CHAPTER 5

BLENDED CEMENTS- OVERVIEW

5.1 GENERAL
Rising level of greenhouse gas in the atmosphere and the associated increase in

temperature of the environment are potentially able to alter the ability of the planet to

support present life forms. Green house gases results in an increased temperature for

the earth‟s troposphere. The intergovernmental panel on climatic change estimates

that the average rise in temperature of the environment should reach between 1.9 and

5.3ºC in the next 100 years. The need to reduce the consumption of energy and the

release of carbon-di-oxide increased the emphasis on the use of blended cements.

Pozzolanic materials are widely used in concrete and mortars for various reasons,

particularly for reducing the amount of cement consumption. Blended cement by

incorporating industrial by-products/pozzolanic materials is a promising area of

research because of their improved properties, such as workability, long-term strength

and durability [Ganesan et al, 2008; Hwang and Chandra, 1997; Khan et al., 2000 and

Toutanji et al., 2004].

In this chapter, a brief review of the work of earlier investigators on blended cement

using various pozzolans in general and in particular about RHA blends has been

presented. A comprehensive review on the mechanisms of lime-RHA and cement-

RHA hydration processes; influence of RHA addition on the properties of mortar and

concrete, namely, workability and compressive strength have also been presented.

5.2 BLENDED CEMENTS

„Blended cement‟ is defined as a hydraulic binder composed of Portland cement and

one or more inorganic materials that take part in the hydraulic reaction. This

definition excludes the chemical admixtures that influence the hydration process.
Recently, blended cements based on industrial and agricultural wastes, are well

known for their improved long-term strength and durability. The blending agents are

fly ash (FA), rice husk ash, silica fume (SF), calcined clay, etc. It is reported that the

incorporation of pozzolanic materials in concrete improve its properties such as

rheology and cohesiveness, lower heat of hydration, lower permeability and higher

resistance to chemical attack [Khan et al., 2000; Nehdi et al., 2003; Aziz et al., 2004

and Bouzoubaa and Fournier, 2001]. In partial replacement of cement, some

pozzolanic materials did not alter the rate of strength gain in concrete and others

retarded it [Toutanji et al., 2004].

5.2.1 Pozzolanic Reaction

The use of industrial and agricultural by-products as mineral admixture is known to

possess pozzolanic properties. Pozzolanic reaction takes place when siliceous or

siliceous and aluminous material come in contact with calcium hydroxide in the

presence of moisture to form compounds possessing cementitious properties. Silica in

amorphous form reacts with lime more readily than those of crystalline form. In

cement hydration process, the calcium silicate hydrate (C-S-H) and calcium hydroxide

(Ca(OH)2, (which is symbolically written as CH) is released in the hydration of two

major compounds of cement, namely tri calcium silicate (C3S) and di calcium silicate

(C2S). So, the pozzolanic reaction will only take place when CH is released. As a

result from this reaction, the pozzolanic material will produce a C-S-H altogether with

calcium aluminate hydrate (C-A-H) which are so called cement gels, that form the

hardened cement paste [James and Rao,1986 ; Qijun et al.,1999 and Aziz et al., 2004].

Pozzolana can accelerate the early hydration rate within one hour, by stimulating the

dissolution of C3S by the absorption of Ca2+ ions on the surface of the pozzolanic

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particles and also by providing increased sites for the precipitation of C-S-H. Hence,

the surface of pozzolana acts as precipitation sites that is preferable to the

precipitation of hydrates and secondly can lower the concentration of Ca2+ ions that

can accelerate the rate of dissolution of C3S. The primary pozzolanic reaction during

the early age is with alkali hydroxides [Aziz et al., 2004].

Secondly, long-term reaction is with calcium hydroxide. Due to the slow pozzolanic

reaction, more porous concrete at early age is obtained and it becomes gradually

denser than plain concrete with increase in time [Aziz et al., 2004]. Pozzolan can

partially replace cement in mortar or concrete mix without affecting strength

development. The effect of the pozzolanic reaction will produce more cement gel

which is the C-S-H and C-A-H, reducing the pore size, blocks the capillary pores and

produces denser concrete thus making it stronger and more durable [Aziz et al., 2004].

