MMB813PE: COMPOSITE MATERIALS UNIT-1 1. Introduction: 1.1 BACKGROUND OF COMPOSITE Many of our modern technologies require materials with unusual combinations of properties that cannot be met by the conventional metal alloys, ceramics, and polymeric materials. This is especially true for materials that are needed for aerospace, underwater, and transportation applications. For example, aircraft engineers are increasingly searching for structural materials that have low densities, are strong, stiff, and abrasion and impact resistant, and are not easily corroded. This is a rather formidable combination of characteristics. Frequently, strong materials are relatively dense; also, increasing the strength or stiffness generally results in a decrease in impact strength. Material property combinations and ranges have been, and are yet being, extended by the development of composite materials. Generally speaking, a composite is considered to be any multiphase material that exhibits a significant proportion of the properties of both constituent phases such that a better combination of properties is realized. According to this principle of combined action, better property combinations are fashioned by the judicious combination of two or more distinct materials. Property tradeoffs are also made for many composites. Within the last forty years there has been a rapid increase in the production of synthetic composite, those incorporating fine fibers in various plastics (polymer) dominating the market. Prediction suggests that the demand for composite will continue to increase steadily with metal and ceramic based composites making a more significant contribution. Nowadays, the composite industry is still evolving, with much of the growth now focused around renewable energy. Wind turbine blades, especially, are constantly pushing the limits on size and require advanced composite materials, for example, the engineers can design to tailor the composite based on the performant requirements, making the composite sheet very strong in one direction by aligning the fibers that way, but weaker in another direction where strength is not so important. The engineers can also select properties such as resistance to heat, chemicals, and weathering by choosing an appropriate matrix material. In recent years, an increasing environmental consciousness and awareness of the need for sustainable development have raised interest in using natural &fibers as reinforcements in composites to replace synthetic fibers. In recent years, the aerospace community has increased the use of composites in aeronautic and space vehicles 1.2 Definition of composite materi Composite materials are those materials that are made from two or more constituent materials with each material having its unique properties and characteristics. The composite materials can be classified based on the two categories of materials that are used, the matrix (i.e. binder) and the reinforcements. The matrix provides support to the reinforcement whereas the reinforcement enhances the physical and mechanical properties of the composite. 1.3 Typical engineered composite materials include: Reinforced concrete and masonry Composite wood such as plywood Reinforced plastics, such as fiber-reinforced polymer or fiberglass Ceramic matrix composites (composite ceramic and metal matrices) Metal matrix composites and other advanced composite materials 1.4 A material is considered as the composite material when 1. Combination of materials should result in significant property changes 2. Content of the constituents is generally more than 10 % 3. In general, the property of one constituent is much greater (2 5) than the other constituent 1.5 Why we need these composite materials? There is unabated thirst for new materials with improved desired properties. All the desired properties are difficult to find in a single material. For example, a material which needs high fatigue life may not be cost effective. The list of the desired properties, depending upon the requirement of the application, is given below. Strength Stiffness: Toughness High corrosion resistance High wear resistance High chemical resistance cee ae er eee7. Reduced weight (the structural elements need to be light as well as strong) 8. High fatigue life 9. Thermal insulation or conductivity 10. Electrical insulation or conductivity 11. Energy dissipation 12. Reduced cost The word “composite” means “consisting of two or more distinct parts”. Thus a material having two or more distinct constituent materials or phases may be considered to be a composite material. Reinforcement and the matrix are the two phases of the composite material. However, we recognize materials as composites only when the constituent phases will not dissolve into one another and have significantly different physical properties, and thus the composite properties are noticeably different from the constituent properties. One constituent is called the reinforcing phase and the one in which it is embedded is called the matrix. The reinforcing phase material may be in the form of fibers, particles, or flakes. The matrix phase materials are generally continuous. One constituent is called the reinforcing phase and the one in which it is embedded is called the matrix. The reinforcing phase material may be in the form of fibers, particles, or flakes. The matrix phase materials are eneral continuous. Reinforcement in the Compo: Reinforcement can be fibers, fabric particles, or whiskers. These reinforcements fundamentally used to increase the mechanical properties of a composite. The main purpose of the reinforcement is to: © Provide superior levels of strength and stiffness to the composite. © Reinforcing materials (graphite, glass, SiC, alumina) may also provide thermal and electrical conductivity, controlled thermal expansion, and wear resistance in addition to structural properties. © These are the main load carrying constituents. The reinforcing materials, in general, have significantly higher desired properties. Hence, they contribute the desired properties to the composite.1.7 Matrix material in the Composites It transfers the strength and stiffness to the matrix material. The matrix material is the homogeneous and monolithic material in which a reinforcement system of acomposite is embedded and is completely continuous. The main purpose of the Matrix is to: To bind the reinforcements together by virtue of its cohesive and adhesive characteristics. To transfer the load to and between reinforcements, the matrix allows the strength of the reinforcements to be used to their full potential by providing effective load transfer from external forces to the reinforcement. The matrix material holds the fibers together. It transfers the load uniformly between fibers. Further, in case a fiber is broken or fiber is discontinuous, then it helps to redistribute the load in the vicinity of the break site. It provides protection to fibers from environmental effects. It provides better finish to the final product. The matrix material enhances some of the properties of the resulting material and structural component (that fiber alone is not able to impart). For example, such properties are: transverse strength of a lamina, impact resistance2. CLASSIFICATION OF COMPOSITE MATERIAL Fveventerceacempontes| | Parcitecompostes | srucura compontes —_ ae] oe] Sa] Se 2.1 Based on Matrix: 2.1.1. Metal Matrix Composites (MMC ‘A metal matrix composite (MMC) is composite material with at least two constituent parts, one being a metal necessarily, the other material may be a different metal or another material, such as a ceramic or organic compound. There is some overlap between MMCs and cermets, with the latter typically consisting of less than 20% metal by volume. Metal matrix composites are composed of a metallic matrix (Al, Mg, Fe, Cu etc) and a disperse ceramic (oxide, carbide) or metallic phase (Pb, Mo, W etc). Some examples of most commonly used metallic matrix configurations are: e@ Aluminum-based composites; aluminum as matrix can be either cast alloy or wrought alloy (ie, AIMg, AIMg, AlCuMn, AlZnMgCu, AlCu, AlCuMg) © Magnesium-based composites(Mg-Ca, Mg—Al, Mg-Zn, Mg-SiC »Mg-Alumina) @ Titanium-based composites(Zr—Ti-based) © Copper-based composites© Super alloy-based composites The first legitimate question that a reader might ask is: Why MMCs? There is a two prong answer to this, advantages with respect to unreinforced metals and with respect to other composites such as polymer matrix composites (PMCs). 1. With respect to metals, MMCs offer: a. Major weight savings due to higher specific mechanical properties b. Dimensional stability (compare, for example, SiC/Al to Al) c. Higher-temperature capabilities, i.e., creep resistance d. Improved cyclic fatigue characteristics 2. With respect to PMCs, MMCs offer: a. Higher strength and stiffness b. Higher service temperatures c. Higher electrical conductivity (electrical grounding, space charging) d. Higher thermal conductivity e. Better transverse properties (i.e., transverse to the fiber) f. Improved joining characteristics Types of MMCs All MMCs have a metal or a metallic alloy as the matrix. The reinforcement can be metallic or ceramic. In an unusual case, the reinforcement is actually in the form of a fiber-reinforced PMC (a sheet of glass fiber-reinforced epoxy or aramid fiber- reinforced epoxy). There are four kinds of MMCs: . Particle-reinforced MMCs . Short fiber- or whisker-reinforced MMCs . Continuous fiber- or sheet-reinforced MMCs . Laminated or layered MMCs Rwnep Figure shows schematically these different types of MMCs. The reader can easily visualize that the continuous fiber-reinforced composites will be the most anisotropic of all. Table provides examples of some important reinforcements used in MMCs as well as their aspect (length/diameter) ratios and diameters.Whiskers Short Fibers sheet Laminate Table Typical reinforcements used in metal matrix composites Type ‘Aspect Diameter Examples ratio Particle 14 Short fiber or 10-10,000 1-5 um_—C, SiC, AlbOs, AbOs + whisker SiO. Continuous >1,000 3-150 umSiC, AhOs, C, B, W, fiber Nb-Ti, Nb3Sn Nanoparticle 1-4 <100 nm C, AbOs, SiC Nanotube >1,000 <100 nm_C Particle or discontinuously reinforced MMCs (one uses the term discontinuously reinforced MMCs to indicate MMCs having reinforcements in the form of short fibers, whiskers, or particles) have assumed special importance because of the following reasons: © Particle-reinforced composites are inexpensive vis-d-vi 9continuous fiber- reinforced composites. Cost is an important and essential item for large volume usage. © Processing by casting or powder metallurgy, followed by conventional secondary processing by rolling, forging, and extrusion, can be used. Higher use temperatures are possible than with the unreinforced metal. Enhanced modulus and strength. Increased thermal stability. Better wear resistance. Relatively isotropic properties compared to those of the fiber- reinforced composites. Characteristics of MMCs One of the major driving forces for MMCs is of course the enhanced stiffness and strength; there are, however, other characteristics which may be equally valuable. As an example, we can cite the ability to control the thermal expansion in applications involving electronic packaging. By adding ceramic reinforcements, one can generally reduce the coefficient of linear thermal expansion of the composite. Electrical and thermal conductivity characteristics may be important in some applications. Superconductors require obviously superconducting characteristics. The metallic matrix provides a high thermal conductivity medium in case of an accidental quench besides holding the tiny filaments together. Other important characteristics that may be of immense values include wear resistance (e.g., in WC-Co composites used in cutting tools or oil drilling inserts SiC/Al_rotor in brakes). Thus, although one commonly uses the term reinforcement, by particle or fibers in the context of MMCs, it is worth pointing out that stiffness and strength enhancement may not always be the most important characteristics in many cases. 2. 1.2. Ceramic Matrix Comy les (CMC Ceramic matrix composites (CMCs) are a subgroup of composite materials as well as a subgroup of ceramics. They consist of ceramic fibers embedded in a ceramic matrix. The matrix and fibers can consist of any ceramic material, whereby carbon and carbon fibers can also be considered a ceramic material. Ceramic Matrix Composites are designed to improve toughness of conventional ceramics, the main disadvantage of which is brittleness, Ceramic Matrix Composites are reinforced by 10either continuous (long) fibers or discontinuous (short) fibers properties of ceramic matrix composite © High mechanical strength even at high temperatures High thermal shock resistance High stiffness High toughness High thermal stability Low density High corrosion resistance even at high temperatures Some examples of ceramic metal composite: Alumina matrix composite Silicon fiber reinforced glass-ceramics Aluminum oxide CMC Carbon-carbon composite CMC materials overcome the major disadvantages of conventional technical ceramics, namely brittle failure and low fracture toughness, and limited thermal shock resistance. Therefore, their applications are in fields requiring reliability at high-temperatures (beyond the capability of metals) and resistance to corrosion and wear. Polymer Matrix Composites (PMC. A polymer matrix composite (PMC) is a composite material composed of a variety of short or continuous fibers bound together by an organic polymer matrix. PMCs are designed to transfer loads between fibers through the matrix. Some of the advantages with PMCs include their lightweight, high stiffness and their high strength along the direction of their reinforcements. Other advantages are good abrasion resistance and good corrosion resistance. The properties of the PMC depend on the matrix, the reinforcement, and the inter phase. Consequently, there are many variables to consider when designing a PMC. These include not only the types of matrix and reinforcement but also their relative proportions, the geometry of the reinforcement, and the nature of the inter phase. Each of these variables must be carefully controlled to produce a structural material optimized for the conditions for which it is to be used. The polymeric matrix materials are further divided into: 1. Thermoplastic — which soften upon heating and can be reshaped with heat and pressure a2. Thermoset — which become cross linked during fabrication and does not soften upon reheating The following are the thermoplastic materials: . polypropylene, . polyvinyl chloride, nylon, . polyurethane, . poly-ether-ether ketone (PEEK), . polyphenylene sulfide (PPS), . polysulpone. The key features of the thermoplastic matrix materials are: 1. higher toughness 2. high volume 3. low cost processing 4. The use temperature range is up to 225 °C The thermoset matrix materials are: 1. polyester 2. epoxy 3. polyimide The key features of these materials are given for individual material in the following. Polyesters 1. Used extensively with glass fibers 2. Inexpensive 3. Light weight 4. Temperature range upto 100 -<. 