Classes Of Polymeric Materials
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Classes Of Polymeric Materials Presentation Transcript

  • 1. Classes of Polymeric Materials Professor Joe Greene CSU, CHICO
  • 2. Topics
    • Introduction
    • Thermoplastics
      • General
      • Commercial plastics
    • Thermosets
      • General
      • Commercial thermosets
    • Elastomers
      • General
      • Commercial elastomers
  • 3. Introduction
    • Polymeric materials can be either
      • Thermoplastics, thermosets, and elastomers.
      • Each section is presented in appropriate groups
    • Thermoplastics come in a variety of forms
      • Pellets, powder (1-100 microns), flake, chip, cube, dice,
      • Shipped in packages of choice
          • Bags (50 lbs), drums (200 lbs), boxes, cartons, gaylords (1000 lb),
          • Tank-truck loads (15 tons), rail cars (40 – 80 tons)
        • Bulk supplies are stored in silos and conveyed pneumatically
    • Thermosets are supplied in powder or liquid form
      • Supplied in drums, tank-trucks, and railroad cars.
    • Rubbers are supplied in bale form.
  • 4. Commercial Thermoplastics
    • Olefins
      • Unsaturated, aliphatic hydrocarbons made from ethylene gas
      • Ethylene is produced by cracking higher hydrocarbons of natural gas or petroleum
    • LDPE commercialized in 1939 in high pressure process
        • Branched, high pressure, and low density polyethylene
    • HDPE commercialized in 1957 in low pressure process
        • Linear, low pressure, high density
    • The higher the density the higher the crystallinity
    • Higher the crystallinity the higher the modulus, strength, chemical resistance,
    • PE grades are classified according to melt index (viscosity) which is a strong indicator of molecular weight.
      • Injection molding requires high flow, extrusion grade is highly elastic, thermoforming grade requires high viscosity or consistency
  • 5. Principal Olefin Monomers
    • Ethylene Propylene
    • Butene-1 4-Methylpentene
    C C H H H H C C C 2 H 5 H H H C C CH 3 H H H C C C 5 H 6 H H H CH 3
  • 6. Several Olefin Polymers
    • Polyethylene Polypropylene
    • Polyisobutene Polymethylpentene
    C C C 5 H 6 H H H CH 3 n C C H H H H n C C C 2 H 5 H H H n C C CH 3 H H H n
  • 7. Polymers Derived from Ethylene Monomer X Position Material Name Abbreviation H Polyethylene PE Cl Polyvinyl chloride PVC Methyl group Polypropylene PP Benzene ring Polystyrene PS CN Polyacrylonitrile PAN OOCCH 3 Polyvinyl acetate PvaC OH Polyvinyl alcohol PVA COOCH 3 Polymethyl acrylate PMA F Polyvinyl fluoride PVF Note : Methyl Group is: | H – C – H | H Benzene ring is:
  • 8. Addition Polymerization of PE
    • Polyethylene produced with low (Ziegler) or high pressure (ICI)
    • Polyethylene produced with linear or branched chains
    OR n C C H H H H C C H H H H C C H H H H C C H H H H C C H H H H C C H H H H … … C C H H H H C C H H H H C C H H H C C H H H H C C H H H H … …
  • 9. Mechanical Properties of Polyethylene
    • Type 1: (Branched) Low Density of 0.910 - 0.925 g/cc
    • Type 2: Medium Density of 0.926 - 0.940 g/cc
    • Type 3: High Density of 0.941 - 0.959 g/cc
    • Type 4: (Linear) High Density to ultra high density > 0.959
  • 10. Physical Properties of Polyethylene
  • 11. Processing Properties of Polyethylene
  • 12. Special Low Versions of Polyethylene Produced through catalyst selection and regulation of reactor conditions
    • Very Low Density Polyethylene (VLDPE)
        • Densities between 0.890 and 0.915
        • Applications include disposable gloves, shrink packages, vacuum cleaner hoses, tuning, bottles, shrink wrap, diaper film liners, and other health care products
    • Linear Low Density Polyethylene (LLDPE)
        • Densities between 0.916 and 0.930
        • Contains little if any branching by co-polymerizing ethylene at low pressures in presence of catalysts with small amounts of  -olefin co-monomers (butene, hexene, octene) which play the role of uniform short branches along linear backbone.
        • Properties include improved flex life, low warpage, improved stress-crack resistance, better impact, tear, or puncture versus conventional LDPE
        • Applications include films for ice, trash, garment, and produce bags at thinner gage.
  • 13. Special High Versions of Polyethylene Produced through catalyst selection and regulation of reactor conditions
    • Ultra High Molecular Weight Polyethylene (UHMWPE)
      • Extremely high MW at least 10 times of HDPE (MW=3M to 6M)
      • Process leads to linear molecules with HDPE
      • Densities are 0.93 to 0.94 g/cc and Moderate cost
      • High MW leads to high degree of physical entanglements that
        • Above T melt ( 130 C or 266F), the material behaves in a rubber-like molecule rather than fluid-like manner causing processing troubles, high viscosities
        • Processed similar to PTFE (Teflon)
          • Ram extrusion and compression molding are used.
  • 14. Special High Versions of Polyethylene Produced through catalyst selection and regulation of reactor conditions
    • Ultra High Molecular Weight Polyethylene (UHMWPE)
      • Properties include outstanding properties like engineering plastic or specialty resin
        • Chemical inertness is unmatched; environmental stress cracking resistance and resistance to foods and physiological fluids,
        • Outstanding wear or abrasion resistance, very low coefficient of friction, excellent toughness and impact resistance.
      • Applications:
        • pump parts, seals, surgical implants, pen tips, and butcher-block cutting surfaces. , chemical handling equipment, pen tips, prosthetic wear surfaces, gears
  • 15. Special Forms of Polyethylene
    • Cross-linked PE (XLPE)
      • Chemical cross-links improve chemical resistance and improve temperature properties.
      • Cross-linked with addition of small amounts of organic peroxides
        • Dicumyl peroxide, etc.
      • Crosslinks a small amount during processing and then sets up after flowing into mold.
      • Used primarily with rotational molding
      • Extruded Products
        • Films (shrink wrap film in particular)
        • Pipes
        • Electrical wire and cable insulation
  • 16. Copolymers of Polyethylene
    • Ethylene-Vinyl Acetate (EVA)
      • Repeating groups is ethylene with a vinyl acetate functional that reduces the regularity of the chain; thus the crystallinity and stiffness
      • Part of the pendent group are highly polar which makes film with increased water vapor permeability, increased oil resistance and cling.
      • Vinyl acetate reduces crystallinity and increases chemical reactivity because of high regions of polarity.
      • Applications include flexible packaging, shrink wrap, auto bumper pads, flexible toys, and tubing with vinylacetate up to 50%
    C C H H H H C C H O C = O C H H n m
  • 17. Copolymers of Polyethylene
    • Ethylene-vinyl alcohol (EVOH)
        • Contains equal amounts of two repeat units that act as
          • Barrier layers or as interlayers (tie layers) between incompatible materials due to strong bonding of vinylalcohol repeat units.
    • Ethylene-ethyl acrylate (EEA) Ethylene-methyl acrylate (EMA)
        • Properties range from rubbery to tough ethylene-like properties
        • Applications include hot melt adhesives, shrink wrap, produce bags, bag-in-box products, and wire coating.
        • Produced by addition of methyl acrylate monomer (40% by weight) with ethylene gas
          • reduces crystallinity and increases polarity
        • Tough, thermally stable olefin with good rubber characteristics.
        • Applications include food packaging, disposable medical gloves, heat-sealable layers, and coating for composite packaging
  • 18. Copolymers of Polyethylene
    • Ethylene-carboxylic acid (EAA, EMAA)
      • Small amounts of acrylic acid (AA) or methacrylic acid (MAA) that feature carboxyl acid groups (COOH) are notable adhesives, especially to polar substrates, including fillers and reinforcements
      • Problems include tackiness and corrosive to metals and crosslinking nature
    • Ionomers
      • Modified ethylene-methacrylic acid copolymers where some of the carboxyl acid groups are converted into corresponding metallic salts (metal metacrylate), where the metals are sodium or zinc.
