ASSIGNMENT

Polymer Modified Systems in Concrete

Introduction
Drawbacks of conventional concrete Concrete is the most widely used structural material in the world. Some of the reasons for this are its simplicity in preparation, the easy availability and low cost of its ingredients, and above all, the satisfactory properties of the structure. Concrete is strong in compression but weak in tension. It is a porous material. The pores in concrete result from the forming of concrete itself. Hardened concrete is a direct product of hydration, which is a reaction between water and cement particles. When the capillary water dries out it leaves interconnected pores. When the environmental conditions are favourable, these pores become the entry points for liquid water, water vapour, different gases and chemical substances that could be damaging to concrete. Some other flaws in the concrete also directly affect its performance. Such as high abrasion encountered on highways and runways, roughness of concrete surface deteriorates rapidly. Poor resistance to aggressive media and to salty water, as well as poor heat resistance and electric insulation, also limit its applications

Honeycombing, corrosion and crack development are some of the other problems affecting the normal concrete. Honeycombing can be recognized by exposed coarse aggregate on the surface without any mortar covering or surrounding the aggregate particles. Honeycombing can be caused by a poorly graded concrete mix, by too large of a coarse aggregate or by insufficient vibration at the time of placement. Severe honeycombing should be repaired to prevent further deterioration of the concrete surface. As corrosion occurs, there is a corresponding drop in the cross-sectional area of the steel reinforcement and the corrosion products occupy a larger volume than steel, and therefore exert substantial tensile forces on the surrounding concrete. The expansive forces caused by rebar corrosion can cause cracking and spalling of the concrete, and therefore loss of structural bond between the rebar and concrete. Corrosion of steel reinforcement happen also due to chloride attack on reinforcement and carbonation effect on concrete. The concrete can crack due to plastic shrinkage, plastic settlement, and differential settlement of staging supports. Cracks in the concrete may classified as structural or surface cracks. Surface cracks are generally less than a few millimetres wide and deep. A small number of surface or shrinkage cracks is common and does not usually cause any problems. Surface cracks can be caused by freezing and thawing, poor construction practices, and alkali-aggregate reactivity. The placement of new concrete over old may cause surface cracks to develop. This occurs because the new concrete will shrink as it cures. Structural cracks in the concrete are usually larger than 3 mm in width. They extend deeper into the concrete and may extend all the way through a wall, slab, or other structural member. Structural cracks are often caused by overloads. The structural cracks may worsen in severity due to the forces of weathering.

Polymer modified systems In this context, incorporating polymer materials into the concrete has got great importance. Based on the mode of their addition polymer cement concrete is classified as polymerimpregnated concrete (PIC), polymer concrete (PC) and polymer cement concrete (PCC).The improvements from adding polymer modifiers to concrete include increased bond strength, flexural and tensile strengths, split strength, and reduced elastic modulus. These lead to improved physical resistance such as impact resistance and abrasion resistance (Shaker et al. 1997; Wong et al. 2003; Colak 2005).The reduced elastic modulus results in a reduction of the stresses developed due to differential shrinkage and thermal strains that would reduce the tendency of the material to crack. Polymer modified systems can also improve corrosion resistance, resistance to chemical attack and severe environment (such as sulphuric acid attack, penetration by water and dissolved salts, and freezing-and-thawing resistance), and it reduces need for sustained moist curing. These improvements are largely due to reduced water permeability (Shaker et al. 1997; Ohama 1995b). Polymers with different kinds of fillers are used as construction materials. They have good binding properties and good adhesion with aggregates. They have long-chain structure, which helps in developing long-range network structure of bonding. In contrast, cement materials provide short-range structure of bonding. As a result, polymer materials usually provide superior compressive, tensile and flexural strength to the concrete compared to Portland cement. Some polymer materials may selectively provide higher tensile and flexural strength to the structure compared to compressive strength. Conventional concrete materials combined with polymers could yield composites with excellent mechanical and physical properties. Polymer Impregnated Concrete (PIC)

Introduction Polymer impregnated concrete (PIC) is a hydrated Portland cement concrete that has been impregnated with a monomer that is subsequently polymerized in situ. In general, almost any shape, size, configuration, orientation, and quality of hardened portland cement concrete can be impregnated to some degree with monomer provided the monomer has access to the void space within the concrete. A substantial portion of this space is usually obtained by removing free water from the pores in the concrete by drying the concrete in some manner. The monomer is introduced into the concrete by soaking at atmospheric pressure or above. The degree to which the available space in the concrete is filled with monomer during soaking determines whether the concrete is partially impregnated or fully impregnated. Full impregnation implies that about 85 percent of the available void space after drying is filled, whereas partial impregnation implies some degree less than full. The usual process for partial impregnation consists of a process in which the concrete is impregnated to only a limited depth beneath the surface. The different production methods used for full and partial impregnation produce concrete of differing physical characteristics.

