Introduction

The term composite refers to any multiphase, multicomponent material that exhibits a significant proportion of the properties of the constituent phases such that a better combination of properties is realized. According to this principle of combined actions, better property combinations are obtained by the judicious combination of two or more distinct materials. Many composite materials are composed of just two phases, one is termed as the matrix, which is continuous and surrounds the other phase, often called the dispersed phase. Polymer nanocomposites are materials in which nanoscopic inorganic particles, typically 10-100 in at least one dimension,are dispersed in an organic polymer matrix in order to dramatically improve the performance properties of the polymer. Polymer nanocomposites have attracted interest in the last few decades providing scope for improvement of various functional properties, such as mechanical, thermal, optical, rheological, magnetic, and electrical. The improvements in functional properties of polymers are achieved at very low loading of nanoparticles. While significant work has been done on preparation and properties of polymer nanocomposites, effort is still needed to the interrelationship between processing, morphology, and functional properties of nanocomposites. The properties of nanocomposites are affected by a large number of factors including microstructural distributions that are generated during nanocomposite processing as well as the state of nanoparticle distribution in polymer systems. It is believed that understanding of the relationship between processing, morphology and functional properties of nanocomposites will be very helpful in optimizing the ultimate properties of nanocomposites as well as improving the models for predicting properties of nanocomposite systems. applications in daily life due to their unique attributes such as ease of production, light weight and often ductile nature. However, polymers have lower modulus and strength as compared to metals and ceramics and hence had restricted applications. In order to improve their mechanical properties, polymers were reinforced with inclusions (fibers, whiskers, platelets, or particles), known as fillers. This addition of fillers into the polymer matrix to make composites was expected to result in material properties (mechanic, thermal stability and expansion, fire retardant, electrical and barrier properties) not achieved by either phase alone, and often lower cost. This practice improved polymer properties while maintaining their light weight and ductile nature; hence, the addition of fillers to polymers gained a lot of importance over the years. Nowadays, nanocomposites offer new technology and

business opportunities for all sectors of industry, in addition to being environmental- friendly.

Classification of Nano composites Polymeric nanocomposites can be broadly classified as: Nanoclay-reinforced composites Carbon nanotube-reinforced composites Nanofibre-reinforced composites, and Inorganic particle-reinforced composites.

Nanoclay-reinforced Composites Historically, the term clay has been understood to be made of small inorganic particles (part of soil fraction < 2 mm), without any definite composition or crystallinity. The clay mineral (also called a phyllosilicate) is usually of a layered type and a fraction of hydrous, magnesium, or aluminum silicates . Every clay mineral contains two types of sheets, tetrahedral (T) and octahedral (O). Hectorite, saponite, and montmorillonite are the most commonly used smectite type layered silicates for the preparation of nanocomposites. Montmorillonite (MMT) has the widest acceptability for use in polymers because of their high surface area, and surface reactivity. It is a hydrous aluminosilicate clay mineral with a 2:1 expanding layered crystal structure, with aluminum octahedron sandwiched between two layers of silicon tetrahedron. Each layered sheet is approximately 1 nm thick (10 ), the lateral dimensions of these layers may vary from 30 nm to several microns or larger, depending on the particular layered silicate. The aspect ratio is about 10-1000 and the surface area is in the range6 of 750 m2/g. When one octahedral sheet is bonded to one tetrahedral sheet, a 1:1 clay mineral results. The 2:1 clays are formed when two tetrahedral sheets bond with one octahedral sheet. The aspect ratio of 1000 is possible when a clay platelet is well-dispersed into the polymeric matrix without breaking. Practically, breaking up of clay platelets during mixing process at high shear and large shear stress condition results in an aspect ratio of 30-300. Graphite has a similar geometry (layered structure) with nanoclay, therefore a claypolymer reinforcement concept is applicable. Graphite flakes have been known as host materials for intercalated compounds. By applying rapid heating, some of the graphiteintercalated compounds (GICs) expand and a significant increase in volume takes place. Many literature citations identify the expanded graphite flakes with polymer systems for lightweight and conductive polymer composites. In polymer-layered silicate (PLS) nanocomposites, stacking of the layers leads to a regular van der Waals gap between the layers called the interlayer or gallery. Isomeric substitution (for example tetrahedral Si4+ by Al3+ or octahedral Al3+ by Mg2+ or Fe2+) within the layers generates negative charges
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that are counterbalanced by alkali and alkaline earth cations (typically Na + or Ca2+) situated inside the galleries. This type of layered silicate is characterised by a moderate surface charge known as the cation exchange capacity (CEC). Details regarding the structures and chemical formulae of the layered silicates are provided in Fig. 1. In general, the organically modified silicate nanolayers are referred to as nanoclays or organosilicates.

