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ABSTRACT
The addition of superplasticizers with mineral admixtures like fly ash, alccofine etc.
to concrete imparts a high strength and workability to it, even at very small water cement
ratios. But to get the maximum benefit from this amalgamation of concrete and admixtures,
the incompatibility issues between these two need to be studied. In the present work, the aim
is to find the optimum dosage for different superplasticizers, for a particular grade of cement,
using Marsh Cone test. The results of these rheological tests conducted on the cement slurry
are analyzed graphically to find the optimum dosage of a superplasticizer and its
compatibility with the concrete. It has been found that Polycarboxylate Ether (PCE) based
superplasticizers show greater compatibility and economical dosage as compared to
Sulphonated Napthalene Formaldehyde (SNF) based superplasticizers. A cost analysis is
further done to assess the overall practical utility of the admixtures.

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CONTENTS

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1. INTRODUCTION

Over the course of time, the concrete industry has to cope with the day to day
challenges and the use of mineral and chemical admixtures has been a magic wand for the
same. To achieve the desired properties in a high quality concrete, these admixtures,
particularly uperplasticizers, are added to the cement. Superplasticizers are the high range
water reducers used for the proper dispersion of the cement particles in a concrete suspension
[Ramachandran (1995)]. The addition of the superplasticizers can reduce the water-cement
ratio of the concrete to the range of 0.250.30, without affecting its strength and workability.
This also increases the durability of the concrete. Thus, we get a homogeneous workable
concrete at low water cement ratios, which is less susceptible to bleeding and segregation.
The addition of superplasticizers not only improves the rheological properties of the concrete
but imparts it more compactness and strength in the hardened state. These days, due to the
availability of different types of admixtures and cement in the market, there is flexibility in
choosing the right composition of the concrete according to the desired parameters, keeping
in mind the overall economy and environmental safety. Admixtures, especially new
superplasticizers are being developed regularly, which dramatically change the properties of
the concrete. But if there is incompatibility between the cement and the admixture, it may
cause rapid loss of workability, excessive quickening/retardation of setting and low rates of
strength gain, in addition to the economic loss.
The incorporation of mineral additions to Portland cement reduces the amount of
clinker required in cement manufacture improving the eco-efficiency of this process by
lowering both greenhouse gas emissions and energy consumption. These additions also
enhance mainly the long-term strength and durability of the material obtained. Additions may
be natural materials (limestone, pozzolans, schist) or industrial by-products (vitreous
granulated blast furnace slag, fly ash or silica fume) with pozzolanic or hydraulic properties.
The use of fly ash in cement compositions is very common because it raises product
strength and reduces alkali silica reaction induced expansion. Fly ash fineness determines the

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properties of the end material, which is more fluid and less porous than non-blended cement
pastes.
Cement paste, mortar and concrete microstructure, and in particular the homogeneity,
density and porosity of the reaction products, must be closely monitored to attain the desired
properties in the hardened material. Fresh cement paste rheology is regarded to be closely
associated with the development of mortar and concrete microstructure. Given the direct
impact of the presence of mineral additions on such microstructure, and consequently
behaviour rheology, an understanding of blended cement behaviour in this regard is
imperative. As a rule, the incorporation of mineral additions raises yield stress and to a lesser
extent, plastic viscosity.
The fresh characteristics of concrete made with Portland cement and rheology can be
modified and controlled with superplasticizers. Achieving the steepest decline in the water
cement ratio, greatest workability and decreasing the viscosity and the yield stress is,
however, contingent upon the compatibility between the admixture chosen and the cement
used. The presence of mineral additions such as limestone, fly ash and silica fume may
affect the interaction between the superplasticizer and the cement. The performance of
additions could be also influenced by admixtures. Conventional superplasticizers such as
naphthalene (PNS)-, melamine (PMS)- or lignosulfonate (LS)-based disperse the particles
due to a electrosteric mechanism while the PCE form a steric obstacle to any direct interparticle contact. The compatibility of mineral additions with, and affinity for, a given
admixture must therefore be determined.
The use of fly ash has been reported to improve cement rheology and lower the dose
of superplasticizer needed (PCE and PMS) to obtain the desired reological properties [45,47].
Due to the nearly spherical shape and the size of fly ash particles, these cement pastes
demand a lower concentration of admixture than limestone blended cements.

