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Materials Science of Polymers for Engineers
MSE 460/560 Doug Loy
Physics Chemistry
Processing Properties Applications
Adhesives Barriers
Structural components
Insulation
Major Functions of Polymers
epoxies superglue Polyethylene landfill
Garbage bags Sarah wrap
Polyurethane foam Styrofoam Polyethylene wire coatings Bakelite (phenol-formaldehyde)
PPMA or PC transparent sheets Molded ABS or HIPS
polyesters
polyethylene
COURSE WEBSITE: Loy group website, courses, MSE 460/560 Spring 2010
http://www.loyresearchgroup.com/
http://www.loyresearchgroup.com/mse-460560-polymer-science-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: 650 pts possible Graduates: 750 pts possible
First exam before drop date
Homework
Assignments will be on D2L Not up yet but should be by Monday.
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
Learn:
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 un-
ethical 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
Food Packaging Electronics
Medical Supplies
Construction
Manufactured Goods
PVC
SAN
PES
Transportation PVC
PSty
PVC
PC
Polyester
PP Polyisoprene
Clothing
Nylon
We use a lot of polymers.
1012 bags/year!!
What are polymers?
Poly = many & meros = parts (Greek) Macromolecules = large molecules
H
H
H
H
catalystH Hn
n
A nomenclature exists to describe polymers
polyethylene
ethylene
What are polymers? H
H
H
H
catalystH Hn
n
Chemical Formula: C500H1002Molecular 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
13 0.2
8
0.6
1
Magnesium,Aluminum
Platinum
Silver, Gold
Tantalum
Zinc, Ti
Steel, NiMolybdenum
Graphite
Si crystal
Glass-soda
Concrete
Si nitrideAl oxide
PC
Wood( grain)
AFRE( fibers)*
CFRE*
GFRE*
Glass fibers only
Carbon fibers only
Aramid fibers only
Epoxy only
0.4
0.8
2
46
10
20
406080
100
200
600800
10001200
400
Tin
Cu alloys
Tungsten
Si carbide
Diamond
PTFE
HDPE
LDPE
PP
Polyester
PSPET
CFRE( fibers)*
GFRE( fibers)*
GFRE(|| fibers)*
AFRE(|| fibers)*
CFRE(|| fibers)*
Metals Alloys
Graphite Ceramics Semicond
Polymers Composites
/fibers
E(GPa)
109 Pa
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.
YOUNGS MODULI: COMPARISON
17
Room T values
y(ceramics)>>y(metals) >> y(polymers)
Based on data in Table B4, Callister 6e. a = annealed hr = hot rolled ag = aged cd = cold drawn cw = cold worked qt = quenched & tempered
YIELD STRENGTH: COMPARISON
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 from petra oleum (rock oil)"
Petroleum
Natural gas
Origins: Two Families of Polymers Biological Polymers
Synthetic
* *n
polystyrene
NN
O
O O
O
O **n
polyimide (PI)
*Me CO2Me
*n
polymethylmethacrylate (PMMA)
Men
latex rubber
Me
*
*n
gutta percha
Physical Behavior & Architecture
Thermoplastics
Elastomers
Thermosets Phenolic Resins Melamines epoxies
Synthetic rubbers Poly-cis-isoprene
Polystyrene Polyvinylchloride
Applications/Function
Structural
Coatings
Fibers
Adhesives
NH
N
N
N NH
NH
N
N
N NH
NH HN
O
O O
OOO
Urea-Formaldehyde
O
O*
O
OO*n
Poly(ethylene terephthalate) or PETE
* *
O On
Poly(vinyl acetate) or PVA
NH
*O
*n
Nylon-6
Taxonomy by polymerization mechanism
