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Characteristic properties of Polymer Modified Fly ash Concrete

CHAPTER 1

INTRODUCTION
1.1 Polymer in Concrete
Polymer-modified cementitious materials date back more than 70 years. In the 1940's they were developed for use on ships decks and bridges. The history of research and development of concrete polymer composites is considerably different in various countries because of differences of background. Active research and development of the concrete polymer composites has been performed all over the world, particularly in the U.S.A & the soviet union (Russia). In the Japanese construction industry, the active research and development of the polymer-modified mortar and concrete have been

performed for the past about 50 years, and they are currently used as popular construction materials in various applications because of their high performance, multi functionality and sustainability compared to conventional concrete. Polymers are made from simple organic molecules (monomers) that combine to form more complex structures through a process called polymerization. Because the use of a polymer instead of Portland cement represents a substantial increase in cost, polymers should be used only in applications in which the higher cost can be justified by superior properties, low labour cost or low energy requirements during processing and handling. It is therefore important that architects and engineers have some knowledge of the capabilities and limitations of PC materials in order to select the most appropriate and economic product for a specific application. Polymers are used for imparting certain special properties to the conventional concrete. They have been used primarily for the following reasons  To modify the flow characteristics of fresh concrete.  To improve strength and durability of hardened concrete.  To improve chemical resistance and impermeability of hardened concrete.  To improve the bond characteristics between old and new concrete for repair work. Some of the most commonly employed polymers in concrete are as listed below. a. Urethanes b. Acrylics
M. Tech (Structural Engineering) 2011 Department Of Civil Engineering, KLESCET Belgaum

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Characteristic properties of Polymer Modified Fly ash Concrete

c. Styrene butadiene resins (S.B.R) d. Vinyl e. Epoxies.

1.1.1. Classification of polymers


Polymer is a generic name given to a vast number of materials of high molecular weight. These materials exist in countless forms and numbers because of a very large and types of atoms present in their molecules. Polymers can have different chemical structures, physical properties, mechanical behavior, thermal characteristics, etc., and can be classified in different ways, as now discussed.

Natural and synthetic polymers Depending on their origin, polymers can be classified as natural or synthetic.

Those isolated from natural materials are called natural polymers. Typical example are: cotton, silk, wool and rubber. Cellophane, cellulose rayon, leather and so on are, in fact, chemical modifications of natural polymers. Polymers synthesized from low molecular weight compounds are called synthetic polymers .Typical examples are: polyethylene, PVC, nylon and Terylene.

Thermoplastic and thermosetting polymers Some polymers soften on heating and can be converted into any shape that they

can retain on cooling. The process of heating reshaping and retaining the same on cooling can be repeated several times. Such polymers, that soften on heating and stiffen on cooling, are termed thermoplastics. Polyethylene, PVC, nylon and sealing wax are examples of thermoplastic polymers. Some polymers, on the other hand, undergo some chemical change on heating and convert themselves into an infusible mass. They are like the yolk of the egg, which on heating sets into a mass, and once set, cannot be reshaped. Such polymers, that become an infusible and insoluble mass on heating, are called thermosetting polymers.

Plastics, Elastomers, fibers and liquid resins Depending on its ultimate form and use, a polymer can be classified as plastic,

Elastomers, fiber or liquid resin. When, for instance, a polymer is shaped into hard and
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Characteristic properties of Polymer Modified Fly ash Concrete

tough utility articles by the application of heat and pressure, it is used as a plastic. Typical examples are polystyrene, PVC and polymethyl methacylate. When vulcanized into rubbery products exhibiting good strength and elongation, polymers are used as Elastomers. Typical examples are natural rubber, synthetic rubber, silicone rubber. If drawn into long filament-like materials, whose length is at least 100 times its diameter, polymers are said to have been converted into fibres. Typical examples are nylon and terylene. Polymers used as adhesives, potting compounds, sealants, etc, in a liquid form are described as liquid resins. Commercially available epoxy adhesives and polysulphide sealants are typical examples.

1.1.2 Types of polymer concrete


a) Polymer impregnated concrete In polymer-impregnated concrete, low viscosity liquid monomers are partially or completely impregnated into the pore systems of hardened cement composites and are then polymerized. The partial impregnation improves durability and chemical resistance. The ways in which the polymer is introduced into the hardened concrete vary widely and depend upon the commercial objective. These include the following operations:  The concrete is thoroughly dried, usually by heating.  Then dry concrete is evacuated.  The concrete is immersed in the chosen monomer.  Pressure is applied.  The impregnated concrete is sealed to avoid loss of monomer.  The monomer is converted to polymer either by gamma radiation or by thermal catalytic method.  The concrete is cooled. Polymers can be broadly categorized as thermoplastics and thermosetting resins. Thermoplastics soften at an elevated temperature (usually between 100 and 150 C and called glass transition temperature), and as such the advantage of using thermoplastic impregnated concrete is lost at such temperatures. Thermoplastic monomers have a low viscosity and are able to penetrate hardened concrete well and fill a large part of the pores. Their polymerization is accomplished by addition reactions not leading to low
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Characteristic properties of Polymer Modified Fly ash Concrete

molecular weight by-products. Thermosetting resins, on the other hand, are more viscous and difficult to impregnate into concrete. However, they can withstand higher temperatures without softening. But the condensation reactions which occur may lead to the formation of low molecular weight by-products which would occupy some of the space. It is necessary that a monomer or its polymer is chemically compatible with the compounds of cement and the constituents of hydrated cement paste to prevent their adverse effects. Monomer/resin systems used for polymer impregnated concrete are styrene, polyester, methylmethacrylate, butylacrylate, acrilonitrite, epoxies and their copolymer combinations.
y

