Chemical Admixtures

Prof. Ravindra Gettu

IIT Madras

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
Concrete and Self-Compacting Concrete.

1
 Chemical Admixtures: Significance

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
effects.

• Know the specifications and recommendations

of the supplier.

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.

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.

3
 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.

4
 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.

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.

5
 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.

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.

6
 Types of Chemical Admixtures
• Admixtures that mainly affect the fresh state
• Water-reducing agents
• Superplasticizers
Reduce the amount of water needed for increasing
the workability or yield higher workability without
any change in the water content.

• Admixtures that mainly affect the setting stage

• Set-accelerators
• Set-retarders
Reduce/increase the initial rate of reaction
between cement and water. This causes a
reduction/increase in the time taken by mortars
and concrete to pass from the plastic to solid state.

Types of Chemical Admixtures

• 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.

7
 Types of Chemical Admixtures
Special purpose admixtures:
• Shrinkage-reducing admixtures
• Alkali-aggregate expansion-reducing admixtures
• Corrosion inhibitors
• Viscosity-modifying, Antiwashout or Pumping-aid
admixtures
• Surface retarders
• Washwater admixtures
• Fungicides
• Damp-proofers or water-repellents
• Multi-functional admixtures

Admixtures in Use
• 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

8
 WATER-REDUCERS OR
PLASTICIZERS

Mechanisms of action
and effects

Water Reducers

• Admixture that reduces the water content of a

mortar or concrete for a given workability. Usually
has a secondary effect of retarding the setting of
the concrete.

• Mainly based on pure or modified lignosulfonic

acids and their salts, hydroxycarboxylic acid and
hydroxylated polymers.

• Lignosulfonates have been used since the 1930s

in concrete.

9
 Ligosulfonates

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

• During paper-making, products of lignin are
obtained as by-products.

• After processing, lignosulfonates are produced.

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

Ligosulfonates

• Lignosulfonates incorporate air into the concrete.

• The lignosulfonate molecule and the sugars
present have a retarding effect on the hydration of
cement.

• Secondary materials are added to the

lignosulfonates to decrease/increase air
entrainment, to compensate retardation and to
accelerate setting.

10
 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.
• There is a modification of the normal process of
ettringite formation and a delay in the C3S
hydration.
• 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.

Effect of Water-Reducing Admixtures

• 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.
• Drying shrinkage and creep seem to increase with
water-reducing admixture addition.

11
 SUPERPLASTICIZERS

Mechanisms of action,
dosage and use

History of Superplasticizers

• 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

• Present: Synthesis of new and more efficient

copolymer formulations.

12
 Usage of Superplasticizers
Constant w/c: Increase Constant workability:
in the workability Lower w/c

same workability
No MLS SMF SC
admixture

LOWER WATER CONTENT

Lower w/c

Superplasticizer Action
Flocculation in the absence
of superplasticizer Effect of the superplasticizer
Water Cement
Water Cement particle
particle

Entrapped
water

13
 Agglomeration of Cement in Water
after 48 hours
50 gm of cement in 1 liter of water
+ 5 ml of (super)plasticizer

W in water hf
L in water + water-reducing agent
SUP In water + superplasticizer

W L SUP

hw hl h

closer view

W L SUP
Aïtcin

Consequences of Superplasticizer Usage

• Reduces placing and compaction time, leading

to lower construction costs.

• Facilitates the casting of elements with

complex shapes and dense reinforcement.

• Improves the surface finish of the concrete

elements.

• Leads to superior strength and durability with

lower cement contents.

14
 Consequence of Superplasticizer Action
Decrease in the entrapped air and water contents of the
fresh paste leads to lower porosity and crystallinity of the
hydrated cement paste

Unhydrated
cement grains

Water

Aïtcin w/c = 0.65 w/c = 0.25

HIGH PERFORMANCE CONCRETE

• Superior mechanical properties and

durability, at minimum cost.
• Compact microstructure (low permeability
and high strength).