Chain Growth Mechanism Free radical Anionic Cationic Ring opening
metathesis
Step growth Condensation Metathesis
R
Initiator I
I
Initiation
RI
R RPRP R
Propagation
RP R
R PR
RP R
R PR
Termination
Free radical chain mechanism
Polymer Functionality Vinyl Polymers Polyethers Polyarylenes Polyesters Polyamides Polyureas Polyurethanes Polysiloxanes Polycarbonates Polysulfones Polyimides Polysulfides Fluoropolymers Polyionomers Polyacetylenes
* *
Rn
* R O *n
* R S *n
* *
FnF
F F
R O
O
* *n
**n
R NH
O
* *n
NH
NH
O
R *n
O NH
O
R *n
* SiR R
O *nO O
O
R *n
N
O
O
*N
O
O
*n
S*n
O
OO
* N *n
* *n
Polymer Functionality Vinyl Polymers Polyethers Polyarylenes Polyesters Polyamides Polyureas Polyurethanes Polysiloxanes Polycarbonates Polysulfones Polyimides Polysulfides Fluoropolymers Polyionomers Polyacetylenes
* *
Rn
* R O *n
* R S *n
* *
FnF
F F
R O
O
* *n
**n
R NH
O
* *n
NH
NH
O
R *n
O NH
O
R *n
* SiR R
O *nO O
O
R *n
N
O
O
*N
O
O
*n
S*n
O
OO
* N *n
* *n
Recycling symbols O
O*
O
OO*n
Poly(ethylene terephthalate) or PETE
**n
high density polyethylene
**n
low density polyethylene
**n
polyvinyl chlorideCl
**n
poly(propylene)Me
* *n
polystyrene
Not recyclable
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)
Polypropylene Polyethylene
Polystyrene
Low cost, temp. resistance and strength Good dimensional stability Bonds well Typically, but not always, transparent
Polyvinylchloride
Some History: First there were Bio-Polymers
Animal Hides (Proteins): Fiber & Films Ligaments (Collagen): Hinges Silk Fibers (Protein): Fibers Plant Fibers (Cellulose): Fibers
Yucca-fiber sandals
Bison-Hide teepee
Structural Materials: High Modulus & Strong Wood (Cellulose & Lignin): S Antlers (Keratin): Tools, jewelry & weapons Horn (Keratin): Tools, jewelry & weapons Tusks (enamel & dentin): Tools, jewelry & weapons
Ivory lunar cycle charts
Charles Goodyear (1800 - 1860)
Invented vulcanization of rubber in 1839
Key Figures in Polymer History:
S
SSS S
SS
SS
S
> 140 C
CH2HC C
H2C CH2
CH3
HC CH2C
CH3
CH2HC C
H2C CH2
CH3
HC CCH3
H2C
Poly-cis-isopreneIUPAC: cis-poly(1-methyl-1-butene-1,4-diyl)
Enabled commercialization of natural rubber
Elastomer:
50% of Rubber tires
Latex rubber gloves
Gutta percha (GP), also known as balata, is a natural thermoplastic and is of fundamental importance in the history of the plastics industry.
William Montgomerie (1840s)
Saw usefulness of gutta percha
HH
trans-Polyisoprene or Gutta perchaIUPAC: trans-poly(1-methyl-1-butene-1,4-diyl)
Gutta Percha
Thermoplastic:
Golf ball covers
Wire coating (until 1940s)
History of Polymers Date
1868 1909 1919 1927 1927 1929 1936 1936 1938 1938 1938 1939 1939
Material
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
Example Use
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
1942 1942 1943 1943 1947 1948 1954 1956 1957 1957 1964 1964
Material
Polyester Polyethylene Fluorocarbon Silicone Epoxy Acrylonitrile-Butadiene-Styrene Polyurethane or Urethane Acetal Polypropylene Polycarbonate Ionomer Polyimide
Example Use
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 Common Name IUPAC Trade name
