MODULE 3

Pozzolanic or Mineral Admixtures

 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

The best pozzolans in optimum proportions mixed with Portland cement improves many
qualities of concrete, such as:

(a) Lower the heat of hydration and thermal shrinkage;

(b) Increase the water tightness;

(c) Reduce the alkali-aggregate reaction;

(d) Improve resistance to attack by sulphate soils and sea water;

(e) Improve extensibility;

(f) Lower susceptibility to dissolution and leaching;

(g) Improve workability;

(h) Lower costs.

Pozzolanic Materials

Pozzolanic materials are siliceous or siliceous and aluminous materials, which in

themselves possess little or no cementitious value, but will, in finely divided form and in the
presence of moisture, chemically react with calcium hydroxide liberated on hydration, at
ordinary temperature, to form compounds, possessing cementitious properties.
 On hydration of tri-calcium silicate and di-calcium silicate, calcium hydroxide is formed
as one of the products of hydration. This compound has no cementitious value and it is soluble in
water and may be leached out by the percolating water. The siliceous or aluminous compound in
a finely divided form react with the calcium hydroxide to form highly stable cementitious
substances of complex composition involving water, calcium and silica. Generally, amorphous
silicate reacts much more rapidly than the crystalline form. It is pointed out that calcium
hydroxide, otherwise, a water soluble material is converted into insoluble cementitious material
by the reaction of pozzolanic materials.

The reaction can be shown as

Pozzolan + Calcium Hydroxide + Water C – S – H (Gel)

This reaction is called pozzolanic reaction. The characteristic feature of pozzolanic

reaction is firstly slow, with the result that heat of hydration and strength development will be
accordingly slow. The reaction involves the consumption of Ca(OH)2 and not production of
Ca(OH)2. The reduction of Ca(OH)2 improves the durability of cement paste by making the paste
dense and impervious.

Pozzolanic materials can be divided into two groups:

a) Natural pozzolana and

b) Artificial pozzolana

a) Natural Pozzolans
1) Clay and Shales
2) Opalinc Cherts
3) Diatomaceous Earth
4) Volcanic Tuffs and Pumicites

b) Artificial Pozzolans
1) Fly ash
2) Blast Furnace Slag
3) Silica Fume
 4) Rice Husk ash
5) Metakaoline
6) Surkhi.

Other mineral admixtures, like finely ground marble, quartz, granite powder are also
used. They neither exhibit the pozzolanic property nor the cementitious properties. They just act
as inert filler. Natural pozzolans such as diatomaceous earth, clay and shale, pumicites, opaline
cherts etc., needs further griding and sometimes needs calcining to activate them to show
pozzolanic activities.

Fly Ash:

Fly ash is a by-product obtained during the combustion of coal in thermal power plants.
Nearly 73% of India’s 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. In India, Fly ash was used in Rihand dam construction
replacing cement upto about 15 per cent.

The quality and composition of fly ash depends on the type of coal being burnt. Fly ash
use is not very common for the following reasons:

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

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 µm,
and the fineness (Blaine) is 300 – 400 m2/kg. The particles are primarily solid spheres
with a smooth texture. The average particle size is less than 20 µm.
  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 µm, and the fineness is 200 – 300 m2/kg.
Particles are solid spheres with a smooth texture, and the average particle size is 20 µm.

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 (SO3) 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.

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 µm 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
 As a synthetic aggregate
 High volume fly ash concrete: Concrete with 50% of the Portland cement replaced by
Class F fly ash. Has low water content, generally less than 130 kg/m3. 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.

As the water content is low in high volume fly ash, the bleeding is very low and often
negligible. Setting time is little longer than that of conventional concrete. As the water content is
low in high volume fly ash, the bleeding is very low and often negligible. Setting time is little
longer than that of conventional concrete.

Silica Fume

According to ACI 116R, silica fume is a very fine amorphous (non crystalline) 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.

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 SiCl4 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

Ferrosilicon alloys SiO2 content

FeCrSi 18 – 48%
FeMgSi 44 – 48%
50% ferrosilicon 72 – 77%
70% ferrosilicon 84 – 88%
Silicon metal (98%) 93 – 98%
Figure 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 : Process of silicon metal extraction

Silica fume is available in the following states

 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)

 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 dandified 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.

Different forms of silica fume

Properties

 Specific gravity: 2.2

 Typical fineness: 20000 m2/kg (average particle size ~ 0.1 – 0.5 µm)
 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

Pozzolanic Action

Microsilica is much more reactive than fly ash or any other natural pozzolana. The
reactivity of a pozzolana can be quantified by measuring the amount of Ca(OH)2 in the cement
paste at different times. In one case, 15% of microsilica reduced the Ca(OH)2 of two samples of
cement from 24% to 12% at 90 days and from 25% to 11% in 180 days. Most research workers
agree that the C – S – H formed by the reaction between microsilica and Ca(OH)2 appears dense
and amorphous

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.

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.
 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.

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, while the molten iron, which is heavier,
stays at the bottom.

The use of blast-furnace slag as a cementitious material is very old. 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.
 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).
 Pelletized slag: The reactivity is similar to GGBFS, but the process of pelletization is a
complex one. The schematic diagram in Figure shows the process of pelletization.
Typically, this type of slag is not used as much as GGBFS
 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.
 Fineness of GGBFS and PC – Higher fineness implies a faster reaction.
 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), Na2CO3, 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
 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 µm, and a surface area of 60000 m 2/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

AS2 + 6CH + 9H —›C4AH13 + 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.