Figer1 Basic structure of 2:1 clay minerals It is important to know that the physical mixture of a polymer and layered silicate may not form nanocomposites. Pristine-layered silicates usually contain hydrated Na+ or K+ ions. To render layered silicates miscible with other polymer matrices, it is required to convert the normally hydrophilic silicate surface to an organophilic one, which can be carried out by ion-exchange reactions with cationic surfactants. Sodium montmorillonite (Nax(Al2-xMgx)(Si4O10)(OH)2 .H2O) type layered silicate clays are available as micron size tactoids, which consist of several hundreds of individual plate-like structures with dimensions of 1 micrometer * 1 micrometer * 1 nm. These are held together by electrostatic forces (gap in between two adjacent particles ~ 0.3 nm). The MMT particles, which are not separated, are often referred to as tactoids. The most difficult task is to breakdown the tactoids to the scale of individual particles in the dispersion process to form true nanocomposites, which has been a critical issue in current research in different literatures. Properties and Applications of Nanoclay-reinforced Composites Theoretical predictions have shown that the modulus for well aligned platelets can be three times that for wellaligned fibres, especially as the aspect ratio of clay layers
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increases. Other studies however, suggest that the modulus increase is not entirely due to the load-carrying ability of the platelets, but is caused by the volume of polymer constrained by the platelets. This suggests that to optimize the increase in modulus, the degree of dispersion must be optimised to maximise the degree of matrix/filler interaction. Work on PP nanocomposites in which adding malefic anhydride (MA) to the matrix changed the degree of filler dispersion supports this suggestion that despite the plasticising effect of MA, the modulus improved due to enhanced dispersion of the clay. Lan and Pinnavaia found that, .as the degree of exfoliation increased by changing the length of alkylammonium intercalating chain, the modulus and strength improved. As the polymer intercalates and swells, the layers and the area of interaction between the polymer and the filler increases and the modulus increases significantly. Figure 2 represents three main types of composites for layered silicate materials.

Phase separated

Figure 2. Scheme of three main types of layered silicates in polymer matrix The polymer/clay interaction plays a significant role in controlling mechanical behavior is also evident from the fact that improvement in properties tends to be higher above the glass transition temperature than below it. However, proper dispersion is critical for achieving this. Hasegawa, et al. studied the dispersion of clays in polypropylene. They found that the strain-to-failure ratio in nanocomposites remains high (>200 per cent) even at reinforcement loadings of 3per cent. But even a small amount of aggregation decreased the strain-to-failure ratio to 5 per cent-8 per cent. A similar effect was also observed in

polyimide matrices, in which the strain-to-failure ratio decreases by 72 per cent due to aggregation. Xu68, et al.have reported similar improvements in tensile strength and impact strength of the composites with a nanoclay addition of 10 per cent to 15 per cent. Unprecedented combinations of properties have been observed in some thermoplastics too. The inclusion of equi-axed nanoparticles in semicrystalline thermoplastics has resulted in increase in yield stress, the tensile strength, and Young.s modulus of the polymers. A volume fraction of only 0.04 mica-type silicates (MTS) in epoxy increases the modulus below the glass transition temperature by 58 per cent and the modulus in the rubbery region by 450 per cent. In addition, the permeability of water in poly (-caprolactone) decreases by an order of magnitude with the addition of 4.8 per cent silicate by volume. Yuno, et al. showed a 50 per cent decrease in the permeability of polyimides at a 2 per cent loading of MTS. Many of these nanocomposites are optically transparent and/or optically active. Carbon Nanofiber-reinforced Composites Carbon nanotubes are graphitic sheets rolled into seamless tubes (i.e., arrangements of carbon hexagons into tube-like fullerenes) and have diameters ranging from about a nanometer to tens of nanometers with lengths up to centimeters. Nanotubes have received much attention due to their interesting properties (high modulus and electrical/thermal conductivity) since their discovery by Iijima in 1991. Since then, significant effort has been made to incorporate nanotubes into conventional materials (such as polymers) for improved strength and conductivity. Moreover, many potential applications have been proposed for carbon nanotubes, including conductive and high-strength composites; energy storage and energy conversion devices; sensors; field emission displays and radiation sources; hydrogen storage media and nanometer-sized semiconductor devices; probes and interconnects. Classifications of Carbon nanotubes. Carbon nanotubes can be grouped as single-wall (SWNT), multiwall (MWNT), and the newly established small-diameter (SDNT) material, based on the number of walls present in the carbon nanotubes, as illustrated in Fig. 3. By definition, SWNTs are single walled carbon nanotubes about 1 nm in diameter with micrometer-scale lengths; MWNTs are multiwalled carbon nanotubes with an inner diameter of about 2 to 10 nm, an outer diameter of 20 to 70 nm, and a length of about 50 (micrometer; and SDNTs have diameters of less than 3.5 nm and have lengths from several hundred nanometers to several micrometers. These SDNTs generally have one to three walls.

Figure 3 Definition of single- and multiwall carbon nanotubes.

Figure 4. Schematic of a: (a) single-wall and (b) multiwall nanotube. The packing of the carbon hexagons in the graphitic sheets defines a chiral vector (m, n) and angle. The indices of the vector determine the morphology of the nanotube. Variations in the nanotube morphology can lead to changes in the properties of the nanotube. When m_n/3 is an integer, the resulting structure is metallic; otherwise, it is a semiconducting nanotube For instance, the electronic properties of an armchair nanotube are metallic; however, the electronic properties of zigzag and chiral nanotubes are semiconducting.

Figure 5. Schematic of nanotube morphologies. (a) Armchair, (b) zig-zag, and (c) chiral.