Monomer systems The selection of a suitable monomer for PIC is usually based on the impregnation and polymerization characteristics, the availability and cost, and the resultant properties of the polymer and the PIC. In principle, any monomer capable of undergoing polymerization in the void system of a hardened concrete can be used. At ambient temperature and pressure, the monomers can be either gases or liquids, although liquid-type monomers are more easily adaptable to impregnating hardened concrete. In practice, impregnation is usually done using vinyl monomers that contain a polymerisation initiator that can be activated by heat. These include acrylonitrile, methyl methacrylate, and other acrylic monomers, styrene, and vinyl acetate. In general, best results in terms of process and performance are achieved with methyl methacrylate, often in combination with an acrylic cross-linking agent, such as trimethylolpropane trimethacrylate. In general, systems based on methyl methacrylate are the most widely used. They offer superior rates of both impregnation and polymerization and lead to an optimum combination of pore-sealing and mechanical properties, including durability. Viscosity-The rate and degree of monomer penetration into hardened concrete depends on the density and pore structure of the concrete, the viscosity of the monomer (Steinberg et al. 1968; Dikeou et al. 1969), and the type of impregnation process used. Monomers of low viscosity at ambient temperature are suitable for impregnation. With greater effort, precast concrete can be impregnated with higher viscosity monomers Vapour pressure-When selecting a monomer for impregnating precast concrete, considerations must be given to its vapour pressure for safety and process ability. The high vapour pressure of vinyl chloride, for example, requires special precautions in handling. Considerations must also be given to the effect of curing temperature on vapour pressures, since monomer depletion on the surface of the specimen may occur due to evaporation (Steinberg et al.1968; Steinberg et al. 1969; ACI SP-40). Toxicological considerations-Most monomers have annoying odours and varying degrees of toxicity. Precautions recommended for handling monomers include adequate ventilation to keep concentrations in air below the maximum limits recommended by the manufacturers. Emergency washes and drains should be available, and environmentally acceptable provisions should be established for handling an accidentally spilled monomer. Additives and modifiers Various co-monomers and other additives to the monomer system are frequently used to modify or produce desired changes in the properties of the resulting polymer and hence in the properties and characteristics of PIC. Plasticizers and extendersPlasticizers such as dibutyl phthalate may be added to monomers to improve the flexibility of inherently brittle polymers such as polymethyl methacrylate and polystyrene (PS). Cross-linking agents-Cross-linking by means of the addition of an appropriate bi-functional or poly-functional monomer increases the rigidity of the polymer, its resistance to the action of solvents, and its softening-point temperature. The amount of change depends on cross-linking density of the polymer. The cross-linking agent most commonly

