4.

1 Chemical Admixtures
Acknowledgements
Portland Cement Association (PCA)
Dr. Kevin J. Folliard, University of Texas
Dr. Maria Juenger, University of Texas

2
Definition
Chemical Admixture – a liquid, or dispersible
powder, used as an ingredient in a cementitious
mixture to improve its economy and/or properties in
the plastic and/or hardened state (ACI CT-18)

3
Overview
The major reasons for using chemical admixtures in
concrete mixtures are:
1. To achieve specific properties in fresh and
hardened concrete
2. To maintain the consistency of the mix
3. To overcome certain emergencies during
concreting operations
4. To make the mixture more economical
5. To enable use of a wider selection of concrete
materials (including marginal materials)

4
Chemical Admixture Specifications

ASTM C 494 Chemical ASTM C 260

Admixtures

Water Specific
Retarding Accelerating Air-Entraining
Reducing Performance

Type A – Water Type C – • Corrosion Air-Entraining

Type B – Retarding Inhibitors
Reducing Accelerating Admixtures
• ASR inhibitors
• Shrinkage-
Type D – Water Type E – Water Reducing
Reducing and Reducing and Admixtures
Retarding Accelerating • Integral water
repellants
• Others
Type F – High-Range Type G – High-Range
Water Reducing Water Reducing and
Retarding

Type A or F – Mid-
Range Water
Reducing

5
 Water-Reducing Admixtures (WRAs) -
History
WRAs were discovered accidentally…

Regular Regular
Concrete Concrete

• Concrete with carbon black

• Mix included chemical to disperse carbon black to
minimize strength loss and provide uniform color
• Found that chemical also dispersed cement
• Interest in learning more about chemical
Three-lane road built in the Midwest 6
WRAs

Plasticizer
• Slump increased while
Water Reducing Admixture - maintaining water content (&
an admixture that either increases W/CM).
slump of freshly mixed mortar or • Improves placing
concrete without increasing water characteristics without
content, adversely affecting strength
and durability.
OR
maintains slump with a reduced Water Reducer
amount of water, the effect being due • Water content reduced while
to factors other than air entrainment. maintaining slump.
(ACI CT-18) • Reduces w/cm, leading to
improved strength and
durability.

7
WRAs: Case Study

Case Water Cement w/cm 28-day Slump

compressive
(lb/yd3) (lb/yd3) strength (in)
(psi)
A – Control 300 600 0.50 5000 4
-10% -10% + 500 psi

B - Water Reducer 270 600 0.45 5500 4 + 3 in.

-10% -10%

C – Plasticizer 300 600 0.50 5000 7

D – $ Reducer 270 540 0.45 5000 4

8
Water-Reducer vs. Plasticizer

Plasticizer

Water-Reducer

Adapted from Neville 1995

9
WRAs
High-Range
Mid-Range
Water Reducing Water Reducing
Water Reducing
(HRWR)

• Type A, D, or E • Does not have • Type F or G

• 5-10% water specific ASTM • 12-30% water
reduction (typical) designation. reduction (typical)
• Used by itself or in • Typically meets Type • Polycarboxylates are
combination with A or D most common.
high-range water • 6-12% water • Key component in
reducers reduction (typical) self-consolidating
• Used often in concrete.
“superflat” floors • Can be used across
range of concretes.
10
 Cement Flocculation
Cement grains electrically attract other cement
grains. The cement conglomerates and “flocs” of
cement and trapped water are formed.

Cement grain with

excess, unbalanced
surface charges

Surface area of cement

grains is also more limited
à reduced hydration
Notice the trapped water
11
Cement Flocculation
It is desirable to break up the flocs of cement to allow all of the mix water to
lubricate cement grains, aggregates, SCMs, etc.

Flocculated Deflocculated

12
 How do WRAs Work?
Electrostatic Repulsion Steric Repulsion

+
+ +
+
+ Cement + Cement
+ Cement
+ + +
+ +
+ + +
+ Cement Cement
Cement

+ + Cement
+ +

• Contributes to dispersion of all water • Contributes to dispersion of

reducing admixtures (normal, mid- polycarboxyates only.
range, and high-range) • More powerful mode of dispersion
than electrostatic repulsion.
• Can extend slump life of concrete

13
 Normal Range Water-Reducers
Normal range water-reducers consist of:

Lignosulfonate Sulfonated naphthalene formaldehyde

Waste product of
paper industry

Hydrophilic head
Polar chain (anionic)
14
Normal Range Water-Reducers

Hydrophilic head

Polar chain selectively adsorbs

onto surface of cement
particles.