Low water/cement ratio (w/c)

SUPERPLASTICIZER

15
 Applications where a
Superplasticizer is Essential

• Fluid/Flowing/Pumpable concrete
• Shotcrete
• Self-compacting concrete
• High-strength concrete
• High-durability concrete
• Concrete with low shrinkage and creep

Chemical Formulation

Surfactants soluble in water, with different

functional groups:
• Modified Lignosulphonates (MLS)
• Salts of naphthalene sulphonate and
formaldehyde condensates (SNF)
• Sulphonate (SO3-) • Salts of melamine sulphonate and
formaldehyde condensates (SMF)

• Comb-type polymers

• Carboxylate (COO-),
• Hydroxide (OH-) or
Hydrophobic group
• Phosphonate (PO3-)
Hydrophilic group

16
 Mechanisms of Action
Types of interaction between cement
particles and the superplasticizer

PHYSICAL CHEMICAL
Adsorption and Chemisorption,
generation of formation of
repulsive forces admixture-Ca2+
between cement complexes and
particles interaction with the
hydration reactions

MECHANISMS: Physical Interactions

1. FORMATION OF AN ADSORBED LAYER ON

THE CEMENT PARTICLES.

2. GENERATION OF REPULSIVE FORCES

BETWEEN CEMENT PARTICLES:
DEFLOCCULATION. - - - - - -
- -
- -
• Electrostatic Repulsion -
- -
- - - - -
(SNF & SMF)

• Steric hindrance due to the

lateral chains of the
comb-type polymers

17
 MECHANISMS: Chemical Interactions

 Chemisorption
 Change in chemical composition as a function of
the thickness of the adsorbed layer.

 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.

Superplasticizer-Silica Fume Interaction

Without superplasticizer, the cement + water +

silica fume system tends to coagulate, making
the use of a superplasticizer essential.

REPULSIVE
Silica Silica
FORCES
fume fume

COAGULATION DISPERSION

18
Superplasticizers

Determination of the optimum dosage.

Superplasticizer-cement compatibility

Selection of the Superplasticizer

Study of the compatibility

Optimum superplasticizer dosage

Cost-benefit considerations

In several cases, this order is inverted,

resulting in costly consequences

19
 Marsh Cone Test: Evaluation of the
compatibility and dosage
Comparison with yield shear stresses
800-1000 ml obtained with viscometer

35

Fluidity
Marsh cone flow time
15.5 cm 16 Marsh cone flow time 30
Bingham Yield stress

Marsh cone flow time (sec)

Bingham Yield stress (Pa)

25
Cement 53 grade opc
w/c 0.35
20
sp-SMF
29 cm 14
15

10
6 cm
5
Diameter: 8 mm 12
% sp/c0
SATURATION
POINT
200-500 ml 0.0 0.2 0.4 0.6 0.8 1.0

sp/c%

Practical Significance of the

Saturation Point
210
w/c = 0.35
T = 22°C
60 min
Marsh cone flow time, s

170

130 Saturation Point

90 5 min

50
0.0 0.4 0.8 1.2 1.6 2.0 2.4 2.8
Superplasticizer dosage (% sp/c)
Aïtcin

20
 Cement/Superplasticizer Compatibility
200
w/c = 0.35
180 T = 23° C
60 min

160
Marsh cone flow time, s

140

120
60 min
100 Cement A
Cement B
80
5 min 5 min
60
0 0.4 0.8 1.2 1.6 2.0 2.4 2.8

Superplasticizer dosage (% sp/c)

Aïtcin

Selection of Superplasticizer
sp/c% Vs Marsh cone flow time

70
Cement 53 Grade opc
w/c - 0.35
60 Ambient temp

Type of sp Saturation Dosage

50 SMF1
(corresponding to 140 degrees)
SMF1 0.23 SNF1
flow time (sec)

SNF1 0.2
40 PCE1
PCE1 0.2
PCE2 0.07 PCE2
SNF2 0.24 SNF2
30 SNF3 0.23
Ligno 1 0.25 SNF3
SMF2 0.2 LIGNO1
20
SMF2

10

0
0 0.1 0.2 0.3 0.4 0.5 0.6
sp/c%

21
 Selection of Superplasticizer
COST-BENEFIT RATIO

 cost/kg time (s)

% sp/c
CBR 
s.r.

