Module 3 Mineral Admixtures

Admixtures in Concrete 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”.

NAJEEB M
Assistant Professor,
MEA Engineering College ,
Perinthalmann.

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

Challenges in concrete technology Admixture

• We need high quality concrete

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

High quality concrete essentially contains

admixtures

4
2

Dept. of Civil Engineering, MEAEC 1

Module 3 Mineral Admixtures

What are mineral admixtures and supplementary

Cement hydration
cementitious materials (SCMs)?
• Reaction of cement with water • A mineral admixture is a finely ground solid material
• Exothermic; heat released is called ‘Heat of Hydration’ that, when used in conjunction with portland
• Rate of heat evolution is faster if the reaction is quicker cement, contributes to the properties of the
hardened concrete through hydraulic or pozzolanic
• Heat evolved depends on heat of hydration of individual activity, or both.
compounds, and also on the clinker morphology!
• 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.

5 7
PCA

Reactions - Specifics What is a pozzolan?

• 2 C3S + 6 H  C3S2H3 + 3 CH • The American Society for Testing and Materials

• 2 C2S + 4 H  C3S2H3 + CH (ASTM C595) defines pozzolan as
• 2 C3A + 21 H  C4AH13 + C2AH8 – “a siliceous or siliceous and aluminous material,
Flash set reaction! which in itself possesses little or no cementitious
value, but will, in finely divided form and in the
• C2AH8 is a metastable phase that deposits as hexagonal presence of moisture, chemically react with
platelets (similar to CH). Above 30 oC, it is converted to calcium hydroxide at ordinary temperatures to
cubic hydrogarnet (C3AH6). form compounds possessing cementitious
• In the presence of gypsum, properties”
C3A + 3 CSH2 + 26 H  C6AS3H32

6 8
PCA

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Module 3 Mineral Admixtures

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
PCA aggregates and/or increase the paste content without
increasing the cement dosage (i.e., as a filler material).
Fly ash Silica • To decrease the environmental impact of concrete (i.e., by
Slag
(Class C) fume saving cement and/or utilising a waste product)
Metakaolin Fly ash Calcined
(calcined clay) (Class F) shale
NOTE: 9 11
Color may vary, mostly depending on the iron, carbon, and other impurities Mehta and Monteiro

Classification of mineral admixtures Aggregate-paste interface

• Cementitious • In usual concrete, zone of

– Hydraulic lime
0.05 to 1 mm thickness
– Ground granulated blast-furnace slag (GGBS)
• Pozzolanic contains large crystals of
– Materials of natural origin Ca(OH)2 and pores.
• volcanic ashes and metakaolin
– Fly ash
• One reason for the higher
– Microsilica or silica fume porosity of this zone is the
• Materials of low or negligible reactivity accumulation of
– Limestone (CaCO3), quartz (SiO4) or other rock dust
– Bentonite
bleed water at the surface of coarse aggregate
– Hydrated lime particles.

10 12
PCA http://www.silicafume.org

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Module 3 Mineral Admixtures

Effects of adding mineral admixture to concrete –

Better aggregate-paste interface
Summary on fundamentals
• If the transition zone is strengthened, the weakest
Mineral
link is no longer the interface. admixture

13 15
http://www.silicafume.org http://www.silicafume.org

The Transition Zone in concrete with mineral

admixture Fly Ash
• 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.

14 16
http://www.silicafume.org PCA

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Module 3 Mineral Admixtures

Source Rank of coal

• By-product obtained during combustion of coal in thermal

power plants 5. Lignite (brown coal)
• The quality and composition of fly ash depends on the type 4. Sub-bituminous coal (70 – 80% C)
of coal being burnt 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.

17 19

Need for fly ash utilization Uses of fly ash

· As a mineral admixture
• Nearly 73% of India’s total power generation is
thermal (mostly using coal) • As a filler
• 140 million tons of fly ash being generated annually · As a synthetic aggregate: Fly ash aggregate
• World Bank - Disposal of coal ash would require can be produced by sintering. The resultant
1000 square kilometres or one square metre of land aggregate can be used for lightweight
per person in India concrete. However, it is very expensive.
• Increased disposal implies more environmental Aggregate can also be synthesized by
hazards (lead and arsenic pollution), diseases, etc. 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
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admixtures 20