WRAs are ”surfactants”, they act on the surface

15
Normal Range Water-Reducers

16
 Normal Range Water-Reducers

Negatively-charged heads
repel each other

This mechanism is known as electrostatic repulsion and

contributes to dispersion of all WRAs (Normal, mid-range, and
17
high-range)
Dispersive Action
The WRA will also adhere to aggregate particles and
will help to disperse cement, aggregate and air-
entrained bubbles
- + - +
+ -
WRA molecules -
+
+
- -
+ Aggregate
+
-
-
+
- +
+ -
- +

18
HRWRs (Polycarboxylates)

Polycarboxylates (only)

Polar Chain

Hydrophilic side chains

19
HRWRs (Polycarboxylates)

Polar chain adsorbs onto and

envelopes portland cement grains

Hydrophilic side chains

20
HRWRs (Polycarboxylates)

21
 HRWRs (Polycarboxylates)

Polycarboxylate-based HRWRs work using electrostatic repulson AND

steric repulsion (sometimes referred to as steric hindrance) 22
 Steric Repulsion and Slump Retention

Polycarboxylat
9 es
8 Side chains extend beyond early
hydration products (C-S-H),
7
increasing slump retention
Slump (in)

6
5
4
3 Naphtha
Early hydration products (C-S-H) le
cover electrostatic charges on range w ne-based high-
2 ater red
cement surface, leading to rapid ucer
slump loss
1

30 60 90 120
Time (min)

23
 Self-Consolidated Concrete
The introduction of polycarboxylates opened the door for self-
consolidated concrete (SCC)
SCC - Fresh concrete that can flow around reinforcement and consolidate
within formwork under its own weight without vibration (ACI –CT18)

• Only possible with polycarboxylates

• Typically requires higher fines content,
lower FA/CA ratio, and smaller max. size
aggregate in order to avoid segregation.
• Can also use viscosity modifying admixtures
(VMAs) to prevent segregation.
• Used in precast plants and special
applications

https://youtu.be/C9g5fAkpWNA
https://youtu.be/4OA8Ar5JZq8 24
Mid-Range Water-Reducers

• Introduced in mid-1980’s (yet still does not have specific designation in

ASTM C 494)
• Set time generally not sensitive to dosage rate
• Designed for enhanced finishability
• Slumps in 5-8 inch range typical
• Very common in superflat floor specifications

25
Impact of WRAs on Concrete
Fresh Concrete
• Increases slump
• Increases slump retention
• Improves flow
• Improves pumpability
• Improves finishability (MRWR)
• Improves appearance of formed
surface
• May increase setting time
Hardened Concrete*
• Increases strength
• Reduces permeability to water
and ions (sulfates, chlorides,
etc.)
• Increases sulfate resistance
• Increases abrasion resistance
* When using water reducers to
lower w/cm ratio
26
WRAs and Setting Time

Whiting and Dziedzic 1992

27
Set Modifying Admixtures
Set modifiers include accelerators and retarders

Accelerating admixture - an admixture that causes an

increase in the rate of hydration of the hydraulic cement and
thus shortens the time of setting, increases the rate of
strength development, or both.

Retarding admixture - an admixture that causes a decrease in

the rate of hydration of the hydraulic cement and lengthens
the time of setting.

28
 Hydration and Set Modifiers
Set control admixtures primarily work by slowing down or speeding up
the dissolution of cement grains (by strengthening or weakening the
diffusion barrier that forms around cement grains in early hydration).

x final
set

initial
x
set
29
 Setting Time
Initial Set –
• Time from moment water is
added until the paste ceases to
be fluid and plastic
• Time when average worker’s foot
leaves ¼” indentation and bleed
water appears and disappears.
Recall!
Final Set –
• Time from moment water is
added for the paste to acquire a
certain degree of hardness
• Time after which no further
modifications to concrete surface
are possible.
30
 Effect of Temperature on Set Time
Temperature Final Set Time
(°F) (Hours)
20 Concrete will freeze
30 19 Potential Need
for Accelerator
40 14
50 11
60 8
70 6
Potential Need 80 4
for Retarder
90 3
100 2

31
 Effect of Temperature on Strength Gain

200%
200
Compared to Lab Cure (%)
Relative Hydration Rate

150

100%
100

50%
50
52°F 73°F 96°F

20 40 60 80 100 120
Temperature (°F)
32
 Accelerators
• Most commonly used in cold weather to
maintain normal setting times and strength
development.
• Minimizes impact on construction schedule.
• Can reduce risk of damage to concrete from
early freezing.

