Composite materials

The term composite can be defined in few ways. A composite is the combination of two or more dissimilar materials having a distinct interface between them such that the properties of the resulting material are superior to the individual constituting components. Composites can be defined as two or more dissimilar materials that are intimately bonded to form integrated structure. In general, two phases Matrix which is continuous and surrounds the discontinuous second phase reinforcement are present. An advanced composite material is defined as a resin, metal or ceramic matrix reinforced with the high strength and high stiffness material in continuous fiber or filament form. Example for this is Glass Fiber Reinforced Plastics (GRP) which combines the advantages of both plastics (less strong & stiff) and glass fibers (less load bearing ability & ductility). Function: i) The reinforcing phase is of low density, strong, stiff and thermally stable. The major load on the composite is born by the reinforcing phase; ii) The matrix performs the following functions. It takes the load and transfers it to the reinforcement, it binds or holds the reinforcement and protects them from mechanical and chemical damage, it also separates the individual fibers and prevents brittle cracks from passing completely across the composite section.
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General requirements of composite materials 1. The second phase (fibers or particles) must be uniformly distributed throughout the matrix and not in contact with one another 2. The constituents should not react with one another at high temperatures, otherwise the interfacial bond will become weak leading to premature failure of the composite 3. In no case the second phase loose its strength, it should be well bonded with matrix 4. Lower modulus of elasticity is expected in matrix when compared to fiber 5. Both matrix and fiber should not have different coefficient of linear expansion

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Flow chart showing classification of composites

R. Ganesh Narayanan, IITG materials polymers, ceramics, composites; Ref: engineering A. K. Bhargava

Some classes of composites

R. Ganesh Narayanan, IITG materials polymers, ceramics, composites; Ref: engineering A. K. Bhargava

Reinforcements
Reinforcements need not necessarily be in the form of long fibers. One can have them in the form of particles, flakes, whiskers, short fibers, continuous fibers, sheets. It turns out that most reinforcements used in composites have a fibrous form because materials are stronger and stiffer in the fibrous form than in any other form. The use of fibers as high performance engineering materials is based on three important characteristics => 1) smaller the fiber size, lower is the probability of having imperfections in the material. The strength of the carbon fiber decreases as its diameter increases; 2) a high aspect ratio (l/d), which allows a very large fraction of the load applied to be transferred via matrix to the stiff and strong fiber; 3) a very high degree of flexibility, which is really a characteristic of a material that has a high modulus and a small diameter. This flexibility permits the use of variety of techniques for making composites with the fibers. glass fibers, Boron fibers, carbon fibers, organic fibers, ceramic fibers, Nonoxide fibers, whiskers are generally used reinforcement material

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Matrices
Polymer matrices: A polymer is defined as a long chain molecule containing one or more repeating units of atoms joined together by strong covalent bonds. A polymeric materials is a collection of a large number of polymer molecules of similar chemical structure. IN the solid state, these molecules are frozen in space either in a random fashion or in a mixture of random and orderly fashion. Thermoplastic polymers individual molecules are linear in structure with no chemical linking between them. They are held in place by week secondary bonds such as vander waals forces. With the application of heat and pressure, these intermolecular bonds in a solid thermoplastic polymer can be temporarily broken and the molecules can be moved relative to each other to flow into new positions. Upon cooling, the molecules freeze in their new positions, restoring the secondary bonds between them and resulting in a new solid shape. Thermoset polymer in this case, the molecules are chemically joined together by crosslinks, forming a rigid, three dimensional network structure. Once these cross-links are formed during the polymerization reaction, the thermo set polymer can not be melted and reshaped by the application of heat and pressure. Thermoplastic polymers => high impact strength and fracture resistance, imparting excellent damage tolerance to the composite material; higher failure strains than thermoset R. Ganesh Narayanan, IITG polymers that provide a better resistance to matrix micro-cracking in the composite laminate

Fabrication techniques for polymeric matrices Leaky mold technique using carbon fiber and a cold-setting resin: - The apparatus has an open ended metal trough with a loose fitting top force that is T-shaped in cross section. The mold is lightly coated with stearate grease parting agent, a quantity of freshly catalyzed resin (like epoxy, polyester) is poured into the bottom of the mold and weighted amount of fiber is dropped in to it. -The resin wets the fiber bundle. After 10 mts the top force of the mold is placed over the array and heavy weight is placed on top. The excess resin is removed through topbottom face clearance. -After the resin is hardened, the mold may be opened and the smooth parallel-sided rectangular specimen is removed. The sample can be trimmed to required size.

