7.2 The Structure of Polymers 201 7.2 The Structure of Polymers Many of the polymer properties depend largely om the structure of individual polymer molecules, molecule shape and size, and how they are arranged to form a polymer structure. Polymer molecules are characterized by their extraordinary size, 4 feature that distinguishes them from other organic chemical compositions. Polymers are long- chain molecules, also called macromolecules or giant molecules, which are formed by polymerization, that is, by linking and cross-linking of different monomers. A mono- mer is the basic building block of polymers. The word mer, from the Greek meros, meaning part, indicates the smallest repetitive unit, similar to the term unit cell used in connection with erystal structures of metals. The term poly-mer means many mers or units, generally repeated hundreds or thousands of times in a chainlike structure. Most monomers are organic materials in ‘which carbon atoms are joined in covalent (electron-sharing) bonds with other atoms, such as hydrogen, oxygen, nitrogen, fluorine, chlorine, silicon, and sulfur. An ethyl. ene molecule, shown in Fig. 7.2a, is a simple monomer consisting of carbon and hydrogen atoms. 7.2.1 Polymerization Monomers in polymers can be linked in repeating units to make longer and laeger molecules by a chemical reaction known as the polymerization reaction. Polymeriza~ tion processes are complex and can be deseribed only briefly here. Although there are many variations, two basic polymerization processes are condensation and addition polymerization. In condensation polymerization, polymers are produced by the formation of bonds berween two types of reacting mers. One characteristic of this reaction is that reaction by-products such as water are condensed out, hence the term condensation. This process is also known as step-growth or step-reaction polymerization because the polymer molecule grows step by step until all of one reactant is consumed. In addition polymerization, also known as chain-growth or chain-reaction poly- merization, bonding takes place without reaction by-products. It is called chain- reaction because of the high rate at which long molecules form simultaneously, usvally within a few seconds. This rate is much higher than that for condensation polymeriza- tion. In this reaction, an initiator is added to open the double bond between the carbon atoms and begins the linking process by adding maay mote monomers to 2 growing chain. For example, ethylene monomers (Fig. 7.2a) link to produce a polymer known as polyethylene (Fig, 7.26). Other examples of addition-formed polymers are shown in Fig. 7.2c. Molecular weight. The sum of the molecular weight of the mers in the polymer chain is the molecular weight of the polymer. The higher the molecular weight in a given polymer, the greater the chain length. Because polymerization is a random202 7 « Polymers: Structure, General Properties, and Applications: a a ob ne wali ala w Heat, pressure Lids itl cat Heat. pressure, —C-C46—C46—C~ } Polyethytene Ih catalyt Polet vith t HOH Ania Win oH Jn © Monomer Palymer repeating unit aH HoH il il onc =c-0- | Polypropylene io lot HCH Hook Jn HoH HoH Io !oL gmc —C-C- } posing rides HO Kat Jn a HOH | il c —C-6— \ Polystyrene I iI H HGH fo FFL nA 11 | cae —C—C— | Polytetratuoroethylene PTFE! it if (Tefon) A FL Fir Ja LO, Basie structure of polymer molecules: (a) ethylene molecule; (b} polyethylene, a linear chain of many ethyiene molecules; (c) molecular structure of various polymers. These ere examples of the basie building blocks for plastics. event, the polymer chains produced are not all of equal length, but the chain lengths produced fall into a traditional distribution curve, We determine and express the aver- age molecular weight of a polymer on a statistical basis by averaging, The spread of the molecular weight distribution is referred to as the molecular weight distribution (MWD). Molecular weight and MWD have a strong influence on the properties of the polymer. For example, tensile and impact strength, resistance to cracking, and vis- cosity in the molten state all increase with increasing molecular weight (Fig. 7.3). Most commercial polymers have a molecular weight between 10,000 and 10,000,000. Degree of polymerization. In some cases, itis more convenient to express the size of a polymer chain in terms of the degree of polymerization (DP), defined as the7.2. The Structure of Polymers 203 1 Commercial polymers Tensile and impact strength Property Viscosity CUTS Effect of molecular weight and degree of poly- T0000) 70,000,000 merization on the strength and viscosity of Molecular weight polymers. egtee of polyme:izaiion ratio of the molecular weight of the polymer to the molecular weight of the repeat unit, For example, polyvinyl chloride (PVC) has a mer weight of 62.5, thus the DP of PYC having a molecular weight of 50,000 would be 50,000/62.5 = 800. In terms of polymer processing (see Chapter 18), the higher the DP, the greater is the polymer’ viscosity, or resistance to flow (Fig. 7.3), thus affecting ease of shaping and overall cost of processing, Bonding. During polymerization the monomers are linked together in a cova lene bond, forming a polymer chain. Because of their strength, covalent bonds are also called primary bonds. The polymer chains are, in turn, held together by the second- ary bonds, such as van der Waals bonds, hydrogen bonds, and ionic bonds. Secondary bonds are much weaker than primary bonds, by one to two orders of magnitude. Ina given polymer, the increase in strength and viscosity with molecular weight comes in part from the fact that the longer the polymer chain, the greater is the energy needed to overcome the secondary bond strength. For exanaple, ethylene mers having a DP of 1, 6, 35, 140, and 1350 are, respectively, in the form of gas, liquid, grease, wax, and hard plastic at room temperature. Linear polymers. ‘The chainlike polymers shown, in Fig. 7.2 are called linear polymers because of their linear structure (Fig, 7.4a). A linear molecule is not steaight in shape. In addition to those shown, other inear polymers are polyamides (nylon 6,6) and polyvinyl fluoride, Generally, a polymer consists of more than onc type of strue- ture. Thus a linear polymer may contain some branched and cross-linked chains. As a result of branching and cross-linking, the polymer’s properties can change.204 7 + Polymers: Structure, General Properties, and Applications fa) Linear TO (e) Crose-linked @ Network CRE ‘Schematic illustration of polymer chains. (a) Linear Structure. Thermoplastics such as acrylics, nylons, polyethylene, and polyvinyl chioride have linear struc {ures. [b} Branched structure, such as in polyethylene. (c) Cross-linked structure. Many rubbers or elastomers, have this structure. Vulcanization of rubber produces ‘this structure. (d) Network structure, which is basically highly cross-linked. Examples are thermosetting plas ties, such as epoxies and phenolics. Branched polymers. ‘The properties of a polymer depend not only on the type of monomers, but also on their arrangement in the molecular stracture, In branched polymers (Fig, 7.4), side-branch chains are attached to the main chain during the syathesis of the polymer. Branching interferes with the relative movement of the molecular chains. Asa result, resistance to deformation and stress-crack resistance are affected. Also, the density of branched polymers is lower than that of linear-chain polymers as branches interfere with the packing efficiency of polymer chains. The behavior of branched polymers can be compared to that of linear-chain polymers by making an analogy with a pile of cree branches (branched polymers) and a bundle of straight logs (linear). You will note that it is more difficult to move a branch within the pile of branches than to move a log in its bundle. The three-dimensional entanglements of branches make movements more difficult, a phenomenon akin to increased strength. Cross-linked polymers. Generally three-dimensional in structure, cross-linked polymers have adjacent chains linked by covalent bonds (Fig, 7-c). Polymers with cross-linked chain structure are called thermosets, or thermosetting plastics, such as epoxies, phenolics, and silicones. Cross-linking has a major influence on the proper- ties of polymers (generally imparting hardness, strength, stiffness, brittleness, and bet-‘7.2 The Structure of Polymers: 205 lass Increas: cee roe inking Elastic modulus (log seale} Elastic modulus (og seale) ‘Temperature ‘Temperature FIGURE 7.5 Behavior of polymers as a function of temperature and (a) dagree of erystallinity and {b) cross- linking. The combined elastic and viscous behavior of polymers is known as viscoelasticity. ter dimensional stability; see Fig. 7.5), as well as in the oulcenization of rubber. Network polymers consist of spatial (three-dimensional) networks of three active covalent bonds (Fig, 7.44). A highly cross-linked polymer is also considered a net- work polymer. Thermoplastic polymers that have already been formed or shaped can be cross linked to obtain greater strength by subjecting them to high-energy radiation, such as ultraviolet light, x-rays, or electron beams, However, excessive radiation can cause degradation of the polymer. Copolymers and terpolymers. Ifthe repeating units in a polymer chain are ail of the same type, we call the molecule a homopolymer. However, as with solid- solution metal alloys, two or three different types of monomers can be combined to impart certain special properties and characteristis to the polymer, such as improving both the strength and toughness as well asthe formability of the polymer. Copalymers contain two types of polymers, such as styrene-butadiene, used widely for automobile ties. Terpolymers contain three types, such as ABS (acrylonitrile-butadiene-styrene) used for helmets, telephones, and refrigerator liners. 7.2.2 Crystallinity Polymers such as polymethylmethacrylate, polycarbonate, and polystyrene are gen- erally araorphous; that is, the polymer chains exist without long-range order (see also amorphous alloys in Section 6.14). The amorphous arrangement of polymer chains is often described as a bow! of spaghetti, or worms in a bucket, all intertwined with each206 7 Polymers: Structure, General Properties, and Applications FIGURES --—Amorphous fi . reson Crystalline region Amorphous and crystalline regions in a polymer. The crystalline region crystallite} has an orderly arrange- ment of molecules. The her the crystallinity, the harder, stiffer, and less ductile is the polymer. other, However, in some polymers it is possible to impart some crystallinity and thereby modify their characteristics. This may be done either during the synthesis of the polymer or by deformation during its subsequent processing. The crystalline regions in polymers are called crystallites (Fig, 7.6). These crystals are formed when the long molecules arrange themselves in an orderly manner, similar to folding a fire hose in a cabinct or facial tissues in a box. Thus we can regard a partially crystalline (semi-crystalline) polymer as a two-phase material, one phase being crystalline and the other amorphous. By controlling the rate of solidification during cooling and chain structure, itis possible to impart different degrees of crystallinity to polymers, although never com- pletely 100 percent. Crystallinity ranges from an almost complete erystal, up to about 95 percent by volume in the case of polyethylene, to slightly crystallized but mostly amorphous polymers. Effects of crystallinity. The mechanical and physical properties of polymers are greatly influenced by the degree of crystallinity. As it increases, polymers become stiffer, harder, less ductile, more dense, less rubbery, and more resistant to solvents and heat (Fig. 7.5). The increase in density with increasing crystallinity is caused by crystallization shrinkage and a more efficient packing of the molecules in the crystal lattice. For example, the highly crystalline form of polyethylene, known as high: density polyethylene (HDPE), has a specific gravity in the range of 0.941 to 0.970 (80 to 95 percent crystalline) and is stronger, stiffer, tougher, and less ductile than low- density polyethylene (LDPE), which is about 60 to 70 percent crystalline and has a specific gravity of about 0.910 to 0.925. Optical properties are also affected by the degree of crystallinity. The reflection of light from the boundaries between the crystalline and amorphous regions in the polymer causes opaqueness. Furthermore, because the index of refraction is pro- portional to density, the greater the density difference between the amorphous and7.2. The Structure of Polymers 207 crystalline phases, the greater is the opaqueness of the polymer. Polymers that are completely amorphous can be transparent, such as polycarbonate and acrylics. 7.2.3. Glass-transition temperature Amorphous polymers do not have a specific melting point, bue they undergo a distinct change in cheir mechanical behavior across a narrow range of temperature. At low temperatures they are hard, rigid, brittle, and glassy and at high temperatures ate rub- bery or leathery. The temperature at which this ransition occurs is called the glass- transition temperature, 7,, and is also called the glass point or glass temperature. The term glass is included in this definition because glasses, which are amorphous solids, behave in the same manner (as you can see by holding a glass rod over a fame and observing its behavior). Although most amorphous polymers exhibit this behavior, here are some excep- tions, such as polycarbonate, which is not rigid or brittle below its glass-transition temperature. Polycarbonate is tough at ambient temperature and is thus used for safety helmets and shields. ‘To determine 7,, we measure the specific volume ofthe polymerand plorit against temperature to find the sharp change in the slope of the curve (Fig. 7.7), However, in the case of highly cross-linked polymers, he slope of the curve changes gradually neat T,, making it difficult to determine T, for these polymers. The glass-transition tem- erature varies with different polymers (Table 7.2). For example, room temperature Amorphous: g alors i Panty é erytline i olymers FIGURE 7) ‘Specific volume of polymers as a function af tempera- ture. Amorphous polymers, such as acrylic and poly- carbonate, have a glass-transition temperature, T,, but do not have a spacific melting point, T,. Partly crystal: Z line polymers, such as polyethylene and nytons, con- * tract sharply at their melting points during cooing, Temperature208 7 « Polymers: Structure, General Properties, and Applications AE. ———— GLASS-TRANSITION AND MELTING TEMPERATURES OF SOME POLYMERS Materi TCC) TC) Nylon 66 37 265 Polycarbonate 150 288 Polyester 3 265 Polyethylene High density 90 437 Low density -110 115 Polymethylmathacrylate 105 - Polypropylene -4 176 Polystyrene 700 239 Polytctrafluoroethyiene -90 327 Polyvinyl chloride 87 22 Rubber -73 - is above T, for some polymers and below it for others. Unlike amorphous poly mers, partly crystalline polymers have a distinct melting point, T, (Fig. 7.7; see also Table 72). Because of the structural changes (first-order changes) occurring, the spe~ cific volume of the polymer drops suddenly as its temperature is reduced, 7.2.4 Blends To improve the brittle behavior of amorphous polymers below their glass-transition temperature, we can blend them (mix them with another polymer), usually with small quantities of an elastomer. These tiny particles are dispersed throughout the amor- phous polymer, enhancing its toughness and impact strength by improving its resis tance to crack propagation. These are known as rubber modified polymers. More recent trends in blending involve several components, or polyblends, that utilize the favorable properties of different polymers. Some advances have been made in miscible blends (mixing without separation of two phases), process similar to alloying of met- als, enabling polymer blends to become more ductile. Polymer blends account for about 20 percent of all polymer production. pt SR SS 7.3 Thermoplastics We noted earlier that the bonds between adjacent long-chain molecules (secondary bonds) are much weaker than the covalent bonds (primary bonds) within each mole- cule. Also, it is the strength of the secondary bonds that determines the overall strength of the polymer. Linear and branched polymers have weak secondary bonds73 Thermoplastics 209 For certain polymers, as the temperature is raised above the glass-transition tem: perature 7, or melting point 7.,, we find that it becomes easier to form or mold them into desired shapes, The increased temperature weakens the secondary bonds via ther mal vibration of the long molecules, and the adjacent chains can thus move more easily under the shaping forces. If we then cool the polymer, it returns to its original hard- ress and strength. In other words, the process is reversible. Polymers that exhibit this behavior are known as thermoplasties. Typical examples are acrylics, cellulosics, nylons, polyethylenes, and polyvinyl chloride. In addition to their structure and composition, the behavior of thermoplastics depends on a number of variables. Among the most important are temperature and rate of deformation, Below the glass-transition temperature, most polymers are glassy (brittle) and behave like an elastic solid; that is, the relationship berween stress and strain is linear, For exarnple, below its T,, polymethylmethacrylace (PMMA) i glassy, whereas polycarbonate is not glassy below its T,. The glassy behavior can be represented by a spring whose stiffness is equivalent to the modulus of elasticity of the polymer. When the applied stress is increased, the polymer fractures, just asa piece of glass does at ambient temperature. The mechanical properties of several polymers listed in Table 7.1 indicate that thermoplastics are about two orders of magnicude less stiff than metals. Their ultimate tensile strength is about one order of magnitude lower than that of metals (see Table 2.1). Typical stress-strain curves for some thermoplastics and thermosets at room tem- perature are shown in Fig. 7.8. Note that these plastics exhibit different behaviors, which we may deseribe as rigid, soft, brite, flexible, and so on, Plastics undergo fatigue and creep phenomena, just as metals do. Rigid and brittle ‘melamine, phenolic) ‘Tough and ductile (ABS, nylon) Stress Soft and flexible FIGURE 7.2 — ite General terminology describing the behavior of three (polyethylene, PTFE! types of plastics. PTFE (polytotrafiuoroathylene)is Tel: 0 Jon,a trade name. Source: R.L.E. Brown, Strain210 7 = Polymers: Structure, General Properties, and Applications ie Effect of temperature on the stress-strain curve for cellulose acetate, a thermoplastic. Note the large drop in strength and increase in ductility with a relatively small increase intemperature. Source: After. S. Cars- well and H.K. Nason, ‘Stress (psi x 10% wl ko 60 . 4 » 8 400 € wes os wis Bas 30 Strain (1 Effects of temperature, If we raise the temperature of a thermoplastic polymer above its T,, it first becomes leathery, and then rubbery with increasing temperature (Fig. 7.5). Finally, at higher temperatures, e.g., above T,, for crystalline thermoplastics, it becomes a viscous fluid, with viscosity decreasing with increasing temperature. At still higher temperatures, the response of a thermoplastic can be likened to ice cream, Itcan be softened, molded into shapes, refrozen, softened, and remolded a number of FICE. ———— Effect of temperature on the impact strength of various plastics. Small changes in temperature can have a significant effect on impact strength. Source: P, C. Powell Impact strength c =18 ° 2 Low-density Polyethylene High-impact polypropylene Polyvinyl chloride Polymethylmethacrylate L L 0 3 Ey ‘Temperature CP)7.3. Thermoplastics 21 times. In practice, however, repeated heating and cooling causes degradation, or ther- mad aging, of thermoplastics. ‘The typical effects of temperature on the strength and elastic modulus of thermo- plastics are similar to those for metals. Thus with increasing temperature, the streng:h and modulus of elasticity decrease, and toughness increases (Fig. 7.9). The effect of temperature on impact strength is shown in Fig. 7.10. Note the large difference in the impact behavior of various polymers. Effect of rate of deformation. ‘The behavior of thermoplastics is similar to the strain-rate sensitivity of metals, indicated by the strain-rate sensitivity exponent m in Eq, (2.9). Thermoplastics in general have high m values, indicating that they can undergo large uniform deformations in tension before fracture (Fig. 7.11). Note how—unlike in ordinary metals—the necked region elongates considerably. You can @ mm © 0 25, 50 15, 100 195 100) 4 vw 19 1 aif | qi ' a 4 oy 1 a] | 3 4 5 ' Blagation Gn) I Testes Meese L FIGURE 7.11 (a) Load-elongation curve for polycarbonate, a thermoplastic. Source: f. P. Kambour and R. E Robertson. (b) High-density polyethylene tensile-test speciman, showing uniform elongation ithe Jong, narrow region in the speci212 7 + Polymers: Structure, General Properties, and Applications easily demonstrate this phenomenon by stretching 4 piece of the plastic holder for Gepack beverage cans. Observe that the sequence of necking and stretching behavior is as shown in Fig. 7.11a, This characteristic, which is the same as in the supesplastic metals, enables the thermoforming of thermoplastics into complex shapes such as bottles for soft drinks, meat trays, and lighted signs. Orientation. When thermoplastics are deformed, say by stretching, the long- chain molecules aliga in the general direction of elongation. This process is called orientation and, just as in metals, the polymer becomes anisotropic. The specimen becomes stronger and stiffer in the elongated (stretched) direction than in its trans- verse direction. This is an important technique to enhance the strength and toughness of polymers, However, orientation weakens the polymer in the transverse direction, Crazing. Some thermoplastics, such as polystyrene and polymethylmethacry- late, develop localized, wedge-shaped, narrow regions of highly deformed material when subjected to tensile stresses or to bending. This phenomenon is called crazing. Although they may appear to be like cracks, crazes are spongy material, typically ‘containing about 50 percent voids. With increasing tensile load on the specimen, these voids coalesce to form a crack and eventually lead to fracture of the polymer. Crazing has been observed both in transparent glassy polymers and in other types The environment and the presence of solvents, lubricants, and water vapor enhance the formation of crazes (environmental stress cracking and solvent crazing). Residual stresses in the material contribute to crazing and cracking of the polymer. Radiation and ultraviolet radiation can adversely affect the crazing behavior in certain polymers. A related phenomenon is stress whitening. When subjected to tensile stresses, such as by folding or bending, the plastic becomes lighter in color. This phenomenon, is usually attributed to the formation of microvoids in the material. As a result, the material becomes less translucent (transmits less light), or more opaque. You can easily demonstrate this result by bending plastic components commonly found in house~ hold products and toys, Water absorption. An important limitation of some polymers, such as nylons, is their ability to absorb wacer. Water acts as a plasticizing agent; that is, it makes the polymer more plastic. Thus in a sense, it lubricates the chains in the amorphous region. Typically, with increasing moisture absorption, the glass-transition tempera- ture, the yield stress, and the elastic modulus of the polymer are lowered severely. Dimensional changes also occur because of water absorption, such as in a humid environment. Thermal and electrical properties. Compared to metals, plastics are generally characterized by low thermal and electrical conductivity, low specific gravity (ranging from 0.90 to 2.2), and relatively high coefficient of thermal expansion, which is about an order of magnitude higher. Most polymers are electrical insulators and hence are used for insulators and as packaging material for electronic components. However, the electrical conductivity ofrena SERPS Example: 7.4 Thermosets 213 some polymers can be increased by doping (introducing certain impurities in the polymer, such as metal powder, salts, and iodides). One of the eatliest conducting polymers developed was polyacetylene. Applications for conducting polymers include microelectronic devices, rechargeable batteries, and electric power equipment. The electronic properties of polymers can be changed by irradiation. The electrical con- ductivity of polymers also increases with moisture absozption. Use of conducting polymers in rechargeable batteries —_—_————— One of the earliest applications of conducting polymers was in rechargeable batceries ‘The cathode is made of a conducting polymer and the anode is lithium (a soft, silver- white element that is the lightest metal known) or lithium alloy. Developments are now taking place in making battery cells in which both electrodes are made of con- ducting polymers; one has been constructed with a capacity of 3.5 V. =" Creep and Stress Relaxation. We have defined creep and stress relaxation in Section 2.8, Due to their viscoelastic behavior, thermoplastics are particularly suscep- tible to these phenomena, to a larger extent than metals are. The extent of creep and relaxation depends on the materialy the stress level, remperature, and time. 7.4 Thermosets When the long-chain molecules in a polymer are cross-linked in a three-dimensional arrangement, the structure in effect becomes one giant molecule with strong covalent bonds. As we previously stated, these polymers are called thermosetting polymers, or thermosets, because during polymerization the network is completed and the shape of the partis permanently set, This curing (cross-linking) reaction, unlike that of ther~ moplastics, is irreversible. We can liken the response of a thermosetting plastic to tem- perature to baking a cake or boiling an egg. Once the cake is baked and cooled, or the egg boiled and cooled, reheating it will not change its shape. Some thermosets, such as epoxy, polyester, and urethane, cure at room tempera- ture, Although curing takes place at ambient temperature, the heat of the exothermic reaction cures the plastic. Thermosetting polymers do not have a sharply defined glass-transition temperature. The polymerization process for thermosets generally takes place in two stages. The first is at the chemical plant where the molecules are partially polymerized into linear chains. The second stage is at the parts-producing plant where cross-linking is completed under heat and pressure during the molding and shaping of the part. Because of the nature of their bonds, the strength and hardness of the thermosets, unlike thermoplastics, are not affected by temperature or rate of deformation. A typi- cal thermoset is phenolic, which is a product of the reaction between phenol and form-214 7 Polymers: Structure, General Properties, and Applications aldehyde. Common products made from this polymer are the handles and knobs on ing pots and pans and components of light switches and outlets. Thermosetting plastics generally possess berser mechanical, thermal, and chemical properties; elec trical resistance; and dimensional stability than do thermoplastics. However, if the temperature is increased sufficiently, the thermosetting polymer begins to burn up, degrade, and char. ives In order to impart certain specific properties, polymers are usually compounded with additives. These additives modify and improve certain characteristics of polymers, such as their stiffness, strength, color, weatherability, flammability, arc resistance for electrical applications, and ease of subsequent processing. Fillers used are generally wood flour (fine sawdust), silica flour (fine silica pow- der), clay, powdered mica, and short fibers of cellulose, glass, and asbestos. Because of their low cost, fillers are important in reducing the overall cost of polymers. Depend- ing on their type, fillers improve the strength, hardness, toughness, abrasion resis- tance, dimensional stability, and/or stiffness of plastics. These properties are greatest at various percentages of different types of polymer~filler combinations. As in rein- forced plastics, a filler’ effectiveness depends on the nature of the bond between the filler material and the polymer chains. Plasticizers are added to some polymers to impart flexibility and softness by low- ering their glass-transition temperature. Plasticizers are low molecular weight solvents with high boiling points (nonvolatile). They reduce the strength of the secondary bonds becween the long-chain molecules, thus making the polymer soft and flexible. ‘The most common use of plasticizers is in polyvinyl chloride (PVC), which remains Aexible during its many uses. Other applications of plasticizers are in thin sheet, film, tubing, shower curtains, and clothing materials. Most polymers are adversely affected by ultraviolet radiation (sunlight) and oxy- gen, which weaken and break the primary bonds, resulting in the scission (splicting) of the long-chain molecules. The polymer then degrades and becomes brittle and stiff On the other hand, degradation may be beneficial, a in the disposal of plastic objects by subjecting them to environmental attack. ‘A typical example of protection against ultraviolet radiation is the compounding of certain plastics and rubber with carbon black (soot). The carbon black absorbs a high percentage of the ultraviolet radiation, Protection against degradation by oxide- tion, particularly at elevated temperatures, is done by adding antioxidants to the poly- mer. Various coatings are another means of protecting polymers. The wide variety of colors available in plastics is obtained by adding colorants. ‘These materials are either organic (dyes) or inorganic (pigments). The selection of a colorant depends on service temperature and exposure to light, Pigments are dispersed particles and generally have greater resistance than dyes to temperature and light.7.6 General Properties and Applications of Thermoplasties 215 IE the temperature is sufficiently high, most polymers will ignite. The flamma- biliey (ability to support combustion) of polymers varies considerably, depending on their composition (such as the chlorine and fluorine content). Polymethylmeth~ acrylate, for exaniple, continues to bun when ignited, whereas polycarbonate self- extinguishes. The flammability of polymers can be reduced either by making thei from less flammable raw materials, or by the addition of flame retardants, such as compounds of chlorine, bromine, and phosphorus. Lubricants may be added to polymers to reduce friction during their subsequent processing into useful products and to prevent parts from sticking to the molds, Lubrication is also important in preventing thin polymer films from sticking to each other. 