• Can be used under normal weather

conditions to:
• Increase early strength in repair materials
(e.g. patch repairs in pavements)
• Increase pace of construction.
• Precast and/or prestressed applications.

33
Mechanisms of Accelerators

No Admixture CaCl2 Accelerator

SO4-- Na+ OH- SO4-- Cl- Na+ OH-

C3S C3S Cl- Ca++

SO4-- Ca++ SO4--

SO4-- K+ SO4-- K+ Ca++

Ca++ Cl- Ca++
K+ K+ Cl-
C2S Cl- Ca++ C2S Cl-
Ca++ OH- Ca++ - OH-
OH- Cl Cl- OH-

34
Mechanisms of Accelerators

No Admixture CaCl2 Accelerator

Cl-
SO4-- Na+ SO4-- Na+ OH-
OH-
C3S C3S Cl- Ca++
SO4-- Ca++ SO4--

SO4-- K+ SO4-- K+ Ca++

Ca++ Cl- Ca++
K+ K+ Cl-
C2S Cl- Ca++ C2S Cl-
Ca++ OH- Ca++ - OH-
OH- Cl Cl- OH-

35
Mechanisms of Accelerators

No Admixture CaCl2 Accelerator

Cl-
SO4-- Na+ SO4-- Na+ OH-
OH-
C3S C3S Cl- Ca++
SO4-- Ca++ SO4--

SO4-- K+ SO4-- K+ Ca++

Ca++ Cl- Ca++
K+ K+ Cl-
C2S Cl- Ca++ C2S Cl-
Ca++ OH- Ca++ - OH-
OH- Cl Cl- OH-

Acts as catalyst…. More C-S-H

produced, but it doesn’t contain CaCl2

36
Effect of Accelerators on Heat of Hydration

20% CaCl2
Heat Evolved (x10-3 cal·s-1·g-1)

8
10% CaCl2
6 5% CaCl2

2.5% CaCl2
4

1% CaCl2
2 0.5% CaCl2
0% CaCl2

0
0 4 8 12 16 20 24
Time (h) Ramachandran, 1984

37
Effect of Accelerators on Strength Gain

100
Degree of Hydration (%)

80
2% CaCl2
60

40
Control
20

0
0.5 1 3 10 28
Age (days)

Ramachandran, 1984
38
Accelerators
• Chloride-based accelerators are the most effective
• CaCl2 is the best accelerator
• NaCl will also work
• However, ACI 318 limits the chloride concentration
in reinforced concrete
Concrete Type and Exposure Chloride (%)
Prestressed concrete 0.06

Reinforced concrete exposed to 0.15

chloride in service
Reinforced concrete that will be dry or 1.00
protected from moisture in service
Other reinforced concrete 0.30
construction
39
Other Accelerators

Ramachandran, 1984
40
 Retarders
• Primarily used in hot weather to
slow down the rate of hydration.
• Enable longer haul times
• Keep concrete workable during
placing
• Reduce temperature rise at early
ages
• Avoid cold joints
• Minimize cracking of bridge decks
over supports
• Pure sugar is so effective that it is
actually not used à takes too long if
overdosed
• Instead lignosulfonate is used (also
used as a WRA)
41
Mechanisms of Set Retarders

No Admixture Retarder (e.g. Lignosulfonate)

L/S

C3S C3S L/S

L/S
L/S
L/S L/S
L/S
L/S
C3A L/S C3A L/S

L/S L/S

42
Mechanisms of Set Retarders

No Admixture Retarder (e.g. Lignosulfonate)

SO4-- Na+ OH- L/S L/S Na+

C3S Ca++ C3S L/S

L/S
OH- SO4-- L/S SO4
--

L/S
SO4-- K+ OH-
K+
SO4 --
Ca++ Ca++ L/S
K+ L/S
SO4 --
C3A L/S C3A L/S
Ca++ OH- Ca++ L/S
OH- L/S OH-

43
Mechanisms of Set Retarders

No Admixture Retarder (e.g. Lignosulfate)