5. Resistant to environmental exposures NAWRONE 1. Expensive 2. Better moisture resistance 3. Lower shrinkage on curing 4. Use temperature is about 175 -< Polyimide 1. Higher use temperature about 300 -© 2. Difficult to fabricate What are the problems with the use of polymer matrix materials? 1. Limited temperature range. 2. Susceptibility to environmental degradation due to moisture, radiation, atomic oxygen (in space) 3. Low transverse strength. 4. High residual stress due to large mismatch in coefficients of 12thermal expansion between fiber and matrix. 5. Polymer matrix cannot temperature. Penrose ane Thermoplasti Thermoplastics are usually formed by the addition of polymerization. It contains long-chain linear polymers and held together by weak Van der Waal forces. Usually becomes soften on heating and stiffen on cooling. They are expensive. Thermoplastic is soluble in organic solvents. They are usually soft, weak and less brittle in nature. Can be remolded. An example of thermoplastic is polythene. Advantages of polymer matrix be used near or above the glass transition Prkoraat re aa Thermosetting Plastic Thermosetting plastics are oft formed by the condensation polymerization. It contains a 3D network structure | constructed with strong covalent bonds. It does not become soft on heating. “They are cheap. Thermosetting plastics are insoluble in organic solvents. They are usually hard, strong and more brittle in nature. They can't be remolded. "An example of Thermosetting plastic is Bakelite. e Low densities © Good corrosion resistance ¢ Low thermal conductivities e Low electrical conductivities © Good formability 2.2 Based on Reinforcement reinforced Seructaly reinforced Dispersion srenetened2.2.1 Particulate Composites Particulate Composites consist of a matrix reinforced by a dispersed phase in form of particles. These are the cheapest and most widely used. They fall in two categories depending on the size of the particles. 1. Composites with random orientation of particles. 2. Composites with preferred orientation of particles. Dispersed phase of these materials consists of two-dimensional flat platelets (flakes), laid parallel to each other. 2.2.2 Fibrous Composites 1. Short-fiber reinforced composites. Short-fiber reinforced composites consist of a matrix reinforced by a dispersed phase in form of discontinuous fibers (length < 100*diameter). I. Composites with random orientation of fibers. I. Composites with preferred orientation of fibers. 2. Long-fiber reinforced composites. Long-fiber reinforced composites consi: form of continuous fibers. 1. Unidirectional orientation of fibers. Il. Bidirectional orientation of fibers (woven). 2.2.3 Laminate Comp of a matrix reinforced by a dispersed phase in When a fiber reinforced composite consists of several layers with different fiber orientations, it is called multilayer (angle-ply) composite. Sheets (panels) with different orientation of high strength directions are stacked and glued together, producing a material with more isotropic strength in the plane. Examples are plywood and modern skis. 2.2.4 Sandwich panels Strong, stiff end sheets are bonded to lightweight core structure, for instance honeycomb which provides strength to shear. It is used in roofs, walls and aircraft structures. 143. Functional requirements of reinforcement and matrix The primary functions of the matrix are to transfer stresses between the reinforcing fibers (hold fibers together) and protect the fibers from mechanical and/or environmental damages. A basic requirement for a matrix material is that its strain at break must be larger than the fibers it is holding. The primary function of the fibers is to carry the loads along their longitudinal directions. Common fiber reinforcing agents include The primary functions of the additives (modifiers, fillers) are to reduce cost, improve workability, and/or impart desired properties. 3.1 Role of matr To give shape to the composite part To keep the fibers in place To transfer stresses to the fibers To protect the reinforcement from the environment, such as chemicals and moisture e To protect the surface of the fibers from mechanical degradation © Toact as shielding from damage due to handling 3.2 Role of reinforcement: e = The strength to the composite material is important mainly by reinforcement © They serve additional purpose additional purpose of heat resistance on conduction, resistance © To corrosion and provide rigidity e A reinforcement that embellishes the matrix must be stronger and stiffer than matrix and capable of changing failure mechanism of composites e Also their contribution to other properties such as the co- efficient of thermal expansion and conductivity etc is remarkable e The tensile strength of composite materials is 4-6 times higher than conventional materials such as steel, aluminum, etc. © They have better torsion and stiffness properties. e thas a high fatigue endurance limit (ultimate tensile strength of up to 60%). 15They are 30-45% lighter than aluminum structures designed for the same functional requirements. Also has low embedded energy. Composites make less noise during operation and provide less vibration. Composite materials are additional versatile. 5. Advantages of composite materials: They are light in weight and have low density. It has high creep resistance. Strength-to-weight and stiffness-to-weight are greater than in steel or aluminum. Fatigue properties are higher than normal engineering metals. Composites cannot corrode like steel. Ease of fabrication of large advanced structural shapes or modular-modular constructions. The ability to include sensors into the fabric to monitor its performance-smart composites. It has excessive resistance to impression damage. 6. Disadvantages of composite material: It has an excessive price for raw materials and manufacture. Composites are extra brittle than wrought metals, thus they get additionally damaged. The transverse properties are also weak. The matrix is weak, so there is very little toughness. Reuse and disposal of composite material will be difficult. It is difficult to attach. Difficulty with analysis. Costs may fluctuate. 7. Application of composite material 2. Metal matrix composites are used in amyriad of applications. The high strength-to-weight ratio, enhanced mechanical and thermal properties over conventional materials and tail or ability of properties make them very attractive in a variety of applications. Increasingly MMCs have been used in several areas including: Aerospace Transportation (automotive and railway) 16er anaY Electronics and thermal management Filamentary superconducting magnets Electric power transmission Recreational products and sporting goods Wear-resistant materials In aerospace applications, low density, tailored thermal expansion and conductivity, and high stiffness and strength are the primary drivers. In this industry, performance often outweighs cost considerations in materials development. MMCs have been used in several applications in aerospace components. This stems in large part to the fact that materials with increased specific stiffness and strength can significantly enhance the performance of the aircraft. An important application for MMCs is in missiles. With increasing performance demands for missiles, conventional aluminum alloys do not have the required strength and temperature resistance. The driving force for lightweight railway vehicles has also prompted the use of high-performance MMCs . A conventional brake system for a railway vehicle, consists of four brake disks, calipers, hand brake, and electromagnetic track brake. A very important market area for aluminum and to a lesser degree copper matrix MMCs is in electronic packaging and thermal management. Metal matrix composites can be tailored to have optimal thermal and physical properties to meet requirements of electronic packaging systems, e.g., cores, substrates, carriers, and housings. Extensive use is made of metal matrix composites in applications requiring wear resistance. Carbides, in general, and tungsten carbide, in particular, are very hard materials that is very useful for cutting, grinding, drilling, roll surfaces for rolling mills. 8. What are the factors that affect the composite propert There are various factors upon which the properties of the composite depend. Following are the various factors: 1. ae eee ee Properties of the constituent materials. Apart from this, the properties of other phases present, like additives, fillers and other reaction phases also affect the properties of the composite. Length of the fiber. Orientation of the fibers (with respect to the loading direction). Cross sectional shape of the fiber. Distribution and arrangement of the fibers in the matrix material. Proportions of the fiber and matrix material, that is, volume 17fractions of the constituent materials. 9. What are the different forms of composites? 1. Unidirectional lamina: e It is basic form of continuous fiber composites. @ A lamina is also called by ply or layer. @ Fibers are in same direction. © Orthotropic in nature with different properties in principal material directions. For sufficient number of filaments (or layers) in the thickness direction, the effective properties in the transverse plane (perpendicular to the fibers) may be isotropic. Such a composite is called as transversely isotropic. 2. Woven fabri e@ Examples of woven fabric are clothes, baskets, hats, etc. e Flexible fibers such as glass, carbon, aramid can be woven in to cloth fabric, can be impregnated with a matrix material. 3. Laminate: e Stacking of unidirectional or woven fabric layers at different fiber orientations. © Effective properties vary with: Orientation Thickness Stacking sequence 4. Hybrid composites The hybrid composite are composites in which two or more types of fibres are used. Collectively, these are called as hybrids. The use of two or more fibers allows the combination of desired properties from the fibers. For example, combination of aramid and carbon fibers gives excellent tensile properties of aramid and compressive properties of carbon fibers. Further, the aramid fibers are less expensive as compared to carbon fibers. composites and ceramic matrix composites olymer Matrix (Metal Matrix ‘eramic Matrix ‘omposites ‘omposites ‘omposites 18lodulus Medium Very High Very High Strength ery High (tension) [High (tension) Medium (tension) High (compression) [High (compression) [High (compression) Density Low Medium Medium rep : High High Low [Resistance |Fracture . . High Medium Low (Toughness Fatigue High Medium Low ‘@ Sheet Molding [Solid State © Cold-pressing [Fabrication © Injection e Powder and sintering lethods Molding Metallurgy ¢ Polymer © Prepreg Tape _ [Liquid State Infiltration and Lay-up © Stir Casting Pyrolysis (PIP) e Pultrusion e Pressure Infiltration © Spray Deposition Ease of Easy Difficult Medium Fabrication Cost Low Medium High ‘Current status | Extensively used | Moderately used __| Rarely used 11. Composite Materials — Applications for the Future beyThe world of composite materials has uncapped potential for a wide variety of applications, just waiting to be discovered. Sectors that have predominantly used conventional materials such as metals will be looking to realize gains from the use of composites. The COVID-19 pandemic has accelerated this shift, due to increasing steel prices and reduced availability. Engineers and manufacturers have had to think outside the box, using alternative materials that achieve the same stiffness and weight requirements, within a given space frame. One industry that is growing rapidly and can harness the benefits of composites is the development and manufacture of electric motors. These motors use heavier materials such as copper, magnets and batteries, therefore, the structural elements need to be light as well as strong; composites fit this purpose exactly Companies such as ZeroAvia and Vertical aerospace are looking to push the envelope of what is possible. Their long-term plans of making electric aircraft commercially viable may look to utilize composite materials for the purposes of reduced maintenance, increased range and efficiency. The future of composite materials is an extremely promising one, with the automotive and aerospace sectors driving new developments. With the increase in electric vehicles on the road and the advent of electric urban taxis, we will continue to see the wider use of composites for advanced structures. This will enable price reductions as processes are refined and enable technology to filter down to other industri 20Unit-2 Reinforcements Reinforcement materials for metal matrix composites can be produced in the form of continuous fibers, short fibers, whiskers, or particles. The parameter that allows us to distinguish between these different forms of reinforcements is called the aspect ratio. Aspect ratio is nothing but the ratio of length to diameter (or thickness) of the fiber, particle, or whisker. Thus, continuous fibers have an aspect ratio approaching infinity while perfectly equiaxed particles have an aspect ratio of around one, Table.1 lists some important reinforcements available in different forms for metallic matrix materials. Ceramic reinforcements combine high strength and el with high-temperature capability. Continuous ceramic fibers are also, however, more expensive than ceramic particulate reinforcements. modulus Fibrous Materi One can transform practically any material (polymers, metals, or ceramics) into fibrous form. We can arbitrarily define a fiber as an elongated material having a more or less uniform diameter or thickness of less than 250 imaian aspect ratio of more than 100. Note that this is not only an operational definition but also a purely geometrical one that applies to any material. Fibers