The behavior is determined based on a mathematical model developed using the chiral vector indices. All arm-chair and one-third of zig-zag nanotubes are metallic having a continuous conduction band. The remaining two-thirds of the zig-zag nanotubes are semiconductors, having an energy gap in the conduction band

Properties and Applications Carbon nanofibers Properties of carbon nanotubes have been studied extensively. Carbon nanotubes are excellent candidates for stiff and robust structures, because the carbon-carbon bond in the graphite is one of the strongest in nature. Transmission electron microscopy data revealed that carbon nanotubes are flexible and do not break upon bending. Thermal conductivity of carbon nanotubes can be extremely high, and the thermal conductivity of individual carbon nanotubes was found to several years because of their unique potential uses for structural, electrical, and mechanical properties. Nanotubes have high Young's modulus and tensile strength, and they can be metallic, semiconducting, or semimetallic, depending on the helicity and diameter Synthesis of Carbon nanofibers The three main methods of manufacturing nanotubes include direct-current arc discharge, laser ablation, and chemical vapor deposition (CVD). A thorough discussion on each of these production methods can be found in the April 2004 MRS Bulletin . Direct-arc discharge and laser ablation were the first techniques used to produce gram quantities of SWNTs. In both methods, the evaporation of solid carbon is used to condense carbon gas.
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The products of such methods are normally tangled and poorly oriented. The CVD produces nanotubes from the decomposition of a continuously supplied carbon containing gas onto a substrate. Due to the continuous supply of the gas, high-purity nanotubes can be produced on a larger (or industrial) volume scale. Producing the nanotubes in an ordered array with controlled length and diameter can also be achieved via CVD methods. Furthermore, plasma enhanced chemical vapor deposition (PECVD) results in further nanotube uniformity within the array. Carbon nanotubes have a wide spectrum of potential applications. Examples:- include use in catalysis, storage of hydrogen and other gases, biological cell electrodes, quantum resistors, nanoscale electronic and mechanical devices, electron field emission tips, scanning probe tips, flow sensors, and nanocomposites. Single-walled nanotubes It offer incredible opportunities in electrical properties, mechanical properties, thermal properties, and field emission, as shown below: Electrical properties. Electrically conductive composites for electrostatic dissipation, shield, and conductive sealants; energy storage for super capacitors and fuel cells; electronic materials and devices for conductive inks and adhesives; electronic packaging; device and microcircuit components. Mechanical properties. High-performance composites; coatings for wear-resistance and low friction; high performance fibers; reinforced ceramic composites Thermal properties. Thermally conductive polymer composites; thermally conductive paints and coatings Field emission. Flat-panel displays; electron device cathodes and lighting

Figure 6 SWNTs are the perfect material with unique and extraordinary properties.

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Small-diameter carbon nanotubes (SDNTs). Small-diameter carbon nanotubes are linear polymers of pure carbon with diameters less than 3.5 nm and lengths from several hundred nanometers to several micrometers. Small diameter carbon nanotubes are more cost-effective and affordable than SWNTs. These SDNTs generally have one to three walls. Like Bucky tubes, SDNTs are molecules, not particles or structures like their larger multiwall or vapor-grown carbon fiber relatives, so accordingly, they have a high degree of molecular perfection. It is this high degree of molecular perfection that provides SDNTs with their amazing properties. Small-diameter carbon nanotubes are the strongest, stiffest, toughest molecules available. They have the electrical conductivity of copper and various band-gap semiconductors depending upon their diameter and chirality, which allows them to compete with metals as well as with silicon and other semiconductors. They are the most conductive of the inherently conducting polymers. Small-diameter carbon nanotubes are also the best known conductor of thermal energy along their length, and their thermal stability in air of up to 550 or 1400C in anaerobic conditions makes them the most thermally stable polymer known.

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Multiwall carbon nanotubes. Multiwall carbon nanotubes have an interior diameter of 2 to 10 nm, an exterior diameter of 20 to 75 nm, and a length of 50 micrometer, as shown in Fig. 2.29. Multiwall carbon nanotubes are produced by CVD synthesis of xylene-ferrocene composition at a relatively low temperature of 725C, and with high purity > 95 percent xylene (Fig. 2.30). Multiwall carbon nanotubes are nanoscale carbon fibers with a high degree of graphitization. Multiwall carbon nanotubes are technically neither fullerenes nor molecular. They are attractive materials intermediate between SWNT and CNF with properties vastly superior to graphite and carbon black (Figs. 7 and 8).

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Figure 7 Microstructures of MWNTs in cartoon and TEM micrographs.