SO4-- Na+ OH- L/S L/S Na+

C3S Ca++ C3S L/S

L/S
OH- SO4-- L/S SO4
--

L/S
SO4-- K+ OH-
K+
SO4 --
Ca++ Ca++ L/S
K+ L/S
SO4 --
C3A L/S C3A L/S
Ca++ OH- Ca++ L/S
OH- L/S OH-

44
Mechanisms of Set Retarders

No Admixture Retarder (e.g. Lignosulfonate)

SO4-- Na+ OH- Na+

C3S Ca++ C3S

OH- OH- SO4--
K+ OH-
OH- Na+ K+
K+ SO4 --
Ca++
K+
SO4-- C3A C3A
Ca++ OH- Ca++
OH- OH-

45
Air-Entraining Admixtures
• Also known as AEAs
• AEA - an admixture that causes the development of
a system of microscopic air bubbles in concrete,
mortar, or cement paste during mixing, usually to
increase its workability and resistance to freezing
and thawing.

46
AEAs
Yet another accidental discovery…
In the 1930’s in New York beef tallow was used to
grind clinker more efficiently à grinding aid
Sidewalks and roads made with the cement were
surviving the cold winters much better
Concrete cores were taken and entrained air bubbles
were observed. The improved frost resistance was
attributed to the air bubbles.

47
 AEAs
• Must meet ASTM C260
• Required where concrete is expected to be exposed to
moisture and freeze-thaw cycles, especially if exposed to
de-icing salts.
• A wide variety of air-entraining admixtures are available,
including synthetic types.

48
The Need for Entrained Air
Non air-entrained concrete can be damaged
when exposed to freezing conditions,
especially in the presence of deicing salts.

Internal Frost Damage Salt Scaling

49
 Freeze-Thaw Damage
Mechanism of Frost Non Air-entrained Concrete
Damage in Concrete

0oC, 32oF

Assume concrete is saturated (> 91.7%)

50
 Freeze-Thaw Damage
Mechanism of Frost Non Air-entrained Concrete
Damage in Concrete
Water expands 9% upon freezing
0oC, 32oF

-10oC, 14oF

51
 Freeze-Thaw Damage
Mechanism of Frost Non Air-entrained Concrete
Damage in Concrete

0oC, 32oF

-10oC, 14oF

As freezing progresses, liquid water

is forced ahead of the advancing
freezing front, creating internal
hydrostatic pressures
52
 Freeze-Thaw Damage
Mechanism of Frost Non Air-entrained Concrete
Damage in Concrete

0oC, 32oF

-10oC, 14oF

As freezing progresses, liquid water

is forced ahead of the freezing front,
creating internal hydrostatic
pressures, which may disrupt the
concrete 53
Freeze-Thaw Damage
The Answer = AIR!!!!

Air-Entraining Admixtures
(AEAs) stabilize tiny bubbles
already generated in concrete
to protect against freezing and
thawing cycles.

54
Why is Air Important for
Frost Resistance?
What happens when you put a
What happens if the bottle is
full bottle of coke in the freezer
not full?
and forget about it?

Liquid Liquid

Expands Expands
but bottle
& bottle does not
breaks! break!

55
Why is Air Important for
Frost Resistance?
Like an expansion tank on a
water heater, the air bubbles in
concrete provide space to
accommodate the expanding
water when it freezes

Water-filled pore Air bubble

56
 Freeze-Thaw Damage
Mechanism of Protection by Air-entrained concrete
Air Voids

0oC, 32oF

-10oC, 14oF

Entrained air bubbles

10 – 100 µm 57
 Freeze-Thaw Damage
Mechanism of Protection by Air-entrained concrete
Air Voids

0oC, 32oF

-10oC, 14oF

Air bubbles provide space for water as

freezing advances, relieving
hydrostatic pressure in concrete.
58
 Freeze-Thaw Damage
Mechanism of Protection by Air-entrained concrete
Air Voids

0oC, 32oF

-10oC, 14oF

As temperature starts to increase,

water recedes from the air bubbles.