7.6 General Properties and Applications of Thermoplastics This section outlines the general characteristics and typical applications of major ther- moplastics, particularly as they relate to manufacturing plastic products and their service life, General recommendations for various plastics applications are given in Table 7.3. Acetals (from acetic and alcohol) have good strength, stiffness, and resistance to creep, abrasion, moisture, heat, and chemicals. Typical applications are mechanical parts and components where high performance is required over a long period: beac- ings, cams, gears, bushings, rollers, impellers, wear surfaces, pipes, valves, shower heads, and housings. Common trade name: Delrin. TABLE 7.3 GENERAL RECOMMENDATIONS FOR PLASTIC PRODUCTS Design Requirement Applications Plastics ‘Mechanical strength Gears, cams, rollers, valves, fan Acetal, nylon, phenolic, polycarbonate blades, impellers, pistons Functional and decorativo Handles, knabs, camera and battery ABS, acrylic, cellulosic, phenolic, poly- cases, rim moldings, pipe fittings athylene, polypropylene, polystyre: polyvinyl chloride Housings end hotlow shapes Power tools, pumps, housings, sport AGS, cellulosic, phenolic, polycarbon- helmets, telephone cases ate, polyethylene, polypropylene, polystyrene Functional and transparent Lenses, goggles, safety glazing, signs, Acrylic, polycarbonate, polystyrene, food:processing equipment, labora- polysulfone tory hardware Wear resistance Gears, wear strips and liners, bear- Acetal. nylon, phenolic, polyimide, ings, bushings, roller-skate wheels polyurethane, ultrahigh molecular weight polyathylene216 7 + Polymers: Structure, General Properties, and Applications Acrylics (polymethylmethacrylate, PMMA) possess moderate strength, good optical properties, and weather resistance. They are transparent but can be made opaque, are generally resistant to chemicals, and have good electrical resistance. Typi- cal applications are lenses, lighted signs, displays, window glazing, skylights, bubble tops, auromotive lenses, windshields, lighting fixtures, and furniture, Common trade names: Plexiglas, Lucite. Acrylonitrile-butadiene-styrene (ABS) is dimensionally stable and rigid and has good impact, abrasion, and chemical resistance; strength and toughness; low- temperature properties; and electrical resistance. Typical applications are pipes, fittings, chrome-plated plumbing supplies, helmets, tool handles, aucomotive components, boat hulls, telephones, luggage, housing, appliances, refrigerator liners, and decorative nels. pan elluosies have a wide range of mechanical properties, depending on composi- tion, They can be made rigid, sttong, and tough. However, they weather poorly and are affected by heat and chemicals. Typical applications are tool handles, pens, knobs, frames for eyeglasses, safety goggles, machine guards, helmets, cubing and pipes, light- ing fixtures, rigid containers, steering wheels, packaging film, signs, billiard bas, toys, and decorative parts. Fluorocarbons possess good resistance to temperature, chemicals, weather, and electricity. They also have unique nonadhesive properties and low friction. ‘Typical applications are linings for chemical process equipment, nonstick coatings for cook- ware, electrical insulation for high-temperature wire and cable, gaskets, low-friction surfaces, bearings, and seals. Common trade name: Teflon. Polyamides (from the words poly, amine, and carboxyl acid) are available in two main types: nylons and aramids. Nylons (a coined word) have good mechanical prop- erties and abrasion resistance. They are self-lubricating and resistant to most chemicals. All aylons are hygroscopic (absorb water). Moisture absorption reduces mechanical properties and increases part dimensions. Typical applications are gears, bearings, bushings, rollers, fasteners, zippers, electrical parts, combs, tubing, wear-resistant sur- faces, guides, and surgical equipment. Aramids (aromatic polyamides) have very high tensile strength and stiffness. Typical applications are fibers for reinforced plastics (composite materials), bulletproof vests, cables, and radial tires. Common trade name: Kevlar. Polycarbonates are versatile and have good mechanical and electrical properties. They also have high impact resistance, and can be made resistant to chemicals. Typical applications are safety helmets, optical lenses, bullet-resistant window glazing, signs, bottles, food-processing equipment, windshields, load-bearing electrical components, electrical insulators, medical apparatus, business machine components, guards for machinery, and parts requiring dimensional stability. Common trade name: Lexan Polyesters (thermoplastic; see also Section 7.7) have good mechanical, electrical, and chemical properties; good abrasion resistance; and low friction. Typical applica- tions are gears, cams, rollers, load-bearing members, pumps, and electromechanical components. Common trade names: Dacron, Mylar, Kodel. Polyethylenes possess good electrical and chemical properties. Their mechanical properties depend on composition and steucture. Three major classes are low density7.7 General Properties and Applications of Thermosetting Plastics 217 (LDPE), high density (HDPE), and ultrahigh molecular weight (UHMWPE). Typi- cal applications for LDPE and HDPE ate housewares, bottles, garbage cans, ducts, bumpers, luggage, toys, tubing, bottles, and packaging material; UHMWPE are used in parts requiring high-impact toughness and abrasive wear resistance, Polyimides have the structure of a thermoplastic but the nonmelting characteristic of a thermoset, See Section 7.7. Polypropylenes have good mechanical, electrical, and chemical properties and good resistance to tearing, Typical applications are automotive trim and components, medical devices, appliance parts, wire insulation, TV cabinets, pipes, fittings, drinking cups, dairy-product and juice containers, luggage, ropes, and weather stripping. Polystyrenes are inexpensive, have generally average properties, and are somewhat bridle, Typical applications are disposable containers; packaging; trays for meats, cookies, and candy; foam insulation; appliances; automotive and radio/ TV compo- nents; housewares; and toys and furniture parts (as a wood substitute) Polysulfones have excellent resistance to heat, water, and steamy are highly resis tant to some chemicals; but are attacked by organie solvents, Typical applications are steam irons, coffeemakers, hotwater containers, medical equipment that requires ster~ ilization, power-tool and appliance housings, aircraft cabin interiors, and electrical insulators, Polyvinyl chloride (PVC) has a wide range of properties, is inexpensive and water-resistant, and can be made rigid ot flexible, It is nor suitable for applications requiring strength and heat resistance. Rigid PVC is tough and hard. Rigid PVC is used for signs and in the construction industry, such as pipes and conduits. Flexible PVC is used in wire and cable coatings, low-pressure flexible tubing and hose, foot ‘wear, imitation leather, upholstery, records, gaskets, seals, trim, film, sheet, and coat- ings. Common trade names: Saran, Tygon. 7.7 General Properties and Applications of Thermosetting Plastics This section outlines the general characteristics and typical applications of major ther- mosetting plastics. Allkyds (from alkyl, meaning alcohol, and acid) possess good electrical insulating properties, impact resistance, and dimensional stability and have low water absorp tion. Typical applications are electrical and electronic components. Aminos (urea and melamine) have properties that depend on composition. Gener- ally, aminos are hard and rigid and are resistant to abrasion, creep,and electrical arcing. Typical applications are small appliance housings, countertops, toilet seats, handies, and distributor caps. Urea is used for electrical and electronic components, melamine for dinnerware. Epoxies have excellent mechanical and electrical properties, dimensional stability, strong adhesive properties, and good resistance to heat and chemicals. Typical appli-218 © Example: 7 © Polymers: Structure, General Properties, and Applications cations are electrical components requiring mechanical strength and high insulation, tools and dies, and adhesives. Fiber-reinforced epoxies have excellent mechanical properties and are used in pressure vessels, rocket motor casings, tanks, and similar structural components (see Chapter 9). Phenolics, although britce, are rigid, dimensionally stable, and have high resistance to heat, water, eleccricity, and chemicals. Typical applications are knobs, handles, lami- nated panels, telephones, bond material to hold abrasive grains together in grinding wheels, and electrical components, such as wiring devices, connectors, and insulatoss, Polyesters (thermosetting; see also Section 7.6) have good mechanical, chemical, and electrical properties, Polyesters are generally reinforced with glass or other fibers, ‘Typical applications are boats, luggage, chairs, automotive bodies, swimming pools, and material for impregnating cloth and paper. They also are available as casting resins. Polyimides possess good mechanical, physical, and electrical properties at ele~ vated temperatures. They also have creep resistance and low friction and wear char- acteristics, Polyimides have the nonmelting characteristics of a thermoset but the structure of a thermoplastic. Typical applications are pump components (bearings, seals, valve seats, retainer rings, and piston rings), electrical connectors for high- temperature use, aerospace parts, high-streagth impact-resistant structures, sports equipment, and safety vests, Silicones have properties that depend on composition. Generally, they weather well, possess excellent clectrical properties over a wide range of humidity and tem- perature, and resist chemicals and heat (see also Section 7.9). Typical applications are electrical components requiring strength at elevated temperatures, oven gaskets, heat seals, and waterproof materials Materials for refrigerator door Linc. ——————— In the selection of candidate materials for a door liner for refrigerators—where eggs, butter, salad dressings, and small bores are stored—the following factors should be considered: Mechanical requirements: Strength, toughness (to withstand impact, door slam- ming, racking), stiffness, resilience, and resistance to scratching and wear at oper- ating temperatures, Physical requirements: Dimensional stability and electrical insulation. Chemical requirements: Staining, odor, chemical reactions with food and bever- ages, and resistance to cleaning fluids. Appearance: Color, stability of color, surface finish, texture, and feel Manufacturing properties: Methods of manufacturing and assembly, effects of processing on material properties and behavior over a period of time, compatibil- ity with other components in the door, and cost of materials and manufacturing. An extensive study, considering all the factors involved, idemtfied ewo candidate materials for door liners: ABS (acrylonitrile-butadiene-styrene) and HIPS (high-Example: 7.8 Biodegradable Plastics 7.8 Biodegradable Plastics 219 impact polyszyrene). One aspect of the study involved the effect of vegetable oils, such as salad dressing stored in the door shelf, on the strength of these plastics. Experiments showed that the presence of vegetable oils significantly reduced the load-bearing capacity of HIPS. It was found that HIPS becomes brittle in the presence of oils (sol vent stress cracking), whereas ABS is not affected to any significant extent. Synthetic ivory for piano key$ emacs Piano keys have traditionally been made of ivory, a material that is now banned by an international treaty. Ivory keys have a fine randomly oriented irregular suciace and porosity; thus they have desirable frictional characteristics and function well under sweaty fingers of the player. Plastic substitutes have generally not been suitable and do not have the right feel, according to concert pianists. Research has led to a new polymeric material chat has the look and feel of ivory and duplicates its desirable properties, including thermal conductivity. The porosity was created by mixing the polymer with a powdered material, which is dissolved out with water after molding the Key, thus leaving irregular pores where the powder was, Source: Hi. A. Scarton, Rensselaer Polytechnic Institute. eee, One-third of plastic production is in the disposable products sector, such as bottles, packaging, garbage bags, etc, With the growing use of plastics and increasing concern over environmental issues regarding disposal of plastic products and limited landfills, major efforts are underway to develop biodegradable plastics. Although earlier efforts were not successful in producing true biodegradable plastics, three different bioplas- tics are currently available: starch-based bioplastcs, lactic-based bioplastics, and bio- plastics made from the fermentation of sugar. These three types of material degeade over various periods of time (from a few months to a few years) and have different degradability characteristics. These plastics are designed to degrade completely when exposed to microorganisms in soil or water, without producing toxic by-products. The starch-based system is the farthest slong in terms of production capacity. In this system, starch granules are processed into a powder, which is heated and becomes a sticky liquid. The liquid is then cooled, formed into pellets, and processed in con- ventional plastic-processing equipment, described in Chapter 18, Various additives are blended with the starch to impart special characteristics to the bioplastic materials. In the lactic-based system, fermenting corn or other feedstocks produces lactic acid, which is then polymerized to form a polyester resin, In the third systema, organic acids are added to a sugar feedstock. With the use of a specially developed process, the resulting reaction produces a highly crystalline and very stiff polymer which, after fur- ther processing, behaves in a manner similar to polymers developed from petroleum.229 7 + Polymers: Structure, General Properties, and Applications. Because the development of bioplastis is relatively new, their long-range perfor- mance, both during their useful life cycle as products and in landfills, has not beer fully assessed. There is also concern that emphasis on biodegradability will divert attention from the issue of recyclability of plastics and the efforts for conservation of materials and energy. he SE 7.9 Elastomers (Rubbers) Elastomers comprise a large family of amorphous polymers having a low glass- transition temperature. They have che characteristic ability to undergo large elastic deformations without rupture; they are soft and have a low elastic modulus. The term elastomer is derived from the words elastic and mer. The structure of these polymers is highly kinked (tightly twisted or curled). They stretch but then return to their origi- ral shape after the load is removed (Fig, 7.12). They can be cross-linked. The best example is the elevated-temperature vulcanization of rubber with sulfur, discovered by Charles Goodyear in 1839 and named for Vulcan, the Roman god of fire. Once the elastomer is cross-linked, it cannot be reshaped. For example, an automobile tire, which is one giant molecule, cannot be softened and reshaped, The terms rubber and elastomer are often used interchangeably. Generally, an elastomer is defined as being capable of recovering substantially in shape and size after the load has been removed. Rubber is defined as being capable of recovering from large deformations quickly. ‘The hardness of elastomers, which is measured with a durometer, increases with increasing cross-linking of the molecular chains. A variety of additives can be blended with elastomers to impart specific properties, as with plastics. Elastomers have a wide range of applications, such as high-friction and nonskid surfaces, protection against corrosion and abrasion, electrical insulation, and shock and vibration insulation. FIGURE 7.12 Typical load-elongation curve for rubbers. The clockwise loop, indiceting loading and unloading paths, is the hysteresis loss. Hysteresis gives rubbers the capacity to dissipate energy, damp vibration, and absorb shock loading, as in automobile tires and vibration dempeners placed under machinery. Blongation‘Summary 221 Examples include tires, hoses, weather stripping, footwear, linings, gaskets, seals, printing roils, and flooring A characteristic of elastomersiis their hysteresis loss in strezching or compression (Fig, 7.12). The clockwise loop indicates energy loss, whereby mechanical energy is converted into heat. This property is desirable for absorbing vibrational energy (damp- ing) and sound deadening, Natural rubber. ‘The base for natural rubber is latex, 2 milklike sap obtained from the inner bark of a tropical tree. It has good resistance to abrasion and fatigue and high frictional properties, bur it has low resistance to oil, heat, ozone, and sun- light. Typical applications are tires, seals, shoe heels, coupling, and engine mounts Synthetic rubbers. Further developed than natural rubbers are the synthetic rubbers. Examples are synthetic aatural rubber, butyl, styrene butadiene, polybuta- diene, and ethylene propylene. Compared to natural rubbers, they have improved resistance to heat, gasoline, and chemicals and higher useful temperature range. Exam- ples of synthetic rubbers that are resistant to oil are neoprene, nitrile, urethane, and silicone. Typical applications of synthetic rubbers are tires, shock absorbers, seals, and belts. Silicones (sce also Section 7.7) have the highest useful temperature range, up to 315°C (600 °F), but their other properties—such as strength and resistance to wear and ils—are generally inferior to other elastomers. Typical applications are seals, gaskets, thermal insulation, high-temperature electrical switches, and electronic apparatus. Polyurethane has very good overall properties of high strength, stiffness, and hardness and exceptional resistance to abrasion, cutting, and tearing. Typical applica- tions are seals, gaskets, cushioning, diaphragms for rubber forming of sheet metals, and auto body parts. SUMMARY Polymers are an important class of materials because they possess a very wide range of mechanical, physi- cal, and chemical properties. Compared to metas, polymers are generally characterized by lower den- sity, strength, elastic modulus, and thermal and elec- trical conductivity and a higher coefficient of thermal expansion. Plastics are composed of polymer molecules and various additives. The smallescrepetitive unitin a poly- mer chaia is called a mer. Monomers are linked by polymerization processes to form larger molecules Two major classes of polymers are thermoplasties and thermosets. Thermoplastics become soft and are exsy to form at elevated temperatures; they return to their original properties when cooled. Thermosets, which ave obtained by cross-linking polymer chains, do not become soft to any significant extent with increasing temperature. Polymer structures can be modified by various means to impart a wide range of properties to plastics. Elastomers have the characteristic ability to undergo large elastic deformations and return to their original shapes when unloaded. Consequently, they have important applications as tires, seals, footwear, hose, belts, and shock absorbers.TRENDS + Developments ate taking place to produce ultrs- high-purity polymers, high-temperaturepolymers, polymerblends, high-strengeh Sbers, optical bers, and multilayer films for optical applications, lenses, and recording media. « Recyelability of plastics is—and will continue to be—an important topic in terms of environmental KEY TER 7 + Polymers: Structure, General Properties, and Applications protection, Several biodegradable plastics areunder development. ¢ Improvements are being made in water absorption, flammability, and degradation of plastics, as well as in their physical properties. MS Addicives Latex Polyblends Branched polymers Linear polymer Polymerization Colorants Lubricants Polymers Crazing Mer Primary bonds Crosslinked polymers Moleculae weight Rubber Crystllites Monomer Secondary bonds Degree of polymerization Network polymers Stress whitening Elastomer Orientation Thermoplastics Fillers Plasticizers Thermosets Flame retardants Plastics Vuteanization Glass-transition temperarure BIBLIOGRAPHY Bittence, J C, ed., Engineering Plastics and Com- posits, Materials Park, Ohio: ASM International, 1990. ‘Chanda, M., and S. K. Roy, Plastics Technology Hand- book. New York: Marcel Dekker, 1987, Chatrier, J-M., Polymeric Materials and Processing: Plastics, Elastomers, and Composites. New York Hanser, 1991 Cheremisinoff, NP, Product Design and Testing of Polymeric Materials. New York: Marcel Dekker, 1990 Easterling, K., Tomorrow's Materials, 2d ed. London: The Institute of Metals, 1990. Engineered Materials Handbook, Vol. 2: Engineering Plastics. Metals Patk, Ohio: ASM International, 1988. Engineering Plastics and Composites, 2d ed. Materials Park, Ohio: ASM International, 1993. Harper, C., Handbook of Plastics, Elastomers, and ‘Composites, 24 ed. New York: McGraw-Hill, 1992. Kroschwitz, J. I (ed.), Concise Encyclopedia of Poly- mer Science and Engineering. New York: Wiley, 1990. MacDermots, C.P, Selecting Thermoplastcs for Engi- neering Applications. New York: Marcel Dekker, 1984, Margolis, J. M, Engineering Thermoplastics: Proper- ties and Applications, New York: Marcel Dekker, 1985. McCrum, N. G., C. P. Buckley, and C. B. Bucknall, Principles of Polymer Engineering. Oxford: Ox- ford University Press, 1988 Rosen, S. L., Fundamental Principles of Polymeric Materials, 2d ed. New York: Wiley, 1982.Rubin, I. 1 (ed.}, Handbook of Plastic Materials and Technology. New York: Wiley, 1990. Seymour, R. B., Engineering Polymer Sourcebook, New York: McGraw-Hill, 1990. , Polymers for Engineering Applications. Mec- als Park, Ohio: ASM International, 1987. REVIEW QUESTIONS 71 Summarize the most important mechanical and physical properties of plastis. 7.2 What are the major differences between the prop- erties of plastics and metals? 7.3 What are (a) polymerization and (b) degree of polymerization? What properties aze influenced by the degree of polymerization? 7.4 What is the difference between linear, branched, and cross-linked polymers? Qualitative Problems 223 Ulrich, Hi, Introduction to Industrial Polymers. New ‘York: Hanser, 1993 Young, R. J, and P. Lovell, Introduction to Polymers London: Chapman and Hall, 1991 75 Why would we want to synthesize a polymer witha high degree of crystallinity? 7.6 What is glass-teansition temperature? 77 Compare and contrast thermoplastics and ther- moses. 7.8 Whatis crazing? 7.9 What are polyblends? QUALITATIVE PROBLEMS 7.10 Inspect various plastic components in your auto mobile and state whether you thinks they are made of thermoplastic or thermosetting plastic materials. 7.1 Give applications for which flammability of plas- tics would be a major concern. 7.12 What properties do elastomers have that ther- moplastics in general do not have? 7.13 Do you think that the substitution of plastics for metals in products waditionally made of metal is viewed negatively by the public at large? If so, why? 7.14 Name three plastics chat are suitable for use at elevated cemperatures. 7.15 Is it possible for a material to have a hysteresis behavior that is the opposite of that shown in Fig. 7.12, whereby the arrows are counterclock- wise? Explain, 7.46 Observe the behavior of the specimen shown in Fig. 7.11, and state whether the material has a high or low m value. Explain why. 7.47 Add more to the applications column in Table 7.3. 78 Discuss the significance of the glass-transition temperature, 7,, in engineering applications, 7.19 Why does cross-linking improve the strength of polymers? 7.20 Describe the methods by which optical proper ties of polymers can be altered, 7.21 Can polymers be made to conduct electric- ity? How? 7.22 Explain the reasons why elastomers were devel- oped. Are there any substitutes for elastomers? Explain. 7.23 Give several examples of plasti products or com- ponents where ereep and stress relaxation are important considerations. 7.24 Describe your opinions regarding recycling of plastics vs. developing plasties that are biode- gradable. 