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Fig8 Microstructures of MWNTs in cartoon and TEM micrographs. Inorganic Particle -reinforced Composites Nanoparticles are often defined as particles of < 100 nm in diameter. Nanometer-sized particles have been made from different organic.inorganic particles and these impart improved properties to composite materials Different particles have been used to prepare polymer/inorganic particle nanocomposites, including: Metals (Al, Fe, Au, Ag, etc.) Metal oxides (ZnO, Al2O3, CaCO3, TiO2, etc.) Nonmetal oxide (SiO2)52 Other (SiC)

The selection of nanoparticles depends on the desired thermal, mechanical, and electrical properties of the nanocomposites. For example, Al nanoparticles are often selected due to their high conductivity; calcium carbonate (CaCO3) particles are chosen because of their low cost and silicon carbide (SiC) nanoparticles are used because of their high hardness, corrosion resistance, and strength. Properties and Applications Inorganic Particle-reinforced Composites Polymer/inorganic particle-based nanocomposites have shown significant improvement in mechanical, thermal, and electrical properties. For example, in nylon-6 filled with 5 Wt % 50 nm silica nanoparticles, an increase in tensile strength by 15 per cent, strain-tofailure by 150 per cent, Young.s modulus by 23 per cent and impact strength by 78 per cent. Jiang, et al. investigated ABS (acrylonitrile butadiene styrene) reinforced with both microsized and nanosized calcium carbonate particles through melt compounding. It was found that the ABS/micron-sized particle composites had higher Young.s modulus but lower tensile and impact strengths than neat ABS. However, the ABS/nano-sized particle composites increased the Young.s modulus as well as impact strength. Ma, et al. showed an improvement in electrical properties of polyethylene nanocomposite by introducing functional groups at TiO2 nanoparticles. Zhang and Singh improved the fracture toughness of nominally brittle polyester resin systems by incorporating Al 2O3 (15 nm). An Al2O3 particle has been found to be effective in improving the dielectric constant of a polymer in other studies also. Koo, et al. used AEROSIL (silicon dioxide, 7.40 nm) silica nanoparticles to process different nanocomposites with different resin systems (phenolic, epoxy, cyanate ester) for high-temperature applications. Recently, creep tests were performed on TiO2/PA6,6 nanocomposites by Zhang and Yang. Poor creep resistance and dimensional stability have been improved by adding TiO2 in polyamide 6,6
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thermoplastic composites. Chisholm, et al. investigated micro- and nano-sized SiC in an epoxy matrix system. In their study, an equal amount of loading, nanoparticle infusion bringssuperior thermal and mechanical properties than microsized particle-based composites. Different Types of Nanoparticles. There are different types of commercially available nanoparticles that can be incorporated into the polymer matrix to form polymer nanocom posites. Depending on the application, the researcher must determine the type of nanoparticle needed to provide the desired effect.The most commonly used nanoparticles in the polymer nanocomposite. Montmorillonite organoclays (MMT) Carbon nanofibers (CNFs) Polyhedral oligomeric silsesquioxane (POSS) Carbon nanotubes [multiwall (MWNTs), small-diameter (SDNTs), and single-wall (SWNTs)] Nanosilica (N-silica) Nanoaluminum oxide (A1203) Nanotitanium oxide (TiC) Others How nanocomposites work Polymer nanocomposites are constructed by dispersing a filler material into nanoparticles that form flat platelets. These platelets are then distributed into a polymer matrix creating multiple parallel layers which force gases to flow through the polymer in a torturous path, forming complex barriers to gases and water vapor, as seen in Figure 9. As more tortuosity is present in a polymer structure, higher barrier properties will result. The permeability coefficient of polymer films is determined using two factors: diffusion and solubility coefficients: P = D x S. Effectively, more diffusion of nanoparticles throughout a polymer significantly reduces its permeability. According the Natick Soldier Center of the United States Army, the degree of dispersion of the nanoparticles within the polymer relates to improvement in mechanical and barrier properties in the resulting nanocomposite films over those of pure polymer films. Nanoparticles allow for much lower loading levels than traditional fillers to achieve optimum performance. Usually addition levels of Nano fillers are less than 5%, which significantly impact weight reduction of nanocomposite films. This dispersion process results in high aspect
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ratio and surface area causing higher performance plastics than with conventional fillers.

Figure 9. Schematic of nanoscale fillers.

Factors that affect the polymer nanocomposite properties There are many factors that affect the polymer nanocomposite properties including: Synthesis methods such as melt compounding, solvent blending, in-situ polymerization, and emulsion polymerization. Polymer nanocomposite morphology. Types of nanoparticles and their surface treatments. Polymer matrix such as crystallinity, molecular weight, polymer chemistry, and whether thermoplastic or thermosetting. Table 1 shows several benefits and disadvantages when nanoparticles are incorporated into the polymer matrix.

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Table 1 characteristics of Nanoparticles to polymers

Characteristics of Polymer Nanostructured Materials. There are two main challenges to developing polymer nanostructured materials after the desired nanoparticle has been selected for the polymer of interest. First, the choice of nanoparticles requires an interfacial interaction and/or compatibility with the polymer matrix. Second, the proper processing technique should be selected to uniformly disperse and distribute the nanoparticles or nanoparticle aggregates within the polymer matrix. In most cases, polymer nanostuctured materials exhibit multifunctionality. Several of the functions of these materials are listed below: Thermal: increased thermal resistance, higher glass transition temperature (Tg) or heat deflection temperature (HDT), reduced coefficient of thermal expansion (CTE). Mechanical: increased modulus, strength, toughness, elongation (in some cases). Chemical: improved solvent resistance, improved moisture resistance. Electrical: improved thermal conductivity, lower resistivity (depends on the nanoparticles).
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 Barrier: reduced oxygen, moisture transmission. Optical: clear, transparency provided in selective systems. Others: abrasion resistance, reduced shrinkag

