Mineral Admixtures (SCMs)

(CE 3420 – Concrete Technology)

Radhakrishna G. Pillai
Building Technology & Construction Management (BTCM) Division
Department of Civil Engineering
Indian Institute of Technology Madras, Chennai, India

Courtesy: Prof. Ravindra Gettu

Outline

• Pozzolanic reactions
• Various SCMs
– Production
– Characteristics

1
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) 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

2
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

Ettringite

PCA

Fly ash Silica Slag

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

3
Classification of mineral admixtures

• Cementitious
– Natural cements
– Hydraulic lime
– Ground granulated blast-furnace slag (GGBS)
• Pozzolanic
– Materials of natural origin
• crushed diatomites, 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

4
How to read Ternary diagrams?

1. 60% A + 20%B + 20%C = 100%

2. 25% A + 40%B + 35%C = 100%

3. 10% A + 70%B + 20%C = 100%

4. 0% A + 25%B + 75%C = 100%

http://csmres.jmu.edu/geollab/fichter/SedRx/readternary.html

How to read Ternary diagrams?

5. ___% A + ___%B + ___%C = 100%

6. ___% A + ___%B + ___%C = 100%

7. ___% A + ___%B + ___%C = 100%

8. ___% A + ___%B + ___%C = 100%

5
How to read Ternary diagrams?

Slag = __%SiO2 + __%CaO + __%Al2O3 = 100%

Comparison of the particle sizes of Silica fume,

Fly ash and Cement

Mehta and Monteiro

6
 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.

7
Silica Fume waste – air pollution in earlier days

http://www.silicafume.org

Silica Fume - production

http://www.silicafume.org

8
Silica Fume - production

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

9
Silica Fume Products

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

http://www.silicafume.org

Silica Fume Products: As-produced powder

• As produced directly from

bag house
• Extremely fine and dusty
• Difficult to handle
pneumatically -- sticky
• Self agglomerating with a
tendency to create small
weak lumps
• Low density yields small
loads (8 - 10 tons) (7 - 9 Mg)
in bulk tankers

http://www.silicafume.org

10
Silica Fume Products: Silica Fume Slurry

• 50 - 52% solids (as-produced

silica fume dispersed in
water)
• Storage tanks require
agitation and protection from
freezing
• Transported in bulk tankers
4,000 gallons (12 tons of
silica fume) (15 kL, 10 Mg)

http://www.silicafume.org

Silica Fume Products: Densified Silica Fume

• Reversible agglomeration
process
• Flows well pneumatically
• Bulk transportation is
economical, 22 tons (20 Mg)
on a bulk tanker
• Product density can be
controlled for handling
conditions and applications

http://www.silicafume.org

11
Silica Fume Products: Densified Silica Fume

http://www.silicafume.org

Silica Fume Products: Blended Silica Fume

Cement
• Primarily used in Northeastern Canada, limited availability in
US
• Fixed silica fume content of 7.5% to 8.5%
• Produced from as-produced, densified, or pelletized silica
fume
• Portland cement-silica fume blend is primary product. One
blend of silica fume, fly ash, and portland cement now being
marketed

http://www.silicafume.org

12
Silica Fume Products: Pelletized Silica Fume

• Dustless
• Non-reversible agglomeration
• Small pellets, typically 3/8 to 1 inch (10 to 25 mm) diameter
• Utilized in interground silica fume blended cement
• Not suitable for direct use in concrete!

http://www.silicafume.org

Silica Fume Color

Premium -- White Standard -- Grey

http://www.silicafume.org

13
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

14
Silica Fume: Physical Effect

• The presence of any type of very small particles will improve

concrete properties. This effect is termed either “particle
packing” or “micro filling”.
• The carbon black and plain cement mixes showed
comparable strengths at both 7 and 28 days, even though
the carbon black mixes contained 10 percent less cement
(by mass) ... physical mechanisms do play a significant
role, particularly at early ages

Detwiler and Mehta, ACI Materials Journal

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

15
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

16
The Transition Zone in silica fume concrete

• 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.
• Silica fume plays a significant role in the transition zone
through both its physical and chemical effects.

http://www.silicafume.org

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

17
Better aggregate-paste interface

• If the transition zone is strengthened, the weakest

link is no longer the interface.