7.25 Explain how you would go about determining the hardness of plastics described in this chapter.224 7 Polymers: Structure, General Properties, and Applications QUANTITATIVE PROBLEMS 7.26 Calculate the areas under the stress-strain curve (toughness) for the material in Fig. 7.9, plotthem 8 a function of cemperature, and deseribe your observations. 7.27 Note in Fig. 7.9 that, as expected, the elastic modulus of the polymer decreases as tempera- ture increases. Using the stress~strain curves in the figure, make a plot of the modulus of elas- ticity vs, eemperatuce. 7.28 A rectangular cantilever beam 100 mm high, 25 mm wide, and 1 m long is subjected to a con- centrased load of 100 kg at its end, Select three different uoreinforeed and reinforced materials, a SYNTHESIS AND DESIGN 7.30 What design considerations are involved in replacing a metal beverage container with one nade of plastic? 7.31 Assume that you are manufacturing 2 product in which all the gears are made of metal A salesman Visits you and asks you to consider replacing some of these metal gears with plastic ones. Make alist of the questions that you would raise before making a decision, 7.32 In Sections 7.6 and 7.7, we listed several plasties and their applications. Rearrange this informa- respectively, from Table 7.1 and calculate the maximum deflection of the beam. Then select aluminum and steel for the same beam dimen- sions, calculate the maximum deflection, and compare the results. 7.29 By contacting aucomotive suppliers, determine the dimensions of a tubular steel drive shaft for a typical automobile. If you now replace this shaft with an unreinforced and reinforced plas- tic, respectively, what should be its new dimen- sions to transmit the same torque? Choose the materials from Table 7.1 and assume a Poisson's ratio of 0.4, tion by making a table of products (gears, hel- mets, luggage, electrical parts,etc.) and thetype of plastics that can be used to make these products. 7.33 Make a list of products or parts that are not eur rently made of plastics and explain the possible reasons why they are not. 734 Review the three curves in Fig. 7.8 and name applications for each cype of behavior. Explain yout choices. 7.35 Repeat Question 7.34 for the curves in Fig. 7.10.Ceramics, Graphite, and Diamond: Structure, General Properties, and Applica 8.1 Introduction 8.4 Glasses 82 The Structure of Ceramics 85 Glass Ceramics 8.3 General Properties and 8.6 Graphite Applications of Ceramics 8.7 Diamond Introduction None of the materials discussed thus far are suitable for certain engineering applica tions. Which material, for example, would you select for an electrical insulator to be used at high temperatures? For floor tiles to resist spills, scuffing, and abrasion? For a tuansparent baking dish? For a small ball beaving chat is light, rigid, hard, and resists high temperatures? How do we protect the surfaces of the space shuttle orbiter, made of aluminum, when its skin temperature reaches 1450 °C (2650 °F) as it takes off and reenters the atmosphere? When trying to answer these questions, we soon realize that we are looking for materials with properties such as high-temperature strength; hardness; inertness to chemicals, food, and environment; resistance to wear; and low electrical and thermal conductivity. Ceramics generally have such desirable properties, Ceramics are compounds of metallicand nonmetallic elements, The term ceramics (from the Greek words keramos meaning potter’s clay and keramikos meaning clay products) refers both to the material and to the ceramic product itself, Because of the large number of possible combinations of elements, a great variety of ceramics is now available for widely different consumer and industrial applications. The earliest use of ceramics was in pottery and bricks, dating back 10 before 225226 8 + Geramies, Gr and Diamond: Structure, General Properties, and Applic 4000 B.¢. Ceramics have been used for many years in avtomorive spark plugs as an electrical insulator and for high-temperature strength. They are becoming increasingly important in tool and die materials, heat engines, and various other applications, More recent applications of ceramics are in automotive components, such as exhaust-port liners, coated pistons, and cylinder liners, taking advantage of their desirable proper- ties of strength and corrosion resistance at high operating temperatures. Ceramics can be divided into two general categories: traditional and industrial ceramics, also called engineering, high-tech, or fine ceramics. Examples of products made with traditional ceramics are whiteware, tiles, brick, sewer pipe, pottery, and abrasive wheels. Engineering ceramics are used in products such as turbine, automo- tive, and aerospace components; heat exchangers; semiconductors; seals; prosthetics; and cutting tools. In this chapter, you'll learn about the general characteristics and applications of ceramics, glasses, and glass ceramics that are of importance in engineering applications and manufacturing. Because of their unique characteristics, the properties and uses of two forms of carbon, namely, graphite and diamond, will also be discussed. (The manufacturing of ceramic and glass components, and various shaping and finishing operations, will be detailed in Chapter 19, Composites, which are an important group of materials composed of ceramics, metals, and polymers, are discussed in Chapter 9.) 8.2 The Structure of Ceramics The structure of ceramic crystals, containing various elements of different sizes, is among the most complex of all materials. The bonding between these atoms is gener- ally covalent (electron sharing, hence strong bonds) and ionic (primary bonding between oppositely charged ions, thus strong bonds). These bonds are much stronger than metallic bonds. Consequently, properties such as hardness and thermal and elec- trical resistance are significantly higher in ceramics than in metals. Ceramics are available as a single crystal or in polycrystalline form, consisting of many grains. Grain size has a major influence on the strength and properties of ceram- ies. The finer the grain size, the higher are the strength and toughness—hence the term fine ceramics. 8.2.1 Rawmat Among the oldest raw materials for ceramics is clay, a fine-grained sheetlike structure, the most common example being kaolin (from Kao-ling, a hill in China). It is a white clay, consisting of silicate of aluminum with alternating weakly bonded layers of sili- con and aluminum ions. When added to kaolinite, water attaches itself to the layers (adsorption), makes them slippery, and gives wet clay its well-known softness and plastic properties (bydroplasticity) that make it formable,82 The Structure of Ceramics 227 Other major raw materials for ceramics that are found in nature are flint (rock of very fine-grained silica, SiO.) and feldspar (a group of crystalline minerals consisting of aluminum silicates, potassium, calcium, or sodium). In cheir natural state, these raw materials generally contain impurities of various kinds, which have to be removed prior to further processing of the materials into useful products with reliable perfor- mance. Highly refined raw materials produce ceramics with improved properties, 8.2.2 Oxide ceramics Alumina, Also called corundiem or emery, alumina (aluminum oxide, AlsO;) is the most widely used oxide ceramic, either in pure form or as a raw material to be mixed with other oxides. Ic has high hardness and moderate strength. Although alu- mina exists in nature, it contains unknown amounts of impurities and possesses non- uniform properties, As a result, its behavior is unreliable, Aluminum oxide, as well as ‘on carbide and many other ceramics, are now almost totally manufactured syn~ thetically so their quality can be controlled. First made in 1893, synthetic aluminum oxide is obtained by the fusion of moiten bauxice (an aluminum oxide ore that is the principal source of aluminum), iron flings, and coke in electric furnaces. It is then crushed and graded by size by passing the particles through standard screens. Parts made of aluminum oxide are cold pressed and siotered (white ceramics). Their properties are improved by minor additions of other ceramics, such as titanium oxide and titanium carbide. Structures containing various alumina and other oxides are known as mullite and spinel and are used as refractory materials for high-temperature applications. The mechanical and physical properties of alumina are particularly suitable for applications such as electrical and thermal insulation and as cutting tools and abrasives. Zirconia and partially stabilized zirconia. Zirconia (zirconium oxide, ZrO,, white in color) has good toughness; resistance to thermal shock, wear, and corrosion, low thermal conductivity; and low friction coefficient, A more recent development is partially stabilized zirconia (PSZ), which has high strength and toughness and better reliability in performance than zirconia. It is obtained by doping the zirconia with oxides of calcium, yttrium, or magnesium. This process forms a material with fine particles of tetragonal zirconia in a cubic lattice. Typical applications include dies for hot extrusion of metals (Section 15.4.1) and zirconia beads for grinding and dispersion media for aerospace coatings, for automotive primers and topcoats, and for fine glossy print on flexible food packaging. Another important characteristic of PSZ is the fact that its coefficient of thermal expansion is only about 20 percent lower than that of cast iron, and its thermal con- ductivity is about one-third that of other ceramics. Conscquently, it is very suitable for heat-engine components, such as cylinder liners and valve bushings, to keep the cast-iron engine assembly intact. New developments to fucther improve the properties of PSZ include transformation-toughened zirconia (TTZ), which has higher toughness because of dispersed tough phases in the ceramic matrix.228 8 * Ceramics, Graphite, and Diamond: Structure, General Properties, and Applications 8.2.3 Other ceramics Carbides. ‘Typical examples of carbides are those of rungsten (WC) and titanium (TiC), used as cutting tools and die materials, and silicon carbide (SiC), used as abra- sives, a5 in grinding wheels. Tungsten carbide consists of tungsten-carbide particles with cobalt as a binder. The amount of binder has a major influence on the material's properties. Toughness increases with cobalt content, whereas hardness, strength, and swear resistance decrease. Titaninan carbide has nickel and molybdenum as the binder and is not as tough as tungsten carbide. Silicon carbide (SiC) has good resistance to wear, thermal shock, and corrosion. It has low friction coefficient and retains strength at elevated temperatures. Itis suitable for high-temperature components in heat engines and is also used as an abrasive, First produced in 1891, synthetic silicon carbide is made from silica sand, coke, and small amounts of sodium chloride and sawdust. The process is similar to making synthetic aluminum oxide. Nitrides. Another important class of ceramics is the nitrides, particularly cubic boron nitride (CBN), titanium nitride (TiN), and silicon nitride (SisN,). Cubic boron nizride, the second hardest known substance, after diamond, has spe- cial applications, such as cutting tools and abrasives in grinding wheels. I: does not exist in nature and was first made synthetically in the 1970s, with techniques similar to those used in making synthetic diamond. Titanium nitride is used widely as coatings on cutting tools. Itimproves tool life by virtue of its low frictional characteristics. Silicon nitride has high resistance to creep at elevated temperatures, low thermal expansion, and high thermal conductivicys hence it resists thermal shock. Iris suitable for high-temperature structural applications, such as in automotive-engine and gas- turbine components. Sialon. Sialon consists of silicon nitride, with various additions of aluminum oxide, yttrium oxide, and titanium carbide. The word sialon is derived from silicon, aluminum, oxygen, and nitrogen. It has higher strength and thermal-shock resistance than silicon nitride and thus far is used primasily as a cutting-tool material Cermets. Cermets are combinations of ceramics bonded with a metallic phase, Introduced in the 1960s, they combine the high-temperature oxidation resistance of ceramics and the toughness, thermal-shock resistance, and ductility of metals. An application of cermets is cutting tools, a typical composition being 70 percent alumi- num oxide and 30 percent titanium carbide. Other cermets contain various oxides, carbides, and nitrides. They have been developed for high-temperature applications such as nozzles for jet engines and aircraft brakes. Cermets can be regarded as com- posite materials and can be used in various combinations of ceramics and metals bonded by powder-metallurgy techniques.83 General Properties and Applications of Ceramics 229 824 Silica Abundant in nature, silicais a polymorphic materialythatis, it can have different erystal structures, The cubic structure is found in refractory bricks used for high-temperature furnace applications, Most glasses contain more than 50 percent silica. The most com- mon form of silica is quartz, which is a hard, abrasive kexagonal crystal. Ic is used extensively as oscillating crystals of fixed frequency in communications applications, since it exhibits the piezoelectric effect. Silicates are products of the reaction of silica with oxides of aluminum, magne- sium, calcium, potassium, sodium, and iron. Examples are clay, asbestos, mica, and silicate glasses. Lithium aluminum silicate has very low thermal expansion and thermal conductivity and good thermal-shock resistance. However, it has very low strength and fatigue life. Thus itis suitable only for nonstructural applications, such as catalytic converters, regenerators, and heat-exchanger components. 8.2.5 Nanophase ceramics A recent development is nanophase ceramics, which consist of atomic clusters contain- ing a few thousand atoms, Nanophase ceramics exhibit ductility at significantly lower temperatures than conventional ceramics, and are stronger and easier to fabricate, with fewer flaws. Possible applications in the automotive industry, for example, include valves, rocker arms, turbocharger rotors, and cylinder liners. see se at 8.3 General Properties and Applications of Ceramics Compared to metals, ceramics have the following relative characteristics: brittleness, high strength and hardness at elevated temperatures, high elastic modulus, low tough ness, low density, low thermal expansion, and low therma! and electrical conductivity. However, because of the wide variety of ceramic material composition and grain size, the mechanical and physical properties of ceramics vary significantly. For example, the electrical conductivity of ceramics can be modified from poor to good, which is the principle behind semiconductors. Because of their sensitivity to flaws, defects, and cracks (surface or internal); the presence of different types and levels of impurities; and different methods of manufac- turing, ceramics can have a wide range of properties. Although we stated the individ-~ ual characteristics of ceramics in Section 8.2, we still need to describe their general mechanical and physical properties. 8.3.1 Mechanical properties The mechanical properties of several engineering ceramics are presented in Table 8.1. ‘Note that their strength in tension (transverse rupture strength) is approximately one230 TaSLe 8.1 8 * Ceramics, Graphite, and Diamond: Structure, General Properties, and Applications, ——<—<————_—<—$——— PROPERTIES OF VARIOUS CERAMICS AT ROOM TEMPERATURE Transverse Rupture Compressive Strength Strength Hardness Poisson's Density Material Symbol__( MPa) (mPa) (HK) Ratio(e) —_tka/m*) Aluminum lO; 140-240 1000-2900 310-410 2000-3000 0.26. 4900-4500 oxide Cubicboron CBN 728, 7000 1850 4000-8000 — 3480 siteide jiamond = 1400 7000 930-1000 7000-8000 — 3500 Silica, fused = 1300 70 550 0.25 = Silicon 400-750 700-3500 240-480 ©2100-3000 0.14 3100 carbide Silicon 480-600 - 300-310 2000-2500 0.24 3300 nitride Titanium TiC 1400-1900 3100-3850 310-410 »=1800-3200 — 5500-6800 carbide Tungsten We 1030-2600 4100-6900 520-700 1800-2400 — +—=—10,000-15,000 carbide Partially Psz 620 - 200 1700 0.30 5800 stabilized zirconia ‘Note: Thane progertne vary widely capending onthe condition a he materi. order of magnitude lowerthan their compressive strength. The reasonis their sensitivity to cracks, impurities, and porosity. Such defects lead to the initiation and propagation of cracks under tensile stresses, severely reducing tensile strength. Thus reproduc- ibility and reliability (acceptable performance over 4 specified period of time) is an important aspect in the service life of ceramic components. Tensile strength of poly- crystalline ceramic parts increases with decreasing grain size ‘Although there are exceptions and unlike most metals and thermoplastics, ceram- ics generally lack impact toughness and thermal-shock resistance because of their inherent lack of ductility, Once initiated, a crack propagates rapidly. In addition to undergoing fatigue failure under cyclic loading, ceramics (and particularly glasses) exhibit a phenomenon called static fatigue. When subjected to a static tensile load over a period of time, these materials may suddenly fail. This phenomenon occurs in environments where water vapor is present. Static fatigue, which does not occur in a vacuum or dry air, has been attributed to a mechanism similar to stress-corrosion cracking of metals. Ceramic components that are to be subjected co tensile stresses may be pre- stressed, much like prestressed concrete. Prestressing shaped ceramic components subjects them to compressive stresses. Methods used include (a) heat treatment and chemical tempering, (b) laser treatment of surfaces, (c) coating with ceramics of differ-8.3 General Properties and Applications of Ceramics 231 ent therinal expansion coefficients, and (d) surface-finishing operations, such as grind- ing, in which compressive residual stresses are induced on the surfaces. Significane advances are being macle in improving the toughness and other prop- cities of ceramics. Among these advances are proper selection and processing of raw materials, control of purity and structure, and use of reinforcements, with particular emphasis during design on advanced mechods of stress analysis in ceramic components 8.3.2 Physical properties Most ceramics have a relatively low specific gravity, ranging from about 3 to 5.8 for oxide ceramics, compared to 7.86 for icon. They have very high melting or decompo- sition temperatures. Thermal conductivity of ceramies varies by a much as three orders of magnitude, depending on their composition, whereas metals vary by one order. Thermal conductivity of ceramics, as well as other materials, decreases with inereasing temperature and porosity because air is a poor thermal conductor. The thermal conductivity & is related to porosity by k= bf — P), 8.1) where Apis the thermal conductivity at zero porosity and P is the porosity as a fraction of the total volume. Thus if porosity is 15 percent, then P = 0.15. ‘Thezmal expansion and thermal conductivity induce stresses that can lead to ther tal shock or thermal fatigue. The tendency for thermal cracking (called spalling when a piece or layer from the surface breaks off) is lower with low thermal expansion and high thermal conductivity. For example, fused silica has high thermal-shock resistance because ofits virtually zero thermal expansion. A familiar example that illustrates the importance of low thermal expansion is the heat-resistant ceramics for cookware and stove tops. They can sustain bigh thermal gradients, from hot to cold, and vice versa. Moreover, the relative thermal expansion of ceramics and metals is an important reason for the use of ceramic components in heat engines. The fact that the thermal conductivity of partially stabilized zirco components is close to that ofthe cast iron in engine blocks is an additional advantage in the use of PSZ.in heat engines An additional characteristic is the anisotropy of thermal expansion exhibited by oxide ceramics, whereby thermal expansion varies in different directions of the ceramic, by as much a5 50 percent for quartz. This behavior causes thermal stresses that can lead to cracking of the ceramic component. The optical properties of ceramics can be controlled by various formulations and control of structure, imparting different degrees of transparency and colors, Single- crystal sapphire, for example, is completely transparent, zirconia is white, and fine- grained polycrystalline aluminum oxide is a translucent gray. Porosity influences the optical properties of ceramics much like trapped air in ice cubes, which makes the ice Jess transparent and gives it a white appearance.232 8 » Ceramics, Graphite, and Diamond: Structure, General Properties, and Applications Although basically ceramics are resistors, it has been shown that they can be made electrically conducting by alloying them with certain elements, thus making the ceramic act like a semiconductor or even a superconductor. 8.3.3 Applications Ceramics have numerous consumer and industrial applications. Several types of ceramics are used in the electrical and electronics industry because of their high elec- trical resistivity, dielectric strength (voltage required for electrical breakdown per unit thickness), and magnetic properties suitable for applications such as magnets for speakers. An example is porcelain, which is a white ceramic composed of kaolin, quartz, and feldspar. Certain ceramics also have good piezoelectric properties The capability of ceramics to maintain their strength and stiffness at elevated tem- peratures makes them very attractive for high-temperature applications. Their high resistance to weat makes them suitable for applications such as cylinder liners, bush- ings, seals, and bearings. The higher operating temperatures made possible by the use of ceramic components means more efficient fuel burning and reduced emissions in automobiles, Currently, internal combustion engines are only about 30 percent effi- cient, but with the use of ceramic components the operating performance can be improved by at least 30 percent. However, lubricating the bearings and other compo- nents at high temperatures is a significant problem, as conventional motor oils break down under high heat. Ceramics being used successfully, especially in automotive gas turbine engine components as rotors (Fig, 8.1), are silicon nitride, silicon carbide, and partially sta~ bilized zirconia. Coating metal with ceramics is another application, which may be done to reduce wear, prevent corrosion, and provide a thermal barrier. The tiles on the space shuttle, for example, are made of silica fibers wich an open cellular structure that consists of 5 percent silica. The rest of the tile structure is air, thus making the tile not only very lightweight but also an excellent heat barrier. The tiles (34,000 on each shutcle) are bonded to the aluminum structure of the space shuttle with several layers of silicon-based adhesives. The skin temperature on the shuttle reaches 1400 °C (2550 °F) due to frictional heat with the atmosphere. Other attractive properties of ceramics are their low density and high elastic modulus. Thus engine weight can be reduced and, in other applications, the inertial forces generated by moving parts are lower. Ceramic turbochargers, for example, are about 40 percent lighter than conventional ones. High-speed components for machine tools are also candidates for ceramics. Furthermore, the higher elastic modulus of ceramics makes them attractive for improving the stiffness, while reducing the weight, of machines. Ceramics are also used as ball bearings and rollers. Because of their strength and inertness, ceramics are used as biomaterials (bioceramics) to replace joints in the human body, as prosthetic devices, and for dental work. Furthermore, ceramic implants can be made porous, thus enabling bones to grow into the porous structure (as is also done with porous titanium implants), developing a strong bond with high83 General Properties and Applications of Coramies 233 FIGURE 8.1 A variety of ceramic components for automotive gas turbine engine applications. The three larga parts and the two small ones on the lower right are made of silicon carbide {SiCl, black in color, and the rest are rade of silicon nitride. (Siu), gray in color. These components are subjected to temperatures of up to 1400 “C (2550 *F), Source: T-Taglialavore, Norton Advanced Ceramics. structural integrity between them. Commonly used bioceramics are aluminum oxide, silicon nitride, and various compounds of silica. © Example: Ceramic ball bearings —_____-vee Silicon-nitride ceramic ball bearings are now being used in machines, particularly in high-performance spindle bearings for machine tools. The ceramic balls have a round- ness diameter tolerance of 0.13 wm (5 in.) and a surface roughness of 0.02 yum234 © Example: 34 Glasses 8 + Ceramics, Graphite, and Diamond: Structure, General Properties, and Applications (0.8 piin.). They have high wear resistance, good fracture toughness, and perform well with little or no lubrication. The balls have @ coefficient of thermal expansion one- fourth that of steel and can withstand temperatures of up to 1400 °C (2550 °F}. All-ceramic heat ¢ngi1e “Much research has been conducted in developing materials and techniques for an all- ‘ceramic heat engine capable of operating at temperatures up to 1000 °C (1830 °F). The development of such an engine has, however, been slower than expected because of problems such as unreliability and lack of sufficient toughness, difficulty with lubri- cating bearings and hot components, aecessty for reliable nondestructive evaluation techniques, and capability of structural ceramics (sueh as silicon nitride, silicon ear bide) to be produced economically in near-net shape weighed against the need for machining and finishing processes required for dimensional accuracy of the engine Consequently, all-ceramic engines are not expected until the next century. Glass is an amorphous solid with the structure of a liquid. Tn other words, it has been supercooled, that is, cooled at a rate too high for erystals to form. Generally, we define glass as an inorganic product of fusion that has cooled to a rigid condition without crystallizing. Glass has no distinet melting or freezing poimt; thus its behavior is simi- lar to amorphous polymers (Section 7.2). Glass beads were produced in about 2000 B.C, followed by glass blowing in about 200.8. Silica was used forall glass products until the late 1600s. Rapid developments in glasses began in the carly 1900s. Presently there are some 750 different types of commercially available glasses. The uses of glass range from window glass, bottles, and cookware to glasses with special mechanical, electrical, high-temperature, chemi- cal, corrosion, and optical characteristics. Special glasses are used in fiber optics for communication by light with litle loss in signal power and in glass fibers with very high strength for reinforced plastics (Section 9.2). All glasses contain at least 50 percent silica, which is known as a glass former. ‘The composition and properties of glasses, except strength, can be modified greatly by the addition of oxides of aluminum, sodium, calcium, barium, boron, magnesium, titanium, lithium, lead, and potassium. Depending on their function, these oxides are known as incermediates, or modifiers, Glasses are generally resistant to chemical attack, and are ranked by their resistance to acid, alkali, or water corrosion.84 Glasses 235 8.4.1 Types of glasses Almost all commercial glasses ave categorized by type a) Soda-lime glass (the most common). b) Lead-alleali glass. ©) Borosilicate glass, d) Aluminositicate glass. 