4.

FLY ASH (PULVERISED FUEL

ASH-PFA)

Asst. Prof. Dr. Sevket BOSTANCI

 Introduction
• 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.
1 billions tons of fly ash is produced per year globally. Only a
small part of this is used. The obvious reasons are:

• non-uniformity of the propeties of the fly ash.

• difficulty in transportation.

• conservation in the construction industry & in standards and

specifications.
 4.1. Classification of fly ashes
1. Silica-aluminous

2. Silica-calcic

3. Sulfo-calcic
 4.1.1. ASTM Classification (ASTM C618)
• 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.
 4.1.1. ASTM Classification (ASTM C618)

1. Class F: (S+A+F)70% Obtained from bituminous coals

& antracite.
2. Class C: (S+A+F)>50% Obtained from:
High-lime (high calcium): CaO>10%
Low-lime (low calcium): CaO<10%
The chemical composition of fly ashes differ with the
impurities present in the parent coal.
Besides;
• the combustion technique
• the means of collecting fly ash
• the load of the power plant.
 4.2. Characteristics of fly ashes
1. Composition:
The chemical character is traditionally
described by the oxide analysis. Unlike OPC,
there is no relationship between the oxides
and compounds present in fly ash.
Table 7. Chemical composition of fly ashes.
Oxide (%) OPC Low lime fly ash High lime fly ash
SiO2 20 50 40
Al2O3 5 28 18
Fe2O3 3 9 8
CaO 64 3 20
MgO 2 1 4
SO3 2 1 2
others 4 8 8
• Iron helps during the production of clinker in rotary kiln.

• White Portland Cement: China clay is used instead of ordinary clay. Iron is
less in china clay, therefore temperature should be higher. This is more
costly.

• For pozzolanic reactions to occur, the mineralogical composition of fly ash

is of more important than the chemical composition. The principle active
constituent is the amorphous (glassy) phase.

• Generally speaking, glass content of low-lime fly ash is higher than that of
high-lime fly ashes. Glassy low-lime fly ashes is silicious or silico-aluminous
in nature. It is silico-calcic in high-lime fly ashes.

• In high-lime fly ashes besides the glass, lime (CaO), anhydrite (CaSO4),
tricalcium aluminate (3CaO.Al2O3), and calcium sulfo aluminates, etc are
present as cementitious compounds.
Mineral composition.
Mineral Composition
Phase (%) Minimum Maximum
Glass 20 80
Mullite 7 45
Hematite 2 15
Magnetite 2 10
Quartz 1 12
Carbon 1 13
 4.3 Morphology
• Low-lime fly ashes are composed mainly of small
hollow spherical particles (cenospheres).

High-lime fly ashes have high-crystalline constituents.

The variations in shape, surface texture, surface

coatings depend on;

1. the source of the coal

2. the fineness of the coal
3. the temperature of burning
4. the method of collection.
• 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.
 4.4 Fineness

• Particle size range: 0.5 – 100 microns

• d50 = 10 microns
• Density = 1.9-2.5
• Colour: Creamy to dark grey or brown.
Table. Standards for fly ashes

Property (%) Australia Austria USA Japan UK Turkey

F C
LOI (max) 8 5 12 6 5 7 10
SO3 (max) 2.5 -- 5 5 - 2.5 5
MgO (max) -- 5 - - 5 4 5
Alkalies (max) -- -- 1.5 1.5 - - -
SiO2 (min) -- 42 - - 45 - -
S+A+F -- -- 70 50 70 - 70
(min)
Water req.(%-max) -- -- 105 105 100 95 105
Pozz.Act.Ind. -- 80 75 75 60 85 70
(PAI)
Pozz.Act.Ind. -- -- 5.5 5.5 - - -
With lime (N/mm2)
Fineness-Retained 50 -- 34 34 - 12.5 -
Fineness-Sp.Surface -- -- - - 270 - -
 Explanations for Table
• LOI indicates if OPC is fresh or not (loss on ignition).
• SO3: Forms ettringite.
• Alkalies: Responsible for alkali-aggregate reactions (aggregates are
amorphous silica)
• Most of Turkish fly ashes are Class C.
• Water requirement: % of control.
• PAI: OPC compared with fly ash cements. Strength at 28 days are
compared.
• Fineness: Shown2 as retaied on 45 microc sieve (max) and specific
surface in kg/m .
• 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.
4.5 Use of Fly Ash in Cement Manufacture
Fly ash is used as;
1. Raw material
2. Admixture (ground with clinker)
3. Admixture (directly added to cement)

A typical raw mix for OPC is as follows;

14% SiO2
3% Al2O3
1% Fe2O3
45% CaO
0.5% MgO
0.1% SO3
36% LOI
2% Alkalies
• For this chemical composition calcareous
(limestone) and argillaceous (clay) raw
materials are blended in appropriate
proportions.

• CaCO3 CaO + CO2 (at 900C)

4.6 Low-lime fly ash (silica aluminous)
• 50% SiO2
• 30% Al2O3

• With this composition, low-lime fly ash can be used as an

argillaceous raw material.
 4.7 High-lime fly ash (silico calcic)
• 50% SiO2
• 20% Al2O3
• 15-35% CaO

This is a good argillaceous material.

As all the other types of PC raw materials, Na2O, K2O, free

MgO, free CaO, and SO3 should be limited since they all may
lead to disruptive expansions.
 4.8 Fly Ash as an admixture
• If it is interground with clinker, the grindability is
improved. If used as direct cement replacement, fly
ash should be much finer than the cement.
• 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.
• 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.

• The agenda addressed the issues of (a) climate protection, (b)

fuels and raw materials use, and (c) emission reduction
besides other issues.
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 and
the blast furnace slag; use alternative, low carbon fuels; and adopt CO2
capture and sequestration techniques.
4.9 Properties of Fly Ash Concrete
Properties related with fineness are:
1. Concrete mix proportioning
2. Rheological properties of fresh concrete
3. Rate of hydration of PC

Properties related with chemical or mineralogical

composition:
1. Strength
2. Permeability
3. Heat of hydration
4. Sulfate resistance
 4.9.1 Water requirement
• 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.
• Low-lime fly ashes usually reduce the water requirement.
• Fineness, carbon content, character of glassy phase effects
the water requirement.
 4.9.2 Bleeding & Segregation
• Reduced. (thus pumpability of concrete is
improved.
 4.9.3 Setting Time
Longer. 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.

Depends on;
1. The amount of fly ash
2. The type of fly ash
3. Fineness of PC
4. Fineness of fly ash.

The high calcium fly ashes, which are generally low in carbon and
high in reactive components, sometimes exhibit opposite behavior.
 4.9.4 Heat of Hydration
• Reduced.

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

temperature rise more than high calcium subbituminous
ashes as well as blast furnace slag and silica fume.
 4.9.5 Hydration Products
• Essentially the same (with PC).
 4.9.6 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.
 4.9.7 Strength
• Upon direct cement replacement, early strength is
low. Late (1-3 months) strength is at least equal to
that of non-fly ash concrete.

• 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.
 4.9.8 Creep & Shrinkage
• Less shrinkage, same creep behaviour as long as the
strength is same.
 4.9.9 Durability
• (Relatively) increased.
• The addition of fly ash does not affect the frost resistance of
concrete significantly if the strength and air content are
maintained constant.

• The addition of fly as a mineral admixtures has been found to

improve the sulfate resistance of concrete significantly.
• 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
 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.
 Conclusion
• The addition of FA 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.
 References
• Dodson, V. H. (1990) Concrete Admixtures. 1st Ed., Springer
Science and Business Media, New York.

• O. Eren, Lecture notes.

• 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.