Characteristics of Polymer-impregnated concrete Polymer-impregnated concrete has a higher compressive, tensile and impact

strength. It also has an enhanced durability and a reduced permeability to water and aqueous salt solutions such as sulphates and chlorides as compared to the conventional concrete. However the quantity of polymer that can be introduced depends upon the porosity of the hardened concrete and hence the potential improvement of a particular concrete is substantial if the original concrete is of a highly porous nature. Irrespective of the strength of the basic unmodified concrete, polymer impregnated concrete has cube strength in the range of 120-150 MPa. Polymer modified concrete gains high strengths in an early age which are stable and do not increase further with age. This property of polymer impregnated concrete can be used under circumstances where in high early strength is required. Polymer impregnated concrete have a high modulus of elasticity which lies in the range of 30 kN/mm2 to 60 kN/mm2. Thus this makes the polymer impregnated concrete brittle and cracks, once initiated, propagate rapidly and frequently run through the aggregate. Thus the total energy expended in fracturing polymer impregnated concrete is less than that demanded by more conventional concrete, in which the aggregate delays the propagation of cracks and the failure is relatively ductile and not explosive or catastrophic. Polymer impregnated concrete finds its applications in the construction of high performance structures, industrial floorings, sewer tanks, marine structures, desalination
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Characteristic properties of Polymer Modified Fly ash Concrete

plants, distilled water plants, prefabricated tunnel sections and swimming pools. Partially impregnated concrete is used for the protection of bridges and concrete structures against deterioration. It also finds an application in the repair of structural components like slabs, underground garage decks and bridge decks. Its application for the repair of the roads in dense traffic areas is by the virtue of its high early strength gaining prop erty which minimizes the interruption in the traffic flow.

Applications of Polymer impregnated concrete

 Prefabricated structural elements,  Prestressed concrete,  Marine works,  Desalination plants,  Nuclear power plants,  Sewage works-pipe and disposal works,  Ferro cement products,  For water proofing of structures,  Industrial applications.

b)

Polymer-modified cement concretes Polymer cement concrete more specifically called polymer modified concrete, is

a composite obtained by incorporating a polymeric material into concrete during the mixing stage. However, the polymer so added should not interfere with the hydration process. Since many polymers are insoluble in water, their addition can only be in the form of emulsion or dispersion or latex. The composite is then cast into the required shape in the conventional manner and cured in a manner similar to the curing of cement concrete. The hydrated cement and the polymer film formed due to the curing of the polymeric material constitute an interpenetrating matrix that binds the aggregate. The polymeric materials in the form of lattices and prepolymers may be added to modify cement concretes. In general, the quantities of polymers required for polymermodified cement concretes are relatively small, being in the range of 1 to 4 per cent by mass of the composite. In contrast polymer-impregnated concretes require 5 to 8 per cent and polymer concretes 8 to 15 per cent of polymer. Polymer modified cement concretes, are therefore the least expensive. The processing of PMCC is also simplest. Conventional
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Characteristic properties of Polymer Modified Fly ash Concrete

plant and equipment could be adopted. However, the improvements in mechanical properties have not been as high as observed in PIC or PC. Depending upon the type of modifier, polymer modified cement concretes can be subdivided as follows:  Latex-Modified Cement Concrete (LMCC) Lattices are white milk like suspension consisting of very small-sized polymer particles suspended in water with the of emulsifiers and stabilizing agents. It contains about 50 per cent of polymer solid by mass. Both elastomeric and glassy polymers have been employed in lattices for modifying cement concrete. The elastomeric polymers are characterized by their rubber-like elongation and by their relatively low modulus of elasticity at ambient temperatures. Some of the commonly used elastomeric lattices are: natural rubber latex, styrenebutadiene rubber latex, acrilonitrite-butadiene rubber latex and neoprene. Glassy polymers are characterized by high modulus of elasticity, higher strength, and relatively brittle type of failure. Common examples are polyvinyl acetate, polyvinylidene chloride, styrene-butadiene copolymer latex, and acrylic polymers. The use of polyvinyl acetate latex due to its sensitivity to the moisture is discontinued. Polyvinylidene copolymer latex, due to its residual chloride and possible corrosion of reinforcement, is used only in unreinforced concrete applications. The latex systems for modifying cement concrete are not availability in India. The optimum curing procedure involves the moist curing of composites for 1 to 7 days, followed by dry curing at room temperature. At 28 days, the latex modified composites reach about 80 percent of their final strength.  Prepolymers-modified Cement Concrete (PMCC) Some of the prepolymer systems used are polyester-styrene based system, epoxy systems and furane systems. With exception of epoxies, pre polymers (unlike lattices) do not improve the workability of cement concrete. The strength improvement of PMC over conventional concrete is of the order of 50-100 per cent. Its adhesion to plain concrete is good. The ductility is significantly improved and early micro-cracking is avoided. Consequently, the tensile strength and modulus of rupture are more than twice those of control concrete. There is considerable improvement in durability over conventional concrete due to lower water-cement ratio and filling of pores with polymer. Further research is required since the high cost of polymer addition
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Characteristic properties of Polymer Modified Fly ash Concrete