2) % percent silics glass. £) Fused silica, Glasses are also classified as colored, opaque (white and translucent), multiform (variety of shapes), optical, photochromatic (darkens when exposed to light, asin sun- glasses), photosensitive (changing from clear to opaque), fibrous (drawn into long fibers, as in fiberglass), and foam or cellular glass (containing bubbles, thus 2 good thermal insulator). Glasses are referred to as hard and soft, usually in the sense of a thermal property rather than mechanical, asin hardness. Thus a soft glass softens at a lower temperature than does a hard glass. Soda-lime and lead~alkali glasses are considered soft and the rest hard 8.4.2 Mechanical properties For all practical purposes, we regard che behavior of glass, as for most ceramics, as perfectly clastic and brittle. The modulus of elasticity range for most commercial glasses is 55 to 90 GPa (8 to 13 million psi), and their Poisson’s ratio 0,16 to 0.28. Hardness of glasses, as a measure of resistance to scratching, ranges from 5 to on the Mohs scale, equivalent to a range of approximately 350 to 500 HK. Glass in bulk form has a strength of less thaa 140 MPa (20 ksi) The relatively low strength of bulk glass is attributed to the presence of small flaws and microcracks on its surface, some or all of which may be introduced during normal handling ofthe glass by inadvertent abrading, These defects reduce the strength of glass by two to three orders of magnitude, compared to its ideal defect-free) strength. Glasses can be strengthened by thermal or chemical treatments to obtain high strength and toughness, The strength of glass can theoretically reach as high as 35 GPa (5 million psi) When molten glass is freshly drawn into fibers (Aberglass), its tensile strength ranges from 0.2 GPa to 7 GPa (30 ksi to 1000 ksi), with an average value of abour 2 GPa (300 ksi). Thus glass fibers are stronger than steel and are used to reinforee plastics in applications such as boats, automobile bodies, furniture, and sports equipment. The strength of glass is usually measured by bending it. The surface of the glass is first thoroughly abraded (roughened) to ensure that the test gives a reliable strength level in actual service under adverse conditions. The phenomenion of static fatigue observed in ceramies is also exhibited by glasses. Hf a glass item must withstand a load for 1000 hours of longer, the maximum stress that can be applied to it is approximately236 8.5 Glass Ceramics 8 » Ceramics, Graphite, and Diamond: Structure, General Properties. and Applications one-third the maximum stress that the same item can withstand during the first second of loading. 8.4.3 Physical properties Glasses have low thermal conductivity and high electrical resistivity and dielectric stcength. Their thermal expansion coefficient is lower than those for metals and plas- ties, and may even approach zero, Titanium silicate glass (a clear, synthetic high-silica glass), for example, has a near-zero coefficient of expansion. Fused silica, a clear, syn- thetic amorphous silicon dioxide of very high purity, also has a near-zero coefficient of expansion. Optical properties of glasses, such as reflection, absorption, transi sion, and refraction, can be modified by varying their composition and treatment. Although glasses are amorphous, glass ceramics (such as Pyroceram, a trade name) have a high crystalline component to their microstructure. Glass ceramics contain large proportions of several oxides, and thus their properties are a combination of those for glass and ceramics. Most glass ceramics are stronger than glass. These prod- ucts are first shaped and then heat treated, with devitrification (recrystallization) of the glass occurring. Unlike most glasses, which are cleat, glass ceramics are generally white or gray in color. The hardness of glass ceramics ranges approximately from 520 HK to 650 HK. They havea near-zero coefficient of thermal expansion; hence they have good thermal- shock resistance and are strong because of the absence of porosity usually found in conventional ceramics. The properties of glass ceramics can be improved by modifying their composition and by heat-treatment techniques. First developed in 1957, glass ceramics are suitable for cookware, heat exchangers for gas turbine engines, rzdomes (housing for radar antenna), and electrical and electronics applications. 8.6 Graphite Graphite is a crystalline form of carbon having a layered structure of basal planes or sheets of close-packed carbon atoms. Consequently, graphite is weak when sheared along the layers. This characteristic, in turn, gives graphite its low frictional properties as a solid lubricant. However, frictional properties are low only in an environment of air or moisture; graphite is abrasive and a poor lubricant in a vacuum. A new devel- ‘opment is the production of soccer-ball-shaped carbon molecules, called buckyballs and named after Buckminster Fuller (1895-1983), inventor of the geodesic dome. ‘Also called fullerenes, these chemically inert spherical molecules are produced from8.7 Diamond 237 soot and act much like solid lubricant particles (see Section 32.11.1). Fullerenes become superconductors when mixed with metals Alchough brittle, graphite has high electrical and thermal conductivity and resis tance to thermal shock and high temperature (although it begins to oxidize at 500°C (930 °F). Iris therefore an important material for applications such as electrodes, heat~ ing elements, brushes for motors, high-temperature fixtures and furnace pasts, mold materials such as crucibles for melting and casting of metals, and seals (because of low friction and wear). Unlike other materials, the strength and stiffness of graphite increase with temperature. An important use of graphite is as fibers in composite materials and reinforced plastics. A characteristic of graphite is its resistance to chemicals; hence it is used in filters for corrosive fluids. Also, its low thermal neutron absorption cross-section and high scatcering cross-section make graphite suitable for nuclear applications, Ordi- nary pencil “lead” is a graphite and clay mixture. Graphite is generally graded in decreasing order of grain size: industvial, fine grain, and micrograin, As in ceramics, the mechanical properties of graphite improve with decreasing grain size. Micrograin graphite can be impregnated with copper and isused as electrodes for electrical discharge machining and for furnace fixtures. Amor- phous graphite is known as lampblack (black soo) and is used as a pigment. Graphite 4s usually processed by molding or forming, oven baking, and then machining to the final shape. Ie is available commercially in square, rectangular, or round shapes of various sizes. ee er ten nentnnsnnces 8.7 Diamond ‘The second principal form of carbon is diamond, which has a covalently bonded structure. It is the hardest substance known (7000-8000 HK). This characteristic makes diamond an important cutting-tool material, asa single crystal or in polycrys- talline form, as an abrasive in grinding wheels for grinding hard materials, and for dressing of grinding wheels (sharpening of abrasive grains). Diamond is also used as a die material for drawing chin wire of less than 0.06 mm (0.0025, in.) in diameter. Dia- mond is brittle and it begins to decompose in air at about 700 °C (1300 °F). In non- oxidizing environments, it resists higher temperatures. Synthetic or industrial diamond was first made in 1955 and is used extensively for industrial applications, One method of manufacturing i s to subject graphite to a hydrostatic pressure of 14 GPa (2 million psi) and a temperature of 3000 °C (5400 °F), Synthetic diamond is identical to natural diamond, and has superior properties because of lack of impurities, It is available in various sizes and shapes, the most common abrasive grain size being 0.01 mm (0.004 in.) in diameter. Gem-quality synthetic diamond is now being made with electrical conductivity 50 times higher than that for natural diamond and 10 times more resistant to laser damage. Potential applications are for heat sinks for computers, telecommunications, integrated-circuit industries, and windows for high-power lasers.238 8 + Ceramics, Graphite, and Diamond: Structure, General Properties, and Applications SUMMARY Several nonmetallic materialsare of greatimportance in engineering applications and manufacturing processes. Ceramics, which are compounds of metallic and non- metallic materials, are generally characterized by high hardness and compressive strength, high-temperature resistance, and chemical inertness. These properties make ceramics particularly attractive for heat-engine components, curting tools, and components requiring wear and corrosion resistance. Glasses are supercooled liquids; that is, the rate of cooling is so high that they do not have time to a clearly defined melting point. Glasses are available in 2 wide variety of compositions and mechanical, physical, and optical properties. Their strength can be improved by thermal or chemical treatments. Glass ceramics are predominantly crystalline in structure and have better properties than glasses. Graphite has high-temperatuse and electrical applications; graphite fibers are also used to reinforce plastics. Diamond, the hardest substance knowa, is used in cutting tools, dies for wire drawing, and abra- sives for grinding wheels. solidify into a crystal A AS ES SY steuctuce. They do not have SUMMARY TABLE ‘TYPES AND GENERAL CHARACTERISTICS OF CERAMICS Type General Characteristics Oxide ceramics ‘Alumina Zirconia Carbides Tungsten carbide Titanium carbide Silicon carbide Nitrides Cubic boron nitride Titanium nitride Silicon nitride Siaton Cermets Silica Glasses Glass ceramics Graphite Diamond High hardness, moderate strengths; most widely used ceramic; cutting tools, abrasives, electrical and thermal insulation. High strength and toughness; thermal expansion close to cast iron; suitable for heat engine components. Hardness, strength, and wear resistance depend on cobalt binder content; commonly used for dies and cutting tools. Not as tough as tungsten carbide; has nickel and molybdenum as the binder; used as cutting tool High-temperature strangth and wear resistance; used for heat engines and 2s abrasives. ‘Second-hardest substance known, aftar diamond; used as abrasives and cutting tools, Gold in color; used as coatings because of low frictional characteristics. High resistance to creep and thermal shock; used in heat engines. Consists of silicon nitrides and other oxides and carbides; used as cutting tools. Consist of oxides, carbides, and nitrides; used in high-temperature applications. High temperature resistance; quartz exhibits piezoelectric effect: silicates containing various oxides are used in high-temperature nonstructural applications. Contain at least 60 porcent silica; amorphous structures; several types available with a ranga of mechanical and physical proporties. Have a high crystalline component to their structure; good thermal-shock resistance and strong. Crystalline form of carbon; high electrical and thermal conductivity; good thermal- shock resistance, Hardest substance known; avaliable as single crystal or polyerystalline form; used as cutting tools and abrasives and as dies for fine wire drawingTRENDS + Efforts are under way to improve the strengeh, toughness, fatigue, and resistance to corrosion, ‘wear, and thermal shock of ceramics, as well as the reproducibility of theie properties and reliability in service. + Standardized and nondestructive test methods and techniques are being developed for inspection and sees seat sorecmeceionn eee KEY TERMS Alumina Feldspar Buckyballs Fline Carbides Fullerenes Ceramics Glass Cermers Glass ceramics Chy Glass former Devitrification Graphite Diamond Industrial diamond oc cree RAE BIBLIOGRAPHY Concise Encyclopedia of Advanced Ceramics, Cam- bridge, Mass.: The MIT Press, 1991 Engineered Materials Handbook, Vol. 4: Ceramics and Glasses. Materials Park, Ohio: ASM Inter- national, 1991. Handbook of Ceramics and Composites, vols. New York: Marcel Dekker, 1991. Kingery, W. D., H. K. Bowen, and D. R. Uhlmann, Introduction to Ceramics, 2d ed. New York: Wiley, 1976 ‘McLellen, G. W., and E. B. Shand, Glass Engineering Handbook, New York: McGraw-Hill, 1984. Modern Ceramic Engineering, 2d ed. New York: Mar- cel Dekker, 1992, Bibliography 239 erection of flaws in ceramic components and for assessment of impact and fatigue damage to com- ponents, particularly in large components. @ Laser teatments and ion implantation techniques are being developed to modify ceramic surfaces and theit properties. Nitrides Patially stabilized zirconia Porcelain Porosity Sialon Silica Stati fatigue Zirconia Musikant, 8, What Every Engineer Should Know About Ceramics. New York: Marcel Dekker, 191 Norton, F.H., Elements of Ceramics, 2d ed. Reading, Mass.: Addison-Wesley, 1974 Richerson, D. W., Modem Ceramic Engincering. New York: Marcel Dekker, 1982. Schwartz, M. M. (ed.), Engineering Applications of Ceramic Materials, Source Book. Metals Park, ‘Ohio: American Society for Metals, 1985. Schwartz, M. M. (ed.), Handbook of Structural Ceramics, New York: McGraw-Hill, 1992.240 8 + Ceramics, Graphite, and REVIEW QUESTIONS 8.1 Compare the major differences between the prop- erties of ceramics and chose of metals and plastics, 8.2 List the major sypes of ceramics that are useful in engineering applications 83 What do the following materials consist of? (@) carbides. (b) cermers. (¢) sialon 8.4 List the major limitations of ceramics. 8.5 Whatis porcelain? QUALITATIVE PROBLEMS 8.11 Explain why ceramics are weaker in tension than in compression. 8.12 What are the advantages of cermets? Suggest additional applications to those given in che text, 8.13 Explain why the electrical and thermal con- ductivity of ceramics decreases with incecasing porosity 8.14 Explain why che mechanical property data in ‘Table 8.1 has such a broad range. What is its sig- nificance in engineering practice? 8.15 What reasons can you think of that encouraged the development of synthetic diamond? 8.16 Explain why the mechanical properties of ceram- jes are generally higher than those for metals QUANTITATIVE PROBLEMS 8.24 Plot the UTS, E, and & values for ceramics as a function of porosity B and describe and explain the tends that you observe in their behavior. 8.25 The tensile strength of cecamics is approxi- mately related to porosity by the expression UTS = UTSe-"%, where P is che volume frac- tion of pores in the solid, UTS, is the tensile strength at zero porosity, and the exponent 1 ranges between 4 and 7. Also, the modulus of elasticity is approximately related to porosity by the expression E = E,(1 — 1.9P + 0.9P?) where Ey is the modulus at zero porosity. If a fully dense ceramic has the properties of UTS, = 150 mond: Structure, General Properties, and Applications 8.6 What is glass? Why is ic called a supercooled material? 8.7 Whats devivification? 8.8 List the major types of glasses and their applica tions 8.9 What is static fatigue? 8.10 Describe the major uses of graphite, 8.17 How are ceramies made tougher? 8.18 Describe applications in which static fatigue can be important. 8.19 How does porosity affect mechanical properties of ceramics, and why? 8.20 What properties are important in making heat resistant ceramics for oven tops? Why? 8.21 Describe the differences between the properties of glasses and ceramics. 8.22 A large variety of glasses is available. Why is this so? 8.23 What is the difference between the structures of graphite and diamond? Is it important? Explain. 300 GPs, what are these proper- ties at 20 percent porosity for values of m = 4, 5, 6, and 7, respectively? 8.26 What would be the tensile strength and modulus of elasticity of the ceramic in the previous prob- lem for porosities of 10 and 30 percent, respec- tively, for the four n values given? 8.27 The thermal conductivity & of ceramics is approximately related to porosity by the expres- sion & = ke(1 ~ P), where kis the conductivity at zero porosity. Calculate the thermal conduc- tivities for porosities of 10, 20, and 30 percent for = 05 W/mK.SYNTHESIS AND DESIGN 8.28 Make a list of all che ceramic parts that you can find around your house and in yout ear. Explain wy those parts are made of ceramics. 8.29 Assume that you are in technical siles and are fully familiar with all che advantages and limita- tions of ceramics. Which of the markets tradi= nally using nonceramic materials do you think ceramics can penetrate? What would you say to your potential customers during your sales vis- its? What kind of questions do you think they will ask? 8.30 Describe applications where a ceramic material with a near-zero cocfficient of thermal expan- sion would be desirable. 8.31 The modulus of elasticity of ceramics is main- tained at clevated temperatures. What engi- neering applications could benefit from this characteristic? ‘Synthesis and Design 241 8.32 List and discuss the factors thet you would take inco account when replacing a metal component with @ ceramic component 8.33 Obtain some data from available literature and quantitatively show the effects af temperature on the strength and modulus of elasticity of several ceramics. Comment on how the shape of these curves differ from those for metals. 8.34 Assume that the cantilever beam in Quantitative Problem 3.12 in Chapter 3 is made of ceramic. How different would your answer be compared to a beam made of metal? Explain clearly, giving umerical examples, 8.35 In Section 8.4.1, it was noted that there are sev- ‘eral basic types of glasses available. Make a sur- vey of available literature and prepare a cable for these glasses, indicating various mechanical, physical, and optial propertiesComposite Material : Structure, General Properties, and Applications 9.1. Introduction 9.5 Metal-Matrix and Coramic-Matrix 9.2 Structure of Reinforced Plastics Composites 9.3 Properties of Reinforced Plastics 9.6 Other Composites 9.4 Applications 9.7 Honeycomb Structures 9.1 introduction 242 Among the major developments in materials in recent years are composite materials. In fact, composites are now one of the most important classes of engineered materials, as they offer several outstanding properties as compared co conventional materials. We define these materials as a combination of two or more chemically distinct and insol- ube phases whose properties and structural performance are superior to those of the constituents acting independently. We showed that plastics, for example, possess mechanical properties (particularly strength, stiffness, and creep resistance) that are ‘generally inferior to those for metals and alloys. These properties can be improved by embedding reinforcements of various types, such as glass or graphite fibers, to pro- duce reinforced plastics. As shown in Table 7.1, reinforcements improve the strength, stiffness, and ereep resistance of plastics —and their strength-to-weight and stiffness- to-weight ratios. Composite materials have found increasingly wider applications in aircraft (Fig. 9.1), space vehicles, offshore structures, piping, electronics, automobiles, boats, ladders, and sporting goods. Metals and ceramics also can be embedded with fibers or particles to improve their properties. “The oldest example of composites is the addition of straw to clay for making mud huts and bricks for structural use, dating back to 4000 B.C. In that application the92 Structure of Reinforced Plastics 243 Aft laps Outboard graphite Flap support fairings ‘lnboard graphite! ‘sEwdsegment (graphite/Kevlar) fiberglass! ut ‘tnon-woven Kevlar mat) udder ‘Aft sogmont (graphite Rberglass! (graphite? Atsamentierapiteberslan! ahi — P Ailerons graphite), berglass) Fixed trailing edge panels graphite Keviar Engine serut ‘Faon-woven Kevlar mat) fairings (Kevlar! Tberglasy) Elevators Environmental control graphite) ‘system ducts. raph (Kevlar Kaxiliary ower inlet Fixed trailing edge panels ‘graphite upper (graphite’hiterglass) . lower (graphite/Kevlar +tnon-waven Kevlar mat) Fixed trailing edge panels (graphiteKevlar* non-woven lar mat) Nose landing gear doors lgraphite: components / (Graphite Wing leading edge lower panels (Kevlar/iberglass! ‘Faon-woven Kevlar i ‘Body main landing gear doors (graphite) Trunnion fairings and wing landing gear doors (graphitetKevlar) ‘*Brakes (structural carbon) FIGURE 9.1 Application of advanced composite mat Boeing Commercial Airplane Company. Is in Bosing 757-200 commercial aircraft. Source: straws are the reinforcing fibers, and the clay is the matrix. Another example of a composite material is the reinforcing of masonry and concrete with iron rods, begun in the 1800s. In fact, concrete itself is a composite material, consisting of cement, sand, and gravel. In reinforced concrete, steel rods impart the necessary tensile strength to the composite, since concrete is brittle and generally has little or no useful tensile strength. This chapter describes the structure of composite materials, the type of reinfore- ing fibers used and their characteristics, and various applications of these materials. The processing and shaping of composite materials will be discussed in Chapter 18. — 9.2 Structure of Reinforced Plastics Reinforced plastics consist of fibers (the discontinuous or dispersed phase) in a plastic matrix (the continuous phase), Commonly used fibers are glass, graphite, aramids,244 9 © Composite Materials: Structure, General Properties, and Applications TT PROPERTIES OF REINFORCING FIBERS Tensile Elastic Strength Modulus Density Relative Type (MPa} (GPa) kg/m?) Cost Boron 3500 380 2600 Highest Carbon High strength 3000 275 1900 Low High modulus 2000 a5 1900 Low Glass Etype 3500 73 2480 Lowest Stype 4600 8 2540 Lowest Kevlar 23 2800 62 1440 High 49 2800 7 1440 High Net: Thee properin vary sigifeanly depending onthe mater 1 rd enathod of presaration and boron. These fibers are strong and stiff (Tzble 9.1) and have high specific strength (strength-to-weight ratio) and specific modulus (stiffness-to-weight ratio), as shown, in Fig. 9.2. However, they are generally britele and abrasive and lack toughness. Thus fibers, by themselves, have little structural value. The plastic matrix is less strong and less stiff but rougher than the fibers. Thus reinforced plastics combine the advantages, of cach of the two constituents. When more than one type of fiber is used in a rein- forced plastic, the composite is called a Aybrid, which generally has even better properties. Tn addition to high specific strength and specific modulus, reinforced plastic structures have improved fatigue resistance, greater toughness, and higher creep resis- tance than unreinforced plastics. These structures are relatively easy to design, fabri- cate, and repair. melo" ° s ow Bm sO <2 2h Beas © Cation 3000 HS (BASF) s 8 ee 02 FIGUREG.2 em | sigs Kevlard 2 Specific tensile strength ‘tensile ° (DuPOM Boron sg strength-to-density ratio) and ‘ ow aly specific tensile modulus (modu eE-zlass ‘Thome! 55 (Amoco) Thome P=100 lus of elasticity-to-density ratio) 2 | @Stel (Amoco) |, for various fibors used in reine & © Alysinum forced plastics. Note the wide ° ° range of spocific strengths and ot 2 3 4 5 6 7 8 3 wo Rs stitfresses available. ‘Specific modulus (in x 10')9.2 Structure of Reinforced Plastics 245 The percentage of fibers (by volume) in seinforced plastics usually ranges between 10 percent and 60 percent. Practically, the percentage of fiber in a matrix is limited by the average distance between adjacent fibers or particles. The highest practical ber content is 65 percent; higher percentages generally result in diminished structural properties. 9.2.1 Reinforcing fi ers Glass. Glass fibers are the most widely used and least expensive of all fibers. The composite material is called glass-fiber reinforced plastic (GERP) and may contain between 30 percent and 60 percent glass fibers by volume. Glass fibers are made by drawing molten glass through small openings in a platinum die. There are two prin- cipal types of glass fibers: (1) the E type, a calcium aluminoborosilicate glass, which is used most; and (2) the S type, a magnesia-aluminosilicate glass, which has higher strength and stiffness and is more expensive Graphite. Graphite fibers (Fig. 9.32), although more expensive than glass fibers, have a combination of low density, high strengch, and high stiffness. The product is called carbon-fiber reinforced plastic (CFRP). All graphite fibers are made by pyroly- sis of organic precursors, commonly polyacrylonitrile (PAN) because of its lower cost. Rayon and pitch (the residue from catalytic crackers in petroleum refining) can also be used as precursors. Pyrolysis is the term for inducing chemical changes by heat, such as burning a length of yarn, which becomes carbon and black in color. The temperatures for carbonizing range up to about 1500°C (2730°F) and for graphitizing to 300°C (5400 °F), @ Matrix by {— Diameter 0. mm, }— Diameter 0.012 ram — Matrix Boron ‘Tungsten FIGURE 9.3 (a) Cross-section of a tenni showing graphite and aramid (Kevlar) reinforcing fibers. Source: J. Dvorak, Mercury Marine Corporation, and F. Garrett, Wilson Sporting Goods Co. (b) Cross-section of boron fiber reinforced composite material.246 9 * Composite Materials: Structure, General Properties, and Applications ‘The difference between carbon and graphite, alshough the words are often used interchangeably, depends on the temperature of pyrolysis and the purity of the mate- rial. Carbon fibers are generally 80 t0 95 percent carbon, and graphite fibers are usu- ally more than 99 percent carbon. Aramids. Aramtids are among the toughest fibers and have very high specific strength (Fig. 9.2). A common aramid is marketed under the trade name Kevlar. They can undergo some plastic deformation before fracture and thus have higher toughness than britle fibers. However, aramids absorb moisture, which reduces their properties and complicates their application, as hygrothermal stresses must be considered Boron. Boron fibers consist of boron deposited (by chemical vapor-deposition techniques) on tungsten fibers (Fig. 9.3b), although boron can also be deposited on car- bon fibers. These fibers have favorable properties, such as high strength and stiffness in tension and compression and resistance to high temperatures. However, because of the use of tungsten, they have high density and are expensive, thus increasing the cost and weight of the reinforced plastic component. Other fibers. Other fibers that are being used are nylon, silicon carbide, sili con nitride, aluminum oxide, sapphire, steel, tungsten, molybdenum, boron carbide, boron nitride, and tantelum carbide, Whiskers are also used as reinforcing fibers. ‘They are tiny needlelike single crystals that grow to 1 wm t0 10 jum (40 yin. to 400 pin.) in diameter and have aspect ratios (defined as the ratio of fiber length to diameter) ranging from 100 to 15,000. Because of their small size, either they are free of imperfections or the imperfections they contain do not significantly affect their strength, which approaches the theoretical strength of the material. Recently, a high- performance polyethylene fiber was introduced. Called Spectra fiber (a trade name), it has ultra-high molecular weight and high molecular-chain orientation. The fiber has better abrasion resistance and flexural-fatigue resistance than the aramid fiber (see above) and at a similar cost. In addition, because of its lower density (970 kg/m?) it has higher specific strength and specific stiffness than the aramid fiber. However, a low melting point and poor adhesion characteristics to other polymers are its major limitations to application. 