have some unique features that stem mainly from their relatively small cross- section and large aspect rati + High degree of flexibility. + Higher strength than the bulk material of the same composition. Table.1 some important reinforcements for metal matrix composites Type Aspect Diameter _ Examples ratio Particle 1-4 T25um Sic, AlOs, BN, Bic, WC Short fiber or 10-10,000 1-Sum —C, SIC, Al,Os, AlsO3 + whisker sid, Continuous fiber >1,000 3-150 __—SiC, ALO, C, B, W, Nb~ um Ti, Nbssn Nanoparticle 14 <100nm C, Al:Os, SiC Nanotube 1,000 __<100nm_C The long length of fibers also makes it imperative, in most cases, to incorporate them in some continuous medium, which serves as the matrix to hold fiber together to make a fi reinforced composite. It should be emphasized that this, by no means, is the sole purpose of the matrix in a composite. The metal matrix does make important contributions to the overall performance of an MMCCarbon Fibers Carbon is a very light element, has a theoretical density of 2.27 g/cm3, and exists in a variety of forms. The (wo most important forms of carbon are diamond and graphite. Among the relatively new forms of carbon are the Buckminster Fullerene, also known as Buckyball and the drawn out version of Buckyballs, which may be in the form of nanotubes or nanowires, and graphene which is nothing but sheet of carbon atoms in the form of graphite. It is the graphitic form of carbon that is important in understanding the carbon fibers. The hexagonal structure of carbon in the graphitic form Carbon fibers are fabricated by controlled pyrolysis of an organic fiber precursor. As it turns out, the concept of starting with an organic precursor fiber and converting to an inorganic fiber is quite general, as we shall see for ceramic fibers. Depending on the precursor and the processing route, one can obtain a variety of carbon fibers with different strengths and moduli. Some important types of carbon fibers are high strength (HS), high modulus (HM), intermediate modulus (IM), super high modulus (SHM), etc. Polyacrylonitrile (PAN) is commonly used as a precursor fiber for making carbon fibers. Pitch-based carbon fibers are also important; carbon fibers obtained from pitch can have much superior properties than those obtained from a PAN precursor. The steps common to all processes of carbon fiber manufacture are as follows: (a) Fiberization, i.e., extrusion of a polymer melt or solution into a precursor fiber. (b) Stabilization (oxidation or thermosetting) is done at relatively low temperatures (200- 450°C), usually in air, This renders the precursor infusible during subsequent high- temperature processing. (©) Carbonization is carried out in an inert atmosphere (pure N2 generally) at 1,000-2,000°C. At the end of this step, the fiber has 85-99 % carbon content. (d) Graphitization (optional) is done in Ar or N2 at a temperature greater than 2,500°C. This step increases the carbon content to more than 99 % and imparts a very high degree of preferred orientation to the fiber. Based on precursor fiber materials, carbon fibers are classified into: + PAN-based carbon fibers + Pitch-based carbon fibers + Mesophase pitch-based carbon fibers + Isotropic piteh-based carbon fibers + Rayon-based carbon fibers © Gas-phase-grown carbon fibers PAN-Based Carbon Fibers A flow diagram showing the various processing steps for PAN-based carbon fiber is shown in Fig. The PAN precursor has a flexible polymeric chain structure, but it has an all-carbon backbone chain containing polar nitrile groups. During the stabilization treatment, thePAN precursor fiber is heated to 220°C under tension. During this treatment, the nitrile groups form a ladder structure, a rigid and thermally stable structure. During this stabilization treatment, oxygen is absorbed and it cross-links the chains, the fibers turn black, and a stable ladder structure is formed. This treatment, done under tension, helps in maintaining the orientation of the ring structure even after unloading. During the carbonization treatment around 1,500 C, well-developed hexagonal networks of carbon form and a considerable amount of gases is evolved. This gas evolution is partly responsible for some crack formation in the fiber, resulting in a lower tensile strength. Commercially produced carbon fibers have a protective surface coating, called a sizing or size. The size serves two purposes: (1) Ease of handling of the fiber and (2) Improved adhesion with a polymeric matrix. Uncoated carbon fibers pick up surface charge easily when they come in contact with rubbing surfaces such as rollers, pulleys, guides, and spools. Handling of uncoated carbon fibers (winding, weaving, or braiding) can cause fiber breakage, and tiny fragments of carbon fibers can become airborne and short electrical machinery. PAN Polymer 1 Siig 20) PAN Precursor ‘Fiber ‘Oxdavon (200-4004) yv ‘Stabilized (Oxidized) Fiber ]_cresmon sie Carbon Fiber Grapbiteion 2000-30200) Yv Graphite Fiber Fig: Flow diagram for the fabrication of PAN-based carbon fiberPitch-Based Carbon Fibers Next to PAN, pitch is an important precursor material for producing carbon fibers. Pitch is commonly obtained from one of the following three sources: + Petroleum asphalt * Coal tar + Polyvinyl chloride (PVC) All pitches, irrespective of the source, are thermoplastic in nature. This means the pitch precursor must be first stabilized against melting during pyrolysis. A schematic of the process of making carbon fibers from pitch is shown in Fig. It involves the following steps + Extrusion or melt spinning into fibrous form * Stabilization between 250 and 400 C + Graphitization coat ta Refine Adjust Mal. We and Chemical Composition Pexoleum ‘pia ute ae] tics ach | pia hers yy Macnee “Thermal Degradation oniation Graphite gaton |g ermaty ers Foes [| stale rites seaghiteaon Fig. Schematic of the process of making carbon fiber from a pitch ‘Table presents property data for three different types of PAN-based carbon fibers, Note the high density and high modulus of pitch-based fibers compared to PAN-based fibers. The stress applied at very high temperatures (as high as 3,000°C) during the graphitization step (increases the degree of order in carbon fibers). This is also accompanied by a large increase in the longitudinal elastic modulus of the fiber. ‘The tensile strength of PAN-based fibers when subjected to high-temperature treatment, however, decreases. ‘This is attributed to the presence of discrete flaws on the fiber surface and within the fiber.Structure of Carbon Fibers Here we provide the salient features of the structure of carbon fibers. Scanning electron micrographs of pitch-based carbon fibers showing graphitic, sheet-like morphology at a sub micrometer level, as seen in a transmission electron microscope, the microstructure of carbon fibers is quite heterogeneous. In particular, there is a pronounced irregularity in the packing of graphitic lamellae inward from the fiber surface. The basal planes are much better aligned in the near surface region of the fiber. In very general terms, the graphitic ribbons are oriented more or less parallel to the fiber axis with random interlinking of layers, longitudinally and laterally Carbon Nanotubes, Nanoparticles, and Graphene Carbon nanotubes (CNTs) are essentially cylindrical tubes consisting of carbon atoms. The cylindrical object has a diameter on the nm scale, <50 nm. There length can be several micrometers long. There can be single walled nanotubes (SWNT) or multiwall nanotubes (MWNT). Since they are so small, it is not easy to determine their mechanical properties experimentally. In the literature, one findsall kinds of data. Since they have a hollow tube like structure, their specific gravity is low (1.3-2), very high modulus (1 TPa), and strength between 10 and 50 GPa. The reader should take these values with a grain of salt. Carbon nano particles are more or less spherical particles of carbon with a diameter less than 100 nm. Graphene, on the other hand, is a two-dimensional sheet structure made of carbon atoms arranged in the form of graphitic hexagons. Graphene is very thin and supposed to be very strong. Glass Fibers Glass fiber compositions of steel or aluminum alloys are available, there are many of different chemical compositions of glass fibers that are commercially available. Common glasses fibers are silica based (~50-60 % SiOz) and contain a host of other oxides of calcium, boron, sodium, aluminum, and iron, The designation E stands for electrical because E glass is a good electrical insulator in addition to having good strength and a reasonable ‘Young's modulus; C stands for corrosion and C glass has a better resistance to chemical corrosion than other glasses; S stands for the high silica content that makes S_ glass withstand higher temperatures than other glasses. It should be pointed out that most of the continuous glass fiber produced is of the E glass type but, notwithstanding the designation E, electrical uses of E glass fiber are only a small fraction of the total market. a generic name like carbon fiber or steel or aluminum. Just as differentTable: Approximate chemical compositions of some glass fibers (wt.%) ‘Composition E glass Class SiOz 35.2 65.0 AbOs 8 4 0 0 C20 18.7 14.0 MgO 4 3 6 0 NaO 0. 8 5 K:0 - - B03 2 ZL, 3 Fabrication of glass fiber low Batch mixing Batch hopper stfimace bushing and size applicator Strand traverse Fig. Schematic of glass fiber manufacture Figure shows schematically the conventional fabrication procedure for glass. fibers (specifically, the E glass fibers that constitute the workhorse of the resin reinforcement industry). The raw materials are melted in a hopper and the molten glass is fed into the electrically heated platinum bushings or crucibles; each bushing contains about 200 holes at its base. The molten glass flows by gravity through these holes, forming fine continuous filaments; these are gathered together into a strand and a size is applied before it is a wound on a drum. The final fiber diameter is a function of the bushing orifice diameter; viscosity, which is a function of composition and temperature; and the head of glass in the hopper. In many old industrial plants the glass fibers are not produced directly from fresh molten glass. Instead, molten glass is first tured into marbles, which after inspection are melted in the bushings. Modern plants do produce glass fibers by direct drawing. Figure shows some forms in which glass fiber is commercially available.Glass filaments are easily damaged by the introduction of surface defects. To minimize this and to make handling of these fibers easy, a sizing treatment is given. The size, or coating, protects and binds the filaments into a strand, Structure of Glass fibre Inorganic, silica-based glasses are analogous to organic glassy polymers in that they are amorphous, ie., devoid of any long-range order that is characteristic of a crystalline material. Pure, crystalline silica melts at 1,800 °C. However, by adding some metal oxides, we can break the Si-O bonds and obtain a series of amorphous OP ie ae ae oy Ae © e@ we = ne Loar Fig. Amorphous structure of glass: (a) a two-dimensional representation of silica glass network and (b) a modified network that results when NazO is added to (a). Note that Na* is ionically linked with O~ but does not join the network directly Density (g/em3 ) 2.55 Tensile strength (MPa) ‘1,750 Young’s modulus (GPa) 70 Coefficient of thermal expansion (K1 ) 4.7 X 10° ‘The addition of other metal oxide types (Table) serves to alter the network structure and the bonding and, consequently, the properties. Note the isotropic, three-dimensional network structure of glass; this leads to the more or less isotropic properties of glass fibers. That is, for the glass fiber, Young’s modulus and thermal expansion coefficients are the same along the fiber axis and perpendicular to it. This is unlike many other fibers, such as aramid and carbon, which are highly anisotropic.Boron Fibers Boron is an inherently brittle material. It is commercially made by chemical vapor deposition (CVD) of boron on a substrate, that is, boron fiber as produced is itself a composite fiber. In view of the fact that rather high temperatures are required for this deposition process, the choice of substrate material that goes to form the core of the finished boron fiber is limited. Generally, a fine tungsten wire is used for this purpose. A carbon substrate can also be used. The first boron fibers were obtained by Weintraub (1911) by means of reduction of a boron halide with hydrogen on a hot wire substrate. Fabrication of Boron Boron fibers are obtained by CVD on a substrate. There are two processes: 1. Thermal decomposition of a boron hydride. This method involves low temperatures, and, thus, carbon-coated glass fibers can be used as a substrate. The boron fibers produced by this method, however, are weak because of a lack of adherence between the boron and the core. These fibers are much less dense owing to the trapped gases. 