Materials Science of Polymers

for Engineers

Chemistry
Physics

Applications
Properties
Processing
 Major Functions of Polymers

Adhesives Barriers
superglue
Polyethylene landfill
epoxies polyethylene Garbage bags
polyesters Sarah wrap

Structural Insulation
components Polyurethane foam
PPMA or PC Styrofoam
transparent sheets Polyethylene wire coatings
Molded ABS or HIPS Bakelite (phenol-formaldehyde)
PVC
Polymers are everywhere
PVC
Transportation
PSty Polyester
PES
Food
Packaging Electronics
PVC Polyisoprene
PP

Medical Clothing
Supplies
Nylon Construction
SAN

PC
Manufactured
Goods
We use a lot of polymers.

1012 bags/year!!
 What are polymers?
Poly = many & meros = parts (Greek)
Macromolecules = large molecules

H H catalyst
n H
H polyethylene
H n
H
ethylene

A nomenclature exists to describe polymers

 What are polymers?
H H catalyst
n H
H
H n
H

Chemical Formula: C500H1002

Molecular Weight: 7015.31
Elemental Analysis: C, 85.60; H, 14.40

Contour length: 38.5 nm or 0.0385 microns or 0.0000385 mm

106 Dalton polyethylene (35.7K monomers) = 5.5 microns or
0.0055 mm in length
 Length of DNA

Each DNA polymer = 5 centimeters

DNA (3 billion base pairs) = 2.3 meters long/cell

Total length of DNA in a human: 2 x 1013 meters

 Engineering with Polymers
• Polymers provide a low density structural
alternative for some applications
• Are relatively easy to process into numerous forms
• Provide a high volume, often improved
replacement for materials derived from living
organisms.
• Possess unique properties
• They are often relatively
inexpensive.

Styrofoam ®
 YOUNG’S MODULI: COMPARISON
Graphite
Metals Composites
Ceramics Polymers
Alloys /fibers
1200
10 00
Semicond
E ceramics
Diamond
800
600
400 Tungsten
Si carbide
Al oxide Carbon fibers only
> E metals
Molybdenum
>> E polymers
Si nitride
E(GPa) 200
Steel, Ni
Tantalum <111>
Si crystal
CFRE(|| fibers)*
Platinum
Cu alloys <100> Aramid fibers only
10 0 Zinc, Ti
80 Silver, Gold AFRE(|| fibers)*
60 Aluminum Glass -soda Glass fibers only Based on data in Table B2,
40
Magnesium,
Tin G FRE(|| fibers)* Callister 6e.
Concrete Composite data based on
10 9 Pa 20 GFRE*
CFRE *
reinforced epoxy with 60 vol%
of aligned
G raphite G FRE( fibers)*
10 carbon (CFRE),
8 CFRE( fibers) *
6 AFRE( fibers) *aramid (AFRE), or
Polyester
4 PET
glass (GFRE)
PS fibers.
PC Epoxy only
2
PP
1 HDP E
0.8
0.6 Wood( grain)
PTF E
0.4

0.2 LDPE
13
 YIELD STRENGTH: COMPARISON
Graphite/
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
20 00
Steel (4140) qt
y(ceramics)
10 00
>>y(metals)
y (MPa)

Ti (5Al-2.5Sn) a
700 W (pure) >> y(polymers)
600 Cu (71500) cw
500 Mo (pure)

in ceramic matrix and epoxy matrix composites, since

Steel (4140) a since in tension, fracture usually occurs before yield.

in tension, fracture usually occurs before yield.

400
Steel (1020) cd
300
Al (6061) ag Room T values
Hard to measure ,

Hard to measure,
200 Steel (1020) hr
Ti (pure) a ¨
Ta (pure)
Cu (71500) hr Based on data in Table B4,
Yield strength,

Callister 6e.
100 a = annealed
dry
70 PC hr = hot rolled
60 Al (6061) a Nylon 6,6 ag = aged
50 PET
PVC humid
cd = cold drawn
40 cw = cold worked
PP
30 HDPE qt = quenched & tempered

20

LDPE
Tin (pure) 17
10
 Why use polymers
• Easy to process
– Injection molding (thermoplastics)
– Mold or reaction injection molding (thermosets)
• Cheap
• Lightweight
• Tough
• Flexible
• Transparent (sometimes)
• Insulating (generally)
 How do we classify polymers?