ADMIXTURES
Admixtures are additives used in addition to the other constituents of concrete to alter
or improve the properties and Performance of concrete:
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Chemical Admixtures.

Mineral Admixtures

CHEMICAL ADMIXTURE:
Chemical admixtures are the ingredients in concrete other than portland cement,
water, and aggregate that are added to the mix immediately before or during mixing.
Producers use admixtures primarily to reduce the cost of concrete construction; to modify the
properties of hardened concrete; to ensure the quality of concrete during mixing, transporting,
placing, and curing; and to overcome certain emergencies during concrete operations.
Successful use of admixtures depends on the use of appropriate methods of batching
and concreting. Most admixtures are supplied in ready-to-use liquid form and are added to
the concrete at the plant or at the jobsite. Certain admixtures, such as pigments, expansive
agents, and pumping aids are used only in extremely small amounts and are usually batched
by hand from premeasured containers.
The effectiveness of an admixture depends on several factors including: type and
amount of cement, water content, mixing time, slump, and temperatures of the concrete and
air. Sometimes, effects similar to those achieved through the addition of admixtures can be
achieved by altering the concrete mixture-reducing the water-cement ratio, adding additional
cement, using a different type of cement, or changing the aggregate and aggregate gradation.

Five Functions
Admixtures are classed according to function. There are five distinct classes of
chemical admixtures: air-entraining, water-reducing, retarding, accelerating, and plasticizers
(superplasticizers). All other varieties of admixtures fall into the specialty category whose
functions include corrosion inhibition, shrinkage reduction, alkali-silica reactivity reduction,
workability enhancement, bonding, damp proofing, and coloring. Air-entraining admixtures,
which are used to purposely place microscopic air bubbles into the concrete, are discussed
more

fully

in

Air-Entrained

Concrete.

Water-reducing admixtures usually reduce the required water content for a concrete
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mixture by about 5 to 10 percent. Consequently, concrete containing a water-reducing
admixture needs less water to reach a required slump than untreated concrete. The treated
concrete can have a lower water-cement ratio. This usually indicates that a higher strength
concrete can be produced without increasing the amount of cement. Recent advancements in
admixture technology have led to the development of mid-range water reducers. These
admixtures reduce water content by at least 8 percent and tend to be more stable over a wider
range of temperatures. Mid-range water reducers provide more consistent setting times than
standard water reducers.
Retarding admixtures, which slow the setting rate of concrete, are used to counteract the
accelerating effect of hot weather on concrete setting. High temperatures often cause an
increased rate of hardening which makes placing and finishing difficult. Retarders keep
concrete workable during placement and delay the initial set of concrete. Most retarders also
function

as

water

reducers

and

may

entrain

some

air

in

concrete.

Accelerating admixtures increase the rate of early strength development, reduce the time
required for proper curing and protection, and speed up the start of finishing operations.
Accelerating admixtures are especially useful for modifying the properties of concrete in cold
weather.
Superplasticizers, also known as plasticizers or high-range water reducers (HRWR), reduce
water content by 12 to 30 percent and can be added to concrete with a low-to-normal slump
and water-cement ratio to make high-slump flowing concrete. Flowing concrete is a highly
fluid but workable concrete that can be placed with little or no vibration or compaction. The
effect of superplasticizers lasts only 30 to 60 minutes, depending on the brand and dosage
rate, and is followed by a rapid loss in workability. As a result of the slump loss,
superplasticizers

are

usually

added

to

concrete

at

the

jobsite.

Corrosion-inhibiting admixtures fall into the specialty admixture category and are used to
slow corrosion of reinforcing steel in concrete. Corrosion inhibitors can be used as a
defensive strategy for concrete structures, such as marine facilities, highway bridges, and
parking garages, that will be exposed to high concentrations of chloride. Other specialty
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admixtures include shrinkage-reducing admixtures and alkali-silica reactivity inhibitors. The
shrinkage reducers are used to control drying shrinkage and minimize cracking, while ASR
inhibitors control durability problems associated with alkali-silica reactivity.

MINERAL ADMIXTURE:
Introduction

Also called Supplementary Cementing Materials

Used when special performance is needed: Increase in strength, reduction in water

demand, impermeability, low heat of hydration, improved durability, correcting
deficiencies in aggregate gradation (as fillers), etc.