2. Reduction of boron halide. Hydrogen gas is used to reduce boron trihalide: 2BXs + 3H2 > 2B + 6HX Where, X denotes a halogen: Cl, Br, or I. In this process of halide reduction, the temperatures involved are very high, and, thus, one needs a refractory material, for example, a high-melting-point metal such as tungsten, asa substrate. It turns out that such metals are also very heavy. This process, however, has won over the thermal reduction process despite the disadvantage of a rather high-density substrate (the density of tungsten is 19.3 gicm’) mainly because this process gives boron fibers of a very high and uniform quality. Figure shows a schematic of boron filament production by the CVD technique, y | [~ ett Fig, Schematic of boron fiber production by halide decomposition on a tungsten substrate In the process of BCls reduction, a very fine tungsten wire (10-12 mm diameter) is pulled into a reaction chamber at one end through a mercury seal and out at the other end through another mercury seal. The mercury seals act as electrical contacts for resistanceheating of the substrate wire when gases (BCl + Hz) pass through the reaction chamber, where they react on the incandescent wire substrate. The reactor can be a one or multistage, vertical or horizontal, reactor. BCIs is an expensive chemical, and only about 10 % of it is converted into boron in this reaction. Thus, an efficient recovery of the unused BC; can result in a considerable lowering of the boron filament cost. With the substrate wire stationary in the reactor, this critical temperature is about 1,000 °C. In a system where the wire is moving, this critical temperature is higher, and it increases with the speed of the wire. One generally has a diagram of the type shown in Fig. 2.9, which shows the various combinations of wire temperature and wire drawing speed to produce a certain diameter of boron fiber. Fibers formed in the region above the dashed line are relatively weak because they contain undesirable forms of boron as a result of recrystallization. The explanation for this relationship between critical temperature and wire speed is that boron is deposited in an amorphous state and the more rapidly the wire is drawn out from the reactor, the higher the allowed temperature is. Of course, higher wire drawing speed also results in an increase in production rate and lower costs. Boron deposition on a carbon monofilament (~35-mm diameter) substrate involves pre coating the carbon substrate with a layer of pyrolytic graphite. This coating accommodates the growth strains that result during boron deposition, The reactor assembly is slightly different from that for boron on tungsten substrate, because pyrolitie graphite is applied online. Structure Depending on the conditions of deposition, the elemental boron can exist in various crystalline polymorphs. The form produced by crystallization from the melt or CVD above 1,300 ‘C is b-rhombohedral. At temperatures lower than this, if crystalline boron is produced, the most commonly observed structure is a-rhombohedral, Boron fibers produced by the CVD method described earlier have a microcrystalline structure that is generally called amorphous. This designation is based on the charac- teristic X-ray diffraction pattern produced by the filament in the Debye-Scherrer method, that is, large and diffuse halos with d spacings of 0.44, 0.25, 0.17, 1.4, 1.1, and 0,091 nm, typical of amorphous material. Electron diffraction studies, however, lead one to conclude that this “amorphous” boron is really a nanocrystalline phase with a grain diameter of the order of 2nm Based on X-ray and electron diffraction studies, one can conclude that amorphous boron is really nanocrystalline b-thombohedral. In practice, the presence of micro- crystalline phases (crystals or groups of crystals observable in the electron microscope) constitutes an imperfection in the fiber that should be avoided. Larger and more seriousimperfections generally result from surpass the presence of impurities in the gases. ig the critical temper- ature of deposition or Aramid Fibers Aramid fiber is a generic term for a class of synthetic organic fibers called aromatic polyamide fibers. The definition of an aramid fiber as “a manufactured fiber in which the fiber- synthetic polyamide in which at least 85 % of the amide linkages are attached directly to two aromatic rings” Well-known commercial names of aramid fibers include Kevlar and Nomex (Du Pont) and Twaron (Teijin Aramid), Teijinconex and Technora are two other commercially available fibers from Teijin. Nylon is a generic name for any long-chain polyamide. Arai however, are ring compounds based on the structure of benzene as opposed to the linear compounds used to make nylon. The basic difference between Kevlar and Nomex is that Kevlar has para-oriented aromatic rings, ie., itsbasic unit is a symmetric molecule, with bonds from each aromatic ring being parallel, while Nomex is meta-oriented, with bonds at 120-degree angles to each other. Teijinconex is similar to Nomex while Twaron is similar to Kevlar. Technorais a copolyamide. The basic chemical structure of aramid fibers consists of oriented para-substituted aromatic units, which makes them rigid rod like polymers. The rigid rod like structure results in a high glass transition temperature and poor solubility, which makes fabrication of these polymers, by conventional drawing techniques, forming substance is a long-ch fibers such as Nomex or Kevlar, Eabrication of Aramid Fibers Processing of aramid fibers involves solution-polycondensation of diamines and diacid halides at low temperatures. The most important point is that the starting spinnable solutions that give high-strength and high-modulus fibers have liquid crystalline order. For aramid fibers, the dry jet-wet spinning method is, Solution-polycondensation of diamines and di gives the aramid forming polyamide: product generation and promote linear polyamide formation. The resulting polymer is pulverized, washed, and dried; mixed with concentrated H2SO4; and extruded through a spinneret at about 100 C. The jets from the orifices pass through about 1 cm of air layer before entering a cold water (0-4 C) bath. The fiber solidifies in the air gap, and the acid is removed in the coagulation bath. The spinneret capillary and air gap cause rotation and alignment of the domains, resulting in highly crystalline and oriented as-spun fibers. The air gap also allows the dope to be at a higher temperature than is possible without the air gap. The higher temperature allows a more concentrated spinning solution to be used, and ed. The process is illustrated in Fig. cid halides at low temperatures (near 0 C) Low temperatures are used to inhibit any by-higher spinning rates are possible. Spinning rates of several hundred meters per minute are not unusual. compares the dry jet-wet spinning method used with nematic liquid crystals and the spinning of a conventional polymer. The oriented chain structure, together with molecular extension, is achieved with dry jet-wet spinning. The conventional wet or dry spinning gives precursors that need further processing for a marked improvement in properties The as-spun fibers are washed in water, wound on a bobbin, and dried. Fiber properties are modified by the use of appropriate solvent additives, by changing the spinning conditions, and by means of some post-spinning heat treatments, if necessary cooguting ‘strong @s-spun ‘Guides Spinneret _— Spinning block container coagulating tiquia Fig, The dry jet-wet spinning process of producingaramid fibers Structure of Aramid Fibers Kevlar aramid fiber is the most studied of all aramid fibers. Thus, our description of structure will mostly be from the work done on Kevlar, but it applies to Twaron as well. The chemical formula of aramid. Chemically, the Kevlar- or Twaron-type aramid fiber is poly (p-phenyleneterephthalamide), which is a polycondensation product of terephthaloyl chloride and p-phenylene diamine. The aromatic rings impart the rigid rodlike chain structure of aramid, These chains are highly oriented and extended along the fiber axis, with the resultant high modulus.wom - ct ots— Pora-phenylene Terephthotoy! diomine chloride ea Fig. Chemical structure of aramid fiber Oxide Fibers Ceramic oxide fibers, continuous and discontinuous, have been commercially available since the 1970s. We describe below some important aspects of processing and microstructure of these fiber Alumina can have different allotropic forms such as 7, 6, n, and a; a-alumina being the thermodynamically stable form. Many different alumina-based oxide fibers are available commercially. 3M Co. produces a series of oxide fibers with compositions ranging from pure alumina to mixtures of alumina and silica or alumina and mullite. Sumitomo Chemical Co. produces a fiber that can have a wide composition range: 70-100 % A103 and 0-30 % SiO». A short fiber, called staple fiber, of 8-alumina (96 %) is available commercially. Single crystal continuous aluminum oxide or sapphire fibers can be produced by drawing from molten alumina. A fiber produced by this method, called Saphikon, has a hexagonal crystal structure with its c-axis parallel to the fiber axis, i.e., perpendicular to the fiber axis. The diameter of this fiber is rather large, between 75 and 250 jum. We describe below the salient features of some of these fabrication methods and the properties of the fibers obtained. Alumina + Silica Fibers and a-Alumina Fiber A series of alumina + silica fibers made via sol-gel route is available commercially. In particular, 3M Co. has developed a series of such fibers, trade name Nextel fibers. In this series, Nextel 610 is a polycrystalline, a-alumina fiber. The sol-gel process of making fibers involves the following steps common to all sol-gel processing: (a) Formulate sol(b) Concentrate to form a viscous gel (©) Spin the precursor fiber (d) Caleine to obtain the oxide fiber Specifically, in the case of the 3M process of making AI203 fiber, the following steps are involved: + Use an organic, basic salt solution as a precursor. * Drive out (decompose and volatilize) the organ other defects. + Fire at 1,400 C under carefully controlled conditions. + Apply a low-temperature straightening treatment 13 without causing cracking, blistering, or Nonoxide Fibers Continuous nonoxide ceramic fibers are also available commercially. The development of silicon carbide fiber must be regarded as a major development in the field of ceramic developed by the Yajima in Japan, involving controlled pyrolysis of a polycarbosilane (PCS) precursor to yield a flexible fine diameter fiber is considered to be the harbinger of making ceramic fibers from polymeric precursors. In this section we describe the fibers during the last quarter of the twentieth century. In particular, a proce: processing, microstructure, and properties of silicon carbide and some other nonoxide fibers. Silicon Carbide Fibers Silicon carbide fiber is by far the most important nonoxide ceramic fiber available commercially. The two main varieties of this fiber available commercially are large- diameter fiber made by CVD and small diameter fiber made by controlled pyrolysis of a polymer. Another important type of SiC available for reinforcement purposes is whiskers, Whiskers Whiskers are monocrystalline, short fibers with extremely high strength. This high strength, approaching the theoretical strength, comes about because of the absence of crystalline imperfections such Being monocrystalline, there are no grain boundaries either. Typically, whiskers have a diameter of a few jim and a length of a few mm. Thus, their aspect ratio (ength/diameter) can vary between 50 and 10,000. Whiskers, however, do not have uniform dimensions or properties. This is perhaps their greatest dislocationsthe variability in properties is extremely large. Handling and allgement of whivies na omtts to peoduen a commpeniie re ether problems. Whiskers are normally fabricated by vapor phase growth. Early in the 1970s, a new process was developed, starting from rice hulls to produce SiC particles and whiskers The SiC particles produced by this process are very fine in size. Rice hulls are a waste by-product of rice milling. For each 100 kg of rice milled, about 20 kg of rice hull is produced. Rice hulls contain cellulose, ilica, and other organic and inorganic materials. Silica from soil is dissolved and transported in the plant as monosilicic acid. This is deposited in the cellulosic structure by liquid evaporation. It turns out that most of silica ends up in hull. It is the intimate mixture of silica within the cellulose that gives the near ideal amounts of silica and carbon for silica carbide production. Raw rice hulls are heated in the absence of oxygen at about 700 C to drive out the volatile compounds. This process is called coking. Coked rice hulls, containing about equal amounts of SiO2 and free C, are heated in inert or reducing atmosphere 2.7 Whiskers (flowing N2 or NH3 gas) at a temperature between 1,500 and 1,600 C for about 1 h to form silicon carbide per the following reaction: 3C + SiO2 > SiC + 2CO When the above reaction is over, the residue is heated to 800 C to remove any free C. Generally, both particles and whiskers are produced together with some excess free carbon. A wet process is used to separate the particles and the whiskers. Typically, the average aspect ratio of the as-produced whiskers is ~75. Silicon carbide in particulate form has been available for a long time. It is quite cheap and commonly used for abrasive, refractory, and chemical purposes. Particulate SiC is processed by reacting silica in the form of sand and carbon in the formof coke at 2,400 ‘C in an electric furnace. The SiC produced in the form of large granules is subsequently comminuted to the desired size. Two types of SiC particulate reinforcement with angular and rounded morphology, respectively.Particulate Tungsten Carbide Tungsten carbide is obtained by the carburization of tungsten metal, which is obtained by hydrogen reduction of tungsten oxide. In principle, tungsten carbide can be obtained directly from ore or oxide, but gaseous carburization is usually preferred. Carbon black is added to control particle size and size distribution. A mixture of tungsten powder and carbon black in the correct particle size and distribution is subjected to ball milling or attrition milling Comparison of Fibers A. comparison of some important characteristics of reinforcements Sects and a plot of strength vs. modulus is shown in Fig. We compare and contrast some salient points of these fibers. First of all, we note that all these high-performance fibers have low density values. If we take the general low density of these fibers as a given, the best of thes together in the top right-hand corner of Fig. Also to be noted is the fact that, irrespective of whether in compound or elemental form, they are mostly covalently bonded, which is the strongest bond. Generally, such light, strong, and sti iscussed individually in fibers group materials are very desirable in most applications, but particularly in aerospace, land transportation, energyrelated industry, housing and civil construction, and so on. Fiber flexibility is associated with the Young’s modulus and the diameter. In the general area of high-modulus (ie., high-E) fibers, the diameter becomes the dominant parameter controlling the flexibility. For a given E, the smaller the diameter the more flexible itis. Fiber flexibility is a very desirable characteristic if one wants to bend, wind, and weave a fiber in order to make a complex-shaped final product. Some of these fibers have quite anisotropic characteristics. Consider the situation in regard to thermal properties; in particular, the thermal expansion coefficient of carbon is quite different in the radial and longitudinal directions. This would also be true of any single- 000 we «000 2000] i promi 000) Glass 1000)- yc-piten AL0s tearopie 0 ate a0 ato T0000 Weenie eailieacrystal fiber or whisker, e.g., alumina single-crystal fiber, which has a hexagonal structure, Polycrystalline fibers such as SiC or AI203 are isotropic. Carbon, aramid, and polyethylene are anisotropic because the high degree Fig. Comparison of different fibers Another important characteristic of these high-performance fibers is their rather low values of strain-to-fracture, generally less than 2-3 %. This means that in a CMC, the reinforcement and the matrix may not be much different in terms of strain to fracture. Also, in CMCs the modulus ratio of the reinforcement and the matrix may be 2-3 or as low as 1. This is a very different situation from that encountered in PMCs and MMCs Properties of Carbon, Glass, Boron, Aramide Fiber Diameter Young's Modulus —_Tensile Strength : i 3 Material Density (g/em’) aa Gra) (Gra Carbon HM 18 7-10 400 20-28 Carbon A 19 7-10 20 32 Boron 26 130 400 34 E-Class 25 10 70 15-20 S-Class 26 10 90 46 KEVLAR 49 145 R 130 36 polyethylene 097 R 17 26 * Some non brittle material distorts before breaking, but Kevlar, Carbon Fiber and E glass are brittle and fail with almost no distortion. The tensile strength of Carbon Fiber, Kevlar and Glass is similar. © Kevlar (Aramid) and Carbon Fibers have a high strength-to-weight ratio when tested unidirectional in direction of the fibers, while e glass has a lower strength-to-weight ratio. Glass is still quite high, just not as good as Kevlar or Carbon, Whereas Carbon and Glass are only slightly less strong and stiff in compression than in tension, Kevlar is much less stiff and strong when compressed. In fact in some tests the Kevlar was failing before the resin matrix. © The stiffness of Carbon Fiber, Kevlar and Glass are very different. Carbon Fiber is by far the stiffer of the composite materials. ‘The actual figures presented here are for comparison only. The important thing to take away is that Carbon Fiber is about twice as stiff as Kevlar, and about 5 times stiffer than glass.