9.2.2 ‘iber size and length ‘The mean diameter of fibers used in reinforced plastics is usually less then 0.01 mm (0.0004 in.). The fibers are very strong and rigid in tension. The reason is that the ‘molecules in the fibers are oriented in the longitudinal direction, and their cross sections are so small that the probability is low that any defects exist in the fiber. Glass fibers, for example, can have tensile strengths as high as 4600 MPa (650 ksi), whereas the strength of glass in bulk form is much lower. Thus glass fibers are stronger than steel.9.3 Properties of Reinforced Plastics 247 Fibers are classified as short or long fibers, also called discontinuous or continuous fibers, respectively, Short fibers generally have an aspect ratio between 20 and 60, and long fibers between 200 and 500. The shozt and long fiber designations are, in general, based on the following observations: In a given fiber, if the mechanical properties improve as a result of increasing the fiber length, then it is denoted as a short Ser. When no additional improvement in properties occurs, itis denoted as a long fiber. In addition to the discrete fibers that we have described, reinforcements in composites may be in the form of continuous roving (slightly twisted strand of fibers), woven fabric (similar to cloth), yarn (twisted strand), and mats of various combinations Reinforcing elements may also be in the form of particles and flakes. 9.2.3 Matrix materials ‘The matrix in reinforced plastics has three functions: a) Support and transfer the stresses to the fibers, which carry most of the load. b) Protect the fibers against physical damage and the environment. ©) Reduce propagation of cracks in the composite by virtue of the ductility and toughness of the plastic matrix. Matrix materials are usually epoxy, polyester, phenolic, fluorocarbon, polyether- sulfone, and silicon. The most commonly used are epoxies (80 percent of all reinforced plastics) and polyesters, which are less expensive than epoxies. Polyimides, which resist exposure to temperatures in excess of 300 °C (575 *F), are being developed for use with graphite fibers. Some thermoplastics, such as polyetheretherketone, are also being developed as matrix materials. They generally have higher toughness than ther- mosets, but their resistance to temperature is lower, being limited to 100-200 °C (200-400 °F). 9.3 Properties of Reinforced Plastics ‘The properties of reinforced plastics depend on the kind, shape, and orientation of the reinforcing material, the length of the fibers, and the volume fraction (percentage) of the reinforcing material. Short fibers are less effective thaa long fibers (Fig, 9.4), and their properties are strongly influenced by time and temperature. Long fibers transmit the load through the matrix better and thus are commonly used in critical applications, particularly at elevated temperatures. Fiber reinforcement affects many other proper. ties of composites (Fig. 9.5). A critical factor in reinforced plastics is the strength of the bond between the fiber and the polymer matrix, since the load is transmitted through the fiber-matrix inter- face. Weak bonding causes fiber pullout and delamination of the structure, particularly248 =} 400 6 S300 L sk Carbon bes) P x 7 1200 200 & BF 5 ap 100, 10 2 Carbon titers 0 fd wr ry oa aad Reinforcement Reinforcement 11 6 10 80 400 5 é Carbon Bbers 3 Ba 2 z 300 Bab = aot 3 oat £ 2 oof choo & i Garton thes oo § 5 Tne las ers 3 t i E20 /Short glass fibers z | 10 : hoa 3 a 2 aot glass fers ee 10a —3o—90 Reinforcement 4) Relaforcement FIGURE Effect of the amount of reinforcing fibers and fiber length on the mechanical properties of rein- forced nylon. Note the significant improvement with increasing percentage of fiber reinforce- ment. Source: Courtesy of Wilson Fiberfill international. ‘Thermal conductivity ‘Thermal expansion Electrical reslatance ACUESS cwteat The eto ype ct fim ona. *ORetbn at ‘ous properties of fiber-reinforced 40% glass, nylon 6,6. Source: NASA. ® Unfilled9.3 Properties of Reinforced Plastics 249 FIGURE SS () Fracture surface of glass-fiber reinforced epoxy composite. The fibers are 10 um (400 in.) in diame: ter and have random orientation, (b) Fracture sur. face of a graphite-fier reinforced epoxy composite, Tho fibers, 8-11 um in diameter, are in bundles and are ail aligned in the same direction. Source: L. J. Broutman, under adverse environmental conditions. Poor bonding in composites is analogous to a brick structure with poor bonding between the bricks and the mortar. Adhesion at the interface can be improved by special surface treatments, such as coatings and coupling agents. Glass fibers, for example, are treated with a chemical called silane for improved wetting and bonding between the fiber and the matrix. You can appreciate the importance of proper bonding by looking at Figs. 9.6a and b, which show the fracture surfaces of reinforced plastics. Generally, the greatest stiffness and strength in reinforced plastics is obtained when the fibers are aligned in the direction of the tension force. This composite, of course, is highly anisotropic (Fig. 9.7). As a result, other properties of the composite, such as stifiness, creep resistance, thermal and electrical conductivity, and thermal expansion, 20 Bis unidietont || gg z Bua § 5 FIGURES7 —— 500 The tensile strength of glass. gg Orthogonal Teiforeed polysar as a tution 2 of fiber content and fiber direction = = ‘Random in the matrix. Source: R. M. Ogor- _ Kewiez, The Engineering Proper. A 1 0 ties of Plastics. Oxford: Oxford 20 40 60 20 University Press, 1977. Glasscontent (% by weight)250 © Example: 9» Composite Materials: Structure, General Properties, and Applications are also anisotropic. The transverse properties of such 2 unidirectionally reinforced structure are much lower than the longitudinal properties. Note, for example, how easily you can split fiber-reinforced packaging tape, yet how strong it is when you pull on it (fension) For a specific service condition, we can give a reinforced plastic part an optimal configuration. For example, ifthe reinforced plastic parc is to be subjecced to forces in different directions (such as thin-walled, pressurized vessels), the fibers are criss- crossed in the matrix, Reinforced plastics may also be made with various other mate rials and shapes of the polymer matrix in order to impart specific properties (such as permeability and dimensional stability), make processing easier, and reduce costs. Strength and elastic modulus of reinforced plastics The strength of a reinforced plastic with longitudinal fibers can be determined in terms of the strength of che fibers and matrix, respectively, and the volume fraction of fibers in the composite. In the following equations, ¢ refers to the composite, f to the fiber, and m to the matrix. The total load P, on the composite is shared by the fiber (2) and the matrix (P,); thus, Py + Pa, (on) which we can write as Ay + OAs (9.2) where A., Ay, and A, are the cross-sectional areas of the composite, fiber, and matrix, respectively, and thus A. = A; + A,,. Let's now denote x as che area fraction of the fibers in the composite. (Note that x also represents the volume fraction, because the fibers are uniformly longitudinal in the matrix.) We may now rewrite Eq. (9.2) as follows: o. = x07 + (1 = Xo (93) ‘We can now calculate the fraction of the total load carried by the fibers. First, we note that, in the composite under a tension load, the strains sustained by the fibers and the matrix are the same (that is, ¢, = e/= e,,),and then recall from Section 2.2 chat aft OS EO AE Consequently, Py _ AE; Pp AnEm o#) As.we know the relevant quantities for a specific situation, and using Eq. (9.1), we can determine the fraction P/P.. Then, using the foregoing relationships, we can also cal- culate the elastic modulus E, of the composice by replacing o in Eq, (9.3) with E. Thus, EB. = xEp + (1 — x)Ew (9.5)9.4 Applications 251 Let us assume that a graphite-epoxy reinforced plastic with longitudinal fibers con- tains 20 percent graphite fibers with a strength of 2500 MPa and an elastie modulus of 300 GPa. The strength of the epoxy matrix is 120 MPa, with an elastic modulus of 100 GPa. Calculate the elastic modulus of the composite and the fraction of the load supported by the fibers, SOLUTION. The data given are x = 0.2, Ey = 300 GPa, E, = 100 GPa, = 2500 MPa, and 0, = 120 MPa. Using Eq, (9.5), we find that E, = 0.2(300) + (1 — 0.23100 = 60 + 80 = 140 GPa, ‘We obtain the load fraction P//P,, from Eq. (9.4): Py (300) _ 60 B,, ~ o.(160) ~ 0 > °”> Since P, Pow P+ Py and Py = 52, we find that Py 3 P+ a = 2.33P;, or Py = 0.43P.. Thus the fibers support 43 percent of the load, even though they occupy only 20 per- cent of the cross-sectional area (hence volume) of the composite. 9.4 Applications The first application of reinforced plastics (in 1907) was for an acid-resistant tank, made of a phenolic resin with asbestos fibers. Formica, commonly used for counter tops, was developed in the 1920s. Epoxies were first used as a matrix in the 1930s and beginning in the 1940s, boats were made with fiberglass and reinforced plastics were used for aircraft, electrical equipment, and sporting goods. Major developments in composites began in the 1970s, and these materials are now called advanced compos- ites. Glass- or carbon-fiber reinforced hybrid plastics are now being developed for high-temperature applications, with continuous use ranging up to about 300 °C (550 °F). Reinforced plastics are typically used in military and commercial aircraft and rocket components, helicopter blades, automotive bodies, leaf springs, drive shafts, pipes, ladders, pressure vessels, sporting goods, sports and military helmets, boat252 9 * Composite Materials: Structure, General Properti hulls, and various other structures. Applications of reinforced plastics include com- ponents in DC-10, L-1011, and Boeing 727, 757, 767, and 777 commercial aircraft. ‘The new Boeing 777 is made of about 9 percent composites by total weight, whieh is triple the composite content of existing Boeing transport aircraft. The floor beams and panels and most of the vertical and horizontal tail are made of composite materials. By virtue of the resulting weight savings, reinforced plastics have redaced fuel con- sumption by about 2 percent. Substituting aluminum in large commercial aircraft with graphiteepoxy rein- forced plastics could reduce both weight and production costs by 30 percent, with improved fatigue and corrosion resistance. The structure of the Lear Fan 2100 passen- ger aircraft is almost totally made of graphite-epoxy reinforced plastic, Nearly 99 per- cent of the structure of the lightweight Voyager craft, which circled the earth without refueling, was made of carbon-reinforced plastic. The contoured frame of the Stealth bomber is made of composites consisting of carbon and glass fibers, epoxy-resin matrices, high-temperature polyimides, and other materials. Boron-fiber reinforced composites are used in military aircrafe, golf-club shafts, tennis rackets, fishing rods, and sailboards (Fig. 9.8). Double coating of polyurethane Tacaber with nonskié nish Impact ad uravilet-esistant, Extrtough Eten ‘ented polycarbonate skin ‘nulla glass weave Embedded Ihonejeom Glass fiber shogt (per) reinforcement ‘casbonor Le IS Kevlar Laminated SEM fiber strips comporite stringer ures ——— Cross-section of composite sai board, an example of advanced Glass Section on Ava Glass we materials construction. Source: "enforcement Ultght ass weave Ken Easterling, Tomorrow's Mate- expanded polystyrene reinforcer rials, 2d ed., p, 133. Institute of foam core within honeycomb ‘Compound Metals, 1990 Tayer©) Example: © Example: 9.4 Applications: 253 The processing of reinforced plastics presents significant challenges; several inno- vative techniques have been developed to manufacture both large and small parts by molding, forming, cutting, assembly, etc., as described in Chapter 18 and various other sections in this text. Careful inspection and testing of reinforced plastics is essential in critical applications, in order to ensure that good bonding between the reinforcing fiber and the matrix has been obtained throughout. In some instances, the cost of inspection can be as high as one-quarter of the total cost of the composite product. Composite blades for helicopters. Metal blades on helicopters are now being replaced with blades made of composite materials, principally S-glass fibers in an epoxy matrix. These blades have high stiff- ness, strength, resilience, and temperature and fatigue resistance. They also have high impact strength and consequently, as compared to metal blades, composites can with- stand 2 major ballistic impact without catastrophic failure and the helicopter can return safely to its base. Furthermore, repairs of damaged blades ean be made on the field whereas failure of metal blades requires a more extensive maintenance. $ glass has a higher fatigue life than E glass. It has also been shown that glass-reinforced compos ite blades have a better cost/performance basis, and are superior to aramid- or carbon- reinforced composites, . Fiberglass ladders: eee ‘The traditional material for ladders is wood. Partly because of its weight, a wood lad- der gives the user a sense of security. However, wood can have internal and external defects that, if undetected, can significantly reduce the strength of the ladder. When dry, wood does not conduct electricity; when wet, however, it does. Thus one should be careful with a wet wood ladder near electrical wiring. Aluminum ladders are lightweight and can be designed for high strength and stiff- ness. They are longer lasting then wood ladders and require little maintenance. They do, however, conduct electricity. Composite materials are now used in making ladders for various uses. Fiberglass is the most common reinforcing fiber, with epoxies and polyesters as the matrix, Rein- forced plastics are used for the rails of ladders, while the rungs are made of aluminum. These ladders have advantages similar to aluminum, and since they do not conduct clectricity they are preferred by electricians. Fiberglass-reinforced ladders have a rug ged feel, which gives the user a sense of security, and can be made in various colors. However, fiberglass ladders can absorb moisture and undergo surface weathering when exposed to outdoor environments, especially in warm and moist climates, There isa loss of color and gloss, and the surface appearance changes by fiber prominence due to erosion of the matrix resin and fiber blooming (exposed fibers), Fiberglass lad-254 9.5 Metal-Matrix and Ceramic-Matrix Composites Example: 9 + Composite Materials: Structure, General Properties, and Applications ders can be coated with polyurethane for surface protection. Proper maintenance and periodic inspection of fiberglass ladders are thus important. © Composite military helmets ‘A composite military helmet has been developed which, although weighing about the same as a conventional manganese-steel helmet, covers more of the head and offers twice the ballistic and fragmentation protection. To stop a bullet, a composite material must first deform or flatten it; this occurs when the bullee’s tip comes into contact with as many individual fibers of the composite as possible but without the Albers being pushed aside, A composite helmet has 2 nonwoven fiber construction, made with ultrahigh-molecular-weight polyethylene fibers in a thermosetting polymer matrix, which effectively stops the buliet by flattening it as it strikes the first layer of material. Sovrce: AlliedSignal Corp. and CGS Gallet SA. . New developments in composite materials are continually taking place, with a wide range and form of polymeric, metallic, and ceramic materials being used both as fibers and as matrix materials. Research and development activities in this area are concerned with improving strength, toughness, stiffness, resistance to high temperature, and reli- ability in service. 9.5.1 Metal-matrix composites ‘The advantage of a metal matrix over a polymer matrix is its higher resistance to elevated temperatures and higher ductility and toughness. The limitations are higher density and greater difficulty in processing components. Matrix materials in these composites are usually aluminum, aluminum-lithium, magnesium, and tira- nium, although other metals are also being investigated. Fiber materials are graphite, aluminum oxide, silicon carbide, and boron, with beryllium and tungsten as other possibilities. Because of their high specific stiffness, light weight, and high thermal conductiv- ity, boron fibers in an aluminum matrix have been used for structural tubular supports in the space shuttle orbiter. Metal-matrix composites with silicon-carbide fibers and titanium matrix are being used for the skin, beams, stiffeners, and frames for the hypersonic aircraft under development. Other applications are in bicycle frames and sporting goods. Studies are in progress of techniques for optimal bonding of fibers to the metal matrix, Typical applications for metal-matrix composites are given in Table 9.2.TABLE 9.2 METAL-MATRIX COMPOSITE MATERIALS AND APPLICATIOI 9.6 Other Composites 255 NS Fiber Matrix Applications Graphite Aluminum, Satellite, missile, and helicopter structures Magnesium Space end satellite structures Lead Storage-battery plates Copper Elecirical contacts and bearings Boron Aluminum Compressor blades and structural supports Magnesium Antenna structures Titanium Jetengine fan blades Alumina Aluminum ‘Superconductor restraints in fission power reactors Load Storage-battery plates Magnesium Helicopter transmission structures Siticon carbide Aluminum, titanium Superalloy (cobalt-base! High-temperature structures High-temperature engine components. Molybdenum, tungsten Superalloy High-temperature engine components 9.5.2 Ceramic-matrix composites Composites with a ceramic matrix are another important development in engineered materials because of their resistance to high temperatures and corrosive enviroments, As we described in Chapter 8, ceramics are strong and stiff, resist high temperatures, but generally Jack toughness. New matrix materials that retain their strength co 1700 °C (3000 *F) are silicon carbide, silicon nitride, aluminum oxide, and mullite (a compound of aluminum, silicon, and oxygen), Also under development are carbon— carbon matrix composites that retain much of their strength up to 2500 °C (4500 °F), although they Sack oxidation resistance at high temperatures. Present applications for ceramic-matrix composites are in jet and automotive engines, deep-sea mining equipment, pressure vessels, structural components, cutting tools, and dies for extrusion and drawing of metals, 9.6 Other Composites Composites may also consist of coatings of various kinds on base metals or substrates. Examples are plating of alumiaum and other metals over plastics for decorative pu poses and enamels, dating to before 1006 B.C, or similar vitreous (glasslike) coatings oon metal surfaces for various functional or ornamental purposes. Composites are made into cutting tools and dies, such as cemented carbides, usu= ally tungsten carbide and titanium carbide, with cobalt and nickel, respectively, as a binder. Other composites are grinding wheels made of aluminum oxide, silicon car- bide, diamond, or cubic boron aitride abrasive particles, held together with various organic, inorganic, or metallic binders. Another category of composites is cermets.256 9 * Composite Materials: Structure, General Properties, and Applications FIGURE 9.9 reece ‘Schematic illustration of a honeycomb structure. Source: Courtesy of Ameri- can Cyanamid Company. metal, wood, FRP, or plastie Core! Honeycomb ‘A composite developed relatively recently is granite particles in an epoxy matrix. Ichas high strength, good vibration damping capacity (better than gray cast iron), and good frictional characteristics. It is used as machine~cool beds for some precision grinders (Section 24.3). a 9.7 Honeycomb Structures ‘The honeycomb structure (Fig. 9.9) and similar sandwich, or laminate, structures are another form of composites having high specific strength and specific stiffness. The structure consists basically of a core of honeycomb or other corrugated shapes bonded to two thin outer skins (see Section 18.14). You will readily recognize that the simplest example of such a structure is corrugated cardboard, which has 2 high stiffness-to- ‘weight ratio and is used extensively in packaging for consumer and industrial goods. ‘Honeycomb structures are most commonly made of 3000-series aluminum but are also made of titanium, stainless steels, and nickel alloys. New developments include the use of reinforced plastics, such 2s aramid-epoxy. Bonding between the core and the skins is accomplished either with adhesives or by brazing, Because of their light weight and high resistance to bending forces, honeycomb structures are used for aiccraft and aerospace components, as well as in buildings and transportation equipment. SUMMARY Composite materials and reinforced plastics are an important class of materials that have superior mechanical properties and yet are lightweight. The reinforcing fibers are usually glass, graphite, aramids, and boron; epoxies and polyester commonly serve as a matrix material. Reinforced plasties are being developed rapidly, with wide variety of present and future applications in aircraft, transportation, struc~ tural components, containers, and sporting goods, New developments concern metal-matrix and ceramic-matrix composites and honeycomb struc- tures, These materials have several important aircraft and aerospace applications, as well as high-tempera- ture or lightweight industrial applications.Key Terms 257 SUMMARY TABLE ‘TYPES AND GENERAL CHARACTERISTICS OF COMPOSITE MATERIALS Material Characteristics Fibers Glass High strength, low stitiness, high density; lowest cost; E (calcium aluminoborosilicatel and S (magnesia-aluminosilicate) types commonly used. Graphite Available as high-modulus or high-strength; low cost; less danse than glass. Boron High strength and stiffness; highest density: highest cost; has tungsten filsment at its center. Aramids {Kevlar} ‘Other fibers Highest strength-to-weight ratio of all fibers; high cost. Nylon, silicon carbide, silicon nitride, aluminum oxide, boron carbide, boron nitride, tan- talum carbide, steel, tungsten, molybdenum. Matrix materials Thermosets Epoxy and polyester, with the former most commonly used; others are phenolics, fluoro- carbons, pelyethersulfone, silicon, and polyimides, Thermoplasties Polyetheretherketone; tougher than thermosets but iower resistance to temperature. Metals Aluminum, atuminum-lithium, magnesium, and titanium; fibers are graphite, aluminum oxide, silicon carbide, and boran. Ceramics Silicon carbide, silicon nitride, aluminum oxide, and mullite; fibers are various ceramics. TRENDS + Improvements are being made in methods of fabri- cation, quality assurance, reproducibility, reliabil- ity, and predictability of the behavior of composite materials during their service life. + Developments are taking place in techniques for theee-dimensional reinforcement of plastics and improvements in their resistance to compression and buckling. + An important area of study is reduction in the costs of raw materials and fabrication of composite materials. Major developments in metalematrix and ceramic- snatrix composites are anticipated for applications requiring high strength and stiffness, and low den- sity, particularly for aerospace and automotive use. Ceramic-matrix cutting tools are being devel- oped, made of silicon carbide-teinforced alumina, with greatly improved tool life, Carbon whisker- reinforced ceramic-matrix materials are being developed for valves and bushing because of their high hardness and favorable properties in weat, friction, and lubrication. KEY TERMS Aramids Fibers Ceramic matrix Honeycomb structure Composive materials Matrix Delamination Metal matrix Fiber pullout Precursor Pyrolysis Reinforced plasties Whiskers258 9 + Composite Materials: Structure, General Properties, and Applications: BIBLIOGRAPHY Agarwal, B.D. and L. [ Brourman, Analysis and Pe= ‘formance of Fiber Composites, 2d ed. New York Wiley, 1990. Bittence, [C. (ed.), Engineering Plastics and Compos- ites, Materials Park, Ohio: ASM International, 1590, ‘Chatrier, J-M., Polymeric Materials and Processing Plastics, Elastomers, and Composites. New York: Hanser, 1991 Easterling, K., Tomorrows Materials, 2¢ ed. London: ‘The Institute of Metals, 1999. Engineered Materials Handbook, Vol. 1: Composites. Metals Park, Ohio: ASM International, 1987. Engineering Plastics and Composites, 2d ed. Materials, Park, Ohio: ASM Taternational, 1993. Handbook of Ceramics and Composites, 3 vols. New York: Marcel Dekker, 1991. Harper, C., Handbook of Plastics, Elastomers, and Composites, 2d ed. New York: McGraw-Hill, 1992. Kaelble, D. H., Computer-Aided Design of Polymers cand Composites. New York: Marcel Dekker, 1985, Kelley, A. (ed.), Concise Encyclopedia of Composite Material. New York: Pergamon, 1989. Mallick, P. K., Fiber-Reinforced Composites: Materi- als, Manufacturing, and Design. New York: Mar- cel Dekker, 1993. Schwartz, M., Composite Materials Handbook, 2d ed. ‘New York: McGraw-Hill, 1992. Seymour, R. B., Reinforced Plastics: Properties and ‘Applications. Materials Park, Ohio: ASM Inter- national, 1991, Shook, G. (ed), Reinforced Plastics for Commercial Composites: Source Book. Metals Park, Ohio American Society for Metals, 1986. REVIEW QUESTIONS 941 Distinguish between composites and alloys. 9.2 Describe the functions of the matrix and the rein- forcing fibers. What fundamental differences are there in the characteristics of the two materials? 9.3 What major reinforcing fibers are used to make composites? Which type of fiber is the strongest? ‘Which type is the weakest? 9A What is the zange of length and diameter of rein- forcing fibers? QUALITATIVE PROBLEMS 9.9 How do you think the use of straw in clay came about in making brick for dwellings? 9.10 What products have you personally seen that are made of reinforced plastics? How can you tell that they are reinforced? 9.11 Identify metals and alloys that have strengths ‘comparable to those of reinforced plastics. 95 Lisctheimportaat factors that determinethe prop- exties of reinforced plastics. 9.6 Compare the advantages and disadvantages of mctal-matrix composites, reinforced plastics, and ceramic-matrix composites. 9.7 What are the basic functions and components of a honeycomb structure? 9.8 What is a hybrid composie? 9.12 You studied the many advantages of compos- ite materials in this chapter. What limitations or disadvantages do these materials have? What suggestions would you make ro overcome these limitations? 9.13. What factors contribute to the cost of reinfore- ing fibers?9.14 Give examples of composite materials other than those stated in this chapter, 9.15 A hybrid composite is defined as one containing wo or more differenctypes of reinforcing fibers. What advantages would such a composite have over others? 9.16 Explain why the behavior of the materials shown, in Fig. 9.5 is as shown, 9.17 Why are fibers capable of supporting « major portion of the load in composite materials? QUANTITATIVE PROBLEMS 9.21 Calculate the average increase in the properties of plastics in Table 7.1 as a result of their rein- forcement and describe your observations. 9.22 In the example in Section 9.3, what would be the percentage of the load supported by the fibers if their strength is 1250 MPs and the matrix strength is 240 MPa? SYNTHESIS AND DESIGN 9.25 What applications for composite materials can you think of other than those listed in Sec- tion 9.4? Why do you think your applications are suitable for these materials? 