• By origin
• Physical behavior
• Structure/Architecture
• Application/function
• Polymerization mechanism
• Polymerization chemistry
• Cost
 Origin of Polymers

Biopolymers
– Protein: horn, cartilage, hair, hide, ligaments, tusks
– Composite structures: bone, shells
– Plant materials:
• Cellulose (cotton, sisal, hemp) fiber
• lignin & cellulose (wood)
• Chitan (insect & crustacean exoskeletons)
 Synthetic Polymers

Coal
Petroleum
Natural gas
Petroleum from petra oleum (rock oil)
 Origins: Two Families of Polymers
Biological Synthetic
Polymers
O O

* N N O *
n
n O O
Me
polyimide (PI)
latex rubber

*
*
n

Me *
n
*
polystyrene
gutta percha

*
* n
Me CO2Me

polymethylmethacrylate (PMMA)
Physical Behavior & Architecture

• Thermoplastics
Polystyrene
Polyvinylchloride

• Elastomers
Synthetic rubbers
Poly-cis-isoprene

• Thermosets
Phenolic Resins
Melamines
epoxies
Source: R. Esfand, D.A. Tomalia, A.E. Beezer, J.C. Mitchell, M. Hardy, C. Orford,
Polymer Preprints, 41 (2), 1324 (2000)
 Applications/Function

O
• Structural *
N
*
H n
Nylon-6
• Coatings *
*
n
O
O
• Fibers
Poly(vinyl acetate) or PVA
O O
O
• Adhesives * O O n *

Poly(ethylene terephthalate) or PETE

O O O O

N N N N N N N N
H H H H
N N

O NH HN O

Urea-Formaldehyde
Taxonomy by polymerization mechanism
Chain Growth Mechanism
•Free radical
•Anionic
•Cationic Initiation
•Ring opening Initiator I
metathesis
I I
R R
Propagation

P R P R R
R
Step growth
Termination
•Condensation
•Metathesis R R P R R P

P R R P R R

Free radical chain mechanism

 Polymer Functionality
Vinyl Polymers *
Polyethers *
n
Polyarylenes R
* R O *
Polyesters n
* *
Polyamides O n
Polyureas O
* R O *
Polyurethanes n * R N *
H n O
Polysiloxanes
Polycarbonates O R N N *
H H n
Polysulfones
R O N * R R
Polyimides H n
Si *
Polysulfides * O O
n
Fluoropolymers R O O *
O n
Polyionomers * S O
Polyacetylenes O O
O n
* N N *
n
* R S * F F O O
n *
*
F n
F
* N *
n
*
*
n
 Polymer Functionality
Vinyl Polymers *
Polyethers *
n
Polyarylenes R
* R O *
Polyesters n
* *
Polyamides O n
Polyureas O
* R O *
Polyurethanes n * R N *
H n O
Polysiloxanes
Polycarbonates O R N N *
H H n
Polysulfones
R O N * R R
Polyimides H n
Si *
Polysulfides * O O
n
Fluoropolymers R O O *
O n
Polyionomers * S O
Polyacetylenes O O
O n
* N N *
n
* R S * F F O O
n *
*
F n
F
* N *
n
*
*
n
 Recycling symbols
O O
O
* O O n *
*
* n
Poly(ethylene terephthalate) or PETE Me
poly(propylene)

*
* n
high density polyethylene
*
*
n

polystyrene
*
* n
Cl
polyvinyl chloride
Not recyclable

*
* n
low density polyethylene
Cost: Commodity (Amorphous) Thermoplastics
• Four high volume thermoplastics and applications:
– Polyethylene (PE): Grocery bag, 55-gallon drum, lawn
furniture
– Polypropylene (PP): Washing machine agitator, carpet
– Polyvinylchloride (PVC): Irrigation pipe, wire insulation
– Polystyrene (PS): Toys, pipes, packing material (Styrofoam)

