SUPPLEMENTARY CEMENTING MATERIALS

lecture
Significance Supplementary Cementing Materials

Significance
Supplementary cementing materials (SCMs) contribute to the
properties of hardened concrete through hydraulic or
pozzolanic activity. Typical examples are fly ashes, slag
cement (ground, granulated blast-furnace slag), and silica
fume. These can be used individually with portland or
blended cement or in different combinations. Supplementary
cementing materials are often added to concrete to make
concrete mixtures more economical, reduce permeability,
increase strength, or influence other concrete properties.
Introduction to Supplementary Cementing Materials

Fly ash, ground granulated blast-furnace

slag, silica fume, and natural pozzolans,
(calcined shale, calcined clay or
metakaolin).

When used in conjunction with portland

or blended cement, contribute to the
properties of the hardened concrete
through hydraulic or pozzolanic activity
or both.

These materials are also generally

categorized as supplementary cementing
materials (SCM's) or mineral admixtures.
What do we mean by pozzolan ?
 A POZZOLAN: is a siliceous or alumino-siliceous material
that which, in themselves, possess little or no cementitious value
but which will, in finely divided form and in the presence of
moisture, chemically reacts with the calcium hydroxide released
by the hydration of portland cement to form calcium silicate
hydrate (C-S-H) and other cementing compounds.
 Supplementary cementing materials are added to concrete as
part of the total cementing system. They may be used in
addition to or as a partial replacement of portland cement or
blended cement in concrete, depending on the properties of
the materials and the desired effect on concrete.
Fly ASH
 Fly ash is a finely divided residue (a
powder resembling cement) that results from
the combustion of pulverized coal in electric
power generating plants (See Fig. 3-2).
Upon ignition in the furnace, most of the
volatile matter and carbon in the coal are
burned off.
 During combustion, the coal's mineral
impurities (such as clay, feldspar, quartz,
and shale) fuse in suspension and are
carried away from the combustion chamber
by the exhaust gases. In the process, the
fused material cools and solidifies into
spherical glassy particles called fly ash (See
Fig. 3-3). The fly ash is then collected from
the exhaust gases by electro-static
precipitators or bag filters.
Fly ASH
 For fly ash without close compaction, the bulk density (mass
per unit volume including air between particles) can vary from
540 to 860 kg/m 3 , whereas with close packed storage or
vibration, the range can be 1120 to 1500 kg/m 3 .

 Fly ash is primarily silicate glass containing silica, alumina,

iron, and calcium. Minor constituents are magnesium, sulphur,
sodium, potassium, and carbon. Crystalline compounds are
present in small amounts. The relative density (specific gravity)
of fly ash generally ranges between 1.9 and 2.8 and is
generally tan or grey in colour.
Types of Fly ASH
 Class F materials are low-calcium (less than 8% CaO) fly ashes with
carbon contents less than 5%, but some may be as high as 10%.

 Class C materials have higher calcium contents than Class F ashes.

Class C ashes generally have carbon contents less than 2%. Many
Class C ashes when exposed to water will hydrate and harden in
less than 45 minutes.

 Class F fly ash is often used at dosages of 15% to 25% by mass of

cementing material.
 Class C fly ash is used at dosages of 15% to 40% by mass of
cementing material.
Silica Fume
 Silica fume, also referred to as micro-
silica or condensed silica fume, is a by
product material that is used as a
pozzolan (See Fig. 3-7). This by
product is a result of the reduction of
high-purity quartz with coal in an
electric arc furnace in the manufacture
of silicon metal or ferrosilicon alloy.
 Silica fume rises as an oxidized vapour
from the 2000°C furnaces. When it
cools it condenses and is collected in
huge cloth bags. The condensed silica
fume is then processed to remove
impurities and to control particle size.
Silica Fume
 The relative density of silica fume is generally in the range of
2.20 to 2.25, but can be as high as 2.5. The bulk density of
silica fume varies from 130 to 430 kg/m3. Silica fume is sold in
powder form but is more commonly available in a liquid.

 Silica fume is used in amounts between 5% and 10% by mass

of the total cementing material. It is used in applications where
a high degree of impermeability is needed and in high-
strength concrete.
Slag
 Ground granulated blast furnace slag, also called slag cement, is
made from iron blast-furnce slag; it is a non-metallic hydraulic
cement consisting essentially of silicates and alumino-silicates of
calcium developed in a molten condition simultaneously with iron in a
blast furnace.
 The molten slag at a temperature of about 1500°C is rapidly
cooled by quenching in water to form a glassy sand like granulated
material. The granulated material, which ground to less than 45
microns, has a surface area fineness of about 400 to 600 m2/kg.
the relative density is in the range of 2.85 to 2.95. The bulk density
varies from 1050 to 1375 kg/m3 .
 The slag cement has rough and angular-shaped particles, and in the
presence of water and CaOH or NaOH supplied by Portland
cement, it hardens and sets in a manner similar to Portland cement.
Natural Pozzolans
 Natural pozzolans have been used for centuries.
Many of the Roman, Greek, Indian, and Egyptian
pozzolan concrete structures can still be seen today.