9.26 Using the information in this chapter, develop special designs and shapes for new applications of composite materials. 9.27 Would a composite material with a strong and stiff matrix and soft and flexible reinforcement have any practical uses? Explain, 9.28 Makea listof products for which the use of com- posite materials could be advantageous because of their anisocropic properties, 9.29 Inspect Fig. 9.1 and explain what other compo- nents of an aircraft, including parts ia the eabin, could be made of composites. 9.30 Name applications in which both specific strength and specific stiffness (ig. 9.2) arc important, Synthesis and Design 259 9.18 What advantages do metal-mateix composites have over reinforced plastics? 9.19 Give reasons for the development of cerantic~ matrix composites. Name some possible appli- cations. 9.20 Explain how you would go about determining the hardness of the reinforced plastics and com= posite materials described in this chapter. Are hardness measurements on these types of mate- rials meaningful? Does the size of the indenta- ton make a difference in your answer? Explain, 9.23 Make a survey of cecent literature and present data indicating the effects of Aber length on mechanical properties such as strength, elas- tic modulus, and impact energy of reinforced plastics. 9.24 Calculate the increase in mechanical properties of reinforced nylon from the data shown in Fig. 9.4. 9.31 Do you think honeycomb structures could be used in passenger cars? If so, where? Explain, 9.32 Other than chose described in this chapter, what materials can you think of that can be cegarded as composite materials? 9.33 What applications for composite materials can you think of in which high thermal conductiviey ‘would be desirable? 9.34 This chapter has described methods of produc: ing reinforced plastics and composite materials. As with other material, the mechanical proper- ties of these composites are obtained by pre- paring appropriate specimens and testing them. Explain what problems you might encounter in preparing specimens for and testing these mate- rials in tension. Suggest methods for making appropriate specimens, including their shape and how they are clamped into the jaws of testing machines,260 9 » Composite Materials: Structur 9.35 In the Trends section of this chapter it was stated chat developments are taking place in techniques for three-dimensional reinforcement of plastics Deseribe (a) applications in which strength in the thickness direetion of the composite is impor- tant, and (b) your ideas on how to achieve this strength. Include simple sketches of the struc- ture utilizing such reinforced plastics 9.36 Design and describe a test method to deterinine the mechanical properties of reinforced plastics in their thickness direction. 9.37 As described in this chapter, reinforced plastics can be adversely affected by environment, such as moisture, chemicals, and temperature varia- tions, Desigi and describe test methods to decer= mine the mechanical properties of composite ‘materials under these conditions. 938 Comment on your observations of the design of the sailboard shows in Fig. 9.8, General Properties, and Applications 9.39 Describe the similarities and differences betsreen ordinary corrugated cardboard and a honey- comb structure: 940 Suggest product designs in which corrugated cardboard can be used. Comment on the advan tages and limicazions. 9.4L Suggest consumer product designs that could utilize honeycomb structures. 9.42 Make a survey of a variety of sports equipment and identify the components made of compos- ie materials. Explain the reasons for and advan- tages of using composices for these specific applications. 9.43, We have described several material combinations and structures in this chaprer. In relative terms, identify those that would be suitable for appli- cations involving one of the following: (a) very low temperatuces, (b) very high temperatures, {6) vibrations, (4) high humidiey.PART ] ] Metal-Casting Processes and Equipment ‘Surface treatmants, ‘microelectronics ‘atreaton VI Gialiyaseuanca, ‘on ume aces vol “ora, “ontompettve specs ot menceeureg = | WAT262 Metal-Casting Processes and Equipment ‘We can use several different methods to shape materials into useful products. Making parts by casting molten metal into a mold and letting i solidify is a logical choice. Indeed, casting is among the oldest methods of manufacturing and was first used in about 4000 B.c. to make ornaments, copper arrowheads, and various other objects. In the broad sense, casting is « process that is applied not only to metals but also to nonmetallic materials, Plastics, ceramics, and glasses are also cast into shapes. Although there are certain similarities in the processes of casting different materials, casting of nonmetallic materials will be discussed in Chapters 18 and 19. Basically, metal-casting processes involve the introduction of molten metal into mold cavity where, upon solidification, the metal takes the shape of the cavity. The casting process is thus capable of producing intricate shapes in a single piece, including those with internal cavities. Very large or hollow parts can be produced economically by casting techniques. Typical cast products are engine blocks, crankshafts, pistons, valves, railroad wheels, and ornamental artifacts. Figure 11.1 shows cast components in a typical automobile, a product that was ‘used in the Introduction to Part Ito illustrate the selection and use of materials. The automobile theme will be used throughout this text, in order to give you a compre- hensive view of mamufacturing engineering and technology. FIGURE 11.1 Alternator Engine block, Transmission Thowsing earburelar, Thousing Differenciat housing Cast partsin a typical automobile.Metai-Casting Processes and Equipment 263 Although casting processes allow a great deal of versatility in part size and shape, they most often are selected over other manufacturing methods because they * Can produce complex shapes with internal cavities or hollow sections. * Can produce very large parts * Can utilize workpiece materials that are difficule co process by other means. * Are economical to use, Almost all metals can be cast in (or nearly in) the final shape desired, often with only minor finishing required. This capability places casting among important net- shape manufacturing technologies, as we described in the General Introduction. (Among other similar processes are net-shape forging, powder metallurgy, stamping of sheet metal, and injection molding.) Although cast metals are neither homogeneous or isotropic, with appropriate control of material and process parameters and sub- sequent heat treatment, parts can be cast with neatly uniform properties throughout With moder processing techniques and control of chemical composition, mechanical properties of castings can equal those for forged or welded components in many appli- cations, Furthermore, the anisotropic mechanical properties of castings can be a desir- able characteristic, Several casting processes have been developed to date (Fig. 11.2). As in all manu- facturing, each process has its own characteristics, applications, advantages, and lim tations. Regardless of the method of casting used, we must understand and control certain fundamental aspects of the process so we can economically produce castings of good quality, dimensional accuracy, and surface finish. These aspects are solidif- cation of metals, heat transfer, and flow of the molten metal into the mold cavities. They ae influenced by mold material, casting design, and various other material and ‘Metal casting processes Foundries Expendable mold Permanent mold Single-crystal growing a nd l Sand | | mold Slush ‘Single crystals for microelectronics Shelt Pressure ‘Single-erystai turbine blades Expandable pattern Die Directional solidification Plaster Centrifugal Ceramic Squeeze Investment Semisolid FIGURE 11.2 An outline of m tal casting processes described in Part I264 Metal-Casting Processes and Equipment process variables. Part II presents these fundamental aspects of casting and casting processes, design, and characteristics of metals cast. The knowledge gained in this part will enable you to better evaluate the technical and economic feasibility of using casting to manufscture certain components. After studying other manufacturing processes in the remainder of this book, you will be able to decide whether a particular component should be produced by casting, form- ing, machining, welding, or a combination of manufacturing processes.10 Fundamentals of Metal Casting 10.1 10.1 Introduction 10.2 Solidification of Metals 10.3 Fluid Flow and Heat Transfer = aS SESE Introduction The casting process basically involves pouring molten metal into a mold pacterned after the part to be manufactured, allowing it to cool, and removing the metal from the mold. As with all other manufacturing processes, certain fundamental relation ships are essential to the production of good quality and economical castings, Know|- edge of these relationships helps us establish proper techniques for mold design and casting practice. Our objective is to produce castings that are free from defects and thar mect such requirements as strength, dimensional accuracy, and surface finish. ‘The important factors in casting operations are: + The flow of the molten metal into the mold cavity. * Heat transfer during solidification and cooling of the metal in the mold. * Influence of the type of mold material. + Solidification of the metal from its molten state. Note the similarities between metal casting and pouring cake batter into a mold (pan) and baking it. We first select the kind and size of mold to use, control the com- position of the mix, carefully pour the batter into the mold, set the proper baking 265266 10 + Fundamentals of Metal Casting temperature, set the timer for the proper baking time, and leave the baked cake in the mold a certain amount of time before we remove it ‘Although the methods and procedures involved are similar, we leave the discus- sion of easting plastics and ceramics to Chapters 18 and 19, respectively. 10.2. sol After molten metal is poured into a mold, a series of events takes place during solidi- fication of the casting and its cooling to ambient temperature. These events greatly influence the size, shape, uniformity, and chemical composition of the grains formed throughout the casting, which in turn influence its overall properties. The significant factors affecting these events are the type of metal, thermal properties of both the metal and the mold, the geometric relationship between volume and surface area of the casting, and the shape of the mold. 10.2.1 Pure metals Because a pure metal has a clearly defined melting or freezing point, it solidifies at a constant temperature. Pure aluminum, for example, solidifies at 660 °C (1220 °F), iron at 1537 °C (2798 °F), and tungsten at 3410 °C (6170 °F). (See Fig. 4.4.) ‘When the temperature of the molten metal is reduced to its freezing point, its temperature remains constant while the latent heat of fusion is given off, The solidifi- cation front (solid-liquid interface) moves through the molten: metal, solidifying from the mold walls in toward the center. Once solidification has taken place at any point, cooling resumes. The solidified meral, which we now call the casting, is then taken out of the mold and begins to cool to ambient temperature. The grain structure of a pure metal cast in a square mold is showa in Fig, 10.1a. At the mold walls, the metal cools rapidly since the walls are at ambient temperature. Rapid cooling produces a solidified skin, or shell, of fine equiaxed grains. The grains ‘grow in the direction opposite to the heat transfer out through the mold, Those grains that have favorable orientation will grow preferentially and are called columnar grains (Fig. 10.2). As the driving force of the heat transfer is reduced away from the mold walls, the grains become equiaxed and coarse, Those grains that have substan- tially different orientations are blocked from further growth. Such grain development is known as homogeneous nucleation, meaning that the grains (crystals) grow upon themselves, starting at the mold wall. 10.22 Alloys Solidification in alloys begins when the temperature drops below the liquidus, T., and is complete when it reaches the solidus, 7; (Fig. 10.3). Within this temperature range,10.2 Solidification of Metals 267 Chillzone insed 7m oan on nee FIGURE 10.1 ————— Schematic illustration of three cast structures of metals solidified in a square mold: (a) pure metals; tb) solid-solution alloys; and (c) structure obtained by using nucle- ating agents. Source: G. W. Form, J. F. Wallace, J. L’ Walker, and A.Cibula, the alloy is in a mushy or pasty state with columnar dendrites (from the Greek den- dron meaning akin to, and drys meaning tree). Note the presence of liquid metal berween the dendrite arms. Dendrites have three-dimensional arms and branches (secondary arms) and they eventually interlock, as showa in Fig. 10.4. The study of i scuRe 102 ———.. Gurlace area) The respective surface areas are Sphere: Cube: Cylinders Vi= rr’h = 2mr, r= (4) vad A 2arh = orn = w(t 2n, Thus the respective solidification times t are tiptoe = 0.043C, tyre = 0.028C, and totnte = 0.033C. Hence the cube-shaped casting will solidify the fastest and the sphere-shaped casting will solidify the slowest. 10.3.5 Shrinkage Because of their thermal expansion characteristics, metals shrink (contract) during solidification and cooling, Shrinkage, which causes dimensional changes—and, some- times, cracking —is the result of: a) Contraction of the molten metal as it cools prior to its solidification b) Contraction of the metal during phase change from liquid to solid (latent heat of fusion). ©) Contraction of the solidified mezal (the casting) as its temperature drops to ambi- ent temperature, “The largest amount of shrinkage occurs during cooling of the casting, The amount of contraction for various metals during solidification is shown in Table 10.1. Note that gray cast iron expands, The reason is that graphite has a relatively high specific volume, and when it precipitates as graphite flakes during solidification, it causes a net expansion of the metal. We discuss shrinkage further in Section 12.2.1 in connection with design considerations in casting. 10.3.6 Defects As we will see in this section as well as other sections throughout Parts II-VI, various defects can result in manufacturing processes, depending on factors such as materials,10.3 Fluid Flow and Heat Transfer 279 TABLE 10.1 SOLIDIFICATION CONTRACTION FOR VARIOUS CAST METALS, Volumetric Se Solidification Metal or Alloy Contraction (9) Metal or Alloy Contraction (%) Aluminum 686 70% Cu-30% Zn 45 Al-4.5% Cu 63 90% Cu-10% Al 4 AL 12% Si 38 Gray iron Expansion to 25 Carbon steet 25-3 Magnesium 42 1% carbon steel 4 White iron 4055 Copper 4s Zine 65 a Source: Aer. A, Fnn part design, and processing techniques. While some defects affect only the appearance of parts, others can have major adverse effects on the structural integrity of parts made. Several defects can develop in castings. Because different names have been used to describe the same defect, the International Committee of Foundry Technical Associ ations has developed standardized nomenclature consisting of seven basic categories of casting defects (Figs. 10.11 and 10.12) identified with capital letters in boldface: A. Metallic projections, consisting of fins, flash, or massive projections such as swells and rough surfaces. B. Cavities, consisting of rounded or rough internal or exposed cavities, including blowholes, pinholes, and shrinkage cavities (see porosity below). Hot tear Hot tear Casting Jk, Hot tear care Pouring cup Sprve Casting \ ——. Runner Hot tear FIGURE 10.11 Examples of hot tears in castings. lefects occur because the casting cannot shrink freely during cooling, awing to constraints in various portions of the molds and cores. Exathermie (heat. producing) compounds may be used (as exothermic padding) to control cooling at critical sec. tions to avoid het tearing.280 10 + Fundamentals of Metal Casting i & Surface of casting Biow Sear | Blister 1 @ Seab— ° ore on co : Cold shut FIGURE 10.12 Examples of common defects in castings, These defects can be minimized or eliminated by proper design and prepe- ration of molds and control of pouring procedures. Source Datsko. C. Discontinuities, such as cracks, cold or hot tearing, and cold shuts. If the solidi- fying metal is constrained from shrinking freely, cracking and tearing can occur. Although many factors are involved in tearing, coarse grain size and the presence of low-melting segregates along the grain boundaries (intergranular) increase the tendency for hot tearing, Incomplete castings result from the molten metal being at too low a temperature or from pouring the metal too slowly. Cold shut is an interface in a casting that lacks complete fusion because of the meeting of two streams of liquid metal from different gates. D.. Defective surface, such as surface folds, laps, scars, adhering sand layers, and oxide scale. Incomplete casting, such as misruns (due to premature solidification), insufficient volume of metal poured, and runout (due to loss of metal from mold after pouring). F. Incorrect dimensions or shape, owing to factors such as improper shrinkage allow- ance, pattern mounting error, irregular contraction, deformed pattern, or warped casting.10.3 Fluid Flow and Heat Transfor 281 G. Inclusions, which form during melting, solidification, and molding. Generally nonmetallic, they are regarded as harmful because they act like stress raisers and reduce the steength of the casting. Particles as small as 30 jm can be filtered out during processing of the molten metal. Inclusions may form during melting because of reaction of the molien metal with the environment (usually oxygen) or the crucible material. Chemical reactions among components in the molten metal may produce inclusions; slags and ocher foreign material entrapped in the molten metai also become inclusions. Reactions between the metal and the mold material may produce inclusions. Spalling of the mold and core surfaces also produces inclusions, indicating the importance of the quality and maintenance of molds Porosity. Porosity in a casting may be caused by shrinkage or gases, or both. Porosity is detrimental to the ductility of a casting and its surface finish, making it permeable and thus affecting pressure tightness of a cast pressure vessel Porous regions can develop in castings because of shrinkage of the solidified metal. Thin sections in a casting solidify sooner than thicker regions. As a result, mol- ten metal cannot be fed into the thicker regions that have not yet solidified. Because of contraction, as the surfaces of the thicker region begin to solidify, porous regions develop at their centers. Microporosity can also develop when the liquid mezal solidi- fies and shrinks between dendrites and between dendrite branches. Porosity caused by shrinkage can be reduced or eliminated by various means. Basically, adequate liquid metal should be provided to avoid cavities caused by shrink- age. Internal or external chills, used in sand casting (Fig. 10.13), also are an effective means of reducing shrinkage porosity. The function of chills is to increase the rare of solidification in critical regions. Internal chills are usually made of the same material as the castings and are lefc in the casting. However, there may be problems with proper fusion of the internal chills with the casting. Foundries try to avoid use of internal chills for this reason. External chills may be made of the same material or may be iron, copper, or graphite. With alloys, porosity can be reduced or eliminated by making the temperature gradient steep, using, for example, mold materials that have high thermal conductivity. Subjecting the casting to hot isostatic pressing is another method of reducing porosity (see Section 17.3.2). Liquid metals have much greater solubility for gases than do solid metals (ig. 10.14), When a metal begins to solidify, the dissolved gases are expelled from the solution. Gases may also result from reactions of the molten metal with the mold materials. Gases either accumulate in regions of existing porosity, such as in inter~ dendritic areas, or they cause microporosity in the casting, particularly in cast iron, aluminum, and copper. Dissolved gases may be removed from the molten metal by flushing or purging with an inert gas or by melting and pouring the metal in a vacuum. If the dissolved gas is oxygen, the molten metal can be deoxidized. Steel is usually deoxidized with aluminum, silicon, copper-base alloys with phosphorus copper, tita- nium, and zirconium-bearing materials. Whether microporosity is a result of shrinkage or is caused by gases may be dif- ficult to determine. If the porosity is spherical and has smooth walls, much like the282 10 + Fundamentals of Metal Ca: FIGURE 10.13, Various types of (a) internal and (b) external chills (dark areas at comers}, used in castings to eliminate porosity caused by shrinkage. Chilis are placed in regions where there is a larger val- ume of metal, as shown in (c). Hydrogen solubili Melting point ‘Temperavure FIGURE 1 Solubility of hydrogen in aluminum. Note the sharp decrease in solubility as the molten metal begins to solidity.Trends: 283 shiny surfaces of holes in Swiss cheese, itis genevally from gases, If che walls are rough and angular, porosity is lixely from shrinkage becween dendrites. Gross porosity is from shrinkage and is usually called shrinkage cavities. © Example: Casting of U.S. cannons in the 18605 =v An innovative process for casting cannons was developed by Colonel Thomas J. Rod- man while he was the commander of the Rock Island Arsenal, Illinois, in the 1860s. In this process the cast iron gun was cooled from the interior, while keeping the exte- riot in a liquid state, (Referring to Fig. 10.3, for example, assume thar the mold wal! on the left is the interior surface of the cannon.) Thus the inner walls of the gun solidi- fied first and as the outer layers began to solidify, they underwent shrinkage, subject- ing the already solidified inner wall to compressive residual stresses. The result was a stronger and more reliable cannon, called the Rodman Gun, which reportedly lasted twenty times longer than existing guns. The process revolutionized the art of cannon manufacturing world-wide, Some historians credit this invention with discouraging European naval forces from intervention in the U.S. Civil Wa: (1861-1865). In mak- ing cylindrical high-pressure vessels, the shrinking of successive layers of concentric tubes over each other is now a well-known technique. By this method, the inner layers of the vessel are subjected to high levels of compressive residual stresses which, in turn, allow it to sustain high internal pressures. - “ SUMMARY Casting is a solidification process in which molten caused by gases evolving during solidification isa sig metal is poured into 2 mold and allowed to cool to ambient temperature. Eluid flow and heat transfer are important considerations, as is the design of the mold and gating system to ensure proper flow of the metal into the mold cavities. Because metals contract during solidification and cooling, cavities can form in the casting. Porosity TRENDS + Argon-oxygen decarburization and deoxidation, as well as electroslag remelting, ladle metallurgy, plasma refining, and calcium wire injection for producing high-quality stels, are now being prac ticed by modern foundries. nificant problet, particularly because of its adverse effect on the mechanical properties of castings. The grain structure of castings can be controlled by vari- ‘ous means to obtain the desired properties. The choice of furnaces is important and involves economic con- siderations, Various defects can develop in castings from lack of control of material and process variables. + Electromagnetic stirring of the molten metal in the mold and vibrating the molds to obtain smaller and more uniform grain size during solidification, counter-gravity pouring, and shrouding the pour- ing stream are being investigated.284 10 + Fundamentals of Metal Casting + Computer-aided design and manufacturing tech- niques are being used to predict solidification pat- terns, prevent easting defects, and esleulate weights, volumes, and dimensions for proper mold design and economic production. «Improvements in the efficiency of furnaces, mol- ren metal quality, and purifying end filtering tech niques are being made, KEY TERMS Aspiration Gating system Pouring basin Bernoulli's theorem Heterogeneous nucleation Risers Casting Homogencous nucleation Runners Chills Inoculant Segregation Columnar dendrites Macrosegregation Shrinkage Columaar grains Microsegregation Skin Deadrites Mold Solidification Fluidiey Mushy zone Sprue Freezing range Porosity Turbulence Gate BIBLIOGRAPHY ASM Handbook, Vol. 15: Casting. Macerials Park, Ohio: ASM International, 1988, Flemings, M. C., Solidification Processing, New York: McGraw-Hill, 1974 Flina, R. Au Findamentals of Metal Casting. Read- ing, Mass: Addison-Wesley, 1963. Heine, R, W., C. R. Loper, Jew and C. Rosenthal, Principles of Metal Casting, 2d ed. New York: McGraw-Hill, 1967. nsec RS IEEE Liebermann, H. H. (ed.), Rapidly Solidfied Alloys, ‘New York: Marcel Dekker, 1993. Mikelonis, P. J (ed.), Foundry Technology: A Sonrce Book, Metals Park, Ohio: American Society for Metals, 1982 Minkoff, L, Solidification and Cast Structure. New ‘York: Wiley, 1986. Szekely, J, Fluid Flow Phenomena in Metals Process- ing. New York: Academic Press, 1979. REVIEW QUESTIONS 10.1 Why is casting an important manufacturing process? 10.2 What is the difference between the solidification ‘of pure metals and metal alloys? 10.3 What are dendrites? 104 State the difference between short and long freezing ranges. How is range determined? 405 Describe the parameters on which solidification time depends.10.6 Define shrinkage and porosity. How can you tell whether cavities in 2 casting are due to porosity or to shrinkage? 10.7 What is che function of chills? 10.8 How are dissolved gases removed from molten metal? 10.9 Describe the fearuzes of a gating system, 10.10 How is fuidity defined? Why is it importans? QUALITATIVE PROBLEMS 1015 Describe the stages involved in the contraction of metals during casting 10.16 Explain the reasons why heat transfer and fluid flow are so important in metal casting, 10.17 We know that pouring metal ata high rate into a mold has certain disadvantages. Are there any disadvantages to pouting it very slowly? 1048 Describe the events depicted in Fig. 10.4. 10.19 Would you be concerned about the fact that parts of internal chills ae left within the ease- ing? What materials do you thinle chills should be made of, and why? 10.20 What practical illustrations can you offer to indicate the relationship of solidification time to volume and surface area? 4021 Do you thinks easly formation of dendrites in a ‘mold can impede the fee flow of molen metal into the mold? Give an illustration 10.22 Explain why you may wane to subject a casting to various het treatments 1023 Why does porosity have detrimental effects on the mechanical properties of castings? Would physical properties such as theemal and electci- cal conductivity also be affected by porosity? Explain. 10.24 A spoked handwhee! isto be cast in gray iron In order to prevent hoz tearing of the spokes, would you insulate the spokes or chill them? Explain. 10.25 Which of the following considerations are important for a riser vo function properly? It must: (a) Have a surface area larger than the part being cast. (b) Be kept open toatmospheric pressure. (c) Solidify frst. Why? Qualitative Problems: 285 10.11 Explain the reasons for hot tearing in castings 10.12 Name various defects in castings. 