Lecture1 - Polymer Physics Polymer Overview – Lecture...

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Unformatted text preview: Polymer Physics Polymer Overview – Lecture Notes 1 Lecture 1 Dr. Anthony Brennan University of Florida Department of Materials Science & Department Engineering Engineering EMA 6165 Polymer Physics – AB Brennan 8/2008 1 Syllabus and Schedule Syllabus • • • • • • Syllabus Schedule Proposal UF Honesty Policy Turn-it In Program Turn-it Course Webpage – http://brennan.mse.ufl.edu/ema6165_new.html • Questions? EMA 6165 Polymer Physics – AB Brennan 8/2008 2 Agenda Agenda • • • • Introduction – Chapter 1 Definitions/Nomenclature Configurational States Structure/Property Structure/Property Relationships Relationships • Polymer Classifications • Molar Mass Distribution • Thermal Transitions (General) EMA 6165 Polymer Physics – AB Brennan 8/2008 3 Properties Properties • • • • • Chemical Physical Electronic Magnetic Optical CERAMICS METALS PROPERTIES ELECTRONIC MATERIALS EMA 6165 Polymer Physics – AB Brennan 8/2008 POLYMERS 4 Polymer Polymer • macromolecules macromolecules formed by combining large numbers of low molar mass molecules molecules • molar mass molar exceeds 10 kg/mol for reasonable properties properties EMA 6165 Polymer Physics – AB Brennan 8/2008 5 Vocabulary Vocabulary • Polymer • Chain Structure – monomer (repeat unit) – oligomers – Bond energies • Reactions – Condensation Condensation Polymerization Polymerization – Addition Polymerization – Chain Growth • Structure – – – Thermoplastics Thermosets Elastomers – – – – – Homopolymer Copolymer Branching Stereoregular Isomeric • Molar Mass – Number, Weight Ave – Degree of polymerization Degree (DP) (DP) – Polydispersity (PDI) Refer to Table 2.7 – Intro to Polymer Sci Refer – 4th Ed, L. H. Sperling, Wiley & Sons, 2006 Sons, EMA 6165 Polymer Physics – AB Brennan 8/2008 6 Polymer Chain Structure Polymer • linear chain – homopolymer – random copolymer • branched chain – homopolymer – copolymer • block copolymer block – AAAAABBBBB • • • star polymer comb graft chain – copolymer EMA 6165 Polymer Physics – AB Brennan 8/2008 7 Polymer Chain Composition Polymer • homopolymer – condensation • AA + BB • AB – addition •A • copolymer – random – alternating – block – graft EMA 6165 Polymer Physics – AB Brennan 8/2008 8 General Classification of Polymers Polymers • • • • • Thermoplastic Thermoset Rubber Elastomers Natural Natural Macromolecules Macromolecules EMA 6165 Polymer Physics – AB Brennan 8/2008 9 Thermoplastic vs. Thermoset Thermoplastic • Thermoplastic – can be formed with can heat/pressure/time heat/pressure/time – recyclable – crystalline or noncrystalline • Thermoset – can be formed with can heat/pressure/time once once – not recyclable! EMA 6165 Polymer Physics – AB Brennan 8/2008 10 Rubber and Elastomers Rubber • Rubber • Elastomers – butadiene, butadiene, isoprene isoprene – cross linked cross structure structure – high strength – high recovery – Thermoplastic – Thermoset – lightly cross lightly linked linked – high elongation high (>400%) (>400%) EMA 6165 Polymer Physics – AB Brennan 8/2008 11 Importance of Chemistry Importance Protein Tertiary Structure Conformational Structure Random Confirmation - Dilute Lamellar Configuration - Secondary Helical Configuration - Tertiary EMA 6165 Polymer Physics – AB Brennan 8/2008 12 Importance of Chemistry Importance • Balance of Three Energies – Intermolecular – Intramolecular – Thermal (kT) • Structures – Linear – Branched EMA 6165 Polymer Physics – AB Brennan 8/2008 13 Polymer Physics Polymer Overview – Lecture Notes 1 Lecture 2 Dr. Anthony Brennan University of Florida Department of Materials Science & Department Engineering Engineering EMA 6165 Polymer Physics – AB Brennan 8/2008 14 Characteristic Bonds Characteristic EMA 6165 Polymer Physics – AB Brennan 8/2008 15 CH3 CH3 CH3 CH3 CH3 CH3 Si Si Si Si Si Si O H3C H3C O H3C O H3C O H3C O H3C O n Tg = ­123C, Tm = ­60C H H H H H C H H n C C H H H C C H H H C C H H C C H H C H H C H H C H H H