59
 Freeze-Thaw Damage
Mechanism of Protection by Air-entrained concrete
Air Voids

0oC, 32oF

-10oC, 14oF

As temperature starts to increase,

water recedes from the air bubbles
leaving them empty to accommodate
the next freeze cycle
60
Freeze-Thaw Damage

61
 Mechanism of Air-Entrainment
• Air is generated in concrete
during the mixing process

• Normally the air-water interface

is unstable due to the high
surface tension of water and
small bubbles coalesce to form
larger voids (entrapped air)
which are removed by
compaction of the concrete

Air-entraining admixtures are surfactants (surface-active agents)

which concentrate at the air-water interface and reduce the
surface tension encouraging the formation of stable bubbles
62
Mechanism of Air-Entrainment

Hydrophilic Head
(negatively charged)

Hydrophobic Tail

Typical Anionic Surfactant

63
 Mechanism of Air-Entrainment

The hydrophobic end is

attracted to air within
bubbles while the polar
end (hydrophilic) is
AIR
oriented towards water.

Water

After Lee, 1998

64
 Mechanism of Air-Entrainment

The hydrophobic end is

attracted to air within
bubbles while the polar
end (hydrophilic) is
AIR
oriented towards water.

More surface-active agents

concentrate at the air-
water interface, reducing Water
surface tension and
encouraging the formation After Lee, 1998
of stable bubbles. 65
 Mechanism of Air-Entrainment

The charge around

each bubble leads to Air Air

repulsive forces which

prevent the
coalescence of
bubbles
Water

After Lee, 1998

66
 Mechanism of Air-Entrainment

The charge around

each bubble leads to Air
Air
repulsive forces which
prevent the
coalescence of
bubbles
Water

After Lee, 1998

67
Recommended Air Content

Requirements For Durability:

• When volume of air in mortar fraction of
concrete is about 9 ± 1% (or about 18% by
paste volume).
• Required air increases as coarse aggregate
size is reduced (due to greater paste volume)
• Required air increases as exposure conditions
become more severe.

68
 ACI 318 - Required Air Content

Specified Air Contents (tolerance ± 1.5 %)

Exposure Nominal Maximum Aggregate Size

10 mm 12.5 mm 20 mm 25 mm 37.5 mm 50 mm 75 mm

3/8 in. 1/2 in. 3/4 in. 1 in. 1-1/2 in. 2 in. 3 in.

Mild 4.5 4.0 3.5 3.0 2.5 2.0 1.5

Moderate 6.0 5.5 5.0 4.5 4.5 4.0 3.5

Severe 7.5 7.0 6.0 6.0 5.5 5.0 4.5

* ACI 318 allows air content to be reduced by 1% if concrete strength >

5000 psi (35 MPa)

69
Frost Exposure Class

70
Impact of Air on Concrete Properties

Air Content ↑, Workability ↑

Air Content ↑, Compressive Strength ↓

Rule of thumb: For every 1% increase in air content,

there is a 5-6% decrease in compressive strength

71
 Other Factors Affecting Frost
Resistance
In addition to the presence of an adequate air-void system the
following criteria must be met to ensure no damage occurs due to
freezing and thawing:

Ø the aggregate is frost-resistant

Ø sufficient strength is attained prior to
first freezing (> 500 psi)

Ø sufficient strength is attained prior to

cyclic freezing & thawing (4000 psi)

72
 Measuring Air Content

Pressure Method – ASTM C231 Volumetric Method – ASTM C173

(not suitable for lightweight aggregate) (suitable for all types of aggregate)

73
Measuring Air Content in
Hardened Concrete

ASTM C457 - Standard Test Method for Microscopical

Determination of the Air-Void System in Hardened Concrete

74
Specialty Admixtures

• Hydration-Control Admixtures
• Corrosion Inhibitors
• Shrinkage-Reducing Admixtures (SRA)
• Anti-Washout Admixtures
• ASR Inhibitors (lithium)
• “Waterproofing” Admixtures
• Coloring admixtures/pigments
• Anti-freeze admixtures
• Many Others

75
Summary

• Chemical admixtures are used in virtually every load

of concrete produced today.
• It is important to understand the specific
mechanisms by which chemical admixtures work.
• Water reducers, set modifiers, and air-entraining
agents are the most commonly used chemical
admixtures.
• Some specialty admixtures will be discussed later in
this course, especially admixtures aimed at
improving long-term durability.

76