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1
Chemical Admixtures: Significance
Aïtcin
2
Factors that Affect the Action of the
Chemical Admixture
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.
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.
• 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.
• 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.
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
9
Ligosulfonates
Ligosulfonates
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.
11
SUPERPLASTICIZERS
Mechanisms of action,
dosage and use
History of Superplasticizers
12
Usage of Superplasticizers
Constant w/c: Increase Constant workability:
in the workability Lower w/c
same workability
No MLS SMF SC
admixture
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
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
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
• 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
17
MECHANISMS: Chemical Interactions
Chemisorption
Change in chemical composition as a function of
the thickness of the adsorbed layer.
REPULSIVE
Silica Silica
FORCES
fume fume
COAGULATION DISPERSION
18
Superplasticizers
Cost-benefit considerations
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
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%
170
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
Selection of Superplasticizer
sp/c% Vs Marsh cone flow time
70
Cement 53 Grade opc
w/c - 0.35
60 Ambient temp
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
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.
22
Factors that Affect the Saturation Point
• Type of superplasticizer
• Type of cement
• Water/cement ratio
• Presence of mineral admixtures
• Mixing sequence
• Temperature
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(%)
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 (%)
24
Effect of Temperature
20 14
c = I 52.5 R
sp = SN c = I 52.5 R
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.
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
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 )
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
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.
28
Application of Set-Retarding Admixtures
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
31
AIR ENTRAINING AGENTS
32
Effect of Air Entraining Admixtures
33
Freezing and Thawing of Concrete
34
Effect of Air Entraining Admixtures
35
DAMP-PROOFERS
WATER-REPELLING
ADMIXTURES
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.
37
CORROSION-INHIBITING
ADMIXTURES
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.
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).
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
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
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
Evaporation pan
Prisms
Environment
Sensors
Panel
46
Plastic Shrinkage Tests: Prism specimen
Plastic sheet
D E F
Crack width
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.
Admixtures Studied
48
Plastic Shrinkage Test Results
500
400
400 HPD-0
300
300
200
200 CG-S
CG-0
100
100
CG-E
HPD-E
0 0
CG-R
-100 -100
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)
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
0
0.1 1 10 100
Tiempo de secado (días)
Time (days)
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
0.4
Coeficiente
Observed Trends
53
Observed Trends
• The incorporation of an SRA leads to a
significant reduction in the drying creep
(33-46% for SRA/c = 1-2%).
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