has not been commensurately reflected in improved strength. The excellent bond of latex concrete to existing concrete, superior shear bond strength, good freeze-thaw resistance, resistance to the penetration of chloride ions, improved ductility, and superior tensile and flexural strengths makes latex modified an eminent material for overlays and resurfacing applications for bridge decks, industrial flooring, food processing factories, fertilizer stores, damp resistant floors, for railway platforms, and nuclear processing areas. Surface deterioration is a major problem in marine and irrigation structures. Excellent resistance to salt water makes LMCC very effective repair material. LMCC are used for fixing ceramic tiles, lining effluent ducts, reservoirs, and sewerage and industrial waste handling structures. Latex and fibre-reinforced composites have a great potential in cement composites due to their synergistic behavior and improvement in matrix fibre bond. Applications of Polymer-modified cement concretes  For factory floors, particularly where chemicals or oils are liable to be split.  For repair of old or damaged concrete.  For concretes subjected to large doses of de-icing salts.  For flooring in frozen food factories.  For load ramps, where the abrasive wear of concrete is high.

c) Polymer Concrete
Polymer concrete is a composite wherein the polymer replaces the cement-water matrix in the cement concrete. Monomers or pre-polymers are added to the graded aggregate and the mixture is thoroughly mixed by hand or machine. The thoroughly mixed polymer concrete material is cast in moulds of wood, steel or aluminum etc. to the required shape or form. Mould releasing agents can be added for easy demoulding. This is then polymerized either at room temperature or at an elevated temperature. The polymer phase binds the aggregate to give a strong composite. Polymerization can be achieved by any of the following methods.  Thermal-catalytic reaction  Catalyst-promoter reaction  Radiation
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Characteristic properties of Polymer Modified Fly ash Concrete

In the Thermal-catalytic reaction method, only the catalyst is added to the monomer (thermoplastic) and polymerization is initiated by decomposing the catalyst by the application of elevated temperatures up to 900C. Typical catalysts used for different monomer systems Include, benzoyl peroxide, methyl-ethyl-ketone peroxide,

benzenesulphonic acid, etc. In the second method, a constituent called promoter or accelerator is also added, which decomposes the catalyst or accelerates the reaction, at the ambient temperature itself. Typical promoters include cobalt naphthanate, dimethyl-ptoluidine, ferric chloride, etc. Some promoters ensure polymerization at the ambient temperature within an hour. Gamma radiation is applied in the radiation polymerization method. Depending on the method of polymerization and the other condition, polymerization takes place within a period ranging from a few minutes to a few hours. Special precautions are to be taken in handling and cleaning because the monomers are highly inflammable. Fire safety precautions are to be observed. A thoroughly dry aggregate system is to be used as the monomers may not polymerize in the presence of moisture. Moreover, the catalyst and promoter should never be added to each other as it will result in an explosion. Some of these materials are toxic and are carcinogenic, and have to be handled with extreme care. The polymer systems which have been successfully used for polymer concrete include methyl-methacrylate, polyester-styrene, epoxy-styrene, styrene and furfuryl acetone. Others are furane, acrylic, polyurethane, urea formaldehyde, etc. The design considerations for polymer concrete are:  The binder content to fill the voids of the aggregate system. Smaller the polymer content greater is the economy.  Workability for easy mixing and placing of cement concrete without bleeding and segregation.  Film forming ability of the polymer, and bonding with the aggregate surface to transmit load forces.  Economic curing (cross-linking) times and temperatures.

 Durability in environments to which the polymer concrete composite is exposed.


The polymer systems which have been successfully used for polymer concrete include methyl-methacrylate, polyester-styrene, epoxy-styrene, styrene and furfuryl acetone. Others are furane, acrylic, polyurethane, urea formaldehyde, etc.

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Characteristic properties of Polymer Modified Fly ash Concrete

Advantages of polymer concrete.

Even though the initial cost of polymer cement concrete is high, the material cost efficiency is estimated to be 400% compared to polymer cement concrete is used to manufacture pipes for carrying chemicals in industries.

1.1.3 Advantages of concrete polymer composites


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Flexural strength of polymer concrete is much higher than conventional concrete. Tensile and compressive strength are high compared to conventional concrete.

 Shear capacity of flexural member is higher than conventional concrete because of higher strength capacity of polymer concrete.  Bond strength between polymer concrete and reinforcing bars is high.  Deflection of polymer concrete elements is less compared to conventional concrete because of greater modulus of elasticity.  Long term loading of polymer concrete member is significant due to viscoelastic nature of the material, which is different than conventional concrete cree p mechanism.  Polymer concrete is lighter in weight than conventional concrete.  Resistance to acids, salts and other chemicals is relatively higher than conventional concrete.  Freeze-thaw cycles have little effect on the polymer concrete since little or no water is absorbed into the mix.

1.1.4 Limitations of polymer concrete composites


 Temperature and humidity of the environment concrete.  Aggregate gradation and maximum particle size affect the amount of resin to be affect the creep of the polymer

added to fill the voids and bind the aggregates.  Thermosetting polymer concrete has high expansion coefficient of 4 to 5 times of conventional concrete.  Thermosetting polymerization.  Shrinkage and hardening and temperature expansion can be controlled by the addition of aggregate filler.
M. Tech (Structural Engineering) 2011 Department Of Civil Engineering, KLESCET Belgaum

polymer such as epoxy and

polyester produce shrinkage during

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Characteristic properties of Polymer Modified Fly ash Concrete

 Abrupt change can occur in the mechanical properties of the polymer when the temperature exceeds glass transition temperature.