‘© There are many types of Kevlar, glass, and carbon fiber and they all differ. The exact, figures here are almost meaningless what is important is the relative stiffness. Applications of Carbon, Glass, Boron, Aramide : * Graphite and diamonds are two important allotropes of carbon that have wide appli © Diamonds are expensive and attractive and hence used in ions. th end jewellery. Industrial diamonds are used to cut, polish and grind glass because of their extreme hardness, * The embedded grit surface of fiberglass grating ensures slip resistance in the areas that are wet or in places where hydraulic fluids or oils are present «Fiberglass is used to manufacture parts for both military and civilian aerospace industry including test equipment, ducting, enclosures, and others. ‘+ allistic protective applications such as bullet proof vests * Protective apparel such as gloves, motoreycle protective clothing and hunting gaitors, chaps and pants. © Sails for sailboats, yachts ete ‘© Belts and hosing for industrial and automotive applications * Aircraft body partsInterfaces We can define an interface between a reinforcement and a matrix as the bounding surface between the two, across which a discontinuity in some parameter occurs. The discontinuity across the interface may be sharp or gradual. Mathematically, interface is a bi dimensional region. In practice, we have an interfacial region with a finite thickness. In any event, an interface is the region through which material parameters, such as concentration of an element, crystal structure, atomic registry, elastic modulus, density, coefficient of thermal expansion, etc., change from one side to another. Clearly, a given interface may involve one or more of these items. The behavior of a composite material is a result of the combined behavior of the following three entities: + Fiber or the reinforcing element » Matrix + Fiber/matrix interface 4, Interfaces The reason the interface in a composite is of great importance is that the internal surface area occupied by the interface is quite extensive. It can easily go as high as 3,000 cm2 /cm3 in a composite containing a reasonable fiber volume fraction, We can demonstrate this very easily for a cylindrical fiber in a matrix. The fiber surface area is essentially the same as the interfacial area, Ignoring the fiber ends, one can write the surface-to-volume ratio (S/V) of the fiber as SIV = 2arl/nrl = 2/r where r and | are the fiber radius and length of the fiber, respectively. Thus, the surface area of a fiber or the interfacial area per unit volume increases as r decreases. Clearly, it is important that the fibers not be weakened by flaws because of an adverse interfacial reaction. Also, the applied load should be effectively transferred from the matrix to the fibers via the interface. Thus, it becomes extremely important to understand the nature of the interface region of any given composite system under a given set of conditionsSpecifically, in the case of a fiber reinforced composite material, the interface, or more precisely the interfacial zone, consists of near-surface layers of fiber and matrix and any layers of material existing between these surfaces. Wettability of the fiber by the matrix and the type of bonding between the two components constitute the primary considerations. Additionally, one should determine the characteristics of the interface and how they are affected by temperature, diffusion, residual stresses, and so on. We discuss some of the interfacial characteristics and the associated problems in composites in a general way. The details regarding interfaces in polymer matrix, metal matrix, and ceramic matrix composites are given in specific chapters devoted to those composite types. Crystallographic Nature of the Interfac In crystallographic terms, one can describe an interface between two crystalline phases as coherent, semi-coherent, or incoherent. A coherent interface implies a one-to-one correspondence between lattice planes on the two sides of the interface. The lattice constants of any two phases are not likely to be exactly the same. Thus, in order to provide continuity of lattice planes across an interface, ie., a coherent interface, there will be some coherency strains associated with the interface because of the straining of the lattice planes in the two phases. Commonly, such coherent interfaces are observed between some precipitates and the metallic matrix where the mismatch in the lattice parameter of the two phases is quite small. For example, in the Al-Li system, AISLi precipitate is coherent with aluminum matrix. An incoherent interface, on the other hand, consists of such severe atomic disorder that no matching of lattice planes occurs across maintained across the interface. Thus, the boundary, ie., no continuity of lattice planes, an incoherent boundary or interface will have no coherency strains, but the energy associated with the interfacial boundary is high because of severe atomic disorder associated with such an interface. A situation that is intermediate between coherent and incoherent can exist, ie, we can have a semi-coherent interface. A semi-coherent interface has some lattice mismatch between the phases which can be accommodated by the introduction of dislocations at the interface. Crystallographically, most of the interfaces that one encounters in fiber-, whisker-, or particle-reinforced MMCs are incoherent and high-energy interfaces. Accordingly, they can act as efficient vacancy sinks and provide rapid diffusion paths, segregation sites, sites of heterogeneous precipitation, as well as sites for precipitate-free zones. Among the possible exceptions to this are the eutectic composites and the XD-type particulate composites wherein particlesare dispersed exothermically into a metal matrix, in which the interfaces can be semi- coherent. Weettability Wettability is defined as the ability of a liquid to spread on a solid surface. Figure shows two conditions of a liquid drop resting on a solid substrate, There are three specific energy (energy per unit area) terms: ysv, the energy of the solid—vapor interface; y1s, the energy of the liquid-solid interface; and y.v, the energy of the liquid—vapor interface. It should be mentioned here that the term surface tension is also used to denote surface energy, . When although rigorously speaking, surface energy is more appropriate term for soli ‘we put a liquid drop on a solid substrate, we replace a portion of the solid—vapor interface by a liquid-solid and a liquid-vapor interface. Thermodynamically, spreading of the liquid will occur if this results in a decrease in the free energy of the system, ie., YsL + YLv < Ysv hy Figure serves to define these terms. An important parameter in regard to wettability is the contact angle, 0, which is a measure of wettability for a system. From the equilibrium of forces in the horizontal direction, we can write ‘ysi. + Lv cosO= ysv = cos" (ysv - Ys) / YLv From this equation, we see that for 0 = 0°, we have perfect wetting, while for 0 = 180°, we have no wetting. For 0° <0 < 180°, there will be partial wetting. It should be pointed outthat the contact angle for a given system can vary with temperature, stoichiometry, hold time, interfacial re: tions, presence of any adsorbed gases, roughness and geometry of the substrate, ete. Itis worth emphasizing that wettability only describes the extent of intimate contact between a liquid and a solid. It does not necessarily mean a strong bond at the interface. One can have excellent wettability but only a weak physical, low energy bond. A low contact angle, implying good wettability, is a necessary but not sufficient condition for strong bonding. Wettability of ceramic reinforcement by molten metal is very important for liquid-state processing of MMCs. One can modify the contact angle by changing the composition of the liquid matrix, which changes the value of its surface energy. The effect of roughness of the solid substrate can be evaluated in terms of a ratio, r, defined as rue surface area / mean plane surface area In general, if 0 < 90°, wettability is enhanced by roughness while if © > 90°, wettability is reduced by roughnes ‘Types of Bonding at the Interface It is important to be able to control the degree of bonding between the matrix and the reinforcement. To do so, it is necessary to understand all the different possible bonding types, one or more of which may be acting at any given instant. We can conveniently classify the important types of interfacial bonding as follows: * Mechanical bonding + Physical bonding * Chemical bonding * Dissolution bonding © Reaction bonding1. Mechanical Bonding O; Matrix Fiber Mechanical (or Frictional) Bond Fig, Mechani gripping due to radial shrinkage of a matrix in a composite being more than that of the fiber on cooling from a high temperature ‘Simple mechanical keying or interlocking effects between two surfaces can lead to a considerable degree of bonding. In a fiber reinforced composite, any contraction of the matrix onto a central fiber would result in a gripping of the fiber by the matrix. Imagine, for example, a situation in which the matrix in a composite radially shrinks more than the fiber on cooling from a high temperature. This would lead to a gripping of the fiber by the matrix even in the absence of any chemical bonding . The matrix penetrating the crevices on the fiber surface, by liquid or viscous flow or high- temperature diffusion, can also lead to some mechanical bonding. In Fig we show a radial gripping stress, st. This is related to the interfacial shear stress, ti, as Ti = 1G, where #1 is the coefficient of friction, generally between 0.1 and 0.6. ‘A good example of excellent wetting (contact angle, 0 = 0°) is between WC and cobalt liquid. If, on the other hand, the matrix, liquid polymer or molten metal, unable to penetrate the asperities on the fiber surface, then the matrix will solidify and leave interfacial voids, as shown in Fig. Examples of surface roughness contributing to interfacial strength include: 1. Surface treatments of carbon fibers, e.g., nitric acid oxidation of carbon fibers, which increase specific surface area and lead to good wetting in PMCs, consequently an improved inter laminar shear strength (ILSS) of the composite2. Most metal matrix composites will have some roughness-induced mechanical bonding between the ceramic reinforcement and the metal matrix 3. Most CMC systems also show a mechanical gripping between the fiber and the matrix, a Matix Fiber b Matrix Fiber Void: Fig. (a) Good mechanical bond. (b) Lack of wettability can make a liquid polymer or metal unable to penetrate the asperities on the fiber surface, leading to interfacial voids 2. Physical Bonding Any bonding involving weak, secondary or van der Waals forces, dipolar interactions, and hydrogen bonding can be classified as physical bonding. The bond energy in such physical bonding is very low, approximately 8-16 kJ/mol. 3. Chemical Bonding, Atomic or molecular transport, by diffusional processes, is involved in chemical bonding. Solid solution and compound formation may occur at the interface, resulting in a reinforcement/matrix interfacial reaction zone having a certain thickness. This encompasses all types of covalent, ionic, and metallic bonding. Chemical bonding involves primary forces and the bond energy is in the range of approximately 40-400 ki/mol. There are two main types chemical bonding: 1. Dissolution bonding. In this case, interaction between components occurs at an electronic scale. Because these interactions are of rather short range, it is important that the components come into intimate contact on an atomic scale. This implies that surfacesshould be appropriately treated to remove any impurities. Any contamination of fiber surfaces, or entrapped air or gas bubbles at the interface, will hinder the required intimate contact between the components. 2. Reaction bonding. In this case, a transport of molecules, atoms, or ions occurs from one or both of the components to the reaction _T te, that is, the interfé atomic transport is controlled by diffusional processes. Such a bonding can exist at a variety of interfaces, e.g., glass/polymer, metal/metal, metal/ceramic, or ceramic/ceramic Measurement of Interfacial Bond Strength Once the matrix and the reinforcement of a composite are chosen, the set of characteristics of the interface region become very important in determining the final properties of the composite. In this regard a thorough micro structural and mechanical characterization of the interface region assumes a great deal of importance. A variety of sophisticated techniques is available for this purpose. A quantitative measure of the strength of the interfacial bond between the matrix and reinforcement is of great importance. We describe below some of the important techniques to measure interfacial bond strength. 