  Rs. 300/kg  5 s  1250

0.25 % sp/c
CBR 
0.3 s.r.

 Rs.100/kg 7 s  2630
1.5 % sp/c
w/c = 0.33 CBR 
0.4 s.r.

Paste-Mortar-Concrete
Comparison
• In general, there is
good correlation
between the
behaviour of paste,
mortar and
concrete.

• Sand with a high

coefficient of
absorption can
increase the
superplasticizer
demand in mortar
and concrete.

22
Factors that Affect the Saturation Point

• Type of superplasticizer
• Type of cement
• Water/cement ratio
• Presence of mineral admixtures
• Mixing sequence
• Temperature

Effect of Cement Type

Aïtcin

23
 Effect of water-cement ratio
40 100 I 42.5 cement
I 42.5 cement superplasticizer SD (naphthalene)
superplasticizer SD (naphthalene) silica fume E (sf/c=0.1)
Marsh cone flow time (s)

80
30 w/c= 0.28
w/c= 0.33
w/c= 0.40 60

20

40 w/c = 0.33
w/c = 0.40
10
20

0 0

0 1 2 3 4 0 1 2 3 4
solidsuperplasticizer/cement ratio (%) solidsuperplasticizer/cement ratio(%)

• Flow time decreases with a increase in w/c

• Saturation point increases with a decrease in w/c
• Flow times and saturation dosages depend on silica
fume content

Effect of silica fume type and dosage

100 100
I 42.5 cement
silica fume E I 42.5 cement
superplasticizer SD (naphthalene) silica fume R
w/c= 0.33 superplasticizer SD (naphthalene)
80 80 w/c = 0.33

sf/c=0
60 sf/c=0 60 sf/c=0.05
sf/c=0.05 sf/c=0.10
sf/c=0.10 sf/c=0.15
40 40
sf/c=0.15

20 20

0 0
0 1 2 3 4 0 1 2 3 4
solid superplastizicer/cement dosage (%) solid superplasticizer/cement dosage (%)

• Saturation dosage of superplasticizer increases with

silica fume content
• Superplasticizer demand may be unaffected in silica
fumes that are marketed as a mixture with plasticizers

24
 Effect of Temperature
20 14
c = I 52.5 R
sp = SN c = I 52.5 R

Marsh Cone flow time (s)

Marsh Cone flow time (s)

w/c = 0.33 12 sp = SC
w/c = 0.33
16 5 ºC 10
5 ºC
8 35 ºC
15 ºC 15 ºC
12 25 ºC
6
25 ºC 35 ºC
4 45 ºC
45 ºC
8
2
Saturation point = 1% sp/c Saturation point = 0.3% sp/c
0
0.0 1.0 2.0 3.0 4.0 0.0 1.0 2.0 3.0
% sp/c % sp/c
• Fluidity generally increases with increase in
temperature.
• The saturation point is unaffected by temperature
variations.

Effect of Temperature on the

Water Demand of Cement
0.30 • Comparison of pastes
c = I 52.5 R with normal consistency
sp = SN
0.28
(i.e., same Vicat
Water demand (w/c)

0.26
penetration).

0.24
45 ºC
• The water demand of
35 ºC
cement increases with an
0.22
increase in temperature.
25 ºC
0.20
15 ºC
5 ºC • This demand decreases
0.18 due to incorporation of
0.0 1.0 2.0 3.0 4.0
superplasticizer until the
% sp/c
saturation point.

