UNIT 8(COMPOSITE MATERIALS)

Why Study Composites? With knowledge of the various types of composites, as well as an understanding of the dependence of their behaviors on the characteristics, relative amounts, geometry/distribution, and properties of the constituent phases, it is possible to design materials having property combinations that are better than those found in the metal alloys, ceramics, and polymeric materials.

Phases of Composites
Matrix Phase: Polymers, Metals, Ceramics Also, continuous phase, surrounds other phase (e.g.: Metal, ceramic, or polymer) Reinforcement Phase: Fibers, Particles, or Flakes Interface between matrix and reinforcement: Common FRP are composed of fibers and a matrix. Fibers are the reinforcement and the main source of strength while the matrix 'glues' all the fibers together in shape and transfers stresses between the reinforcing fibers. Sometimes, fillers or modifiers might be added to smooth Manufacturing process, imparts special properties, and/or reduce product cost. Examples: Straw in mud

Resins(PLASTICS)
Primary Function: To transfer stress between reinforcing fibers and to protect them From mechanical and environmental damage Polymer Matrix Composite Combinations

Some of the significant differences between thermosets and thermoplastics are given below:

2.3.4.1 Thermosetting Materials The major group of materials used today in the aircraft industry contains thermosetting matrix resins. Thermoset Resin Polyesters, epoxy and other resins in liquid form contain monomers (consisting of simple

molecules), which convert into polymers (complex cross-linked molecules) when the resin is cured. The resulting solid .is called thermosets, which is tough, hard, insoluble and infusible. The property of infusibility distinguishes thermosets from the thermoplastics. Cure and polymerization refer to the chemical reactions that solidify the resin. Curing is accomplished by heat, pressure and by addition of curing agents at room temperature. Thermosetting materials can be further divided into two groups depending on how they react to form their network structure. For example, epoxies and polyesters react to form a network structure without formation of a volatile by-product. The fact that some thermosets form volatile by-products means that high pressure laminating techniques must be used to prevent the

formation of voids or other defects. Epoxies and polyesters can be cured at atmospheric pressures and also at ambient temperatures. Polyester matrices have been in use for the longest period in the widest range of structures. Polyesters cure with the addition of a catalyst (usually a peroxide) resulting in an exothermic reaction, which can be initiated at room temperature. The most widely used matrices for advanced composites have been the epoxy resins. These resins cost more than polyesters and do not have the high temperature capability of the Polyimides. However, they are widely used due to the following advantages.
Adhesion to fibres and to resin; No by-products formed during cure; Low shrinkage during cure; High or low strength and flexibility; Resistance to solvents and chemicals; Resistance to creep and fatigue; Wide range of curative options; Adjustable curing rate; Good electrical properties.

Epoxies do have few inherent disadvantages also, viz.

Resins and curatives are somewhat toxic in uncured form; Moisture absorption resulting into change in dimensions and physical properties; Limited to about 200C (392F) upper temperature use; Difficult to combine toughness and high temperature resistance; High thermal coefficient of expansion; High degree of smoke liberation in a fire; May be sensitive to ultraviolet light degradation; Slow curing.
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Typical Properties of Thermosetting Materials Salient properties of some of the above-referred thermosetting materials are given in the following paras. Phenolics Low cost, Capability to be B-Staged, Excellent high temperature resistance up to 205-260C (400-500F), Good mechanical strength, Dimensional and thermal stability, Good laminate properties, Hot molding (cold molding very rarely), Good fire resistance and very low smoke emission, Curing temperature is 175C (350F), High chemical resistance, and Good dielectric properties. Some of the disadvantages are: by-products are produced during curing, there is high shrinkage on cure, and phenolic laminates are porous.

Polyesters:
Low cost, Good handling characteristics, Low viscosity and versatility, Good mechanical strength, Good electrical properties, Good heat resistance, Cold and hot molding, Flame resistant with fire proof additive, and Curing temperature is 120C (250F). Some of the disadvantages are: interlaminar shear is less than that of epoxies, lower strength than that of epoxies, high curing shrinkage, and poor chemical resistance.
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Vinyl Ester Vinyl ester combines inherent toughness with outstanding heat and chemical resistance, Corrosion-resistance, and Possesses low ester content and low unsaturation resulting in greater resistance to hydrolysis and less shrinkage during cure. Some of the disadvantages are: vinyl esters are not as good as epoxy resins with regard to bondability to other surfaces and high cost. Polyimides Excellent strength retention for long term in 260-315C (500-600F) range and short term in 370C (700F) range, Excellent electrical properties, Excellent mechanical strength, Good fire resistance and low smoke emission, Hot molding under pressure, and Curing temperature is 175C (350F) and 315C (600F). Some of the disadvantages are: laminates are porous, volatile by-products are given off during cure, and long post cure is required. 2.3.4.1.5 Epoxies Make an excellent matrix material because of their versatility, Good handling characteristics, Low shrinkage, Excellent adhesive properties, Flame resistant, Good chemical resistance, Good mechanical properties including toughness, Offer considerable variety for formulating Prepreg resins,
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 Hot molding (cold molding rarely), High smoke emission, Curing temperature is 120-175C (250-3500F), and No by-products formed during cure.

