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Plastics

2.008 Design & Manufacturing


$120 Billion shipments, Applications
II
„ „

1999 US Name it
„ One of the greatest
inventions of the
Spring 2004 millennium – Newsweek
„ Music LPs, CDs
No-sticking TEFLON
Polymer Processing I
„

„ Stre-e-e-tching SPANDEX
-What is polymer?
-Polymer Science
1
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Automotive Plastics and


Plastic Intensive Vehicles Composites Use
„ Exterior
„ doors
„ hoods
„ fenders
„ bumper covers (most cars have soft fascia)
Corvette
„ Interior
„ instrument panels, door trim, seats, consoles
„ Engine
„ valve covers, intake manifolds, fluid containers,
etc.
Lotus
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Recreational Plastics and


Composites Use Commercial Plastics Usage
„ Snow Equipment
„ Packaging
„ skis, snow boards, snow mobiles, etc.
„ Wrapping, bags, bottles, foams, shrink wrap.

„ Water Sports Equipment „ Textiles


„ water skis, water crafts, snorkel equipment, „ Clothing, carpets, fabrics, diapers, netting for sports

fishing gear „ Furniture, Appliances, House wares


„ Telephones and other communication equipment, computer
„ diving equipment and clothes
housings and cabinets, luggage, seating, components for
„ Land Sports Equipment washers, dryers, etc.
„ shoes, roller blades, skate boards, tennis, golf, etc. „ Musical instruments, CDs, VCRs, TVs, cases

„ Construction
„ Moldings, counter tops, sinks, flooring, cups, paints, etc.

„ Tyvek

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1
Medical Plastics and Composites
Use Materials
„ Containers Solid materials
„ Bottles, bags

Drug delivery
Plastics
„

„ IV bags, syringes
metals ceramics
„ tubing and tools for surgery

„ Implants, artificial skins thermoplastics thermosetts elastomers


„ The use of plastic materials in the medical field, about 4 billion
dollars in 2000 (US). Plastic: Greek, plastikos, means to form or mold

excerpt from Prof. J. Greene, CSU


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Plastics,
Polymers, Macromolecules
„ Poly (many) + mer (structural unit)
-[C2H4]n- ,poly[ethylene] spaghetti
H H H H
C C C C
H H H H

„ Metal: single atoms, metallic bond


„ Ceramic: metallic oxides, ionic bond or dipole
interactions, van der Waals bonds

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Thermoplastics Crystalline vs. amorphous


„ Crystals, lamella
amorphous crystalline structure

„ Degree of
crystallinity

Transparent
Translucent „ Translucent/opaque
Opaque

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2
Amorphous vs. Semi
crystalline Polymers Early Plastics
•Phenolics (named Bakelite by Leo Bakeland)
–Resin could be shaped and hardened with heat
Vˆ Melt Vˆ Tough and
Melt
–Phenol and formaldehyde reaction after heat
Rubbery
–Replacement for shellac, natural plastic (1907)
Brittle flexible
Glassy solid

•Nylon66
- W. H. Carothers of DuPont (1920’s)
•PVC
Tg Tg+60°C Tg Tm
- W. Semon of B.F. Goodrich (1929)
(a) (b)

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Polymers Major Plastic Materials (1995)


„ PE (Polyethylene)-Crystalline
„ LDPE ($0.38/lb) 6.4 M metric tons (1000 kg)
„ PVC (Polyvinyl chloride)-Amorphous „ HDPE ($0.29/lb) 5.3 M metric tons
„ PP (Polypropylene)-C „ PVC ($0.26/lb) 5.1 M metric tons
„ PS (Polystyrene)-A „ PP ($0.28/lb) 4.4 M metric tons
„ PS ($0.38/lb) 2.7 M metric tons
„ PU (Polyurethane)-Thermoset „ PU ($0.94/lb) 1.7 M metric tons
„ PET (Polyethyleneterephthalate)-C „ PET ($0.53/lb) 1.6 M metric tons
„ PPO (Polyphenyleneoxide)_A „ Phenolic ($0.75/lb) 1.5 M metric tons
Total 28.6 M metric tons (82% of market)
„ PMMA (Polymethylmethacrylate) -A
„ Nylon ($1.40/lb) 0.4 M metric tons
„ PEEK (Polyether-ether-ketone )-C „ PTFE ($6.50/lb) <0.1 M metric tons
„ Acetal, TEFLON -C „ PEEK ($36.00/lb) <0.05 M metric tons
excerpt from Prof. J. Greene, CSU
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Polyethylene
Recycling of Plastics
„ Ethylene is produced by cracking higher hydrocarbons of natural gas or
petroleum
„ LDPE commercialized in 1939
„ Density of 0.910 - 0.925 g/cc