The small particles of pozzolans are less reactive than Portland cements [Mehta and

Aitcin, 1990]. Nevertheless they generate a large number of nucleation cites for the

precipitation of the hydration products when it dispersed in cement pastes. Therefore,

this mechanism makes the paste more homogeneous and dense as for the distribution

of the fine pores. This is due to the reaction between the amorphous silica of the

pozzolanic and the calcium hydroxide produced by the cement hydration reactions

[Isai et al., 2003].

5.3 TYPES OF POZZOLANIC MATERIALS

The pozzolanic materials can be divided into two groups namely, natural pozzolanas

and artificial pozzolanas. The typical examples of natural pozzolana are clay, shales,

opaline cherts, diatomaceous earth, and volcanic tuffs and pumicites. The commonly

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produced artificial pozzolanas are fly ash, silica fume, rice husk ash, metakaolin,

surkhi, etc.

5.3.1 Fly Ash

Fly ash is the industrial by-product of coal combustion process for producing

electricity. The shales and clays (contents of silica, alumina and iron oxide) and the

other matters in coal, melt whilst in suspension, and then with rapid cooling, they are

carried out by the flue gases and form into fine spherical particles [Weshe, 1991].

The method to remove fly ash from the flue gases can affect the quality of fly ash

being produced at power stations. Fly ash obtained from cyclone separators is

comparatively coarse and contains a large proportion of un-burnt fuel. While, fly ash

that obtained from electrostatic precipitators is relatively fine having a specific surface

of about 3500 cm2/g or as high as 5000 cm2/g. The shape is generally of spherical and

some of which may be like glass and hollow and irregularly shaped of un-burnt fuel or

carbon. The colours may vary from light grey to dark grey or even brown [Weshe,

1991].

Fly ash can be divided into two distinct categories that are generally associated with

type of coal used at the power station. The categories namely are low lime and high

lime fly ash [Ravindra, 1986]. Low lime fly ash contains calcium oxide (CaO) content

less than 10 percent and usually produced from anthracite and bituminous coals,

classified into “class F” fly ash. Whereas high lime fly ash with CaO content greater

than 10 percent and are usually produced from sub bituminous and lignite coals,

roughly corresponds to ASTM “class C” fly ash. The sum of three significant oxides

namely silicon di oxide, aluminium oxide and iron oxide has a minimum value of 70

percent and 50 percent for class F and class C fly ash respectively. Class F should be

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defined as truly pozzolanic and Class C as having some cementitious properties itself.

In Indian context, the fly ash has been classified into two grades depending upon its

characteristics [IS: 3812, 1981]. The fineness of fly ash for grade-I and grade-II

categories has a minimum value of 320 m2/kg and 250 m2/kg respectively.

The reactivity of fly ash for class F depends on the nature and proportion of the glass

phase. In general, the greater fineness and lower loss on ignition of fly ash have been

found to be a great potential to enhance the performance of fly ash concrete. Fly ash

normally results in lower early strength but improved workability. The reduction in

water requirement in fly ash-cement system is due to the spherical shaped particles

and their smooth surface which also roll in fresh paste thereby reduce the fraction

resistance of cement particles and improve the fluidity of the mixture [Sun et al.,

2003].

It is well documented that the use of FA increase workability for given water content

because of lubrication effect of its spherical particles [Yamazaki, 1962; Ravina, 1981;

Lane, 1983 and Dhir, et al., 1988]. The use of fly ash can physically disperse the

cement flocs, thus freeing more paste to lubricate aggregates and improving

workability [Ravindra, 1986]. Fly ash also improves cohesion and plasticity. Fly ash

can restrict the movement of free water in the plastic concrete thus reducing bleeding

more effectively than OPC. However, it is also known that the use of fly ash causes

delay in the early age strength development. But on later ages fly ash concrete goes on

progressively to develop higher strength value. Ho (1988) studied the incorporation of

30 percent fly ash in concrete reported that the 7 days strength of FA concrete is lower

than OPC concrete but at 28 days it achieved higher strength. Naik and Ramme

(1989) concluded that the optimum cement replacement level for FA is 40 percent

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with respect to strength studies. Besides that, if early strength is not a major aspect, as

high as 60 percent of FA can be used for making concrete [Naik and Ramme, 1989].

