PGRPE 2013-2015

TRANSPORTATION ENGINEERING

Semester II

Elective No. 1-466

Advanced Concrete Technology

Dr. V.V.L. Kanta Rao

(vvlkrao.crri@nic.in)

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Cement and CO2 Emission

The cement industry contributes about 5% of the global

generation of CO2.

The principal sources of green house gas generation in the

cement industry are the manufacturing process, fossil fuels,
transport, and power.

Global average - 0.87 kg CO2 per kg cement

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.
Need to develop alternative cement formulations and new
technologies to improve energy efficiency;

Use alternative building materials such as FA and the blast

furnace slag;

Use alternative, low carbon fuels

Adopt CO2 capture and sequestration techniques.

Cement manufacturers are not expecting the emergence of

major environmentally friendly cement manufacturing
technologies in the foreseeable future.
The answer to the problem of greenhouse gas emissions, on
account of cement manufacturing, therefore lies in reducing
the output of clinker and overcoming the loss in clinker
production by the use of PFA and other supplementary
cementitious or pozzolanic materials (mineral admixtures) in
cement and concrete.
 Cement Energy Energy
type consumption consumption
(Thermal) % (Electrical) %
OPC 100 100
PPC 84 89
PBSFC 47 47

The ideal energy consumption for a new large capacity plant:

Thermal: 680–720 kcal/kg

Electrical: 72–74 kWh/ton.

Pozzolana: Secondary Hydration
A silicious and aluminous material, which, in finely divided
form and in the presence of water, react chemically at room
temperature with the calcium hydroxide, generated during
cement hydration to form additional compounds possessing
cementitious properties

They may be naturally occurring materials, industrial and

agricultural wastes or by-products, or materials that require
less energy to manufacture

Cement + water = hydrated paste + Ca(OH)2

Mineral admixture + water = slurry
Mineral admixture + Ca(OH)2 + H2O = Calcium-silicate-
hydrate or C-S-H
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, at ambient temperature, they will
chemically react with alkalis to form cementing compounds
Mineral Admixtures Collectively called “Pozzolans”

Fly Ash Silica Fume Metakaolin

Ground Granulated Blast Furnace Slag

Rice Husk Ash

Volcanic ash, pumice, opaline shales, burnt clay and fly ash.

Supplementary Cementitious Materials (SCM)

Fly ash

Also called “Pulverized Fuel Ash”, “Hopper Ash”, or “Chimney

Ash”

Ash that results from burning of pulverised or powdered, or

broken bituminous and coal or sub-bituminous coal

80 % of ash is finely divided and get out the boiler along with
the flue gases.

Bottom Ash Fly ash

Pond Ash or Lagoon Ash

 Preparation of fly ash

When coal burns in a power station

furnace between 1250°C and 1600°C, the
incombustible materials coalesce to form
spherical glassy droplets of silica (SiO2),
alumina (Al2O3), iron oxide (Fe2O3) and
other minor constituents.

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While the carbon burns in the high-temperature surroundings,
the inorganic mineral matter gets sintered and liquefied at
high temperatures. The melt flows down the walls of the
furnace and about 25% gets collected as Bottom Ash.

The rest gets entrained in the up-flowing hot gas in the form of
fine particles and gets trapped in the economizer, air-preheater,
mechanical separator, and, finally, battery of ESP.

When the hot melt comes in contact with the hot gas, it gets
divided into fine droplets.

In the droplet, the silicate melt covers the UBC particles.

The BA and the FA distinctly differ in particle size, shape, and

mineralogy.
The incorporation of carbon particles inside droplets favors the formation of
gases such as CO, CO2, SO2, and H2O and gives rise to cenospheres (ash
particles hollow on the inside) and plerospheres (hollow ash particles with
smaller particles inside) that are so common in FA.

Scanning electron micrographs of Fly Ash:

Cenospheres Plerospheres.
The particles in raw FA range mostly from 1 to 100 μm. The particles under
10 μm are the ones that contribute to the early (7 and 28 day) strength. The
particles between 10 and 45 μm react slowly and contribute toward late
strength (up to 1 year). The particles above 45 μm may be considered as
inert and largely act as fine sand (filler).