      • Ionic bonds are formed between these cationic and the remaining anionic acid groups. Results in a quasi crosslinked polymer at low temperature and is reversible at high temperature
      • Useful properties, e.g., adhesive and paints to metals (polarity), resistance to fats and oils, Flex, puncture, impact resistance
      • Applications: golf balls, bowling pin covers, ski boot shells, films
  • 19. Copolymers of Polyethylene
    • Ethylene-Propylene (EPM)
      • Ethylene and propylene are copolymerized in random manner and causes a delay in the crystallization.
      • Thus, the copolymer is rubbery at room temp because the Tg is between HDPE (-110C) and PP (-20C).
      • Ethylene and propylene can be copolymerized with small amounts of a monomer containing 2 C=C double bonds (dienes)
      • Results in a co-polymer, EPR, or thermoplastic rubber, TPR
    C C H H H H n C C CH 3 H H H m
  • 20. Mechanical Properties of PE Blends
  • 21. Processing Properties of PE Blends
  • 22. Polypropylene History
    • Prior to 1954 most attempts to produce plastics from polyolefins had little commercial success
      • PP invented in 1955 by Italian Scientist F.J. Natta by addition reaction of propylene gas with a sterospecific catalyst titanium trichloride.
      • Isotactic polypropylene was sterospecific (molecules are arranged in a definite order in space)
      • PP is not prone to environmental stress-cracking like PE
    • Polypropylene is similar in manufacturing method and in properties to PE
    • Tg of PP = -25C versus Tg of PE of -100C
  • 23. Chemical Structure
    • Propylene
    • Isotactic- CH 3 on one side of polymer chain (isolated). Commercial PP is 90% to 95% Isotactic
    n C C CH 3 H H H C C CH 3 H H H C C CH 3 H H H C C CH 3 H H H C C CH 3 H H H C C CH 3 H H H
  • 24. Polypropylene Stereostatic Arrangements
    • Atactic- CH 3 in a random order (A- without; Tactic- order) Rubbery and of limited commercial value.
    • Syndiotactic- CH 3 in a alternating order (Syndio- ; Tactic- order)
    C C CH 3 H H H C C H H H CH 3 C C CH 3 H H H C C H H H CH 3 C C CH 3 H H H C C CH 3 H H H C C H H H CH 3 C C H H H CH 3 C C CH 3 H H H C C H H H CH 3
  • 25. Addition Polymerization of PP
    • Polypropylene produced with low pressure process (Ziegler)
    • Polypropylene produced with linear chains
    • Polypropylene is similar in manufacturing method and in properties to PE
    • Differences between PP and PE are
      • Density: PP = 0.90; PE = 0.941 to 0.965
      • Melt Temperature: PP = 176 C; PE = 110 C
      • Tg of PP = -25C versus Tg of PE of -100C
      • Service Temperature: PP has higher service temperature
      • Hardness: PP is harder, more rigid, and higher brittle point
      • Stress Cracking: PP is more resistant to environmental stress cracking
  • 26. Advantages/Disadvatages of Polypropylene
    • Advantages
      • Low Cost
      • Excellent flexural strength
      • Good impact strength
      • Processable by all thermoplastic equipment
      • Low coefficient of friction
      • Excellent electrical insulation
      • Good fatigue resistance
      • Excellent moisture resistance
      • Service Temperature to 126 C
      • Very good chemical resistance
    • Disadvantages
      • High thermal expansion
      • UV degradation
      • Poor weathering resistance
      • Subject to attack by chlorinated solvents and aromatics
      • Difficulty to bond or paint
      • Oxidizes readily
      • flammable
  • 27. Mechanical Properties of Polypropylene
  • 28. Physical Properties of Polyethylene
  • 29. Processing Properties of Polyethylene
  • 30. Several Olefin Polymers
    • Polybutylene (PB)
      • Based on butene-1 monomer
      • Plus comonomers (small amt)
      • Melt Point 125C similar to PE
      • Tg, -25C is closer to PP
      • Good creep & ESC resistance
      • Good for pipe and film extrusions
    • Polymethylpentene (PMP)
      • Trade name is TPX
      • Crystallizes to high degree (60%)
      • Highly transparent (90% transmis)
      • Properties similar to PP
      • Density is 0.83 g/cc, Tg =30C
      • Stable to 200C, Tm=240C
      • Creep and chemical resistance is good and low permeability.
      • Electrical properties are excellent
      • Process by injection & extrusion
      • Good for lighting, packaging, trays, bags, coffee makers, wire covering, connectors, syringes.
      • Poor ESC and UV
    H C C C 2 H 5 H H H n C C HCH H H H H 3 C C CH 3 n
  • 31. Polyolefin_Polybutylene
    • History
      • PB invented in 1974 by Witco Chemical
      • Ethyl side groups in a linear backbone
    • Description
      • Linear isotactic material
      • Upon cooling the crystallinity is 30%
      • Post-forming techniques can increase crystallinity to 55%
      • Formed by conventional thermoplastic techniques
    • Applications (primarily pipe and film areas)
      • High performance films
      • Tank liners and pipes
      • Hot-melt adhesive
      • Coextruded as moisture barrier and heat-sealable packages
    C C CH 2 H H H CH 3
  • 32. Properties of Polybutylene
  • 33. Polyolefin_Polymethylpentene (PMP)
    • Description
      • Crystallizes to 40%-60%
      • Highly transparent with 90% transmission
      • Formed by injection molding and blow molding
    • Properties
      • Low density of 0.83 g/cc; High transparency
      • Mechanical properties comparable to polyolefins with higher temperature properties and higher creep properties.
      • Low permeability to gasses and better chemical resistance
      • Attacked by oxidizing agents and light hydrogen carbon solvents
      • Attacked by UV and is quite flammable
    • Applications
      • Lighting elements (Diffusers, lenses reflectors), liquid level
      • Food packaging containers, trays, and bags.
    H 3 C-CH-CH 3 C C CH 2 H H H
  • 34. Properties of Polymethylpentene
  • 35. PVC Background
    • Vinyl is a varied group- PVC, PVAc, PVOH, PVDC, PVB
      • Polyvinyls were invented in 1835 by French chemist V. Regnault when he discovered a white residue could be synthesized from ethylene dichloride in an alcohol solution. (Sunlight was catalyst)
      • PVC was patented in 1933 by BF Goodrich Company in a process that combined a plasticizer, tritolyl phosphate, with PVC compounds making it easily moldable and processed.
      • PVC is the leading plastic in Europe and second to PE in the US.
      • PVC is made by suspension process (82%), by mass polymerization (10% ), or by emulsion (8%)
      • All PVC is produced by addition polymerization from the vinyl chloride monomer in a head-to-tail alignment.
      • PVC is amorphous with partially crystalline (syndiotactic) due to structural irregularity increasing with the reaction temperature.
      • PVC (rigid) decomposes at 212 F leading to dangerous HCl gas
  • 36. PVC and Vinyl Products
    • Rigid-PVC
      • Pipe for water delivery
      • Pipe for structural yard and garden structures
    • Plasticizer-PVC or Vinyl
      • Latex gloves
      • Latex clothing
      • Paints and Sealers
      • Signs
  • 37. PVC and PS Chemical Structure
    • Vinyl Groups (homopolymers produced by addition polymerization)
      • PVC - poly vinylidene - polyvinylalcohol (PVOH)
            • chloride (PVDC)
      • polyvinyl acetate (PVAc) - PolyStyrene (PS)
    C C H Cl H H n C C H Cl H Cl n C C H OCOCH 3 H H n C C H OH H H n C C H H H n
  • 38. Mechanical Properties of Polyvinyls
  • 39. Physical Properties of Polyvinyls
  • 40. Processing Properties of Polyvinyls
  • 41. Vinylchloride Co-Polymers
    • Chlorinated PVC (CPVC)
      • Possible to chemically modify PVC by substituting Cl for H
      • Cl content can be raised from 56.8% in PVC to 62%-72%
      • CPVC has improved chemical and temperature resistance that can be used for pipe and hot water applications, even boiling water.
    • Vinylchloride-vinylacetate (PVC-VAC)
      • Internally plasticizing PVC with 3% to 30% vinyl acetate
      • Impact properties and processing ease are improved for
        • Floor coverings, phonograph records.
    • Polyalloys
      • Improves impact resistance of rigid PVC by blending with elastomers, e.g., EVA, Nitrile rubber (NBR), Chloronated PE.