„ State and Federal Regulation „ Properties include good flex life, low warpage, and improved stress-
crack resistance
„ Codes for plastics
„ Disposable gloves, shrink packages, vacuum cleaner hoses, hose,
„ 1 PET bottles, shrink wrap, diaper film liners, and other health care
„ 2 HDPE products, films for ice, trash, garment, and product bags
HDPE commercialized in 1957
„ 3 Vinyl/PVC „

„ Density of 0.941 - 0.959 g/cc


„ 4 LDPE „ MW from 200K to 500 K

„
5
6
PP
PS
1 „ Densities are 0.941 or greater-Ultra HDPE

„ Properties include improved toughness, chemical resistance, impact

strength, and high abrasion resistance, high viscosities


„ 7 Other
„ Trash bags, grocery bags, industrial pipe, gas tanks, and shipping
containers, chairs, tables
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3
Polypropylene PVC
„ Polyvinyls were invented in 1835 by French chemist V. Semon. PVC
„ PP invented in 1955 by Italian Scientist F.J. Natta. was patented in 1933 by BF Goodrich Company in a process that
„ Advantages combined a plasticizer which makes it easily moldable and
„ Low Cost, Excellent flexural strength, good impact strength processed.
„ Processable by all thermoplastic equipment

„ Low coefficient of friction, excellent electrical insulation „ Rigid-PVC


„ Good fatigue resistance, excellent moisture resistance „ Pipe for water drain, sewage

„ Service Temperature to 160 C, very good chemical resistance


„ Pipe for structural yard and garden structures
„ Disadvantages „ Plasticizer-PVC or Vinyl
„ High thermal expansion, UV degradation
„ Latex gloves
„ Poor weathering resistance
„ Latex clothing
„ Subject to attack by chlorinated solvents and aromatics
„ Paints and Sealers
„ Difficulty to bond or paint
„ Signs
„ Oxidizes readily

„ Flammable

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PS (Polystyrene) ABS
„ PS Homopolymer (crystal): „ ABS was invented during WWII as a replacement for rubber
„ Clear and colorless with excellent optical properties and high
„ ABS is a terpolymer: acrylonitrile (chemical resistance),
stiffness. butadiene (impact resistance), and styrene (rigidity and easy
processing)
„ Brittle.
„ Graft polymerization techniques are used to produce ABS
„ Impact polystyrene (IPS): Graft copolymer or blend with

elastomers „ Family of materials that vary from high glossy to textured finish,
and from low to high impact resistance.
„ Properties are dependent upon the elastomer content, medium

impact high impact and super-high impact „ Additives enable ABS grades that are flame retardant,
transparent, high heat-resistance, foamable, or UV-stabilized.
„ Copolymers include SAN (poly styrene-acrylonitrile), SBS

(butadiene), ABS. „ Office machines


„ Expandable PS (EPS) is very popular for cups and insulation foam.

„ EPS is made with blowing agents, such as pentane and

isopentane. ABS: terpolymer


„ cell size and distribution
= acronitrile+butadiene+styrene

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Polyamide (Nylon) Polyester


„ Polyesters is used for films and fibers.
„ PA is considered the first engineering thermoplastic. „ Blow molded bottles (PET bottles)
„ PA invented in 1934 by Wallace Carothers, DuPont. First commercial „ Fiber applications
nylon in 1938. „ Tire cords, rope, thread, cord, belts, and filter cloths.
„ Nylons are described by a numbering system which indicates the „ Monofilaments- brushes, clothing, carpet, bristles
number of carbon atoms in the monomer chains; nylon 6, nylon 6,6 „ Film and sheets
or nylon 6,10 „ photographic and x-ray films; biaxially oriented sheet for food
„ Water absorption packages
„ Fiber applications „ Transparencies (Mylar)

„ 50% into tire cords (nylon 6 and nylon 6,6) „ Molded applications- Reinforced PET (ValoxTM)
„ rope, thread, cord, belts, and filter cloths. „ luggage racks, grille-opening panels, functional housings

