1885.
temperature rise of the concrete, reducing the
possibility of thermal cracking.
• Non-chloride accelerators
• For maintenance of slump during long transportation • Calcium formate, triethanolamine, calcium nitrate, etc.
periods and placing duration.

• To avoid partial hardening during the casting of large

elements (ensures bond with reinforcement,
decreases cracking due to self-weight).

42 44

Dept. of Civil Engineering, MEAEC 11

Module 2 Chemical Admixtures

Effect of Accelerators Drawbacks of Calcium Chloride

• The rates of hydration of C3A and/or C3S are generally
increased.
• Calcium chloride decreases the dormant period of C3S,
accelerates the hydration of C2S, and the reaction
between C3A and gypsum. It may also combine with C3A
and gypsum.
• Calcium formate increases the hydration rate of C3S.
However, it is not as effective as calcium chloride.
• Triethanolamine accelerates the hydration of C3A, and
retards the hydration of C3S and C2S.
• Higher early strength results from the increased amount of
hydration products.
45
Based Accelerators
• Tend to increase the corrosion of the
reinforcement, especially at dosages higher
than 1.5%.
• May reduce the long-term strength
• May reduce the resistance against sulphate
attack and increase alkali-aggregate reactivity
• May increase the creep and drying shrinkage
• Can cause stains on the concrete surface due
to efflorescence
47

Application of Accelerators

• Primary application is in cold-weather concreting.

• For improving the bonding of shotcrete to the base or
previously-placed layers.

• Used for obtaining higher early-age strengths. AIR ENTRAINING AGENTS

46 48

Dept. of Civil Engineering, MEAEC 12

Module 2 Chemical Admixtures

Freezing and Thawing of Concrete Effect of Air Entraining Admixtures

• When the temperature of concrete drops to below 0°C, the
water does not all freeze immediately. • The entrained air increases workability and
decreases segregation.
• Water in smaller pores will need a lower temperature to
freeze (e.g., water in 10 nm pores will not freeze until -
5°C, and pores of 3.5 nm will not freeze until - 20°C; gel
• Results in fine uniformly-distributed voids in the
water will not freeze until -78°C). hardened concrete.

• As the water freezes, it dilates and compresses the
remaining water. The pressure is relieved if the water
diffuses to open voids. If no voids are available near
enough, the pressure may build up and cause rupture.
• In air-entrained concrete, the bubbles relieve the pressure
and prevent damage from occurring. Instead of dilation,
49
there is contraction on freezing.
• If there are enough small voids, then the concrete
is protected from freeze-thaw damage. The
spacing factor should be less than 0.2 mm. The
air volume for optimum protection is about 9% of
the mortar.
51

Freezing and Thawing of Concrete

Effect of Air Entraining Admixtures

A surfactant used to produce air bubbles and disperse

them throughout the cement paste.

Air entraining surfactant

50 52
Mehta and Monteiro Mehta and Monteiro

Dept. of Civil Engineering, MEAEC 13

Module 2 Chemical Admixtures

Effect of Air Entraining Admixtures Applications of Air Entraining Agents

Durability and Strength • Protection against the damage produced in
Effect of spacing factor Effect of air content the concrete by freeze-thaw.

• Reduction of bleeding and improvement of

the uniformity of the concrete, as well as
the workability and consistency.

• Lowering the density of concrete.

Strength decreases by about 5% for

every 1% of additional entrained air
53 55
Mindess & Young

Effect of Air Entraining Admixtures

The quantity of air incorporated not only

depends on the type and dosage of the DAMP-PROOFERS
admixture but also on several other factors:
• Composition and fineness of the cement
• Type and proportions of the aggregates WATER-REPELLING
• Temperature ADMIXTURES
• Mixing and compaction processes
• Interaction with other admixtures

54 56

Dept. of Civil Engineering, MEAEC 14

Module 2 Chemical Admixtures

Effect of the Dampproofer Benefits of Using a Dampproofer

Makes the concrete surface less wettable or • Prevents rain water from entering the concrete surface
water-repellent. and capillary absorption. Thereby, increases the durability.

High contact angle between water Low capillary rise with • Improves the performance of concrete pavers, tiles,
and dampproofed concrete dampproofing bricks, blocks and cladding panels.

• Are being combined with corrosion inhibitors to get dual

benefits from lower chloride ingress and corrosion
protection.

• Aesthetic benefits due to cleaner surface and less

efflorescence.

57 59
Rixom and Mailvaganam Rixom and Mailvaganam

Action of the Damp-proofer

• Provides a thin hydrophobic layer within the pores and
voids, and on the surface of the concrete by:
– Reaction with the cement hydration products,
– Coalescence from emulsion form, or
CORROSION-INHIBITING
– Incorporation in a very finely divided form.

• Those that react with the hydration products are based on

ADMIXTURES
liquid fatty acids, such as stearic acid and butyl stearate.
• Those that coalesce on contact with the hydration
products are fine wax emulsions.
• Those that are fine hydrophobic materials are based on
calcium and aluminium stearates.