1.1.5 Proportioning of polymer concrete


While using it should be noted that polymer dispersion is water based and the ratios of mixing vary from manufacturer, depending upon solid contents. Ultimately, it is the proportion of solid content of polymer and cement content that reflects on the quality and cost of polymer cement concrete (PCC). Typical mixing ratios for various applications are shown in table 1.1

Economy is one of the most decisive guiding factors in determining the amount of polymer, in a particular PCC. More the content o polymer, the more is the enhancement in the properties of PCC and the durability of the repaired structure. Depending on the type of polymer and its contents, the degree of elasticity also varies.

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Characteristic properties of Polymer Modified Fly ash Concrete

Table 1.1 Typical ratios for various applications Type of application Thickness/motor type Mixing ratios (parts by volume)

Bonding slurry for bonding Very thin,<10mm new layers to hardened bases Patching motors and repairing Above 10mm thick Up to 10mm thick

Cement: sand=1:1 Polymer: water =1:1 Cement: sand=1:2 Polymer: water =1:2 Cement: sand=1:3 Polymer: water =1:3

Cement screeds with high Above 10mm thick abrasion resistance, high Above 30mm thick elasticity, and less dust formation Leveling and smoothing mortars with increased oil and petrol resistance Plastic reinforced mortars Cement mortars

Polymer: water =1:4 Polymer: water =1:6

Cement: sand=1:2 Polymer: water =1:2

Polymer: water =1:5

for plasters, bonding and Lime and lime cement Polymer: water =1:10 joint mortars, with better mortars bonding and higher Joint mortars Bonding mortars Polymer: water =1:2 Polymer: water =1:2

weather resistance

1.1.6 Tests on polymer concrete


The best way to ensure the advantage of polymers is to conduct a series of tests on the polymer-modified mortars and to compare the results with mortars without polymers. In most of the practical cases, it suffices only to conduct the tests on polymer-modified concrete if the base concrete values are known. It is normally sufficient that the repair mortar has 10@ higher strength than the base concrete. The following tests can be conducted to determine the suitability of the formulation:

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Characteristic properties of Polymer Modified Fly ash Concrete

 Compressive strength test  Flexural strength test  Bond test  Air entrainment test  Alkali resistance test  Chloride content test In the case of specialized repairs, the following tests may also be conducted:  Water permeability test  Vapour permeability test  Carbonation resistance test  Wear resistance test  Impact resistance test  Chloride ion penetration test  Shrinkage characteristics test  Bond and shrinkage tests in typical repair case  UV resistance test  Modulus of elasticity test  Dynamic modulus of elasticity test  Coefficient of thermal expansion test.

1.2. Fly ash in concrete


Fly ash is one of the residues generated in combustion, and comprises the fine particles that rise with the flue gases. Ash which does not rise is termed bottom ash. In an industrial context, fly ash usually refers to ash produced during combustion of coal. Fly ash is generally captured by electrostatic precipitators or other particle filtration equipments before the flue gases reach the chimneys of coal-fired power plants, and together with bottom ash removed from the bottom of the furnace is in this case jointly known as coal ash. In the past, fly ash was generally released into the atmosphere via the smoke stack, but pollution control equipment mandated in recent decades now require that it be captured prior to release. This created environmental and health concerns that prompted laws which have reduced fly ash emissions to less than 1% of ash produced. Worldwide, more than 65% of fly ash produced from coal power stations is disposed of in
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Characteristic properties of Polymer Modified Fly ash Concrete

landfills. In India alone, fly ash landfills cover an area of 40, 000 acres (160 km2). Depending upon the source and makeup of the coal being burned, the components of the fly ash produced vary considerably, but all fly ash includes substantial amounts of silica dioxide (SiO2) (both amorphous and crystalline) and calcium oxide (CaO). Fly ash is commonly used to supplement Portland cement in production, where it can bring both technological and economic benefits, and is increasingly finding use in synthesis of geopolymers and zeolites

. Fig 1.2 a view of fly ash

1.2.1. Properties of fly ash


Though the fly ash has various applications due to its beneficial properties its use is very limited. This is because of the lack of knowledge about the properties of fly ash and the environmental concern. Properties of fly ash not only vary from different thermal power plants but also from the same thermal power plant. The properties of fly ash depend upon the following factor  Type of coal used  Treatment to which coal has been subjected prior to combustion  The method of combustion  Furnace temperature  Amount of air circulation  Collection and storage places adopted

 Method of disposal

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Characteristic properties of Polymer Modified Fly ash Concrete

1.2.2. Chemical composition


Fly ash material solidifies while suspended in the exhaust gases and is collected by electrostatic precipitators or filter bags. Since the particles solidify while suspended in the exhaust gases, fly ash particles are generally spherical in shape and range in size from 0.5 m to 100 m. They consist mostly of silicon dioxide (SiO2), which is present in two forms: amorphous, which is rounded and smooth, and crystalline, which is sharp, pointed and hazardous; aluminum oxide (Al2 O3 ) and iron oxide (Fe2 O3). Fly ashes are generally highly heterogeneous, consisting of a mixture of glassy particles with various identifiable crystalline phases such as quartz, mullite, and various iron oxides. Table 1.2.1 the chemical composition of fly ash. Component Bituminous SiO2 (%) Al2 O3 (%) Fe2 O3 (%) CaO (%) LOI (%) 20-60 5-35 10-40 1-12 0-15 Sub bituminous 40-60 20-30 4-10 5-30 0-3 Lignite 15-45 20-25 4-15 15-40 0-5

1.2.3. Physical properties


Fly ash consists of fine, powdery particles that are predominantly spherical in shape, either solid or hollow, and mostly glassy (amorphous) in nature. The carbonaceous material in fly ash is composed of angular particles. The particle size distribution of most bituminous coal fly ashes is generally similar to that of a silt (less than a 0.075 mm or No. 200 sieve). Although sub bituminous coal fly ashes are also silt-sized, they are generally slightly coarser than bituminous coal fly ashes. The specific gravity of fly ash usually ranges from 2.1 to 3.0. The color of fly ash can vary from tan to gray to black, depending on the amount of unburned carbon in the ash. The lighter the color, the lower the carbon content. Lignite or sub bituminous fly ashes are usually light tan to buff in color, indicating relatively low amounts of carbon as well as the presence of some lime or calcium. Bituminous fly ashes are usually some shade of gray, with the lighter shades of gray generally indicating a higher quality of ash.

