MINERAL ADMIXTURES

Fly Ash

Asst. Prof. Dr. Şevket Can BOSTANCI

Classification of Admixtures
 Chemical Admixtures

 Mineral Admixtures

 Polymer base
Introduction
Mindess et al. (2003) recognized that admixture terminology
is complex and proposed a classification of concrete
admixtures into four different categories:

 Mineral admixtures that are finely divided solids added to

concrete to improve its durability or to provide additional
cementing properties (slags and pozzolans are important
categories of mineral admixtures)
Introduction
 The data in Table given should be viewed along with the
estimated cement demand and carbon dioxide (green house
gas) generation by cement industry for that period. The
principal sources of green house gas generation in the cement
industry are the manufacturing process, fossil fuels,
transport, and power.
Introduction
 Table gives an estimate of possible reduction in CO2
emission using the mineral admixtures, namely, the PFA and
the blast furnace slag. As per several estimates, the cement
industry contributes about 7% of the global generation of
carbon dioxide.

 The cement industry’s sustainable program developed by the

World Business Council for Sustainable Development
(WBCSD) prepared an “Agenda for Action” for a 5 year
period from 2002 to 2007, endorsed by the leading cement
manufacturers of the world.
Introduction
 The agenda addressed the issues of (a) climate protection, (b)
fuels and raw materials use, and (c) emission reduction
besides other issues.
Introduction
WBCSD, envisaged the following scenario, insofar as the CO2 emissions
are concerned:

 Considering 1990 as the base, the global demand for cement in 2020
shall increase 1.15–1.8 times regionwise. The demand in developing
countries (China, India, and others) shall far exceed that in developed
countries.

 At the global level, the cement industry will be required to reduce the
CO2 generation by 30%–40% in 2020 and by about 50% in 2050,
above the 1990 measure.

 In order to achieve the desired level of CO2 reduction, the cement

industry will have to develop alternative cement formulations and new
technologies to improve energy efficiency; use alternative building
materials such as PFA (FA) and the blast furnace slag; use alternative,
low carbon fuels; and adopt CO2 capture and sequestration techniques.
Introduction
 Notwithstanding the WBCSD’s agenda of action and the
aforementioned observations, cement companies are not
expecting the emergence of major environmentally friendly
cement manufacturing technologies in the foreseeable future.
That leads us to the conclusion that the answer to the
problem of greenhouse gas emissions, on account of cement
manufacturing, lies in reducing the output of clinker (raw
cement before grinding, in the form of coarse particles
obtained from the manufacturing process) and overcoming
the loss in clinker production by the use of FA and other
supplementary cementitious or pozzolanic materials (mineral
admixtures) in cement and concrete.
Mineral Admixtures
 Cementitious
 Pozzolanic
 Ground Granulated Blast Furnace Slag (GGBS)
 Fly ash (FA) (or Pulverized Fuel Ash, PFA)
 Silica Fume (SF)
 Rice Husk Ash
 EN 197-1 defines fly ash (FA) as follows;
Fly ash
 Fly ash (FA) or Pulverized fuel ash (PFA) is a by-product
obtained from the burning of coal in power stations.

 The “pulverized fuel ash” (PFA) or the so-called “fly ash”

(FA), used as a mineral admixture in cement and concrete, is
a product of the pulverized coal firing system, through
conventional boilers, mostly used in the thermal power
plants.
Fly ash
 FA is finely divided residue resulting from the combustion of
powdered coal and transported by the flue gases.

 It is the most widely used pozzolanic material in the world.

Fly ash
 This refers to finely divided, glassy material, which is
separated from the flue gases during combustion of
pulverized coal in suspension fired furnaces of modern
thermal power plants. During the coal combustion, the
volatile matter is vaporized and carbon is burned off, whereas
most of the mineral matter, such as clays, quartz, and
feldspar, disintegrates or slags to varying degrees. The slagged
individual particles on cooling solidify as spherical glassy
particles which comprise coal ash.
Fly ash
 The “pulverized fuel ash” (PFA) or the so-called “fly ash”
(FA), used as a mineral admixture in cement and concrete, is
a product of the pulverized coal firing system, through
conventional boilers, mostly used in the thermal power
plants.

 While carbon burns in oxidizing surroundings, the inorganic

mineral matter gets sintered and liquefied at high
temperature. Fly ash constitutes 75% to 85% ofthe total ash
and the remaining is bottom ash or boiler slag.
Fly ash
 The addition of PFA to cement and concrete improves
performance in terms of long term strength and the
durability. The production of blended cement (cement with
mineral admixtures) also leads to substantial reduction in the
energy consumption.

 The reduction in energy consumption leads to the

corresponding reduction in the consumption of fossil fuels
required for the generation of thermal and electrical energy.
In the last few years, the emphasis in construction industry
has shifted from high-strength to high-performance cement
and concrete.
 Early History of Fly ash

 The use of FA in construction lies back to for almost 1,000 years

in Roman times due to its properties (such as water resistance
and durability).