http://www.silicafume.org

Improved Compressive Strength

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

http://www.silicafume.org

18
 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

2% chloride solution

Dhir & Jones

19
Improved Resistance Against Acid Attack

Cycles to 25% Mass Loss

60
50
0% sf
No. of cycles

40 7.5% sf
12.5% sf
30
15% sf
20 25% sf
30% sf
10
0
1% 5% 5% 5%
H2SO4 CH3COOH HCOOH H2SO4
(Sulfuric) (Acetic) (Formic) (Sulfuric)

Improved Shotcreting

• Reduction of rebound loss

up to 50%
• Increased one-pass
thickness up to 30 cm
• Higher bond strength
• Improved cohesion to
resist washout in tidal
rehabilitation of piles and
seawalls

20
Effects of adding silica fume to concrete –
Summary on fundamentals

http://www.silicafume.org

Fly Ash

PCA

21
Fly-Ash in India

• ≈ 73% of India’s electricity

generation is through coal-burning
thermal power stations.
• Coal ash generation, C ≈ 200 million tons/year
• India’s population, P ≈ 1.2 billion = 1200 million
• India’s area, A ≈ 3.3 million km2
• C/P = 0.17 tons/year/person
• C/A = 60 tons/year/km2
• Only about 25% of fly ash is being utilized in
various industries; remaining gets dumped in
landfills.

Coal - Basics

Peat Anthracite

The higher the rank of a piece of coal, the harder and more lustrous it is.

http://www.uky.edu/KGS/coal/coalkinds.htm; http://www.wou.edu/las/physci/GS361/Fossil%20fuels/Coal.htm

22
Fly-Ash - Basics

• Class F fly ash

– Derived from bituminous coal, is mainly siliceous
– Generally low in lime (say, < 15%)
– Has pozzolanic properties
• Class C fly ash
– Derived from sub-bituminous coal and lignite
– An ash with higher lime content (say, > 15 to 30)
– Has both pozzolanic and cementitious properties

Component Bituminous Subbituminous Lignite

SiO2 (%) 20-60 40-60 15-45
Al2O3 (%) 5-35 20-30 20-25
Fe2O3 (%) 10-40 4-10 4-15
CaO (%) 1-12 5-30 15-40
LOI (%) 0-15 0-3 0-5
http://www.flyash.com

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

23
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

24
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
Fly ash test Setting time, relative to
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

25
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

26
Influence of Fly Ash on Hardened Concrete

• Durability: Chloride Diffusion

Dhir & Jones

Barriers for Higher Usage of Fly Ash in the

Cement and Concrete Industry
• Variable quality of fly ash. Uniformity is not maintained even
from a single source of supply. Processing and continuous
monitoring is needed.
• Small variations in chemical composition do not affect the
concrete properties as much as the fineness of fly ash.
• Strength development and durability issues are not well
understood.
• Design codes impose limits on dosage of fly ash.
• Presence of leachable toxic chemicals in fly ash. However,
these chemicals are bonded by the hydration products. Less
harmful than leaching from landfills.

27
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 very 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

28
 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

www.nationalslag.org

29
Ground Granulated Blast-Furnace Slag (GGBS)

Chemical composition of GGBS

• Quenched slag is a glass

containing CaO, SiO2 and
Al2O3.

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

30
Water-quenching of slag

http://www.generalkinematics.com/foundry-equipment/vibratory-quenching-conveyors/

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

31
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

32
Influence of GGBS on Hardened Concrete

• Durability: Chloride Diffusion (D)

Dhir & Jones

Metakaolin

33
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

34
Metakaolin Reactions

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

– 40- 45% Al2O3
– 50- 55% SiO2
• 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

Comparison between Metakaolin and Silica Fume

• Faster strength development at early ages compared to

silica fume but final strength is same.
• Performance comparable to silica fume as a mineral
admixture in concrete in terms of ultimate strength and
chloride permeability.
• Production process of metakaolin is more energy intensive.
• Applications of silica fume and metakaolin

35
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

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

36
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

37
Effects of Supplementary Cementing Materials on
Fresh Concrete

PCA

Effects of Supplementary Cementing Materials on

Hardened Concrete

PCA

38
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

39