Some of the disadvantages are: require 4.4C (40F) storage and shipment, service temperature is only 93-1O7C (200-225F) and laminate displays light brittleness

Thermoplastic Resin: thermoplastics can be repeatedly softened by heating, and hardened by cooling. Thermoplastics possess several advantages over the thermosets, one of the most important being that they do not need storing under refrigeration. They also possess improved damage tolerance, environmental resistance, fire resistance, recyclability and potential for fast processing. Primary reason for the use of thermoplastics is their cost effective processing. Increased use for thermoplastics is also due to three different reasons, viz. First - Processing can be faster than that of thermoset composites since no curing reaction is required. Thermoplastic composites require only heating, shaping and cooling. Second - The properties are attractive, in particular, high delamination resistance and damage tolerance, low moisture absorption and the excellent chemical resistance of semicrystalline polymers. Third- In the light of environmental concerns, thermoplastic composites offer other advantages also. They have low toxity since they do not contain reactive chemicals (therefore storage life is infinite). Because it is possible to remelt and dissolve thermoplastics, their composites are also easily recycled or combined with other recycled materials in the market for molding compounds. Since the release of gases during processing and inherent brittleness is serious disadvantage of some thermoset resins, thermoplastic composites are of great interest. Thermoplastics usually require high temperature and pressure during processing and generally lack good solvent resistance. Process conditions for high performance thermoplastics are temperature in the range of 300 to 400C (570 to 750F) and pressure between atmospheric pressure for thermofolding process to 20 times the atmospheric pressure for high performance press forming. Due to their high strains to failure, thermoplastics are the only matrices currently available that are suited to thermoforming and other forms of rapid manufacture. Thermo-loading is the most straight forward thermoplastic forming technique where a straight line is heated and folded. The process is used in volume applications like aircraft floor boards. Thermofolding operations can be carried out on solid laminate materials as well as on sandwich panels.
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Press Forming process for thermoplastic composites is related to that used for metals, the difference being that the blank material is heated to a high temperature and processed within a very short time span. Applications for press forming are reinforcement ribs. To date, applications of thermoplastic composites have ranged from small, simple, structural details such as ribs or spars up to relatively large structures. Table given below lists some of these applications in aircraft industry.

Carbon Fiber Reinforcement:

Good modulus at high temperatures Excellent stiffness More expensive than glass Brittle Low electric insulating properties

DISPERSION-STRENGTHENED COMPOSITES
Metals and metal alloys may be strengthened and hardened by the uniform dispersion of several volume percent of fine particles of a very hard and inert material. The dispersed phase may be metallic or nonmetallic; oxide materials are often used. Again, the strengthening mechanism involves interactions between the particles
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and dislocations within the matrix, as with precipitation hardening. The dispersion strengthening effect is not as pronounced as with precipitation hardening; however, the strengthening is retained at elevated temperatures and for extended time periods because the dispersed particles are chosen to be unreactive with the matrix phase. For precipitation-hardened alloys, the increase in strength may disappear upon heat treatment as a consequence of precipitate growth or dissolution of the precipitate phase. The high-temperature strength of nickel alloys may be enhanced significantly by the addition of about 3 vol% of thoria (ThO2 ) as finely dispersed particles; this material is known as thoria-dispersed (or TD) nickel. The same effect is produced in the aluminumaluminum oxide system.Avery thin and adherent alumina coating is caused to form on the surface of extremely small (0.1 to 0.2 m thick) flakes of Aluminum, which are dispersed within an aluminum metal matrix; this material is termed sintered aluminum powder (SAP).