cis-poly(1-methyl-1-butene-1,4-diyl)* *n cis-Polyisoprene latex
poly(1-chloro-1-butene-1,4-diyl)*Cl
*n Polychloroprene
ClNeoprene
*Me Me
*n
Me
Mepoly(1,1-dimethyl-ethene-1,2-diyl)Polyisobutylene Butyl Rubber
b cPolystyrene-block-poly-1,4-butadiene-block-polystyrenea
Block-copolymer[styrene-butadiene-styrene]
SBS
Block Copolymers
Alternating Copolymers
Ph
CO2Me Poly[styrene-alt-(methyl methacrylate)]CN
*Ph Me CO2Me
Alt-copoly[styrene/methyl methacrylate]
Alternating Copolymers
PhPoly[styrene-alt-(acrylonitrile)-alt-(vinylidene dichloride)]
CN*
Ph NCAlt-copoly[styrene/acrylonitrile/vinylidene dichloride]
Cl ClCl
Cl
Alternating Copolymers
Block Copolymers
Ph
Poly[methyl acrylate-block-(poly(maleic anhydride)-alt-styrene)]
CO2Me*MeO2C NC Block-copoly[alt-co(styrene/maleic anhydride)methyl acrylate]
Cl Cl
OO O
Block & Alternating Copolymer
Nomenclature of Thermoplastics
NH
*O
*n
Nylon-6
HO
ONH2
NH
O
6-aminohexanoic acid
azepan-2-oneor caprolactam
polycaprolactam
poly(6-hexanomide)poly(imino(1-oxohexamethylene))
Structure Monomer Common Name IUPAC Trade name
O *O
*n
O
O
polycaprolactone poly(oxy(1-oxohexamethylene))
HO2C CO2H
HOOH
OO
O* O*n
poly(ethylene terephthalate) Poly(oxyethylene-oxyterephthaloyl)PETE
Nomenclature of Polyether Thermoplastics
Structure Monomer Common Name IUPAC
polyethyleneoxide polyoxyethyleneO
* O *nethylene oxideor oxirane
* O *n HO OH poly(ethylene glycol) polyoxyethylene
O ** nO poly(tetrahydrofuran) poly(oxytetramethylene)
* O *Me n
O
Mepropylene oxide
poly(propylene-oxide) poly(oxy(1-methylethylene)
tetrahydrofuran
ethylene glycol
PEG
Nomenclature of Polyether Thermoplastics
Structure Monomer Common Name IUPAC
* O * H H
O
nformaldehyde
poly(formaldehyde) poly(oxymethylene)
* O * Me H
O
nacetaldehyde
poly(acetaldehyde) poly(oxyethylidene)Me
O **
Me
Men
OH
Me
Me
poly(phenyleneoxide) poly(oxy-2,6-dimethyl-1,4-phenylene)
Delrin
Delrin
Nomenclature of Vinyl Thermoplastics
Structure Monomer Common Name IUPAC Trade Name
* *npoly(ethylene)Polyethylene PE
* *npoly(propylene)Polypropylene
Me MePP
* *npoly(1-chloroethylene)Polyvinyl chloride
Cl ClPVC
* *npoly(1-phenylethylene)Polystyrene
PhPS
* *npoly(1-(methoxycarbonyl)-1-methylethylene)
Polymethyl methacrylateCO2Me PMMA
MeO
OMe
Me
Nomenclature of Vinyl Thermoplastics Structure Monomer Common Name IUPAC Trade Name
* *npoly(1-hydroxyethylene)Polyvinyl alcohol PVA
* *npoly(1-acetoxyethylene)Polyvinyl acetate
AcO
* *npoly(1-cyanoethylene)Polyacrylonitrile
NC CNPAN
* *npoly(1-cyano-1-(ethoxycarbonyl)ethylene)
Poly(ethyl cyanoacrylate)CO2Et Super glue
* *nPoly(tetrafluoroethylene)
FTeflon
F
F
HO O
O
Me
O
O
Me
NCO OEt
CN
F
F F
F
FPoly(tetrafluoroethylene)
Tacticity: How groups are arranged along polymer
R R R R R R R R R RR
isotactic
R R R R R R R R R RR
syndiotactic
Vinyl Monomers
R R R R R R R R R RR
atactic
Isotactic and syndiotactic pack into lattices easier: crystalline
Tacticity: disubstituted monomers
R R R R R R R R R R
R R R R R R R R RR
R
R R R R R R R R R R
R R R R R R R R R
RR
isotactic
syndiotactic
H
Polymer
R
H
Polymer
R
Looksing at indicated atoms from the left
H
Polymer
R
R
Polymer
H