      • Blend PVC with PMMA and SAN for better transparency
      • Blend PVC with ABS for improved combustion resistance
  • 42. Vinylchloride Co-Polymers
    • Polyvinylidenechloride (PVDC)
      • Homopolymer can crystallize. Tg = -18C, Tm = 190C
        • Decomposition temperature is slightly above melt temperature of abut 200C
        • PVDC has outstanding barrier properties for O 2 , CO 2 , and H 2 O.
        • Copolymerized with 10-15% vinyl chloride to create Saran Wrap.
        • Copolymerize with acrlonitrile and acrylate esters up to 50%.
        • Coplymerization reduces crystallinity to 35-45% and the Tmelt ot 175C
    • Polyvinyl acetate (PVAC)
      • Not used as a plastic
        • Noncrystallizing
        • Low Tg = 30C, it is
          • It is best as a major ingredient in adhesives and paint, Elmers Glue
      • Vinylacetate repeat units form the minor component in imporant copolymers with vinylchloride (PVC-PVAC) and ethylene (EVA)
    C C H Cl H Cl n C C H OCOCH 3 H H n
  • 43. Vinylchloride Co-Polymers
    • Polyvinylalcohol (PVAL or PVOH)
      • Homopolymer is very polar can crystallize
      • Water soluable. Tg = 80C, Tm = 240C
      • Random copolymer that is derived from PVAC
      • Used as a release film for reinforced plastics or barrier film.
    • Polyvinylbutyral (PVB)
      • Random copolymer (PVB-PVAL)
        • containing 10-15% VAL
        • Low Tg = 50C
      • Used in plasticized form as adhesive interlayer
        • For windshield safety glass (Saflex from Monsanto)
        • Powder is extruded into sheet and then placed between two layers of glass
      • Requires
        • Toughness, transparency, weatherability, and adhesion to glass.
    C C H OH H H n C C H CH 2 H H n CH 2 CH 3
  • 44. PS Background
    • PS is one of the oldest known vinyl compounds
      • PS was produced in 1851 by French chemist M. Berthelot by passing benzene and ethylene through a red-hot-tube (basis for today)
      • Amorphous polymer made from addition polymerization of styrene
      • Homopolymer (crystal): (2.7 M metric tons in ’94) GPPS (General Purpose PS)
        • Clear and colorless with excellent optical properties and high stiffness.
        • It is brittle until biaxially oriented when it becomes flexible and durable.
      • Graft copolymer or blend with elastomers- High Impact Polystyrene (HIPS):
        • Tough, white or clear in color, and easily extruded or molded.
        • Properties are dependent upon the elastomer %, but are grouped into
          • medium impact (Izod<1.5 ft-lb), high impact (Izod between 1.5 to 2.4 ft-lb) and super-high impact (Izod between 2.6 and 5 ft-lb)
      • Copolymers include SAN (poly styrene-acrylonitrile), SMA (maleic anhydride), SBS (butadiene), styrene and acrylic copolymers.
      • Expandable PS (EPS) is very popular for cups and insulation foam.
        • EPS is made with blowing agents, such as pentane and isopentane.
        • The properties are dependent upon cell size and cell size distribution
  • 45. Polystyrene Polymers
    • Poly-para-methyl-styrene (PPMS)
      • Similar to PS (Tg=100C) with a slightly higher Tg=110C
      • Low cost alternative to PS in homo and co-polymers
    • Poly-alpha-methyl-styrene (PAMS)
      • High Tg =160C and better Temp resistance
      • Not much commercial importance by itself
      • Has significant use in copolymers
    • Rubber-toughened impact polystyrene (HIPS)
      • Random copolymerization with small fraction of elastomer type repeat units. Lowers Tg
      • Block copolymerization of elastomeric component is more expensive, but keeps Tg same as PS
    C C H H H n CH 3 C C H H n CH 3
  • 46. PSB, SAN, ABS Chemical Structure
    • PSB (copolymer -addition) * Styrene- acrylonitrile (SAN)
    • ABS acrylonitrile butadiene styrene (Terpolymer- addition)
    C C H H H k m C C H C:::N H H n C C CH 3 CH 3 H H C C H H H k m C C CH 3 CH 3 H H C C H H H k C C H C:::N H H n
  • 47. Polystyrene Co-Polymers
    • Styrene-Butadiene (PSB)
      • Tg= % of each PS (100C) and Butadiene (-80C)
        • Example, 50% PS and 50% B, Tg=10C
      • Easy to copolymerize and can be rubbery (butadiene-dominant) or plastic like (styrene-like), out 70% of the PSB is styrene dominant
      • Random (styrene dominant) copolymers have been used in emulsion (latex) form to produce coatings (paints).
      • Block copolymers are commercial butadiene styrene-plastics
    • Styrene Acrylonitrile (SAN)
      • Random copolymer of 30% polyacrylonitrile repeat units yields
        • Increased Temp performance and transparent, ease to process
        • Resistant to food and body oils
      • Used for transparent medical products, houseware care items
      • Polyalloys (blends) with polysulphone
  • 48. Polystyrene Co-Polymers
    • Acrylonitrile Butadiene Styrene (ABS)
      • First introduced in the late 1940s as replacement for rubber.
      • Terpolymer: Three repeat units vary according to grade (20%A, 20%B, 60%S)
        • Acrylonitrile for chemical and temperature resistance
        • Butadiene for impact resistance; Styrene for cost and processability
        • Graft polymerization techniques are used to produce ABS
      • Very versatile applications that are injection molded and extruded
        • Rigid pipes and fittings, thermoformed refrigerator door liners, Legos toys
        • Small boat hulls, telephone and computer housings
        • Family of materials that vary from high gloss to low matte finish, and from low to high impact resistance.
        • Additives enable ABS grades that are flame retardant, transparent, high heat-resistance, foamable, or UV-stabilized
    • ABS-based polyalloys (blends)
      • PVC/ABS for flame resistance
      • TPU/ABS for polyurethane; PSU/ABS for polysulphone
      • PC/ABS for temperature and impact resistance (Saturn door)
        • .
  • 49. Mechanical Properties of PS, ABS, SAN Tg =100C C C H H H n
  • 50. Physical Properties of PS, ABS, SAN
  • 51. Processing Properties of PS, ABS, SAN
  • 52. Acrylic and Cellulosic Background
    • Acrylics (1901)
      • Includes acrylic and methacrylic esters, acids, and derivatives.
      • Used singularly or in combination with other polymers to produce products ranging from soft, flexible elastomers to hard, stiff thermoplastics and thermosets.
    • Cellulosics (1883)
      • Cellulose nitrate was first developed in the 1880s.
      • First uses were billiard balls, combs, and photographic film.
      • Cellulose acetate was developed in 1927 reduced the limitations of flammability, and solvent requirement.
      • In 1923, CA became the first material to be injection molded.
      • Cellulose acetate butyrate (CAB) in1938 and Cellulose acetate propionate (CAP) in 1945 found applications for hair brushes, toothbrushes, combs, cosmetic cases, hand tool handles, steering wheels, knobs, armrests, speakers, grilles, etc.
  • 53. Acrylics Chemical Structure
    • Acrylics- Basic formula - Polymethyl acrylate
    • Polymethyl methacrylate -AcrylateStyreneAcrylonitrile (ASA)
    C C H COOR 2 H R 1 n C C H COOCH 3 H H n C C H COOCH 3 H CH 3 n C C H C:::N H H k C C H H H m C C H COOH H H n
  • 54. Applications for PC and Acrylics
    • PC (high impact strength, transparency, excellent creep and temperature)
      • lenses, films, windshields, light fixtures, containers, appliance components and tool housings
      • hot dish handles, coffee pots, popcorn popper lids, hair dryers.
      • Pump impellers, safety helmets, beverage dispensers, trays, signs
      • aircraft parts, films, cameras, packaging
    • Acrylics
      • Optical applications, outdoor advertising signs, aircraft windshields, cockpit covers, bubble bodies for helicopters
      • Plexiglass, window frames, (glass filled): tubs, counters, vanities
  • 55. Mechanical Properties of Acrylic, PC, PC/ABS
  • 56. Physical Properties of Acrylic, PC, PC/ABS
  • 57. Advantages
    • PC
      • High impact strength, excellent creep resistance, transparent
      • Very good dimensional stability and continuous temp over 120 C
    • Acrylics
      • Optical clarity, weatherability, electrical properties, rigid, high gloss
    • Disadvantages
    • PC
      • High processing temp,UV degradation
      • Poor resistance to alkalines and subject to solvent cracking
    • Acrylics
      • Poor solvent resistance, stress cracking, combustibility, Use T 93C
  • 58. Polyamide History
    • PA is considered the first engineering thermoplastic
    • PA is one of many heterochain thermoplastics, which has atoms other than C in the chain.
