Materials Science of Polymers

for Engineers

Physics

Applications

MSE 460/560
Doug Loy

Properties

Chemistry

Processing

Major Functions of Polymers

Adhesives
superglue
epoxies
polyethylene
polyesters

Structural
components
PPMA or PC
transparent sheets
Molded ABS or HIPS

Barriers
Polyethylene landfill
Garbage bags
Sarah wrap

Insulation
Polyurethane foam
Styrofoam
Polyethylene wire coatings
Bakelite (phenol-formaldehyde)

COURSE WEBSITE:
Loy group website, courses, MSE 460/560 Spring 2010
http://www.loyresearchgroup.com/
http://www.loyresearchgroup.com/mse-460560-polymerscience-for-engineers.html

Office Hours

Old Chemistry 309

Tuesday 1-3 pm
Monday and Wednesday 11am-noon
or by appointment

Textbook:
Yes, you will need it.

Read Chapter 1
by next Wednesday

Grading

Three exams:
300 pts
Final:
200 pts
HWK:
150 pts
Research Paper:
100 pts
Graduates (MSE 560)
Oral Presentation: 100 pts

Drop lowest 100 point score

Undergraduates:
Graduates:

650 pts possible

750 pts possible

First exam before drop date

Homework
Assignments will be on D2L
Not up yet but should be by Monday.

Learn:

Goals

Basic polymer nomenclature

Basic types of polymers and how they are made
Mechanical properties of polymers
Solution properties
Polymer processing
Aging & degradation of polymers
Applications of polymers
Understand where polymers should be used and what
their limitations are.
How to communicate
How to think skeptically

How to succeed in MSE 460/560

Read the Chapter ahead of lectures

Come to class
Start paper early
Study groups
Practice exams (new ones will be written).
Dont cheat, plagiarize, or otherwise participate in unethical behavior
Use office hours
Ask questions
Think skeptically

Thinking skeptically
Dont trust anyone (particularly
anyone over 30)
If it doesnt make sense,
ask questions.
Beware of trusting
experts and textbooks
Acquaint yourself with logic and
logical fallacies

Research Paper
Review of literature topic I provide
Graduates can petition to present topic relating to research or
oral.
> 10 pages, double spaced, times roman font, typed + graphics.
JACS style bibliography
Hard and electronic copy
Must be readable on Mac (your responsibility)
Keyword list due 1/18
Literature search results due 1/25
One draft due during semester
You will edit each others drafts (for HWK assign)

Research Paper Topics & Assignments

polysilsesquioxane photoresists
polysilsesquioxane membranes for separations

polysilsesquioxane membranes for fuel cells and batteries

polysilsesquioxane anti-corrosion coatings
optical application of polysilsesquioxanes
polysilsesquioxane particles
surfactant templating polysilsesquioxanes (organosilica, PMO's)
Composites with polysilsesquioxanes
polysilsesquioxane coupling agents in tires

polysilsesquioxanes for supported enzymes

mechanical properties of polysilsesquioxanes
polysilsesquioxane ceramic precursors
bridged polysilsesquioxane since 2010
polysilsesquioxane for stone conservation
polysilsesquioxanes for shrink-fit plastics
polysilsesquioxane ladder polymers

Fluorescent polysilsesquioxanes
Degradation of polysilsesquioxanes
polysilsesquioxane adsorbents for toxic metals
polysilsesquioxane adsorbents for volatile organics
drug delivery with polysilsesquioxanes
polysilsesquioxane low k dielectrics
Polysilsesquioxanes in cosmetics

Oral Presentations
Graduate students only
20 minute presentations (two per day)
Everyone must attend & compose one
exam question for each presentation
Last two weeks of class
100 points

HWK 1-Due January 20th

DSL
Some figures will be at website in HWK section as pdfs.
Draft of research paper will count as a homework assignment.

MSE 460/560
Todays Logic Lesson:Post Hoc, Ergo Propter Hoc
"After this, therefore because of this."

Correlation does not equate with causation

I ate sushi yesterday, I became sick today, therefore the sushi made me ill.

Polymers are everywhere

PVC

PVC

Transportation
PSty

Polyester
PES

Food
Packaging
PVC

Electronics
Polyisoprene

Medical
Supplies

PP

Clothing
Construction

Nylon
SAN

Manufactured
Goods

PC

We use a lot of polymers.

1012 bags/year!!

What are polymers?