Particle size distribution is important. It determines the reactivity of a

mineral admixture.

Particles with identical specific surface areas may actually exhibit different
size distributions.

Farther the ESP hopper from the boiler, finer the FA particles, higher the
specific surface area, smaller the mean particle size higher the pozzolanic
reactivity, but lower the yield.

The pozzolanic activity is more influenced by the finer particles than the
amorphous silica content.
Processing of raw FA

1. Separate the FA in to fine and coarse fractions during

collection stage and use it directly.
2. Feed the raw FA to a classifier to separate out < 45 micron
fraction and use that fraction for concrete. The coarser
fraction is used as a sand replacement.
3. Grind the raw FA to reduce the particle size to less than45
micron.
4. Chemical activation by treating the fly ash with alkali
materials such as calcium hydroxide, sodium sulphate or
potassium sulphate. Fly ash with high un-burnt carbon
content which is otherwise un-usable as admixture can be
activated by this method.
Ultra Fine Fly Ash

The Ultra Fine Fly Ash (UFFA) should have at least 90%
particles below 8.5 μm size and at least 50% below 3.25 μm
size and the amount of material retained after wet sieving on
45 μm sieve shall be less than 6%.

.
UFFA is reported to exhibit

 higher pozzolanic activity,

 lower water demand in proportion with the fineness
 larger slump and reduction in the slump loss ,
 lower drying shrinkage and restrained shrinkage cracking
 reduced requirement of total binder content in concrete to
achieve target strength,
 reduced porosity thereby indicating better durability, and
 higher compressive Strength

Typical dosages of ultrafine fly ash will range from 8 % of total

cementitious to as high as 12 % depending on the particular
performance desired. In a high-strength application, the typical
additional rate is 8 to 9 %t. If low permeabilities are required,
then the dosage rate typically ranges from 9 to 12 %
depending on how low the permeability target is for the project.
The UFFA was produced from the pond ash using hydraulic
classification technology.

Substantial reduction in the concrete permeability and the

expected improvement in the concrete durability were
observed.

It has been recommended that the pond ash can be used to

produce high-performance concrete at a competitive cost.
Indian fly ash

India is a major FA producing country.

The thermal power plants generate about 125 × 106 ton/

annum FA.

The FA utilization was just about 3% in 1994, which rose to

about 15% by 2001, due to the sustained efforts by the Fly Ash
Mission of the Government of India
Fly ash Classification Based on source of coal

Less than 10 % CaO - Type F fly ash -

Low calcium type
Anthracite and Bituminous coals
Principally contain Aluminosilicate
materials (amorphous)

Quality of fly ash (reactivity) depends on the fineness to which

the coal was crushed before burning.

More than 10 % (15-35 %) – Type C fly ash -

High calcium type
More reactive than Type F
(Hydraulic also)
The Indian PFA is characterized by relatively higher contents
of SiO2 and Al2O3 and lower contents of Fe2O3. The American
PFA is mostly rich in Fe2O3, which acts as a flux during coal
combustion.

The higher Al2O3 in Indian PFA also implies higher fusion

temperature; therefore, unless the ash is heated to higher
temperatures, the glass content is likely to be lower.

This perhaps could be an explanation for the comparatively

lower glass content and lower activity of some of the Indian
PFA.
60- 85 % Amorphous
10 – 30 % crystalline
About 10 % un-burnt carbon ( in modern furnaces – maximum
5 %)
Fly ash IS 3812 Pt. 1 (Pozzolanic)
Silicon dioxide (Si02) + aluminium oxide (Al203) + Iron oxide
Class F Class C

min. 70 min. 50

LOI 5 5

Fineness - Not less than 320 m2 / kg

Particles retained on 45 micron Max 34 %

Lime Reactivity Not less than 4.5 MPa

Comp Strength at 28 days

Not less than 80 % of the control mortar

Soundness (Autoclave test) Not more than 0.8 %

Tests on Pozzolanic materials IS 1727

Chemical Analysis & Loss on ignition

Fineness - Blain’s method and sieving

Not less than 320 m2 / kg
Soundness 0.2 N : 0.8 by weight

Setting Time

Lime Reactivity 50 mm cube molds

1 : 2M : 9
8 day test
35 kg/cm2/min
Not less than 4.5 MPa
Compressive Strength 0.2 N : 0.8 : 3
7, 28 and 90 days
140 kg/cm2/min.