Leaky mold technique R. Ganesh Narayanan, IITG

High pressure compression molding

Used mainly for molding thermosetting (like phenolic, alkyd) powders and rubber compounds. This method has some advantages over injection molding process. This method is performed using relatively simple tools with no sprues, runners, gates. Very little material is wasted in this. High fiber volume fractions and long fiber lengths can be made using compression molding. The compression molding process can be divided into three basic steps:

1) Charge preparation: The stack of SMC plies placed in the preheated mold (called charge). The plies are die cut in the desired shape and size from a properly matured SMC roll. Rectangular ply patterns are commonly used in the charge, however, circular, elliptical or other ply patterns can also be used 2) Mold closing: After placing the charge in the bottom half, the top mold is quickly moved to touch the top surface of the charge. The top mold is closed at a slower rate of 5-10 mm/s. As the molding pressure increases with continued mold closure, the SMC flows toward the extremities, forcing the air in the cavity to escape through the shear edges or other vents. The mold pressure ranges from 1-40 MPa. The common mold temperature is 150C. Both top and bottom are externally heated to maintain the mold surface temperature within 5C of desired value
SMCs are thin sheets of fiber pre-compounded with a thermoset resin and are employed primarily in compression molding processes.
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3) Curing: After the cavity has been filled, the mold remains closed for a fixed period of time to ensure curing and ply consolidation. The curing time will depend on factors like mold temperature, part thickness etc. At the end of curing, the part is removed and allowed to cool outside the mold. As the part cools outside the mold, it continues to cure and shrink. The location of charge placement in the mold, amount of flow in the compression molding process, temperature distribution during cooling are important parameters in compression molding process. Applications: Computer enclosures, dishwasher inner doors, light truck tailgate, automotive road wheels etc.

Compression molded rubber boots

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Schematic of composite molding press

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Autoclave molding - This is well suited for large components where double curvature and the highest quality molding are specified. - The autoclave is a pressure vessel that can generate a pressure of several atmospheres. It is also equipped with a means of producing a vacuum within any airtight membranes placed within the vessel so that volatile matter such as solvents or water vapor can be removed. Heating is closely controlled by electric heaters that warm the atmosphere (usually nitrogen), and this transfers heat to the composite layup by convection and conduction. -This method produces denser, void free moldings because of higher heat and pressure are used in the cure. Curing pressures are generally in the range 3.4 to 7x105 Pa.

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Pressure bag molding - Air pressure, usually 2.04-3.4x105 Pa, is applied to a rubber bag or sheet that covers the laid composite on the mold. Excess resin and entrapped air are removed during this process. Pressurized steam can also be used to accelerate the cure. Only female molds can be employed. Vacuum bag molding - This method uses vacuum to eliminate entrapped air and excess resin. A nonadhering file of polyvinyl alcohol or nylon is placed over the layup and sealed at the edges. A vacuum is drawn on the bag formed by the film and the composite is cured at room temperature.

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Injection molding - Widely used for high volume production of thermoplastic resin parts, reinforced and also thermoset resins. - Pellets of resin containing fiber reinforcement are fed into a hopper and then into a heated barrel containing a rotating screw that mixes and heats the material. The heated resin in then forced at high pressure through sprues and runners into a matched metal mold. Precise and complex parts can be made. - Process parameters - Melt temperature: controlled by the temperature control system of the injection unit but may be affected by injection speed and back pressure; Injection speed: Speed profile is used instead of single constant value; Injection pressure: This is not constant during mold filling stage. Injection pressure builds up during mold filling stage as the resistance to flow increases. When the mold is full, transfer from speed control to pressure control takes place. - Thermoplastic materials: Every thermoplastic resin is injection molded. They are present in filled and reinforced forms. Filled and reinforced indicate that a second, discontinuous, usually rigid phase has been blended into the polymer. Aspect ratio (largest to smallest dimension ratio) is close to 1, the second phase is referred as filler. If the aspect ratio is much larger than 1 (like in fibers), the term reinforcement is used. - Glass fibers provide higher room and high-temperature rigidity than unfilled PP.
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- Reinforcing material can be either fibrous or planar shape. In practice fibrous reinforcements are almost exclusively used with glass fibers dominating the market. Carbon or aramid fibers are also used but expensive comparatively. Planar reinforcements => talc, mica, glass flake can be used where stiffness and isotropy are required. - Orientation and redistribution of the reinforcing fibers occurs during injection molding and can exert a strong influence on the mechanical properties of the composite part. - Applications: housing for electrical tools, automotive applications, plastic drawers, R. Ganesh Narayanan, IITG metal inserts