Dept. of Civil Engineering, MEAEC 5

Module 3 Mineral Admixtures

ASTM Classification Collection of fly ash

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

 Type C: This is also called High Calcium fly ash, and ash flies out with the flue gas, and is thus
possesses both cementitious and pozzolanic
properties. 10 – 15% of the material has a particle called ‘fly ash’. The ash that doesn’t fly out
size greater than 45 μm, and the fineness (Blaine) is is called ‘bottom ash’. This can be
300 – 400 m2/kg. The particles are primarily solid processed as aggregate, but is generally
spheres with a smooth texture. The average particle
size is less than 20 μm. not used in concrete.
• The collection of fly ash is done using the
 Type F: This is also called Low Calcium fly ash, and following two types of precipitators:
is a normally pozzolanic material. 15 – 20% of the
material is larger than 45 μm, and the fineness is 200 - Bag-house precipitator
– 300 m2/kg. Particles are solid spheres with a - Electrostatic precipitator
smooth texture, and the average particle size is 20
μm. • The bag-house precipitator is found to be
more efficient, and removes out very fine
21
material 23

Fly-Ash – Major uses Precipitators

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

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

22 24
http://www.flyashindia.com

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Module 3 Mineral Admixtures

Fly-Ash – Production 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?

25 27
http://www.flyashindia.com

Fly-Ash – Structure and physical properties Influence of Fly Ash on Fresh Concrete

• Spherical glassy particles formed due to rapid • Water demand is reduced for a given consistency
cooling of the molten ash in the furnace. – Due to the small size and glassy texture
• Apart from the solid spheres, there also may exist • Increased setting time
hollow spheres. Retardation
– Cenospheres - small hollow spheres with entrapped gas Setting time, relative to
Fly ash test mixtures hr:min control, hr:min
– Plerospheres - large hollow spheres with solid spheres
inside them. Initial Final Initial Final
• Particle size Average Class C
4:40 6:15 0:25 0:45
– between <1 μm and 100 μm of:
– Blaine specific surface is usually Class F 4:50 6:45 0:35 1:15
between 250 and 600 m2/kg Control mixture 4:15 5:30 — —
26 28
PCA Scanning electron microscope (SEM) micrograph of fly ash particles at 1000X PCA

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Module 3 Mineral Admixtures

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

• Improved workability and flowability of concrete • Creep and shrinkage of fly ash concrete are
– Due to the spherical shape of the fly ash typically lower than normal concrete
particles, which has a “ball-bearing” effect. – lower amount of paste in the concrete
– Due to the reduction in the size & volume of • Resistance against corrosion, alkali aggregate
voids because of finely divided particles. reaction and sulphate attack is increased
– Therefore, the paste demand decreases. – less permeable and porous microstructure and reduced
• Reduced bleeding and segregation for well- portland cement content
proportioned fly ash concrete
Fly ash Bleeding
mixtures Percent ml/cm2
Class C 0.34 0.011
Class F 1.31 0.044 29 31
PCA Control 1.75 0.059 PCA

Influence of Fly Ash on Hardened Concrete High-Volume Fly Ash (HVFA) Concrete

• Ultimate strengths are reached much after 28 days. • Concrete with 50% of the portland cement replaced
• Strength gain due to pozzolanic activity of fly ash concrete is by Class F fly ash
slower than normal concrete.
• Low water content, generally less than 130 kg/m3.
– Up to 28 days, due to particles < 10 μm in diameter
– After 28 days, due to particles between 10 and 45 μm in diameter
For slumps of 150-200mm, the use of a
• This leads to lower thermal cracking. 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-
30 compacting concrete. 32
PCA

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Module 3 Mineral Admixtures

High-Volume Fly Ash Concrete Specialized applications

• Comparison of mixes for a 25 MPa strength

concrete  In high strength concrete, as an additional
Components for Conventional High-Volume cementitious material.
1 m3 of concrete Concrete Fly Ash  In roller-compacted concrete. Fly ash is good
Concrete for bonding in-between the layers of this
Cement 307 154 concrete.
Fly Ash -- 154  In controlled low-strength materials (CLSM),
Water 178 120
which are flowable mortars used as backfill
Coarse aggregate 1040 1210
Fine aggregate 825 775  As a synthetic aggregate
• For manufacture of bricks
33 35
Mehta, 2002

Barriers to use of fly ash Issues with fly ash

1. Difficult quality assurance

2. Poor marketing • Due to transportation cost, the use of fly ash far from
3. Conservative attitudes the thermal power plant becomes uneconomical
4. Storage problems • Lack of appropriate technologies for handling and
5. It is called a ‘waste’ instead of pozzolan or cement transportation

