polymers - university of rhode island 240/polymers_general.pdf · structure of polymers • mainly...
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Plastics and Polymers
• Polymers first used as a word in 1866 for natural organic
polymers such as cellulose (for photographic film,
packaging, textile fibers)
• Plastics first used as a noun in 1909 (used as synonym)
• The first synthetic polymer was a thermoset (phenol-
formaldehyde) Bakelite was developed in 1906
• Extremely large molecules (macromolecules)
• Wide variety of uses developed throughout 20th century
• From Greek work plastikos – able to be molded and
shaped
• Plastics can be machined, cast, formed, and joined with
relative ease requiring little post-processing or surface-
finish operations
Plastics Pros and Cons
• Advantages over metals• Corrosion resistance and resistance to chemicals
• Low electrical and thermal conductivity
• Low density (good for lightweight components)
• High strength-to-weight ratio, particularly when reinforced
• Noise reduction
• Wide choice of colors and transparencies
• Ease of manufacturing and complexity of design possibilities
• Relatively low cost
• Possible disadvantages• Low strength and stiffness
• High coefficient of thermal expansion
• Low useful temperature range (up to 350°C, 660°F)
• Less dimensional stability in service over time
• Water absorption
Structure of Polymers
• Mainly hydrocarbons
• Monomer –
basic building block
• Long-chain molecules
formed by polymerization,
the linking and cross-linking
of different monomers with
secondary bonds (van der
Waals, hydrogen, ionic)
Figure 7.4 (a) Linear structure--thermoplastics such as acrylics, nylons, polyethylene, and polyvinyl chloride have linear structures. (b) Branched structure, such as in polyethylene. (c) Cross-linked structure--many rubbers or elastomers have this structure, and the vulcanization of rubber produces this structure. (d) Network structure, which is basically highly cross-linked--examples are thermosetting plastics, such as epoxies and phenolics.
Thermosets
Lower density,
because branches
interfere with
packing efficiency
Thermo-
plastics
treated
with UV,
x-rays, or
electron
beams
Linked with primary
covalent bonds
Structure
of
Polymers
Figure 7.2 Basic structure of polymer molecules: (a) ethylene molecule; (b) polyethylene, a linear chain of many ethylene molecules; (c) molecular structure of various polymers. These are examples of the basic building blocks for plastics
Molecular Weight and DP
• The higher the molecular
weight of a polymer, the greater
the average chain length
• Commercial polymers usually
have molecular weight between
10,000 and 10,000,000
• Degree of polymerization (DP)
is the ratio of molecular weight
of the polymer to the molecular
weight of the repeating unit –
the higher the DP, the higher
the polymer’s viscosity and thus
higher processing costs. Also
equals average number of mers
in the molecule.
Crystallinity
Figure 7.6 Amorphous and crystalline regions in a polymer. The crystalline region (crystallite) has an orderly arrangement of molecules. The higher the crystallinity, the harder, stiffer, and less ductile the polymer.
Effects of Crystallinity
Polyethylene type Low Density (LDPE) High Density (HDPE)
Degree of crystallinity 55% 92%
Specific gravity 0.92 0.96
Modulus of elasticity 20,000 psi 1000,000 psi
Melting temperature 239°F (115°C) 275°F (135°C)
High Temperature Behavior
• Amorphous polymers do not have a specific melting
point, but do have a glass transition temperature
• Below Tg they are hard, rigid, brittle, and glassy
• At high temperatures they are rubbery or leathery
• Partly crystalline
polymers do have
a melting point Tm
• Repeating heating
and cooling can
cause degradation
or thermal aging
of thermoplastics
TABLE 7.2
Material Tg (°C) Tm (°C)
Nylon 6,6
Polycarbonate
Polyester
Polyethylene
High density
Low density
Polymethylmethacrylate
Polypropylene
Polystyrene
Polytetrafluoroethylene
Polyvinyl chloride
Rubber
57
150
73
–90
–110
105
–14
100
–90
87
–73
265
265
265
137
115
—
176
239
327
212
—
Types of Plastics
• Thermoplastics• Become easier to form or mold above the glass transition
temperature or melting point
• Increased temperature weakens secondary bonds
• Reversible process
• Can become anisotropic as
chains align during stretching
• Crazing and stress
whitening occurs under
tensile stress or bending
• Thermosets• Cross-linking and three
dimensional arrangements
• Irreversible curing process
• Elastomers (Rubber)
Additives
• Plasticizers• Low molecular weight solvents with high boiling points that impart
flexibility and softness by lowering the glass-transition temperatures
• Often used in PVC and to make thin sheets, films, tubing, shower
curtains, and clothing materials
• Carbon black (soot)• To protect against ultraviolet radiation degradation
• Fillers• To reduce the cost of the polymer, or possibly improve properties
• Wood flour, silica flour, clay, talc, fibers of glass/cellulose/asbestos
• Colorants – organic dyes or inorganic pigments
• Flame retardants
• Lubricants• To reduce friction during processing or prevent sticking to molds
Thermoplastics
• Acetals• good strength, stiffness, and resistance to creep, abrasion, moisture,
heat, and chemicals
• bearings, cams, shower heads