Filament winding
- This is a process in which a filamentary yarn or tow is first wet by a resin and then uniformly and regularly wound about a rotating mandrel. The finished pattern is cured and the mandrel removed. The result can be as simple as a piece of pipe or as complex as an aircraft fuselage or an automobile frame. - Advantages: low material and labor costs, reproducibility due to robotic motions - disadvantages: tooling limitations for removable mandrels and inability to wind on negatively curved surfaces Materials: fibers => fiberglass, carbon, aramid; resins => thermoset polyesters, vinyl esters, epoxies, phenolics Fibers: fiber glass either single end or multi strand roving. Single end roving is one strand of glass filament collected into a discrete bundle during the spinning operation. Aramid fiber High strength to weight ratio compared to fiber glass, good abrasive wear resistance hence used as an external layer for structures that receive considerable wear and abrasion. Carbon fiber It is brittle comparatively and hence has tendency to break. The no. R. Ganesh Narayanan, IITG of turns and twists must be kept low when using this.

Filament winding process

Resin Filament winding can utilize resin in three distinct forms. The predominant one is as a liquid, where fiber is wet as it passes through a resin bath. Another form is prepreg tow, where the fiber is impregnated in an early step, and wound on a bobbin. A third form utilizes thermoplastic resins, which may be in the form of a dry bobbin, a powdered coating.
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Basics of process -A large number of fiber rovings are pulled from a series of creels into a liquid resin bath containing liquid resin, catalyst and other ingredients such as pigments and UV absorbers. Fiber tension is controlled by fiber guides or scissor bars located between each creel and the resin bath. - At the end of the resin tank, the resin impregnated rovings are pulled through a wiping device that removes excess resin from the rovings and controls the resin coating thickness around each roving. The most commonly used wiping devices are squeeze rollers and orifice (like wire drawing). Pulling through orifice provides better control of resin content. - Once the rovings are thoroughly impregnated and wiped, they are gathered together in a flat band and positioned on the mandrel. Typical winding speed range from 90110 linear m/min. - The filament winding can be either helical or polar winding (in figure).

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Helical winding

Polar winding
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Equipment
- Winders, mandrel & curing systems; Mandrel: metal mandrels, expandable mandrels, single use mandrels; curing system: ovens, hot oil, lamps, steam, autoclave, microwave

Process parameters
- Fiber tension: adequate fiber tension is required to maintain fiber alignment on the mandrel as well as to control resin content in the wound part. Excessive fiber tension can cause differences in resin content in the inner & outer layers, undesirable residual stresses in the finished part and large mandrel deflections. - Good fiber wet out is needed for reducing voids in a filament wound part. The following material and process parameters control fiber wet out 1) viscosity of the catalyzed resin, 2) no. of strands in a roving, which determines the accessibility of resin in each strand, 3) fiber tension, 4) speed of winding and duration of resin bath. - Proper resin content and uniform resin distribution

Defects: voids, delaminations, fiber wrinkles are predominantly occuring; voids => poor
fiber wet out, presence of air bubbles in the resin bath, improper band width resulting in gapping or overlapping, excessive resin squeeze out from the interior layers; delaminations => reducing the time lapse and brushing the wound layer with fresh resin just before starting the next winding are recommended for reduced delamination; wrinkles => improper winding tension & misalinged rovings IITG R. Ganesh Narayanan,

Layout of computer controlled filament winding machine

Layout of numerical controlled filament winding machine

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Resin transfer molding: - RTM has the potential of becoming a dominant low cost
process for the fabrication of large, integrated, high performance products Process definition: - Used to make wide variety of articles from small armrests to large water treatment plant components -A dry reinforcement material that has been shaped into a preform piece, generally called as a preform, is placed in a prepared mold cavity. The mold is closed and sealed properly. Then resin is injected into the mold cavity where it flows through the reinforcement preform, expelling the air in the cavity and wetting out or impregnating the reinforcement. -The optimum range for the low viscosity premixed resin is 200-300 cps. Important resins used are polyester, vinyl ester, epoxy. -Once curing is completed, it is removed from the mold and the process can begin again to form additional parts.