    • PA invented in 1928 by Wallace Carothers, DuPont, in search of a “super polyester” fiber with molecular weights greater than 10,000. First commercial nylon in 1938.
    • PA was created when a condensation reaction occurred between amino acids, dibasic acids, and diamines.
    • Nylons are described by a numbering system which indicates the number of carbon atoms in the monomer chains
      • Amino acid polymers are designated by a single number, as nylon 6
      • Diamines and dibasic acids are designated with 2 numbers, the first representing the diamine and the second indicating the adipic acid, as in nylon 6,6 or nylon 6,10 with sebacic acid.
  • 59. Chemistry & Chemical Structure linear polyamides
    • Thermoplastic nylons have amide ( CONH ) repeating link
    • Nylon 6,6 - poly-hexamethylene-diamine (linear)
      • NH 2 (CH 2 ) 6 NH 2 + COOH(CH 2 ) 4 COOH
      • hexamethylene diamine + Adipic Acid
      • n[NH 2 (CH 2 ) 6 NH . CO (CH 2 ) 4 COOH ] + (heat)
      • nylon salt
      • [NH 2 (CH 2 ) 6 NH . CO (CH 2 ) 4 CO ] n + nH 2 O
      • Nylon 6,6 polymer chain
    • Nylon 6 - polycaprolactam (linear)
      • [ NH (CH 2 ) 5 CO ] n
  • 60. Chemistry & Chemical Structure linear polyamides
    • Nylon 6, 10 - polyhexamethylenesebacamide (linear)
      • [NH 2 (CH 2 ) 6 NH . CO (CH 2 ) 8 CO] n
    • Nylon 11 - Poly(11-amino-undecanoic-amide (linear)
      • [ NH (CH 2 ) 10 CO ] n
    • Nylon 12 - Poly(11-amino-undecanoic-amide (linear)
      • [ NH (CH 2 ) 11 CO ] n
    • Other Nylons
      • Nylon 8, 9, 46, and copolymers from other diamines and acids
  • 61. Chemistry & Chemical Structure Aromatic polyamides (aramids)
    • PMPI - poly m-phenylene isophthalamide (LCP fiber)
    • [ -NHCO - NHCO ] n
    • PPPT - poly p-phenylene terephthalamide (LCP fiber)
    • [ -NHCO - NHCO ] n
    • Nomax PMPI -
      • first commercial aramid fiber for electrical insulation. LCP fibers feature straight chain crystals
    • Kevlar 29 PPPT-
      • textile fiber for tire cord, ropes, cables etc.
    • Kevlar 49 PPPT - reinforcing fiber for thermosetting resins
  • 62. Chemistry & Chemical Structure Transparent polyamides
    • PA- (6,3,T)
    • [CH 2 C 3 H 6 C 2 H 4 -NHCO - NHCO ] n
    • PA - (6,T)
        • [(CH 2 ) 6 NHCO - NHCO ] n
    • Transparent polyamides are commercially available
    • Reduced crystallization due to introduction of side groups
  • 63. Applications for Polyamides
    • Fiber applications
      • 50% into tire cords (nylon 6 and nylon 6,6)
      • rope, thread, cord,belts, and filter cloths.
      • Monofilaments- brushes, sports equipment, and bristles (nylon 6,10)
    • Plastics applications
      • bearings, gears, cams
      • rollers, slides, door latches, thread guides
      • clothing, light tents, shower curtains, umbrellas
      • electrical wire jackets (nylon 11)
    • Adhesive applications
      • hot melt or solution type
      • thermoset reacting with epoxy or phenolic resins
      • flexible adhesives for bread wrappers, dried soup packets, bookbindings
  • 64. Mechanical Properties of Polyamides
  • 65. Physical Properties of Polyamide
  • 66. Advantages Disadvantages of Polyamide
    • Advantages
      • Tough, strong, impact resistant
      • Low coefficient of friction
      • Abrasion resistance
      • High temperature resistance
      • Processable by thermopalstic methods
      • Good solvent resistance
      • Resistant to bases
    • Disadvantages
      • High moisture absorption with dimensional instability
        • loss of up to 30 % of tensile strength and 50% of tensile modulus
      • Subject to attack by strong acids and oxidizing agents
      • Requires UV stabilization
      • High shrinkage in molded sections
      • Electrical and mechanical properties influenced by moisture content
      • Dissolved by phenols
  • 67. Additives and Reinforcements to PA
    • Additives- antioxidants, UV stabilizers, colorants, lubricants
    • Fillers
      • Talc
      • Calcium carbonate
    • Reinforcements
      • Glass fiber- short fiber (1/8” or long fiber 1/4”)
      • Mineral fiber (wolastonite)
      • carbon fibers
      • graphite fibers
      • metallic flakes
      • steel fibers
  • 68. Properties of Reinforced Nylon
  • 69. Other Heterochain Polymers
    • Polyimide
      • Developed by Du Pont in 1962
      • Obtained from a condensation polymerization of aromatic diamine and an aromatic dianhydride
      • Characterized as Linear thermoplastics that are difficult to process
      • Many polyimides do not melt but are fabricated by machining
      • Molding can occur if enough time for flow is allowed for T>Tg
    • Advantages
      • High temperature service (up to 700C)
      • Excellent barrier, electrical properties, solvent and wear resistance
      • Good adhesion and ezpecially suited for composite fabrication
    O N C O N C O C O C O
  • 70. Other Heterochain Polymers
    • Polyimide Disadvantages
      • Difficulty to fabricate and requires venting of volatiles
      • Hydroscopic and Subject to attacks by alkalines
      • Comparatively high cost
    • Applications
        • Aerospace, electronics, and nuclear uses (versus flurocarbons)
        • Office and industrial equipment; Laminates, dielectrics, and coatings
        • Valve seats, gaskets, piston rings, thrust washers, and bushings
    • Polyamide-imide
        • Amorphous member of imide family, marketed in 1972 (Torlon), and used in aerospace applications such as jet engine components
        • Contains aromatic rings and nitrogen linkage
        • Advantages include: High temperature properties (500F), low coefficient of friction, and dimensional stability.
  • 71. Other Heterochain Polymers
    • Polyacetal or Polyoxymethylene (POM)
        • Polymerized from formaldehyde gas
        • First commercialized in 1960 by Du Pont
        • Similar in properties to Nylon and used for plumbing fixtures, pump impellers, conveyor belts, aerosol stem valves, VCR tape housings
    • Advantages
        • Easy to fabricate, has glossy molded surfaces, provide superior fatigue endurance, creep resistance, stiffness, and water resistance.
        • Among the strongest and stiffest thermoplastics.
        • Resistant to most chemicals, stains, and organic solvents
    • Disadvantages
        • Poor resistance to acids and bases and difficult to bond
        • Subject to UV degradation and is flammable
        • Toxic fumes released upon degradation
    H-O-(CH 2 -O-CH 2 -O)NH:R
  • 72. Mechanical Properties
  • 73. Polyester History
    • 1929 W. H. Carothers suggested classification of polymers into two groups, condensation and addition polymers.
    • Carothers was not successful in developing polyester fibers from linear aliphatic polyesters due to low melting point and high solubility. No commercial polymer is based on these.
    • p-phenylene group is added for stiffening and leads to polymers with high melting points and good fiber-forming properties, e.g., PET.
    • Polymers used for films and for fibers
    • Polyesters is one of many heterochain thermoplastics, which has atoms other than C in the chain.
    • Polyesters includes unsaturated ( thermosets ), saturated and aromatic thermoplastic polyesters.