25
 Loss of fluidity with time

su perplasticizer SD (naphthalene), sp/c = 1.5%

su perplasticizer SR (naphthalene), sp/c = 1.5% • Loss of fluidity varies

su perplasticizer SS (vinyl copolymer), sp/c = 1%
200
su perplasticizer SM (melamine), sp/c = 1.5%
considerably with
superplasticizer type
160 and commercial brand
Marsh cone flow time (s)

120
cement I 42.5 • Some superplasticizers
silica fume E, sf/c = 0.1
80
w/c= 0.33 are capable of
sustaining high fluidity
40 up to one hour

0 15 30 45 60
time after initial mixing (minutes )

Effect of Temperature on the

Loss of Fluidity
20 16
c = I 52.5 R c = I 52.5 R
35ºC
Marsh Cone flow time (s)
Marsh Cone flow time (s)

sp = SN sp = SC
w/c = 0.33 w/c = 0.33
sp/c = 1% sp/c = 0.3%
15 12
35ºC
45ºC 5ºC 25ºC

10 8 15ºC
15ºC

25ºC 45ºC
5ºC
5 4

0 5 15 30 45 60 75 90 0 5 15 30 45 60 75 90
Time (min) Time (min)
• Loss of fluidity in the paste is lower for polycarboxylate
based superplasticizers.
• There is no clear trend with respect to temperature.

26
Mechanisms that Control the Fluidity of
Pastes at High Temperatures

There are two competing

mechanisms:

• The increase in fluidity due to the

lowering of the viscosity.

• Increase in the water demand of

cement, which tends to decrease
the fluidity.

SET-RETARDERS

27
 Effect of Set-Retarding Admixtures
• When a retarder is added to cement-water
system, physical adsorption and chemical
reactions generally occur with the C3A and C3S.
The result is the retardation of setting of the
cement and hardening of the concrete.

• The initial and final setting times are increased.

• Workability is maintained longer.

• Heat of hydration and temperature rise of

concretes are lesser at early ages.

Effect of Set-Retarding Admixtures

• When there is plasticizing effect in addition to

retardation, strength increases as water content is
consequently reduced.

• Set retardation generally leads to slower

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.

28
Application of Set-Retarding Admixtures

• Primary application is in hot-weather concreting.

• Used in mass concrete to permit the control of the
temperature rise of the concrete, reducing the
possibility of thermal cracking.

• For maintenance of slump during long transportation

periods and placing duration.

• To avoid partial hardening during the casting of large

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

SET-ACCELERATORS
&
HARDENING-ACCELERATORS

29
 Types of Accelerators

• Chloride-based
• Calcium chloride (CaCl2) is the most common
accelerator. Has been used since 1885.

• Non-chloride accelerators
• Calcium formate, triethanolamine, calcium nitrate, etc.

Effect of Accelerators
• 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.

30
 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.

Drawbacks of Calcium Chloride

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

31
 AIR ENTRAINING AGENTS

Freezing and Thawing of Concrete

• When the temperature of concrete drops to below 0°C, the
water does not all freeze immediately.

• 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
water will not freeze until -78°C).

• 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,
there is contraction on freezing.

32
 Effect of Air Entraining Admixtures

A surfactant used to produce air bubbles and disperse

them throughout the cement paste.

Air entraining surfactant

Mehta and Monteiro

Effect of Air Entraining Admixtures

• The entrained air increases workability and

decreases segregation.

• Results in fine uniformly-distributed voids in the

hardened concrete.

• 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.

33
 Freezing and Thawing of Concrete

Mehta and Monteiro

Effect of Air Entraining Admixtures

Durability and Strength
Effect of spacing factor Effect of air content

Strength decreases by about 5% for

every 1% of additional entrained air
Mindess & Young

34
 Effect of Air Entraining Admixtures

The quantity of air incorporated not only

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

Applications of Air Entraining Agents

• Protection against the damage produced in

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.

35
 DAMP-PROOFERS

WATER-REPELLING
ADMIXTURES

Effect of the Dampproofer

Makes the concrete surface less wettable or
water-repellent.
High contact angle between water Low capillary rise with
and dampproofed concrete dampproofing

Rixom and Mailvaganam

36
 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
– Incorporation in a very finely divided form.

