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Advance Structural Materials

Lecture – 4
Mineral Admixtures

Dr. Muazzam Ghous

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Admixtures
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Admixtures
ASTM C 125 defines an :

“a material other than water, aggregates, hydraulic cements, and

fiber reinforcement that is used as an ingredient of concrete or
mortar and added to the batch immediately before or during
mixing”

Added in small quantity either in powder or liquid form

Combination is used when more than one property to be altered

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Admixtures
PURPOSE

 To modify fresh property

 Increase the workability without increasing the water cement ratio

or decrease the water content at the same workability

 Retard or accelerate the time of initial setting

 Modify the rate or capacity of bleeding

 Reduce the heat of evolution

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Admixtures
PURPOSE

 To modify harden property

 Accelerate the rate of strength development at early stages

 Increase the durability

 Decrease the permeability of concrete.

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Admixtures
Types of Admixtures
Mineral Admixtures
 Natural materials
 By-product materials

Chemical Admixtures
 Surface-active chemicals
 Set-controlling chemicals
Admixtures
 Pozzolans Admixtures
A more formal definition of ASTM 618-94a describes pozzolana
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.

It is essential that pozzolana be in a finely divided state as it is

only then that silica can combine with calcium hydroxide
(produced by the hydrating Portland cement) in the presence of
water to form stable calcium silicates which have cementitious
properties.
 Pozzolanic reaction & Concrete
• A pozzolana is a natural or artificial material containing silica in a reactive form.
• By themselves, pozzolanas have little or no cementitious value.
• However, in a finely divided form and in the presence of moisture they will chemically react
with alkalis to form cementing compounds.
• Examples of pozzolanic materials are volcanic ash, pumice, opaline shales, burnt clay and
fly ash.
• The silica in a pozzolana has to be amorphous, or glassy, to be reactive.
• Fly ash from a coal-fired power station is a pozzolana that results in low-permeability
concrete, which is more durable and able to resist the ingress of deleterious chemicals.
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Admixtures
Mineral Admixture:
Fly Ash:
1MW consumes around 3750 tonnes of coal and 1 ton of coal
generates around 250-300 kg of fly ash

Overall, Pakistan is producing 2000MW from coal so the annual

production of fly ash is 10.08 millions tons

Value added product to be used as mineral admixture

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Admixtures
Fly Ash:
CLASSIFICATION
The Characteristics of FA vary according to combustion operation
system as well as coal composition

Coals produce type F FA (low calcium) and type C FA (high

calcium)

ASTM C 618 states that for class F FA, the sum of SiO2,
Al2O3 and Fe2O3 should be ≥ 70% while for class C FA it
should be ≥ 50%
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Admixtures
ASTM REQUIREMENTS FOR FA CLASSIFICATION
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Admixtures
Chemical Composition-Different Types of FAs
We should note that the silica has to be amorphous, that is, glassy
because crystalline silica has very low reactivity_ The ' glass content can
be determined by X-ray diffraction spectroscopy or by solution in
hydrochloric acid and potassium hydroxide

The natural pozzolanic materials most commonly met with are:

volcanic ash - the original pozzolana - pumicite, opaline shales
and cherts, calcined diatomaceous earth, and burnt clay. ASTM
C 618-94a describes these materials as Class N.
 Fly Ash
• Fly ash is supplementary cementitious materials used in the concrete mix to reduce the
amount of cement and to improve concrete properties.
• Fly ash is a by-product of burning pulverized coal in an electrical generating station.
• Upon ignition in the furnace, most of the volatile matter and carbon in the coal are burned
off.
• In the process, the fused material cools and solidifies into spherical glassy particles (less
than 50 μm) called fly ash.
 Fly Ash
• Owing to its pozzolanic properties, fly ash is used as a replacement for Portland cement in
concrete.
• The use of fly ash as a pozzolanic ingredient was recognized as early as 1914, although
the earliest
noteworthy study of its use was in 1937.
• Fly ash often replaces up to 30% by mass of Portland cement, but can be used in higher
dosages in certain applications.
• In some cases, fly ash can add to the concrete's final strength and increase its chemical
resistance and durability.
• Fly ash can significantly improve the workability of concrete.
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Admixtures
Fly Ash:
Morphology of FA
 Fly Ash
• The fly ash is then collected from the exhaust gases by electrostatic precipitators or
bag filters.
• The performance of fly ash depends on physical and chemical properties.
• Chemical composition is dependent on coal composition, and it can vary for a different
type of coal.