Result in cost and energy savings: Replacement of cement leads to cost savings;
energy required to process these materials is also much lower than cement

Environmental damage and pollution is minimized by the use of these by-products

about 6 7% of total CO2 emission occurs from the production of cement

Usage depends on supply and demand forces, as well as the market potential and
attitudes

Typical compositions
% by mass

PC

GGBFS

F-FA

C-FA

SF

SiO2

21

35

50

35

90

Al2O3

25

20

Fe2O3

10

CaO

65

40

20

PC: Portland cement, GGBFS: Ground granulated blast furnace slag, F-FA: Type F fly ash,
C-FA: Type C fly ash, SF: Silica fume
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Figure 1 shows the compositions of cement and supplementary cementing materials plotted
on a C-S-A ternary diagram.

Figure 1: Composition of cement and mineral admixtures

Classification of mineral admixtures by RILEM

Cementitious

Highly pozzolanic: Silica fume, Rice husk ash (controlled burning)

Normally pozzolanic: Class F fly ash

Cementitious and pozzolanic: GGBFS, Class C fly ash

An additional category is also suggested by researchers Weak pozzolans, such

as slowly cooled and ground slag, bottom ash, and field-burnt rice husk ash

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Pozzolans
Pozzolans are siliceous or aluminous materials, which possess by themselves little or no
cementitious properties, but in finely divided form react with calcium hydroxide in the
presence of moisture at ordinary temperatures to form compounds possessing cementitious
properties

(definition

according

to

ASTM

C595).

CH

Portland-pozzolan cement reaction:

C3S/C2S

H2O

C-S-H

CH + Reactive SiO2 Pozzolanic C-S-H

The pozzolanic C-S-H is generally more porous than the normal C-S-H, and also has a lower
C/S ratio. A pozzolan may also have reactive Al 2O3, in which case the reaction with CH leads
to the formation of C-A-H, which can give rise to problems in sulphate attack.
Pozzolanic activity is evaluated using the Pozzolanic Activity Index test, which defines the
index as:
PAI

(%)

Strength

(PC/pozzolan

mixture)*100

Strength

(PC

mixture)

In this test, the mix design is done using a volumetric replacement of cement by the pozzolan
(ASTM C311) as opposed to the Slag Activity Index test (ASTM C989) where a mass
replacement

is

used.

Characteristics of pozzolanic reaction:

Lime consuming

Pore refiner (although there is not much decrease in the total pore volume)

Interface refiner (leads to higher strengths)

Slow rate of reaction; low heat of hydration. Time to attain same strength as PC may
be termed as teff, or effective time. Figure 2 shows some typical values of teff for
various mineral admixtures

Better durability, due to reduced permeability and reduced CH content

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Alkalis and gypsum accelerate the pozzolanic reaction

Figure 2: Strength of pozzolanic mixtures

Fly Ash
Fly ash is a by-product obtained during the combustion of coal in thermal power plants.
Nearly 73% of Indias electricity generation is through coal-burning thermal power stations.
About 120 million tons of coal ash now being generated annually; could reach 200 million
tons in 2010. Only about 10% of fly ash is being utilized in various industries; remaining
amount gets dumped in landfills. According to World Bank estimates, by 2015, the disposal
of coal ash would require 1000 square kilometers or one square meter of land per person.
Thus, the utilization of fly ash is a matter of primary concern.
The quality and composition of fly ash depends on the type of coal being burnt. The rank (or
purity) of coal increases in this order:
5.

Lignite

4.

Sub-bituminous

(brown
coal

(70

coal)

80%

C)

3. Bituminous coal (80 90% C) Soft coal, used for ordinary purposes
2.

Semi-bituminous

coal

Good

heating

value,

has

smokeless

flame

1. Anthracite (90 95% C) hard coal; high temperature needed to burn it

Low rank coals contain impurities such as clay, shale, quartz, carbonates, and sulfides. It is
these impurities which give fly ash its composition.
Fly ash use is not very common for the following reasons:
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1. Difficult quality assurance
2. Poor marketing
3. Conservative attitudes
4. Storage problems
5. Presence of toxic chemicals inside fly ash
6. It is called a waste instead of pozzolan or cement
Collection of fly ash
During combustion of coal, 75 80% of the ash flies out with the flue gas, and is thus called
fly ash. The ash that doesnt fly out is called bottom ash. This can be processed as
aggregate,

but

is

generally

not

used

in

concrete.