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 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.
 Mix Design

One of the ultimate aims of studying the various properties of the materials of concrete,
plastic concrete and hardened concrete is to enable a concrete technologist to design a concrete
mix for a particular strength and durability.

Mix design can be defined as the process of selecting suitable ingredients of concrete and
determining their relative proportions with the object of producing concrete of certain minimum
strength and durability as economically as possible.

The objects of designing

 The first object is to achieve the stipulated minimum strength and durability.
 The second object is to make the concrete in the most economical manner.

Variables in Proportioning

With the given materials, the four variable factors to be considered in connection with
specifying a concrete mix are:

(a) Water-Cement ratio

(b) Cement content or cement-aggregate ratio

(c) Gradation of the aggregates

(d) Consistency.

Water/cement ratio expresses the dilution of the paste cement content varies directly with
the amount of paste. Gradation of aggregate is controlled by varying the amount of given fine
and coarse aggregate.

Consistency is established by practical requirements of placing. In brief, the effort in

proportioning is to use a minimum amount of paste (and therefore cement) that will lubricate the
mass while fresh and after hardening will bind the aggregate particles together and fill the space
between them. Any excess of paste involves greater cost, greater drying shrinkage, greater
susceptibility to percolation of water and therefore attack by aggressive waters and weathering
action. This is achieved by minimising the voids by good gradation.

Various Methods of Proportioning

 (a) Arbitrary proportion

(b) Fineness modulus method

(c) Maximum density method

(d) Surface area method

(e) Indian Road Congress, IRC 44 method

(f ) High strength concrete mix design

(g) Mix design based on flexural strength

(h) Road note No. 4 (Grading Curve method)

(i ) ACI Committee 211 method

(j ) DOE method

(k) Mix design for pumpable concrete

(l ) Indian standard Recommended method IS 10262-82

ACI Method of Concrete Mix Design

Required Data:

Before starting concrete mix design, basic information on raw materials shall be prepared which
include:

 Sieve analyses of fine and coarse aggregates.

 Unit weight (dry rodded density) of coarse aggregate.
 Bulk specific gravities and absorptions or moisture content of aggregates.
 Mixing-water requirements of concrete developed from experience with available
aggregates.
 Specific gravities of Portland cement and other cementitious materials, if used.
 Relationships between strength and water-cement ratio or ratio of water-to-cement plus
other cementitious materials, for available combinations of cements, other cementitious
materials if considered, and aggregates.
Procedure for ACI Method of Concrete Mix Design.

1.Choice of slump

If slump is not specified, a value appropriate for the work can be selected from Table 1. The
values provided in table can be used only when vibration is used to consolidate concrete.

2. Choice of maximum size of aggregate

Commonly, maximum aggregate size should be the largest that is economically available
and consistent with dimensions of structural element. ACI 211.1-91 specify that, maximum
aggregate size shall not surpass:

 One-fifth of the narrowest dimension between sides of forms.

 one-third the depth of slabs
 3/4-ths of the minimum clear spacing between individual reinforcing bars,
bundles of bars, or pre-tensioning strands.

3. Estimation of mixing water and air content

The quantity of water per unit volume of concrete required to produce a given slump is
dependent on:

 nominal maximum size

 particle shape
 grading of the aggregates
 concrete temperature
  amount of entrained air
 use of chemical admixtures.

4. Selection of water-cement or water-cementitious material ratio

Strength, durability, and determine water to cement ratio:Without strength vs. w/c ratio
data for a certain material, a conservative estimate can be made for the accepted 28-day
compressive strength from Table 2.

Additionally, if there are severe exposure conditions, such as freezing and thawing, exposure to
seawater, or sulfates, the w/c ratio can be obtained from table 3.

5. Calculation of cement content

The amount of cement is fixed by the determinations made in Steps 3 and 4 above.

6. Estimation of coarse aggregate content

The most economical concrete will have as much as possible space occupied by coarse aggregate
since it will require no cement in the space filled by coarse aggregate.
7. Estimation of fine aggregate content

At the completion of Step 6, all ingredients of the concrete have been estimated except
the fine aggregate.There are two standard methods to establish the fine aggregate content, the
mass method and the volume method. the “volume” method will be used because it is a
somewhat more exact procedure.

8.Adjustments for aggregate moisture

Aggregate weights

Aggregate volumes are computed based on oven dry unit weights, but aggregate is typically
batched based on actual weight.

Therefore, any moisture in the aggregate will increase its weight and stockpiled aggregates
almost always contain some moisture. Without correcting for this, the batched aggregate
volumes will be incorrect.

Amount of mixing water

If the batched aggregate is anything but saturated surface dry it will absorb water (if oven dry or
air dry) or give up water (if wet) to the cement paste.

This causes a net change in the amount of water available in the mix and must be compensated
for by adjusting the amount of mixing water added.

9. Trial Batch Adjustments

The ACI method is written on the basis that a trial batch of concrete will be prepared in the
laboratory, and adjusted to give the desired slump, freedom from segregation, finishability, unit
weight, air content and strength.