• ASTM classifies fly ash into two types:

 Fly Ash
• The strength of fly ash concrete will depend on whether a water reduction is achieved, plus
the pozzolanic
performance of the cement/fly ash combination.
• Development of concrete mix design has seen an increase in the proportion of cement
being replaced by fly ash
 Fly Ash
• The elastic modulus of fly ash concrete is generally equal to or slightly better than that for
an equivalent
grade of concrete.
• The greater long-term strength for fly ash concretes gives lower creep values,
particularly under conditions of no moisture loss.
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Admixtures
COMPRESSIVE STRENGTH DEVELOPMENT WITH DIFFERENT
FA PER CENTAGES
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Admixtures

Fly Ash
FA Contributions to Formulations

FA offers sites for nucleation of hydration products mostly

Ettringite and CH. Encapsulation of FA particles

FA containing concrete is more susceptible to carbonation due to

consumption of CH by FA as a result of pozzolanic reactivity
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Admixtures
Fly Ash:
Environmental Benefits of FA
 Increase the life of concrete roads and structure by improving
concrete durability

 Reduction in energy use and green house gas and other adverse air
emissions when fly ash is used to replace or displace manufactured
cement

 Reduction in amount of coal combustion products that must be

disposed in landfills

 Conservation of natural resources

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Mineral Admixtures:
Ground Granulated Blast-Furnace Slag

Ground-granulated blast-furnace slag (GGBS or GGBFS) is

obtained by quenching molten iron slag from a blast furnace in
water or steam

ASTM C 989, Standard Specification for Ground Iron Blast-

Furnace Slag for Use in Concrete and Mortars
The hydraulic potential of ground granulated blastfurnace slag (ggbs) was first
discovered as long ago as 1862 in Germany by Emil Langen.

In 1865 commercial production of lime-activated ggbs began in Germany and around

1880 ggbs was first used in combination with Portland cement (PC).
 Production of GGBS
• The ground granulated blast furnace slag (GGBS)
is a by- product of iron manufacturing which when
added to concrete improves its properties such as
workability strength, and durability.
• The material obtained by the heating of iron ore,
limestone, and coke at a temperature of about
1500 °C. the process is carries out in blast furnace.
• The formation if GGBS is not direct.
• The by-product of iron manufacturing is molten
iron and molten slag.
• The molten slag consists of silica and alumina,
also with a
certain amount of oxides.
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 Production of GGBS
• The slag is later granulated by cooling it. For this it is allowed to pass through a high pressure
water jet.
• This results in the quenching of the particles which result in granules of size lesser than 5
mm in diameter.
• The particles are further dried and ground in a rotating ball mill to form a fine powder.
Known as ground granulated blast furnace slag.
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 Properties of GGBS in Concrete
• Water demand/workability: For concrete made
with equal slump, a lower water content is
required compared to Portland cement
although the reductions are small and are
no more than about 3 per cent.
• Stiffening times: Because the GGBS is slower to
react with water than Portland cement its use
is likely to lead to an increase in the stiffening
times of the concrete.
• Heat of hydration and early age thermal cracking:
The rate of heat evolution associated
• with GGBS is reduced as the proportion of
slag is increased.
 Properties of GGBS in Concrete
• Surface finish: The slight improvement in workability and small increase in paste volume of
GGBS concretes generally makes it easier to achieve a good surface finish.
• Compressive strength and strength development: Since GGBS hydrates more slowly than Portland
cement
the early rate of strength development of slag concretes is slower, the higher the slag content
the slower the
strength development.
• However, provided adequate moisture is available, the long-term strength of the slag concretes
is likely to be higher.
• This higher later age strength is due in part to the prolonged hydration reaction of the slag
cements and to the more dense hydrate structure that is formed as a result of the slower
hydration reaction.
• Durability & Permeability: Provided the concretes have been well-cured slag concretes are likely
to be more
durable & permeable than similar Portland cement concretes.
 Properties of GGBS in Concrete
• Surface finish: The slight improvement in workability and small increase in paste volume of
GGBS concretes generally makes it easier to achieve a good surface finish.
• Compressive strength and strength development: Since GGBS hydrates more slowly than Portland
cement
the early rate of strength development of slag concretes is slower, the higher the slag content
the slower the
strength development.
• However, provided adequate moisture is available, the long-term strength of the slag concretes
is likely to be higher.
• This higher later age strength is due in part to the prolonged hydration reaction of the slag
cements and to the more dense hydrate structure that is formed as a result of the slower
hydration reaction.
• Durability & Permeability: Provided the concretes have been well-cured slag concretes are likely
to be more
durable & permeable than similar Portland cement concretes.
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Admixtures
Ground Granulated Blast-Furnace
Slag
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Admixtures
Mineral Admixtures:

Silica Fume

Known as micro-
silica, is an
amorphous (non-
crystalline)
polymorph of
silicon dioxide

Ultrafine powder
collected as a by-
product of the Silica Fume (TEM)
silicon and
ferrosilicon alloy
production
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Admixtures
Silica fume particles are extremely small, with more than
95% of the particles finer than 1 micron.

Alloy Type SiO2 Content of SF

50% ferrosilicium 61-64%
75% ferrosilicium 84-91%
98% silicon metal 87-98%

SF comes in various forms including powder SF, slurred

SF and pelletized SF

SF generally produces cementing and pozzolanic effects

when added into cement based materials
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Admixtures
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Admixtures
EFFECTS OF SF IN CONCRETE
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Admixtures
EFFECTS OF SF IN CONCRETE
Silica fume is amorphous in nature and may contain some
crystalline silica in the form of quartz or cristobalite

 The higher surface area and amorphous nature of silica fume

make it highly reactive. The hydration of C3S, C2S, and C4AF
are accelerated in the presence of silica fume

Additionally silica fume reduces bleeding by physically

blocking the pores in the fresh concrete(physical filler effect)
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Admixtures
SF in cement paste
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Admixtures
SCBA (Sugar Cane Bagasse Ash)
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Admixtures
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Types of Cements
From the knowledge of relative rates of reactivity and products of hydration of the
individual compounds it is possible to design cement with special characteristics such as
high early strength, low or moderate heat of hydration, and high or moderate sulfate
resistance. Accordingly, ASTM C 150, Standard Specification for Portland Cement, covers
the following eight types of Portland cement

Type I. For use when the special properties specified for any other type are not
required. No limits are imposed on any of the four principal compounds.

Type IA. Air-entraining Type I cement, where air entrainment is desired (e.g., for
making frost-resisting concrete).

Type II. For general use, especially when moderate sulfate resistance is desired. The
C3A content of the cement is limited to a maximum of 8 percent. Also, an additional
maximum limit of 58 percent of the sum of C3S and C3A applies when a moderate
heat of hydration is desired and test data for the heat of hydration are not available.

Type IIA. Air-entraining Type II cement, where air entrainment is desired

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Type III. For use when high early strength is desired. To ensure that the high strength is
not due mainly to the hydration products of C3A, the Specification limits the C3A
content of the cement to a maximum of 15 percent.

It may be noted from Fig. 6-11 that generally the high early strength of the Type III
portland cement is partly due to the higher specific surface that is approximately 500
m2/kg Blaine, instead of 330 to 400 m2/kg typical for Type I portland cement.
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Type IIIA.Air-entraining Type III cement.

Type IV. For use when a low heat of hydration is desired. As C3S and C3A produce high
heats of hydration, and C2S produces much less heat, the specification calls for maximum
limits of 35 and 7 percent on C3S and C3A, respectively, and requires a minimum of 40
percent C2S.

Type V. For use when high sulfate resistance is desired. The specification calls for a
maximum limit of 5 percent on C3A to be applied when the sulfate expansion test is not
required.
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Figure 6-11 (a) Influence of cement composition on strength;

(b) influence of cement composition on heat of hydration; (c)
influence of cement fineness on strength. [Data for (a) and (b)
are adapted from Concrete Manual, U.S. Bureau of
Reclamation, 1975, pp. 45–46; data for (c) is taken from
Beton-Bogen, Aalborg Cement Company, Aalborg, Denmark,
1979.
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Thank you