Tg = ­120C; Tm = 140C EMA 6165 Polymer Physics – AB Brennan 8/2008 EMA 16 H H H H H C H H H H n C C H H C C H H C C H H C C H H C H H C H C H H H H Tg = ­120C; Tm = 140C H H N H H H H H C C C C C C H H H H H H H H N C O Tg = 55C; Tm = 265C EMA 6165 Polymer Physics – AB Brennan 8/2008 EMA H H H C C C C H H H H O C n 17 H H N H H H H H C C C C C C H H H H H H H H N C O H H H C C C C H H H H O C Tg = 55C; Tm = 265C n H H N N O C C O n EMA 6165 Polymer Physics – AB Brennan 8/2008 EMA 18 Polymer Physics Polymer Overview – Lecture Notes 1 Lecture 3 Dr. Anthony Brennan University of Florida Department of Materials Science & Department Engineering Engineering EMA 6165 Polymer Physics – AB Brennan 8/2008 19 Isomerism – "Isomers" Isomerism • The same chemistry, but different The architecture, i.e., arrangement of atoms architecture, • Types of Isomers – Optical (Chem Draw – alanine) – Stereo – Geometric – Substitutional Substitutional EMA 6165 Polymer Physics – AB Brennan 8/2008 EMA 20 Configuration - Symmetry Configuration Chem Draw Pro: Isobutane EMA 6165 Polymer Physics – AB Brennan 8/2008 21 Asymmetry – 2,4-dimethyl pentane pentane file: 2,4-dimethylpentane EMA 6165 Polymer Physics – AB Brennan 8/2008 22 Optical Isomers – Amino Acids:Alanine Optical Chiral Center EMA 6165 Polymer Physics – AB Brennan 8/2008 23 Configurational States Configurational • Configuration Configuration permanent stereostructure. Rearrangement requires bond disruption. disruption. • Tacticity – Isotactic – Syndiotactic – Atactic EMA 6165 Polymer Physics – AB Brennan 8/2008 24 Configurational States Configurational • Configuration Configuration permanent stereostructure. Rearrangement requires bond disruption. disruption. • Tacticity – Isotactic – Syndiotactic – Atactic EMA 6165 Polymer Physics – AB Brennan 8/2008 25 Configurational States Configurational • Configuration Configuration permanent stereostructure. Rearrangement requires bond disruption. disruption. • Tacticity – Isotactic – Syndiotactic – Atactic EMA 6165 Polymer Physics – AB Brennan 8/2008 26 Stereochemistry • Optical – Polypropylene Polypropylene oxide oxide • Geometric isomers Geometric (dienes) (dienes) • Stereoisomers – poly(1,2- butadiene) – – – Isotactic Syndiotactic Atactic • syndio, iso, atactic – poly(2,3- butadiene) • cis & trans – Head to Head – Head to Tail EMA 6165 Polymer Physics – AB Brennan 8/2008 27 Chain architecture Chain "Branched" or "graft“ Blend A A B Block or triblock EMA 6165 Polymer Physics – AB Brennan 8/2008 Net 28 Copolymer Chain Terminology Copolymer Unknown/specified -co- poly (A-co-B) Statistical -stat- poly(A-stat-B) Random -rand- poly(A-rand-B) Alternating -alter- poly(A-alter-B) Block -block- poly(A-block-B) Graft -graft- poly(A-graft-B) Star -star- poly(A-star-B) Blend -blend- poly(A-blend-B) Cross-linked -net- poly(A-net-B) Interpenetrating -inter- poly(A-inter-B) EMA 6165 Polymer Physics – AB Brennan 8/2008 Adapted from Intro Phys Poly Sci-Sperling, 4th Ed, Wiley & Sons 29 Importance of Chemistry Importance • Copolymers – – – – • Molar Mass – – – – – Random Block Graft Star • Ionomers – Telechelic – Polyelectrolytes Distribution Viscosity Creep Stability Processability • Networks – Irreversible – Reversible EMA 6165 Polymer Physics – AB Brennan 8/2008 30 Polymer Physics Polymer Overview – Lecture Notes 1 Lecture 4 Dr. Anthony Brennan University of Florida Department of Materials Science & Department Engineering Engineering EMA 6165 Polymer Physics – AB Brennan 8/2008 31 Synthetic Processes Synthetic • • • • Condensation Addition Chain Growth Anionic/Cationic EMA 6165 Polymer Physics – AB Brennan 8/2008 32 Polymerizations Polymerizations O C + C H O OC H3 H3CO H H O C C O H HH Condensation Condensation polymerization polymerization Loss of low molar Loss mass molecule(s) mass e.g. Polyethyethylene e.g. Terephthalate (PET) Terephthalate Catalyst O O C C O + H H H H Addition Addition polymerization polymerization C H3OH R C CC n C H2 O C H2 C C C C C C C radical reaction e.g. Polyethylene (PE) n-3 EMA 6165 