10.13 Why is ic important to remove dross or slog during the pouring of molten metal inzo the mold? What methods are used to remove them? 1014 What are the effects of mold materials on Fuld flow and heat transfer? 10.26 Explain why the constant C in Eq. (10.7) depends on mold material, metal properties, and temperature, 10.27 Are external chills as effective as internal chills? Explain, 10.28 Explain why gray cast iron undergoes expan- sion, rather than contraction, during soliditica- tion, as shown in Table 10.1. Referring to Fig. 10.10, explain why internal corners (as A) develop a thinner skin chan exter- nal corners (as B) during solidification, 10.30 Nove the shape of the two risers in Fig, 10.7, and discuss your observations with respect to Eq. (10.7), 1031 Is there any difference in the tendency for shrinkage void formation for metals with short freezing and long free2ing ranges, respectively? Explai 10.32 Whatis the influence of the cross-sectional area of the spiral channel in Fig. 10.8 on fluidity tese results? What is the effect of sprue height? If this testis nan with the test secup heated to ele- vated temperatures, would the test results be useful? Explain, 10.33 Make a list of safety considerations and pre- cautions that should be taken concerning all aspects of melting and casting of metals, includ- ing the equipment involved, 1034 Ichas long been observed by foundrymen and jngot casters that low pouring temperatures (hat is, low superheat) promote equiaxed grains over columnar grains. Also, equiaxed Brains become finer as the pouring temperature decreases. Explain these phenomena.286 40 + Fundamentals of Metal Casting pee ht TR ESET QUANTITATIVE PROBLEMS 1035 Sketch a graph of specific volume versus tem- perature for a metal that shrinks as it cools from the liquid state to room temperature. On the graph, mark che atea where shrinkage is com- pensated for by risers 10.36 A round casting is 0.1 m in diameter and 0.5 m in length. Another casting of che same metal is eliptical ia crors-scetion, with a major-to- minor axis ratio of 2, and has the same lengeh and cross-sectional area as the round casting. Both pieces are cast under the same conditions. ‘What isthe difference in the solidification times of the two castings? 1037 A50-mm (2-in.) thick square plate and a right, circular cylinder with a radius of 100 mm (4 in.) 10.38 10.39 and height of 50 mm each have the same vol ume, If each is to be cast sing a cylindrical riser, will each part require the same size riser to ensure proper feeding? Explain. Determine the dimensions of each of the parameters in the Reynolds number, given in Eq. (10), and check for consistency. Assume that the top of a round sprue has @ iamecer of 3 in. (75 mum) and is ata height of 10 in. (254 mm) from the runner. Based on Eq. (105), plot the profile of the sprue diameter asa function of its height. SYNTHESIS AND DESIGN 40.49 Can you think of fluidity cests other that that shown in Fig, 10.82 Explain your tess 10.41 The figures below indicate various defects and discontinuities in cast products. Review each ‘one and offer solutions to avoid thern @) (b) Risr me ok cm Simkar (gy iil Cote tearing 10.42 10.43 ‘The fluidity test shown in Fig. 10.8 only illus- tuates the principle of this eest. Design a setup for such a test, showing the type of materials and the equipment to be used. Explain the method by which you would determine the length of the solidified metal in the spiral passage Utilizing the equipment and materials avail- able in a typical kitchen, design an experiment to reproduce results similar t0 those shown in Fig. 10.10. Comment on your observations.Metal-Casting Processes soar inwr Eran nt cin 11.1 11.1 Introduction 11.12 Die Casting 11.2 Sand Casting 11.13 Centrifugal Casting 11.3 Shell-Mold Casting 11.14 Squeeze Casting and Semisolid 11.4 Expandable Pattern Casting Metal Forming (Lost Foam) 11.15 Casting Techniques for Singie- 11.8 Plaster-Mold Casting Crystal Components 116 Ceramic-Mold Casting 11.16 Rapid Solidification (Amorphous 11,7 Investment Casting Alloys} 118 Vacuum Casting 11.17 Inspection of Castings 11.9 Permanent-Mold Casting 11.18 Melting Practice and Furnaces 11.10 Slush Casting 11.19 Foundries and Foundry 11.11 Pressure Casting Automation Introdu In Chapter 10, you learned the fundamentals that underlie all casting processes. This chapter focuses on the major meral-casting processes and their principles, advantages, and limitations. Many parts and components are made by casting, including earbure- tors, frying pans, engine blocks, crankshafts, railroad-cac wheels, plumbing fixtures, power tools, gun barrels, and machine bases. Various casting processes have been developed over a long period of time, each with its own characteristics and applica- tions, to meet specific engineering and service requirements. In fact, the frst castings were made during the period of 4000-3000 B.C, using stone and metal molds for casting copper. Two trends currently are having a large impact on the casting industry. The frst is continuing mechanization and automation of the casting process, which has led to significant changes in the use of equipment and labor. Advanced machinery and auto- mated process-control systems have replaced traditional methods of casting. More- over, casting processes that especially lend themselves to advances in technology are developing significant economic advantages over other processes. The second major trend affecting the casting industry is the increasing demand for high-quality castings with close tolerances. This demand is spurring the further 287288 11 + Metal-Casting Processes TALE GENERAL CHARACTERISTICS OF CASTING PROCESSES. Typical Typical Weight (kg) Surface Materials —————— Finish Process Cast Minimum = Maximum (um, f,) Sand All 0.05, No limit 5-25 Shell all 0.05, 190+ 1-3 Expandable pattern al 0.05 No lirit 5-20 Plaster Nonferrous 0.05, 50+ 1-2 (Al, Mg, Zn, Cu) Investment All 0.005 100+ 1-3 (High melting pt.) Permanent mold all 05 300 -3 Die Nonferrous <0.05 50 1-2 4A, Mg, Zn, Cul Centrifugal all = 5000~ 2-10 continued development of casting processes that produce high-quality castings (Table 11.1; see also Fig, 13.10). This chapter will emphasize the significance of these trends in the major casting processes This chapter is organized around the major classifications of casting practices (see Fig. [1.2 in the Introduction to Part Il). These classifications are related to mold mate- rials, molding processes, and methods of feeding the mold with the molten metal. The two major categories are expendable-mold and permanent-mold casting. Expendable molds are made of sand, plaster, ceramics, and similar materials, which are generally mixed with various binders, or bonding agents. As described in Chapter 8, these materials are refractories, that is, they have the capability to withstand, the high temperatures of molten metals. After the casting has solidified, the molds in these processes are broken up to remove the casting. Permanent molds, as the name implies, are used repeatedly and are designed in such 2 way that the casting can be easily removed and the mold used for the next casting. These molds are made of metals that maintain their strength at high tempera~ tures and thus can be used repeatedly. Because metal molds are better heat conductors than expendable molds, the solidifying casting is subjected to a higher rate of cooling, which in turn affects the microstructure and grain size within the casting, Composite molds are made of wo or more different materials, such as sand, graphite, and metal, combining the advantages of each material. They are used in vari- us casting processes to improve mold strength, cooling rates, and overall economics of the process, ‘The major expendable-mold processes are introduced in Sections 11.2-11.8, the permanent-mold processes in Sections 11.91.14. Because of their unique character- istics and applications, particularly in manufacturing microelectronic devices, basic erystal-growing techniques are also described. The chapter concludes with an over- view of modern foundries.‘M2 Sand Casting 289 TABLE 11.1 (continued) aacescseenetse ee tee Section Thickness (mm) Shape _ Dimensional Process Porosity” Complexity” Accuracy* Minimum Maximum Sand ‘ 1-2 3 3 No limit Shell 4 23 2 2 - Expandable pattern 4 1 2 2 No limit Plaster 3 102 2 1 — Investment 3 1 1 1 1 Permanent mold 2-3 3-4 1 2 50 Die 1-2 3-4 1 os 2 Centrifugal 1-2 34 3 2 100 ‘Relate ating: best Bwore, Note: These cats are only ganerl:argneant vavatinns en secur depending onthe methous vie 11.2) sand Casting The traditional method of casting metals is in sand molds and has been used for mil lenis. Simply stated, sand casting consists of placing a pattern (having the shape of the desired casting) in sand to make an imprint, incorporating a gating system, filling the resulting cavity with molten metal, allowing the metal to cool until it solidifies, break. ing away the sand mold, and removing the casting (Fig. 11.1), Although the origins of sand casting date to ancient times, itis still the most prevalent form of casting, In the United States alone, about 15 million tons of metal are cast by this method each year. Typical parts made by sand casting are machine-tool bases, engine blocks, cylinder heads, and pump housings (Fig. 11.2). 11.2.1 Sands Most sand casting operations use silica sand (SiO,), Sand is the product of the disin- tegration of rocks over extremely long periods of time, It is inexpensive and is suitable as mold material because of its resistance to high temperatures. There are two general types of sand: naturally bonded (bank sands) and synthetic (Jake sands). Because its composition can be controlled more accurately, synthetic sand is preferred by most foundries. Several factors are important in the selection of sand for molds. Sand having fine, round grains can be closely packed and forms a smooth mold surface. Good permeability of molds and cores allows gases and steam evolyed during casting to escape easily. The mold should have good collapsibility (the casting shrinks while cooling) to avoid defects in the casting, such as hot tearing and cracking290 ‘11+ Metal-Casting Processes | = Pattern making Molding | — Core making = Gating system Sand ——*—] Meld Mating of |, [Pouring Heat metal into mold Casting teeatment finishing Inspection 7 7 7 T 7 i ! ! t Furnaces Solidifcation _ Shakeout Adgitional heat Defects Removal of risers ‘estment Pressure tightness fad gates Dimensions FIGURE 11.1 Outline of production steps in a typical sand-casting operation. The selection of sand involves certain tradeoffs with respect to properties. For example, fine-grained sand enhances mold strength, but the fine grains also lower mold permeability. Sand is typically conditioned before use. Mulling machines are used to uniformly mull (mix thoroughly) sand with additives. Clay (bentonite) is used as a cohesive agent to bond sand particles, giving the sand strength. Zircon (ZrSiO.), CRED. —— Typical gray iron castings used in auto- mobiles, including transmission body (left); hub rotor with disk cylinder (front). Source: Courtesy of Central Foundry Division of General Motors Corporation.11.2. Sand Casting 291 olivine (Mg,SiO,), and iron silicate (Fe:SiO,} sands are often use! in steel foundries for their low thermal expansion. Chromice (FeCr,O,) is used for is high hese transfer property: 11.2.2. Types of sand molds Sand molds are characterized by the types of sand that comprise them and by che methods used to produce them. There are three basie types of sand molds: green-sancl, cold-box, and no-bake molds The most common mold material is green molding sand. The term green refers to the fact that the sand in the mold is moisc or damp while the me: is being poured into it. Green molding sand is 2 mixture of sand, clay, and water. Grocn-sand molding is the least expensive method of making molds. In the skin-dvied method, the mold surfaces are dried, either by storing the mold inair or drying ic with torches. Skin-dried molds are generally usec. “or large castings because of their higher strength. Sand molds are also oven dried (baked) prior to receiving the molten metal. They are stronger than green-sand molds and impart bet ter dimensional accuracy and surface finish to the casting. However, distortion of the mold is greater, the castings are more susceptible to hot tearing because of the lower collapsibility of the mold, and the production rate is slower because of the drying time required, In the cold-box mold process, various organic and inorganic binders are blended into the sand to bond the grains chemically for greater strength. These molds are dimensionally more accurate than green-sand molds but are more expensive In the no-bake mold process, a synthetic liquid resin is mixed with the sand, and the mixcure hardens at room temperature, Because bonding of the mold in this and the cold-box process takes place without heat, they are called cold-setting processes Major components of sand molds, as shown in Fig. 11.3, are: + The mold itself, which is supporced by a flask. Two-piece molds consist of a cope fon top and a drag on the bottom. The seam between them is the parting line. ‘When more than two pieces are used, the additional parts are called checks. + A pouring basin or pouring eup, into which the molten metal is poured. + A sprue, through which the molten metal flows downward. + The ranmer system, which has channels that catry the molten metal from the sprue to the mold cavity: Gates are the inlets into the mold eavity. + Risers, which supply additional metal to the casting as it shrinks during solidifi- cation. Figure 11.3 shows two different types of risers: a blind riser and an open riser. + Cores, which are inserts made from sand. They are placed in the mold to form hollow regions or otherwise define the interior surface of the casting, Cotes are also used on the outside of the casting to form features such as lettering on the side of a casting or deep external pockets.292 11 + Metal-Casting Processes iu? — Schematic illustration of @ sand mold showing various features, Openriser Vent Pouring basin cup! | Cope Drag —Fresk sana Posting Tine | Sand Vents, which are placed in molds to carry off gases produced when the molten metal comes into contact with the sand in the molds and core. They also exhaust air from the mold cavity as the molten metal flows into the mold. 11.2.3. Patterns TE. CHARACTERISTICS OF PATTERN MATERIALS Rating” Characteristic Wood Aluminum Steel Plastic Cast Iron Machinability E 6 F 6 6 Wear resistance Pp G E F E Strength F 6 E 6 6 Weight? E G Pe G P Repairabiity e e 6 F G Resistance to: Corrosion E £ e E P Swelling e E E E E rcollent G, good: Fe: 8 poor. factorinoperstrfatiges ‘ay wate. ‘Seure: D. Eeey and W. Winey, Iocan Foundry Technolgy. Now Yor: Mera 1968. Patterns are used to mold the sand mixture into the shape of the casting. They may be made of wood, plastic, or metal. The selection of a pattern material depends on the size and shape of the casting, the dimensional accuracy and the quantity of castings required, and the molding process to be used (Table 11.2). Because patterns are used repeatedly to make molds, the strength and durability of the material selected for pat- terns must reflect the number of castings that che mold will produce. They may be11.2 Sand Casting 293 FIGURE 11.4 enon Atypical metal match-plate pattarn used in sand casting made of a combination of materials to reduce wear in critical regions, Patterns are usually coated with a parting agent co facilitate their removal from the molds. Patterns can be designed with a variety of features to fit application and economic requirements. One-piece patterns also called loose ot solid patterns, are generally used for simpler shapes and low-quantity production. They are generally made of wood and are inexpensive, Split patterns are two-piece patterns mace so that exch part forms 2 postion of the cavity for the casting, In this way castings having complicated shapes can be produced. Match-plate patterns area popular type of mounted pattern in which two-piece patterns are constructed by securing each half of one or more split patterns to the opposite sides of a single plate (Fig, 11.4). In such constructions, che gating system can be mounted on the drag side of the pattern. This type of pavvera is used most often in conjunction with molding machines and large production runs to pro- duce smaller castings. An important recent development is the application of rapid prototyping to mold and pattern making. In investment casting, for example, wax patterns can now be replaced with accurate resin patterns made directly by rapid prototyping (using CAD data and without the need for dies), ata fraction of the time and cost of dies for making wax patterns. As described in detail in Section 18.17, there are several tech nologies using computer-aided design and manufacturing by which these parts and related components can be made rapidly, reducing production time and cost. Pattern design is a crucial aspect of the total casting operation, The design should provide for metal shrinkage, ease of removal rom the sand mold by means of a taper or draft (Fig. 11.5), and proper metal flow in the mold cavity. These topies are dis- cussed in greater detail in Chapter 12. 11.24 Cores For castings with internal cavities or passages, such as in an automotive engine block or a valve body, cores are utilized. Cores are placed in the mold cavity before casting to form the interior surfaces of the casting and are removed from the finished part during shakeout and further processing. Like molds, cores must possess strength, per- meability, ability to withstand heat, and collapsibility. Therefore cores are made of sand aggregates.294 11 + Metal-Casting Processes. FIGS ——— Taper on patterns for ease of removal from the sand mold. Pater te angle Flask Sand mold Good The core is anchored by core prints. These are recesses that are added to the pattern to support the core and to provide vents for the escape of gases (Fig, 11.6). A common problem with cores is that for certain casting requirements, as in the case where a recess is required, they may lack suffeient structural support in the cavity. To keep the core from shifting, metal supports, known as chaplets, may be used to anchor the core in place. Cores are generally made in a manner similar to that used in making molds, and the majority are made with shell, no-bake, or cold-box processes. Cores are formed in core boxes, which are used much like patterns are used to form sand molds. The sand can be packed into the boxes with sweeps or blown into the box by compressed air from core blowers. Core blowers have the advantages of producing uniform cores and operating ata very high production rate. 11.2.5 Sand-molding machines The oldest known method of molding, which is still used for simple castings, is to compact the sand by hand hammering or ramming it around the pattern. For most operations, however, the sand mixture is compacted around the pattern by molding Core’ pants [ese Seep core x eS raring Te “ a : Tine Pe ry Examples of sand cores supported by core prints.‘11.2 Sand Casting 295 bi @ ol Squeezehead Diaphragm {| Hydesatc eylinder FIGURE 11.7 Verious designs of squeeze heads for mold making: (ab conventional fat head: (b) profile head, (6) equalizing squeeze pistons; and (d) flexible diaphragm. Source: & Institute of British Foundry. men. Used with permission machines (Fig, 11.7). These machines eliminate arduous labor, offer high quality cast- ing by improving the application and distribution of forces, manipulate the mold in a carefully controlled fashion, and increase the rate of production, Mechanization of the molding process can be further assisted by jolting the assembly. The flask, molding sand, and pattern are placed on a pattern plate mounted onan anvil, and jolted upward by air pressure at rapid intervals (Fig. 11.8), The inertial forces compact the sand around the pattern, Jolting produces the highest compaction at the horizontal parting line, whereas in squeezing, compaction is highest at the squeezing head (Fig. 11.7). Thus more uniform compaction can be obtained by com- bining them (Fig. 11.86), In vertical flaskeless molding, the halves of the pattern form a vertical chamber wall against which sand is blown and compacted (Fig. 11.9). Then the mold halves are packed horizontally, with the parting line oriented vertically and moved along a pour- ing conveyor. This operation is simple and eliminates the need to handle flasks, mal_ ing potential production rates very high, particularly when other aspects of the operation, such as coring and pouring, are automated. Sandslingers fil the flask uniformly with sand under a stream of high pressure. They are used to fil large flasks and are typically operated by machine. An impeller in the machine throws sand from its blades or cups at such high speeds that the ‘machine not only places the sand but also rams it appropriately.296 ‘11 + Metal-Casting Processes aa wo Air Hinder <—— Lo —— fo Paati iron, Putri on ae onstripping frame Piston Piston FIGURE 11.8 (a) Schernatic illustration of a jott-type mol ‘which combines jolting and squeezing ‘aking machine, (b} Schematic illustration of a mold: In impact molding, the sand is compacted by controlled explosion or instantane- cous release of compressed gases. This method produces molds with uniform strength and good permeability. Tn vacewm molding, also known as the “V” process, the pattern is covered tightly by a thin sheet of plastic. A flask is placed over the coated pattern and is filled with (b) Metal poured here Sand Bor Ram Pattern ia} 7 FIGURE 11.9 Vertical flaskless molding. (a) Sand is squeezed between two helves of the pattern. (b) Assembled molds pass along an assembly line for pouring.V2 Sand Casting 297 dry binderless sand. A second sheet of plastic is placed on top of the sand, and a vacuum action hardens the sand so that the pattern can be withdeawa, Both halves of the mold are made this way and then assembled. During pouring, the mold remains under a vacuum but the casting cavity does not, When the metal has solidified, the vacuuim is turned off and the sand falls away, releasing the casting, Vacuum molding produces castings having very good detail and accuracy, Its especially well suited for large, relatively flat castings. 11.2.6 The sand-casting operation After the mold has been shaped and the cores have been placed in position, the two balves (cope and drag} are closed, clamped, and weighted down. They are weighted to prevent the separation of the mold sections under the pressure exerted when the mol ten metal is poured into the mold cavity. The design of the gating system is important for proper delivery of the molten metal into the mold cavity. As we described in Section 10.3, turbulence must be mini. mized, air and gases must be allowed to escape by such means as vents, and proper temperature gradients must be established and maintained to minimize sheinkage and porosity. The design of risers is also important in order to supply the necessary molten metal during solidification of the casting. The pouring basin may also serve as a riser. A complete sequence of operations ia sand casting is shown in Fig. 11.10 Alter solidification, the casting is shaken out of its mold, and the sand and oxide layers adhering to the casting are removed by vibration (using a shaker) or by sand blasting, Ferrous eastings are also cleaned by blasting with steel shot (shor blasting) or arit. The risers and gates are cut off by oxyfuel-gas cutting, sawing, shearing, and abrasive wheels, or they are trimmed in dies. Gates and risers on steel castings are also removed with air carbon-arc ot powder-injection torches. Castings may be cleaned by electrochemical means or by pickling with chemicals to remove surface oxides The surface of castings is important in subsequent machining operations, because machinability can be adversely affected if the castings are not cleaned properly and sand particles remain on the surface, If regions of the casting have not formed properly ot have formed incompletely, the defects may be repaired by welding by filing them with weld metal. Sand-mold castings generally have rough, grainy surfaces, although that depends on the quality of the mold and the materials used. Depending on the metal used, the casting may subsequently be heat treated to improve certain properties needed for its intended service use; these processes are par ticularly important for stel castings. Finishing operations may involve straightening ot forging with dies to obvain final dimensions, and machining, Minor surface imper- fections may also be filled with a metal-filled epoxy, especially for cast-iron castings because they are difficult to weld. Inspection is an important final step and is carried ut to ensure that the casting meets all design and quality-control requirements Almost all commercially used metals can be sand cast. The surface Gnish obtained is largely a function of the materials used in making the mold. Dimensional accuracy is not as good as that of other casting processes, However, intricate shapes can be castow rc) tet Core prints. Goto nena dein compan sme a wo 1 ere Spruce Qe Se «= conten com ae Se ccattnd Cope after ramming with Rand pad removing Drag ready for sand pattern, sprue, and risers removing Pattern Oo a Sateg ay cass Stes rigune 1.10 ‘Schematic illustration of the sequence of operations for sand casting. Source: Steel Founders’ Society of America (a) A mechanical drawing of the part is used to generate a design for the pattern. Considerations such as part shrink syn nd draft must be built into the drawing, (b~e) Patterns have been mounted on plates equiaped with pins for “alignment. Note the presence of core prints designed to hold the core in place. (de) Core boxes produce core halves, Gitich are pasted together. The cores will be used to praduce the hollow area of the part shown in (2). (f) The cope half of the mold is assembled by taking the cope pattern plate, securing it to the flask through aligning pins, and attaching inserts to form the sprue and ig) The flask is rammed with sand and the piate end inserts are Pemoved. th) The drag half is produced in a similar manner, with the pattern inserted. A bottom board is placed below the drag and aligned with pins. (i) The pattern, flask, and battom board are inverted, and the pattern is with- Grawn, leaving the appropriate imprint. () The core is set in place within the drag cavity. {k) The mold is closed by placing the cope on top of the drag and securing the assembly with pins. The flasks are then subjected to pressure to Pountaract buoyant forces in the liquid, which might lift the cope. (I) After tha metal solidifies, the casting is removed from the mold. im) The sprue and risers are cut off and recycled, and the casting is cleaned, inspected, and heat treated (when necessary). 