Transverse Strength

Drying Shrinkage

Permeability

Reduction in alkalinity and silica release

Specific gravity
Fly ash IS 3812 Pt. 2 (Admixture)

Bottom ash, fly ash, mound ash or pond ash

Fineness Min. 200 m2 / kg

Particles retained on 45 micron sieve Max 50 %

Soundness (Autoclave) Not more than 0.8 %

Fly ash blended cement (PPC) IS 1489

Fineness Not less than 300 m2 / kg

72 ± 1 h 16 MPa, Min
168 ± 2 h 22 MPa, Min
672 ± 4 h 33 MPa, Min

Av. Drying shrinkage - Not more than 0.15 %

 Reduction of calcium hydroxide with the use
of fly ash in cement

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OPC = 3.15 Fly ash = 2.4

Volume difference per unit mass (cm3/ g)

= (1/2.4) – (1/3.15) = 0.094

At 10 % replacement of OPC (by weight)

OPC = 90 % Fly ash = 10 %

Increase in volume (%) =

[(90/3.15) + (10/2.4)] – [100/3.15)] / [(100/3.15)]

= 2.92 % or 3 %
Blast furnace slag
Slag is a non-metallic product consisting essentially of glass
containing silicates and aluminates of lime and other bases.

The blast furnace slag is developed simultaneously with iron

in blast furnace or electric pig iron furnace.

1 ton of pig iron generates 250–350 kg of slag, depending

upon the iron content of the ore

Granulated slag is obtained by further processing the molten

slag by rapidly chilling or quenching it with water or steam
and air.
The hydraulic activity of BFS refers to its capacity to react with
calcium hydroxide in the hydrated cement paste and form
strength-giving compounds, mainly the calcium silicate
hydrates (C-S-H) which depends largely on its glass content.

In order to convert the inorganic mineral phases present in the

molten state at 1325 –15250 C into amorphous glass, molten
slag must be rapidly cooled (quenched) to a temperature
below 8750 C.

The process of quenching and converting the molten slag into

granules of 3–5 mm size is known as granulation or
pelletization.

The activity of BFS is proportional to the glass content.

 Production of blast furnace slag

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 GGBFS

It is a fine, off-white, and

lighter in colour than both
Portland cement and
granulated slag

Specific gravity = 2.9 – 3.0

Blast furnace slag IS 12089

Glass content Not less than 85 %

(Optical microscopic method)
Portland Slag Cement IS 455

Fineness Not less than 225 m2 / kg

Made with OPC 33 grade clinker

ASTM Classification of GGBFS C-989

Grade 120, Grade 100, and Grade 80.

The three Grades, 80, 100, and 120, are classified according to
their slag activity index, which is the average compressive
strength of the slag-reference cement cubes (SP) divided by
the average compressive strength of the reference cement
cubes (P) and multiplied by 100

Slag activity index (%) = (SP/P) x 100

Up to 95 % GGBFS can be added to replace OPC.

It also stipulates

the requirement of residue left on a 45 μm (No.325 sieve ) to

be 20%. and
air content in the slag mortar not to be greater than 12%.

The chemical requirements are:

the sulfur and ion sulfate contents are not to exceed 2.5% and
4.0%, respectively.
Silica fume

Condensed silica fume or Micro-silica

Composed of submicron particles of amorphous silicon
dioxide.

A by-product of the smelting process in the production of

silicon metal and ferrosilicon alloys, containing more than
75% silicon.