  • 74. Chemistry & Chemical Structure linear polyesters (versus branched)
    • Thermoplastic polyesters have ester(-C-O) repeating link
    • Polyester (linear) PET and PBT
      • C 6 H 4 (COOH) 2 + (CH 2 ) 2 (OH) 2 -[(CH 2 ) 2 -O- C - C-O]-
      • terephthalic acid + ethylene glycol Polyethylene terephthalate (PET)
      • C 6 H 4 (COOH) 2 + (CH 2 ) 4 (OH) 2 -[(CH 2 ) 4 -O- C - C-O]-
      • terephthalic acid + butylene glycol Polybutylene terephthalate (PBT)
    O O O O O
  • 75. Chemistry & Chemical Structure linear polyesters (versus branched)
    • Wholly aromatic copolyesters (LCP)
      • High melting sintered: Oxybenzoyl (does not melt below its decomposition temperature. Must be compression molded)
      • Injection moldable grades: Xydar and Vectra
      • Xydar (Amoco Performance Products)
        • terephthalic acid, p,p’- dihydroxybiphenyl, and p-hydroxybenzoic acid
          • Grade 1: HDT of 610F
          • Grade 2: HDT of 480 F
      • Vectra (Hoechst Celanese Corp.)
        • para-hydroxybenzoic acid and hydroxynaphtholic acid
          • Contains rigid chains of long, flat monomer units which are thought to undergo parallel ordering in the melt and form tightly packed fibrous chains in molded parts.
  • 76. PET Chemical Structure and Applications
    • The flexible, but short, (CH 2 ) 2 groups tend to leave the chains relatively stiff and PET is notes for its very slow crystallization. If cooled rapidly from the melt to a Temp below Tg, PET solidifies in amorphous form.
    • If PET is reheated above Tg, crystallizaiton takes place to up to 30%.
    • In many applications PET is first pre-shaped in amorphous state and then given a uniaxial (fibers or tapes) or biaxial (film or containers) crystalline orientation.
    • During Injection Molding PET can yield amorphous transparent objects (Cold mold) or crystalline opaques objects (hot mold)
  • 77. PBT Chemical Structure and Applications
    • The longer, more flexible (CH 2 ) 4 groups allow for more rapid crystallization than PET.
    • PBT is not as conveniently oriented as PET and is normally injection molded.
    • PBT has a sharp melting transition with a rather low melt viscosity.
    • PBT has rapid crystallization and high degree of crystallization causing warpage concerns
  • 78. Thermoplastic Aromatic Copolyesters
    • Polyarylesters
      • Repeat units feature only aromatic-type groups (phenyl or aryl groups) between ester linkages.
      • Called wholly aromatic polyesters
      • Based on a combination of suitable chemicals
        • p-hydroxybenzoic acid
        • terephthalic acid
        • isophthalic acid,
        • bisphenol-A
      • Properties correspond to a very stiff and regular chain with high crystallinity and high temperature stability
      • Applications include bearings, high temperature sensors, aerospace applications
      • Processed in injection molding and compression molding
      • Most thermoplastic LCP appear to be aromatic copolyesters
  • 79. Applications for Polyesters (PET)
    • Blow molded bottles
        • 100% of 2-liter beverage containers and liquid products
    • Fiber applications
        • 25% of market in tire cords, rope, thread, cord, belts, filter cloths.
        • Monofilaments- brushes, sports equipment, clothing, carpet, bristles
        • Tape form- uniaxially oriented tape form for strapping
    • Film and sheets
        • photographic and x-ray films; biaxial sheet for food packages
    • Molded applications- Reinforced PET [Rynite, Valox, Impet]
        • luggage racks, grille-opening panels, functional housings such as windshield wiper motors, blade supports, and end bells
        • sensors, lamp sockets, relays, switches, ballasts, terminal blocks
    • Appliances and furniture
        • oven and appliance handles, coil forms for microwaves
        • panel pedestal bases, seat pans, chair arms, and casters
  • 80. Applications for Polyesters (PBT and LCP)
    • PBT - 30 M lbs in 1988
    • Molded applications (PBT) [Valox, Xenoy, Vandar, Pocan]
      • distributers, door panels, fenders, bumper fascias
      • automotive cables, connectors, terminal blocks, fuse holders and motor parts, distributor caps, door and window hardware
    • Extruded applications
      • extrusion-coat wire
      • extruded forms and sheet produced with some difficulty
    • Electronic Devices (LCP) [26 M lbs] [Terylene, Dacron, Kodel]
      • fuses, oxygen and transmission sensors
      • chemical process equipment and sensors
      • coil
  • 81. Mechanical Properties of Polyesters
  • 82. Physical Properties of Polyester
  • 83. Advantages and Disadvantages of Polyesters
    • Advantages
      • Tough and rigid and PBT has low moisture absorption
      • Processed by thermoplastic operations
      • Recycled into useful products as basis for resins in such applications as sailboats, shower units, and floor tiles
      • PET flakes from PET bottles are in great demand for fiberfill for pillows and sleeping bags, carpet fiber, geo-textiles, and regrind for injection and sheet molding
    • Disadvantages
      • Subject to attack by acids and bases
      • Low thermal resistance
      • Poor solvent resistance
      • Must be adequately dried in dehumidifier prior to processing to prevent hydrolytic degradation.
  • 84. Thermoplastic Copolyesters
    • Copolyester is applied to those polyesters whose synthesis uses more than one glycol and/or more than one dibasic acid.
    • Copolyester chain is less regular than monopolyester chain and as a result has less crystallinity
    • PCTA copolyester (Poly cyclo-hexane-dimethanol-terephthalate acid) [amorphous]
      • Reaction includes cyclohexanedimethanol and terephthalic acid with another acid substituted for a portion of the terephthalic acid
      • Extruded as transparent film or sheets that are suitable for packaging applications (frozen meats shrink bags, blister packages, etc..)
    • Glycol-modified PET (PETG) [amorphous]
      • Blow-molded containers, thermoformed blister packages.
  • 85. ABS, PC Background
    • ABS was invented during WWII as a replacement for rubber
      • ABS is a terpolymer: acrylonitrile (chemical resistance), butadiene (impact resistance), and styrene (rigidity and processing ease)
      • Graft polymerization techniques are used to produce ABS
      • Family of materials that vary from high gloss to low matte finish, and from low to high impact resistance.
      • Additives enable ABS grades that are flame retardant, transparent, high heat-resistance, foamable, or UV-stabilized.
    • PC was invented in 1898 by F. Bayer in Germany
      • Commercial production began in the US in 1959.
      • Amorphous, engineering thermoplastic that is known for toughness, clarity, and high-heat deflection temperatures.
      • Polycarbonates are linear, amorphous polyesters because they contain esters of carbonic acid and an aromatic bisphenol.
  • 86. Polyamide History
    • PA is considered the first engineering thermoplastic
    • PA is one of many heterochain thermoplastics, which has atoms other than C in the chain.
    • PA invented in 1928 by Wallace Carothers, DuPont, in search of a “super polyester” fiber with molecular weights greater than 10,000. First commercial nylon in 1938.
    • PA was created when a condensation reaction occurred between amino acids, dibasic acids, and diamines.
    • Nylons are described by a numbering system which indicates the number of carbon atoms in the monomer chains
      • Amino acid polymers are designated by a single number, as nylon 6
      • Diamines and dibasic acids are designated with 2 numbers, the first representing the diamine and the second indicating the adipic acid, as in nylon 6,6 or nylon 6,10 with sebacic acid.
  • 87. Chemistry & Chemical Structure linear polyamides
    • Thermoplastic nylons have amide ( CONH ) repeating link
    • Nylon 6,6 - poly-hexamethylene-diamine (linear)
      • NH 2 (CH 2 ) 6 NH 2 + COOH(CH 2 ) 4 COOH
      • hexamethylene diamine + Adipic Acid
      • n[NH 2 (CH 2 ) 6 NH . CO (CH 2 ) 4 COOH ] + (heat)
      • nylon salt
      • [NH 2 (CH 2 ) 6 NH . CO (CH 2 ) 4 CO ] n + nH 2 O
      • Nylon 6,6 polymer chain
    • Nylon 6 - polycaprolactam (linear)
      • [ NH (CH 2 ) 5 CO ] n
  • 88. Chemistry & Chemical Structure linear polyamides
    • Nylon 6, 10 - polyhexamethylenesebacamide (linear)
      • [NH 2 (CH 2 ) 6 NH . CO (CH 2 ) 8 CO] n
    • Nylon 11 - Poly(11-amino-undecanoic-amide (linear)
      • [ NH (CH 2 ) 10 CO ] n
    • Nylon 12 - Poly(11-amino-undecanoic-amide (linear)
      • [ NH (CH 2 ) 11 CO ] n
    • Other Nylons
      • Nylon 8, 9, 46, and copolymers from other diamines and acids
  • 89. Chemistry & Chemical Structure Aromatic polyamides (aramids)
    • PMPI - poly m-phenylene isophthalamide (LCP fiber)
    • [ -NHCO - NHCO ] n
    • PPPT - poly p-phenylene terephthalamide (LCP fiber)
    • [ -NHCO - NHCO ] n
    • Nomax PMPI - first commercial aramid fiber for electrical insulation. LCP fibers feature straight chain crystals
    • Kevlar 29 PPPT- textile fiber for tire cord, ropes, cables etc.