According to Fraay et al., (1989) the glass materials in fly ash is broken down only

when the pH value of the pore water is at least 13.2, and the increase in alkalinity of

the pore water requires that a certain amount of hydration of OPC in the mix has been

taken place [Neville, 1995]. Fly ash mixes made without additives exhibited

outstanding performance at 91 days. However, fly ash mixes with too much dosage of

super plasticizer may cause segregation, resulting in lower strength [Toutanji et al.,

2004].

For almost 70 years, it has been used as a constituent of concrete by replacing a minor

portion of OPC. However it has recently been determined that large percentages of fly

ash can be used in concrete mixtures with large success. High Volume Fly Ash

(HVFA) mix design developed by Malhotra and Biliodeau (1990) incorporates 50-60

percent fly ash by mass which obtains excellent strength and durability characteristics.

This mix has low cement content (not more than 200 kg/m3), a very low water to

cementitious materials ratio (less than 0.35), very low water content (less than

130 kg/m3), and low dosage of super plasticizers, if needed. From extensive tests, it

was concluded that modulus of elasticity, creep, drying shrinkage and freezing and

thawing characteristics of HVFA concrete are comparable to OPC concrete. In

general, it is very practical to use fly ash in concrete in concentrations of 35-70

percent of total cementitious content depending upon the usage.

5.3.2 Silica Fume

Silica fume is a by-product of the silicon metal or ferrosilicon alloy production

process. It consists primarily of amorphous silicon-di-oxide. Due to its fineness, large

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surface area, and higher silica content, it is a very reactive pozzolana, making it a

beneficial addition to concrete mixtures.

The amorphous silica is highly reactive, and the smallest of the particles speeds up the

reaction with calcium hydroxide. The very small particles of SF be able to go through

the void between the particles of cement hence improve packing. The particles are

extremely fine and having diameter ranging between 0.03 and 0.3µm (approximately

1/100 the size of an average cement particle). The specific surface of SF is 13 to 20

times higher than that of other pozzolans. It also has a very low bulk density (200 to

300 kg/m3) [Neville, 1995]. The maximum of 3 to 5 percent of SF is used in cement

replacement because of its very high reactivity. The high surface area of SF would

increase the water demand. Super plasticizer is required when the low water to

cementitious materials ratio is concerned in making concrete. The use of SF can

reduce bleeding and improves cohesion of the mix. The voids caused by trapped bleed

water are also absent. SF due to its high pozzolanicity and its extreme fineness is very

effective in producing low permeability and high strength concrete but, generally has

the drawback of low workability as a result of its high specific surface area [Bagel,

1998 and Khan et al., 2000]. The action as a filler through improvement in packing

and interface effects probably contributes the early strength development at 7 days of

concrete [Neville, 1995].

The strength of concrete containing SF increases with an increase of SF content in the

mix (up to certain limit). The highest rate of strength development was achieved at

early ages (3 and 7 days). The optimum field applications are limited to a maximum

dosage of 15 percent SF by weight of cement [Mehta, 1994].

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5.3.3 Metakaolin
Metakaolin is a reactive alumino silicate pozzolan formed by burning purified kaolin

or kaolinite clays at a specific temperature range and by grinding it to a higher

fineness. In general, the average particle size of high reactivity metakaolin ranges

from 0.5 to 20µm. Metakaolin increases the normal consistency of cement; as a

consequence its presence in concrete increases the water demand. But, it does not

increase the risk of aggregate segregation in concrete [Sabir et al., 2001]. However the

reduction in slump of concrete due to MK blending was less than experienced with

silica fume. The strength development of MK blended concrete depends on the level

of blending and binder content used in the concrete. Replacement level of 10-20

percent achieved higher strength at about 28 days. The efficiency of metakaolin to

improve the strength of concrete does not only depends on the blending percentage,

but also on the binder content. Mixtures containing 8-12 percent of metakaolin

replacement at 0.3 to 0.4 water-cementitious materials ratio greatly improved the

compressive strength at all ages [Gruber et al., 2001].