 The first reported use of high volume FA in 20th century was in

the USA for the repairing a tunnel spillway at the Hoover Dam in
1942. Second was the Hungry Horse dam (with 35% FA
replacement level)

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 Fly Ash
 The Colosseum (70-80 AD)

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 Fly Ash
 The Pantheon (126 AD)

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Close history of Fly ash
 FA obtained from coal combustion has become PFA in order
to classify fly ashes extracted from other processes in the mid
1950’s.

 With the construction of power plants, FA use was increased.

 FA was accepted to use by British standards in BS 3892 as

fine aggregate.
 Fly Ash
 A tunnel spillway in Hoover Dam (1942)

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 The estimate on coal ash production in 2020
 Structure of Fly ash
 It is a pozzolanic material and a finely-divided amorphous
alumino-silicate with varying amounts of calcium.

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 Structure of Fly ash
 Does not harden by itself and hence used with PC to trigger
pozzolanic reactions.

 Mainly, composed of reactive Silicon dioxide (SiO2) and

Aluminium oxide (Al2O3) and the rest includes Iron oxide
(Fe2O3) and some other compounds.

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Chemical and Mineralogical Composition
 FA is a heterogeneous mixture of complex
aluminosilicate glasses and some crystalline constituents.

 The aluminosilicate glass is amorphous and its structure

gets modified due to the inclusion of alkaline and metal
oxides like Na2O, K2O, MgO, CaO, and FeO.
Chemical and Mineralogical Composition
 The composition of glass in low calcium FA (ASTM
Class F) is different from that of the high-calcium PFA
(ASTM Class C).

 The glass in the FA of ASTM Class F has a highly

polymerized network. The glass matrix depolymerizes
when CaO content increases above Al2O3 (alumina)
content.
Classification
 ASTM C618 classifies PFA based on the source of mineral coal. It
defines two classes of PFA suitable for use in concrete—Class F
and Class C.

 While the two classes have identical physical characteristics, they

are distinguished by their chemical compositions. The Class F PFA,
which normally results from the burning of anthracite or
bituminous coal, is the more readily available of the two.

 The sum of silica (SiO2), alumina (Al2O3), and iron oxide

(Fe2O3) in Class F must constitute at least 70% of the total mass.
It also has low (typically less than 10%) calcium oxide (CaO)
content. Even though its crystalline mineral constituents are not
reactive, Class F PFA has pozzolanic properties.
Classification
Physical Characteristics
 The physical characteristics of PFA—shape, specific gravity,
size and fineness, and UBC content—affect its performance
in the concrete in terms of volume, rheology, and water
demand at a given slump, porosity, and reactivity.
Particle Shape
Particle Shape
 The shape and surface characteristics of PFA particles affect
the water requirement of concrete at the desired slump. The
spherical particles reduce inter-particle friction (ball bearing
effect) in the concrete mix, improve its flow properties and
reduce water requirement. This phenomenon is commonly
observed, when PFA replaces cement in concrete.
Particle Specific Gravity
 When cement is replaced by a mineral admixture of lower
density, on a mass-to-mass basis, the volume of the mixture
increases.

 If the strength and durability characteristics are kept

reasonably constant, then such an addition may actually result
in lowering the quantity of cementitious (in terms of mass)
per unit volume of concrete. This aspect is important from
the point of view of optimum use of cementitious materials
in concrete.
Particle Specific Gravity
Color
 The PFA from bituminous coal is darker in color (gray) and
that from lignite or subbituminous coal is lighter in color
(buff to tan).
Unburned Carbon
 The UBC particles in PFA are usually the largest contributor
to the loss on ignition. The carbon particles do not take part
in the chemical reactions during the cement hydration but
influence its water demand for standard consistency.
Effect on the plastic concrete
 Improves workability because of fine particle size and the spherical
shape of particles of fly ash

 When fly ash is used in the mix, workability can be increased to

the point that sand content can be decreased and coarse aggregate
content increased, thereby reducing the total surface area to be
coated with cementitious material.

 Thus, reduces the water demand

 Bleeding and segregation are considerably reduced with the use of

fly ash as a mineral admixture in concrete and thus pumpability of
concrete is improved.
Setting Time
 Addition of mineral admixtures to portland cement generally
results in set retardation. This is especially true of low
calcium fly ashes with high carbon content. The high calcium
fly ashes, which are generally low in carbon and high in
reactive components, sometimes exhibit opposite behavior.
Heat of Hydration
 Adding mineral admixtures such as natural pozzolans, fly ash,
blast furnace slag in concrete as replacement of cement,
result in reduction of temperature rise due to heat of
hydration almost in proportion to the amount of cement
replacement.

 Low calcium bituminous fly ashes tend to reduce the rate of

temperature rise more than hgh calcium subbituminous ashes
as well as blast furnace slag and silica fume.
Air Entrainment
 Addition of mineral admixtures increases the demand for air
entraining admixture (MA) in concrete required to entrain a
given amount of air for freeze-thaw durability.