34 36

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Module 3 Mineral Admixtures

Silica Fume Silica Fume waste – air pollution in earlier days

37 39
http://www.silicafume.org

Silica Fume Silica Fume - production

• ACI 116R definition • After being collected over the

furnace, the silica fume must
– A very fine amorphous (noncrystalline) silica produced in electric be transferred, cooled, and
arc furnaces as a byproduct of the production of elemental physically trapped.
silicon or alloys containing silicon; also known as condensed • The large pipe on the left is
silica fume or microsilica. bringing the silica fume from
the furnaces.
• ASTM C1240 definition
• The vertical elements are
– A finely divided residue resulting from the production of silicon, cyclones that are used to
ferro-silicon, or other silicon-containing alloys that is carried from remove oversize and other
the burning surface area of an electric-arc furnace by exhaust unwanted materials.
gases. • The large building is the bag
house where the fume is
38 captured. 40
http://www.silicafume.org

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Module 3 Mineral Admixtures

Silica Fume Products: Densified Silica Fume Silica Fume Color

Premium -- White Standard -- Grey

41 43
http://www.silicafume.org http://www.silicafume.org

Silica Fume Products Silica Fume – Physical characteristics

• As-produced powder • Particle size (typical) <1µm

• Water-based slurry • Bulk density
• Densified as-produced = 130 to 430 kg/m3
• Blended silica-fume cement slurry = 1320 to 1440 kg/m3
• Pelletized densified = 480 to 720 kg/m3
• Specific gravity 2.2
• Surface area 13,000 to 30,000 m2/kg

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

42 44
http://www.silicafume.org http://www.silicafume.org

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Module 3 Mineral Admixtures

Silica Fume – Particle size Silica Fume: Chemical properties and effects

Cement Particles Silica fume particles • Amorphous

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

45 47
http://www.silicafume.org http://www.silicafume.org

Consequences of Silica Fume: Fresh concrete is

Silica Fume: Effects in Concrete
more cohesive
• Physical effect: Acts as a • Due to the increased fineness (than cement), the use of
micro-filler due to its small silica fume causes an increase in the water demand of
particle size 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.
• Chemical effect: Has high Consequently, a higher slump is needed to place silica fume
concrete. Also, concrete mixes with silica fume are prone to
pozzolanicity 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.
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http://www.silicafume.org http://www.silicafume.org

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Module 3 Mineral Admixtures

Although the slump may be higher in silica fume

Improved Corrosion Protection
concrete, compaction is required
 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

49
>10% < 500 coulombs > 65 MPa
http://www.silicafume.org http://www.silicafume.org

Improved Compressive Strength Improved Corrosion Protection

• Chloride Diffusion after 6 months of exposure to

1.9% chloride solution

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

50 52
http://www.silicafume.org Dhir & Jones

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Module 3 Mineral Admixtures

..(contd.) Improved Shotcreting

• Reduction of rebound loss

 Corrosion rate is reduced with the use of
silica fume. This is because of two reasons: up to 50%
the low permeability of SFC causes a lower • Increased one-pass
availability of moisture and oxygen at the thickness up to 300 mm
cathodic sites, and the high resistivity of SFC • Higher bond strength
makes the flow of electrons difficult.
• Improved cohesion to
 Carbonation depth is generally lowered.
resist washout in tidal
 SFC has very good abrasion and erosion
rehabilitation of piles and
resistance.
seawalls
 Fire performance of SFC is not very good

53 55

Improved Resistance Against Acid Attack

Blast-furnace Slag
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
54 56

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Module 3 Mineral Admixtures

Ground Granulated Blast-Furnace Slag (GGBS) Structure and action of GGBS

• Blast furnace slag is a by-product of • Water quenched slag: the non-metallic, granulated
the extraction of pig iron from iron ore. slag remains in an amorphous state (calcium
• Coke and limestone are added as alumino silicate glassy), which gives it hydraulic
fluxes inside the blast furnace.
qualities.
• The impurities in iron ore combine
– Slow air-cooled slag (crystalline calcium magnesium
with the lime and rise up to the
silicate) is hydraulically inert
surface of the blast furnace as slag,
while the heavier molten iron stays at • The hydraulicity of slag is activated by calcium
the bottom. hydroxide in concrete
• The slag is subsequently granulated – Other alkali hydroxides also contribute
and can be ground later to the desired • GGBS is reactive, forming an alumina-substituted
fineness
– usually greater than 350 m2/kg
C-S-H as follows:
57 C-S-A + H → C-S-H 59

Chemical composition of GGBS Influence of GGBS on Fresh Concrete

• Quenched slag is a glass • Water demand is reduced for a given consistency

containing CaO, SiO2 and – Due to the small particle size and glassy texture
Al2O3. • 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