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Characteristic properties of Polymer Modified Fly ash Concrete

Fig. 1.2.2 microscopic view of fly ash

1.2.3 Classification of fly ash


Two classes of fly ash are defined by ASTM C618: Class F fly ash and Class C fly ash. The chief difference between these classes is the amount of calcium, silica, alumina, and iron content in the ash. The chemical properties of the fly ash are largely influenced by the chemical content of the coal burned (i.e., anthracite, bituminous, and lignite).

1.2.4 Class F fly ash


The burning of harder, older anthracite and bituminous coal typically produces Class F fly ash. This fly ash is pozzolanic in nature, and contains less than 20% lime (CaO). Possessing pozzolanic properties, the glassy silica and alumina of Class F fly ash requires a cementing agent, such as Portland cement, quicklime, or hydrated lime, with the presence of water in order to react and produce cementitious compounds. Alternatively, the addition of a chemical activator such as sodium silicate (water glass) to a Class F ash can leads to the formation of a geopolymers.

1.2.5 Class C fly ash


Fly ash produced from the burning of younger lignite or sub bituminous coal, in addition to having pozzolanic properties, also has some self-cementing properties. In the presence of water, Class C fly ash will harden and gain strength over time. Class C fly ash generally contains more than 20% lime (CaO). Unlike Class F, self-cementing Class C fly

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Characteristic properties of Polymer Modified Fly ash Concrete

ash does not require an activator. Alkali and sulfate (SO4) contents are generally higher in Class C fly ashes.

1.2.6 Utilization of fly ash


The use of fly ash as an engineering material primarily stems from its pozzolanic nature, spherical shape, and relative uniformity. Fly ash is being used in the following.  Concrete production, as a substitute material for Portland cement and sand  concrete improving its performance  Embankments and other structural fills (usually for road construction)  Grout and Flow able fill production  Waste stabilization and solidification  Cement clinkers production - (as a substitute material for clay)  Stabilization of soft soils  Use of fly ash as controlled low strength material(CLSM)  Road sub base construction  As Aggregate substitute material (e.g. for brick production)  Loose application on rivers to melt ice  Loose application on roads and parking lots for ice control  Other applications include kitchen counter tops, floor and ceiling tiles etc.

1.2.7 Portland cement


Owing to its pozzolanic properties, fly ash is used as a replacement for some of the Portland cement content of concrete. The use of fly ash as a pozzolanic ingredient was recognized as early as 1914, although the earliest noteworthy study of its use was in 1937. Before its use was lost to the Dark Ages, Roman structures such as aqueducts or the Pantheon in Rome used volcanic ash (which possesses similar properties to fly ash) as pozzolan in their concrete. As pozzolan greatly improves the strength and durability of concrete, the use of ash is a key factor in their preservation. Use of fly ash as a partial replacement for Portland cement is generally limited to Class F fly ashes. It can replace up to 30% by mass of Portland cement, and can add to the concretes final strength and increase its chemical resistance and durability. Recently concrete mix design for partial cement replacement with High Volume Fly Ash (50 % cement replacement) has been developed. For Roller Compacted Concrete (RCC)[used in dam construction]
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Characteristic properties of Polymer Modified Fly ash Concrete

replacement values of 70% have been achieved with processed fly ash at the Ghatghar Dam project in Maharashtra, India. Due to the spherical shape of fly ash particles, it can also increase workability of cement while reducing water demand. The replacement of Portland cement with fly ash is considered by its promoters to reduce the greenhouse gas "footprint" of concrete, as the production of one ton of Portland cement produces approximately one ton of CO2 as compared to zero CO2 being produced using existing fly ash. New fly ash production, i.e., the burning of coal, produces approximately twenty to thirty tons of CO2 per ton of fly ash. Since the worldwide production of Portland cement is expected to reach nearly 2 billion tons by 2010, replacement of any large portion of this cement by fly ash could significantly reduce carbon emissions.

1.2.8 concrete improving its performance


 How fly ash contributes to concrete durability and strength
Typically, concrete made with fly ash will be slightly lower in strength than straight cement concrete up to 28 days, and substantially higher strength with in a years time. Fly ash chemically reacts with this lime to create more CSH, the same glue produced by the hydration of cement and water, there by closing off the capillaries that allow the movement of moisture through the concrete. The result is concrete that is less permeable, as witnessed by the reduction in efflorescence. Fly ash increased the durability of concrete. Increased density and long term pozzolanic action of fly ash, which ties up free lime, results in fewer bleed channels and decreased the permeability. Dense fly ash concrete helps keep aggressive compounds on the surface, where destructive action is lessened. Fly ash concrete is also more resistant to attack by sulfate, mild acid, soft water, and sea water. Fly ash also contributes to combine with free lime, increasing compressive strength over lime.