1, Bend Tests Bend tests are easy to perform, but they do not give a true measure of the interfacial strength. We describe below some variants of bend tests. (a) Transverse Bend Test A three-point bend test configuration with fibers aligned perpendicular to the specimen length is called a transverse bend test. There are two possible arrangements of fibers, one with fibers parallel to the width of the specimen and the other with fibers perpendicular to the width of fibers. Under either one of these configurations, the fracture will occur on the outermost surface of the specimen which is under a tensile stress and thus will put the fiber/matrix interface under tension, which gives us a measure of tensile strength of the fiber/matrix interface. The transverse strength is given by 0 = 3PS / 2bh? where P is the applied load, S is the load span, b is the specimen width, and h is the specimen height. (b) Longitudinal Bend Test or Short Beam Shear Test This test is also known as the interlaminar shear strength (ILSS) tes In this test, the fibers are aligned parallel to the length of the three-point bend bar. In such a test, the maximum shear stress, t, occurs at the midplane and is given byt= 3P/4bh ‘The maximum tensile stress occurs at the outermost surface and is given by. Dividing above two equations, we get vo=h/2S According to this equation, we can maximize the shear stress by making the load span(S) arbitrarily small and thus ensure that the specimen fails under shear with a crack running along the midplane. The test becomes invalid if the fibers fail in tension before shear- induced failure occurs. The test will also be invalid if shear and tensile failure occur simultaneously. It is advisable to make an examination of the fracture surface after the test and make sure that the crack is along the interface and not through the matrix. 2. Fiber Pullout and Pushout Test: Single fiber pullout and pushout tests have been devised to measure interfacial characteristics. Such tests give load vs. displacement curves, with a peak load corresponding to fiber/matrix debonding and a fri tional load corresponding to the fiber pullout from the matrix. (a) Single Fiber Pullout Tests Single fiber pullout tests can provide useful information about the interface strength in model composite systems. They are not very helpful in the case of commercially available composites. One must also carefully avoid any fiber misalignment and introduction of bending moments. The mechanies of the single fiber pullout test is complicated. In all variants of such test, the fiber is pulled out of the matrix in a tensile testing machine, and a load vs. displacement record is obtained. Figure shows the exper yental setup for such a test. A portion of fiber, length C, is embedded in a matrix. We apply a pulling tensile force, as shown, and measure the stress required to pull the fiber out of the matrix as a function of the embedded fiber length. The stress required to pull the fiber out without breaking it increases linearly with the embedded fiber length, up to a critical length, Cc. This critical fiber length is the length of fiber that is used in load transfer from the matrix to fiber. We discu: s the concept of critical fiber length in Chap. 6. For an embedded fiber length, € > (, the fiber will fracture under the action of the tensile stress, 6, acting on the fiber. When we apply a tensile force on the fiber, there will result a shear force at the fiber/matrix interface. A simple force balance along the embedded fiber length, €, and radius, ry, gives on waryMate / Freee . ee n 2 Fig, A fiber of radius r embedded in a matrix and being pulled out. The longitudinal tensile force on the fiber generates shear at the fiber/matrix interface (b) Pushout or Indentation Tests In the pushout test, one pushes a fiber out, by means of an indenter, in a thin sample with the fibers aligned perpendicular to the viewing surface. Such a fiber pushout test can give the frictional shear stress, t, acting at the fiber/matrix interface. In a valid pushout test, a three-region curve is obtained. In the first region, the indenter is in contact with the fiber and the fiber sliding is less than the specimen thickness t. This is followed by a horizontal region in which fiber sliding length is greater than or equal to the sample thickness. In the third region, the indenter comes in contact with the matrix. From the second region, we can determine the interfacial shear stress. The specimen thickness should be much greater than the fiber iameter for this relationship to be valid, In the horizontal region (region two), the interfacial shear stress is given by G=P/Qnrt Interactions at the Interface due to Thermal Mismatch Thermal stresses arise in composite materials because of the mismatch between the coefficients of thermal expansion of the components making up the composite. Mismatch in the elastic constants of the components exacerbates the problem. It is easy to see that in a fiber reinforced composite, if the matrix thermal expansion coefficient is higher than that of the fiber, then on cooling from high temperature, radial compression will result, i.e., the matrix will grip the fiber. Such a radial gripping of the fiber by the matrix will increase the strength of the interface, thus, increasing the tendency toward brittleness in the composite. This will make phenomena such as fiber debonding and pullout, desirable for enhanced toughness, difficult to operate. Quite frequently, the very process of fabrication of a composite can involve interfacial interactions that can cause changes in the constituent properties and/or interface structure. For example, if the fabrication process involves cooling from high temperatures to ambient temperature, then thedifference in the expansion coefficients of the two components can give rise to thermal stresses of such a magnitude that the softer component (generally the matrix) will deform plastically. observed in a tungsten reinforced single crystal copper matrix (non reacting components) that liquid copper infiltration of tungsten fibers at about 1,100 C followed by cooling to room temperature resulted in a dislocation density in the copper matrix that was much higher in the vicinity of the interface than away from the interface. The high disloca jon density in the matrix near the interface resulted from the plastic deformation of the matrix caused by high thermal stresses near the interface. Other researchers observed similar results in the system SiC whiskers in an aluminum matrix and in a composite consisting of short alumina fibers in aluminum matrix. If powder metallurgy fabrication techniques are used, the nature of the powder surface will influence the interfacial interactions. For example, an oxide film on the powder surface affects its chemical nature. Topographic characteristics of the components can also affect the degree of atomic contact obtainable between the components. This can result in geometrical irregularities (e.g., asperities and voids) at the interface, which can be a source of stress concentrations. 10's (PMCs) have established themselves as engineering structural materials not just as laboratory curiosities or cheap stuff for making chairs and tables. This came about not only because of the introduction of high performance fibers such as carbon, boron, and aramid glass fiber but also because of some new and improved matrix materials. Nevertheles reinforced polymers represent the largest class of PMCs. Carbon fiber reinforced PMCs are perhaps the most important structural composites; especially in the aerospace field. In this chapter, we and carbon fibers. iscuss polymer composite systems containing glass, aramid, polyethylene, boron, Processing of PMCs 1. Hand Layup Techniques Hand lay-up technique the simplest method of composite processing. The infrastructural requirement for this method is also minimal. The processing steps are quite simple. of all, a release gel is sprayed on the mold surface to avoid the sticking of polymer to the surface. Reinforcement in the form of woven mats or chopped strand mats are cut as per the mold size and placed at the surface of mold after. Then thermosetting polymer in liquid form is mixed thoroughly in suitable proportion with a prescribed hardener (curing agent) and poured onto the surface of mat already placed in the mold, The polymer is uniformly spread with the help of brush. Second layer of mat is then placed on the polymer surface and a rollei moved with a mild pressure on the mat-polymer layer to remove any air trapped as well as the excess polymer present. The process is repeated for each layer of polymer and mat, till the required layers are stacked. Afier curing either at room temperature or at some specific temperature, mold is opened and the developed composite part is taken out and further processed.Reinforcement Laminate Hand Roller Contact Mold Gel Coat Fig: Hand Layup Techniques Teel ues The spray lay-up technique can be said to be an extension of the hand lay-up method. In this technique, a spray gun is used to spray pressurized resin and reinforcement which is in the form of chopped fibers. Generally, glass roving is used as a reinforcement which passes through spray gun where it is chopped with a chopper gun. Matrix material and reinforcement may be sprayed simultaneously or separately one after one. Spray release gel is applied on to the mold surface to facilitate the easy removal of component from the mold. A roller is rolled over the sprayed material to remove air trapped into the lay-ups. After spraying fiber and resin to required thickness, curing of the product is done either at room temperature or at elevated temperature. After curing, mold is opened and the developed composite part is taken out and further processed further. The time of curing depends on type of polymer used for composite processing. t|Poinnr cmon L3. Filament Winding Filament winding is another very versatile technique in which a continuous tow or roving is passed through a resin impregnation bath and wound over a rotating or stationary mandrel. A roving consists of thousands of individual filaments. (Fig a) shows a schematic of this process, while (Fig. b) shows a pressure vessel made by filament winding. The winding of roving can be polar (hoop) o helical, In polar winding, the fiber tows do not cross over, while in the helical they do. The fibers are, of course, laid on the mandrel in a helical fashion in helical windings; the helix angle depends on the shape of the object to be made. Successive layers are laid on at a constant or varying angle until the desired thickness is attained, Curing of the thermosetting resin is done at an elevated temperature and the mandrel is removed. Very large cylindrical (e.g., pipes) and spherical (e.g., for chemical storage) vessels are built by filament winding. Glass, carbon, and aramid fibers are routinely used with epoxy, polyester, and vinyl ester resins for producing filament wound shapes. There are two types of filament winding processes: wet winding and prepreg winding. In wet winding, low-viscosity resin is applied to the filaments during the winding process. Polyesters and epoxies with viscosity less than 2 Pas are used in wet winding In prepreg winding, a hot-melt or solvent-dip process is used to preimpregnate the fibers. Rigid amines, novolacs, polyimides, and higherviscosity epoxies are generally used for this process. In filament winding, the most probable void sites are roving crossovers and regions between layers with different fiber orientations. Aber Traversing Mandeet b Taneded Pod iper Helical windings Hoop windings Fig, (a) Schematic of filament winding process. (b) Schematic of a filament wound pressure vessel with a liner; helical and hoop winding are shown’4. Pultrusion In this process continuous sections of polymer matrix composites with fibers oriented mainly axially are produced. Filaments are pulled from a lot of fibre creels through a resin bath. They then go through an performer which gives it the required cross sectional shape. The F and C dies conclude the required shape and expel overabundant resin and fix the composite so it is available for easy cutting into required length. This process has the advantages of high-volume productivity, rapid processing, low material scrap rate and good quality control. However, improper fibre wet-out, fibre breakage, die jamming and complex die design pose potential problems in manufacturing. The chief applications of this process are panels, beams, ladders, tool handles, electrical insulators, light poles, hand rails, roll-up doors etc. Pultrusion a G aes plate Preformer ums Pulling system Fiber Creel Resin bath wwwsubstech.com Fig : Pultrusion Process of manufacturing PMCs Interface in PMCs We provide below a summary of some important features of the interface region in PMCs with glass, carbon, aramid, and polyethylene fibers. LG er/Polymer The inorganic, silica-based glasses are analogous to many organic polymers in that they are amorphous and pure, crystalline silica melts at 1,800°C and can be worked in the range of 1,600— 1,800°C. However, by adding some metal oxides, one can break the Si-O bonds and obtain a series of amorphous glasses with low glass transition temperatures so that they can be processedat much lower temperatures than pure silica. In general, the atomic or molecular arrangement in any material is different at the surface than in the interior. In particular, in the case of silica-based glasses containing a variety of oxides, a complex hydroxyl layer is formed rather easily. Nonhygroscopic oxides absorb water as hydroxyl groups while hygroscopic oxides become hydrated. The activity of a glass surface is thus a function of the hydroxyl content and the cations just below the surface. That is, the surface activity of E-glass will be different from that of fused silica, 2. Carbon Fiber/Polymer Interface As in any other composite, the carbon fiber/polymer matrix interface is very important in determining the final properties of the composite. Carbon fiber is a highly inert material. This makes it difficult to have a strong adhesion between carbon fiber and a polymer matrix. One