5.4 RICE HUSK ASH

RHA is highly pozzolanic mineral admixture when it is burnt under controlled

conditions. Fig.5.1 shows the SEM micrographs of cement grains and various

pozzolans.

5.4.1 Lime –RHA Interactions

Though the use of rice husk ash-lime mixture as a cementitious material is an

established fact, the reaction of silica in RHA with lime is little studied. James and

Rao (1986) made an attempt to understand the chemistry involved in the reaction

between RHA and lime in the presence of water. They revealed that, the strength

increases up to 28 days and later a gradual decrease is noticed.

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They studied the morphology of the reaction products of RHA and lime and revealed

that C-S-H gel looks like dense fibrillar structure made up of fine hollow tubes

radiating in a procupine fashion from the individual silica grain. The solubility of

silica increases with pH and at pH = 12, the solution surrounding the each grain of

silica react with calcium ions and forms gelatinous precipitate of C-S-H which

envelope each grain as a semi permeable membrane. Diffusion of water through this

membrane dissolves more of silica and set up an osmotic pressure. The membrane

bursts at higher pressure and the silica solution streams into the surrounding calcium

ions solution. This leads to the formation of hollow tubular form of C-S-H precipitate.

They concluded that alkalis act as catalysts in the formation of calcium silicate

hydrate from lime and silica; the long-term decrease in strength of RHA-lime cement

might be due to changes in morphology/crystallinity of C-S-H and un-reacted silica

[James and Rao,1986].

5.4.2 OPC- RHA Interactions

When pozzolanic materials are admixed with cement, understanding of hydration

mechanism is essential for controlling the properties of paste. Hwang and Chandra

(1997) revealed that heat evolution curve of cement paste with RHA are similar in

shape to that of reference mixture. Heat of hydration depends on the water-cement

ratio and amount of RHA added. High water-cement ratio and high RHA content

significantly reduces the heat of hydration.

The setting and hardening of Portland cement occurs as a result of the reaction

between the compounds of cement and water. Cement hydrates to C-S-H gel, calcium

hydroxide, ettringite and mono sulfo-aluminate. The type of capillary pores and un-

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hydrated core varies with age and depends on cement composition, curing conditions

and addition of additives.

The hydration mechanism of RHA and cement are different than RHA reaction with

lime. A cement paste formed with water-cement ratio of 0.4 containing RHA was

investigated using scanning electron microscope [Hwang and Chandra, 1997]. After

one day, the C-S-H gel was in the form of a dense sponge matrix. Some hexagonal

plates (about 0.1µm) grow on the surface of the RHA similar to that of mono sulfo

aluminate. After 7 days, the C-S-H crystal looks like a bundle of fibers, constrained in

the middle, but flower-like at the ends. After 28 days, the matrix has become denser

and CH crystals clog the matrix. After 60 days, the matrix bonds together and the

presence of CH become unclear [Hwang and Chandra, 1997]. The hydration

mechanism of paste with RHA can be hypothesized, may appear as shown

schematically in Fig. 5.2.

The formation of CH at the surface of RHA may be due to the adsorption by cellular

structure of RHA. In such case, the bleeding water will be significantly reduced. The

adsorbed water enhances the pozzolanic reaction inside the inner cellular spaces.

After 40 hours, the pozzolanic reaction further binds silica in RHA with CH to form

C-S-H gel and solid structures.

And also the image analysis by Zhang and Malhotra (1996) reveals that after 28 days

of curing, the reduction of un-hydrated cement particles in RHA paste was 18 percent

when OPC is replaced by 10 percent of RHA. Qijun et al. (1999), who studied the

reaction between RHA and CH, observed that the amount of CH by 30 percent RHA

in cement paste begins to decrease after 3 days, and by 91 days it reaches nearly zero,

whereas in the control paste, it significantly increased with hydration time.