 How fly ash contributes to concrete workability


First, fly ash produces more cementitious paste. It has a lower unit weight, which means that on a pound of pound basis, fly ash contributes roughly 30% more volume of cementitious material per pound versus cement. The greater the percentage of fly ash ball bearings in the paste, the better lubricated the aggregates are and the better concrete flows.

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Characteristic properties of Polymer Modified Fly ash Concrete

Second, fly ash reduces the amount of water needed to produce a given slump. The spherical shape of fly ash particles and its dispersive ability provide water-reducing characteristics similar to a water reducing admixer. Typically, water demand of a concrete mix with fly ash is reduced by 2% to 10% depending on a number of factors including the amount used and class of fly ash.

 How Fly Ash Reduces Heat of Hydration in Concrete


The hydration of cement is an exothermic reaction. Heat is generated very quickly, causing the concrete temperature to rise and accelerating the setting time and strength gain of concrete. For most concrete installations, the heat generation is not detrimental to its long-term strength and durability. However, many applications exist where the rapid heat gain of cement increases the chances of thermal cracking, leading to reduced concrete strength and durability. In these applications, replacing large percentages of cement with fly ash (fly ash generates only 15-35 percent as much heat as compared to cement at early ages) can reduce the damaging effects of thermal cracking.

 How fly ash protects concrete


An extremely important aspect of the durability of concrete is its permeability. Fly ash concrete is less permeable because fly ash reduces the amount of water needed to produce a given slump, and through pozzolanic activity, creates more durable CSH as it fills capillaries and bleeds water channels occupied by water-soluble lime (calcium hydroxide). Fly ash improves corrosion protection. By decreasing concrete permeability, fly ash can reduce the rate of ingress of water, corrosive chemicals and oxygen thus protecting steel reinforcement from corrosion and its subsequent expansive result.

1.2.9 Road and embankments works Fly ash can be used in the different applications such as  Core fills material for road/rail embankment constructions.  As reinforced fill material.  Sub base/base course of flexible pavements.  Construction of semi-rigid /rigid pavements.

1.2.10.Fly ash and IRC specifications :


Indian Roads Congress Special Publication 58 (IRC: SP: 58)-2001 details Guidelines for use of fly ash in Road Embankments.
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Characteristic properties of Polymer Modified Fly ash Concrete

Fly ash denotes any type of coal ash unless specifically mentioned.

1.2.11 Advantages of using fly ash for road construction :


  Fly ash is a light weight material, as compared to commonly used fill material (local soil), therefore, causes lesser settlements. It is especially attractive for embankment construction over weak sub grade such as alluvial clay or silt where excessive weight could cause failure.

 Fly ash embankments can be compacted over a wide range of moisture content, and therefore, results in less variation in density with changes in moisture content. Easy to handle and compact because the material is light and there are no large lumps to be broken down can be compacted using either vibratory or static rollers.

 High permeability ensures free and efficient drainage. After rainfall, water gets drained out freely ensuring better workability than soil. Work on fly ash fills/embankments can be restarted with a few hours after rainfall, while in case of soil it requires much longer period.

 Considerable low compressibility results in negligible subsequent settlement with in the fill.  Conserves good earth, which is precious top soil, thereby protecting the environment.  Higher value of California Bearing Ratio (CBR) as compared to soil provides for a more efficient design of road pavement.

 Pozzolanic hardening property imparts additional strength to the road pavements/ embankments and decreases the post construction horizontal pressure on retaining Walls.

 Amenable to stabilization with lime and cement.

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Characteristic properties of Polymer Modified Fly ash Concrete

1.2.12 Soil stabilization


Soil stabilization involves the addition of fly ash to improve the engineering performance of a soil. This is typically used for a soft, clayey sub grade beneath a road that will experience many repeated loadings. Improvement can be done with both class C and class F fly ashes. If using a class F fly ash, an additive (such as lime or cement) is needed whereas the self-cementing nature of class C fly ash allows it to be used alone.

1.2.13 Flowable fill


Fly ash is also used as a component in the production of flowable fill (also called controlled low strength material, or CLSM), which is used as self-leveling, selfcompacting backfill material in lieu of compacted earth or granular fill. The strength of flowable fill mixes can range from 50 to 1,200 lbf/in (0.3 to 8.3 MPa), depending on the design requirements of the project in question. Flowable fill includes mixtures of Portland cement and filler material, and can contain mineral admixtures. Fly ash can replace either the Portland cement or fine aggregate (in most cases, river sand) as a filler material. High fly ash content mixes contain nearly all fly ash, with a small percentage of Portland cement and enough water to make the mix flowable. Low fly ash content mixes contain a high percentage of filler material, and a low percentage of fly ash, Portland cement, and water. Class F fly ash is best suited for high fly ash content mixes, whereas Class C fly ash is almost always used in low fly ash content mixes.

1.2.14 Asphalt concrete


Asphalt concrete is a composite material consisting of an asphalt binder and mineral aggregate. Both Class F and Class C fly ash can typically be used as a mineral filler to fill the voids and provide contact points between larger aggregate particles in asphalt concrete mixes. This application is used in conjunction, or as a replacement for, other binders (such as Portland cement or hydrated lime). For use in asphalt pavement, the fly ash must meet mineral filler specifications outlined in ASTM D242. The hydrophobic nature of fly ash gives pavements better resistance to stripping. Fly ash has also been shown to increase the stiffness of the asphalt matrix, improving rutting resistance and increasing mix durability.

