Admixtures in Concrete

Elson John
Assistant Professor,
M A College of Engineering,
Kothamangalam.

Courtesy: Prof. Ravindra Gettu, Dr. Manu Santhanam, Dr. Radhakrishan Pillai
IIT Madras
 Challenges in concrete technology

• We need high quality concrete

• High quality  High strength & High
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

2
What is an admixture?
• ACI 116R defines the term admixture as “a
material other than water, aggregates,
hydraulic cement, and fiber reinforcement,
used as an ingredient of concrete or mortar,
and added to the batch immediately before or
during its mixing”.
 Admixture

Chemical Admixtures Mineral Admixtures

 Cement hydration

• Reaction of cement with water

• Exothermic; heat released is called ‘Heat of Hydration’
• Rate of heat evolution is faster if the reaction is quicker
• Heat evolved depends on heat of hydration of individual
compounds, and also on the clinker morphology!
Reactions - Specifics

• 2 C3S + 6 H  C3S2H3 + 3 CH
• 2 C2S + 4 H  C3S2H3 + CH
• 2 C3A + 21 H  C4AH13 + C2AH8
Flash set reaction!
• C2AH8 is a metastable phase that deposits as hexagonal
platelets (similar to CH). Above 30 oC, it is converted to
cubic hydrogarnet (C3AH6).
• In the presence of gypsum,
C3A + 3 CSH2 + 26 H  C6AS3H32
What are mineral admixtures and supplementary
cementitious materials (SCMs)?
• A mineral admixture is a finely ground solid material
that, when used in conjunction with portland
cement, contributes to the properties of the
hardened concrete through hydraulic or pozzolanic
activity, or both.
• An SCM is a mineral admixture that contains some
form of amorphous reactive silica, which in the
presence of water, combines with calcium
hydroxide to form calcium silicate hydrate similar to
that formed in the hydration of portland cement.

PCA
What is a pozzolan?

• The American Society for Testing and Materials

(ASTM C595) defines pozzolan as
– “a siliceous or siliceous and aluminous material,
which in itself possesses little or no cementitious
value, but will, in finely divided form and in the
presence of moisture, chemically react with
calcium hydroxide at ordinary temperatures to
form compounds possessing cementitious
properties”

PCA
What are pozzolanic reactions?

  S     CH
   C -S- H
Amorphous silica Calcium hydroxide

  S     CH
   H  C - S - H
Amorphous silica Calcium hydroxide Water

  A      CH
   H  C - A - H
Reactive alumina Calcium hydroxide Water

C - A - H  S  C 6 A S3 H 32
• Reaction is    
Ettringite
- Lime consuming
- Pore refining
- Interface refining (why?)
- Slow (low heat of hydration)
- Accelerated by alkalis and gypsum
 PCA

Fly ash Silica Slag

(Class C) fume
Metakaolin Fly ash Calcined
(Class F) shale
(calcined clay)
NOTE:
Color may vary, mostly depending on the iron, carbon, and other impurities
Classification of mineral admixtures

• Cementitious
– Hydraulic lime
– Ground granulated blast-furnace slag (GGBS)
• Pozzolanic
– Materials of natural origin
• volcanic ashes and metakaolin
– Fly ash
– Microsilica or silica fume
• Materials of low or negligible reactivity
– Limestone (CaCO3), quartz (SiO4) or other rock dust
– Bentonite
– Hydrated lime

PCA
Why SCMs are added?

• To improve fresh characteristics of concrete

• To improve strength and durability of concrete
• To decrease the heat of hydration
– A thump rule: The total heat of hydration of pozzolanic reactions is
equal to one-half the total heat of hydration of cementitious reactions
(i.e., of portland cement hydration).
• To correct deficiencies in the packing density of the
aggregates and/or increase the paste content without
increasing the cement dosage (i.e., as a filler material).
• To decrease the environmental impact of concrete (i.e., by
saving cement and/or utilising a waste product)

Mehta and Monteiro

Comparison of the particle sizes of Silica fume,
Fly ash and Cement

Mehta and Monteiro

Rate of pozzolanic reaction
Aggregate-paste interface

• In usual concrete, zone of

0.05 to 1 mm thickness
contains large crystals of
Ca(OH)2 and pores.
• One reason for the higher
porosity of this zone is the
accumulation of
bleed water at the surface of coarse aggregate
particles.