Structural reaction injection molding: - Preform and mold preparation are similar in
RTM and SRIM. Some changes in mold release and reinforcement sizings are incorporated. After mold closing is done, the resin is rapidly introduced into the mold and reacts with the reinforcement. Curing is completed shortly after the resin reaches extremities of the components. The part is removed from the mold after curing.
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SRIM process schematic

RTM process

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Difference between RTM & SRIM

- RTM resins are typically low viscosity liquids in the range 100-1000cP. Resin has two components and required preinjection mixing ratio of 100:1. The liquid parts can be mixed at low pressure. SRIM also has two part, low viscosity liquids in the viscosity range of 10-100cP. They are very reactive in comparison to RTM resins and require very fast, high pressure impingement mixing to achieve thorough mixing before entering the mold. Mix ratios of 1:1 are desirable. - In RTM there are possibilities to position the preform in the mold that provides control of the fiber content and the mechanical properties. RTM provides minimum movement of
reinforcement during filling and curing process, that allows optimum performance at minimum weight. But in SRIM there is the tendency for fiber particles to move during

the filling process as a result of rapid flow. - RTM process occurs within the mold and hence offers limited chemical exposure and limits the release of emissions during the process. - RTM disadvantages: difficult to automate the process, long cycle times possible, lack of reinforcement at the edges of the preform inside the mold, filling large parts containing a high glass content at low injection pressures and with the undeveloped nature of higher speed versions of the process.
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Process variations in RTM

Pressure injection: The method previously described utilize resin that was initially placed in reservoir and flowed by pressure differential between the reservoir and the mold outlet. The pressure differential could be caused by gravity, vacuum applied to the mold outlet, pressure applied to the reservoir or a combination of all. This process is termed as pressure injection. Resin film infusion: In this flow through thickness of the preform is seen. A mold is required on only one side of the preform. Resin is placed on the mold surface in film form so that the preform may be placed and vacuum bagging material applied without uncontrolled flow of resin. To infiltrate the preform, air is evacuated from the vacuum bag and heat is applied. The resin flows through preform. If a pressure higher than atmospheric pressure is required, an autoclave is used.

Pressure injection

Resin film infusion

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Recently developed processes Thermoformed thermoplastic materials

The laminate is loaded into the clamp frame and placed in the oven for heating stage of the process. Once the forming temperature is reached, the laminate is rapidly transferred via the clamp frame to the forming station, at which point the tool is closed and pressure is applied. The clamp frame is released just before the upper and lower tools close, allowing the laminate to slip the mold as required. Vacuum forming is also applicable for thermoplastic composites.

Thermo forming

Vacuum forming
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Metal matrix composite processing

-The critical need of high strength, light weight, high stiffness materials has in recent years resurrected much interest in continuous and discontinuous reinforced MMCs. -MMCs consists of two components at least, 1. metal matrix, 2. reinforcement. Matrix is generally an alloy. In the production of composite, the matrix and reinforcement are mixed together unlike in any alloy with two or more phases. -MMC reinforcement is divided into five types, i) continuous fibers, ii) discontinuous fibers, iii) whiskers, iv) wires, v) particulates. Reinforcements are generally ceramics like oxides, carbides, nitrides. They have excellent combinations of specific strength, stiffness at ambient temperature and elevated temperature. The typical reinforcement used are given in table.

