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2.008 Design & Manufacturing II: Plastics
2.008 Design & Manufacturing II: Plastics
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
2.008 spring 2004 S. Kim 2
Construction
Moldings, counter tops, sinks, flooring, cups, paints, etc.
Tyvek
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
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
Degree of
crystallinity
Transparent
Translucent Translucent/opaque
Opaque
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)
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
5
6
PP
PS
1 Densities are 0.941 or greater-Ultra HDPE
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
Flammable
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
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
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.
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)
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
2.008 spring 2004 S. Kim 29 2.008 spring 2004 S. Kim 30
5
Secondary bonding
weaker than ionic, metallic, covalent
Hydrogen bonding
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
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
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
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
2.008 spring 2004 S. Kim 41 2.008 spring 2004 S. Kim 42
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
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
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