 The most common natural pozzolans used today are

process materials, which are heat treated in a kiln
and then ground to a finer powder, they include:
Calcined clay, Calcined shale, Metakaolin.
Effects on Freshly Mixed Concrete
Water Requirements
 Concrete mixtures containing fly ash generally require less
water (1% to 10% less) for a given slump than concrete
containing only Portland cement. Similarly ground slag
decreases water demand by 1% to 10% depending on
dosage.
 The water demand of concrete containing silica fume increases
with increasing amounts of silica fume, unless water reducer or
super plasticizer is used.
 Natural pozzolans have little effect on water demand at normal
dosages.
Effects on Freshly Mixed Concrete
Workability
 Fly ash, slag, and some natural pozzolans generally improve
the workability of concretes of equal slump. While silica
fume may reduce the workability and contribute to the
stickiness of a concrete mixture.
Bleeding and Segregation
 Due to the reduced water demand, concretes with fly ash
generally exhibit less bleeding and segregation than plain
concretes.
 Ground slag (with similar fineness as cement) may increase
the rate and amount of bleeding with no adverse effect on
segregation. Ground slag finer than cement reduce
bleeding.
Effects on Freshly Mixed Concrete
Setting Time
 Fly ash, ground slags, and natural pozzolans will
generally increase the setting time of concrete. Silica
fume may reduce the setting time of concrete.
Plastic Shrinkage Cracking
 Silica fume concrete may exhibit an increase in plastic
shrinkage cracking due to the effect of low bleeding
characteristics. Proper protection against drying is
required during and after finishing. Other
supplementary cementing materials that significantly
increase setting time can increase the risk of plastic
shrinkage.
Effects on Freshly Mixed Concrete
Curing
 Concrete containing supplementary cementing
materials need proper curing. The curing should
start immediately after finishing. A seven-day moist
curing or membrane curing should be applied.
Some organizations specify at least 21 days of
curing for all concrete containing pozzolanic
materials.
Effects on Hardened Concrete
Strength
 All supplementary materials contribute to the strength
gain of concrete. However, the strength of concrete
containing these materials can be higher or lower than
concrete with only cementing materials.
 The strength gain can be increased by one or
combination of the following:
 Increasing the amount of cementitious materials in concrete.
 Adding high-early strength cementitious materials.
 Decreasing the w/c ratio.
 Increasing the curing temperature.
 Using an accelerating admixture.
Effects on Hardened Concrete
Drying Shrinkage and Creep
 When used in low to moderate contents, the effect of
supplementary materials on the drying shrinkage and
creep is small and of little practical significance.
Permeability and Absorption
 With adequate curing the concrete with supplementary
materials will reduce the permeability and water
absorption. Silica fume and other pozzolanic materials
can improve the chloride resistance under 1000
Coulombs using ASTM C 1202.
Effects on Hardened Concrete
Sulphate Resistance
 The sulphate and seawater damaging effect on concrete can
be reduced significantly by using silica fume, fly ash, and
ground slag. The improvement can be reached by reducing
the permeability and reducing the reactive materials such as
calcium needed for expansive sulfate reactions.
Corrosion of Embedded Steel
 The improvement in corrosion resistance of concrete can be

achieved by reducing the permeability and increasing the

electrical resistivity of concrete. Fly ash can reduce the
permeability of concrete to water, air, and chloride ions. Silica
fume greatly reduce the permeability and increase the
electrical resistivity.
 Sulfate attack mechanism and prevention in
concrete
Introduction
 Sulfate attack is a chemical breakdown mechanism where sulfate ions
attack components of the cement paste.
 The compounds responsible for sulfate attack are water-soluble sulfate-
containing salts, such as alkali-earth (calcium, magnesium) and alkali
(sodium, potassium) sulfates that are capable of chemically reacting with
components of concrete.
Sulfate attack might show itself in different forms Depending on;
• The chemical form of the sulfate.
• The atmospheric environment which the concrete is exposed to.
What happens when sulfates get into concrete?

 It combines with the C-S-H, or concrete paste, and begins

destroying the paste that holds the concrete together. As
sulfate dries, new compounds are formed, often called
ettringite.

 These new crystals occupy empty space, and as they continue

to form, they cause the paste to crack, further damaging the
concrete.
 Sulfate Sources
1. INTERNAL SOURCES:
More rare but, originates from such concrete-making materials as hydraulic
cements, fly ash, aggregate, and admixtures.
• Portland cement might be over-sulfated.
• Presence of natural gypsum in the aggregate.
• Admixtures also can contain small amounts of sulfates.