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5.4.3 Properties of Cement Paste/Mortar/Concrete Admixing RHA

The shape, fineness, particle size distribution, density, and composition of rice husk

ash influence the properties of fresh concrete and the strength development of

hardened concrete.

a) Bleeding: At a given water to cement ratio, even a small addition (less than 3

percent by weight of cement) of RHA may be helpful to improve the stability and

workability of concrete thereby the tendency towards bleeding and segregation is

reduced. This is mainly due to the large surface area of rice husk ash about 50 to 60

m2/g [Hwang and Chandra, 1997].

b) Workability: The grain particles of RHA are irregular and porous in nature,

required a higher water binder ratio to produce the paste of same flow (workability) as

that of fly ash. Large additions of RHA would produce dry or unworkable mixtures

unless water-reducing admixtures are used. Due to the adsorptive character of cellular

rice husk ash particles, its addition to a concrete mix will increase its water demand to

produce a workable concrete [Cook, 1987]. The very fine particles of RHA fill the

spaces between the cement grains, thus stabilizing and improving the cohesiveness of

the concrete mix but adversely affecting its workability [Mahmud et al., 1996].

Therefore, an increase in water demand is expected with increasing RHA content

because of the water absorbing characteristics of RHA.

c) Setting time: Unlike other pozzolanic materials, like fly ash and slag, the addition

of rice husk ash tends to shorten the final setting time. This may be due to the water

adsorption ability of the cellular form of rice husk ash and the surrounding water-

cement ratio is reduced. Higher water-cement ratio tends to increase the setting time

because there is less contact between the open matrix and the silica cellular structure

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which leads to reduction in early strength development. Ganesan et al., (2008)

revealed that increasing the RHA percentage up to 15 percent increases the initial

setting time. There is a decrease in the setting time for replacement range of 20- 35

percent. On the other hand, the final setting time continues to decrease with increase

in RHA up to 35 percent.

d) Compressive strength: Khalaf and Yousif (1984) studied the strength

characteristics of mortars containing various percentages of RHA as partial

replacement with constant consistency for various mix proportions. They revealed that

regardless of the aggregate/cement ratio of the mix, the rate of increase in the

compressive strength of cement-RHA mortars increases relative to those of plain

mortars with the progress of hydration. Further, this rate of increase in compressive

strength is higher for mixes of high aggregate/cement ratio than that for the

corresponding mixes of low aggregate/cement ratio. In general, the higher the

percentage of RHA content (above 20 percent), the lower is the compressive strength

at early ages. On the other hand, at 60 days 1:2 mortar mixes with 30 percent cement

replacement reached nearly the same strength as those of the corresponding plain

mortar. For 50 percent cement replacement mixes, there was a significant reduction in

the compressive strength at early ages as well as at 60 days. This may be due to the

fact that the quantity of RHA present in the mix is higher than that required to

combine with the liberated lime during the process of hydration thus leading to excess

silica leached out and causing deficiency in strength.

Moreover, the effect of water cementitious materials ratio (w/cm) upon the

compressive strength at various ages was studied for 30 percent RHA addition.

Initially, the strength increases with decrease in water cementitious materials ratio up

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to 0.65. Beyond this level, the compressive strength of cement-RHA mortars

decreases for all ages. This is mainly due to the reduction in the flow of the fresh

mortars so that full compaction cannot be achieved [Khalaf and Yousif, 1984].

Maeda et al., (2001) studied the strength development properties of RHA mortar

specimens and also compared the compressive strength characteristics with silica

fume. They concluded that the compressive strength of mortar incorporating RHA is

higher than the mortar incorporating silica fume, irrespective of RHA content, water-

cementitious materials ratio and age. Unlike other pozzolanic materials, the

compressive strength of mortar incorporating RHA was almost the same or more than

the reference mix even at the age of one day. The relative compressive strength of

mortar incorporating RHA tends to increase with age and reaches 125 percent for

mortar incorporating 20 percent RHA with w/cm of 0.3.