The smoke from the smelting furnace contains silicon

monoxide (SiO (g)). It gets oxidized in air during
condensation and is collected in the dust collectors as SF
(SiO2 (s)).
Production take place in large electric smelting furnaces at
temperatures > 2000 oC
Chemical Reaction

SiO2 + 2C = Si + 2CO

where
SiO2 is normally quartz
C is a mix of coal, coke and wood chips

For ferrosilicon - an iron source is added, e.g iron oxide

1000 kg Si -> 400 - 500 kgs silica fume

1000 kg FeSi (75%) -> 200 - 250 kgs silica fume
Important production countries are China (leading), Norway,
South Africa, USA, Canada, Spain, Russia/CIS and France
Fiskaa Plant in Kristiansand, Norway ca. 1970
Silica fume is not

Silica flour
Condensed silica
Fumed silica
Gel silica
Precipitated silica
 Dark gray in colour

Specific gravity = 2.2.

The important characteristics that make SF an effective pozzolanic

material are (a) fineness (15,000–25,000 m2/kg), with an average
particle diameter 100 times smaller than that of Portland cement, (b)
spherical shaped particles that improve the rheology of concrete, and (c)
glassy structure

Fineness is determined by N2 adsorption (BET) method.

Forms of Silica Fume

a) Undensified SF (bulk density, up to 350 kg/m3)

b) Densified SF (480–720 kg/m3)
c) Pelletized SF (about 1000 kg/m3)
d) SF slurry (bulk density 1300–400 kg/m3)

The undensified SF particles (as produced) are spherical in

shape and on average 0.02–0.25 μm in diameter, nearly 100
times smaller than the average cement particle.
Silica fume IS 15388

SiO2 Min 85 %

Specific surface m2 / gm Min 15

Particles retained on 45 micron sieve Not more than 10%

Loss on Ignition = Max. 4 %

Compressive strength at 7 days

Min. 85 % of control specimen
 Rice Husk is a waste material produced in the rice mills.
 India produced about 143 million tones of paddy in 2010.
Paddy contains about 20-22% of rice husk.
The rice husk, on burning produces about 18-25% (average
– 20 %) of ash, known as rice husk ash. It is rich in silica
content.
Elemental composition Oxide composition of
of Rice Husk Rice Husk

Element Mass
Oxide Mass
Fraction (%) Fraction (%)
Carbon 41.44 Silica (SiO2) 80 – 90 %
Hydrogen 4.94
Alumina 1 –2.5 %
Oxygen 37.32
Nitrogen 0.57
Ferric oxide 0.5 %
Silicon 14.66 Titanium dioxide Nil
Potassium 0.59 Calcium oxide 1–2%
Sodium 0.035
Magnesium oxide 0.5 – 2.0 %
Sulfur 0.3
Phosphorous 0.07 Sodium oxide 0.2 – 0.5 %
Calcium 0.06 Potash 0.2 %
Iron 0.006
Loss on Ignition 10 – 20 %
Magnesium 0.003

Specific gravity of RHA = 2.05 – 2.23

 IS 456:2000
SECTION 2 MATERIALS, WORKMANSHIP,
INSPECTION AND TESTING
5 MATERIALS
5.2.1.3 Rice husk ash

Rice husk ash giving required performance and uniformity

characteristics -may be used with the approval of the deciding
authority.
NOTE: Rice husk ash is produced by burning rice husk and contain
large proportion of silica. To achieve amorphous state, rice husk
may be burnt at controlled temperature. It is necessary to evaluate
the product from a particular source for performance and uniformity
since it can range from being as deleterious as silt when
incorporated in concrete. Water demand and drying shrinkage
should be studied before using rice husk.

No specifications exist for Rice Husk Ash.

Ashes produced at controlled burning conditions, such as

• specified temperature
• duration of burning
• heating rate
• type of furnace, and
• oxidizing conditions

contain, a white highly reactive pozzolan with non-crystalline

silica, small carbon content, and high specific surface area is
produced.
A large amount of rice husk is being used as fuel to power the
boilers of modern rice milling factories. It is used to produce
steam, either for drying and parboiling (i.e., precooking) of the
rice grains, or for the production of electricity in cogeneration
systems. Within these processes, the RHA generally has
physical-chemical characteristics different from those of the
ones produced under controlled conditions.
For example, the burning temperature in the boiler, which
should be less than 9000 C to avoid the formation of a-
cristobalite (a crystalline polymorph of quartz), is not always
effectively controlled. Also, if sufficient oxygen is not
available, and if the residence time for the husk in the boiler is
not long enough, organic material in the form of un-burnt or
partially burnt rice husk, will remain within the bulk RHA after
the burning process.
 The ash obtained by controlled burning of rice husk at about
6000 C contains high amounts of amourphous silica (up to
about 85-90 %)
 The ash obtained by burning rice husk at high temperatures
is predominantly crystalline silica.
 The amourphous rice husk ash is pozzolanic in nature and
can useful as a supplementary cementitious material
(SCM)
 Properties of RHA mixed OPC concrete at 20 and 30
% replacements