58 60
Rixom and Mailvaganam

Dept. of Civil Engineering, MEAEC 15

Module 2 Chemical Admixtures

Action of the Corrosion Inhibitor

• Provides a second line of defence to prevent the corrosion
of the steel reinforcement in concrete, augmenting the VISCOSITY-ENHANCING
protection provided by the alkaline nature of the concrete.
AGENTS
• The most common corrosion inhibitors are nitrite-based
compounds (e.g., calcium nitrite). They act by interfering
with the corrosion reaction through the formation of a
protective ferric oxide layer on the steel and/or reducing
VISCOSITY-MODIFYING
access to the steel (less chemisorption and dissolution). AGENTS

61 63
Rixom and Mailvaganam

Action of the Corrosion Inhibitor Action of the Viscosity Modifying Agent

Results of a 4-year study with different concretes
demonstrate that calcium nitrite delays the onset of
corrosion and lowers the rate. The corrosion resistance is
better at lower w/c.
• Induces cohesion but does not inhibit the flow significantly.
Its flow behavior is pseudoplastic (i.e., has a decreasing
viscosity with higher shear rate).
• The cohesion increases due to:
– The increase in the viscosity of water (water-soluble
organic polymers such as Welan gum, starch,
cellulose ethers and polyacrylamide), or
– Higher interparticle attraction after the admixture is
adsorbed on the cement particles (organic water-
soluble flocculants such as styrene copolymers)

62 64
Rixom and Mailvaganam Rixom and Mailvaganam

Dept. of Civil Engineering, MEAEC 16

Module 2 Chemical Admixtures

Action of the Viscosity Modifying Agent Underwater Concreting

Critical Aspects
Underwater test • Area to be concreted should be cleared of mud, silt,
marine growth and debris.
• If the concrete is being used to repair an existing
structure, anchors should be provided in the old concrete
to bond it to the new concrete.
• The concrete should be protected such that the fines are
not washed away. This can be achieved by using tremies
and pumps, and employing a concrete with high
cohesiveness.
• Normally a higher fines content and a viscosity modifying
admixture is used in underwater concrete.
65 67
Nagataki

Applications of Viscosity-Modifying Agents

 Underwater concrete
 Facilitates sufficient mobility of the concrete
under water with little loss of cement. COLD WEATHER
 Self-compacting concrete ADMIXTURE SYSTEMS
 Leads to high flowability with no segregation.
 Grouting
 Eliminates the migration of water from the
grout due to the differential pressure.
 Helps maintain the cement particles in
suspension once injection ceases.
66 68

Dept. of Civil Engineering, MEAEC 17

Module 2 Chemical Admixtures

Action of Cold Weather Admixture Shrinkage Mechanisms

Systems (CWAS)
• CWAS can be developed from existing admixtures for
concretes to be placed at temperatures down to -5 ºC.
They help protect the concrete against freezing and
maintain productivity.
• Generally, setting time doubles for each 10 ºC drop in
temperature. However, the CWAS should not allow the set
retardation to occur. Also, the water in the concrete should
not be allowed to freeze.
• CWAS can consist of accelerating admixtures, corrosion
inhibitors and water-reducing admixtures. The
accelerating admixtures and corrosion inhibitors tend to
depress the freezing point of the concrete.
69
C.J. Korhonen & A.A. Jeknavorian, Concr. Intnl., V. 27, No. 11, 2005, pp. 38-43
• Plastic shrinkage: Due to the loss of water in the
plastic state due to evaporation.
• Autogenous shrinkage: Chemical shrinkage (lower
volume of hydrates than cement and water) + Self-
desiccation (reduction in the pore water due to
hydration).
• Thermal contraction (or thermal shrinkage): Due to the
decrease in temperature after setting.
• Drying shrinkage: Due to the loss of water to the
environment in the hardened state.
• Carbonation shrinkage: Volume reduction due to the
reaction of hydrated cement paste with CO2 in the
71
presence of moisture.

Shrinkage
Drying

SHRINKAGE-REDUCING Autogenous

ADMIXTURES
Thermal
(contraction)

Plastic
Carbonation

Time
70 72
hours days weeks months years

Dept. of Civil Engineering, MEAEC 18

Module 2 Chemical Admixtures

Ways of Reducing Shrinkage Plastic shrinkage

Occurs in the fresh concrete, principally due to
• Reduction of the water content (by using high evaporation rates.
superplasticizers).
Factors:
• Reduction of the cement content (by optimizing - Environment (temperature, humidity and wind
the paste volume, using complementary velocity)
materials). - Concrete composition
- Boundary conditions (geometry and
• Utilization of special cements and expansive restraints)
agents.

• Utilization of shrinkage-reducing admixtures.

73 75

Shrinkage Reducing Admixture (SRA) Plastic Shrinkage Cracking

First used in Japan, in the 1980s.
It acts by reducing the surface tension of the  When the bleed water does not compensate the water
evaporable water in the pores. loss due to evaporation, shrinkage occurs.
Leads to lower capillary stresses during drying.
Cement particle
 When plastic shrinkage is restrained, surface cracking
occurs.

 Elements and structures with high surface/volume

ratios, such as pavements, tunnel linings and bridge
decks, are prone to cracking.

Water

74 76

Dept. of Civil Engineering, MEAEC 19

Module 2 Chemical Admixtures

Why Use Admixtures in Concrete ?

• To satisfy the growing demands of the

society and the construction sector.

• To provide better stability under certain

environmental conditions.

• To increase the productivity/efficiency during

fabrication, transport and placing.

The capacity of traditional materials to satisfy

these demands is limited. 77

References
• Application of Admixtures in Concrete, Ed.
A.M. Paillere, E&FN Spon, London, 1995
• High-Performance Concrete, P.-C. Aïtcin, E&FN
Spon, London, 1998
• Chemical Admixtures for Concrete, R. Rixom and
N. Mailvaganam, E&FN Spon, London, 1999
• Concrete: Microstructure, properties and
materials, P.K. Mehta and P.J.M. Monteiro, Indian
Concrete Institute, Chennai, 1999
• Concrete, S. Mindess and J.F. Young, Prentice-
Hall, USA, 1981
• A Guide to the Selection of Admixtures for
Concrete, Technical Report No. 18, The Concrete
Society, UK, 2002
78

Dept. of Civil Engineering, MEAEC 20