 Concretes made with Class C (high calcium) fly ash generally

require less air entraining admixture than those made with
Class F (low calcium) fly ash to entrain around 6% air in
concrete.
Hydration and Strength Development
 Incorporation of mineral admixtures in concrete influences
the rate of hydration of cement and thereby the strength
development.

 Thus, with the replacement of cement by mineral admixture,

early rate of hydration of cement concrete is retarded.

 The effect of pozzolanic reactions is generally manifested at

late ages by increased strength and reduced permeability.
Hydration and Strength Development
 The rate of strength development of concrete containing
mineral admixtures is dependent upon several factors such as
the type and replacement level of mineral admixture, mix
proportions, ambient temperature and curing conditions,
and presence of other additives.

 For Fly ash added concretes, the strength development is

delayed and takes place at longer ages (>28 days). Therefore,
it contributes to strength at long term.
 Modulus of Elasticity, Drying Shrinkage and Creep
 The effect of mineral admixtures used as replacement of cement
on modulus of elasticity of concrete follows about the same
trend as on compressive strength in that it is generally reduced,
particularly with fly ash, at an early age and is slightly increased
at late ages.

 Drying shrinkage values reported are observed to be similar as

PC concretes.

 Since creep is influenced by compressive strength and modulus

of elasticity of concrete, higher creep strains were observed in fly
ash concrete at early age loading when strength was low;
however, the creep rate decreased at later ages.
Permeability
 The addition of mineral admixtures can cause considerable
pore refinement, ex: transformation of bigger pores into
smaller ones due to their pozzolanic reactions concurrent
with cement hydration.

 By this process, the permeability of hydrated cement paste as

well as the porosity of the transition zone between cement
paste and aggregate are reduced.
Freeze-Thaw Durability
 it is known that the resistance of air entrained concrete to
freezing and thawing depends upon several factors such as the
degree of saturation, air void system, type and content of
cementitious materials, W/C ratio, curing conditions, rate of
cooling, and minimum cooling temperature.

 Because of pore refinement due to the addition of mineral

admixtures, the freezing temperature of water in small
capillary pores is reduced and thus freeze-thaw durability of
concrete at some intermediate low temperatures is
improved.
Freeze-Thaw Durability
 The addition of fly ash does not affect the frost resistance of
concrete significantly if the strength and air content are
maintained constant.
 Resistance to Aggressive Chemicals: Sulfate Attack
 With the incorporation of mineral admixtures in concrete,
Ca(OH)2 which is highly vulnerable to attack by harmful
chemicals, is consumed progressively in pozzolanic reaction.
It also leads to pore refinement and reduces the rate of
molecular difision of aggressive elements through concrete
due to the decreased permeability.

 The addition of mineral admixtures such as fly ash, blast

fbrnace slag, and silica fume has been found to improve the
sulfate resistance of concrete significantly.
 Resistance to Alkali-Aggregate Reaction
 The alkali-silica gel formed can swell in the presence of
moisture and can cause internal disruption of concrete due to
the expansive pressures induced by swelling of the gel.

 The use of finely divided mineral admixtures not only

improves the pachng of cementitious materials but also
reduces permeability of cement paste due to their pozzolanic
action. Therefore, alkali-aggregate reactions are retarded or
minimized by use of fly ash in concrete.
 Corrosion of Reinforcing Steel: Carbonation of Concrete
 With the additions of mineral admixtures at high
replacement levels by cement weight, the pH of concrete can
decrease since less cement is used. Moreover, the decrease in
Ca(OH), content due to pozzolanic reaction and the
reduction of alkali pore water concentration contribute to
the reduction of steel corrosion resistance of concrete. All
these factors combined may reduce alkalinity of concrete,
thus increasing the corrosion potential of steel in reinforced
and prestressed concrete structures when concrete made
with mineral admixtures is used.
 ECONOMICS OF USE OF MINERAL ADMIXTURES
 The most efficient method of disposing a waste by-product is to
use it. However, this may not be possible all the time because of
economic constraints. Industrial by-product mineral admixtures,
particularly fly ash which is produced in abundance, can find
productive use in concrete only when the concrete construction
site is in close proximity to the available source of waste by-
product.

 If the market for use is very far from the generating source, then
the transportation costs escalate and it may become more
economical to dispose the waste in landfills rather than use it as
mineral admixture.
References
 Dodson, V. H. (1990) Concrete Admixtures. 1st Ed., Springer
Science and Business Media, NewYork.

 Proceeding of the International RILEM Symposium. (1990)

Admixtures for Concrete. Edited by E. Vasquez., 1st Ed.,
Chapman and Hall, UK.

 Ramachandran, V.S. (1995) Concrete Admixtures Handbook. 2nd

Ed., Noyes Publication, New Jersey, USA.