Property RHA OPC

Specific gravity 2.05 3.15
Material retained on 21.87% 6.12 %
45 micron sieve
BET fineness 10.857 – 1.757
17.463 m2/gm m2/gm
Av. Particle size 25.83 µm 21.20 µm
Chemical composition (%) OPC RHA

Silicon dioxide (SiO ) 2 21.38 96.70

Aluminium oxide (Al O ) 2 3 5.60 1.01
Ferric oxide (Fe O )
2 3 3.36 0.05
Calcium oxide (CaO) 64.64 0.49
Magnesium oxide (MgO) 2.06 0.19

Sodium oxide (Na O) 2 0.05 0.26

Potassium oxide (K O) 2 - 0.91
Phosphorous oxide (P O ) 2 5 - 0.01

Titanium oxide (TiO ) 2 - 0.16

Sulphur trioxide (SO ) 3 2.14 -
Loss on ignition 0.64 4.4
The adverse effects of high carbon content in RHA
produced under un-controlled burning conditions, i.e.
reduced pozzolanic activity and rheology of cement paste
or concrete was sought to overcome by grinding RHA to
finer levels.
Microwave incinerator
A commercial TORBED Rice Husk Combustor in
Haryana State
Metakaolin
High Reactivity Metakaolin (HRM)

A whitish, purified, manufactured, thermally activated kaolinite

(a constituent of kaolin clay)

- is amorphous, alumino-silicate which reacts aggressively

with calcium hydroxide

MK is unique in that it is not the by-product of an industrial

process nor is it entirely natural; it is derived from a naturally
occurring mineral and is manufactured specifically for
cementing applications.
MK is generally produced by the calcination (also called
thermal activation) of raw kaolin clay.

The natural sources of kaolin are found in several countries.

Kaolinite = Kaolin Clay = China Clay = Al2Si2O5 (OH)4

Al2O3·2SiO2·2H2O

A material is considered to constitute kaolin when the amount

of kaolinite in it (such as rock) is greater than 50% besides
the other mineral constituents.
 Kaolin mine in Russia

Kaolin Rock
The calcination process, under the moderate temperature
range of 600°C–800°C, transforms a crystallized, organized
phase (kaolinite) into a disorganized transition phase (MK)
through crystal lattice failure.

The dehydroxylation and disorganization of the kaolinite

generate anhydrous and amorphous aluminosilicate
(Al2Si2O7 or Al2O3 ⋅ 2SiO2), which is a reactive admixture
with pozzolanic properties.

The kaolinite can also be converted into amorphous and

reactive phases by grinding kaolin under controlled
conditions
 Meta-kaolin

Specific gravity = 2.5 – 2.6

Metakaolin

a) Silicon dioxide (SiO2) plus aluminium oxide (Al2O3) plus

iron oxide (Fe2O3) in percent by mass shall not be less than
95 percent when tested as per IS 1727

b) Loss on ignition shall not be more than 1 percent when

tested as per IS 1727

c) Total alkalis as sodium oxide (Na2O) in percent by mass

shall not be more than 0.6 percent when tested as per IS 4032

d) Particles retained on 45 micron IS sieve (wet sieving) shall

not be more than 1 percent when test as per IS 1727
Other Mineral Admixtures

 Corn Cob Ash

 Palm Oil Residue Ash
 Sugarcane Bagasse Ash
 Wheat Straw Ash
 Wood Waste Ash

 Calcined Wastepaper Sludge

 Electric-Arc Furnace Dust
 Sewage Sludge Ash
 Municipal Solid Waste Ash