58 60
http://www.bvslag.com/blast_furnace_slag_uses.htm

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Module 3 Mineral Admixtures

Influence of GGBS on Hardened Concrete Types of slag

• The microstructure is denser

– less CH and more C-S-H are produced · Air cooled slag: Low reactivity slag that finds use as aggregate.
The strength and toughness of this aggregate makes it a very
• Heat development is lowered
suitable material for railroad ballast.
– Rate of hydration of slag is similar to that of C2S
· Expanded or foamed slag: Low reactivity slag that is foamed
• Activation energy is 55 kJ/g as opposed to 40 kJ/g of cement
with air. Makes a very good lightweight aggregate, and is used
• Higher long-term strength gain, especially when the fineness for thermal insulation.
is high · Granulated: This is a high reactivity slag, and is usually
• Resistance against corrosion is increased quenched. The hardened matter is then ground to a fineness
similar to cement. Thus the name: Ground Granulated Blast
– due to a less permeable and porous microstructure
Furnace Slag (GGBFS).
• Resistance to sulphate attack is improved · Pelletized slag: The reactivity is similar to GGBFS, but the
– due to lower calcium hydroxide content process of pelletization is a complex one. Typically, this type of
• Alkali aggregate reactivity is lowered slag is not used as much as GGBFS.
– due to the reduction in the alkali mobility by the lower permeability
61 63

Influence of GGBS on Hardened Concrete Factors governing properties

• Durability: Chloride Diffusion (D)

 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

62 64
Dhir & Jones

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Module 3 Mineral Admixtures

Hydration of slag
Metakaolin
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.

65 67

Effects on concrete properties Metakaolin

• Metakaolin is a white pozzolan made by calcining

 Apart from delaying the initial set and strength gain, (heating below melting temperature) the kaolin clay
slag does not significantly alter the fresh concrete to 600-800°C.
properties.
• The crystalline clay loses its structure at this
 The ultimate strengths with slag are generally
improved; the durability is also improved with the temperature by the loss of bound water.
replacement of cement by slag. Especially in marine – Due to dehydroxylation, a disordered amorphous state is
environments, slag is the material of choice produced which is highly reactive.
– Higher temperatures should be avoided since
recrystallization of the clay occurs beyond 1000°C.

66 68

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Module 3 Mineral Admixtures

Properties of Metakaolin Other Mineral Admixtures – Rice Husk Ash

• An alumina silicate [Al2O3 2(SiO2)] containing • Rice milling industry generates a lot of
rice husk during milling of paddy
– 40- 45% Al2O3
which comes from the fields.
– 50- 55% SiO2
• Use of rice husk
• The particle size of metakaolin is smaller than – fuel in the boilers for processing of paddy
cement but larger than silica fume. – fuel for power generation
• Colour white • Rice husk ash (RHA) is about
• Specific gravity 2.6 25% by weight of rice husk when
burnt in boilers
• Bulk density 300 kg/m3
• About 70 million tones/year of
• Specific surface 12000 m2/kg
RHA
– Environmental hazard
69 71
www.ricehuskash.com

Metakaolin Reactions Rice husk ash

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

reaction • This is a high reactivity pozzolan obtained by
controlled calcination of rice husk.
• Metakaolin reacts rapidly with CH in the cement
• Field-burnt rice husk is almost crystalline in nature,
paste and makes a weak pozzolan. Thus, to obtain a high
AS2 + 6CH + 9H  C4AH13 + 2C-S-H 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%).
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Module 3 Mineral Admixtures

Other Mineral Admixtures - Titanium Dioxide Advantages of mineral admixtures - Summary

• Titanium dioxide (TiO2) has photocatalytic properties. In the • Consumption of CH or portlandite

presence of ultraviolet light, it oxidises organic pollutants. • Densification
• Self-cleaning action • Improve durability
– a combination of white
• Reduce thermal cracking
cement and TiO2 can
• Improve workability and cohesiveness
oxidise the dirt that
accumulates on a • Reduce bleeding and segregation
concrete surface • Increase ultimate strength

73 75
Concrete Intnl., Vol. 27, No. 10, 2005

Effects of Supplementary Cementing Materials on

Titanium Dioxide: Application
Fresh Concrete
• 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.
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Concrete Intnl., Vol. 27, No. 10, 2005 PCA

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Module 3 Mineral Admixtures

Rate of pozzolanic reaction

THANK YOU

77 79

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 78
• ACI Materials Journal

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