„ sensors, lamp sockets, relays, switches, ballasts, terminal blocks


„ Filaments- brushes, bristles (nylon 6,10)

„ Plastics applications „ Appliances and furniture


„ oven and appliance handles, and panels
„ bearings, gears, cams
-- pedestal bases, seat pans, chair arms, and casters
„ rollers, slides, door latches, thread guides

„ clothing, light tents, shower curtains, umbrellas

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4
PC (Polycarbonate) PMMA, Acrylics
„ PC was invented in 1898 by F. Bayer in Germany
„ A special family of Polyester „ Optical applications, outdoor advertising signs, aircraft
„ Amorphous, engineering thermoplastic that is known for windshields, cockpit covers
toughness, clarity, and high-heat resistance. „ Plexiglas ™ for windows, tubs, counters, vanities
„ LexanTM form GE „ Optical clarity, weatherability, electrical properties, rigid, high
„ High impact strength, transparency, excellent creep and glossy
temperature „ Poor solvent resistance, stress cracking, combustibility, Use
„ lenses, films, windshields, light fixtures, containers, below Tg.
appliance components and tool housings
„ Lenses for cameras
„ hot dish handles, coffee pots, hair dryers.

„ pump impellers, safety helmets, trays, traffic signs

„ aircraft parts, films, cameras, packaging

„ High processing temp, UV degradation, poor resistance to


alkalines and subject to solvent cracking

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Acetal or Polyoxymethylene (POM) PEEK


„ Polyether-ether-ketone (PEEK) and Polyether ketone (PEK)
Trade name: Derlin „ PEEK invented by ICI in 1982. PEK introduced in 1987
„ Expensive
„ First commercialized in 1960 by Du Pont,
„ Advantages
„ Similar in properties to Nylon and used for plumbing fixtures, pump
„ Very high continuous use temperature (480F)
impellers, conveyor belts, aerosol stem valves
„ Outstanding chemical resistance, wear resistance
„ Advantages
„ Excellent mechanical properties, Very low flammability and smoke
„ Easy to fabricate, has glossy molded surfaces, provide superior fatigue
generation, Resistant to high levels of gamma radiation
endurance, creep resistance, stiffness, and water resistance. „ Disadvantages
„ Among the strongest and stiffest thermoplastics.
„ $$$, high processing temperatures

„ Resistant to most chemicals, stains, and organic solvents „ Aerospace: replacement of Al, replacement of primary structure
„ Disadvantages „ Electrical, wire coating for nuclear applications, oil wells, flammability-
„ Poor resistance to acids and bases and difficult to bond critical mass transit.
„ Subject to UV degradation and is flammable
„ Semi-conductor wafer carriers which can show better rigidity, minimum
weight, and chemical resistance to fluoropolymers.
„ Toxic fumes released upon degradation
„ Internal combustion engines (replacing thermosets)

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Polymers’ Structure Covalent bonding


Occurs when two nonmetal atoms are in close proximity.
„ Poly (many) + mer (structural unit) -

- Both atoms share outer electron shells.


-[C2H4]n- ,poly[ethylene] spaghetti - Strong Bond

H H methane
C C H Polyethylene
e- e-
H H H H e-
e- H H H H
e- e-
„ Metal: single atoms, metallic bond H H e- C e-
e- H
e-
e-
e- e-
e- Ce- Ce-
e-
e- H e- e- e-C e- e-C e-e- e- e- e-
„ Ceramic: metallic oxides, ionic bond or dipole e- e- e-
e- C e- e- e-
e- e- e-
interactions, van der Waals bonds H
e-
H
e- H H H
from J. Greene, CSU
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5
Secondary bonding
weaker than ionic, metallic, covalent
„ Hydrogen bonding

„ Between the positive end of a bond and the


negative end of another bond.
Example, water
„ van der Waals
„ Due to the attraction of all molecules have for
each other, e.g. gravitational. Forces are weak
since masses are small.