GLASS FIBER-REINFORCED POLYMER (GFRP) COMPOSITES:

Fiberglass is simply a composite consisting of glass fibers, either continuous or discontinuous, contained within a polymer matrix; this type of composite is produced in the largest quantities. The composition of the glass that is most commonly drawn into fibers (sometimes referred to as E-glass) is contained in Table 13.10; fiber diameters normally range between 3 and 20 _m. Glass is popular as a fiber reinforcement material for several reasons: 1. It is easily drawn into high-strength fibers from the molten state. 2. It is readily available and may be fabricated into a glass-reinforced plastic Economically using a wide variety of composite-manufacturing techniques. 3. As a fiber, it is relatively strong and when embedded in a plastic matrix, it produces a composite having a very high specific strength. 4. When coupled with the various plastics, it possesses a chemical inertness that renders the composite useful in a variety of corrosive environments. The surface characteristics of glass fibers are extremely important because even minute surface flaws can deleteriously affect the tensile properties. Surface flaws are easily introduced by rubbing or abrading the surface With another hard material. Also, glass surfaces that have been exposed to the

Normal atmosphere for even short time periods generally have a weakened surface layer that interferes with bonding to the matrix. Newly drawn fibers are normally coated during drawing with a size, a thin layer of a substance that protects the fiber surface from damage and undesirable environmental interactions. This size is ordinarily removed prior to composite fabrication and replaced with a coupling agent or finish that promotes a better bond between the fiber and matrix. There are several limitations to this group of materials. In spite of having high strengths, they are not very stiff and do not display the rigidity that is necessary for some applications (e.g., as structural members for airplanes and bridges). Most fiberglass materials are limited to service temperatures below 2000C at higher temperatures, most polymers begin to flow or to deteriorate. Service temperatures may be extended to approximately 3000C by using high-purity fused silica for the fibers and high-temperature polymers such as the polyimide resins. Many fiberglass applications are familiar: automotive and marine bodies, plastic pipes, storage containers, and industrial floorings. The transportation industries are utilizing increasing amounts of glass fiber-reinforced plastics in an effort to decrease vehicle weight and boost fuel efficiencies. A host of new applications are being used or currently investigated by the automotive industry.

CARBON FIBER-REINFORCED POLYMER (CFRP) COMPOSITES:

Carbon is a high-performance fiber material that is the most commonly used reinforcement in advanced (i.e., nonfiberglass) polymer-matrix composites. The reasons for this are as follows: 1. Carbon fibers have the highest specific modulus and specific strength of all reinforcing fiber materials. 2. They retain their high-tensile modulus and high strength at elevated temperatures; high-temperature oxidation, however, may be a problem. 3. At room temperature carbon fibers are not affected by moisture or a wide variety of solvents, acids, and bases. 4. These fibers exhibit a diversity of physical and mechanical characteristics, allowing composites incorporating these fibers to have specific engineered properties.
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5. Fiber and composite manufacturing processes have been developed that are relatively inexpensive and cost effective. Manufacturing techniques for producing carbon fibers are relatively complex and will not be discussed. However, three different organic precursor materials are usedrayon, polyacrylonitrile (PAN), and pitch. Processing technique will vary from precursor to precursor, as will also the resultant fiber characteristics. One classification scheme for carbon fibers is according to tensile modulus; on this basis the four classes are standard, intermediate, high, and ultrahigh moduli. Furthermore, fiber diameters normally range between 4 and 10 _m; both continuous and chopped forms are available. In addition, carbon fibers are normally coated with a protective epoxy size that also improves adhesion with the polymer matrix. Carbon-reinforced polymer composites are currently being utilized extensively in sports and recreational equipment (fishing rods, golf clubs), filament-wound rocket motor cases, pressure vessels, and aircraft structural componentsboth military and commercial, fixed wing and helicopters (e.g., as wing, body, stabilizer, and rudder components).

CARBONCARBON COMPOSITES:
One of the most advanced and promising engineering material is the carbon fiberreinforced carbon-matrix composite, often termed a carboncarbon composite; as the name implies, both reinforcement and matrix are carbon. These materials are relatively new and expensive and, therefore, are not currently being utilized extensively. Their desirable properties include high-tensile module and tensile strengths that are retained to temperatures in excess of 2000C (3630F), resistance to creep, and relatively large fracture toughness values. Furthermore, carbon carbon composites have low coefficients of thermal expansion and relatively high thermal conductivities; these characteristics, coupled with high strengths, give rise to a relatively low susceptibility to thermal shock. Their major drawback is a propensity to high-temperature oxidation. The carboncarbon composites are employed in rocket motors, as friction materials in aircraft and high-performance automobiles, for hot-pressing molds, in
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components for advanced turbine engines, and as ablative shields for re-entry vehicles. The primary reason that these composite materials are so expensive is the relatively complex processing techniques that are employed. Preliminary procedures are similar to those used for carbon-fiber, polymer-matrix composites. That is, the continuous carbon fibers are laid down having the desired two- or three-dimensional pattern; these fibers are then impregnated with a liquid polymer resin, often a phenolic; the workpiece is next formed into the final shape, and the resin is allowed to cure.

Nano-composite: scale of reinforcement is ~ nm

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