Polymer Matrices In general, polymers can be classified into the three basic families of resins namely thermoplastics, thermosets, and elastomers. Table 2 lists several characteristics of the thermosetting and thermoplastic resin systems. Thermoplastic-based nanocomposites. Materials are often classified as metals, ceramics, or polymers. Polymers differ from the other materials in a variety of ways, but generally they exhibit lower densities, and moduli. The lower densities of polymeric materials offer an advantage in applications where lighter weight is desired. The addition of thermally and/or electrically conducting fillers allows the polymer formulator the opportunity to develop materials from insulating to conducting type characteristics. Themoplastic materials are used in a vast array of products. In the automotive area, they are used for interior parts and in under-the hood applications. The packaging applications area is a large area for thermoplastics, from carbonated beverage bottles to plastic wrap. Table 2 comparisons of thermoplastic and thermosetting resion characteristic.

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Application requirements vary widely; fortuitously, plastic materials can be formulated to meet these different business opportunities. It remains for designers to select from the array of thermoplastic materials that are available to meet the particular needs of their applications. Many thermoplastics have been nanomodified into polymer nanocomposites by incorporating nanoparticles into the polymers as shown in Table 3. Table4 Thermoplastic - based of nanocomposites.

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Thermoset-based nanocomposites. Thermosetting type resins consist of solid, semi-solid, or liquid organic reactive intermediate material that cures or crosslinks into a high molecular weight product with no observable melting point. The basic characteristic of these intermediate reactive hermosetting resins is that they will, upon exposure to elevated temperature from ambient to above 450F, undergo an irreversible chemical reaction often referred to as polymerization, or cure. Each family member has its own set of individual chemical characteristics based on its molecular structure and its ability to either homopolymerize, copolymerize, or both. This transformation process separates the thermosets from the thermoplastic polymers. The important beneficial factor lies in the inherent enhancement
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of the physical, electrical, thermal, and chemical properties of thermoset resins because of that chemical cross-linking polymerization reaction, which contributes to their ability to maintain and retain these enhanced properties when exposed to severe environmental conditions. An intermediate reactive thermosetting species is defined as a liquid, semisolid, or solid composition capable of curing at some defined temperature that can be from ambient to several hundred degrees and cannot be reshaped by subsequent reheating. In general, these intermediate reactive thermosetting compositions contain two or more components: a reactive resinous material with a curing agent that causes the intermediate material to polymerize (cure) at room temperature, or a low molecular weight resinous material and curing agent that, when subjected to elevated temperatures, will commence polymerization and cure. Several thermosetting resins have been nanomodified into polymer nanocomposites by introducing the nanoparticle into the thermosetting resin as shown in Table 5. These intermediate thermosetting nanocomposites can be impregnated into fiber reinforcements such as glass, silica, quartz, carbon/graphite, aramid, poly(p-phenylene-2-6- benzobisoxazole) (PBO), polyethylene, boron, or ceramic and upon curing lead to laminates or nanomodified polymer matrix composites (PMCs). Table 5 thermoset- based nanocomposite

Elastomer-based nanocomposites rubberlike, known as elastomers. These elastomeric materials can be block copolymers or multi-phase systems containing soft (low Tg) segments and hard segments (high Tg, possibly crystalline). They are processable under thermoplastic conditions. A few elastomers have been nanomodified into elastomer nanocomposites as shown in Table 6. For completeness, some rubber materials (synthetic, isoprene, natural, etc.) that are nanomodified are also listed in Table 6.
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TABLE 6 Elastomer-Based Nanocomposite Examples

Scientists and engineers can develop formulations for a range of polymer nanocomposites to fit their requirements and applications. The challenge is to select the baseline polymers with the proper nanoparticles to solve specific problems. Processing and morphological characterization are the keys to understanding the fundamentals of this new class of nanomaterials.

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Applications of polymer nanocomposites. The improvements in mechanical properties of nanocomposites have resulted in major interest in numerous automotive and general/industrial applications. It includes potential for utilization as mirror housing on various types of vehicles, door handles, engine covers, and belt covers. More general applications include: packaging, fuel cell, solar cell, fuel tank, plastic containers, impellers and blades for vacuum cleaners, power tool housing, and cover for portable electronic equipment such as mobile phones and pagers. Coatings. Coatings are important for modifying properties of surfaces. One of the well versed developments is nanoclay based polymer coatings. Nanoclay incorporated thermoset polymer nano coatings exhibit superior properties such as superhydrophobicity, improved wettability, excellent resistance for chemicals, corrosion resistance, improved weather resistance, better abrasion resistance, improved barrier properties and resistance to impact, scratch, etc. Energy storage systems and sensors. Fuel cells act as electrochemical `devices, which convert chemical energy of carbon, hydrogen and oxygen directly and efficiently into useful electrical energy with heat and water as the only byproducts. Due to incorporation of nano materials their efficiency increases considerably. In fuel cells, proton exchange membranes role is to allow proton transport from the anode to the cathode, to be an electron nonconductive material and to act as a gas separating barrier. Gas barriers for plastic bottles, packaging and sports goods Hybrids made of poly(dimethyl siloxane) rubber and nanosilica generated in-situ by hydrolysis of tetraethyl orthosilicate can be specifically shaped, giving objects such as golf balls. A number of polymer nanocomposites based on polymers, such as butyl rubber, styrene butadiene rubber, ethylene propylene diene monomer rubber, ethylene vinyl acetate copolymer, ethylene-octene copolymer, have been used commercially for barrier applications. These polymers can act as excellent barriers for many gases such as CO2, O2,N2, and chemicals such as toluene, HNO3, H2SO4, HCl, etc. Due to excellent solvent barrier properties PNCs have been utilized in chemical protective and surgical gloves in