• Acrylics (PMMA)• moderate strength, good optical properties (often transparent, can be
opaque, and resistance to weather, chemicals, electricity
• Lenses, lighted signs, skylights, windshields, lighting fixtures,
(Lucite), (Plexiglas)
• ABS (acrylonitrile-butadiene-styrene)• Dimensionally stable and rigid, good strength and toughness, good
resistance for impacts, abrasion, chemicals, and electricity
• Legos, helmets, luggage, refrigerator liners, telephones
• Cellulosics• Rigid, strong, tough, but weather poorly, affected by heat, chemicals
• Pens, knobs, eyeglass frames, safety goggles, toys, machine guards
Thermoplastics
• Fluorocarbons• Good resistance to high temperature (Tm = 327°C)
• Teflon cookware, chemical-process equipment, electrical insulation
for high temperature wire and cable, gaskets, seals
• Polyamides – Nylons• Good mechanical properties, abrasion resistant, self-lubricating
• Fasteners, zippers, tubing, surgical equipment, gears, bearings
• Polyamides – Aramids• High tensile strength and stiffness
• Kevlar bulletproof vests, radial tires, fibers for reinforced plastics
• Polycarbonates• Good mechanical and electrical properties, high impact resistance
• Food-processing equipment, bottles, bullet-resistant window glazing,
optical lenses, safety helmets, machine guards (Lexan), medical
aparatus
Thermoplastics
• Polyesters (also thermosets)• Good mechanical, electrical, chemical properties
• Gears, cams, load-bearing members, pumps, (Mylar)
• Polyethylenes – low density (LDPE), high density (HDPE)• Good electrical and chemical properties
• Bumpers, housewares, garbage cans, bottles, toys, packaging
• Polyethylenes – ultra high molecular weight (UHMWPE)• High impact toughness and resistance to abrasive wear
• Artificial knee and hip joints
• Polypropylenes• Good mechanical, electrical, chemical props., resistance to tearing
• Milk & juice containers, weather stripping, auto trim & components
Thermoplastics
• Polystyrenes (Styrofoam)• Inexpensive, average properties, somewhat brittle
• Disposable packaging for meat, cookies, and candy, insulation
• Polysulfones• Excellent resistance to heat, water, and steam, highly resistant to
chemicals but are attacked by organic solvents
• Steam irons, coffeemakers, medical equipment that is sterilized,
aircraft cabin interiors, power tool & appliance housings, insulators
• Polyvinyl chloride (PVC)• Wide range of properties, inexpensive, rigid or flexible
• Signs, construction pipes and conduits
• Wire and cable coatings, flexible tubing, footwear, imitation leather,
upholstery, records, gaskets, seals, films and coatings, (Saran)
• Polyimides –• structure of thermoplastic but nonmelting characteristic of thermoset
Thermosets
• Polyimides • Structure of thermoplastic but nonmelting characteristic of thermoset
• Pump components, electrical connectors for high-temperature use,
sports equipment, safety vests, aerospace parts
• Alkyds• Good electrical insulating properties, impact resistant, low water
absoption, dimensional stability
• Electrical components
• Aminos (Urea and Melamine)• Hard and rigid, resistant to creep, abrasion, electrical composition
• Countertops, small appliance housings, handles, dinnerware
• Epoxies• Excellent mechanical and electrical properties, good dimensional
stability, strong adhesive properties, can be fiber-reinforced
Thermosets
• Polyesters• Often reinforced with glass (or other fibers)
• Available as casting resins
• Boats, luggage, chairs, automotive bodies, swimming pools
• Phenolics• Brittle, but rigid and dimensionally stable, high resistance to heat,
water, electricity, chemicals
• Knobs, handles, telephones, bond material to hold abrasive grains
together in grinding wheels, electrical devices, insulators
• Silicones• Weather well and excellent electrical properties over a wide range of
humidity and temperature, resist chemical and heat
• Oven gaskets, heat seals, waterproof materials
Elastomers
• Amorphous polymers with low Tg
• Highly kinked, twister, and curled polymer structure
• Stretch, but return to original shape after load is removed
• Soft with low elastic modulus
• Natural and synthetic rubber,
silicones, polyurethane
• Also cross-linked structure, as
formed through vulcanization
Figure 7.12 Typical load-elongation curve for rubbers. The clockwise lop, indicating the loading and the unloading paths, displays the hysteresis loss. Hysteresis gives rubbers the capacity to dissipate energy, damp vibration, and absorb shock loading, as is necessary in automobile tires and in vibration dampers placed under machinery.
Environmental Considerations
• Plastics contribute 10% of municipal solid waste
• High volume, relative to their weight
• 1/3 of plastic production is for disposable products
• Most plastics are made from synthetic polymers that are
derived from nonrenewable natural resources (coal,
petroleum, etc), not biodegradable, and difficult to recycle
• 3 biodegradable plastics have been developed thus far but
more research is needed
• Material conservation efforts are best
• Thermoplastics are recycled by remelting them and
reforming them into other products – watch for symbols!• 1 –Polyester (PETE), 2 –Polyethylene -HDPE, 3 – vinyl (PVC),
4 – Polyethylene -LDPE, 5 – Polypropylene (PP),
6 – Polystyrene (PS), 7 – other
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