used in PIC is trimethylolpropane trimethacrylate (TMPTMA) (Steinberg et al. 1968), that is a tri-functional acrylic monomer that can copolymerize with other vinyl monomers such as methyl methacrylate (MMA) or styrene. Initiators Initiators are often called catalysts in the context of PIC. In reality they are not catalysts in the pure chemical sense since they are consumed during the polymerization reaction. Only small amounts of initiators are generally used. Promoters Promoters, often called accelerators are reducing agent compounds added to the monomer system to cause the decomposition of the peroxide initiators in the system. This decomposition produces the necessary free radicals needed for polymerization at ambient temperatures.Several promoters that have been successfully used are N,N-dimethyl-ptoluidine, N,N-dimethyl aniline, cobalt napthenate and mercaptans. Silane coupling agents Silane coupling agents are silicon compounds used to chemically bond organic polymers to such inorganic materials as sand, rock, glass and metals (Sterman and Maisden 1963; Plueddlemann 1970;Marsden 1970). They have the general formula (HO) 3SiR, where R is an organic group compatible with thermoplastic or thermosetting resins. Coupling agents are used frequently in PIC for improvements in strength (Dikeou et al. 1972) and to improve aggregate bond in long-term exposure to moisture. Polymerization techniques Two general methods for the polymerization of monomers are commonly used in PIC. These are the thermal-catalytic and promoted-catalytic. Both methods result in free radical initiated polymerization of properly formulated monomer systems. The selection of a particular polymerization process depends on its particular advantages for a specific application and evaluation of the effects of drainage and evaporation losses from the concrete during the polymerization, safety problems associated with the storage and reuse of large quantities of monomer and initiator, and the economics of the entire process. Thermal-catalytic method- The polymerization method involving the use of chemical initiators and heat, commonly referred to as the thermal-catalytic process, has been used extensively for preparing PIC. The process can be performed in air or under water. Several initiators that have been used in this method are described in. The primary advantage of the thermal-catalytic polymerization method is that the polymerization rates are very rapid and, therefore, processing times are short. Relatively simple electric ovens, water, or raw steam can be used as a heat source . Promoted-catalytic methodDecomposition of organic peroxide initiators can be accomplished by the use of promoters or accelerators, instead of temperature or heat, as in the case of the thermal-catalytic method. The decomposition produces the free radicals, which then allows the polymerization to take place at ambient temperature without the need for an external source of energy. Promoted-catalyst systems can induce polymerization at an ambient temperature of 40 F (5 C) or lower. Disadvantages of this method are the difficulties in obtaining predictable polymerization times and in being able to match the monomer saturation time with that of the onset of polymerization. As the induction period for

polymerization begins immediately on adding the promoter to the monomer-initiator system, its use in PIC is limited.

Schematic for the method of producing PIC

From the studies done by Won Mook Lee, J Priya Nair, Chul Woo Lee, Du Hyun Ku, Jeong Soon Park, Department of Chemical Engineering, Hanbat National University, South Korea the following conclusions were inferred regarding PICs: 1. The degree of polymerization of monomer is greater in case of PIC specimen prepared by microwaves than ones prepared from conventional thermal methods. 2. The mechanical and chemical resistant properties of PIC composites are superior to the conventional cement mortar. 3. Porosity of the conventional cement mortar is greatly reduced when it is impregnated with polymers thereby increasing its durability when it is exposed to chemically polluted environments. 4. Polymers give a more compact structure to the cement matrix and seal the cracks in cement mortar matrix. Field Applications Applications of concrete impregnated in depth in building and construction include structural floors, high performance structures, sewer pipes, storage tanks for seawater, desalination plants and distilled water plants. Marine structures, wall panels, tunnel liners, prefabricated tunnel sections and swimming pools. Partially impregnated concrete is used for the protection of bridges and concrete structures against deterioration and repair of deteriorated building structures, such as ceiling slabs, underground garage decks and bridge decks. PICs possess superior strength, chemical resistance and low water absorption compared to other polymer cement composites The disadvantage is the relatively high cost, as the polymer is more expensive than cement and the production process is more complicated.

Polymer Cement Concrete (PCC)