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Typical reinforcements used in MMCs

Interfaces in MMCs - The interface region in a composite is extremely important in determining the ultimate properties of the composite. An interface is a bi-dimensional region through which there occurs a discontinuity in one or more material parameters. In practice, there is always some volume associated with the interface region over which a gradual transition in one or more material parameters occurs. -Important discontinuities are elastic moduli, thermodynamic parameters such as chemical potential, leading to chemical compound formation, thermal expansion coefficient. -The applied load is transferred from the matrix to the reinforcement via a well-bonded interface. There is a chemical potential gradient across the fiber matrix interface. The interface region thus formed generally have characteristics different from those of either of the components. -Ceramic metal interfaces are generally formed at high temperatures. Diffusion and chemical reaction kinetics are faster at elevated temperatures. Various parameters like time, temperature, pressure combined with the thermodynamic, kinetic and thermal data can be used to obtain an optimum set of interface characteristics in a given MMC. -Mechanical and chemical bonding can contribute to the bond strength.
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Processing
The MMCs can be manufactured by processes in any of the three categories, liquid phase processes, solid-phase processes, two phase (solid-liquid) processes 1) Liquid phase processes: The particulates are incorporated into a molten metallic matrix using various techniques. This is followed by mixing and eventual casting of the resulting composite mixture into shaped components or billets for further fabrication. The selection criteria for ceramic reinforcement includes, 1. elastic modulus, 2. tensile strength, 3. density, 4. melting temperature, 5. thermal stability, 6. size and shape of the reinforcing particles. Pressure infiltration or squeeze casting: IN this process, liquid metal is forced into a fibrous preform. Pressure is applied until solidification is complete. By forcing the molten metal through small pores of a fibrous preform, this method requires good wettability of the reinforcement by the molten metal. Composites fabricated by this method involves minimal reaction of reinforcement with molten metal and free of common casting defects such as porosity and shrinkage cavities. Inexpensive for making near net shaped parts. When the infiltration of fiber preform occurs readily, reactions between the fiber and the molten metal can significantly degrade fiber properties. Fiber coatings applied prior to infiltration, which improve wetting and control reactions, have been developed and can produce impressive results. In this case, caution should be taken such that fiber coatings must not be exposed to air prior to infiltration because surface oxidation alters the positive effects of coating.
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squeeze casting

Melt infiltration: In this process, a molten alloy is introduced into a porous ceramic preform, utilizing either inert gas or a mechanical device as a pressurizing medium. The pressure required to combine matrix and reinforcement is a function of the friction effects due to the viscosity of the molten matrix as it fills the ceramic preform. Wetting of the ceramic preform by the liquid alloy depends on alloy composition, ceramic preform material and surface morphology, temperature, time. This method is used to make toyota diesel piston. Drawbacks include reinforcement damage, preform compression, micro-structural non-uniformity, coarse grain size, undesirable interfacial reactions
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2) Solid phase processes

The fabrication of particulate reinforced MMCs from blended elemental powders involves a number of steps prior to final consolidation. Two methods viz., powder metallurgy method and high energy rate processing are generally used. Powder metallurgy technique: This includes blending of rapidly solidified powders with particulates, platelets, whiskers using number of steps. They are, sieving of rapidly solidified powders, blending with the reinforcement phase, pressing to 75% density, degassing, final consolidation by extrusion, forging, rolling or other hot working methods. PM methods involving cold pressing, sintering or hot pressing produce MMCs. The matrix and the reinforcement powders are blended to produce a homogeneous distribution. The blending stage is followed by cold pressing to produce green compact that is app. 80% dense. The green compact is degassed to remove any absorbed moisture from the particle surfaces. The final step is hot pressing to make fully dense composite. PM hot pressing method produces properties superior to those obtained by casting and by liquid metal infiltration methods. This process produces homogeneous distribution of whiskers when compared to that obtained with melt infiltration. Limitations: limited availability of appropriate prealloyed metal powders, high cost of metal powders, high cost of hot pressing
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Powder metallurgy technique

Processing route for continuous fiber reinforced MMCs

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Processing route for discontinuous fiber, whisker, particulate reinforced MMCs