The collection of fly ash is done using the following two types of precipitators (see Figure 3):
1. Bag-house precipitator
2. Electrostatic precipitator
The bag-house precipitator is found to be more efficient, and removes out very fine material.
Sometimes, beneficiation of fly ash is done where coarse particles are ground to a fineness
compatible with the intended use.

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Figure 3: Electrostatic precipitator for fly ash collection

Uses of fly ash in concrete

As a mineral admixture

As a synthetic aggregate: Fly ash aggregate can be produced by sintering. The

resultant aggregate can be used for lightweight concrete. However, it is very
expensive. Aggregate can also be synthesized by agglomeration using lime or cement
as binder, as in cold bonding.

Types of fly ash (ASTM classification)

Type C: This is also called High Calcium fly ash, and possesses both cementitious and
pozzolanic properties. 10 15% of the material has a particle size greater than 45 m,
and the fineness (Blaine) is 300 400 m 2/kg. The particles are primarily solid spheres
with a smooth texture. The average particle size is less than 20 m.

Type F: This is also called Low Calcium fly ash, and is a normally pozzolanic
material. 15 20% of the material is larger than 45 m, and the fineness is 200 300
m2/kg. Particles are solid spheres with a smooth texture, and the average particle size
is 20 m.

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Apart from solid spherical particles, there also may exist hollow spheres. The small hollow
spheres with entrapped gas are called cenospheres, while the large hollow spheres with solid
spheres inside them are called plerospheres (see Figure 4).

Figure 4. Structure of fly ash

The loss on ignition of fly ash can represent the amount of unburnt carbon present. Too much
of unburnt carbon can interfere with the air-entraining agent, leading to poor air void
parameters. Restrictions are also placed on the sulfate (SO 3) content, MgO content, alkali
content, and moisture content of fly ash.
Effect on fresh concrete properties

The setting time is increased when fly ash is used.

Workability and flow of concrete are increased due to the spherical shape of the fly
ash particles, which lends a ball-bearing type effect on the concrete mixture.

Bleeding and segregation are usually reduced for well-proportioned fly ash concrete.

The paste volume is increased when mass replacement of cement by fly ash is done.

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Effect on hardened concrete properties

Strength gain of fly ash concrete is slower than normal concrete, as stated in the
previous sections. The potential for thermal cracking is much reduced compared to
ordinary PC concrete. Ultimate strengths are usually improved when fly ash is used.

Pozzolanic activity is proportional to the amount of particles under 10 m in diameter.

Creep and shrinkage of fly ash concrete are typically higher than normal concrete,
because of the increased amount of paste in the concrete (when mass replacement is
done).

More air-entraining admixture is needed to entrain air in fly-ash concrete.

The results on the effects of fly ash on sulphate resistance are inconclusive.

Expansions during alkali aggregate reaction are reduced by the use of fly ash, because
of the dilution of Portland cement (implying there are lesser alkalis available).

For properly cured fly ash concrete, the rate of chloride diffusion is reduced compared
to ordinary PC concrete.

Use of fly ash in specialized applications

In high strength concrete, as an additional cementitious material.

In roller-compacted concrete. fly ash is good for bonding in-between the layers of this
concrete.

In controlled low-strength materials (CLSM), which are flowable mortars used as

backfill

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High volume fly ash concrete: Concrete with 50% of the Portland cement replaced by
Class F fly ash. Has a low water content, generally less than 130 kg/m 3. For slumps of
150-200 mm, the use of a superplasticizer is mandatory. The range of characteristic
compressive strengths that can be achieved using HVFA concrete is 20-50 MPa. This
concrete possesses excellent pumpability, and exhibits little bleeding (therefore, prone
to plastic shrinkage cracking) and low drying shrinkage. It has applications in mass
concrete blocks, building columns and foundations, caissons and piles, dams,
highways, shotcrete and self-compacting concrete.