• Those that react with the hydration products are based on

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.

Rixom and Mailvaganam

Benefits of Using a Dampproofer

• Prevents rain water from entering the concrete surface
and capillary absorption. Thereby, increases the durability.

• Improves the performance of concrete pavers, tiles,

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.

Rixom and Mailvaganam

37
 CORROSION-INHIBITING
ADMIXTURES

Action of the Corrosion Inhibitor

• Provides a second line of defence to prevent the corrosion
of the steel reinforcement in concrete, augmenting the
protection provided by the alkaline nature of the concrete.

• 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
access to the steel (less chemisorption and dissolution).

Rixom and Mailvaganam

38
 Action of the Corrosion Inhibitor
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.

Rixom and Mailvaganam

VISCOSITY-ENHANCING
AGENTS

VISCOSITY-MODIFYING
AGENTS

39
Action of the Viscosity Modifying Agent
• 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)

Rixom and Mailvaganam

Action of the Viscosity Modifying Agent

Underwater test

Nagataki

40
Applications of Viscosity-Modifying Agents

 Underwater concrete
 Facilitates sufficient mobility of the concrete
under water with little loss of cement.

 Self-compacting concrete
 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.

Underwater Concreting
Critical Aspects
• 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.

41
 COLD WEATHER
ADMIXTURE SYSTEMS

Action of Cold Weather Admixture

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.

C.J. Korhonen & A.A. Jeknavorian, Concr. Intnl., V. 27, No. 11, 2005, pp. 38-43

42
 SHRINKAGE-REDUCING
ADMIXTURES

Shrinkage Mechanisms
• 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
presence of moisture.

43
Shrinkage
Drying

Autogenous

Thermal
(contraction)

Plastic
Carbonation

Time
hours days weeks months years

Ways of Reducing Shrinkage

• Reduction of the water content (by using

superplasticizers).

• Reduction of the cement content (by optimizing

the paste volume, using complementary
materials).

• Utilization of special cements and expansive

agents.

• Utilization of shrinkage-reducing admixtures.

44
 Shrinkage Reducing Admixture (SRA)
First used in Japan, in the 1980s.
It acts by reducing the surface tension of the
evaporable water in the pores.
Leads to lower capillary stresses during drying.
Cement particle

Water

Plastic shrinkage
Occurs in the fresh concrete, principally due to
high evaporation rates.

Factors:
- Environment (temperature, humidity and wind
velocity)
- Concrete composition
- Boundary conditions (geometry and
restraints)

45
 Plastic Shrinkage Cracking

 When the bleed water does not compensate the water

loss due to evaporation, shrinkage occurs.

 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.

Plastic shrinkage: Test configuration

Wind tunnel

Evaporation pan
Prisms
Environment
Sensors

Panel

46
 Plastic Shrinkage Tests: Prism specimen

Concrete prism,150x142x600 mm Anchor bolts,

5 mm
diameter
Displacement sensor

Plastic sheet

“Stress riser”, 106 mm high

Insulation

Displacement-Time Curves in the Prism

Horizontal displacements

D E F
Crack width

A-B: No shrinkage or some expansion

B-C: Increasing displacement at a

decreasing rate

C C-D: Displacement remains constant

E: Air flow is stopped after four

hours

E-F: Displacement unaffected by

A
B cooling
Time

47
 Plastic Shrinkage Tests
 Normal strength concrete (35 MPa, w/c = 0.45): Fresh
concrete specimens subjected to a temperature of 47°C,
relative humidity of 26% and a wind velocity of 26 km/hr;
evaporation rate = 1.5 kg/m2/hr.

 High strength concrete (70 MPa, w/c = 0.35): Fresh

concrete specimens subjected to a temperature of 37°C,
relative humidity of 31% and a wind velocity of 25 km/hr;
evaporation rate = 0.6 kg/m2/hr.

