Materials Science of Polymers for Engineers

MSE 460/560

Doug LoyPhysics

Chemistry

ProcessingPropertiesApplications

Adhesives Barriers

Structural components

Insulation

Major Functions of Polymers

epoxies

supergluePolyethylene landfillGarbage bagsSarah wrap

Polyurethane foamStyrofoamPolyethylene wire coatingsBakelite (phenol-formaldehyde)

PPMA or PC transparent sheetsMolded 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 1by 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 scoreUndergraduates: 650 pts possibleGraduates: 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).• Don’t cheat, plagiarize, or otherwise participate in un-

ethical 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 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

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

FoodPackaging Electronics

Medical Supplies

Construction

ManufacturedGoods

PVC

SAN

PES

TransportationPVC

PSty

PVC

PC

Polyester

PPPolyisoprene

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

0.280.61Magnesium,AluminumPlatinumSilver, GoldTantalumZinc, TiSteel, NiMolybdenumGraphiteSi crystalGlass-sodaConcreteSi nitrideAl oxidePCWood( grain)AFRE( fibers)*CFRE*GFRE*Glass fibers onlyCarbon fibers onlyAramid fibers onlyEpoxy only0.40.8246102040608010020060080010001200400TinCu alloysTungsten<100><111>Si carbideDiamondPTFEHDPELDPEPPPolyesterPSPETCFRE( fibers)*GFRE( fibers)*GFRE(|| fibers)*AFRE(|| fibers)*CFRE(|| fibers)*

MetalsAlloys

GraphiteCeramicsSemicond

PolymersComposites/fibers

E(GPa)

Eceramics> Emetals>> Epolymers

109 Pa

Based on data in Table B2,Callister 6e.Composite data based onreinforced epoxy with 60 vol%of alignedcarbon (CFRE),aramid (AFRE), orglass (GFRE)fibers.

YOUNG’S MODULI: COMPARISON

17

Room T values

σ ( )y ceramics>>σ ( )y metals >> σ ( )y polymers

Based on data in Table B4,Callister 6e.a = annealedhr = hot rolledag = agedcd = cold drawncw = cold workedqt = 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)

Me

n

latex rubber

Me

*

*n

gutta percha

Physical Behavior & Architecture

• Thermoplastics

• Elastomers

• Thermosets

Phenolic ResinsMelaminesepoxies

Synthetic rubbersPoly-cis-isoprene

PolystyrenePolyvinylchloride

Source: R. Esfand, D.A. Tomalia, A.E. Beezer, J.C. Mitchell, M. Hardy, C. Orford,Source: R. Esfand, D.A. Tomalia, A.E. Beezer, J.C. Mitchell, M. Hardy, C. Orford,Polymer Preprints, Polymer Preprints, 41 41 (2), 1324 (2000) (2), 1324 (2000)

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

**

OO

n

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 FunctionalityVinyl 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

*Si

R R

O*

nO O

O

R *n

N

O

O

*N

O

O

*

n

S*n

O

O

O

* N *n

**n

Polymer FunctionalityVinyl 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

*Si

R R

O*

nO O

O

R *n

N

O

O

*N

O

O

*

n

S*n

O

O

O

* N *n

**n

Recycling symbolsO

O*

O

OO

*n

Poly(ethylene terephthalate) or PETE

**

nhigh density polyethylene

**

nlow density polyethylene

**

n

polyvinyl chloride

Cl

**

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)

PolypropylenePolyethylene

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 & FilmsLigaments (Collagen): HingesSilk Fibers (Protein): FibersPlant Fibers (Cellulose): Fibers

Yucca-fiber sandals

Bison-Hide teepee

Structural Materials: High Modulus & StrongWood (Cellulose & Lignin): SAntlers (Keratin): Tools, jewelry & weaponsHorn (Keratin): Tools, jewelry & weaponsTusks (enamel & dentin): Tools, jewelry & weapons

Ivory lunar cycle charts

Charles Goodyear(1800 - 1860)

Invented vulcanizationof rubber in 1839

Key Figures in Polymer History:

S

SS

S SSS

SS

S

> 140 °C

CH2

HC C

H2C CH2

CH3

HC C

H2C

CH3

CH2

HC C

H2C CH2

CH3

HC C

CH3

H2C

Poly-cis-isoprene

IUPAC: 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 (1840’s)

Saw usefulness of gutta percha

HH

trans-Polyisoprene or Gutta percha

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

Gutta Percha

Thermoplastic:

Golf ball covers

Wire coating (until 1940’s)

History of PolymersDate

1868190919191927192719291936193619381938193819391939

Material

Cellulose NitratePhenol-FormaldehydeCaseinCellulose AcetatePolyvinyl ChlorideUrea-FormaldehydeAcrylicPolyvinyl AcetatePolystyrene or StyreneNylon (Polyamide)Polyvinyl ButyratePolyvinylidene ChlorideMelamine-Formaldehyde

Example Use

FigurinesElectrical equipmentBeauty accessoriesCellophane package wrapping Pipe, Synthetic LeatherLighting fixtures, Plywood glueBrush backs, displaysSynthetic flooringDisposable utensils HosierySafety glass interlayerSaran wrapCountertops, Cabinets

History of Polymers

Date

194219421943194319471948195419561957195719641964

Material

PolyesterPolyethyleneFluorocarbonSiliconeEpoxyAcrylonitrile-Butadiene-StyrenePolyurethane or UrethaneAcetalPolypropylenePolycarbonateIonomerPolyimide

Example Use

Clothing, Boat hullsMilk JugsIndustrial gaskets, Non-stick linersGaskets, Tubing, UtensilsGluesLuggageFoam cushions, Shoe soles, WheelsAutomotive parts, Toilet partsLiving hinges, Safety helmetsWater bottles, Eye protectionGolf balls, Skin packagesGears

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 PolychloropreneCl

Neoprene

*

Me Me

*n

Me

Me

poly(1,1-dimethyl-ethene-1,2-diyl)Polyisobutylene Butyl Rubber

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

a

Block-copolymer[styrene-butadiene-styrene]

SBS

Block Copolymers

Alternating Copolymers

Ph

CO2MePoly[styrene-alt-(methyl methacrylate)]

CN

*

Ph Me CO2Me

Alt-copoly[styrene/methyl methacrylate]

Alternating Copolymers

Ph

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

*

Ph NC

Alt-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

*n

ethylene oxideor oxirane

*O

*n

HOOH poly(ethylene glycol) polyoxyethylene

O** n

Opoly(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

* *n

poly(ethylene)Polyethylene PE

* *n

poly(propylene)PolypropyleneMe Me

PP

* *n

poly(1-chloroethylene)Polyvinyl chlorideCl Cl

PVC

* *n

poly(1-phenylethylene)PolystyrenePh

PS

* *n

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

Polymethyl methacrylateCO2Me

PMMAMe

OOMe

Me

Nomenclature of Vinyl Thermoplastics Structure Monomer Common Name IUPAC Trade Name

* *n

poly(1-hydroxyethylene)Polyvinyl alcohol PVA

* *n

poly(1-acetoxyethylene)Polyvinyl acetateAcO

* *n

poly(1-cyanoethylene)PolyacrylonitrileNC CN

PAN

* *n

poly(1-cyano-1-(ethoxycarbonyl)ethylene)

Poly(ethyl cyanoacrylate)CO2Et

Super glue

* *n

Poly(tetrafluoroethylene)F

Teflon

F

F

HO O

O

Me

O

O

Me

NC

O 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