Silica Fume
According to ACI 116R, silica fume is a very fine amorphous (noncrystalline) silica produced
in electric arc furnaces as a byproduct of the production of elemental silicon or alloys
containing silicon; also known as condensed silica fume or microsilica. Despite previous
knowledge about the benefits of silica fume, its use as mineral admixture for concrete really
picked up only in the 80s.
There

are

numerous

variants

of

this

highly

pozzolanic

material

available:

Condensed silica fume, microsilica, silica flour, fume silica (a white fluffy material produced
from vapour phase hydrolysis of chlorosilanes such as SiCl 4 in the flame of hydrogen and
oxygen, used in the paint industry as filler), silica gel, and precipitated silica.
Silica fume is a by-product of the ferrosilicon industry. The purity of silica fume depends on
the ferrosilicon alloy from which Si metal is being extracted (see Table 1).
Table 1. Silica purity in various ferrosilicon alloys

15

Ferrosilicon alloys

SiO2 content

FeCrSi

18 48%

FeMgSi

44 48%

50% ferrosilicon

72 77%

70% ferrosilicon

84 88%

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Silicon metal (98%)

93 98%

Figure 5 depicts the process of collection of silica fume. After being collected over the
furnace, the silica fume is transferred, cooled, and physically trapped. Cyclones are used to
remove oversize and other unwanted materials. Similar to fly ash, silica fume is also collected
using baghouse precipitator.

Figure 5: Process of silicon metal extraction

Silica fume is available in the following states (see Figure 6):

As is bulk powder: Due to the low specific gravity of silica fume (~2.2), the bulk
powder becomes very bulky and difficult to handle and transport. It is difficult to
handle pneumatically; it is sticky and self agglomerating with a tendency to create
small weak lumps. Furthermore, its low density yields small loads in bulk tankers. It
is primarily used in bagged products (e.g., grouts, pre-mixed mortars)

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Dry-densified silica fume: Densification is performed by aerating and tumbling the

silica fume powder with compressed air, until the desired bulk density is reached due
to the agglomeration caused by electrostatic charges that develop. An efficient
superplasticizer is required to deflocculate and cause a good dispersion of the silica
fume in concrete. Unlike the as is powder, the densified version is easy to handle and
transport, and flows well pneumatically.

Slurry: 50% water + 47% silica fume + 3% chemical agent, that keeps the particles in
suspension and prevents gelling. The slurry form is susceptible to gelling in cold
climates. However, it is a very efficient way of dispensing silica fume. Also, storage
space can also be reduced.

Figure 6: Different forms of silica fume

Properties

Specific gravity: 2.2

Typical fineness: 20000 m2/kg (average particle size ~ 0.1 0.5 m)

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Bulk density: As-produced - 130 to 430 kg/m3, slurry - 1320 to 1440 kg/m3, densified
- 480 to 720 kg/m3

Colour: light grey to dark grey (lighter implies purer)

Cost: almost 10 times as much as PC

Typically used at 5 15% replacement level

Benefits from silica fume are due to the pozzolanic reaction that produces additional
C-S-H, as well as due to the particle packing (filler effect) of the fine silica fume
particles

Effects on fresh concrete properties

Because of its high fineness, the use of silica fume causes an increase in the water
demand of concrete. Typically it is always used in conjunction with a superplasticizer.

Silica fume causes the mix to be sticky and cohesive. Also, concrete mixes with silica
fume are prone to slump loss problems. Because of its cohesiveness, a higher slump is
needed to place silica fume concrete.

Bleeding is reduced drastically. In fact, most silica fume mixes do not show any
bleeding. In dry areas, if the evaporation rate exceeds the rate at which concrete sets,
plastic shrinkage may occur. Figure 7 shows the increase in capillary pressure with a
decrease in the pore diameter. Silica fume concrete is especially susceptible to this
problem in case curing is not done properly. A simple calculation of the capillary
tension

due

to

plastic

shrinkage

can

be

shown

as

follows:

Pc (capillary tension) = 0.001YS/(w/c), where Y = surface tension of water = 0.0073

N/m, and S = surface area of particles (20000 m2/kg for SF, 350 m2/kg for cement).
Assuming
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w/c

of

0.35,

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For

PC

concrete,

Pc

0.07

MPa

For

SF

concrete,

Pc

4.20

MPa

(for more information on plastic shrinkage problems with silica fume, see the paper:
M. D. Cohen, J. Olek, and W. L. Dolch, Plastic Shrinkage Cracking in Portland
Cement and Portland Cement-Silica Fume Paste and Mortar, Cement and Concrete
Research Vol. 20, 1990, pp. 103 119.

Figure 7: Relation between capillary pressure and diameter

Effects on hardened concrete properties

Pore size refinement and reduction in permeability occurs when silica fume is used.
Due to a combined effect of silica fume as a highly reactive pozzolan and filler, the
transition zone between aggregate and paste is strengthened.

Compressive and flexural strengths are increased, while the chloride permeability and
diffusion are reduced significantly compared to ordinary PC concrete.