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order to protect against chemical warfare agents and for avoiding contamination from medicine. PNCs also have been widely used in food packaging and plastic containers, both flexible and rigid. Specific examples include packaging for processed meat, cheese, cereals and dairy products, printer cartridge seals, medical container seals for blood collection tubes, stoppers for medical containers and blood bags, baby pacifiers and drinking water bottles. Products with low flammability. Electronics and automobile sectors. Optical glass and membranes Clay incorporated polymers have been shown, when employed to coat transparent materials, to enhance both toughness and hardness of these materials without sacrificing light transmission characteristics. An ability to resist high velocity impact combined with substantially improved abrasion resistance of PLS nanocomposites was demonstrated by Triton Systems. Owing to this reason and improved optical properties it has been widely commercialized in contact lens and optical glass. Polymer/clay nanocomposites can also be used to fabricate various types of membranes, such as solvent filters, filters for bacteria and virus , solid electrolytes for fuel cells, membrane for gas separation, etc Biomedical applications The applicability of polymer nanotechnology and nanocomposites to emerging biomedical/biotechnological applications is a rapidly emerging area of development of which this discussion can only briefly cover. One area of intense research involves electrospinning for producing bioresorbable nanofiber scaffolds for tissue engineering applications. This might be construed as a nanocomposite as the resultant scaffold allows for cell growth yielding a unique composite system. Another area also involving nanofibers is the utilization of electrically conducting nanofibers based on conjugated polymers for regeneration of nerve growth in a biological living system. Refractive Index Tuning In many optical applications such as telecommunications and optical computing, polymer optical fibres are very attractive to adjust the refractive index of the connecting optical fibre (due to ease of mass production and low cost). This can be done by the addition of nanoparticles with various refractive indices to the polymer. Bohm79, et al. reported
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additions of nanoparticle zirconia, alumina, and silica to poly (methyl methacrylate) and they were able to adjust the refractive index over a sufficient range. Levels up to 10 Wt % loading were reported. Tuning the refractive index of surface coatings is important in signature management. Damage resistance (abrasion and scratching) of the fibre is likely to be improved by addition of ceramic nanoparticles. Solid Lubricants It is possible to produce inorganic fullerene-like (IF) nanoparticles of tungsten sulphide (WS2), which have a characteristic structure like a hollow onion. have reported that by adding small quantities of WS2 nanoparticles (about 100 nm dia) to two polymer matrices: epoxy and polyacetal, it was possible to reduce coefficient of dry friction between polymer and a steel disc to less than half in both the cases. If a simple lubricant was present, friction coefficient was further reduced significantly. Fracture toughness of the epoxy was also improved. These lubricants may be used for rotating and sliding bearings. Porous Nanocomposites. The additions of nanoparticles can serve to improve the foaming properties of a polymer as reported by Siripurapu81, et al. who used additions of silica nanoparticles to act as nucleation sites for nanopore formation using carbon dioxide as a blowing agent. A disadvantage of porous polymer foams (e.g., polyurethane) is their large surfacetovolume ratios, which increase the rate of heat and gas release in case of fire. By introducing nanoparticles with a flake-like morphology, the rate of burning can be significantly reduced. Nanoporous polyurethane is being considered for automotive seat applications. Other applications include shock-absorbing materials, and acoustic absorbents, etc. Microwave Absorbers Nanocomposites as microwave absorbers are receiving much attention. Nguyen and Diaz78 have reported a method to synthesize polypyrrole nanocomposites containing iron oxides (g and a), tin oxide, tungsten oxide and titanium dioxide. Pyrrole containing a dispersion of nanoparticle metal oxides was polymerised in situ and the magnetic properties reported. The electrical conductivity and dielectric losses can be tuned by varying the concentration and orientation of the nanotubes additions. Only a few weight per cent of nanotubes need be added to the polymer to achieve useful properties.
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Efforts have been made to utilise CNTs for developing economical microwave (in the range 8 GHz to 24 GHz) absorbers103,104. These materials have wide applications in electrical energy storage (condensers) integrated into load-carrying structures for UAVs, high strength CNTspolymer fibres for energy absorption, electromagnetic shielding, etc. Ballistic Protection. The reports of ballistic testing of PNCs are very few and this may be due to secrecy associated with such materials and lack of suitable nanocomposite materials. Reports from the US Army Research Laboratory indicate promising results when combining inorganic nanoparticles (of silica) in polyethylene glycol. When this shear thickening fluid is impregnated into conventional Kevlar, the ability of the material to absorb energy is greatly improved. In one example, the ballistic performance (in terms of absorbed energy) was more than doubled so that four layers of Kevlar impregnated with the shear thickening fluid absorbed as much energy as would have been absorbed by 10 layers without the shear thickening fluid. This will lead to a more flexible armour with reduced weight. Such materials find applications for body/personal armour where flexibility of movement is required besides protection against blunt weapons (stones, sticks and bars) for arms and legs. Corrosion Protection