http://www.silicafume.org
Better aggregate-paste interface

• If the transition zone is strengthened, the weakest

link is no longer the interface.

http://www.silicafume.org
The Transition Zone in concrete with mineral
admixture
• The transition zone is a thin layer between the bulk hydrated
cement paste and the aggregate particles in concrete.
• This zone is the weakest component in concrete, and it is
also the most permeable area.
• Mineral admixtures plays a significant role in the transition
zone through both its physical and chemical effects.

http://www.silicafume.org
Effects of adding mineral admixture to concrete –
Summary on fundamentals

Mineral
admixture

http://www.silicafume.org
 Fly Ash

PCA
 Source

• By-product obtained during combustion of coal in thermal

power plants
• The quality and composition of fly ash depends on the type
of coal being burnt
Need for fly ash utilization

• Nearly 73% of India’s total power generation is

thermal (mostly using coal)
• 140 million tons of fly ash being generated annually
• World Bank - by 2015, disposal of coal ash would
require 1000 square kilometres or one square metre
of land per person in India
• Increased disposal implies more environmental
hazards (lead and arsenic pollution), diseases, etc.
Rank of coal

5. Lignite (brown coal)

4. Sub-bituminous coal (70 – 80% C)
3. Bituminous coal (80 – 90% C) – Soft coal, used for
ordinary purposes
2. Semi-bituminous coal – Good heating value, has a
smokeless flame
1. Anthracite (90 – 95% C) – hard coal; high
temperature needed to burn it
Low rank coals contain impurities such as clay, shale,
quartz, carbonates, and sulfides. It is these impurities
which give fly ash its composition.
Uses of fly ash

· As a mineral admixture
• As a filler
· As a synthetic aggregate: Fly ash aggregate
can be produced by sintering. The resultant
aggregate can be used for lightweight
concrete. However, it is very expensive.
Aggregate can also be synthesized by
agglomeration using lime or cement as
binder, as in ‘cold bonding’.
• Fly ash beneficiation – Grinding of coarse fly
ash to make it suitable for use as a mineral
admixtures
ASTM Classification

 Type C: This is also called High Calcium fly ash, and

possesses both cementitious and pozzolanic
properties. 10 – 15% of the material has a particle
size greater than 45 μm, and the fineness (Blaine) is
300 – 400 m2/kg. The particles are primarily solid
spheres with a smooth texture. The average particle
size is less than 20 μm.

 Type F: This is also called Low Calcium fly ash, and

is a normally pozzolanic material. 15 – 20% of the
material is larger than 45 μm, and the fineness is 200
– 300 m2/kg. Particles are solid spheres with a
smooth texture, and the average particle size is 20
μm.
Fly-Ash – Major uses

• Portland Cement Concrete

– Supplementary Cementitious Material
• Asphalt Concrete
– Mineral Filler
• Stabilized Base
– Supplementary Cementitious Material
• Embankment and Fill Material

http://www.flyashindia.com
 Collection of fly ash

• During combustion of coal, 75 – 80% of the

ash flies out with the flue gas, and is thus
called ‘fly ash’. The ash that doesn’t fly out
is called ‘bottom ash’. This can be
processed as aggregate, but is generally
not used in concrete.
• The collection of fly ash is done using the
following two types of precipitators:
- Bag-house precipitator
- Electrostatic precipitator
• The bag-house precipitator is found to be
more efficient, and removes out very fine
material
 Precipitators

P.J.Tikalsky,"The effect of Fly ash on the Surface Resistance of Concrete”

Fly-Ash – Production

http://www.flyashindia.com
Fly-Ash – Structure and physical properties

• Spherical glassy particles formed due to rapid

cooling of the molten ash in the furnace.
• Apart from the solid spheres, there also may exist
hollow spheres.
– Cenospheres - small hollow spheres with entrapped gas
– Plerospheres - large hollow spheres with solid spheres
inside them.
• Particle size
– between <1 μm and 100 μm
– Blaine specific surface is usually
between 250 and 600 m2/kg

PCA Scanning electron microscope (SEM) micrograph of fly ash particles at 1000X
 Structure of fly ash