29811.3. Shell-Mold Casting 299 by this process, such as cast-iron engine blocks and very large propellers for ocean liners. Sand casting can be economical for relatively small production runs, and equip- ‘ment costs are generally low The character‘stics of sand casting and other casting pro- cesses are given in Table 11.1 (see also Chapter 12). Sn 11.3 Sheil-Mold Casting Shell-mold casting was first developed in the 1940s and has grown significantly because it can produce many types of castings with close tolerances and good surface finishes at a low cost. In this process, a mounted pattern made of a ferrous metal or aluminum is heated to 175-370 °C (350-700 "E), coated with a parting agent such as silicone, and clamped to a box or chamber containing a fine sand containing 2.5 to 4.0 percent thermosetting resin binder such as phenol-formaldehyde, which coats the sand particles, The box is either rotated upside down (Fig. 11.11) or the sand mixture is blown over the pattern, allowing it to coat the pattern. The assembly is chen placed in an oven for a short period of time to complete the curing of the resin. The oven in most shell-molding machines is a metal box with gas- fired burners that swings over the shell mold to cure it. The shell hardens around the pattern and is removed from the pattern using built-in ejector pins. Two half-shells Cotted sane Patter Coated sand J-~Dump box y (@) Pater rorated (b) Pattern and dump and clamped to dump box ‘box rotted Shety Excess FIGURE 11.11 Coated & sone sand common method of making shell sand molds. Called dump-box technique, the fr Investment voids in the shell and pealback (when sections of the shell fall off as the pattern is raised). Source: ASM {) Pater dump box. (4) Patera und shel! International in position forthe investment removed from dump box300 11 + Metal-Casting Processes are made in this manner and are bonded or clamped together in preparation for pouring. The thickness of the shell can be accurately determined by controlling the time that the pattern is in contact with the mold. In this way, the shell can be formed with the required strength and rigidity co hold the weight of the molten liquid. The shells are light and thin, usually 5~10 mm (02-044 in.), and consequently their thermal characteristics are different from those for thicker molds. Shell sand has a much lower permeability than sand used for green-sand molding, because a sand of much smaller grain size is used for shell molding. The decomposition of the shell-sand binder also produces a high volume of gas. Unless the molds are properly vented, trapped air and gas can cause serious problems in shell molding of ferrous castings. Shell molds are generally poured with the parting line horizontal and may also be supported by sand. The walls of the mold are relatively smooth, offering low resis- tance to flow of the molten metal and producing castings with sharper corners, thinner sections, and smaller projections than are possible in green-sand molds. With the use oof multiple gating systems, several castings can be made in a single mold, Nearly any ‘metal suiced for sand casting may be cast by the shell-mold process. Shell-mold casting may be more economical than other casting processes, depend- ing on various production factors. The cost of the resin binders is offset somewhat by the fact that only 5 percent as much sand is used, compared co sand casting, The rela~ tively high cost of metal patterns becomes a smaller factor as the size of production runs increases. The high quality of the finished casting can significantly reduce clean- ing, machining, and other finishing costs, Complex shapes can be produced with less labor, and the process can be automated fairly easily. Shell-molding applications include small mechanical parts requiring high precision, such as gear housings, cylin- der heads, and connecting rods. Shell molding is also widely used in producing high- precision molding cores. 11.3.1 Composite molds Composite molds are made of two or more different materials and are used in shell molding and other casting processes. They are generally employed in casting complex shapes, such as impellers for turbines. Examples of composite molds ace shown in Figs. 11.12 and 11.13. Molding materials commonly used are shells (made as previ- ously described), plaster, sand with binder, metal, and graphite, Composite molds may also include cores and chills to control the rate of solidification in critical areas of castings. Composite molds increase the strength of the mold, improve the dimensional accuracy and surface finish of castings, and may help reduce overall costs and process ing time. 11.3.2 Sodium si ite process The mold material in the sodium silicate process is a mixture of sand and 1.5 to 6 percent sodium silicate (waterglass) as the binder for sand. This mixture is packed113 Shell-Mold Casting 301 FIGURE. ‘Schematic illustration of a semipermanent composite ‘mold. Source: Stee! Castings Handbook, 5th ed, Steel Founders’ Society of America, 1980, Graphite around the pattern and hardened by blowing carbon dioxide (CO,) gas through it This process, also known as silicate-bonded sand ox the carbon-dioxide process, was first used in the 1950s and has been developed further, for example, by using various other chemicals for binders. Cores made by this process redace the tendency to teat because of their compliance at elevated temperatures. FIGURE 11.13 A composite mold used in casting alloy ‘torque converter. This part was previously cast in an all-plaster mold, Source: Metals Handbook, vol. 5, component athed. (permanent mold!302 11.4 Expandable Pattern Casting (Lost Foam) 11 # Metal-Casting Processes 11.3.3 Rammed graphite molding Rammed graphite, instead of sand, is used to make molds for casting reactive metals, such as titanium and zirconium. Sand cannot be used because these metals react vig- orously with silica. The molds are packed rather like sand molds (see Section 11.2.5), then air dried, baked at 175 °C (350 °F), ficed at 870 °C (1600 °F), then stored under controlled humidity and temperature, The casting proced.ures are similar to those for sand molds. ‘The expandable pattern casting process uses a polystyrene pattern, which evaporates upon contact with molten metal to form a cavity for the casting. The process is also known as evaporative-pattern or lost-pattern casting, and under the trade name Full- Mold process. It was formerly known as the expanded polystyzene process, and has become one of the more important casting processes for ferrous and nonferrous met- als, particularly for the automotive industry. First, raw expandable polystyrene (EPS) beads, containing 5 to 8 percent pentane (a volatile hydrocarbon) are placed in a preheated die, usually made of aluminum. The polystyrene expands and takes the shape of the die cavity. Addicional heat is applied to fuse and bond the beads together. The die is then cooled and opened, and the poly- styrene pattern is removed, Complex patteras may also be made by bonding various individual pattern sections using hot-melt adhesive. ‘The pattern is then coated with a water-base refractory slurry, dried, and placed ina flask. The flask is filled with loose fine sand, which surrounds and supports the pattern. The sand may be dried or mixed with bonding agents to give it additional strength, The sand is periodically compacted by various means (see Figs. 11.7 and 11.8). Then, without removing the polystyrene pattern, the molten metal is poured into the mold. This action immediately vaporizes the pattern (an ablation process) and fills the mold cavity, completely replacing the space previously occupied by the poly- styrene pattern, The heat degrades (depolymerizes) the polystyrene and the degrada- tion products are vented into the surrounding sand. ‘The flow velocity in the mold depends on the rate of degradation of the polymer. Studies have shown that the flow of the molten metal is basically laminar, with Reyn- olds numbers in the range of 400 to 3000 (Section 10.3.1). The velocity of the molten ‘metal at the metal-polymer pattern fronts estimated to be in the range of 0.1-1.0 m/s. The velocity can be controlled by producing patterns with cavities or hollow sections, thus the velocity will increase as the molten metal crosses these hollow regions, similar to pouring in an empty cavity as is done in sand casting. Furthermore, because the polymer requires considerable energy to degrade, large thermal gradients are present at the metal-polymer interface; in other words, the molren metal cools faster than it would if it were poured into a cavity. Consequently, fluidity (see Section 10.3.2) is less11.5. Plaster-Moid Casting 303 than in sand casting. This has important effects on the microstructure throughout the casting and also leads to directional solidification of the metal ‘The evaporative-pattern process has a number of advantages over other casting methods: a) Icis a relatively simple process because there are no parting lines, cores, or riser systems; hence ir has design flexibility. b) Inexpensive flasks are sufficient for the process. ©) Polystyrene is inexpensive and can be easily processed into patterns having very complex shapes, various sizes, and fine surface detail 4d) The casting requires minimum finishing and cleaning operations. @) The process is economical for long production runs. A major factor is the cost to produce the die for expanding the polystyrene beads to make the pattern, £) The process can be automated. Typical applications for this process are cylinder heads, crankshafts, brake com- ponents and manifolds for automobiles, and machine bases. The aluminum engine blocks and other components of the General Motors Saturn automobile are made by this process. Recent developments include the use of polymethylmethaerylace (PMMA) and polyalkylene carbonate as pattern materials for ferrous castings. In a modification of the evaporative-pattern process, a polystyrene pattern is surrounded by a ceramic shell (Replicast C-S process). The pattern is burned out prior to pouring the molten metal into the mold. Its principal advantage over investment casting (with its wax patterns) is that carbon pickup into the metal is entirely avoided. New developments in evaporative-pattern casting include production of metal- matrix composites (Section 9.5). During the process of molding the polymer pattera, itis embedded throughout with fibers or particles, which then become an integral part of the casting, Further studies include modification and grain refinement of the casting by the use of grain refiners and modifier master alloys (Section 11.18) within the par- tern while itis being molded. 11.5 Plaster-Mold Casting In the plaster-mold casting process, the mold is made of plaster of paris (gypsum, or calcium sulfate), with.the addition of tale and silica flour to improve strength and control the time required for the plasser t0.set. These components are mixed with water, snd the resulting slurry is poured over the pattern. After the plaster sets, usually within 15 minutes, the pattern is removed and the mold is dried at 120-260 met (250-500 °F) to remove the moisture. Higher drying temperatures may be used depending on the type of plaster. The mold halves are then assembled to form the mold cavity and preheated to about 120°C (250 °F). The molten metal is then poured into the mold. Because plaster molds have very low permeability, gases evolved during solidifi- cation of the metal cannot escape. Consequently, the molten metal is poured either in304 11 © Matal-Casting Processes a vacuum or under pressure. Plaster-mold permeability can be increased substantially by the Antioch process: The molds are dehydrated in an autoclave (pressurized oven) for 6-12 hours, then rehydrated in air for 14 hours. Another method of increasing permeability is to use foamed plaster, containing trapped air bubbles. Patterns for plaster molding are generally made of aluminum alloys, thermoset- ting plastics, brass, or zinc alloys. Wood patterns are not suitable for making a large number of molds, because the patterns are repeatedly subjected to the water-based plaster slurry. Since there is a limit to the maximum temperature that the plaster mold can withstand, generally about 1200 °C (2200 °F), plaster-mold casting is used only for aluminum, magnesium, zine, and some copper-base alloys. The castings have fine details with good surface finish, Because plaster molds have lower thermal conductiv- ity than others, the castings cool slowly, and more uniform grain structure is obtained with less warpage, Wall thickness of parts can be 1~2.5 mm (0.04-0.1 in.). This process and the ceramic-mold and investment casting processes (described below) are known as precision casting because of the high dimensional accuracy and good surface finish obtained. Typical parts made are lock components, gears, valves, fittings, tooling, and ornaments. Castings usually weigh less than 10 kg (22 Ib) and are typically in the range of 125-250 g (1-3 Ib), although parts as light as 1 g (0.035 oz) have been made 11.6 Ceramic-Mold Casting The ceramic-mold casting process is similar to the plaster-mold process, with the exception that jt uses refractory mold materials suitable for high-temperature appli- cations. The process is also called cope-ared-drag investment casting. The slurry is @ mixcure of fine-grained zircon (Z:Si0,), aluminum oxide, and fused silica, which are mixed with bonding agents and poured over the pattern (Fig. 11.14), which has been placed in a flask. "The pattern may be made of wood or metal, After setting, the molds (ceramic facings) are removed, dried, burned off to remove volatile matter, and baked. The molds are clamped firmly and used as all-ceramic molds. In the Shaw process, the ceramic facings are backed by fireclay (clay used in making firebricks that resist high temperatures) to give strength to the mold. The facings are then assembled into a com- plete mold, ready to be poured (Fig. 11.15). The high-temperature resistance of the refractory molding materials allows these molds to be used in casting ferrous and other high-temperature alloys, stainless steels, and tool steels. The castings have good dimensional accuracy and surface finish over a wide range of sizes and intricate shapes, but the process is somewhat expensive. Typi- cal parts made are impellers, cutters for machining, dies for metalworking, and molds for making plastic or rubber components. Parts weighing as much as 700 kg (1500 Ib) have been cast by this process.Flask Pouring slurry Stripping green mold Bumof FIGURE 11.14 Sequence of operations in making a ceramic mold, Source: Metals Handbook. vel. &thed Ceramic facing. Ceramic 1 Firecay backup Ceramic facing FIGURE 11.15 A typical ceramic mold (Shaw process} for casting steel dies used in hot forging. Source: Metals Handbook, vol. 5, 8th ed. 305306 11 ¢ Matal-Casting Processes 11.7 investment Casting The investment-casting process, also called the Jost-wax process, was first used dur~ ing the period 4000-3000 Bc. The pattern is made of wax or a plastic such as polysty- rene, The sequences involved in investment casting are shown in Fig. 11.16. The pattern is made by injecting molten wax or plastic into a metal die in che shape of the Mote te make pattern < ® wo os \ Wa Injecting wa Dern or plastic pattern Ejestngattern allemamembly “Tree! wn Completed mold 1 Heat Molten astie Pattern meltout Pouring Pattern FIGURE 11.16 LT Schematic illustration of investment casting (lost-wax process). Castings by this method can be made with very fine detail and from a variety of metals. Source: Steel Founders’ Society of America.© Example: 11.7 Investment Casting 307 pattern. The patvern is then dipped into a slusry of refractory material, such as very fine silica and binders, including water, ethy! silicate, and acids, After this initial cont ing has dried, the pattern is coated repeatedly to increase its thickness. The term investment comes from the fact that the pattern is invested with the refractory mate- Hal, Wax patterns require careful handling because they are not strong enough to withstand the forces involved during mold making. However, unlike plastic patterns, wax can be reused. The one-piece mold is dried in air and heated to a temperature of 90-175 °C (200-375 °F)—in an inverted position to melt out the wax—for about 12 hours. The mold is then fired to 650-1050 °C (1200-1900 °F) for about + hours, depending on the metal to be cast, to drive off the water of crystallization {chemically combined water). After the mold has been poured and the metal has solidified, the mold is bro- ken up and the casting is removed, A number of patterns can be joined to make one mold, called a tree (Fig. 11.16c), thus increasing the production rate. Although the labor and materials involved make the lost-wax process costly, it is le for casting high-melting-point alloys with good surface finish and close toler- ances. Thus little or no finishing operations are required, which would otherwise add significantly vo the total cast of the casting. This process is capable of producing intri- cate shapes, with parts weighing from 1 g to 35 kg (0.035 oz to 75 lb}, from a wide variety of ferrous and nonferrous metals and alloys. Typical parts made are compo- nents for office equipment and mechanical components such as gears, cams, valves, and ratchets. Eliminating porosity in casting ————— In investment casting of an aluminum-alloy valve body, porosity developed at the core-casting interface, The mold was originally heated to 200 °C (400 °F), which was too high for the metal around the core to solidify at a sufficiently high rate. Thus the casting began to solidify from the outside wall toward the core, and the gas (hydrogen) expelled during freezing of the metal accumulated at the area near the core-metal interface, thus producing porosity. By lowering the mold temperature to around 90°C (200 °E), the metal around the core solidified at a high enough rate to prevent expul- sion of gases around the core area, thus eliminating porosity. a sS—SEn Ceramic-shell investment casting. A variation of the investment-casting pro- cess is ceramic-shell casting, It uses the same type of wax or plastic pattern, which is dipped first in ethyl silicate gel and then into a fluidized bed of fine-grained fused silica or zircon flour. The pattern i then dipped into coarser-grained silica to build up additional coatings and thickness to withstand the thermal shock of pouring. The rest of the procedure is similar to investment casting. This process is economical and is used extensively for precision casting of steels and high-temperature alloys. The sequence of operations involved in making a turbine disk by this method is shown in Fig. 11.17, Another complex part—an exhaust duct of a gas turbine made308 11 + Metai-Casting Processes a) © ©. @ FIGURE 11.17 Investment casting of an integrally cast rotor for a gas turbine. (a) Wax pattern assembly. {b) Ceramic shell eround wax pattern. (c) Wax is melted out and mold is filled. under a vacuum, with molten superalloy. [d) The cast rotor, produced to net or neer-net shape. Source; Howmet Corporation. by this process is shown in Fig. 11.18. Ifceramic cores are used in the casting, they are removed by leaching with caustic solutions under high pressure and temperature. The molten metal may be poured in a vacuum to extract evelved gases and reduce oxida- tion, thus improving the quality of the casting. To further reduce microporosity, the castings made by this and other processes are subjected to hot isostatic pressing (see Section 17.3). Aluminurn castings, for example, are subjected co a gas pressure up to 100 MPa (15 ksi) at 500 °C (900 °F), FIGURE ——n Integrally cast exhaust duct for the General Electric 1700 gas turbine, made by invest- ment casting. Note the part's complexity ‘and fine surface finish. Parts up to 1.5 m (60 in.) in diameter and weighing as much ‘a5 1140 kg (2500 Ib) have been made suc: ‘cessfully by this process. Source: Howmet Corporation,11.8 Vacuum Casting 309 * Example: Investment-cast superalloy components for gas turbines am=_-_—- Since the 1960s, investment-cast superalloys have been replacing wrought counter- parts in high-performance gas turbines. Much development has been taking place in producing cleaner superalloys (nickel-base and cobalt-base). Improvements have been ‘made in melting and casting techniques, such as by vacuum-induction mehing, using microprocessor controls, Impurity and inclusion levels have continually been reduced, thus improving the strength and ductitity of these components, Such control is essen- tial because these parts operate at a temperature only about 50°C (90 °F) below the solidus. ‘The microstructure of an integrally investment-cast, gas-turbine rotor is shown in the upper portion of Fig. 11.19. Note the fine, uniform, equiaxed grain size through ‘out the cross section. Recent techniques to obtain this result include the use of a nucleant addition to the motten metal, as well as close control ofits superheat, pouring techniques, and control of cooling rate of the casting. In contrast, the lower portion of Fig. 11.19 shows the same type of rotor cast conventionally; note the coarse grain structure. This rotor will have inferior properties compared to the fine-grained-rotor. Due to developments in these processes, the proportion of cast parts to other parts in aircraft engines has increased from 20 percent to about 45 percent by weight. FIGURE 11.19 ‘Top rotor was investment-cast; lower rotor was cast conven: tionally. Source: Advanced Materials and Processes, Oc- tober 1990, p. 26. ASM In- tornational. re 11.8 Vacuum Casting A schematic illustration of the vacuum-casting process, or counter-gravity low- pressure (CL) process (not to be confused with the vicuum-molding process described in Section 11.2.5), is shown in Fig. 11.20, A mixture of fine sand and urethane is310 11 + Metal-Casting Processes FIGURE 20 ‘Schematic illustration of the vacuum: Casting process, Note that the mold has 2 bottom gate. (a) Before immersion of the mold in metal, Source: From Dr. Robert Black: burn, “Vacuum Casting Goes Com- ia co Mold ° ° ° ° ° ° ind (B) af ° ° °} the molten ° ° } mercial," Advanced Materials “and Processes, February 1990. p. 18. ASM International Induction furnace molded over metal dies and cured with amine vapor. Then the mold is held with a robot arm and partially immersed into molten metal held in an induction furnace. The metal may be melted in air (CLA process) or in a vacuum (CLY process). The vacuum reduces the air pressure inside the mold to about two-thirds of atmospheric pressure, drawing the molten metal into the mold cavities through a gate in the bottom of the mold. The molten metal in the furnace is at a temperature usually 55 °C (100 °F) above the liquidus temperature; consequently, it begins to solidify within a fraction of 2 sec- ond. After the mold is filled, it is withdrawn from the molten metal. “This process is an alternative to investment, shell-mold, and green-sand casting, and is particularly suitable for thin-walled (0.75 ram; 0.03 in.) complex shapes wit! uniform properties. Carbon and low- and high-alloy steel and stainless steel parts, weighing as much as 70 kg (155 1b), have been vacuum cast by this method. CLA parts are easily made at high volume and relatively low cost. CLV parts usually contain reactive metals, such as aluminum, titanium, zirconium, and hafnium. These parts, which are often in the form of superalloys for gas turbines, may have walls as thin as 0.5 mm (0.02 in.). The process can be automated and production costs are similar to those for green-sand casting. 11.9 Permanent-Mold Casting Inthe permanent-mold casting process, also called hard mold casting, two halves of a mold are made from materials such as cast iron, steel, bronze, graphite, or refractory metal alloys. The mold cavity and gating system are machined into the mold and thus become an integral part of it. To produce castings with internal cavities, cores made of11.10 Slush Casting 311 metal or sand aggregate are placed in the mold prior to casting. Typical core materials are oil-bonded or resin-bonded sand, plaster, graphite, gray iron, low-carbon steel, and hot-work die steel. Gray iron is the most commonly used, particularly for large molds for aluminum and magnesium castings. Inserts are also used for various parts of the mold. In order to increase the life of permanent molds, the surfaces of the mold cavity are usually coated with a refractory slurry, such as sodium silicate and clay, or sprayed with graphite every few castings. These coatings also serve as parting agents and as thermal barriers, controlling the rate of cooling of the casting. Mechanical ejectors, such as pins located in various parts of the mold, may be needed for removal of com: plex castings. Bjectors usually leave small round impzessions on castings. The molds are clamped together by mechanical means and heated to about 150— 200 °C: (300-400 °F) to facilitate metal flow and reduce thermal damage to the dies. ‘The molten metal is then poured through the gating system. After solidification, the molds are opened and the casting is removed. Special means employed to cool the mold include water or the use of fins, similar to those found on motorcycle or lawn mower engines that cool the engine block. Although the permanent-mold casting operation can be performed manually, the process can be automated for large production runs. This process is used mostly for aluminum, magnesium, and copper alloys and gray iron because of their generally lower melting points. Steels can also be cast using graphite or heat-resistant metal molds This process produces castings with good surface finish, close tolerances, uniform and good mechanical properties, and at high production rates. Typical parts made by permanent-mold casting are automobile pistons, cylinder heads, connecting rods, gear blanks for appliances, and kitchenware. Parts that can be made economically generally weigh less than 25 kg (55 Ib), although special castings weighing a few hundred kilo- grams have been made by this process. Although equipment costs can be high because of die costs, the process can be mechanized, thus keeping labor costs low. Permanent-mold casting is not economical for small production runs. Furthermore, because of the difficulty in removing the cast- ing from the mold, intricate shapes cannot be east by this process, However, easily collapsed sand cores can be used and removed from castings to leave intricate incernal cavities, The process is then called sernipermanent-mold casting. 11.10 stush Casting We noted in Fig, 10.10 that a solidified skin first develops in a casting and that this skin becomes thicker with time. Hollow castings with thin walls can be made by permanent-mold casting using this principle. This process is called slush casting, The molten metal is poured into the metal mold, and after the desired thickness of solidi-312 11 + Metal-Casting Processes fied skin is obtained, the mold is inverted or slung, and the remaining liquid metal is poured out, The mold halves are then opened and the casting is removed. The process is suitable for small production runs and is generally used for making ornamental and decorative objects (such as lamp bases and stems) and toys from low-melting-point metals, such as zinc, tin, and lead alloys. 11.11 Pressure Casting In the two permanent-mold processes that we have just described, the molten metal flows into the mold cavity by gravity. In the pressure-casting process, also called pressure pouring or low-pressure casting (Fig. 11,21a), the molten metal is forced upward by gas pressure into a graphite or metal mold, The pressures maintained until the metal has completely solidified in the mold. The molten metal may also be forced upward by a vacuum, which also removes dissolved gases and gives the casting lower porosity. Pressure casting is generally used for high-quality castings. An example of this process is steel railroad-car wheels. These wheels may also be cast in sand molds or semipermanent molds made of graphite and sand (Fig. 11.216). fat wh __-Rallroad wheel | Graphite mota Pouringbasin Gates st i “TR | Airtight | chamber Ladle Refractory tube Wheel Hub Plate FIGURE 11.21 (a) The bottor-pressure casting process utilizes graphite moids for the production of steel railroad wheels. Source: The Griffin Wheel Division of Amsted Industries Incorporated. (b) Gravity-pouring method of casting a railroad wheel, Note that the pouring basin also serves as a riser. Railroad wheels can also be manufactured by forging.