Poly = many & meros = parts (Greek)
Macromolecules = large molecules

catalyst
H

H
n

polyethylene

ethylene

A nomenclature exists to describe polymers

What are polymers?

n

catalyst
H

H
n

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

YOUNGS MODULI: COMPARISON

Metals
Alloys
1200
1000
800
600
400

E(GPa)

200
100
80
60
40

109 Pa

Graphite
Composites
Ceramics Polymers
/fibers
Semicond
Diamond

Tungsten
Molybdenum
Steel, Ni
Tantalum
Platinum
Cu alloys
Zinc, Ti
Silver, Gold
Aluminum
Magnesium,
Tin

Si carbide
Al oxide
Si nitride

Carbon fibers only

CFRE(|| fibers)*

<111>

Si crystal

Aramid fibers only

<100>

AFRE(|| fibers)*

Glass-soda

Glass fibers only

GFRE(|| fibers)*
Concrete
GFRE*

20
10
8
6
4
2
1
0.8
0.6
0.4
0.2

CFRE*
GFRE( fibers)*

Graphite

Polyester
PET
PS
PC

CFRE( fibers)*
AFRE( fibers)*

Epoxy only

Based on data in Table B2,

Callister 6e.
Composite data based on
reinforced epoxy with 60 vol%
of aligned
carbon (CFRE),
aramid (AFRE), or
glass (GFRE)
fibers.

PP
HDPE

PTFE
LDPE

Wood( grain)

13

YIELD STRENGTH: COMPARISON

y(ceramics)
>>y(metals)
>> y(polymers)
Room T values
Based on data in Table B4,
Callister 6e.
a = annealed
hr = hot rolled
ag = aged
cd = cold drawn
cw = cold worked
qt = quenched & tempered

17

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
Polymers

Synthetic
O

* N

n
Me

*
n

O
polyimide (PI)

latex rubber

*
n

*
Me

*
n

polystyrene
gutta percha

*
n
CO
Me
2Me

polymethylmethacrylate (PMMA)

Physical Behavior & Architecture

Thermoplastics
Polystyrene
Polyvinylchloride

Elastomers
Synthetic rubbers
Poly-cis-isoprene

Thermosets
Phenolic Resins
Melamines
epoxies

Applications/Function
O

Structural

*
n

N
H
Nylon-6

Coatings

*
O

Fibers
O

Adhesives

* O

O
O

n
O

Poly(vinyl acetate) or PVA

O
n *

Poly(ethylene terephthalate) or PETE

O
N
H

O
N

O
N
H

N
H

O
N

N
O

N
N

NH

HN

Urea-Formaldehyde

N
H

Taxonomy by polymerization mechanism

Chain Growth Mechanism
Free radical
Anionic
Cationic
Ring opening
metathesis

Initiation
I

Initiator
I

Propagation

Step growth
Condensation
Metathesis

Termination
R
P

P
P

Free radical chain mechanism

Polymer Functionality
Vinyl Polymers
Polyethers
Polyarylenes
Polyesters
Polyamides
Polyureas
Polyurethanes
Polysiloxanes
Polycarbonates
Polysulfones
Polyimides
Polysulfides
Fluoropolymers
Polyionomers
Polyacetylenes

*
n

*
R

* R O *
n
*

O
* R

O *
n

* R

N *
H n

O
R N
H

O
R O

N *
H n

N *
H n

R R
Si
*
*
O
n

O
R O

O
S
O

O *
n

n
*

N *
n

* R S *
n

F F
*

*
n
*

*
n

*
n

Polymer Functionality
Vinyl Polymers
Polyethers
Polyarylenes
Polyesters
Polyamides
Polyureas
Polyurethanes
Polysiloxanes
Polycarbonates
Polysulfones
Polyimides
Polysulfides
Fluoropolymers
Polyionomers
Polyacetylenes

*
n

*
R

* R O *
n
*

O
* R

O *
n

* R

N *
H n

O
R N
H

O
R O

N *
H n

N *
H n

R R
Si
*
*
O
n

O
R O

O
S
O

O *
n

n
*

N *
n

* R S *
n

F F
*

*
n
*

*
n

*
n

Recycling symbols
O

* O

O
n *

*
Poly(ethylene terephthalate) or PETE

Me

*
n

poly(propylene)
*
n

high density polyethylene

*

*
n

polystyrene
*
Cl

*
n

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 BioPolymers

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
of rubber in 1839

CH3
HC

CH3

CH2 H2C

HC
CH2 H2C
HC

CH2 H2C

CH2
HC

CH3

CH3
C
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

trans-Polyisoprene or Gutta percha

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

William Montgomerie (1840s)

Saw usefulness
of gutta percha

Thermoplastic:
Golf ball covers
Wire coating (until 1940s)

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
1909
1919
1927
1927
1929
1936
1936
1938
1938
1938
1939
1939

Cellulose Nitrate
Phenol-Formaldehyde
Casein
Cellulose Acetate
Polyvinyl Chloride
Urea-Formaldehyde
Acrylic
Polyvinyl Acetate
Polystyrene or Styrene
Nylon (Polyamide)
Polyvinyl Butyrate
Polyvinylidene Chloride
Melamine-Formaldehyde

Figurines
Electrical equipment
Beauty accessories
Cellophane package wrapping
Pipe, Synthetic Leather
Lighting fixtures, Plywood glue
Brush backs, displays
Synthetic flooring
Disposable utensils
Hosiery
Safety glass interlayer
Saran wrap
Countertops, Cabinets