    • Kevlar 49 PPPT - reinforcing fiber for thermosetting resins
  • 90. Chemistry & Chemical Structure Transparent polyamides
    • PA- (6,3,T)
    • [CH 2 C 3 H 6 C 2 H 4 -NHCO - NHCO ] n
    • PA - (6,T)
        • [(CH 2 ) 6 NHCO - NHCO ] n
    • Transparent polyamides are commercially available
    • Reduced crystallization due to introduction of side groups
  • 91. Applications for Polyamides
    • Fiber applications
      • 50% into tire cords (nylon 6 and nylon 6,6)
      • rope, thread, cord,belts, and filter cloths.
      • Monofilaments- brushes, sports equipment, and bristles (nylon 6,10)
    • Plastics applications
      • bearings, gears, cams
      • rollers, slides, door latches, thread guides
      • clothing, light tents, shower curtains, umbrellas
      • electrical wire jackets (nylon 11)
    • Adhesive applications
      • hot melt or solution type
      • thermoset reacting with epoxy or phenolic resins
      • flexible adhesives for bread wrappers, dried soup packets, bookbindings
  • 92. Mechanical Properties of Polyamides
  • 93. Physical Properties of Polyamide
  • 94. Advantages Disadvantages of Polyamide
    • Advantages
      • Tough, strong, impact resistant
      • Low coefficient of friction
      • Abrasion resistance
      • High temperature resistance
      • Processable by thermopalstic methods
      • Good solvent resistance
      • Resistant to bases
    • Disadvantages
      • High moisture absorption with dimensional instability
        • loss of up to 30 % of tensile strength and 50% of tensile modulus
      • Subject to attack by strong acids and oxidizing agents
      • Requires UV stabilization
      • High shrinkage in molded sections
      • Electrical and mechanical properties influenced by moisture content
      • Dissolved by phenols
  • 95. Additives and Reinforcements to PA
    • Additives- antioxidants, UV stabilizers, colorants, lubricants
    • Fillers
      • Talc
      • Calcium carbonate
    • Reinforcements
      • Glass fiber- short fiber (1/8” or long fiber 1/4”)
      • Mineral fiber (wolastonite)
      • carbon fibers
      • graphite fibers
      • metallic flakes
      • steel fibers
  • 96. Properties of Reinforced Nylon
  • 97. Other Heterochain Polymers
    • Polyimide
      • Developed by Du Pont in 1962
      • Obtained from a condensation polymerization of aromatic diamine and an aromatic dianhydride
      • Characterized as Linear thermoplastics that are difficult to process
      • Many polyimides do not melt but are fabricated by machining
      • Molding can occur if enough time for flow is allowed for T>Tg
    • Advantages
      • High temperature service (up to 700C)
      • Excellent barrier, electrical properties, solvent and wear resistance
      • Good adhesion and ezpecially suited for composite fabrication
    O N C O N C O C O C O
  • 98. Other Heterochain Polymers
    • Polyimide Disadvantages
      • Difficulty to fabricate and requires venting of volatiles
      • Hydroscopic
      • Subject to attacks by alkalines
      • Comparatively high cost
    • Applications
      • Aerospace, electronics, and nuclear uses (competes with flurocarbons)
      • Office and industrial equipment; Laminates, dielectrics, and coatings
      • Valve seats, gaskets, piston rings, thrust washers, and bushings
    • Polyamide-imide
      • Amorphous member of imide family, marketed in 1972 (Torlon), and used in aerospace applications such as jet engine components
      • Contains aromatic rings and nitrogen linkage
      • Advantages include: High temperature properties (500F), low coefficient of friction, and dimensional stability.
  • 99. Other Heterochain Polymers
    • Polyacetal or Polyoxymethylene (POM)
      • Polymerized from formaldehyde gas
      • First commercialized in 1960 by Du Pont
      • Similar in properties to Nylon and used for plumbing fixtures, pump impellers, conveyor belts, aerosol stem valves, VCR tape housings
    • Advantages
      • Easy to fabricate, has glossy molded surfaces, provide superior fatigue endurance, creep resistance, stiffness, and water resistance.
      • Among the strongest and stiffest thermoplastics.
      • Resistant to most chemicals, stains, and organic solvents
    • Disadvantages
      • Poor resistance to acids and bases and difficult to bond
      • Subject to UV degradation and is flammable
      • Toxic fumes released upon degredation
    H-O-(CH 2 -O-CH 2 -O)NH:R
  • 100. Mechanical Properties
  • 101. Polyester History
    • 1929 W. H. Carothers suggested classification of polymers into two groups, condensation and addition polymers.
    • Carothers was not successful in developing polyester fibers from linear aliphatic polyesters due to low melting point and high solubility. No commercial polymer is based on these.
    • p-phenylene group is added for stiffening and leads to polymers with high melting points and good fiber-forming properties, e.g., PET.
    • Polymers used for films and for fibers
    • Polyesters is one of many heterochain thermoplastics, which has atoms other than C in the chain.
    • Polyesters includes unsaturated ( thermosets ), saturated and aromatic thermoplastic polyesters.
  • 102. Chemistry & Chemical Structure linear polyesters (versus branched)
    • Thermoplastic polyesters have ester(-C-O) repeating link
    • Polyester (linear) PET and PBT
      • C 6 H 4 (COOH) 2 + (CH 2 ) 2 (OH) 2 -[(CH 2 ) 2 -O- C - C-O]-
      • terephthalic acid + ethylene glycol Polyethylene terephthalate (PET)
      • C 6 H 4 (COOH) 2 + (CH 2 ) 4 (OH) 2 -[(CH 2 ) 4 -O- C - C-O]-
      • terephthalic acid + butylene glycol Polybutylene terephthalate (PBT)
    O O O O O
  • 103. Chemistry & Chemical Structure linear polyesters (versus branched)
    • Wholly aromatic copolyesters (LCP)
      • High melting sintered: Oxybenzoyl (does not melt below its decomposition temperature. Must be compression molded)
      • Injection moldable grades: Xydar and Vectra
      • Xydar (Amoco Performance Products)
        • terephthalic acid, p,p’- dihydroxybiphenyl, and p-hydroxybenzoic acid
          • Grade 1: HDT of 610F
          • Grade 2: HDT of 480 F
      • Vectra (Hoechst Celanese Corp.)
        • para-hydroxybenzoic acid and hydroxynaphtholic acid
          • Contains rigid chains of long, flat monomer units which are thought to undergo parallel ordering in the melt and form tightly packed fibrous chains in molded parts.
  • 104. PET Chemical Structure and Applications
    • The flexible, but short, (CH 2 ) 2 groups tend to leave the chains relatively stiff and PET is notes for its very slow crystallization. If cooled rapidly from the melt to a Temp below Tg, PET solidifies in amorphous form.
    • If PET is reheated above Tg, crystallizaiton takes place to up to 30%.
    • In many applications PET is first pre-shaped in amorphous state and then given a uniaxial (fibers or tapes) or biaxial (film or containers) crystalline orientation.
    • During Injection Molding PET can yield amorphous transparent objects (Cold mold) or crystalline opaques objects (hot mold)
  • 105. PBT Chemical Structure and Applications
    • The longer, more flexible (CH 2 ) 4 groups allow for more rapid crystallization than PET.
    • PBT is not as conveniently oriented as PET and is normally injection molded.
    • PBT has a sharp melting transition with a rather low melt viscosity.
    • PBT has rapid crystallization and high degree of crystallization causing warpage concerns
  • 106. Thermoplastic Aromatic Copolyesters
    • Polyarylesters
      • Repeat units feature only aromatic-type groups (phenyl or aryl groups) between ester linkages.