M. Tech (Structural Engineering) 2011 Department Of Civil Engineering, KLESCET Belgaum

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Characteristic properties of Polymer Modified Fly ash Concrete

1.2.15 Geopolymers
More recently, fly ash has been used as a component in geopolymers, where the reactivity of the fly ash glasses is used to generate a binder comparable to a hydrated Portland cement in appearance and properties, but with possibly reduced CO2 emissions.

1.2.16 Use of fly ash as controlled low strength material(CLSM)


 Fly ash can be used in the manufacture of Controlled Low Strength Material (CLSM).  CLSM is a fluid mixture made of 90-95% fly ash and 5-10% Portland Cement and Sufficient quantity of water.  It can be poured in All difficult to reach cavities.  Settles within 24 hours.  No settlement after initial settlement

1.2.17 Bricks
Ash bricks have been used in house construction in Windhoek, Namibia since the 1970s. There is, however, a problem with the bricks in that they tend to fail or produce unsightly pop-outs. This happens when the bricks come into contact with moisture and a chemical reaction occurs causing the bricks to expand. In May 2007, Henry Liu, a retired 70-year-old American civil engineer, announced that he had invented a new, environmentally sound building brick composed of fly ash and water. Compressed at 4,000 psi and cured for 24 hours in a 150 F (66 C) steam bath , then toughened with an air entrainment agent, the bricks last for more than 100 freeze thaw cycles. Owing to the high concentration of calcium oxide in class C fly ash, the brick can be described as "self-cementing". The manufacturing method is said to save energy, reduce mercury pollution, and costs 20% less than traditional clay brick manufacturing. Liu intended to license his technology to manufacturers in 2008.

1.2.18 Use of fly ash in mines construction


Fly ash can be gainfully utilized as:   Stowing material in Underground mines.  Filling material for reclamation of abandoned mines.  Filler material along- with overburden of an operating mines.
M. Tech (Structural Engineering) 2011 Department Of Civil Engineering, KLESCET Belgaum

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Characteristic properties of Polymer Modified Fly ash Concrete

1.2.19 Waste management


Fly ash, and its alkalinity, may be used to process human waste sludge into fertilizer. Similarly, the Rhenipal process uses fly ash as an admixture to stabilize sewage and other toxic sludges. This process has been used since 1996 to stabilize large amounts of chromium(VI) contaminated leather sludges in Alcanena, Portugal.

1.2.20 Environmental problem


Fly ash contains trace concentrations of heavy metals and other substances that are known to be detrimental to health in sufficient quantities. Potentially toxic trace elements in coal include arsenic, beryllium, cadmium, barium, chromium, copper, lead, mercury, molybdenum, nickel, radium, selenium, thorium, uranium, vanadium, and zinc. Though these elements are found extremely low concentrations in fly ash, their mere presence has prompted some to sound alarm. In 2000, the United States Environmental Protection Agency (EPA) said that coal fly ash did not need to be regulated as a hazardous waste. Studies by the U.S. Geological Survey and others of radioactive elements in coal ash have concluded that fly ash compares with common soils or rocks and should not be the source of alarm.

1.2.21 Exposure concerns


Crystalline silica and lime along with toxic chemicals are among the exposure concerns. Although industry has claimed that fly ash is "neither toxic nor poisonous," this is disputed. Exposure to fly ash through skin contact, inhalation of fine particle dust and drinking water may well present health risks. The National Academy of Sciences noted in 2007 that "the presence of high contaminant levels in many CCR (coal combustion residue) leachates may create human health and ecological concerns." Fine crystalline silica present in fly ash has been linked with lung damage, in particular silicosis. OSHA allows 0.10 mg/m3, (one ten-thousandth of a gram per cubic meter of air). Another fly ash component of some concern is lime (CaO). This chemical reacts with water (H2O) to form calcium hydroxide [Ca(OH)2], giving fly ash a pH somewhere between 10 and 12, a medium to strong base. This can also cause lung damage if present in sufficient quantities.
M. Tech (Structural Engineering) 2011 Department Of Civil Engineering, KLESCET Belgaum

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Characteristic properties of Polymer Modified Fly ash Concrete

These hazardous can be minimized by controlling emissions of fly ash from bulk handling operations via close pumping systems, and use of storage and handling equipment with approved automated spill containment equipment.

1.2.22 Source of Fly Ash in India


According to Central Electricity authority of India, there are around 83 major coal fired thermal power plants and 305 hydro plants existing in India. As per the ministry of power statistics, the total installed generating capacity (Thermal + wind) during 20032004 was about 79838 MW and hydropower generation was 29500 MW. In addition to this, there are more than 1800 selected industrial units which had captive thermal power plants of >1MW.

Some of the prominent Power Plants which are also producing and providing good quality Fly Ash includes the following: Ropar Dadri Vindyanchal Annapara kota Raichur Rihand Singrauli Ramagundam Unchahar Chandrapur Korba Dahanu Trombay

1.2.23 PRESENT SCENARIO ON FLY ASH IN INDIA


 Over 75% of the total installed power generation is coal-based
 230 - 250 million MT coal is being used every year  High ash contents varying from 30 to 50%  More than 110 million MT of ash generated every year  Ash generation likely to reach 170 million MT by 2010  Presently 65,000 acres of land occupied by ash ponds  Presently as per the Ministry Of Environment & Forest Figures, 30% of Ash is being used in Fillings, embankments, construction, block & tiles, etc.