Apart from solid spherical particles,

there also may exist hollow spheres. The
small hollow spheres with entrapped gas
are called cenospheres, while the large
hollow spheres with solid spheres inside
them are called plerospheres.

www.ctlgroup.com/group/ content.asp?
Influence of Fly Ash on Fresh Concrete

• Water demand is reduced for a given consistency

– Due to the small size and glassy texture
• Increased setting time
Retardation
Setting time, relative to
Fly ash test mixtures hr:min control, hr:min
Initial Final Initial Final
Average Class C
4:40 6:15 0:25 0:45
of:
Class F 4:50 6:45 0:35 1:15
Control mixture 4:15 5:30 — —

PCA
Influence of Fly Ash on Fresh Concrete (cont’d)

• Improved workability and flowability of concrete

– Due to the spherical shape of the fly ash
particles, which has a “ball-bearing” effect.
– Due to the reduction in the size & volume of
voids because of finely divided particles.
– Therefore, the paste demand decreases.
• Reduced bleeding and segregation for well-
proportioned fly ash concrete
Fly ash Bleeding
mixtures Percent ml/cm2
Class C 0.34 0.011
Class F 1.31 0.044
PCA Control 1.75 0.059
Influence of Fly Ash on Hardened Concrete

• Ultimate strengths are reached much after 28 days.

• Strength gain due to pozzolanic activity of fly ash concrete is
slower than normal concrete.
– Up to 28 days, due to particles < 10 μm in diameter
– After 28 days, due to particles between 10 and 45 μm in diameter
• This leads to lower thermal cracking.

PCA
Influence of Fly Ash on Hardened Concrete

• Creep and shrinkage of fly ash concrete are

typically lower than normal concrete
– lower amount of paste in the concrete
• Resistance against corrosion, alkali aggregate
reaction and sulphate attack is increased
– less permeable and porous microstructure and reduced
portland cement content

PCA
Influence of Fly Ash on Hardened Concrete

• Durability: Chloride Diffusion

Dhir & Jones

High-Volume Fly Ash (HVFA) Concrete

• Concrete with 50% of the portland cement replaced

by Class F fly ash
• Low water content, generally less than 130 kg/m3.
For slumps of 150-200mm, the use of a
superplasticizer is mandatory.
• Range of compressive strengths: 20-50 MPa.
• Excellent pumpability, and little bleeding and low
drying shrinkage.
• Applications
– mass concrete blocks, building columns and foundations,
caissons and piles, dams, highways, shotcrete and self-
compacting concrete.
High-Volume Fly Ash Concrete

• Comparison of mixes for a 25 MPa strength

concrete
Components for Conventional High-Volume
1 m3 of concrete Concrete Fly Ash
Concrete
Cement 307 154
Fly Ash -- 154
Water 178 120
Coarse aggregate 1040 1210
Fine aggregate 825 775

Mehta, 2002
 Barriers to use of fly ash

1. Difficult quality assurance

2. Poor marketing
3. Conservative attitudes
4. Storage problems
5. It is called a ‘waste’ instead of pozzolan or cement
Specialized applications

 In high strength concrete, as an additional

cementitious material.
 In roller-compacted concrete. Fly ash is good
for bonding in-between the layers of this
concrete.
 In controlled low-strength materials (CLSM),
which are flowable mortars used as backfill
 As a synthetic aggregate
• For manufacture of bricks
Issues with fly ash

• Due to transportation cost, the use of fly ash far from

the thermal power plant becomes uneconomical
• Lack of appropriate technologies for handling and
transportation
Silica Fume
Silica Fume

• ACI 116R definition

– A very fine amorphous (noncrystalline) silica produced in electric
arc furnaces as a byproduct of the production of elemental
silicon or alloys containing silicon; also known as condensed
silica fume or microsilica.