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High energy, high rate processes This approach has been used successfully to consolidate rapidly quenched powders containing a fine distribution of ceramic particulates. In this approach, consolidation is done by applying high energy over a shot time period. Both mechanical and high electrical energy can be used for this. For eg., Al/SiC MMCs can be made by heating a customized powder blend through a fast electric discharge obtained from a generator. The high energy, high rate pulse facilitates rapid heating of the conducting powder in a die with cold walls. The rapid energy controls phase transformation, microstructural aspects that are not possible by other methods. Diffusion bonding Common solid state welding technique for joining similar or dissimilar metals. Interdiffusion of atoms at elevated temperature leads to welding. Advantages: ability to process a wide variety of matrix materials, control of fiber orientation and volume; disadvantages: processing times of several hours, cost of high processing temperature and pressure, objects of limited size can be made.
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DB process: - Two materials are pressed together (typically in a vacuum) at a specific bonding pressure with a bonding temperature for a specific holding time. -Typically 50-70% of the melting temperature of the most fusible metal in the composition. Raising the temperature aids in the inter-diffusion of atoms across the face of the joint.
Sequence for diffusion bonding a ceramic to a metal a) Hard ceramic and soft metal edges come into contact. b) Metal surface begins to yield under high local stresses. c) Deformation continues mainly in the metal, leading to void shrinkage. d) The bond is formed Making MMCs: Here primarily the metal or alloys in the form of sheets and the reinforcement material in the form of fiber are chemically surface treated for the effectiveness of interdiffusion. The fibers are placed on the metal foil in predetermined orientation and bonding takes place by press forming. However, the fibers are sometimes coated by plasma spraying or ion plating to enhance bonding strength before diffusion R. Ganesh Narayanan,the IITG bonding. DB can be done under vacuum conditions also.

Composite fabrication by diffusion bonding

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3) Two phase processes This involves mixing of ceramic and matrix with matrix containing both solid and liquid phases. Applicable two phase processes include the Osprey, rheocasting and variable codeposition of multiphase materials (VCM). Osprey deposition: In this process, the reinforcement particulates are introduced into a stream of molten alloy which is subsequently atomised by jets of inert gas. The sprayed mixture is collected on a substrate in the form of a reinforced metal matrix billet. Similar to blending and consolidation steps in PM processes for making MMCs. Rheocasting: fine ceramic particulates are added to a metallic alloy matrix at a temperature with the solid-liquid range of the alloy. This is followed by agitation of the mixture to form a low viscosity slurry. The ceramic particles are mechanically entrapped initially and are prevented from agglomeration. The ceramic particles interact with liquid matrix to effect bonding. Compocasting is an application of the rheocasting process in which particulate or fibrous materials are added to the semisolid slurry. The particles or short fibers are mechanically entrapped and prevented from settling or agglomerating because the alloy is already partially solid. This is one of the most economical methods of R. Ganesh Narayanan, fabricating a composite with discontinuous fibers.IITG

Advantages: - performed at temperatures lower than those conventionally employed in foundry practice during pouring, resulting in reduced thermochemical degradation of the reinforced surface; - Can be carried out by conventional foundry methods Disadvantages: residual pores between fibers cannot be eliminated completely, method cannot be used for fabricating fiber reinforced composites. Variable codeposition of multiphase materials:

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Deposition methods like spray forming, electroplating, CVD, PVD etc. are also used

Ceramic matrix composite processing - Occupies 40% of the total market - continuous fiber composites => fiber orientation, architecture is important - Typical fiber architecture is obtained with fine fibers is the use of fiber tows. Handling of fiber tows becomes a major factor in fiber composite processing. The most common approach in introducing the matrix is to put fiber tows through a bath that is the source of the matrix. Matrix can be a slurry, but can be a sol or a preceramic polymer too. Distribution of matrix in the tows is important. Fiber-matrix interface: -Fiber-matrix interface region is important like in the cases of MMCs and PMCs -For high toughness in fiber reinforced CMCs it is essential to produce and maintain a desirable level of interfacial shear stress to permit fiber debonding during the fracture process -Exhibit low inter-laminar and transverse tensile and shear strengths (say 2-3 MPa) -The interface must serve the various functions like controlling interfacial strength and prevent fiber matrix reactions not only during processing and fabrication but R. Ganesh and Narayanan, IITG also during service at high temperatures in aggressive environments.

Processing routes for CMCs

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Processing methods This can be classified under two broad groups like powder consolidation and chemically based methods. Powder based methods: Powder consolidation methods, like hot pressing, is extensively used for both glass based and crystalline matrices. The most common way of introducing such powders is to draw fibers (or tows) through a slurry or a sol. Hot pressing allows achievement of low to zero porosity levels is applicable to all ceramic materials. Limitations of hot pressing are two fold 1) applicable to simple shapes like plates, blocks, cylinders and not a low cost process; 2) other limitation include temperatures commonly required for low level of porosity. This temperature is of the order of 100-200 C higher than required for matrix alone, present limitations with regard to both reaction between fibers and matrices and degradation of the fibers.