It is also reported that the RHA replacement up to 30 percent in mortar produced

higher strength than control mix [Salihuddin, 1993]. According to Ganesan et al.

(2008), the rate of increase in compressive strength was higher up to 15 percent

addition of RHA and beyond this level of RHA addition, the rate started decreasing.

However, at 30 percent RHA addition the compressive strength was equivalent to that

of reference mixture. At 35 percent RHA, the compressive strength decreases to a

value which is lower than that of control concrete.

Mehta and Folliard (1995) reported that except RHA, no other pozzolanic addition

including SF has the ability to contribute to the strength of Portland cement concrete

at the early ages of 1 and 3 days. Mahmud et al., (1996) found that the optimum level

for maximum strength gain of RHA concrete was 15 percent. The RHA contributes to

strength development much earlier age than SF and OPC, which was similar to the

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findings of Mehta (1992). Zhang et al., (1996) found that 10 percent RHA concrete

exhibited higher strength than control OPC at all ages but had equivalent strength at

one-day. However, the strength was lower than the strength of SF concrete (10

percent level) up to 28 days, but equivalent strength reached at 90 and 180 days.

The similar studies conducted by Abu (1990) shows that at 20 percent cement

replacement with RHA at 0.55 water binder ratio give a higher compressive strength

compared to OPC. Zhang et al., (1996) reported that higher compressive strength gain

and reduction of permeability in concrete incorporating RHA is probably due to the

reduced porosity, reduced calcium hydroxide content, and reduced width of the

interfacial zone between the paste and the aggregate. The formation of more CSH gel

and less CH in concrete with RHA may improve the concrete properties due to the

reaction between RHA and calcium hydroxide in hydrating cement [Qijun et al.,

1999].

Many researchers has agreed that the performance of RHA blended cement has

similarity with SF blended cement due to its considerable silicon dioxide content like

SF [Mehta 1992 ; Zhang et al. 1996 and Mahmud et al. 1996]. RHA is a viable

alternative material to SF. But the optimum replacement level of RHA is reported

different by the various researchers like, Mahmud et al. (1996), concluded with 15

percent as optimum whereas, Salihuddin (1993) and Abu (1990) reported that an

optimum replacement of RHA is about 20 percent level, whilst, the others

recommended ranging between 10 percent to 30 percent as optimum replacement of

RHA. All these replacement levels of RHA are in percentage by mass of the total

binder material.

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5.5 SUMMARY
From the literature studies, it is found that the use of pozzolans as cement replacement

is viable and has engineering potential and economic benefits. Formation of additional

products due to pozzolanic reaction results in denser and durable concrete. As a

supplementary cementing material, many distinctive properties of RHA have been

reported. Based on the reported literature on the use of RHA as a binder in

mortar/concrete, the following observations have been drawn:

(i) In general, incorporation of RHA increases the water demand and tends to

shorten the final setting time and performs like set accelerator;

(ii) At smaller percentage of replacement (less than 3 percent), it improves the

workability and cohesiveness and also reduces the bleeding and

segregation;

(iii) Addition of RHA in partial replacement of cement invariably results in

higher strength of concrete right from the day one. The maximum increase

in strength is reported to be 125 percent in mortar and 120 percent in

concrete. The range of RHA addition for the above benefit varies between

10 and 30 percent by mass.

(iv) RHA has the ability to contribute to strength to the strength of cement

concrete at early age of 1 day, which is a unique behaviour of RHA.

(v) Studies on RHA-cement mortars and concretes were intended to achieve

comparable or higher strength characteristics than reference mortar/

concrete.

It should be noted that effect of RHA on OPC hydration system may vary depending

upon its quality/reactivity. So, there is an immense need to carry out research on

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effects of reactive rice husk ash in concrete on cement hydration system and to assess

the optimum level of replacement of RHA in concrete.

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Fig. 5.1: SEM micrographs of cement particles and various pozzolans [Mehta, 1992;
Salihuddin, 1993 and Malhotra, 1990]

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Fig. 5.2: Schematic drawing of the hydration of cement paste with RHA [Hwang and
Chandra, 1997]

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