• ASTM C1240 definition

– A finely divided residue resulting from the production of silicon,
ferro-silicon, or other silicon-containing alloys that is carried from
the burning surface area of an electric-arc furnace by exhaust
gases.
Silica Fume waste – air pollution in earlier days

http://www.silicafume.org
Silica Fume - production

• After being collected over the

furnace, the silica fume must
be transferred, cooled, and
physically trapped.
• The large pipe on the left is
bringing the silica fume from
the furnaces.
• The vertical elements are
cyclones that are used to
remove oversize and other
unwanted materials.
• The large building is the bag
house where the fume is
captured.
http://www.silicafume.org
Silica Fume Products: Densified Silica Fume

http://www.silicafume.org
Silica Fume Products

• As-produced powder
• Water-based slurry
• Densified
• Blended silica-fume cement
• Pelletized

http://www.silicafume.org
Silica Fume Color

Premium -- White Standard -- Grey

http://www.silicafume.org
Silica Fume – Physical characteristics

• Particle size (typical) <1µm

• Bulk density
as-produced = 130 to 430 kg/m3
slurry = 1320 to 1440 kg/m3
densified = 480 to 720 kg/m3
• Specific gravity 2.2
• Surface area (BET) 13,000 to 30,000 m2/kg

BET = Brunauer, Emmett and Teller (inventors of the test method)

http://www.silicafume.org
Silica Fume – Particle size

Cement Particles Silica fume particles

http://www.silicafume.org
Silica Fume: Chemical properties and effects

• Amorphous
• Silicon dioxide (SiO2) > 85%
• Trace elements depending
upon type of fume
• Silica fume is simply a very
effective pozzolanic material

http://www.silicafume.org
Consequences of Silica Fume: Fresh concrete is
more cohesive
• Due to the increased fineness (than cement), the use of
silica fume causes an increase in the water demand of
concrete. It is, therefore, almost always used in conjunction
with a superplasticizer. However, when a small quantity of
silica fume is used, water molecules are displaced and freed
from the vicinity of cement grains, leading to more fluidity.
• Silica fume causes the mix to be sticky and cohesive.
Consequently, a higher slump is needed to place silica fume
concrete. Also, concrete mixes with silica fume are prone to
slump loss problems.
• Bleeding is reduced drastically. Consequently, if the
evaporation rate is high, plastic shrinkage cracking may
occur. Therefore, water curing must be performed as soon
and as long as possible.

http://www.silicafume.org
 Silica-fume
Although concrete
the slump requires
may be higher in silica fume
concrete, compaction
thorough is required
consolidation

http://www.silicafume.org
Improved Compressive Strength

Control mixture
cement: 390 kg/m3
w/c: 0.41
air: 5%

http://www.silicafume.org
 Improved Corrosion Protection
 5-10% silica fume added by mass of cement
 Mixture may include fly ash or slag
 w/b < 0.40
 Total binder < 415 kg/m3
 Permeability estimated using ASTM C 1202

Silica fume Chloride Permeability Compressive Strength

(by mass of cement)
0% > 3,000 coulombs = 35 MPa

7-10% < 1,000 coulombs > 50 MPa

>10% < 500 coulombs > 65 MPa

http://www.silicafume.org
Improved Corrosion Protection

• Chloride Diffusion after 6 months of exposure to

1.9% chloride solution

Dhir & Jones

..(contd.)

 Corrosion rate is reduced with the use of

silica fume. This is because of two reasons:
the low permeability of SFC causes a lower
availability of moisture and oxygen at the
cathodic sites, and the high resistivity of SFC
makes the flow of electrons difficult.
 Carbonation depth is generally lowered.
 SFC has very good abrasion and erosion
resistance.
 Fire performance of SFC is not very good
Improved Resistance Against Acid Attack

Cycles to 25% Mass Loss

60
50
0% sf
40 7.5% sf
12.5% sf
30
15% sf
20 25% sf
30% sf
10
0
1% 5% 5% 5%
H2SO4 Acetic Formic H2SO4
Beneficial effect in ASR

Reduction in expansion
due to ASR by the use of
silica fume
Improved Shotcreting

• Reduction of rebound loss

up to 50%
• Increased one-pass
thickness up to 300 mm
• Higher bond strength
• Improved cohesion to
resist washout in tidal
rehabilitation of piles and
seawalls
Blast-furnace Slag
Ground Granulated Blast-Furnace Slag (GGBS)