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Homopolymers
Homopolymers
„ Single monomers
„ Plastics Involving Single Substitutions
„ Plastics Involving Two Substitutions
H H H H H H
C C H Y
C C C C
H H H CH4 H Cl C C
n n n

PE PP PVC H X
n

H H PS F F Polyvinylidene fluoride PVDF


Cl Cl Polyvinyl dichloride PVDC
C C CH3 (Methyl group) CH3 Polyisobutylene PB
COOCH3 CH3 Polymethyl methacrylate PMMA
H n

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Copolymers
Homopolymers
„ Structure
„ Three or more substitutions
„ Alternating - ABABABABABABAB
„ Random - AABBABBBAABABBBAB
F F „ Block copolymer- AABBBAABBBAABBBAABBB
PTFE
C C „ Graft copolymer- AAAAAAAAAAAAAAAA
polytetrafluoroethylene
B B
(Teflon) F F
n B B
B B

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6
Copolymers
„ ABS
Molecular orientation
„ Three mers (terpolymer)
σ
σ

H H H H H H
Covalent Bond
C C C C C C σ
C C C C C C σ
H C:::N
n
CH2CH2
m
H
k C C C C C C C σo
ABS (acronitrile butadiene Van der Waals bond σ
styrene) C C
C C C C
C C C C C C C
Degree of Orientation

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Birefringence Molecular Weight


-Optical anisotropy „ Poly (many) + mer (structural unit)
-Mechanical anisotropy
-[C2H4]n- ,poly[ethylene]
„ Degree of Polymerization, n
„ Molecular Weight
M= nMo
Monomers adhesives
plastics
Cross linked
Organic compounds fibers
proteins rubbers
10 101 102 103 104 105 106 107
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Degree of Polymerization Molecular Weight


Number Averaged

Bowling ball Mn =
∑N M i i
=
N 1 M 1 + N 2 M 2 + N 3 M 3 + ...
∑N N 1 + N 2 + N 3 + ...
σ
i

Weight Averaged

Mw =
∑N M i i
2

=
N 1 M 12 + N 2 M 22 + N 3 M 32 + ...
∑N M i i N 1 M 1 + N 2 M 2 + N 3 M 3 + ...

M
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7
Number Average Molecular Weight, Mn Weight Average Molecular Weight, Mw
Number Average Molecular Weight gives the same weight to „ Favors large molecules versus small ones
all polymer lengths, long and short. „ Useful for understanding polymer properties that relate to
the weight of the polymer, e.g., penetration through a
membrane or light scattering.
„ Example, What is the molecular weight of a polymer sample in
which the polymers molecules are divided into 5 categories. „ Example,
„ Group Frequency „ Same data as before would give a higher value for the

„ 50,000 1 M = ∑ N i M i = N 1 M 1 + N 2 M 2 + N 3 M 3 + ... Molecular Weight. Or, Mw = 420,000 g/mole


∑ Ni N 1 + N 2 + N 3 + ...
n
„ 100,000 4
„ 200,000 5 M n = 1(50 K ) + 4(100 K ) + 5(200 K ) + 3(500 K ) + 1(700 K )
(1 + 4 + 5 + 3 + 1)
„ 500,000 3
M n = 260,000
„ 700,000 1
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Mechanical Properties Step loading and unloading


σ, N/m2
„ Rigid plastic σ
109 t
x
ε Glassy region
x
108
„ Flexible plastic Transition region
ε (leather like)
107
T Elastomeric region
106 increase
ε (rubber like)
„ Rubber 1 2 3 4 5 6
ε,% Liquid flow region
ε
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Modulus-temperature of PS
1010 Tg Tm
109
Ε, N/m2 semi crystalline
108 amorphous
107 cross linked
106
105
104 uncross linked
50 100 150 200 250
T, 0C

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8
Time-Temperature Superposition WLF equation
Experiment window
Log a(T) = - C1 (T-To)
1010 T1 C2+ T-To
109 T2 At To=Tg, C1= 17.44, C2=51.6
Ε, N/m2 T3
108 T4 Empirical equation for the shift factor a(T)
T5
107 Master curve at T6 T6 T
106 by William, Landel, and Ferry
T7
105 T8 Amorphous, glassy polymers Tg< T < Tg+100oC
104 T9

10-6 10-4 10-2 1 102


t, hours
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example Master Curve, PC


„ A plastic part made of PC requires 100 years of leak
proof performance at 23oC. Accelerated test?
4.8
100 yrs = 3.16 x 109 sec
Log a(T) = 9.5

From data, log a(23) Æ4.8 to the master curve.


Log a(T) from the master curve = - 4.7 4.7
4.7 (51.6+ (T-Tg))= 17.44 (T-Tg)
T = Tg + 19oC = 119oC

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