Engineering Thermoplastics_

Nylons (PA), Acetals (POM), Polyesters (PBT and PET), PC, Acrylics (PMMA), PTFE, PPO, PPS, PEEK

Professor Joe Greene CSU, CHICO

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.
2

Chemistry & Chemical Structure

linear polyamides

Thermoplastic nylons have amide (CONH) repeating link Nylon 6,6 - poly-hexamethylene-diamine (linear)
NH2(CH2)6NH2 + COOH(CH2)4COOH
hexamethylene diamine + Adipic Acid

n[NH2(CH2)6NH . CO (CH2)4COOH ] + (heat)

nylon salt

[NH2(CH2)6NH . CO (CH2)4CO ]n + nH2O

Nylon 6,6 polymer chain

Nylon 6 - polycaprolactam (linear)

[NH(CH2)5CO ]n
3

Chemistry & Chemical Structure

linear polyamides

Nylon 6, 10 - polyhexamethylenesebacamide (linear)

[NH2(CH2)6NH . CO (CH2)8CO]n

Nylon 11 - Poly(11-amino-undecanoic-amide (linear)

[NH(CH2)10CO ]n

Nylon 12 - Poly(11-amino-undecanoic-amide (linear)

[NH(CH2)11CO ]n

Other Nylons
Nylon 8, 9, 46, and copolymers from other diamines and acids

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
5

Chemistry & Chemical Structure

Transparent polyamides

PA- (6,3,T) [CH2C3H6C2H4-NHCO PA - (6,T) [(CH2) 6NHCO -

NHCO ]n

NHCO ]n

Transparent polyamides are commercially available Reduced crystallization due to introduction of side groups
6

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
7

Mechanical Properties of Polyamides

Mechanical Properties of Nylon Nylon 6 1.13-1.15 Density, g/cc Crystallinity Molecular Weight Tensile Strength, psi Tensile Modulus, psi Tensile Elongation, % Impact Strength
ft-lb/in

Nylon 6,6 1.13-1.15 30-% - 50% 10,00030,000 14,000 230K 550K 15%-80% 0.55 1.0 R120

Nylon 6,10 1.09 30-% - 50% 10,00030,000 8,500 8,600 250 K 70% 1.2 R111

Nylon 6,12 1.06-1.10 30-% - 50% 10,00030,000 6,500 8,800 220 - 290 K 150% 1.0 1.9 M78

30-% - 50% 10,00030,000 6,000 24,000 300K 30% - 100% 0.6 2.2 R80 - 102

Hardness

Physical Properties of Polyamide

Optical Tmelt Tg H2 0 Absorption Oxidation Resistance UV Resistance Solvent Resistance Alkaline Resistance Acid Resistance Cost $/lb 1.3-1.9% (24h) 8.5-10 (Max) good Poor Dissolved by phenol & formic acid Resistant Poor 1.0-2.8% (24h) 8.5% (Max) good Poor Dissolved by phenol & formic acid Resistant Poor 1.4% (24h) 3.3% (Max) good Poor Dissolved by phenol & formic acid Resistant Poor 0.4 1.0% (24h) 2.5 3 % (Max) good Poor Dissolved by phenol & formic acid Resistant Poor Nylon 6 Translucent to opaque 210C -220 C Nylon 6,6 Translucent to opaque 255C 265C Nylon 6,10 Translucent to opaque 220 C Nylon 6,12 Translucent to opaque 195 -219 C

$1.30

$1.30

$3.00

$3.10

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

10

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
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Properties of Reinforced Nylon

Nylon 6,6 Density, g/cc Crystallinity Molecular Weight Tensile Strength, psi Tensile Modulus, psi Tensile Elongation, % Impact Strength
ft-lb/in

1.13-1.15 30-% - 50% 10,00030,000 14,000 230K 550K 15%-80% 0.55 1.0 R120 1.0-2.8% (24h) 8.5% (Max) $1.40

Nylon 6,6 with 30% short glass 1.4 30-% - 50% 30,000 28,000 1,300K 3% 1.6-4.5 R120 0.7-1.1 (24h) 5.5-6.5 (Max) $1.70

Nylon 6,6 with 30% long glass 1.4 30-% - 50% 10,00030,000 28,000 1,400 K 3% 4.0 E60 0.9 (24h) 5.5-6.5 (Max) $2.00

