Materials Science of Polymers
for Engineers
MSE 460/560
Doug Loy
Chemistry
Physics
Applications
Properties
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
http://www.loyresearchgroup.com/
http://www.loyresearchgroup.com/mse-460560-polymerscience-for-engineers.html
Office Hours
• Old Chemistry 309
• M 12-1 pm, W 7 F 2-3 pm
• or by appointment
Textbook:
Yes, you will need it.
Read Chapter 1
Grading
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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.
Course Objectives
1) Recognize (structure and acronym) and name commodity thermoplastics: acrylics, polystyrene,
ABS, PVC, PETG, CAB, HDPE, LDPE, PP, poly(methylpentane), polyvinyl alcohol, polyvinyl
acetate
2) Recognize (structure and acronym) and name engineering thermoplastics: polycarbonate,
polyphenylene oxide, thermoplastic urethane, nylons, acetal, PET, PBT, UHMW-PE, PEG, PPG
3) Recognize (structure and acronym) and name high performance thermoplastics: polysulfones,
polyetherimide, polyvinylidene fluoride, teflon, polyphenylene sulfide, PEEK
4) Recognize (structure and acronym) and name imide thermoplastics: PI, PBI, PAI
5) Recognize and name thermosets: epoxies, polyesters, acrylics
6) Recognize and name elastomers: diene polymers, fluoro elastomers, polysiloxanes
7) Know how to identify polymers in field or in lab.
8) Know how to characterize polymer molecular weight and how it affects properties
9) Know how to characterize thermomechanical properties
10) Know the phase behavior of polymers (glass transition temperature, melting point) and how
mechanical properties change
11) Know degradation pathways and propensities of major polymer types
12) Understand polymer solubility as a function of molecular weight, crosslinking and crystallinity.
13) Understand polymer-polymer phase segregation and how it can be used to make superior
materials.
14) Understand the origins of adhesive properties of polymers.
15) Understand how to measure the mechanical properties of polymers and how they compare to
other materials (including some idea of the properties of classes of polymers and common
polymers).
16) Understand the advantages and disadvantages of using polymers.
17) Understand how polymers are processed and shaped.
18) Understand time dependent processes in polymers.
How to succeed in MSE 460/560
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Read the Chapter ahead of lectures
Come to class
Start paper early
Study groups
Practice exams (new ones will be written).
Don’t cheat, plagiarize, or otherwise participate in unethical behavior
• Use office hours
• Ask questions
• Think skeptically
Thinking skeptically
• Don’t trust anyone (particularly
anyone over 30)
• If it doesn’t 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
• Literature search
• One draft due during semester
• You will edit each others drafts (for HWK assign)
Research Paper Topics & Assignments
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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
Today’s 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
H
n
H
catalyst
H
H
H
H
n
polyethylene
ethylene
A nomenclature exists to describe polymers
What are polymers?
H
n
H
catalyst
H
H
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 ®
YOUNG’S 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
O
* N
n
O
N
O
*
n
O
Me
polyimide (PI)
latex rubber
*
n
*
Me
*
n
*
polystyrene
gutta percha
*
Me
*
n
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
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
N
O
N
H
N
H
O
N
N
O
N
N
NH
HN
Urea-Formaldehyde
O
N
H
Taxonomy by polymerization mechanism
Chain Growth Mechanism
•Free radical
•Anionic
•Cationic
•Ring opening
metathesis
Initiation
I
Initiator
I
R
I
R
R
R
Propagation
P
Step growth
•Condensation
•Metathesis
P
R
R
Termination
R
P
R
R
R
R
P
P
R
R
Free radical chain mechanism
R
P
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
n
O
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
O *
n
O
n
*
O
N
N *
n
* R S *
n
O
F F
*
F
F
O
*
n
*
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
n
O
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
O *
n
O
n
*
O
N
N *
n
* R S *
n
O
F F
*
F
F
O
*
n
*
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 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
C
CH2 H2C
HC
CH2 H2C
HC
C
CH2 H2C
C
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
H
H
trans-Polyisoprene or Gutta percha
IUPAC: trans-poly(1-methyl-1-butene-1,4-diyl)
William Montgomerie (1840’s)
Saw usefulness
of gutta percha
Thermoplastic:
Golf ball covers
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
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
*
*
n
Cl
Me Me
*
Common Name
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
Polyisobutylene
*
n
Me
Block Copolymers
a
Polystyrene-block-poly-1,4-butadiene-block-polystyrene
b
c
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
O
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
O
*
O
O
*
n
O
polycaprolactone
HO2C
O
CO2H
*
* O
O
poly(oxy(1-oxohexamethylene))
poly(ethylene terephthalate)
n
HO
OH
Poly(oxyethylene
-oxyterephthaloyl)
PETE
Nomenclature of Polyether Thermoplastics
Structure
Monomer
IUPAC
O
O
*
Common Name
*
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
*
O
*
n
tetrahydrofuran
O
*
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)
O
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
n
Me
*
Me
*
n
Cl
*
Cl
*
n
Ph
*
*
n
O
Me
*
OMe
CO2Me
*
n
Me
Nomenclature of Vinyl Thermoplastics
Structure
Monomer
Common Name
IUPAC
Trade Name
O
HO
O
*
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
n
O
AcO
*
O
Me
*
n
NC
*
CN
*
n
O
OEt
NC
*
CO2Et
*
n
F F
*
CN
F
F
*
FF
n
F
F
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
R
R
R
R
R
R
syndiotactic
R
R
R
R
R
atactic
Isotactic and syndiotactic pack into lattices easier: crystalline
Tacticity: disubstituted monomers
R
H
Polymer
R
R
R
R
R
R
R
R
Polymer
R
R
R
R
R
R
R
R
R
R
R
R
R
R
isotactic
H
Looksing at indicated atoms from the left
R
H
Polymer
R
R
R
R
R
R
R
R
R
R
R
R
Polymer
H
R
syndiotactic
R
R
R
R
R
R
R
R
R