      • Called wholly aromatic polyesters
      • Based on a combination of suitable chemicals
        • p-hydroxybenzoic acid
        • terephthalic acid
        • isophthalic acid,
        • bisphenol-A
      • Properties correspond to a very stiff and regular chain with high crystallinity and high temperature stability
      • Applications include bearings, high temperature sensors, aerospace applications
      • Processed in injection molding and compression molding
      • Most thermoplastic LCP appear to be aromatic copolyesters
  • 107. Applications for Polyesters (PET)
    • Blow molded bottles
      • 100% of 2-liter beverage containers and liquid products
    • Fiber applications
      • 25% of market in tire cords, rope, thread, cord, belts, and filter cloths.
      • Monofilaments- brushes, sports equipment, clothing, carpet, bristles
      • Tape form- uniaxially oriented tape form for strapping
    • Film and sheets
      • photographic and x-ray films; biaxial sheet for food packages
    • Molded applications- Reinforced PET [Rynite, Valox, Impet]
      • luggage racks, grille-opening panels, functional housings such as windshield wiper motors, blade supports, and end bells
      • sensors, lamp sockets, relays, switches, ballasts, terminal blocks
    • Appliances and furniture
      • oven and appliance handles, coil forms for microwaves, and panels
      • -- pedestal bases, seat pans, chair arms, and casters
  • 108. Applications for Polyesters (PBT and LCP)
    • PBT - 30 M lbs in 1988
    • Molded applications (PBT) [Valox, Xenoy, Vandar, Pocan]
      • distributers, door panels, fenders, bumper fascias
      • automotive cables, connectors, terminal blocks, fuse holders and motor parts, distributor caps, door and window hardware
    • Extruded applications
      • extrusion-coat wire
      • extruded forms and sheet produced with some difficulty
    • Electronic Devices (LCP) [26 M lbs] [Terylene, Dacron, Kodel]
      • fuses, oxygen and transmission sensors
      • chemical process equipment and sensors
      • coil
  • 109. Mechanical Properties of Polyesters
  • 110. Physical Properties of Polyester
  • 111. Advantages/Disadvantages of Polyesters
    • Advantages
      • Tough and rigid
      • Processed by thermoplastic operations
      • Recycled into useful products as basis for resins in such applications as sailboats, shower units, and floor tiles
      • PET flakes from PET bottles are in great demand for fiberfill for pillows and sleeping bags, carpet fiber, geo-textiles, and regrind for injection and sheet molding
      • PBT has low moisture absorption
    • Disadvantages
      • Subject to attack by acids and bases
      • Low thermal resistance
      • Poor solvent resistance
      • Must be adequately dried in dehumidifier prior to processing to prevent hydrolytic degradation.
  • 112. Thermoplastic Copolyesters
    • Copolyester is applied to those polyesters whose synthesis uses more than one glycol and/or more than one dibasic acid.
    • Copolyester chain is less regular than monopolyester chain and as a result has less crystallinity
    • PCTA copolyester (Poly cyclo-hexane-dimethanol-terephthalate acid) [amorphous]
      • Reaction includes cyclohexanedimethanol and terephthalic acid with another acid substituted for a portion of the terephthalic acid
      • Extruded as transparent film or sheets that are suitable for packaging applications (frozen meats shrink bags, blister packages, etc..)
    • Glycol-modified PET (PETG) [amorphous]
      • Blow-molded containers, thermoformed blister packages.
  • 113. ABS Background
    • ABS was invented during WWII as a replacement for rubber
      • ABS is a terpolymer: acrylonitrile (chemical resistance), butadiene (impact resistance), and styrene (rigidity and processing ease)
      • Graft polymerization techniques are used to produce ABS
      • Family of materials that vary from high gloss to low matte finish, and from low to high impact resistance.
      • Additives enable ABS grades that are flame retardant, transparent, high heat-resistance, foamable, or UV-stabilized.
  • 114. PEEK History
    • Polyether-ether-ketone (PEEK) and Polyether ketone (PEK)
      • PEEK invented by ICI in 1982. PEK introduced in 1987
    • PEEK and PEK are aromatic polyketones
      • Volume for polyketones is 500,000 lbs per year in 1990. Estimated to reach 3 to 4 million by 2000.
      • Cost is $30 per pound (as of October 1998)
    • Product Names
      • ICI: Vivtrex
      • BASF: Ultrapak
      • Hoechst Celanese: Hostatec
      • DuPont: PEKK
      • Amoco: Kadel
  • 115. Chemistry & Chemical Structure
    • PEEK- Poly-ether-ether-ketone
      • O O C
    • PEK- Poly-ether-ketone
      • O C
    O n O n
  • 116. Chemical Synthesis
    • Synthesis of polyketones
      • PEK : Formation of the carbonyl link by polyaroylation from low cost starting materials. Requires solvents such as liquid HF. Excessive solvents and catalyst cause the high material cost.
      • PEEK : Formation of ether link using phenoxide anions to displace activated halogen.
    O C Cl O HF, catalyst O n O C + HCl + CO 2 +H 2 0 PEK K 2 CO 3 , DPS O C F F OH OH + PEEK + CO 2 +H 2 0 +KF
  • 117. PEEK and PEK Applications
    • Aerospace: replacement of Al
      • Fuel line brakes to replacement of primary structure
    • Electrical
      • wire coating for nuclear applications, oil wells, flammability-critical mass transit.
      • Semi-conductor wafer carriers which can show better rigidity, minimum weight, and chemical resistance to fluoropolymers.
    • Other applications
      • Chemical and hydrolysis resistant valves (replaced glass)
      • Internal combustion engines (replaced thermosets)
      • Cooker components (replaced enamel)
      • Automotive components (replaced metal)
      • High temperature and chemical resistant filters from fiber
      • Low friction bearings
  • 118. Mechanical Properties of PEEK
  • 119. Physical Properties of PEEK
  • 120. Properties of Reinforced PEEK
  • 121. Processing Properties of PEEK
  • 122. Advantages and Disadvantages of Polyketones
    • Advantages
      • Very high continuous use temperature (480F)
      • Outstanding chemical resistance
      • Outstanding wear resistance
      • Excellent hydrolysis resistance
      • Excellent mechanical properties
      • Very low flammability and smoke generation
      • Resistant to high levels of gamma radiation
    • Disadvantages
      • High material cost
      • High processing temperatures
  • 123. Polyphenylene Materials
    • Several plastics have been developed with the benzene ring in the backbone
      • Polyphenylene
      • Polyphenylene oxide
      • (amorphous)
      • Poly(phenylene sulfide)
      • (crystalline)
      • Polymonochloroparaxylene
    O O O S S S CH 2 CH 2 Cl Cl
  • 124. PPO and PPS Materials
    • *Advantages of PPS *Advantages of PPO
      • - Usage Temp at 450F - Good fatigue and impact strength
      • - Good radiation resistance - Good radiation resistance
      • - Excellent dimensional stability - Excellent dimensional stability
      • - Low moisture absorption - Low oxidation
      • - Good solvent and chemical resistance
      • - Excellent abrasion resistance
    • *Disadvantages of PPS *Disadvantages of PPO
      • - High Cost - High cost
      • - High process temperatures -Poor resistance to certain chemicals
      • - Poor resistance to chlorinated hydrocarbons
  • 125. PPO and PPS Applications
    • *PPS Applications *PPO Applications
      • - Computer components - Video display terminals
      • - Range components - Pump impellers
      • - Hair dryers - Small appliance housings
      • - Submersible pump enclosures - Instrument panels
      • - Small appliance housings - Automotive parts
  • 126. PPS and PPO Mechanical Properties
  • 127. PPS and PPO Physical Properties
  • 128. PPS and PPO Processing Properties
    • PPS frequently has glass fibers loaded up to 40% by weight
      • Tensile strength = 28 kpsi, tensile modulus = 2 Mpsi, HDT = 500F
    • PPO is frequently blended with PS over a wide range of percentages.
    • (Noryl from G.E.)
  • 129. Section Review
      • Polyesters is one of many heterochain thermoplastics, which has atoms other than C in the chain.
      • Polyesters includes unsaturated ( thermosets ), saturated and aromatic thermoplastic polyesters.