Nylon 6,6 with 30% carbon fiber 1.06-1.10 30-% - 50% 10,00030,000 32,000 3,300 K 4% 1.5 R120 0.7 (24h) 5 (Max) $2.70
12

Hardness Moisture %

Cost $/lb

Other Heterochain Polymers

O C N O C N O

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
13

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. 14

Other Heterochain Polymers

Polyacetal or Polyoxymethylene (POM)
H-O-(CH2-O-CH2-O)NH:R 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

15

Mechanical Properties
Density, g/cc Crystallinity Molecular Weight Tensile Strength, psi Tensile Modulus, psi Tensile Elongation, % Impact Strength
ft-lb/in

Nylon 6 1.13-1.15 30-% - 50% 10,00030,000 6,000 24,000 300K 30% - 100% 0.6 2.2 R80 - 102 210 - 220 C 1.3 - 1.9% 8.5 - 10% Translucent to opaque

Acetal 1.42

Polyimid 1.43

Polyamide-imide 1.41

10,000 520K 40% - 75% 0.07 R120 175-181 C 0.25 to 0.40% 1.41% Translucent to opaque

10,000

26,830

0.9 E50

2.5 E78 Tg=275C .28%

Hardness Tmelt Moisture 24 hr max Optical

0.32%

opaque

Transparent to opaque
16

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.
17

Chemistry & Chemical Structure

linear polyesters (versus branched) O

Thermoplastic polyesters have ester(-C-O) repeating link O O Polyester (linear) PET and PBT
C6H4(COOH)2 + (CH2)2(OH)2
terephthalic acid + ethylene glycol

-[(CH2)2 -O- C

- C-O]-

Polyethylene terephthalate (PET)

O
C6H4(COOH)2 + (CH2)4(OH)2
terephthalic acid + butylene glycol

O
- C-O]-

-[(CH2)4 -O- C

Polybutylene terephthalate (PBT)

18

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.
19

PET Chemical Structure and Applications

The flexible, but short, (CH2)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)
20

PBT Chemical Structure and Applications

The longer, more flexible (CH2)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

21

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
22

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
23

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
24

Mechanical Properties of Polyesters

Mechanical Properties of polyester PET 1.29-1.40 Density, g/cc Crystallinity Molecular Weight Tensile Strength, psi Tensile Modulus, psi Tensile Elongation, % Impact Strength ft-lb/in CLTE 10-6 in/in/C HDT 264 psi 7,000 10,500 400K - 600K 30% - 300% 0.25 - 0.70 65 70F -100F 8,200 280K 435K 50%-300% 0.7 - 1.0 60-95 122F - 185F 16,000 27,000 1,400K - 2,800K 1.3%-4.5% 2.4 - 10 25-30 356F -671F 10% - 30% PBT 1.30 - 1.38 60% LCP Polyester 1.35 - 1.40 >80%

25

Physical Properties of Polyester

Optical Tmelt Tg H20 Absorption Oxidation Resistance UV Resistance Solvent Resistance Alkaline Resistance Acid Resistance Cost $/lb PET Transparent to Opaque 245C -265 C 73C - 80C 0.1 - 0.2% (24h) 0.085% (24h) 0.45% (Max) good Poor good <0.1% (24h) <0.1% (Max) good none good PBT Opaque 220C 267C LCP Polyester Opaque 400 C - 421 C

good Poor Attacked by halogen hydrocarbons Poor Poor

Poor Poor

Poor fair

$0.53

$1.48

$7.00 - $10.00
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Advantages and 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.
27

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-dimethanolterephthalate 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.
28

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.
29

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.
30

Acrylics Chemical Structure

Acrylics- Basic formula
H R1 C C H COOR2
n

- Polymethyl acrylate
H H C C H COOCH3
n

Polymethyl methacrylate
H CH3

-AcrylateStyreneAcrylonitrile (ASA)
H H C C n H
m

H H C C
n

H H C C H C:::N
k
31

C C
H COOCH3

H COOH

PS, PC, ABS Chemical Structure

PS (homopolymer -addition)
atactic, amorphous

- PC (condensation polymerization)
CH2 O
C CH2 O O C
n

C
H

C
n

ABS acrylonitrile butadiene styrene (Terpolymer- addition)