Corrosion protection of metals and alloys is normally achieved by a surface coatings which must resist both mechanical damage (scratching, impact, abrasion) and chemical attack (salts, acids and bases, solvents). It should also not be damaged (cracked) by having a coefficient of thermal expansion greatly different from the metal to be protected. PNCs have improved scratch and abrasion resistance, due to their higher hardness combined with improved elastic modulus. Gentle and Baney87 reported preliminary experiments using a silica-reinforced silicone nanocomposite coating deposited to protect aluminium surfaces and electronic circuits.

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Properties of polymer nanocomposites Barrier properties and flame retardancy The search for non-halogenated flame retardants has led to nanoclays, one nm thick by 1000 nm diameter. Initial research showed that the addition of as little as 5% of nanosized clay particles could produce a 63% reduction in the flammability of nylon-6. More recent studies have shown that flame retardancy in many other polymers can be boosted by dispersing clay at the molecular level. Clays are believed to increase the barrier properties by creating a maze or tortuous path (Scheme 8) that retards the progress of the gas molecules through the matrix resin (Neilson, 1967). For example, polyimide/layered silicate nanocomposites with a small fraction of O-MMT exhibited reduction in the permeability of small gases, e.g. O2, H2O, He, CO2, and ethyl acetate.

. Scheme 8. Neilsons tortuous path model for barrier enhancement of nanocomposites (from Neilson, 1967).

Optical clarity The presence of reinforcement incorporation at nano-levels has been shown to have significant effects on the transparency and haze characteristics of films. In comparison to conventionally filled polymers, nanoclay incorporation has been shown to significantly enhance transparency and reduce haze.
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Clays are just into thin, albeit their micro- lateral size. Thus, when single layers are dispersed in a polymer matrix the resulting nanocomposite is optically clear in the visible region (Figure 10). At the same time, there is a loss of intensity in the UV region (for < 300 nm), mostly due to scattering by the MMT particles. There is no marked decrease in the clarity due to nano-dispersed reinforcements.

Fig. 10. UV-visible transmittance for MA-functionalized PP and its MMT nanocomposites as a function of MMT loading A plausible reason for the above observations could be that the size of nanoclay particles is less than the wavelength of visible light; hence, visible light rays are not appreciably scattered by nanoclay particles. But, visible light rays could be appreciably scattered by regions where clay particles form agglomerates. This fact could be understood by looking at scheme 9 (Wilson et al., 2002).

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Scheme 9. Light rays passing mostly undeflected through an array of nanoparticles, so the array is transparent. When the particle size of the same material increases, light rays are scattered and the material becomes . Nanocomposite mechanical properties: reinforcement A common reason for adding fillers to polymers is to increase the modulus or stiffness via reinforcement mechanisms described by theories for composites [58,165185]. Properly dispersed and aligned clay platelets have proven to be very effective for increasing stiffness. This is illustrated in Fig. 7 by comparing the increase in the tensile modulus, E, of injection molded composites based on nylon 6, relative to the modulus of the neat polyamide matrix, Em, when the filler is an organoclay versus glass fibers [58]. In this example, increasing the modulus by a factor of two relative to that of neat nylon 6 requires approximately three times more mass of glass fibers than that of montmorillonite, MMT, platelets. Thus, the nanocomposite has aweight advantage over the conventional glass fiber composite. Furthermore, if the platelets are aligned in the plane of the sample, the same reinforcement should be seen in all directions within the plane, whereas fibers reinforce only along a single axis in the direction of their alignment [165]. In addition, the surface finish of the nanocomposite is much better than that of the glass fiber composite owing to nanometer size of the clay platelets versus the 10 15 m diameter of the glass fibers.
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Fig. 7. Comparison of modulus reinforcement (relative to matrix polymer) increases for nanocomposites based on MMT versus glass fiber (aspect ratio w20) for a nylon 6 matrix

Nanocomposite thermal properties: dimensional stability The high thermal expansion coefficients of neat plastics causes dimensional changes during molding and as the ambient temperature changes that are either undesirable or in some cases unacceptable for certain applications. The latter is a particular concern for automotive parts where plastics must be integrated with metals which have much lower coefficients of thermal expansion, CTE. Fillers are frequently added to plastics to reduce the CTE. For low aspect ratio filler particles, the reduction in CTE follows, more or less, a simple additive rule and is not very large; in these cases, the linear CTE changes are similar in all three coordinate directions. However, when high aspect ratio fillers, like fibers or platelets, are added and well oriented, the effects can be much larger; in these cases, the CTE in the three coordinate directions may be very different. The fibers or platelets typically have a higher modulus and a lower CTE than the matrix polymer. As the temperature of the composite changes, the matrix tries to extend or contract in its usual way; however, the fibers or platelets resist this change creating opposing stresses in the two phases.