Polymer Physics – AB Brennan 8/2008 33 Condensation Polymerization Condensation Step Growth Process • • • • • Monomer + Monomer Monomer Monomer + Dimer Monomer + Trimer Dimer + Trimer n-Mer + m-Mer EMA 6165 Polymer Physics – AB Brennan 8/2008 Dimer Dimer Trimer Tetramer Pentamer (n + m) Mer 34 Characteristics Characteristics • Condensation Condensation polymerization polymerization – stepwise reaction – monomer monomer consummed early consummed – DP rises steadily DP rises – long reaction time long gives high molar mass – PDI ~ 2 mass – monomers, dimers, monomers, trimers, etc. present trimers, – reaction by products • Addition Addition polymerization polymerization – chain reaction – one group added per one reaction reaction – DP peaks instantly – long reaction time long gives high conversion – PDI ~40 conversion – only polymer and only monomer present monomer – no reaction by no products products EMA 6165 Polymer Physics – AB Brennan 8/2008 35 Condensation Polymers Condensation • Lexan - poly(bisphenol A carbonate) • Mylar, Dacron - poly(ethylene Mylar, terephthalate) terephthalate) • Nylons - polyamides • Kevlar, Nomex - poly(arylamide) • Kapton - (polyimide) EMA 6165 Polymer Physics – AB Brennan 8/2008 36 Condensation Polymers Condensation • Nylon 6,6 – A-A Monomer: adipic acid – B-B Monomer: 1,6 hexane diamine – A Monomer: End group – B Monomer: EMA 6165 Polymer Physics – AB Brennan 8/2008 37 Condensation Polymers Condensation • Poly(bis phenol A carbonate) – A-A Monomer: Bis phenol A – B-B Monomer: phosgene – A Monomer: End group O CH3 HO C OH + Cl C Cl CH3 O CH3 O C O CH3 EMA 6165 Polymer Physics – AB Brennan 8/2008 C n 38 Condensation Polymers Condensation • Kevlar – A-A Monomer: HOOC • terephthalic acid COOH – B-B Monomer: • p-phenylene diamine COOH – A Monomer: Monomer: HOOC • End group • Nomex – A-A Monomer: • isophthalic acid O H N O C N H EMA 6165 Polymer Physics – AB Brennan 8/2008 C n 39 Chain Growth Polymer Chain • Nylon 6 – A-A Monomer: caprolactam – A Monomer: – B Monomer: EMA 6165 Polymer Physics – AB Brennan 8/2008 40 Addition Polymerizations Addition • • • Initiation Propagation Termination – combination – disproportionation EMA 6165 Polymer Physics – AB Brennan 8/2008 41 Addition Polymerization Addition Y+I 1 R 2 Y + * C 3 Y H C C* * H H R Y C Y H R H Y 5 2 Y H CC C C* H n H HH RH Y R HH 2 H R H CC C C* HH H n H H R H CC C C* HH C RH 4 H RH H H H C C* H C + R H H RH Y H H R HR CC C C C C CC H H H H HH RH Y R R H H R HR CC C C +H C C CC HH H n H H H HH n EMA 6165 Polymer Physics – AB Brennan 8/2008 Y n Y 42 Addition Polymers Addition • polyethylene (PE, polyethylene HDPE, LDPE, LLPE) LLPE) • polystyrene • polypropylene • polyacrylamide • polyacrylate, polyacrylate, polyacrylic acid, polymethyl methacrylate methacrylate • • • • • polybutadiene polyisoprene polybutene polyvinylchloride polytetrafluoroethy lene (Teflon) • polyethylene-copropylene-cobutadiene (EPDM) EMA 6165 Polymer Physics – AB Brennan 8/2008 43 Polymerization Processes Polymerization • • • • • • Solution Bulk Emulsion Suspension Interfacial Supercritical EMA 6165 Polymer Physics – AB Brennan 8/2008 44 Summary Summary • Thermoplastics, thermosets and Thermoplastics, elastomers elastomers • Condensation, addition, chain growth, Condensation, and ionic and • Condensation kinetics slow • Condensation polydispersity is high • Addition polymers exhibit Addition stereisomerism stereisomerism • Composition control is critical EMA 6165 Polymer Physics – AB Brennan 8/2008 45 Additional References Additional • Macromolecules, An Introduction to Macromolecules, Polymer Science, F. A. Bovey, F.H. Winslow, ed, Academic Press (1979) ISBN 0-121-19755-7 ISBN • Fundamental Principles of Polymeric Fundamental Materials, 2nd Edition, Stephen L. Rosen, Wiley Interscience (1993) ISBN 0-471-57525-9 0-471-57525-9 • Polymer Science and Technology, Joel Polymer R. Fried, Prentice Hall PTR (1995) ISBN EMA 6165 Polymer Physics – AB Brennan 8/2008 EMA 46 ...
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