solution is to make the fiber surface rough by oxidation or etching in an acid. This results in an increased specific surface area and improved wetting, which in turn results in improved inter laminar shear strength because of the mechanical keying effect at the fiber/matrix interface. Recall that the carbon fiber microstructure is inhomogeneous through its cross. section. Specifically, in the surface layer, the basal planes are better aligned parallel to the surface. This graphitic layer is very smooth and weak in shear and hard to bind with a matrix. That is the reason that a surface treatment is given to carbon fibers. A variety of surface treatments can be used to accomplish the following: (a) Increase the surface roughness (b) Increase the surface reactivity The interface region between a carbon fiber and the polymer matrix is quite complex. It is therefore not surprising that a unified view of the interface in such composites does not exist.Fiver oxis 1 (A) Bulk ber (8) Bulk epoxy (C) Fiber surtace (0) Intertoce {E) Epoxy surtoce mH /]\ (ch 1) Fig, Schematic structure of a carbon fiber/epoxy composite showing carbon fiber, interface, and epoxy matrix 3. Aramid Fiber/Polymer Interface Most polymers show rather poor adhesion to aramid fibers. This is evidenced by the generally poor interlaminar shear strength and transverse tensile strength values obtained with aramid reinforced PMCs. Typically, aramid/epoxy interfacial strengths are about half of the interfacial strengths of glass/epoxy or carbon/ epoxy composites. A highly oriented chain microstructure and skin/core heterogeneity are responsible for this low, poor interfacial strength. This may not be a disadvantage in aramid/polymer composites used to make impact-resistant items such as helmets or body armor, where ease of delamination may be an advantage from a toughness point of view. However, in high-strength and high-stiffness composites, poor interfa adhesion can be a disadvantage. Various fiber surface treatments have been tried to alleviate this problem. Structure of PMCs Continuous fiber reinforced polymer composites show anisotropic properties. The properties of a composite will depend on the matrix type, fiber type, interface, amount or volume fraction of fiber (or that of the matrix), fabrication process, and, of course, the fiber orientation. Structural Defects in PMCs ‘The final stage in any PMC fabrication is called debulking, which serves to reduce the number of voids, one of the common defects in PMCs. Nevertheless, there are other common structural defects in PMCs. Following is a list of these: + Resin-rich (fiber-poor) regions.* Voids (¢.g., at roving crossovers in filament winding and between layers having different fiber orientations, in general). This is a very serious problem; a low void content is necessary for improved interlaminar shear strength. Hence, the importance of the debulking step. * Microcracks (these may form due to curing stresses or moisture absorption during processing). + Debonded and delaminated regions. * Variations in fiber alignment, Mechanical Properties of PMCs + High specific strength, high specific modulus - The unmistakable points of interest of polymer matrix composite materials are their high specific strength and high specific modulus. The specific strength is the proportion of strength and density and the specific modulus is the proportion of modulus and density, and measurements or units are both lengths * Good fatigue resistance and high damage tolerance - The interface among fibre and lattice in composite materials can keep the expansion of cracks. The weakness disappointment reliably begins from the delicate associations of fibre. + Good damping characteristics - The ordinary frequency of vibration of obliged structure relates to the condition of the structure itself, too it is comparing to the square establishment of the particular modulus of assistant materials. + Multi-functional performance - High flitting temperature restriction and incredible evacuation block. Warm conductivity of FRP (fibreglass strengthened plastics) is only 1% of metal materials + Anisotropic and properties designability - PMCs are portrayed noticeably by anisotropy, which is related to the organizing of execution. The mechanical and physical properties of fibre composite materials are settled not simply by the sort of fibre and +h type and relative volume divide, yet moreover immovably related with by the heading of fibre strategy, utilize stacking progression and layer number. Applications of Polymer Matrix Composites + Aerospace — the use of PMCs for aerospace application has increased ever since it was fir t used, ‘Their superior strength-to-weight r: and high durability of PMCs in comparison to metals in fact is the principal reason of their use. 50% of advanced composites production in the United States is consumed by the aerospace industry + Military — The PMCs made using Kevlar can serve as bullet proof jackets. Parts of tanks and guns often see use of PMC.+ Medical Field - PMC materials are as of now being created for prosthetic body parts and inserts. ‘The effect of PMCs on orthopaedic gadgets is required to be particularly critical. Albeit therapeutic gadgets are not liable to give a substantial volume consumption for PMCs, their social and monetary esteem are high. + Transportation - Composite materials have been associated in vehicle, train, convey and other transport instruments. * Construction - PMCs is broadly utilized in an assortment of bridges, light houses, huge building structure, compositional component and model, sterile, cooling tower, capacity tank, waveform tile, entryway and window segments, pressure drive development furthermore, the ground, etc. Carbon fibre composite as reinforcing and fix for foundation has appeared extensive market lately. + Ship Building — Polymer matrix composite materials are utilized in the generation of an assortment of work vessel, angling watercraft, transport pontoon, speedboat, raft, voyage, military minesweeper and submarine. + Anti-corrosion Materials — PMCs, particularly glass fibre, strengthened plastics are very impervious to destructive synthetics, and give the new concoction against consumption 29 materials. * Ordnance - PMCs are generally used in the production of circuits, shots, cartridge cases (coach shells), holding ring shells, knob, rocket launcher, shield of enormous firearms, and so forth,INIT-4 Metal Matrix Composites Metal matrix composites consist of a metal or an alloy as the continuous matrix and a reinforcement that can be pa important techniques to process metal matrix composites, then we describe the interface region le, short fiber or whisker, or continuous fiber. In this chapter, we first describe and its characteristics, properties of different metal matrix composites, and finally, we summarize different applications of metal matrix composites. Important Metallic Matrices A variety of metals and their alloys can be used as matrix materials, We describe briefly the important characteristics of some of the more common ones. Aluminum Alloys Aluminum alloys, because of their low density and excellent strength, toughness, and resistance to corrosion, find important applications in the aerospace field. Of special mention in this regard are the ALCu-Mg and Al-ZnMg-Cu alloys, very important precipitation-hardenable alloys. Aluminumlithium alloys form one of the most important precipitation-hardenable aluminum alloys. Lithium, when added to aluminum as a primary alloying element, has the unique characteristic of increasing the elastic modulus and decreasing the density of the alloy. Understandably, the aerospace industry has been the major target of this development. AHLi alloys are precipitation hardenable, much like the Al-Cu-Mg and Al-Zn-Mg-Cu alloys. The precipitation hardening sequence in AI-Li alloys is, however, much more complex than that jon-hardenable aluminum alloys. Generally, these alloys observed in conventional precipi contain, besides lithium, some copper, zirconium, and magnesium. These provide an account of the heat treatments and structure/property aspects of various aluminum alloys. Magnesium Alloys Magnesium and its alloys form another group of very light materials. Magnesium is one of the lightest metals; its density is 1.74 g/em? . Magnesium alloys, especially castings, are used in aircraft gearbox housings, chain saw housings, electronic equipment, etc. Magnesium, being a hexagonal close-packed metal, is difficult to cold work.Copper Copper has a face centered cubic structure. Its use as an electrical conductor is quite ubiquitous. It has good thermal conductivity. It can be cast and worked easily. One of the major applications of copper in a composite as a matrix material in niobium-based superconductors, Proc Many processes for fabricating metal matrix composites are available. For the most part, these processes involve processing in the liquid and solid state. Some processes may involve a variety of deposition techniques or an in situ process of incorporating a reinforcement phase. We provide a summary of these fabrication processes. 1. Liquid-State Processing Liquid-state processing of metal matrix composites involves incorporating or combining a liquid metal matrix with the reinforcement. There are several advantages to using a liquid-phase route in processing. These include near net shape (when compared to solid-state processes like extrusion or diffusion bonding), faster rate of processing, and the relatively low temperatures associated with melting most light metals, such as Al and Mg. The most common liquid-phase processing techniques can be subdivided into four major categories: * Casting or liquid infiltration: This involves infiltration of a fiber or particulate preform by a liquid metal. In the case of direct introduction of short fibers or particles, the molten mixture, consisting of liquid metal and ceramic particles or short fibers, is often stirred to obtain a homogeneous distribution of particles. In centrifugal casting, a gradient in reinforcement particle loading is obtained. This can be quite advantageous in applications where the reinforcement needs to be tailored from a machining or performance perspective. + Squeeze casting or pressure infiltration: This method encompasses pressureassisted liquid infiltration of a fibrous or particulate preform. This process is particularly suited for complex shape components, selective or localized reinforcement, and where production speed is critical + Spray co-deposition: In this process the liquid metal is atomized or sprayed, while a particle injector introduces ceramic particles in the spray stream to produce a granulated mixture of composite particles> Go» es, — fin ie Coram Parle Ingot- Grade Atri ting Bink Fig. Conventional casting route for processing particle reinforced MMCs Casting or Liquid Infiltration 2.Conventional Casting. Casting of MMCs can typically be accomplished with conventional equipment used to cast Iti aluminum alloys ly used with particulate reinforcement because of the difficulty in typi infiltrating fibrous performs without pressure. The particles and matrix mixture are cast into ingots and secondary mechanical processing, such as extrusion or rolling, is applied to the composite. Casting of MMCs requires some modifications to existing conventional casting processes, which are summarized as follows: + Alloys that minimize reactivity with the reinforcement must be used. Al-Si alloys (with Si levels of up to 9 %) are typically used with SiC reinforcement. Figure 4.2 shows that with increasing temperature, an increase in the amount of silicon is required to prevent the formation of the undesirable compound. + Stirring of the composite melt is often required. The density of SiC (3.2 g/cm ) is higher than that of AL (2.5 g/cm ), so the particles will sink unless the melt is agitated. Alternating currents in a magnetic field and mechanical vibration have also been used to improve wetting and permeability of the reinforcement in the liquid matrix.Particles Fig, Stirring of composite melt with ceramic particles to minimize settling of the particles during processing Solid-State Processing 1, Powder Metallurgy Processing Powder Metallurgy comprises a family of production technologies, which process a feedstock in powder form to manufacture components of various types. These production technologies generally involve all or most of the following process steps: Powder production Virtually all iron powders for PM structural part production are manufactured using either the sponge iron process or water atomization. Non ferrous metal powders used for other PM applications can be produced via a number of methods. Mixing of powders This can often involve the introduction of alloying additions in elemental powder form or the incorporation of a pressing lubricant. Forming of the mixed powder into a compact ‘The dominant consolidation process involves pressing in a rigid toolset, comprising a die, punches and, possibly, mandrels or core rods. However, there are several other consolidation processes that are used in niche applications.Sintering of the compact to enhance integrity and strength This process step involves heating of the material, usually in a protective atmosphere, 10 a temperature that is below the melting point of the major constituent. In some cases, a minor constituent can form a liquid phase at sintering temperature; such cases are described as liquid phase sintering. The mechanisms involved in solid phase and liquid phase sintering are discussed briefly in a later section, Secondary operations The application of finishing processes to the sintered part. In the Powder Metallurgy industry, such processes are often referred to as “secondary operations” Metat powders ey Piette’ ie} Te ESL) ff erry pees, ire In Situ Processes In situ processes fall into two major categories, reactive and nonreactive processes. In the reactive processes two components are allowed to react exothermically to form the reinforcement phase. The XD process is an example of this process. Typically, a rather high-volume fraction of ceramic particles is formed in the matrix alloy, and this master alloy is diluted with the matrix alloy to obtain a composite of desired reinforcement volume fraction. Typical examples involve TiB2 and TiC as reinforcement particles, which are formed by the following reactions: 2B + Ti+ Al >TiB2 + Al and C+Ti+Al> TIC +ALProcessing variables such as reaction temperature can