Polystyrene

Polyethylene Polypropylene Polyvinylchloride

•Low cost, temp. resistance and strength • Good dimensional stability

•Bonds well • Typically, but not always, transparent
 Some History: First there were Bio-
Polymers
Animal Hides (Proteins): Fiber & Films
Ligaments (Collagen): Hinges
Silk Fibers (Protein): Fibers
Plant Fibers (Cellulose): Fibers

Bison-Hide teepee

Yucca-fiber sandals

Structural Materials: High Modulus & Strong

Wood (Cellulose & Lignin): S
Antlers (Keratin): Tools, jewelry & weapons
Ivory lunar cycle charts
Horn (Keratin): Tools, jewelry & weapons
Tusks (enamel & dentin): Tools, jewelry & weapons
 Key Figures in Polymer History:
Invented vulcanization CH3 CH3
of rubber in 1839 HC C HC C
CH2 H2C CH2 H2C CH2 H2C CH2 CH3
HC C HC C
CH3 H2C

Poly-cis-isoprene

IUPAC: cis-poly(1-methyl-1-butene-1,4-diyl)

Elastomer:
50% of Rubber tires
Latex rubber gloves
Charles Goodyear
(1800 - 1860)
S S
S S
S S
S S > 140 °C

S
S

Enabled commercialization of natural rubber

 Gutta Percha

H
H

trans-Polyisoprene or Gutta percha

IUPAC: trans-poly(1-methyl-1-butene-1,4-diyl)

William Montgomerie (1840’s) Thermoplastic:

Saw usefulness Golf ball covers

of gutta percha Wire coating (until 1940’s)

Gutta percha (GP), also known as balata, is a natural thermoplastic and is of

fundamental importance in the history of the plastics industry.
 History of Polymers
Date Material Example Use

1868 Cellulose Nitrate Figurines

1909 Phenol-Formaldehyde Electrical equipment
1919 Casein Beauty accessories
1927 Cellulose Acetate Cellophane package wrapping
1927 Polyvinyl Chloride Pipe, Synthetic Leather
1929 Urea-Formaldehyde Lighting fixtures, Plywood glue
1936 Acrylic Brush backs, displays
1936 Polyvinyl Acetate Synthetic flooring
1938 Polystyrene or Styrene Disposable utensils
1938 Nylon (Polyamide) Hosiery
1938 Polyvinyl Butyrate Safety glass interlayer
1939 Polyvinylidene Chloride Saran wrap
1939 Melamine-Formaldehyde Countertops, Cabinets
 History of Polymers
Date Material Example Use
1942 Polyester Clothing, Boat hulls
1942 Polyethylene Milk Jugs
1943 Fluorocarbon Industrial gaskets, Non-stick liners
1943 Silicone Gaskets, Tubing, Utensils
1947 Epoxy Glues
1948 Acrylonitrile-Butadiene-Styrene Luggage
1954 Polyurethane or Urethane Foam cushions, Shoe soles, Wheels
1956 Acetal Automotive parts, Toilet parts
1957 Polypropylene Living hinges, Safety helmets
1957 Polycarbonate Water bottles, Eye protection
1964 Ionomer Golf balls, Skin packages
1964 Polyimide Gears
 Nomenclature of Elastomers
Structure Monomer Common Name IUPAC Trade name

* *
n cis-Polyisoprene cis-poly(1-methyl-1-butene-1,4-diyl) latex

* *
n Polychloroprene poly(1-chloro-1-butene-1,4-diyl) Neoprene
Cl Cl

Me Me
Me
*
* Polyisobutylene poly(1,1-dimethyl-ethene-1,2-diyl) Butyl Rubber
n Me
Block Copolymers

Polystyrene-block-poly-1,4-butadiene-block-polystyrene
a c
b

Block-copolymer[styrene-butadiene-styrene]

SBS
 Alternating Copolymers

CO2Me
* Poly[styrene-alt-(methyl methacrylate)]
Ph Me CO2Me Ph
CN
Alt-copoly[styrene/methyl methacrylate]
 Alternating Copolymers