Admixtures Studied

Admixture Type Density Solids

kg/lt %

Superplasticizer D Naphthalene based (Non- 1.15 44.4

surfactant)
Superplasticizer G Polycarboxylate 1.06 21.6

SRA E Glycol based 0.90 3.7

SRA S Glycol based 0.95 26.9
SRA R Wax based 0.94 39.8

48
 Plastic Shrinkage Test Results

NORMAL STRENGTH CONCRETE HIGH STRENGTH CONCRETE

500

Horizontal Displacements, microns

500 CD-0
Horizontal Displacements, microns

400
400 HPD-0
300
300

200
200 CG-S
CG-0
100
100

CG-E
HPD-E
0 0
CG-R
-100 -100

0 60 120 180 240 0 60 120 180 240

Time, min Time, min

Study of Shrinkage and Creep in

Hardened Concrete
Instantaneous strain = εi

εi + Drying
creep
strain
εi + Basic creep strain

Drying
shrinkage strain
Autogenous
shrinkage strain
Curing Age

49
 Test Details
Tests of 15×30 cm cylinders
• 35 MPa concrete (w/c = 0.4), with slump = 19 cm
• superplasticizers: Naphthalene (SN), Melamine (SM),
Polycarboxylate (SC)
• SRAs: 4 different products (3 based on glycols and 1
wax-based), dosages: 1-2%

Test conditions:
• Autogenous shrinkage (sealed specimens) and Drying
shrinkage (specimens at 50% R.H.)
• Basic creep (sealed) and Drying creep (at 50% R.H.)

Test Configuration

50
 Properties of the Concretes

Slump
Concrete sp/c SRA/c (cm)
fc (28 days)

CREF-SN 0.69% 0 17 45.0

CREF-SC 0.14% 0 18 45.2
CSRA1(1.5%)-
0.40% 1.5% 17 42.8
SN
CSRA1(2%)-
0.33% 2% 17 39.8
SN
CSRA2-SC 0.12% 2.3% 20 43.2
CSRA3-SC 0.14% 1.5% 17 42.2

Results: Autogenous Shrinkage

0.12

0.08
Strain (mm/m)
(mm/m)

0.04
Concretes without SRAs
Deformación

0
Concretes with SRAs

-0.04 C-SN
C-SC
C-ARR1%
C-ARR2%
-0.08
100 200 300 400
Tiempo (días)
Time (days)

51
 Results: Drying Shrinkage
REF-SM
(mm/m)
0.4 REF-SC
secado (mm/m)

RE-SN
SRA1(1.5%)-SN Concretes without SRAs
SRA1(2%)-SN
SRA2-SC
0.3
por Strain

SRA3-SC
SRA4-SN
Shrinkage

0.2
DryingDeformación

0.1

Concretes with SRAs

0
0.1 1 10 100
Tiempo de secado (días)
Time (days)

Results: Basic Creep

1.2
C-SN
C-SC
C-ARR1%
Fluencia Básica
de Coefficient

C-ARR2%

0.8
Creep
Coeficiente

0.4
Basic

0
0.01 0.1 1 10 100
log (t-to), días
Log (Time, in days)

52
 Results: Drying Creep
1.2
C-SN
Coefficient

C-SC
por secado

C-ARR1% Concretes without SRAs

C-ARR2%
0.8
Drying Creepde Fluencia

0.4
Coeficiente

Concretes with SRAs

0

0.01 0.1 1 10 100

log (t-to),indías
Log (Time, days)

Observed Trends

• Considerable reduction in the drying

shrinkage of concrete (30-50%), as a
function of the type and dosage of
polypropylene glycol SRA. In the case of a
wax-based SRA, the reduction is 13%.

• Absence of autogenous shrinkage in

concretes with SRA.

53
 Observed Trends
• The incorporation of an SRA leads to a
significant reduction in the drying creep
(33-46% for SRA/c = 1-2%).

• The SRA does not affect the basic creep.

• Slight decrease in the compressive strength

(5-12%) in concretes with SRA.

• Increase in workability due to the

incorporation of glycol based SRAs.

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.

54
 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

55