H H C C
n

H C

H C
m

H H C C H
k

H C:::N

CH2 CH2

32

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

33

Mechanical Properties of Acrylic, PC, PC/ABS

Mechanical Properties Density, g/cc Tensile Strength, psi Tensile Modulus, psi Tensile Elongation, % Impact Strength
ft-lb/in

Acrylic 1.16- 1.19 5,000 - 9,000 200K 500K 20 - 70% 0.65 -2.5 M38-M68 48 - 80 165-209F

PC 1.2 9,500 350 K 110% 16 M70 68 270

ABS 1.16-1.21 3,300 - 8,000 320K-400K 1.5%-25% 1.4-12 R100-120 65- 95 190F - 225F

PC/ABS 1.07 - 1.15 5,800 - 9,300 350K -450K 50%-60% 6.4 - 11 R95 -R120 67 225F

Hardness CLTE 10-6 mm/mm/C HDT 264 psi

34

Physical Properties of Acrylic, PC, PC/ABS

Optical Tmelt Tg H20 Absorption Oxidation Resistance UV Resistance Solvent Resistance Acrylic Transparent 105C 75 -105C 0.01-0.03% (24h) PC Transparent 150C 110 -125C 0.2-0.6% (24h) ABS Transparent 125C 110 -125C 0.2-0.6% (24h) PC/ABS Transparent 135C 120C 0.15-0.25% (24h)

good fair Soluble in Acetone, Benzene, Toluene, ethylene dichloride Excellent Poor: attacked by oxidizing agents $0.41

good fair Partially Soluble in Acetone, Benzene, Toluene. Dissolves in hot benzene-toluene Excellent Poor: attacked by oxidizing agents $0.90

good fair Soluble in Toluene and Ethylene dichloride, Partially in Benzene Excellent Poor: attacked by oxidizing agents $0.90

good fair Soluble in Toluene and Ethylene dichloride, Partially in Benzene Poor: attacked by oxidizing agents good

Alkaline Resistance Acid Resistance Cost $/lb

$0.87

35

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
36

Other Crystalline Thermoplastics

Reference: Appendix E. Industrial Plastics

PEEK
History Chemistry and Chemical Structure Applications Mechanical Properties Physical Properties Processing Characteristics Advantages/Disadvantages

PPO and PPS Review Questions

37

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
38

Chemistry & Chemical Structure

PEEK- Poly-ether-ether-ketone
O

C
n

PEK- Poly-ether-ketone
O O C n
39

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. O O O C Cl O
HF, catalyst

C n

+ HCl + CO2 +H20

PEK

PEEK: Formation of ether link using phenoxide anions to displace activated halogen.
O F C F + OH OH
K2CO3, DPS

PEEK + CO2 +H20 +KF

40

PEEK and PEK Applications

Aerospace: replacement of Al
Fuel line brakes to replacement of primary structure

Electrical
wire coating for nuclear applications, oil wells, flammabilitycritical 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
41

Mechanical Properties of PEEK

Mechanical Properties Density, g/cc Tensile Strength, psi Tensile Modulus, psi Tensile Elongation, % Impact Strength
ft-lb/in

PEEK 1.30-1.32 10,000 15,000 500K 30% - 150% 0.6 2.2 R120 40 - 47 320 F

LCP Polyester 1.35 - 1.40 16,000 27,000 1,400K - 2,800K 1.3%-4.5% 2.4 - 10 R124 25-30 356F -671F

Nylon 6,6 1.13-1.15 14,000 230K 550K 15%-80% 0.55 1.0 R120 80 180F

Hardness CLTE 10-6 mm/mm/C HDT 264 psi

42

Physical Properties PEEK Opaque Optical Tmelt Tg H2 0 Absorption Oxidation Resistance UV Resistance Solvent Resistance Alkaline Resistance Acid Resistance Cost $/lb 334 C 177 C

Physical Properties of PEEK

LCP Polyester Opaque 400 C Nylon 6,6 Translucent to opaque 255C 265C

0.1-0.14% (24h) 0.5% (Max) good Poor good good good

0.1% (24h) 0.1% (Max) Good good good Poor fair

1.0-2.8% (24h) 8.5% (Max) good Poor Dissolved by phenol & formic acid Resistant Poor