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Hot pressing produces the highest densities at higher processing temperatures from 1400-1600 C, which seriously limits the type of fiber used as well as the various fibermatrix combinations. Hot pressing is applied predominantly to 2D composites like cloth laminates assuming adequate infiltration of matrix between the fibers within the cloth can be obtained. Its applicability to three and higher dimensional composites will be limited by fiber damage via buckling and from interference with densification caused by the fibers in the axial direction. HIP Method: -High densities can be achieved at low temperatures than required for hot pressing -Applicable for broader range of shapes than is hot pressing Sintering method: -Green ceramic fiber composite compact is much higher than that of a conventionally green ceramic compact because of higher fiber costs and higher composite body formation costs. - inherent problems in densifying ceramic fiber composites and temperature limitations based on fiber-matrix interactionsR. and fiber temperature limitations. Ganesh Narayanan, IITG

Chemical based methods Our interest here is to know the reactions involving a powder compact that yields a composite product in conjunction with heating, possibly with pressure, such as in HIP. Some of the examples of the processes are, Autocatalytic reaction processes (Al2O3/B4C) Displacement reactions Reactions of organo-metallic compounds Sol-gel and polymer reactions techniques Melting phase infiltration techniques Direct melt oxidation Gas phase infiltration/deposition Self propagating high temperature synthesis (SHS) => exothermic reactions results in a high temperature reaction front that actually sweeps through a compact of the reactants once the reaction is ignited at some point
R. Ganesh Narayanan, IITG High temperature reaction front Compact of reactants

Single phase compounds (TiC, TiB2) can be made & also composites directly

Fe2O3 + 2Al 2Fe + Al2O3 => Metal-ceramic composite product 10Al + 3TiO2 + 3B2O3 5Al2O3 + 3TiB2 4Al + 3TiO2 + 3C 2Al2O3 + 3TiC => Ceramic composite product

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Polymer materials Polymers => complex giant molecules of higher molecular weight (104-107). These big molecules are also called as macromolecules. They are basically hydrocarbons and frequently contain atoms of oxygen, chlorine, fluorine, nitrogen or sulphur. Polymer can be categorized into plastic, fiber, resin Plastics => solid substances in their final state are made plastic at some stage during their fabrication, enabling them to be moulded under the application of heat and pressure is called plastic. Examples => PVC, polyethylene, nylon, perspex, teflon, bakelite. Fibers => Polymers drawn into long thread like molecules (length atleast hundred times its diameter). Examples => nylon, polyester, cellulose etc. Liquid resins => Polymers used in liquid form like adhesives, sealants Polymerization => process by which monomers are joined together to form large, chain like molecules. The chemical reactions in the process can be induced by application of heat and pressure or by using catalyst. Mechanism two types => 1. addition or chain polymerization, 2. condensation or step polymerization
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Addition or chain polymerization Long chain macromolecules are formed by chemical reaction of one or more types of monomer units having one double bond prior to polymerization. The chemical reaction is initiated by a substance called initiator (I). This has one unpaired electron called as free radical (R*).
Monomer (M) combines with free radical Propagation Termination

Single bond Monomer combines with free radical

Propagation
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C* => unpaired electron at right end

Finally two growing chains may react to terminate growth activity of each other and result in macromolecule

Termination reaction

Examples of additional polymers include polyethylene, polypropylene, PVC, poly vinyl alcohol, poly vinyl acetate, polystyrene, poly methyl methacrylate

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Condensation polymerization A polymer is produced by the chemical reaction of at least two bi- or poly-functional monomer units with the production of a non-polymerizable molecule with water as by product. The reaction continues until almost all the monomeric reagent of one type is used up. Examples for condensation polymerization include polyester, phenol formaldehyde, polyurethanes, epoxies.
Polycondensation reaction

dicarboxylic acids

polyamines

polyamide

A molecule of water is given off as by product and the nylon is formed. The properties are determined by the R and R' groups in the monomers.

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