Elastic modulus is increased (ESFC ~ 1.15 EPCC), or, in other words, concrete becomes
stiffer with the use of silica fume.

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Creep and shrinkage are increased at high replacement levels (10 15%) because of
an increase in the volume of the paste. However, due to the higher stiffness, the
resistance to creep and shrinkage deformation is higher.

Amount of air-entraining agent required for a particular volume of air is increased in

silica fume concrete. Freeze-thaw resistance is reduced slightly compared to normal
concrete, but damage is usually limited owing to the extremely low permeability of
SFC.

In most cases, silica fume concrete shows better resistance to chemical attack
(exceptions being ammonium sulphate and magnesium sulphate attack), owing to the
decreased permeability, as well as due to reduced CH in the paste.

Expansions due to ASR are reduced in silica fume concrete.

Corrosion rate is reduced with the use of silica fume. This is because of two reasons:
the low permeability of SFC causes a lower availability of moisture and oxygen at the
cathodic sites, and the high resistivity of SFC makes the flow of electrons difficult.

Carbonation depth is generally lowered.

SFC has very good abrasion and erosion resistance. This makes it an ideal choice for
industrial flooring.

Fire performance of SFC is not very good. This is a consequence of the low
permeability of silica fume concrete. When a fire occurs, the free water inside
concrete transforms to steam and escapes through the interconnected voids. When this
escape is prevented to the dense microstructure, significant pressures get built up
inside, which ultimately cause the concrete to explode and spall. This type of failure
occurred in the late 1990s in the English Channel tunnel.

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Ground granulated blast furnace slag
Blast furnace slag is a by-product of the extraction of iron from iron ore. Coke and limestone
are added as fluxes inside the blast furnace. The impurities in iron ore combine with the lime
and rise up to the surface of the blast furnace (shown in Figure 8), while the molten iron,
which is heavier, stays at the bottom.
The use of blast-furnace slag as a cementitious material is very old. 1892 was the first time
that Portland-blast furnace slag cement was manufactured. In the present day scenario, slag is
used almost in every country to varying degrees.
The reactivity of slag depends on the rate of cooling. In increasing order of reactivity, the
cooling processes may be ranked as: Slow cooling (in air), Rapid cooling (by water spray),
and Quenching (dipping in water).
Amongst mineral admixtures, slag possesses the highest specific gravity (~ 2.8 3.0).
Because it is a processed material, the fineness can be controlled to any desired degree.
However, for most typical applications, slag fineness is only slightly higher than cement
fineness.

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Figure 8: Blast furnace used in iron extraction

Types of slag

Air cooled slag: Low reactivity slag that finds use as aggregate. The strength and
toughness of this aggregate makes it a very suitable material for railroad ballast.

Expanded or foamed slag: Low reactivity slag that is foamed with air. Makes a very
good lightweight aggregate, and is used for thermal insulation.

Granulated: This is a high reactivity slag, and is usually quenched. The hardened
matter is then ground to a fineness similar to cement. Thus the name: Ground
Granulated Blast Furnace Slag (GGBFS).

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Pelletized slag: The reactivity is similar to GGBFS, but the process of pelletization is
a complex one. The schematic diagram in Figure 9 shows the process of pelletization.
Typically, this type of slag is not used as much as GGBFS

Figure 9: Process of pelletization of slag

Factors determining cementitious properties of slag cements

Chemical composition of GGBFS The amount of CaO in slag determines its

cementitious properties. Since slag is almost entirely amorphous, the reactivity of the
CaO will determine the overall slag reaction.

Alkali concentration of reacting system When the alkali content is higher, the
system will be more reactive.

Glass (reactive SiO2) content of GGBFS Glassy SiO2 causes the pozzolanic reaction
to take place with the hydrated lime.

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Fineness of GGBFS and PC Higher fineness implies a faster reaction.

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Temperature during early phase of hydration Slag hydration is greatly enhanced at

high temperatures.

Hydration of slag
GGBFS is a mineral admixture with both cementitious and pozzolanic properties. In fact, it is
classified as a hydraulic cement in most codes. However, an activator is necessary to hydrate
the slag. The activation of slag hydration can be done in the following ways:

Alkali activation: e.g. by caustic soda (NaOH), Na 2CO3, sodium silicate, etc. The
products formed are C-S-H, C4AH13 and C2ASH8 (Gehlenite).

