Polymers ‘+ Polymer is a compound consisting of long-chain molecules, each molecule made up of repeating units connected together. = Derived from Greek words: poly meaning many, and meros, meaning part. + Nearly all polymeric materials used in engineering are synthetic, except natural rubber. ‘+ The materials are made by chemical processing and most of the products are made by solidification processes + Three categories: a. Thermoplastic polymers or thermoplastics (TP): solld materials at room temperature become viscous liquids when heated > easily and economically shaped into products. They can he subjected into heating and cooling cycle repeatedly without significant degradation. b. Thermosetting polymers or thermosets (TS): cannot tolerate repeated heating cycles. ‘When initially heated, they soften and flow for molding. The elevated temperature hardens the material. if reheated, they dearade and char rather than soften. . Elastomers (rubbers): exhibit extreme elastic extensibility at relatively low mechanical stress, similar molecular structure to thermosets but different properties. ‘+ Those three types sometimes overiap: thermoset can be made from thermoplastics, some polymer can be either thermosets or elastomers, and some elastomers are thermoplastics. Importance of polymers: © Can be formed into complex part geometries through molding ‘© Interesting properties for engineering applications: low density, good strength-to-weight ratios, high corrosion resistance, and low electrical & thermal conductivity ‘+ Economically competitive with metals (cost, required energy for production) ‘+ Some are translucentitransparent > competitive with glass. ‘+ Widely used in composite Limitation of polymers: ‘+ lower strength compared to metals and ceramics; ‘+ low modulus of elasticity or stiffness ‘+ limited service temperatures ‘+ prone to degradation due to sunlight and radiation; ‘= viscoelastic properties mits usage for load bearing applications Polymer fundamentals ‘+ Polymers are synthesized by joining many small molecules (monomers) together to form very large molecules in a chain-like structure (macromolecules). ‘+ Atoms in the molecule and the links of the chain are held together by covalent bonds-> strong primary bonding in each large molecule, + Amass of polymer material consists of many macromolecules bonded by van der Waals and other secondary bonding types > less stiff and strong than metals & ceramics.Polymerization ‘+ Addition (chain) polymerization: (1) initiation > (2) rapid addition of monomore > (3) long-chain polymer molecule with n mers. vo Monomers Mers Initaten x) oo) A @o° 0 00000 ees ay c ® ) ® ‘+ _ step polymerization, two types of reactions: (a) n-mer attaching a single monomer to form a (n+1) -mer; and (b) n; -mer combining with nz -mer to form a (n; + nz) -mer. nua (oye ng-mer a = Oe Ra oe ode age 0 a o @ ® ” ‘A macromolecule produced by polymerization consists of n repeating mers, and value of n is called the degree of polymerization (DP). Degree of polymerization affects polymer properties, such as mechanical strength and viscosity. ‘The molecular weight( MW): sum of the molecular weights of the mers in the molecule; Polymer Structures and Copolymers Throc aspeots: 1. Stereoregularity: spatial arrangement of the atoms and groups of atoms in the repeating Units of the polymer molecule. Specifically, the way the atom groups are located along the chain for a polymer that has one of the H atoms in its mers replaced by some other atom or atom group This tactic structure is. important in determining the polymer properties, and influences the tendency of polymer crystallization. ‘a. Isotactio: the odd atom groups are all on the same side; b. Syndiotactic: the atom groups alternate on opposite sides; ‘c. Atactic: the groups are randomly along either side HOH HO HO HO = HOH H HOH -G-¢-c-¢-¢-¢-e-¢- -¢-¢-¢-¢-¢-e -e-e~ Hehe HH HOH HH ly © ” HOH HOH HoH HOH tot tot i —c-¢-¢-c-¢-¢-c-c- rr rt T HCH HCH, HOH H CH ©2. Linear, Branched, and Cross-Linked Polymers This aspect has a significant effect on properties, and the basis of the three different categories of polymers: thermoplastics, thermosets, and elastomers, ‘a. Linear: macromolecules form a chain-like structure > thermoplastics. b. Branched: side branches form along the chain > thermoplastics c. Crosslinked: primary bonding occurs between branches and other molecules at certain connection points > thermosets (highly crosslinked/network) and elastomers (lightly crosslinked) (©) finear ©) branched © crosslinked (highly crosslinked 8. Copolymers 1. Homoplymer: the molecules consist of repeating mers with same type. 2. Copolymer: molecules are made of repeating units of two different types. Different mers arrangement: a b. °. alternating copolymer: the mers repeat every other place; random: the mers are in random order, the frequency depending on the relative proportions of the starting monomers; block: mere of the came type tend to group into long segments along the chain; graft: mers of one type are attached as branches to a main backbone of mers of the other type. eo9Moqq000000 00 oa 99008 (a) © P2950008090000 werCrystallinity + Polymere can be amorphous and/or cryetalline, but tendency to cryetallize ié much lose than for metals or non-giass ceramics. ‘+ Degree of erystallinity: the mass proportion of crystallized material > always less than 100% for polymer. ‘= Apolymer that crystallizes is a two-phase system: crystallites interspersed throughout an ‘amorphous matrix. ‘+ Higher crystallinity > increased density, stifiness, strength, toughness, heat resistance, ‘and more opacity for amorphous transparent polymer ‘+ Crystallites: the crystallized regions in a polymer. They take the form of lamellae and are randomly mixed in with the amorphous material, ‘Amorphous ion ~) ‘+ Determining factors for the formation of crystalline region: 1, General rule: only linear polymers can form crystals, 2, Molecule sterecregularity: isotactic always form crystals, syndiotactic sometimes form erystals, atactic nover form erystale, Copolymers rarely form crystals due to their molecular irregularity, Slower cooling promotes crystal formation and growth, Mechanical deformation tends to align the structure and increase crystallization, Plasticizers reduce the degree of erystallnity. o9ee Thermal Behavior of Polymers Liquid Partially (6094) eyetaline polymor Specific volume d | Cystine polymer (100%) % To Temperature‘+ Highly crystalline polymer. © Tm (molting tomperature): a point at which ite volume undergooe an abrupt chango. © Above T.: the thermal expansion of the molten material is greater ‘+ Amorphous polymer. © No abrupt change at T,,.. Below T,: change from liquid to rubbery. 9. T, (glass transition temperature)” a point at which the thermal expansion suddenly becomes lower. Below T,;: hard & brittle material ‘+ Thermoplastics can behave follawing the curve above, up and down muttiple times. ‘+ Thermosets and elastomers, cooled from the liquid state, behave like an amorphous polymer until cross-linking occurs. Their molecular structure restricts the formation of crystals. After cross-linked, they cannot be reheated to the molten state Additives 1. Fillers: improve mechanical properties, reduce cost, improve stability 2, Plasticizere: to make polymere cofter and more flexible, improve flow charactorietice during forming, Colorants: in pigment and dies. Lubricants: reduce friction and promote flow at the mold interface. Flame retardants: reduce flammability Cosstinking ayenl, cause & cross-linking reativn. Ultraviolet light absorbers: protect from ultraviolet attack, Antioxidants: protect from oxidant attack eNegee Thermoplastics ‘* It consist of linear (and/or branched) macromolecules > do not cross-link when heated, ‘* so it-can be heated from a solid state to a viscous liquid state and then cooled back down to solid Mechanical properties Soli (glassy) region 1 Crate pohmer (100%) Paially (-50%) crystalline polymer Deformation resistance % Tm Temperature + at room temperature: 1. much lower stiffness (modulus of elasticity) than metals and ceramics;2. lower tensile strength (10% of the metals) 3.._much lower hardness 4. greater ductility on average, ‘+ Mechanical properties of thermoplastics depend on temperature, ‘+ Amorphous thermoplastics 9 Relow T," rigid, elastic and strong © At Ty: transforms into its rubbery phase, viscoelastic behavior, rather sudden drop in deformation resistance © Just above T,; flexible or rubberclke. © Increased temperature above T,: increasingly soft, & become a viscous fluid + Crystalline thermoplastics (assumed 100% crystalinity) ‘© distinct metting point Tm at which it transforms from solid to liquid, © no perceptible T, point ‘© Partially-crystalline thermoplastics © Resistance to deformation ie characterized by the curve that lies between the two extremes, determined by the relative proportions of the crystalline-amiorphous phase. © Below T,* elastic, decreasing deformation resistance with rising temperatures. © Above T,: the amorphous portions soften, the crystalline portions remain intact, generally viscoelastic. 0 ALTin. Ue crystals mel, iquid consistency, viscous Nuit ‘+ Higher degree of polymerization and molecular weight > reduce flow, difficult to process, but higher strength Physical Proportios (compared to motale or coramice) + lower densities ‘+ much higher coefficient of thermal expansion ‘© much lower melting temperatures; higher specific heats ‘+ lower thermal conductivities ‘+ insulating electrical properties. Important Commercial Thermoplastics Acetals, Acrylics, Acrylonitrle-Butadiene-Styrene (ABS), Cellulosics, Fluoropolymers, Polyamides, Polycarbonate, Polyesters, Polyethylene, Polypropylene, Polystyrene, Polyvinylchlorice Thermosets ‘+ Highly cross-linked structure, always amorphous and exhibit no glass. transition temperature. General properties ‘+ Compared to thermoplastics: More rigid Brittle, no ductility Less soluble in common solvent Higher service temperature SeNe5, Cannot be remelted, instead they degrade or bum, ‘+ Proportics depend on crose-linking: thermally etable, throe-dimeneional, covalently bonded structure within the molecule. ‘= Crosslinking methods’ 1. Temperature-activated systems 