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Processing of Nanomaterials. Synthesis Methods. After the selection of a particular polymer matrix and the appropriate nanoparticles for a specific application, the next challenge is to determine the proper synthesis method to create the desired polymer nanocomposite. Figure 4.1 shows the processing challenge of transforming ( particles into > 1 million platelets.

Figure 4.1 Processing challenge of layered silicate. In general, for solid thermosetting reactive prepolymers or thermoplastic polymers with solid nanoparticles, the following processing methods are recommended: Solution intercalation Melt intercalation Roll milling For liquid thermosetting reactive prepolymers or thermoplastic polymers with solid nanoparticles, the following processing methods are recommended: In-situ polymerization Emulsion polymerization High-shear mixing Structure of PNC. Two types of structures are obtained, namely intercalated nanocomposites, where the polymer chains are sandwiched between silicate layers, and exfoliated nanocomposites, where the separated, individual silicate layers are more or less uniformly dispersed in the polymer matrix.

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 Characterization Techniques for Nanocomposites. Characterization tools are crucial to comprehend the basic physical and chemical properties of PNCs. For structural applications, it facilitates the study of emerging materials by giving information on some intrinsic properties. Various techniques for characterization have been used extensively in polymer nanocomposite research . The commonly used powerful techniques are wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The SEM provides images of surface features associated with a sample. However,there are two other microscopies, scanning probe microscopy (SPM) and scanning tunneling microscopy (STM), which are indispensable in nanotube research. The SPM uses the interaction between a sharp tip and a surface to obtain an image. In STM, a sharp conducting tip is held sufficiently close to a surface (typically about 0.5 nm), such that electrons can tunnel across the gap . This method provides surface structural and electronic information at atomic level. The invention of the STM inspired the development of other scanning probe microscopes, such as the atomic force microscope (AFM) . The AFM uses a sharp tip to scan across the sample. Raman spectroscopy has also proved a useful probe of carbon-based material properties . Due to the easiness and availability, WAXD is the most commonly used to probe the nanocomposite structure, and occasionally to study the kinetics of the polymer melt intercalation. In layered silicate nanocomposite systems, a fully exfoliated system is characterized by the absence of intensity peaks in WAXD. Therefore, a WAXD pattern concerning the mechanism of nanocomposite formation and their structure. On the other hand, TEM allows a qualitative understanding of the internal structure, spatial distribution of the various phases, and views of the defective structure through direct visualization, in some cases of individual atoms. Therefore, TEM complements WAXD data . Small-angle X-ray scattering (SAXS) is typically used to observe structures on the order of 10A or larger . For thermal characterization and to study the cure behavior (typically for thermoset resin systems) of PNCs, the commonly used techniques are differential scanning calorimeter (DSC), DSC is an analytical tool which helps to understand the thermal behavior of polymer nanocomposites. It helps in finding glass transition temperature (Tg) of polymer and its polymer composites. The increase in Tg values shows the presence of inorganic materials in the polymer matrix. thermomechanical analysis (TMA), Fourier-transform infrared (FTIR), dynamic modulus analysis (DMA), etc. Both, XRD and Thermogravimetric analysis
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(TGA), are important techniques used to characterize the microstructure of nanocomposites. In general, TGA is used to assess the amount of organic matter exchanged on the clay surface during the surface modifi cation process. XRD is also used to quantify increases in basal plane spacing in the filler following surface modifi cation, and also after composite generation.

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Reffrencess.

NANOCOMPOSITES AND THEIR APPLICATIONS BY,SHIVANI PANDYA CENTRE FOR NANOSCIENCE

LITERATURE SURVEY ON POLYMER NANOCOMPOSITE. By RAVI NARAIAN PANDEY M Tech.-2nd year.DTUDELHI. INTRODUCTION AND APPLICATIONS OF NANOTECHNOLOGY . BY TAHIRA IRUM M.Phil 1st

CHAPTER 9POLYMER MATRIX NANOCOMPOSITES(PMN) NoraihamMohamad, Ph.D,Department of Engineering Materials Faculty of Manufacturing Engineering,UniversitiTeknikalMalaysia Melaka

5 - Polymer Nano-composites Robert J Young FREng* School of Materials, University of Manchester, UK Advanced Polymer Nanocomposites: Novel Properties and Applications Ramanan Krishnamoorti ,Department of Chemical &BiomolecularEngineering,University of Houston Polymer Nanocomposites: From Synthesis to Applications S. Anandhan1 and S. Bandyopadhyay2 1National Institute of Technology Karnatak The University of New South Wales
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 Polymer Nanocomposites: Synthesis, Microstructure, and Properties Vikas Mittal Polymer Nanocomposites Processing, Characterization, and Applications, by Joseph H. Koo

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Content

Title Introduction Classification of Nano composite Nanoclay-reinforced composite. Inorganic particale reinforced composition Different type nanoparticles How nanocomposite properties Factors that affect the polymer nanocomposite properties Characteristic of polymer Applications of polymer nanocomposite PROPERTIES OF PNC. PROCESSING OF PNC STRUCTURE OF PNC

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Characterization Techniques for Nanocomposites

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