Sulphate activation: e.g. by gypsum, hemihydrate, anhydrite, phosphogypsum, etc.

The products formed are C-S-H, ettringite, and aluminium hydroxide (AH3).

Mixed activation: When both alkali and sulphate sources are present, such as in a
cement system.

Effects on fresh and hardened concrete

Apart from delaying the initial set, slag does not significantly alter the fresh concrete
properties. The workability of slag concrete is similar to an equivalent PC concrete,
primarily because slag possesses the same level of fineness as PC.

The rate of strength gain is slowed down considerably when cement is replaced by
slag. The delay increases with increasing replacement. 100% slag concrete is also
possible, although the curing duration to produce the required strengths would need to
be substantially increased

The ultimate strengths with slag are generally improved; the durability is also
improved with the replacement of cement by slag.

Slag is the ideal admixture for marine concrete, as slag concrete shows excellent
resistance to chemical attack and corrosion

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Slag concrete is reported to have higher carbonation rates compared to ordinary PC

concrete

Other mineral admixtures

Rice husk ash (RHA)
This is a high reactivity pozzolan obtained by controlled calcination of rice husk. Field-burnt
rice husk is almost crystalline in nature, and makes a weak pozzolan. Thus, to obtain a high
degree of pozzolanicity, a good control is needed while burning. RHA usually contains a
large amount of unburnt carbon which might adversely affect air entrainment.
RHA is a fine material, with particle sizes less than 45 m, and a surface area of 60000
m2/kg. The particles are typically cellular. A high amount of reactive silica is present in the
system (> 90%).
Metakaolin
This is obtained from calcination of kaolinite clay in the range of 740 840 oC. The
crystalline clay loses its structure at this temperature by the loss of bound water. Burning
should strictly be done in this range, since beyond 1000 oC, recrystallization of the clay
occurs.
A general formula of metakaolin can be written as AS2. This aluminosilicate compound reacts
with CH produced during cement hydration in the following form (suggested by Murat in
Cement
AS2

and
+

Concrete
6CH

Research,
9H

C4AH13

Vol.

13,
+

1983):

2C-S-H

C-S-H formed in this reaction is aluminous, with a C/S ranging from 0.83 (for crystalline
forms of C-S-H) to > 1.5 (for amorphous and semi-crystalline forms of C-S-H).
The content of C-S-H and its formation rate depends on the mineralogical characteristics of
the kaolin precursor. Metakaolin has a performance comparable to silica fume as a mineral
admixture in concrete. Since MK is not a by-product, its processing is an expensive affair.
Thus the marketability of MK is not as good as silica fume, which is a proven by-product.

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Proportioning methods for mineral admixtures

Simple replacement method: This is the traditional method of proportioning.

Replacement of cement can be done either on a volume basis or a mass basis. Volume
replacement does not change the overall volume of the paste. However, when mass
replacement is done, volume of the paste increases, and this increase is usually
compensated by a decrease in the volume if sand. Mixture characteristics can be
adversely affect by the removal of sand if the volume removed is substantial (which
can happen for large amounts of low specific gravity admixtures such as silica fume).
For slow reacting pozzolans like Type F fly ash, this method results in low early age
strengths. Another disadvantage of this method is that it does not account for the
variations in characteristics of the mineral admixtures. The advantages of this method
are its simplicity and positive effects on workability (when replacing material is fly
ash).

Addition method: This method involves a direct addition of the mineral admixture to
the concrete without replacing any part of the cement. In high performance concrete,
this is the method of choice, since it increases the cementitious content. This increase
is compensated by a decrease in the fine aggregate content. Addition method usually
results in higher strengths.when fine materials such as silica fume are used, this
method can cause a substantial increase in the water demand.

Modified replacement method: In this case, part of the admixture is added, and part of
it is used as a replacement. The quantity of mineral admixture put into the mix is
greater than the quantity of cement removed. This method is typically used to obtain
sufficiently high early age strengths with fly ash. However, workability and water
demand can be difficult to control in this method.

Rational method: This is an efficient method of proportioning admixtures. It

quantifies the influence of the admixture using a factor K, which is the cementing
efficiency factor. This factor qualifies the mineral admixture as a lower grade or
higher grade cement. In other words, K represents the amount of the mineral

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admixture that can replace 1 unit of Portland cement in the mixture to achieve similar
properties. This method is able to overcome the slow early age strength development
for fly ash concrete.

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