2. Calalyst-activated systems 3. Mixing-activated systems ‘Chemical reactions associated with cross-linking are called curing or setting. Important Thermosetting Polymers ‘+ not as widely used as the thermoplastics, likely due to added processing complication in curing. ‘+ Amino Resins, Epoxies, Phenolics, Polyesters, Polyimides, Polyurethanes, Silicones Elastomers, ‘= Capable of large elastic deformation when subjected to relatively low stresses. Some ‘can withstand extensions of 500% or more and still return to their original shape, ‘+ Elastomers ~ rubbers: 11. natural rubber: derived from certain biological plants, 2. synthetic elastomers: produced by polymerization processes Characteristics = Long-chain molecules that is crosslinked. ‘+ Highly impressive elastic properties due to two features: 1. the long molecules are tightly kinked when unstretched, 2. degree of cross-linking is substantially below that of the thermosets. ‘© Greater cross-linking: stifer, more linear elastic modulus ‘+ Condition for elastomeric properties: amorphous when unstretched, and temperature above Ty. + Below T5: hard and brittle; above Ty; “rubbery” state. + Vulcanization: curing used in the context of natural rubber (and certain synthetic rubbers), involving the formation of chemical cross-links between the polymer chains. + Degree of cross-linking in elastomers is less than that in thermosets, + Reactive system elastomers: when curing involves the use of starfing chemicals that form elastomers with relatively infrequent cross-links between molecules > can be classified as either thermosets or elastomers. ‘+ Thermoplastic elastomers: have elastomeric properties that result from the mixture of two thermoplastic phases. ‘One is above its T, at room temperature the other is below its T, > soft rubbery regions intermixed with hard particles that act as cross-links > elastic behavior. Natural rubber © Consists primarily of polyisoprene, a high-molecular-welght polymer of Isoprene (CsHe). © Source: latex (water emulsion of polyisoprene) produced by various plants, mainly rubber tree. ‘+ Natural crude rubber: sticky in hot weather, but stiff and brittle in cold weather‘© Vulcanization: form natural rubber into useful elastomer through cross-linking, resulting in incroaced etrongth, etiffneee, and maintained oxteneibilty. ‘+ General properties: high tensile strength and tear strength, resilience, wear and fatigue resistant. ‘+ Weakness: degradation by exposure of heat, sunlight, oxygen, ozone, and oil. ‘+ Applications: mainly automotive tires, also choe coles, bushings, seals, and shock. absorbing components. ‘+ For those applications, rubber is compounded to achieve the required specific properties. ‘Synthetic rubbers © Higher market than natural rubber ‘© Source: petroleum = Products: styrene-butadiene rubber (SBR, the mast important product), Polybutadiene (BR), Butyl Rubber, Chloroprene Rubber, Ethylene-Propylene Rubber, Isoprene Rubber, Nitile Rubber, Polyuretianies, Silicones, Thermoplastic Elastomers, Polymer Recycling and Biodegradability Plastic trash could be around for centuries, because the primary bonds that make plastics so durable also make them resistant to degradation. Polymer recycling ‘+ Recycling: recovering and reprocessing the discarded plastic items into new products. ‘+ 1S generally more aimoutt man recycling glass and metal products: 1. Less economical since most plastic items are lightweight 2. Plasties came in a variety of chemical compositions that da not mix wall 3. many plastic products contain fillers, dyes, and other additives that difficult to separate Plastic Identification Code (PIC - developed by the Society of the Plastics Industry): umber to identity the plastic for recycling purposes, to facilitate the item separation. The plastics are all thermoplastics: (1) polyethylene terephthalate, (2) high-density polyethylene, (3) polyvinyl chloride, (4) low-density polyethylene (5) polypropylene (6) polystyrene and, (7) other, such as polycarbonate or ABS. A. PASRecycled thermosets: ground up into particulate matter and used as fillers, mostly from used tires, Aleo in granulee forme for landecape mulch, playgrounds, and eimilar purposes. Biodegradable polymers Plastics that are decomposed hy the actions af mieronrganisms necurting in nature, Two forms of biodegradable plastics: 1. Partially degradable: non-biodegradable matrix polymer (petroleum-based) and a natural filler (degradable by microorganisms). Degradation converts the polymer into a sponge-like structure and possibly leading to its complete degradation. 2. Completely degradable: polymer and filler that are both derived from natural and renewable sources. Raw materials: starch from com, wheat, rice, and potatoes. Examples: poiylactide from lactid acid, cellulose. ‘more expensive than potroloum-baced polymere, Applications: where degradabilty is a higher priority than cost savings, ¢.9. packaging materials, disposable food service items, coatings for paper and cardboard, waste bags, ‘and mulches for agricultural crops. Also used in sutures, catheter bags, and sanitary laundry bags in hospitals