$30

$7 - $10

$1.30
43

Properties of Reinforced PEEK

Mechanical Properties Reinforced PEEK Density, g/cc Tensile Strength, psi Tensile Modulus, psi Tensile Elongation, % Impact Strength
ft-lb/in

1.30-1.32 10,000 15,000 500K 30% - 150% 1.6 R120 40 - 47 320 F

PEEK 30% glass fibers 1.52 23,000 29,000 1,300K 1,600K 2%-3% 2.1 2.7

PEEK with 30% carbon fibers 1.43 31,000 1,900K 3,500K 1% - 4% 1.5 2.1 R120

Hardness CLTE 10-6 mm/mm/C HDT 264 psi

12-22 550F -600F

15-22 550F -610F

44

Processing Properties of PEEK

Processing Properties PEEK Tmelt Recommended Temp Range (I:Injection, E:Extrusion) Molding Pressure Mold (linear) shrinkage (in/in) 334 C I: 660F 750F E: 660F 725F 10 -20 kpsi 0.011 LCP Polyester 400 C - 420 C I: 540F 770F Nylon 6,6 255C 265C I: 500F 620F

5 - 16 kpsi 0.001 0.008

1 -20 kpsi 0.007 0.018

45

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

46

Polyphenylene Materials
Several plastics have been developed with the benzene ring in the backbone
Polyphenylene

Polyphenylene oxide (amorphous) Poly(phenylene sulfide) (crystalline)

S Cl

S Cl

Polymonochloroparaxylyene

CH2

CH2

47

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
48

PPO and PPS Applications

*PPS Applications
- Computer components - Range components - Hair dryers - Submersible pump enclosures - Small appliance housings

*PPO Applications
- Video display terminals - Pump impellers - Small appliance housings - Instrument panels - Automotive parts

49

PPS and PPO Mechanical Properties

Mechanical Properties Density, g/cc Tensile Strength, psi Tensile Modulus, psi Tensile Elongation, % Impact Strength
ft-lb/in

PPS 1.30 9,500 480K 1% - 2% < 0.5 R123 49 275 F

PPO 1.04 1.10 7,800 360K 60% - 400% 4-6 R115 60 118F -210F

Nylon 6,6 1.13-1.15 14,000 230K 550K 15%-80% 0.55 1.0 R120 80 180 F

Hardness CLTE 10-6 mm/mm/C HDT 264 psi

50

PPS and PPO Physical Properties

Physical Properties PPS Opaque Optical Tmelt Tg H20 Absorption Oxidation Resistance UV Resistance Solvent Resistance Alkaline Resistance Acid Resistance Cost $/lb 290 C 88 C > 0.02% (24h) PPO Opaque 250 C 110 140 C 0.01% (24h) 1.0-2.8% (24h) 8.5% (Max) good Poor Dissolved by phenol & formic acid Resistant Poor Nylon 6,6 Translucent to opaque 255 C 265 C

good fair Poor in aromatics good poor

good fair Poor in aromatics good good

$2

$1.80

$1.30
51

PPS and PPO Processing Properties

Processing Properties PPS Tmelt Recommended Temp Range (I:Injection, E:Extrusion) Molding Pressure Mold (linear) shrinkage (in/in) 290 C PPO 250 C Nylon 6,6 255C 265C I: 500F 620F

I: 600F 625F I: 400F 600F E: 420F 500F 5 15 kpsi 0.007 12 - 20 kpsi 0.012 0.030

1 -20 kpsi 0.007 0.018

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.)
52

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. O 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.
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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, 10 Kpsi

50
xLDPE 2

xHDPE

5
54

Tensile Strength, Kpsi

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?_________________________________ _________________________________________________.
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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

Section Review

Thermoplastic polyesters have ester(-C-O) repeating link Linear and aromatic polyesters O 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 (CH2)2 ; PBT has more flexible (CH2)4 Copolyester chain is less regular than monopolyester chain and as a result has less crystallinity

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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, 10 Kpsi

50
xLDPE 2

xHDPE

5
57

Tensile Strength, Kpsi

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?_________________________________ _________________________________________________.
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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, 10 Kpsi

50
xLDPE 2

xHDPE

5
59

Tensile Strength, Kpsi

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 __________.

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