Industrial Wastes in Concrete

Fly Ash, GGBS, Micro silica, Rice Husk

Ash, Metakaolin
 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 19-23 35 Upto 60 35 >90

Al2O3 2-6 8 25 20 2

Fe2O3 .5-6 3 10 5 2

CaO 61-67 40 1 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
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, and field-burnt rice husk ash
 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).

• Portland-pozzolana cement reaction:

C3S/C2S+H2O—›C-S-H+CH

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 Al2O3, in which case the

reaction with CH leads to the formation of C-A-H, which can give rise to problems
• 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

• 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.

• Better durability, due to reduced permeability and reduced CH

content

• Alkalis and gypsum accelerate the pozzolanic reaction

 FLY ASH
 Fly Ash:- Fly ash is a fine inorganic material with pozzolanic properties, which

can be added to concrete to improve its properties. However the dimensional

stability may be affected and should be checked.

 (dimensional stability:- The degree to which a material maintains its original

dimensions when subjected to changes in temperature and humidity)

 The diameter of the fly ash particles ranges from 1µm-150µm.

 Surface area 300-700 m2/kg

 Specific gravity 2.1-3

 Silica (SiO2) upto 60%

• 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-(brown-coal)

4.Sub-bituminous-coal (70–80%C)

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

2. Semi-bituminous coal – Good heating value, has a 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.
 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 is 300 – 400 m 2/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 m 2/kg. Particles

are solid spheres with a smooth texture, and the average particle size is 20 µm.

• Class N Fly ash Raw or calcined natural pozzolans such as some diatomaceous earths,

opaline chert and shale, stuffs, volcanic ashes and pumice are come in this category.

Calcined kaolin clay and laterite shale also fall in this category of pozzolans.
 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. 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.

• For properly cured fly ash concrete, the rate of chloride diffusion is reduced compared

to ordinary PC concrete.
 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), flow able mortars used as backfill

• 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

• Silicon, ferrosilicon and other silicon alloys are produced by reducing quartz,

with coal and iron or other ores, at very high temperatures (2000°C) in

electric arc furnaces; also known as condensed silica fume or microsilica.

• There are numerous variants of this highly pozzolanic material available:

Condensed silica fume, microsilica, 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), 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.
 SILICA FUME

• < 0.1 μm to 1 μm spherical particles of amorphous silica.

• Bulk density: As-produced - 130 to 430 kg/m3

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

• This material is usually known as silica fume.

• Surface area 20000 m2/kg

• Specific gravity 2.2 to 2.5

• 85-96 percent SiO2

• 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
• 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. 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. Silica fume concrete is especially vulnerable to this

problem in case curing is not done properly.

 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 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, because of an increase in the volume of

the paste.

• 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.

• 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.

 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 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). the

fineness can be controlled to any desired degree. However, for most typical applications, slag

fineness is slightly higher than cement fineness.

• Surface area 400-600 m2/kg

 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.

• 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)
 Properties of slag cements
• Chemical composition of GGBFS – The amount of CaO and silica in slag

determines its cementitious properties.

• Alkali concentration– 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
also known as a hydraulic cement. However, an
activator is necessary to hydrate the slag.

• Alkali activation: e.g. by caustic soda (NaOH),

Na2CO3, sodium silicate, etc.

 Effects on fresh and hardened concrete

• Apart from delaying the initial setting time, 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

 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 is a fine material, with particle sizes less than 45 µm,

• and a surface area of 60000 m2/kg.

• A high amount of reactive silica is present in the system (> 90%).

 METAKAOLIN
 Metakaolin is an artificial pozzolana produced by burning selected
kaolinite clay within a specific temperature range (between 650 and
800 C).

 When heated to 700–900 C, kaolin becomes calcined, losing up to

14% hydroxyl water and changing into Metakaolin.
 Silica (SiO2) upto 55%

 particles ranges from 1µm- 2µm.

 Specific gravity 2.4-2.6

 Surface area 17000 – 19000 m2/kg

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.

• 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.