      • Condensation polymerization for Polyester
      • Thermoplastic polyesters have ester(-C-O) repeating link
      • Linear and aromatic polyesters
      • Most thermoplastic LCP appear to be aromatic copolyesters
      • Effects of reinforcements on polyester
      • Effects of moisture environment on nylon
      • If cooled rapidly from the melt to a Temp below Tg, PET solidifies in amorphous form. If reheated PET acquires 30% crystallinity
      • PET has rigid group of (CH 2 ) 2 ; PBT has more flexible (CH 2 ) 4
      • Copolyester chain is less regular than monopolyester chain and as a result has less crystallinity
    O
  • 130. Section Review
      • PEEK and PEK are aromatic polyketones.
      • Ketone groups have R - O - R functionality.
      • Chemical structure of PEEK and PEK depicts benzene - oxygen - benzene in backbone.
      • PEEK and PEK are used primarily in applications requiring high temperature use and chemical resistance.
      • AP2C is a special version of PEEK with 68% continuous carbon fiber.
      • Polyphenylene materials are plastics with the benzene ring in the backbone.
      • PPO and PPS are characterized as heterochain thermoplastics, which has atoms other than C in the chain.
      • PPO and PPS are made via Condensation Polymerization.
      • PPS frequently has glass fibers loaded up to 40% by weight.
      • PPO is frequently blended with PS over a wide range of percentages.
    O
  • 131. Section Review
    • Major Topics
      • Vinyl is a varied group- PVC, PVAc, PVOH, PVDC, PVB.
      • PVC is the leading plastic in Europe and second to PE in the US.
      • PVC is produced by addition polymerization from the vinyl chloride monomer in a head-to-tail alignment.
      • PVC is partially crystalline (syndiotactic) with structural irregularity increasing with the reaction temperature.
      • PVC (rigid) decomposes at 212 F leading to dangerous HCl gas
      • X1
      • Vinyls have (CH 2 CX2) repeating link
      • PS is Amorphous and made from addition polymerization
      • PC is amorphous and made from condensation polymerization
      • Effects of reinforcements on PP and PS
  • 132. Section Review
    • Major Topics
      • Isotactic, atactic, sydiotactic polypropylene definitions
      • Differences between PP and PE
      • Molecular Weight definition and forms (Weight Average, M w , and Number Average, M A )
      • Polydispersity definition and meaning
      • Relation between Molecular weight and Degree of Polymerization (DP)
      • Mechanical, physical, and processing properties of PP, Polybutylene, and polymethylpentene
      • PP is produced with linear chains
  • 133. Section Review
    • Key Terms and Concepts
      • Polyolefin
      • Molecular weight
      • Number average molecular weight, weight average MW
      • Polydispersity
      • Polymer shrinkage
      • Polymer blends
      • Tensile Modulus
      • Izod Impact Strength
  • 134. Homework Questions #2
    • 1. Define Polyvinyls, PS, PP, HDPE, chemical structure.
    • 2. Compare the density PVC, PVB, PS, and PVDC which is higher/lower than PP.
    • 3. Compare the density of HDPE, LDPE, UHMWPE, LLDPE to PP?
    • 4. What is the tensile strength of PP with 0%, 30% glass fibers? What is the tensile modulus?
    • 5. Plot tensile strength and tensile modulus of PVC, PS, PP, LDPE and HPDE to look like:
    Tensile Strength, Kpsi Tensile Modulus, Kpsi 200 500 10 50 xLDPE xHDPE
  • 135. Homework Questions #2
    • 6. Four typical Physical Properties of PVC are Optical = _______, Resistance to moisture= ______ , UV resistance= _____, solvent resistance=_______
    • 7. The Advantages of PP are ________, ________, _______, and __________.
    • 8. The Disadvantages of PP are ________, ________, _______, and __________.
    • 9. Glass fiber affects PP by (strength) ________, (modulus)________, (impact)_______, (density) __________, and (cost) ____________.
    • 10. Two Blends PVC are ___________, and __________.
  • 136. Homework Questions #2
    • 11. Define Polypropylene chemical structure
    • 12. Does commercial PP have Isotactic, atactic, sydiotactic form.
    • 13. If MW of PP is 200,000, what is the approx. DP?
    • 14. Polydispersity represents the distribution of _______and _____
    • 15. Density of PP is _____ which is higher/lower than HDPE.
    • 16. PP mechanical properties are higher/lower than LDPE and HDPE
    • 17. Plot tensile strength and tensile modulus of PP, LDPE and HPDE to look like the following
    Tensile Modulus, Kpsi Tensile Strength, Kpsi 2 5 10 50 xLDPE xHDPE
  • 137. Homework Questions #2
    • 18. Four typical Physical Properties of PP are Optical = _______, Resistance to moisture= ______ , UV resisance= _____, solvent resistance=_______
    • 19. The Advantages of PP are ________, ________, _______, and __________.
    • 20. The Disadvantages of PP are ________, ________, _______, and __________.
    • 21. Glass fiber affects PP by (strength) ________, (modulus)________, (impact)_______, (density) __________, and (cost) ____________.
    • 22. Five polyolefins are ________, ________, _______, ______, and __________.
  • 138. Homework Questions
    • 1. Define PEEK, PPO and PPS chemical structures.
    • 2. How are the properties of PEEK and PPS alike?
    • 3. Density of PEEK is _____, PPS is _____ , and PPO is _____ , which is higher/lower than PBT and nylon?
    • 4. What is the tensile strength of PEEK with 0%, 30% glass fibers? What is the tensile modulus?
    • 5. Plot tensile strength and tensile modulus of PEEK, PPO, PPS, PET, PBT, Nylon 6, PP, LDPE and HPDE to look like the following
    Tensile Modulus, Kpsi Tensile Strength, Kpsi 2 5 10 50 xLDPE xHDPE
  • 139. Homework Questions
    • 6. Four typical Physical Properties of PEEK are Optical = _______, Resistance to moisture= ______ , UV resistance= _____, acid resistance=_______
    • 7. The Advantages of PEEK are ________, ________, _______, and __________.
    • 8. The Disadvantages of PEEK are ________, ________, _______, and __________.
    • 9. How are the properties of PPO and PPS alike? How are they different?
    • 10. What are 3 advantages that Nylon has over PPO and PPS?_________________________________ _________________________________________________.
  • 140. Homework Questions
    • 1. Define PBT and PET chemical structure.
    • 2. Why was Carothers not successful in developing polyesters?
    • 3. Density of PET is _____ which is higher/lower than PBT and nylon?.
    • 4. What is the tensile strength of PET with 0%, 30% glass fibers? What is the tensile modulus?
    • 5. Plot tensile strength and tensile modulus of PET, PBT, Nylon 6, PP, LDPE and HPDE to look like the following
    Tensile Modulus, Kpsi Tensile Strength, Kpsi 2 5 10 50 xLDPE xHDPE
  • 141. Homework Questions
    • 6. Four typical Physical Properties of Polyester are Optical = _______, Resistance to moisture= ______ , UV resistance= _____, acid resistance=_______
    • 7. The Advantages of Polyester are ________, ________, _______, and __________.
    • 8. The Disadvantages of Polyester are ________, ________, _______, and __________.
    • 9. Glass fiber affects Polyester by (strength) ________, (modulus)________, (elongation)_______, (density) __________, and (cost) ____________.
    • 10. What affect does the copolymer have on the crystallinity of polyesters and why?_________________________________ _________________________________________________.
  • 142. Homework Questions
    • 1. Define Nylon 6,6 and Nylon 6 and Nylon 6,12 chemical structure
    • 2. If MW of PA is 50,000, what is the approx. DP?
    • 3. Density of PA is _____ which is higher/lower than PP.
    • 4. What is the tensile strength of nylon 6,6 with 0%, 30% glass fibers? What is the tensile modulus?
    • 5. Plot tensile strength and tensile modulus of Nylon 6, PP, LDPE and HPDE to look like the following
    Tensile Modulus, Kpsi Tensile Strength, Kpsi 2 5 10 50 xLDPE xHDPE
  • 143. Homework Questions
    • 6. Four typical Physical Properties of PA are Optical = _______, Resistance to moisture= ______ , UV resisance= _____, solvent resistance=_______
    • 7. The Advantages of PA are ________, ________, _______, and __________.
    • 8. The Disadvantages of PP are ________, ________, _______, and __________.
    • 9. Glass fiber affects PA by (strength) ________, (modulus)________, (impact)_______, (density) __________, and (cost) ____________.
    • 10. Two Aromatic PA are ___________, and __________.