2. EXTERNAL SOURCES:
External sources of sulfate are more common and usually are a result of high-
sulfate soils and ground waters, or can be the result of atmospheric or industrial
water pollution.
• Soil may contain excessive amounts of gypsum or other sulfate.
• Ground water be transported to the concrete foundations, retaining walls,
and other underground structures.
• Industrial waste waters.
Nature of reaction (chemical, Physical)

SULFATE ATTACK processes decrease the

durability of concrete by changing the chemical
nature of the cement paste, and of the mechanical
properties of the concrete.
 SULFATE ATTACK
Chemical process
 The sulphate ion + hydrated calcium aluminate and/or the calcium
hydroxide components of hardened cement paste + water = ettringite
(calcium sulphoaluminate hydrate)
 C3A.Cs.H18 + 2CH +2s+12H = C3A.3Cs.H32
 C3A.CH.H18 + 2CH +3s + 11H = C3A.3Cs.H32

 The sulphate ion + hydrated calcium aluminate and/or the calcium

hydroxide components of hardened cement paste + water = gypsum
(calcium sulphate hydrate)
• Na2SO4+Ca(OH)2 +2H2O = CaSO4.2H2O +2NaOH
• MgSO4 + Ca(OH)2 + 2H2O = CaSO4.2H2O + Mg(OH)2
 SULFATE ATTACK
Physical process
 The complex physico-chemical processes of "sulfate attack" are
interdependent as is the resulting damage.

 physical sulfate attack, often evidenced by bloom (the

presence of sodium sulfates Na2SO4 and/or Na2SO4.10H2O)
at exposed concrete surfaces.

 It is not only a cosmetic problem, but it is the visible displaying

of possible chemical and micro-structural problems within the
concrete matrix.
Both chemical and physical phenomena
observed as sulfate attack, and their
separation is inappropriate.
DIAGNOSIS:- Spalling Due To Sulfate Attack
Micro-Scopical Examination
Prevention measures
Main factors affecting sulfate attack:
1. Cement type and content:
The most important mineralogical phases of cement that affect the
intensity of sulfate attack are: C3A, C3S/C2S ratio and C4AF.
Prevention Measures
2. Fly ash addition
The addition of a pozzolanic
admixture such as fly ash reduces
the C3A content of cement.
 Prevention Measures

3. Sulfate type and concentration

The sulfate attack tends to increase with an increase in the concentration
of the sulfate solution up to a certain level.

Other factors;
• The level of the water table and its seasonal variation

• The flow of groundwater and soil porosity

• The form of construction

• The quality of concrete

Control Of Sulfate Attack

1. The quality of concrete, specifically a low permeability, is the best

protection against sulfate attack.
• Adequate concrete thickness
• High cement content
• Low w/c ratio
• Proper compaction and curing
Control Of Sulfate Attack

Effect of w/c ratio

 Control Of Sulfate Attack

2. The use of sulfate resisting cements provide additional safety against

sulfate attack
Exposure Concentration of water-soluble sulfates
In soil per cent In water ppm
Mild <0.1 <150
Moderate 0.1 to 0.2 150 to 1500
Sever 0.2 to 2.0 1500 to 10000
Very sever >2.0 >10000
Contents

A BACKGROUND:
FORST DAMAGE MECHANISM

B CONTROL METHODS
Background
Freeze-thaw Deterioration
Concrete, like other highly divided
porous media, has the ability to absorb
and retain moisture. This characteristic
has an important consequence since
unprotected concrete structures in
contact with water are usually
susceptible to frost damage.
Background
Frost Damage Mechanism
Concrete Condition: Unsaturated
• The pore structure is filled by small amount of water.
• Once temperature drops to 0ºC – Thermal contraction occurs.
• From 0ºC to minimum temperature – Water in larger pores freezes.

ice

water

• From freezing temperature to thawing – ice melts and water flows to pore spaces.
Background
Frost Damage Mechanism
Concrete Condition: Saturation Process
- Possible only if water is available outside during thawing at temperature above 0ºC.
- When freezing for temperature below 0ºC – water freezes and volume expands (can create tension to
concrete).
- At temperature below -10ºC to minimum temperature – ice contracts in larger pores.
-

Contracted Ice

water
Increment pore space

- From minimum temperature to -5ºC during thawing – ice expands more than surrounding concrete.
 Background
Frost Damage Mechanism
Concrete Condition: Saturated Condition
- In this condition, the pore structure is totally filled by water.
- As temperature continues to drop, the expansion of water creates a very high positive hydraulic
pressure.
- For lowest temperature – water in smaller pores also freezes.

Larger cracks

Smaller pores
begin to freeze

Ice
END OF LECTURE