• Blast furnace slag is a by-product of

the extraction of pig iron from iron ore.
• Coke and limestone are added as
fluxes inside the blast furnace.
• The impurities in iron ore combine
with the lime and rise up to the
surface of the blast furnace as slag,
while the heavier molten iron stays at
the bottom.
• The slag is subsequently granulated
and can be ground later to the desired
fineness
– usually greater than 350 m2/kg
Chemical composition of GGBS

• Quenched slag is a glass

containing CaO, SiO2 and
Al2O3.

http://www.bvslag.com/blast_furnace_slag_uses.htm
Structure and action of GGBS

• Water quenched slag: the non-metallic, granulated

slag remains in an amorphous state (calcium
alumino silicate glassy), which gives it hydraulic
qualities.
– Slow air-cooled slag (crystalline calcium magnesium
silicate) is hydraulically inert
• The hydraulicity of slag is activated by calcium
hydroxide in concrete
– Other alkali hydroxides also contribute
• GGBS is reactive, forming an alumina-substituted
C-S-H as follows:
C-S-A + H → C-S-H
Influence of GGBS on Fresh Concrete

• Water demand is reduced for a given consistency

– Due to the small particle size and glassy texture
• Workability is improved
– Due to the reduction in the size and volume of voids
(because of finely divided slag particles)
• Bleeding and segregation are usually reduced
– Due to reduced water demand
– Results in improved pumpability
• Setting time is increased
– Effectively, less C3S and more C2S
Influence of GGBS on Hardened Concrete

• The microstructure is denser

– less CH and more C-S-H are produced
• Heat development is lowered
– Rate of hydration of slag is similar to that of C2S
• Activation energy is 55 kJ/g as opposed to 40 kJ/g of cement
• Higher long-term strength gain, especially when the fineness
is high
• Resistance against corrosion is increased
– due to a less permeable and porous microstructure
• Resistance to sulphate attack is improved
– due to lower calcium hydroxide content
• Alkali aggregate reactivity is lowered
– due to the reduction in the alkali mobility by the lower permeability
Influence of GGBS on Hardened Concrete

• Durability: Chloride Diffusion (D)

Dhir & Jones

Types of slag

· Air cooled slag: Low reactivity slag that finds use as aggregate.
The strength and toughness of this aggregate makes it a very
suitable material for railroad ballast.
· Expanded or foamed slag: Low reactivity slag that is foamed
with air. Makes a very good lightweight aggregate, and is used
for thermal insulation.
· Granulated: This is a high reactivity slag, and is usually
quenched. The hardened matter is then ground to a fineness
similar to cement. Thus the name: Ground Granulated Blast
Furnace Slag (GGBFS).
· Pelletized slag: The reactivity is similar to GGBFS, but the
process of pelletization is a complex one. Typically, this type of
slag is not used as much as GGBFS.
Factors governing properties

 Chemical composition of GGBFS

 Alkali concentration of reacting system
 Glass (reactive SiO2) content of GGBFS
 Fineness of GGBFS and PC
 Temperature during early phase of hydration
Hydration of slag

An activator is necessary to hydrate the slag. The

activation of slag hydration can be done in the
following ways:
 Alkali activation: e.g. by caustic soda (NaOH),
Na2CO3, sodium silicate, etc. The products formed
are C-S-H, C4AH13 and C2ASH8 (Gehlenite).
 Sulphate activation: e.g. by gypsum, hemihydrate,
anhydrite, phosphogypsum, etc. The products formed
are C-S-H, ettringite, and aluminium hydroxide (AH3).
 Mixed activation: When both alkali and sulphate
sources are present, such as in a cement system.
Effects on concrete properties

 Apart from delaying the initial set and strength gain,

slag does not significantly alter the fresh concrete
properties.
 The ultimate strengths with slag are generally
improved; the durability is also improved with the
replacement of cement by slag. Especially in marine
environments, slag is the material of choice
Metakaolin
Metakaolin

• Metakaolin is a white pozzolan made by calcining

(heating below melting temperature) the kaolin clay
to 600-800°C.
• The crystalline clay loses its structure at this
temperature by the loss of bound water.
– Due to dehydroxylation, a disordered amorphous state is
produced which is highly reactive.
– Higher temperatures should be avoided since
recrystallization of the clay occurs beyond 1000°C.
Properties of Metakaolin