History of Polymers
Date

Material

Example Use

1942
1942
1943
1943
1947
1948
1954
1956
1957
1957
1964
1964

Polyester
Polyethylene
Fluorocarbon
Silicone
Epoxy
Acrylonitrile-Butadiene-Styrene
Polyurethane or Urethane
Acetal
Polypropylene
Polycarbonate
Ionomer
Polyimide

Clothing, Boat hulls

Milk Jugs
Industrial gaskets, Non-stick liners
Gaskets, Tubing, Utensils
Glues
Luggage
Foam cushions, Shoe soles, Wheels
Automotive parts, Toilet parts
Living hinges, Safety helmets
Water bottles, Eye protection
Golf balls, Skin packages
Gears

Nomenclature of Elastomers
Structure
*

Monomer
*

n
Cl

Me Me
*

IUPAC

Trade name

cis-Polyisoprene

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

latex

Polychloroprene

poly(1-chloro-1-butene-1,4-diyl)

Neoprene

poly(1,1-dimethyl-ethene-1,2-diyl)

Butyl Rubber

Cl

Me
*

Common Name

Me

Polyisobutylene

Block Copolymers

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

Block-copolymer[styrene-butadiene-styrene]
SBS

Alternating Copolymers

CO2Me

*
Ph

Me CO2Me

Ph

CN

Poly[styrene-alt-(methyl methacrylate)]
Alt-copoly[styrene/methyl methacrylate]

Alternating Copolymers

CN
*

Cl
Ph

NC

Cl Cl

Ph

Cl

Poly[styrene-alt-(acrylonitrile)-alt-(vinylidene dichloride)]
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
O

Block-copoly[alt-co(styrene/maleic
anhydride)methyl acrylate]

Nomenclature of Thermoplastics
Structure

Monomer

O
*

Common Name

IUPAC

Trade name

O
*
n

N
H

NH2

HO

6-aminohexanoic acid

poly(6-hexanomide)
poly(imino(1-oxohexamethylene))

O
NH

Nylon-6

polycaprolactam

azepan-2-one
or caprolactam

O
*

*
n

polycaprolactone

HO2C

CO2H

*
* O

poly(oxy(1-oxohexamethylene))

poly(ethylene terephthalate)

n
HO

OH

Poly(oxyethylene
-oxyterephthaloyl)

PETE

Nomenclature of Polyether Thermoplastics

Structure

Monomer

Common Name

IUPAC

O
*
n

polyethyleneoxide

polyoxyethylene

ethylene oxide
or oxirane
O

HO

*
n

OH

PEG
poly(ethylene glycol)

polyoxyethylene

poly(tetrahydrofuran)

poly(oxytetramethylene)

poly(propylene-oxide)

poly(oxy(1-methylethylene)

ethylene glycol

O
*
n
tetrahydrofuran

*
Me

O
*
n

Me
propylene oxide

Nomenclature of Polyether Thermoplastics

Structure

Monomer

Common Name

IUPAC

O
*

*
O n

*
O n

Me
*

poly(formaldehyde)

poly(oxymethylene)

poly(acetaldehyde)

poly(oxyethylidene)

Me
*

H
H
formaldehyde

O *
n
Me

Me
H
acetaldehyde

Me
OH

poly(phenyleneoxide)

Me

Delrin

poly(oxy-2,6-dimethyl1,4-phenylene)

Delrin

Nomenclature of Vinyl Thermoplastics

Structure
*

Monomer

Common Name

IUPAC

Trade Name

Polyethylene

poly(ethylene)

PE

Polypropylene

poly(propylene)

PP

Polyvinyl chloride

poly(1-chloroethylene)

PVC

Polystyrene

poly(1-phenylethylene)

PS

Polymethyl methacrylate

poly(1-(methoxycarbonyl)
-1-methylethylene)

PMMA

Me
*

Me
*

Cl
*

Cl
*

Ph
*

O
Me
*

OMe

CO2Me

Me

Nomenclature of Vinyl Thermoplastics

Structure

Monomer

Common Name

IUPAC

Trade Name

O
HO

Me

Polyvinyl alcohol

poly(1-hydroxyethylene)

Polyvinyl acetate

poly(1-acetoxyethylene)

Polyacrylonitrile

poly(1-cyanoethylene)

PAN

Poly(ethyl cyanoacrylate)

poly(1-cyano-1-(ethoxy
carbonyl)ethylene)

Super glue

Poly(tetrafluoroethylene)

Poly(tetrafluoroethylene)

Teflon

PVA

O
AcO
*

Me

NC
*

CN
*

OEt

NC
*

CO2Et
*

F F
*

CN

FF

Tacticity: How groups are arranged along polymer

Vinyl Monomers

isotactic

syndiotactic

atactic

Isotactic and syndiotactic pack into lattices easier: crystalline

Tacticity: disubstituted monomers

R

Polymer
R

R
R

Polymer
R

isotactic

H
Looksing at indicated atoms from the left

Polymer
R
R

Polymer
H

syndiotactic