be used to tailor the desired reinforcement particle size, which is usually in the 0.25~1.5 jm range. The matrix consists of Al, Ni, or an inter ‘metallic matrix. An alternative proce s that combines spray co-deposition and reaction is to atomize an AI-Ti alloy (at sufficiently high temperature) with a C-containing gas to form TiC particles. The advantage of in situ reaction processes, in general, is that the reaction eliminates problems typically associated with wetting of the particle, so a relatively clean and strong interface typically formed, The number of composite systems where reaction processing is beneficial, however, is limited, and the relatively fine size distribution of particles produced can significantly increase the viscosity of the melt. Liquid é wa g ]-_Cooling [-~ coils ‘Composite Fig. Schematic of directional solidification process to obtain in situ composites Interfaces in Metal Matrix Composites ‘As we have repeatedly pointed out, the interface region in any composite is very important in determining the ultimate properties of the composite. In this section, we give examples of the microstructure of the interface region in different metal matrix composite systems and discuss the implications of various interfacial characteristics on the resultant properties of the composite. Recall that we can use contact angle, y as a measure of wettability; a small © indicates goodwetting. Most often, the ceramic reinforcement is rejected by the molten metal because of nonwettability or high contact angle. Sometimes the contact angle of a liquid drop on a solid substrate can be decreased by increasing the surface energy of the solid or by decreasing the energy of the interface between the liquid and the solid. Thus, under certain circumstances, the wettability of a solid ceramic by a molten metal can be improved by making a small alloy addition to the matrix composition. An example of this is the addition of lithium to aluminum to improve the wettability in the alumina fiber/aluminum composite (Champion et al. 1978; Chawla 1989). However, in addition to wettability, there are other important factors such as chemical, ‘mechanical, thermal, and structural ones that affect the nature of bonding between reinforcement and matrix. As it happens, these factors frequently overlap, and it may not always be possible to isolate these effects. ‘Major Discontinuities at Interfaces in MMCs As we said earlier, at the interface a variety of discontinuities can occur. The important parameters that can show discontinuities in MMCs at a ceramic reinforcement/metal matrix interface are as follows: * Bonding. A ceramic reinforcement will have an ionic or a mixed ionic/covalent bonding, while the metal matrix will have a metallic bonding. + Crystallography. The erystal structure and the lattice parameter of the matrix and the reinforcement will be different + Moduli. In general, the elastic moduli of the matrix and the reinforcement will be different + Chemical potential. The matrix and the reinforcement will not be in thermodynamic equilibrium at the interface, i.e., there will be a driving force for a chemical reaction. + Coefficient of thermal expansion (CTE). The matrix and the reinforcement will, in general, have different CTEs. ‘Mechanical Bonding Some bonding must exist between the ceramic reinforcement and the metal matrix for load transfer to occur from matrix to fiber. Two main categories of bonding are mechanical and chemical. Mechanical keying between two surfaces can lead to bonding confirmed this experimentally for tungsten filaments in an aluminum matrix, while observed mechanical gripping effects at ALOs/AL i terfaces, The results in the form of linear density of cracks (number of cracks permm) in alumina as a function of strain in an alumina/aluminum composite for different degrees of interface roughness The main message of this figure is that the crack density continues to sa’ visa 1 increase to larger strain values in the case of a rough interface (deeply etched pits) the rougher the interface, the stronger the mechani smooth or not very rough interface, i bonding. Chemical Bonding Ceramic/metal interfaces are generally formed at high temperatures. Diffusion and chemical reaction kinetics are faster at elevated temperatures. One needs to have knowledge of the chemical reaction products and, if possible, their properties. Molten iron, nickel, titanium, low alloy steels, austenitic and ferritic stainless steels, and nickel-based super alloys react with silicon-containing ceramics to form eutectics, with the reaction products being mainly metal silicides and carbides. It is thus imperative to understand the thermodynamics and kinetics of reactions in order to control processing and obtain optimum properties. Properties of Metal Matrix Composites High Strength One of the most common features of metal matrix composite materials is increased strength and stiffness. Its high strength-to-weight ratio makes the material useful in a wide variety of applications. High Heat Resistance Some composites are built to have higher creep resistance than the pure metal counterparts. This reduces the risk of warping or deformation in the material, especially when exposed to welding or tensile stress with high temperature. Metal matrix composites work best in industries with a high risk of creep fatigue or sudden temperature changes. Other Unique Properties Each composite has its own unique signature set of properties depending on the composition and orientation of the metal and reinforcing material. Some of these properties include the following: lity to absorb moisture + Radiation resistance * Increased resistance to wear and tearApplications of Metal Matrix Composites Aerospace and Aircraft Ind try 's work well as components in transmission systems, gearboxes, engine parts Metal matrix composit and accessories, and other internal elements. Sports ‘The superior strength-to-weight ratio of most metal matrix composites makes the material suitable for tennis rackets, bicycle frames, and other sports that involve speed and strength. Automotive Applications Car and motor racing make use of metal matrix composites for engine and vehicle body parts due to the lightweight nature of the material.Carbon iber/Carbon Matrix Composites We devote this chapter to a very special kind of composite that consists of carbon fibers embedded in a carbonaceous matrix. The carbon fiber in these compositi S can be continuous or short, We described the processing of carbon fibers. Carbon is a very versatile material. It can exist in a variety of forms; amorphous, graphite, diamond, fullerenes, graphene, nanotubes, etc. Below we summarize the salient features of some important forms of carbon. Diamond: Carbon in the diamond form has an FCC structure; it is also called diamond cubic. Each C atom is covalently bonded to four carbon atoms at the vertices of a tetrahedron and the interatomic distance 14 0.154 nm, Carbon in the diamond form has isotropic properties. It is one of the hardest materials. Graphite: Graphitic form of carbon has a hexagonal structure. Carbon atoms are arranged in layers. ‘The bonding between atoms in the plane of the layer is covalent but the bonding between layers is weak, van der Waals type. This difference in the bonding in a and ¢ directions makes graphite is highly anis tropic. Young’s modulus in the basal plane (a direction) is ~1,000 GPa, while in a direction perpendicular to the basal plane (¢ direction) it is ~35 GPa. Tensile s ength, thermal expansion, and thermal conduction are also anisotropic in a similar manner. Pyrolytic graphite: Pyrolytic graphite is produced from a gaseous phase via pyrolysis of hydrocarbons. The pyrolysis of hydrocarbons results in carbon, which is deposited on a hot substrate. Pyrolytic grap! Carbon blacl has a highly oriented structure and therefore is highly anisotropic. A generic term for carbon powder of extremely fine size (nm range) and very high surface area. It is essentially elemental carbon (>97 %), electrically conductive, and finds extensive use as a reinforcement in tires and other rubber products as well as in printing inks and paints. Carbon nanotubes: These are hollow, cylindrical tubes of carbon atoms with diameter in the range of 5-20 nm, They are frequently referred to as CNTs. CNTs can have very large aspect ratios. They show some very unusual properties, such as extremely high stiffness and strength. Processing of Carbon/Carbon Composites Three methods are commonly used to fabricate carbon/carbon composites: 1. A woven preform of carbon fiber is impregnated, under heat and pressure, with thermoplastic pitch, followed by pyrolysis of pitch into carbon. Generally the cycle is repeated to obtain the desired density. A special version of this technique is called high pressure impregnation carbonization or HIPIC (see below). Pitches are mixtures of hydrocarbons of different molecularweights. Yield of carbon from the pitch precursor increases with increasing average molecular weight of the pitch but high molecular weight means high viscosity which makes penetration of the fibrous preform difficult. 2. A carbon fiber/polymer matrix composite is made by one of the conventional PMC fabrication techniques, followed by conversion of the resin, generally a thermoset, to carbon by pyrolysis. Again, reimpregnation and repyrolysis are used to attain the desired density of the composite. Phenolics are one of the common resins used because of the comparatively high carbon yield. 3. CVD of carbon is made from a gaseous phase onto and in between the carbon fibers in a preform. Hydrocarbon gases become unstable with respect to carbon at high temperatures (>550 C).2 (Carbon Fiber] - = — a Fig, Processing of carbon/carbon composites by pyrolysis of carbon fiber/polymer composites cc Composite Fig, Processing of carbon/carbon composites by chemical vapor deposition (CVD) processProperties Carbon Fiber has High Strength to Weight Ratio (also known as specific strength) Strength of a material is the force per unit area at failure, divided by its density. Any material that is strong AND light has a favorable Strength/weight ratio. Materials such as Aluminium, titanium, magnesium, Carbon and glass fiber, high strength steel alloys all have good strength to weight ratios. Carbon Fiber is very rigid Rigidity or stiffness of a material is measured by its Young Modulus and measures how much a material deflects under stress. Carbon fiber reinforced plastic is over 4 times stiffer than Glass reinforced plastic, almost 20 times more than pine, 2.5 times greater than aluminium. Carbon fiber is Corrosion Resistant and Chemically Stable Although carbon fiber themselves do not deteriorate, Epoxy is sensitive to sunlight and needs to be protected. Other matrices (whatever the carbon fiber is imbedded in) might also be reactive Applications of Carbon Composites Carbon/carbon composites use the strength and modulus of carbon fibers to reinforce a carbon matrix to resist the rigors of extreme environments. At one-tenth the density, carbon/carbon composites offer a high performance, cost effective alternative to refractory metals. Aerospace components commonly fabricated from carbon/carbon composites include rocket motor nozzle throats and exit cones, nosetips /leading edges and thermal protection systems. Reliable performance is the most critical requirement of these components. The carbon/carbon composites have demonstrated reliability and reduced systems costs, especially when multiple components in an assembly can be replaced with a one-piece carbon/carbon composite design. Commercial applications of carbon/carbon composite materials include furnace fixturing, heat shields, load plates, heating elements, and X-ray targets. Rocket nozzles must withstand an extremely rapid temperature increase in a highly corrosive atmosphere while maintaining a high degree of integrity. In addition to exposure to severe thermal stresses, the nozzle material must perform predictably and uniformly to provide the required accuracy and range.Chapter 10 Micromechanics of Composites In this chapter we consider the results of incorporating a reinforcement (fibers, whiskers, particles, etc.) in a matrix to make a composite. It is of great importance to be able to predict the properties of a composite, given the properties of the components and the geometric arrangement of the components in the composite, We examine various micromechanical aspects of composites. A particularly simple case is the rule-of-mixtures, a rough tool that considers the composite properties as volume-weighted averages of the component properties. It is important to realize that the rule-of-mixtures works in only certain simple situations. Composite density is an example where the rule-of-mixtures is applied readily. In the case of mechani- cal properties, there are certain restrictions to its applicability. When more precise information is desired, itis better to use more sophisticated approaches based on the theory of elasticity. 10.1 Density Consider a composite of mass m, and volume v.. The total mass of the composite is the sum total of the masses of fiber and matrix, that is, me = My + Mm. (10.1) The subscripts ¢, f, and m indicate composite, fiber, and matrix, respectively. Note that Eq. (10.1) is valid even in the presence of any voids in the composite. The volume of the composite, however, must include the volume of voids, vy. Thus, 1p + Vin +e (10.2) K.K. Chawla, Composite Materials: Science and Engineering, 337 DOI 10.1007/978-0-387-74365-3_10, © Springer Science+Business Media New York 2012338 10 Micromechanics of Composites Dividing Eq. (10.1) by me and Eq. (10.2) by ve and denoting the mass and volume fractions by My, My, and Vs, Vn, Vv, respectively, we can write My +My = 1 (10.3) and Vp + Vn + Vv = (10.4) The composite density p. (= mc/v.) is given by 25% + Pm Ve or Pe = PAVi + PmnVm- (10.5) We can also derive an expression for p. in terms of mass fractions. Thus, Me me Ym tM My/P, Mn] Py PY 1 My / py + Min] Pm + Yv/Me 1 ~ Mp]0; + Mn] Pn + Vo] PM 1 ~Mj]0; + Mn] Pm Vo] Pe (10.6) We can use Eq. (10.6) to indirectly measure the volume fraction of voids in a composite. Rewriting Eq, (10.6), we obtain Pe [Mr/ey + Mn/ Pn] + ¥s or My, Mm ~p.[ 2+"). 10.7) it (% Me) mea Example 10.1 A thermoplastic matrix contains 40 w1.% glass fiber. If the density of the matrix, Pm, is 1.1 g/cm? while that of glass fiber, py, is 2.5 g/cm*, what is the density of the composite? Assume that no voids are present,