• An alumina silicate [Al2O3 2(SiO2)] containing

– 40- 45% Al2O3
– 50- 55% SiO2
• The particle size of metakaolin is smaller than
cement but larger than silica fume.
• Colour white
• Specific gravity 2.6
• Bulk density 300 kg/m3
• Specific surface 12000 m2/kg
Metakaolin Reactions

• In addition to the filler effect, there is a pozzolanic

reaction
• Metakaolin reacts rapidly with CH in the cement
paste
AS2 + 6CH + 9H  C4AH13 + 2C-S-H
Other Mineral Admixtures – Rice Husk Ash

• Rice milling industry generates a lot of

rice husk during milling of paddy
which comes from the fields.
• Use of rice husk
– fuel in the boilers for processing of paddy
– fuel for power generation
• Rice husk ash (RHA) is about
25% by weight of rice husk when
burnt in boilers
• About 70 million tones/year of
RHA
– Environmental hazard
www.ricehuskash.com
Rice husk ash

• This is a high reactivity pozzolan obtained by

controlled calcination of rice husk.
• Field-burnt rice husk is almost crystalline in nature,
and makes a weak pozzolan. Thus, to obtain a high
degree of pozzolanicity, a good control is needed
while burning.
• RHA usually contains a large amount of unburnt
carbon which might adversely affect air entrainment.
• RHA is a fine material, with particle sizes less than 45
μm, and a surface area of 60000 m2/kg.
• The particles are typically cellular. A high amount of
reactive silica is present in the system (> 90%).
Other Mineral Admixtures - Titanium Dioxide

• Titanium dioxide (TiO2) has photocatalytic properties. In the

presence of ultraviolet light, it oxidises organic pollutants.
• Self-cleaning action
– a combination of white
cement and TiO2 can
oxidise the dirt that
accumulates on a
concrete surface

Concrete Intnl., Vol. 27, No. 10, 2005

Titanium Dioxide: Application

• Precast blocks of white

concrete were used to
construct the Jubilee Church
in Rome.
• To “ensure” enduring
whiteness, a special blend of
cement and TiO2 was used.
• Other components in the
concrete included white
metakaolin and crushed
marble.

Concrete Intnl., Vol. 27, No. 10, 2005

Advantages of mineral admixtures - Summary

• Consumption of CH or portlandite
• Densification
• Improve durability
• Reduce thermal cracking
• Improve workability and cohesiveness
• Reduce bleeding and segregation
• Increase ultimate strength
Effects of Supplementary Cementing Materials on
Fresh Concrete

PCA
References

• High-Performance, High-Volume Fly Ash Concrete, V.M. Malhotra & P.K. Mehta,
Supplementary Cementing Materials for Sustainable Development, 2002
• Concrete Technology for Sustainable Development in the Twenty-First Century, Ed. P.K.
Mehta, Cement Manufacturers’ Association, New Delhi, 1999
• Concrete, S. Mindess, J.F. Young, & D. Darwin, 2nd Edition, Prentice-Hall, Englewood
Cliffs, New Jersey, USA, 1981
• Concrete: Microstructure, Properties and Materials, P.K. Mehta & P.J.M. Monteiro, 3rd
Edition, Tata McGraw Hill Education Pvt. Ltd., New Delhi
• High-Performance Concrete, P.-C. Aïtcin, E&FN Spon, London, 1998
• The Science and Technology of Civil Engineering Materials, J.F. Young, S. Mindess, R.J.
Gray and A. Bentur, Prentice Hall, Upper Saddle River, New Jersey, USA, 1998
• Cement Chemistry, H.F.W. Taylor, Thomas Telford Publ., London, 1997
• Euro-Cements, Eds. R.K. Dhir & M.R. Jones, E&FN Spon, London, 1994
• Properties of Concrete, A.M. Neville, Pearson Education, Delhi, 2004
• Concrete Mixture Proportioning, F. de Larrard, E&FN Spon, London, 1999
• Portland Cement Association, USA, web site:
http://www.cement.org/basics/concretebasics_classroom.asp
• Cement Manufacturers’ Association (India), web site: http://www.cmaindia.org/index.html
• http://www.silicafume.org
• http://www.flyash.com
• ACI Materials Journal
THANK YOU