Polymer modified concrete is a modified concrete in which part (10 to 15% by weight) of the cement binder is replaced by a synthetic organic polymer. It is produced by incorporating a monomer, pre-polymer-monomer mixture, or a dispersed polymer (latex) into a cementconcrete mix. To effect the polymerization of the monomer or pre-polymer-monomer, a catalyst is added to the mixture. The process technology used is very similar to that of conventional concrete. Therefore, polymer cement concrete can be cast-in-place in field applications, whereas polymer impregnated concrete has to be used as a pre-cast structure. The properties of polymer cement concrete produced by modifying concrete with various polymers range from poor to quite favourable. Poor properties of certain products have been attributed to the incompatibility of most organic polymers and monomers with some of the concrete mix ingredients. Better properties are produced by using pre-polymers, such as unsaturated polyester cross-linked with styrene or epoxies. To achieve a substantial improvement over unmodified concrete, fairly large proportions of these polymers are required. The improvement does not always justify the additional cost. Modification of concrete with a polymer latex (colloidal dispersion of polymer particles in water) results in greatly improved properties, at a reasonable cost. Therefore, a great variety of latexes is now available for use in polymer cement concrete products and mortars. The most common latexes are based on poly (methyl methacrylate) also called acrylic latex, poly (vinyl acetate), vinyl chloride copolymers, poly (vinylidene chloride), (styrene-butadiene) copolymer, nitrile rubber and natural rubber. Each polymer produces characteristic physical properties. The acrylic latex provides a very good water-resistant bond between the modifying polymer and the concrete components, whereas use of latexes of styrene-based polymers results in a high compressive strength. Curing of latex polymer cement concrete is different from that of conventional concrete, because the polymer forms a film on the surface of the product. Retaining some of the internal moisture needed for continuous cement hydration. Due to the film-forming feature, moist curing of the latex product is generally shorter than for conventional concrete. Generally, polymer cement concrete made with polymer latex exhibits excellent bonding to steel reinforcement and to old concrete. Its flexural strength and toughness are usually higher than those of unmodified concrete. The modulus of elasticity may or may not be higher than that of unmodified concrete, depending on the polymer latex used. The drying shrinkage of polymer cement concrete is generally lower than that of conventional concrete; the amount of shrinkage depends on the water-to-cement ratio, cement content, polymer content and curing conditions. It is more susceptible to higher temperatures than ordinary cement concrete. For example, creep increases with temperature to a greater extent than in ordinary cement concrete, whereas flexural strength, flexural modulus and modulus of elasticity decrease. These effects are greater in materials made with elastomeric latex (e.g., styrene-butadiene rubber) than in those made with thermoplastic polymers (e.g., acrylic). Typically, at about

45C, polymer cement concrete made with thermoplastic latex retains only approximately 50 percent of its flexural strength and modulus of elasticity. PMC polymers Latexes-The majority of PMC placed today uses a polymer in latex form. Latex has been defined as a dispersion of organic polymer particles in water (Walters 1987). The average particle size varies from 100 to 2000 nanometers. Most latexes are made by a process known as emulsion polymerization, where the polymer is formed directly in water. The surfactants used to stabilize these latexes are usually nonionic, such as polyvinyl alcohol or alkyl phenols reacted with ethylene oxide. Polyvinyl acetate (PVAC)- The use of this type of latex is declining because of the poor water resistance ofPVAC-modified mortars. When wet the PVAC hydrolyses, in the high alkalinity of portland cement mixtures, and the reaction products are water soluble. This type of latex is still used extensively for plaster bonding applications. Styrene-butadiene copolymers (S-B)- It has been reported that this type of latex has been used in concrete for over thirty years (Walters 1991). In North America, one of its major applications has been the overlayment of bridge and parking-garage decks to reduce the penetration of water soluble salt (sodium chloride). These salts contribute to the corrosion and deterioration of embedded reinforcing steel that in turn cause deterioration of the concrete deck. This type of latex is widely used where either adhesion or water resistance is required. Field Applications The primary reasons for using PMC are to improve adhesion or water tightness. Major applications include providing corrosion protection to reinforcing steel, providing resistance to attack by dilute aqueous solutions of acids and salts, providing water-resistant coatings and linings, repairing of broken concrete, levelling of floors, and as a bonding agent between fresh and hardened concrete, and between tiles and various surfaces. Renderings of PMC often with low levels of fine aggregates are used to provide water-resistant coatings for basement walls and swimming pools.

Polymer Concrete (PC)

Polymer concrete (PC) is a composite material in which the binder consists entirely of a synthetic organic polymer. Because of 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. Polymer concrete consists of a mineral filler (for example, an aggregate) and a polymer binder (which may be a thermoplastic, but more frequently, it is a thermosetting polymer. Other fillers include crushed stone, gravel, limestone, chalk, condensed silica fume (silica flour, silica dust), granite, quartz, clay, expanded glass, and metallic fillers. Generally, any dry, non-absorbent, solid material can be used as filler.