CN
* Cl Poly[styrene-alt-(acrylonitrile)-alt-(vinylidene dichloride)]
Ph NC Cl Cl
Ph
Cl
Alt-copoly[styrene/acrylonitrile/vinylidene
dichloride]
 Alternating Copolymers

Block Copolymers
 Block & Alternating Copolymer

Poly[methyl acrylate-block-
(poly(maleic anhydride)-alt-styrene)]
CO2Me
*
MeO2C NC Cl Cl
Ph
Block-copoly[alt-co(styrene/maleic
O O
anhydride)methyl acrylate]
O
 Nomenclature of Thermoplastics
Structure Monomer Common Name IUPAC Trade nam

O O
* * NH2
N HO
H n
6-aminohexanoic acid poly(6-hexanomide)
poly(imino(1-oxohexamethylene)) Nylon-6
O

NH polycaprolactam

azepan-2-one
or caprolactam

O
O
* * O
O polycaprolactone poly(oxy(1-oxohexamethylene))
n

O O HO2C CO2H
* poly(ethylene terephthalate) Poly(oxyethylene PETE
* O O -oxyterephthaloyl)
n OH
HO
 Nomenclature of Polyether Thermoplastics
cture Monomer Common Name IUPAC

O O
* *
n polyethyleneoxide polyoxyethylene
ethylene oxide
or oxirane
PEG
O
* * HO poly(ethylene glycol) polyoxyethylene
n OH
ethylene glycol

O
O poly(tetrahydrofuran) poly(oxytetramethylene)
* *
n
tetrahydrofuran

O
O
* * poly(propylene-oxide) poly(oxy(1-methylethylene)
Me n Me
propylene oxide
 Nomenclature of Polyether Thermoplastics

Structure Monomer Common Name IUPAC

O
*
* O n H H poly(formaldehyde) poly(oxymethylene)
formaldehyde

Me O
*
* O n Me H poly(acetaldehyde) poly(oxyethylidene) Delrin
acetaldehyde

Me Me
poly(phenyleneoxide) poly(oxy-2,6-dimethyl-
* O * OH 1,4-phenylene)
n
Me Me

Delrin
 Nomenclature of Vinyl Thermoplastics
Structure Monomer Common Name IUPAC Trade Name

*
* Polyethylene poly(ethylene) PE
n

Me Me
*
* Polypropylene poly(propylene) PP
n

Cl Cl
*
* Polyvinyl chloride poly(1-chloroethylene) PVC
n

Ph
*
* Polystyrene poly(1-phenylethylene) PS
n

O
OMe
Me CO2Me
*
* Polymethyl methacrylate poly(1-(methoxycarbonyl) PMMA
n Me -1-methylethylene)
 Nomenclature of Vinyl Thermoplastics
Structure Monomer Common Name IUPAC Trade Name

O
HO O Me
* * Polyvinyl alcohol poly(1-hydroxyethylene) PVA
n

O
AcO
O Me
*
* Polyvinyl acetate poly(1-acetoxyethylene)
n

NC
CN
*
* Polyacrylonitrile poly(1-cyanoethylene) PAN
n

O OEt
NC CO2Et
*
* Poly(ethyl cyanoacrylate) poly(1-cyano-1-(ethoxy Super glue
n CN carbonyl)ethylene)

F F F F
* * Poly(tetrafluoroethylene) Poly(tetrafluoroethylene) Teflon
n F F
FF
 Tacticity: How groups are arranged along polymer

Vinyl Monomers

R R R R R R R R R R R
isotactic

R R R R R R R R R R R

syndiotactic

R
R R R R R R R R R R

atactic

Isotactic and syndiotactic pack into lattices easier: crystalline

 Tacticity: disubstituted monomers

H R

Polymer

R R R R R R R R R R

R R R R R R R R R R R
Polymer
isotactic
R H
Looksing at indicated atoms from the left

H R

Polymer
R R R R R R R R R

R R R R R R R R R R R R
Polymer
syndiotactic
H R