1.2.24 Ash Content in Indian Coal


The quality of coal depends upon its rank and grade. The coal rank arranged in an ascending order of carbon contents is:

M. Tech (Structural Engineering) 2011 Department Of Civil Engineering, KLESCET Belgaum

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Characteristic properties of Polymer Modified Fly ash Concrete

Lignite --> sub-bituminous coal --> bituminous coal --> anthracite

Indian coal is of mostly sub-bituminous rank, followed by bituminous and lignite (brown coal). The ash content in Indian coal ranges from 35% to 50%.

The coal properties including calorific values differ depending upon the colliery. The calorific value of the Indian coal (~15 MJ/kg) is less than the normal range of 21 to 33 MJ/Kg (gross).

According to National Thermal Power Corporation (NTPC), coal is used for approximately 62.3% of electric power generation in India, oil and gas accounts for 10.2%, hydro's share is 24.1%, nuclear, wind, and other contribute remaining 3.4%.

1.2.25 Fly ash transportation


Fly ash can be supplied in four forms Dry: This is currently the most commonly used method of supplying fly ash. Dry fly ash is handled in a similar manner to Portland cement. Storage is in sealed silos with the associated filtration and desiccation equipment, or in bags. Conditioned: In this method, water is added to the fly ash to facilitate compaction and handling. The amount of water added being determined by the end use of the fly ash. Conditioned fly ash is widely used in aerated concrete blocks, grout and specialist fill applications.

Stockpiled: Conditioned fly ash not sold immediately is stockpiled and used at a later date. The moisture content of stockpiled ash is typically 10 to 15%. This is used mainly in large fill and bulk grouting applications.

Lagoon: Some power stations pump fly ash as a slurry to large lagoons. These are drained and when the moisture content of deposited fly ash has reached a safe level may be recovered. Because of the nature of the disposal technique, the moisture content can vary from around 5% to over 30%. Lagoon fly ash can be used in similar applications to stockpiled conditioned fly ash.

M. Tech (Structural Engineering) 2011 Department Of Civil Engineering, KLESCET Belgaum

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Characteristic properties of Polymer Modified Fly ash Concrete

1.2.25 Current Fly Ash Generation in India


The current electricity generation (as on March 31, 2004) in India is about 1, 12,058 MW, 65-70% of which is thermal (mostly coal based). According to an estimate 100,000 MW capacity or more would be required in the next 10 years due to continually increasing demand for electricity. In India fly ash generation is around 110 million tonnes / year and is set to continue at a high rate into the foreseeable future. Presently majority of the coal ash generated is being handled in wet form and disposed off in ash ponds which are harmful for the environment and moreover ash remains unutilized for gainful applications. India has sufficient coal reserves. In India almost 65-70% of electricity production is dependent on coal which produces a huge quantity of Fly Ash as residue which is allegedly a waste product in Thermal Power Stations. Fly Ash has a vast potential for use in High Volume fly ash concrete especially due its physic -chemical properties. A good amount of research has already been done in India and abroad on its strength and other requisite parameters. Current fly ash generation and utilization in six major states; Gujarat, Maharashtra, Tamil Nadu, Rajasthan, Andhra Pradesh and Uttar Pradesh is presented in the present report.

According to the MOEF Gazette Notification dated Sept. 14, 1999, the existing power stations have to achieve 20% ash utilization within three years and 100% utilization in 15 years from the date of notification. New Stations have to achieve 30% ash utilization within 9 years and 10% ash utilization within 3 years and 100% utilization within 4 years and 100% annual increase. Presently, out of 110 million tonnes of Total ash generated, about (30%) is being utilized. Therefore thermal power stations are under great pressure to find useful applications of fly ash. The technology utilizing fly ash in high volume fly ash concrete can provide an avenue for utilization of fly ash on a bulk scale.

M. Tech (Structural Engineering) 2011 Department Of Civil Engineering, KLESCET Belgaum

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Characteristic properties of Polymer Modified Fly ash Concrete

1.2.26 Applications of fly ash concrete / projects


 Dadri ash has been used successfully in the following applications:
y y y y y

Land fills Road embankments Road construction Portland Pozzolona cement Building products Concrete

Fly ash blocks

fly ash G-blocks

Fig 1.2.26 applications of fly ash

M. Tech (Structural Engineering) 2011 Department Of Civil Engineering, KLESCET Belgaum

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Characteristic properties of Polymer Modified Fly ash Concrete

 Road Construction and Paving

Ash has been used in concrete roads and roller compacted concrete roads which are not only durable but have long service of 30-35 years without much maintenance in comparison to WBM and Bituminous Macadam roads.

 HCC Projects Development of high strength and high performance triple blended concrete for the Bandra-Worli Sea Link project.* High performance concrete for RAPP (5&6) incorporating fly ash.& Development of high volume fly ash concrete mixes for pavement quality concrete for various road works

 ACC Road Project ACC has constructed demonstration roads using high volume fly ash concrete with up to 50 % replacement at its Greater Noida and Faridabad Ready Mix Plants. It has also constructed a small demonstration patch at Tikaria-Amethi, in its Cement Plant.

 Other Projects
y

Construction of road (experimental basis about 1.00 Km length) using fly ash, at Raichur,Karnataka.This Project was implemented by PWD(Public Works

Department), Raichur and CRRI.(Central Road Research Institute) Use of Roller Compacted concrete technology using high doses of fly ash for construction of Saddle Dam and upper Dam of Ghatghar pumped storage Scheme near Nasik, have been implemented in joint co operation of Maharashtra Irrigation Department, Central Soil and Mineral Research Station, University of Roorkee.

M. Tech (Structural Engineering) 2011 Department Of Civil Engineering, KLESCET Belgaum

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