Polymer concrete components Initiators for monomers and resinsthe types of initiators are dibenzoyl, lauroyl, and methyl ethyl ketone peroxides. Dibenzoyl peroxide (BPO) may be obtained in the form of powders or granules, pastes and liquid dispersions. Promoters for monomers and resinsPromoters used are dependent upon the monomer or resin system and initiators selected. In general, they are tertiary amino compounds, such as N, N-dimethylaniline and dimethyl-ptoluidine, and cobalt salts, such as naphthenate and octoate. Epoxy compoundsEpoxy compounds are generally formulated in two or more parts. Part A is most often the portion containing the epoxy resin and Part B is the hardener system. Aggregates-All of the aggregates used in conjunction with the monomer systems should be of the highest quality available. Aggregates composed primarily of silica, quartz, granite, good limestone, and other high-quality material have been used successfully in the production of PC. To produce PC, a monomer or a pre-polymer (i.e., a product resulting from the partial polymerization of a monomer), a hardener (cross-linking agent) and a catalyst are mixed with the filler. Other ingredients added to the mix include plasticizers and fire retardants. Sometimes, silane coupling agents are used to increase the bond strength between the polymer matrix and the filler. To achieve the full potential of polymer concrete products for certain applications, various fibre reinforcements are used. These include glass fibre, glass fibre-based mats, fabrics and metal fibre. Setting times and times for development of maximum strength can be readily varied from a few minutes to several hours by adjusting the temperature and the catalyst system. The amount of polymer binder used is generally small and is usually determined by the size of the filler. Normally the polymer content will range from 5 to 15 percent of the total weight, but if the filler is fine, up to 30 percent may be required. Polymer concrete composites have generally good resistance to attack by chemicals and other corrosive agents; have very low water absorption properties, good resistance to abrasion and marked freeze-thaw stability. The greater strength of polymer concrete in comparison to that of Portland cement concrete permits the use of up to 50 percent less material. This puts polymer concrete on a competitive basis with cement concrete in certain special applications. The chemical resistance and physical properties are generally determined by the nature of the polymer binder to a greater extent than by the type and the amount of filler. In turn, the properties of the matrix polymer are highly dependent on time and the temperature to which it is exposed. The viscoelastic properties of the polymer binder give rise to high creep values. This is a factor in the restricted use of PC in structural applications. Its deformation response is highly variable depending on formulation; the elastic modules may range from 20 to about 50 GPa, the tensile failure strain being usually 1%. Shrinkage strains vary with the polymer used (high for polyester and low for epoxy-based binder) and must be taken into account in an application A wide variety of monomers and pre-polymers are used to produce PC. The polymers most frequently used are based on four types of monomers or pre-polymer systems: methyl

methacrylate (MMA), polyester pre-polymer-styrene, epoxide pre-polymer hardener (crosslinking monomer) and furfuryl alcohol. General Characteristics and Applications of some Polymer Concrete Products Poly methylmethacrylate General Characteristics They have low tendency to absorb water, thus high freeze-thaw resistance. Poly methylmethacrylate has low rate of shrinkage during and after setting also very good chemical resistance and outdoor durability. Typical Applications Used in the manufacture of stair units, faade plates, sanitary products for curbstones. Polyester General Characteristics Polyester is relatively strong and has good adhesion to other materials, good chemical and freeze-thaw resistance, but have high-setting and post-setting. Typical Applications Because of lower cost, widely used in panels for public and commercial buildings, floor tiles, pipes, stairs, various precast and cast-in applications in construction works. Epoxy General Characteristics Strong adhesion to most building materials low shrinkage; superior chemical resistance; good creep and fatigue resistance; low water absorption. Typical Applications Epoxy polymer products are relatively costly; they are mainly used in special applications, including use in mortar for industrial flooring, skid-resistant overlays in highways, epoxy plaster for exterior walls and resurfacing of deteriorated structures. Furan-based polymer General Characteristics Furan-based polymers are composite materials with high resistance to chemicals (most acidic or basic aqueous media), strong resistance to polar organic liquids such as ketones, aromatic hydrocarbons, and chlorinated compounds. Typical Applications Furan polymer mortars and grouts are used for making bricks. (e.g. carbon brick, red shale brick etc.) Floors and linings those are resistant to chemicals, elevated temperatures and thermal shocks References Guide for the use of polymers in concrete reported by ACI Committee 548 (ACI 548.1R-97) Physical and chemical properties of polymer impregnated concrete on the preparation conditions-Won Mook Lee, J Priya Nair, Chul Woo Lee, Du Hyun Ku, Jeong Soon Park. Handbook of polymer-modified concrete and mortars properties and process Technology-Yoshihiko Ohama