ChE 4285 - PRINCIPLES OF HIGH POLYMERS - Fall Semester 2007
Prerequisite: ChE 3101 (Fluids) and Chem 4491 (Phys. Chem.) or equals.
Catalog Statement: Solution and solid-state properties of high polymers; microstructure of polymer chains and effect on macromolecular physical properties of the final plastics.
Textbook: No single text, see below. Reference: Handouts given in class; reference websites given below or in class. All materials posted to APPS Drive (“Dooley”); some also to my webpage at: http://www.che.lsu.edu/faculty/dooley/polymers_class.htm .
Instructors: Kerry Dooley (with help from Paul Russo). We meet jointly with CHEM 4010, in 208 Williams, for certain classes designated in advance.
Grading: Undergrad. Grad. Homework 0.20 0.30 (half homework, half project) Mid-Term 0.30 0.25 Final Exam 0.50 0.45 TOTAL 1.00 1.00
Course Grade: A - 75-100 B - 55-75 C - 40-55 D - 20-40 F - 0-20
The grading scale is absolute. If at the end of the Semester you are "borderline" at C/B, etc., I will decide which side of the line you fall based on homework/project performance.
Homeworks: Due dates given when homework assigned. No late homeworks accepted.
Office Hours: 3:30-6:00 pm, Monday and Thursday. If you find me in my office (Dooley) at other times with the door open, I am available.
Office (Dooley) - Room 262, Chemical Engineering, Ph. 578-3063; e-mail – [email protected] .
COURSE OUTLINE GOOD WEBSITES (see below)
(This is only an approximate order; some shuffling necessary to work out logistics with CHEM 4010.)
1. Intro. Bonding and Structure 4, 6, 7, 10
2. Polymer Molecular Weights, Distributions 4, 6, 12, 15
3. Thermo. of Solutions 2, 10, 18
4. Chain Growth (Addition) Polymerizations 7, 10-12, 15
5. Step Polymerization 7, 10, 12, 15
6. Ionic, Coordination, and Copolymerizations 2, 10, 12
7. Reactor Design - Polymerization 2, 4, 10, 12
8. Blends, liquid crystals, complex phase diagrams 2, 8, 11, 18
9. Measurement of Molecular Weight, Viscosity 2, 4, 10, 11, 15
10. Glassy and Crystalline States 2-4, 11 , 15, 18
11. Rheology and Processing 1, 10, 16
12. Rubbery State and Melts 2-4, 11
13. Viscoelasticity and Mechanical Properties 1-4, 11 , 15
14. Biopolymers 8, 17
14. Thermal, Electrical and Ultimate Properties 3-6
15. Composite Materials 3, 5-6
Polymers Source Books – Check one out.
Physical Chemistry and General
“Introduction to Physical Polymer Science” – L.H. Sperling (2001, 1992) – QD381.S365.
“Polymer Science and Technology” – J.R. Fried (2003, 1995) - QD381 .F73
“The science of polymer molecules : an introduction concerning the synthesis, structure and properties of the individual molecules that constitute polymeric materials” – R.H. Boyd (1993) - QD139 .P6 B69
“An introduction to plastics” – H.-G. Elias (2003) - TP1120 .E45
“Seymour/Carraher’s Polymer Chemistry” – R.B. Seymour and C.E. Carraher, Jr. (2000, 1992) - QD381 .S483
“Polymer chemistry : introduction to an indispensable science” – D.M. Teegarden (2004) - QD381 .T42
“Fundamentals of polymer science : an introductory text” – P.C. Painter (1994) - QD381 .P34
“Structure-Solubility Relationships in Polymers” – R.B. Seymour and C.E. Carraher Jr. (2000) – QD381.8S76
“Principles of Polymer Systems” – F. Rodriguez (1996) – TP156 .P6 R62
“Textbook of Polymer Science” – F.W. Billmeyer, Jr. – (1984) - QD381 .B52
“Polymer chemistry: the basic concepts” - P.C. Hiemenz (1984) - QD381 .H52
"An Introduction to Physical Properties of Large Molecules in Solution" - E.G. Richards, Cambridge, 1980.
Kinetics and Reactor Design (specialized)
“Polymerization Process Modeling” – N.A. Dotson et al. (1996) – TP156.P6.P6187 – the best, also the most challenging
“Handbook of polymer reaction engineering” – T. Meyer and J. Keurentjes (2005) - TP156 .P6 H36
“Reactive Extrusion” – M. Xanthos (1992) – TP117E9R42
"Chemical Reactor Analysis and Design" - G.F. Froment and K.B. Bischoff, Wiley, 1979.
"Chemical Reactor Design" - E.B. Nauman, Wiley, 1987.
Materials Science (specialized)
“Polymer matrix composites : materials, properties (Composite Materials Handbook)” – ASTM (2002) - TA418.9 .C6 P647
“Handbook of advanced electronic and photonic materials and devices” – H.S. Nalwa, Ed. (2001) – v.3. High Tc superconductors and organic conductors ; v.5. Chalcogenide glasses and sol-gel materials; v.6. Nanostructured materials; v.7. Liquid crystals, display and laser materials; v.8. Conducting polymers; v.9. Nonlinear optical materials; v.10. Light-emitting diodes, lithium batteries and polymer devices. - TK 7871 H358 (reference)
“Fundamental Principles of Polymeric Materials” – S.L. Rosen (1993) - TA455.P58.R63
“Thermal and electrical conductivity of polymer materials” – U.K. Godovskii and V.P. Privalko, Eds. (1995) - QD281 .P6 F6 119
“Compounding materials for the polymer industries : a concise guide to polymers, rubbers, adhesives, and coatings’ – J.S. Dick (1987) - TP 1142 D53
“Polymer products : design, materials, and processing” - D.H. Morton-Jones and J.W. Ellis (1986) - TA455.P58 M64
“Analysis of Polymers: An Introduction” – T.R. Crompton (1989) – TP1140.C75 and .C76
“Chemical Microstructure of Polymer Chains” – J.L. Koenig (1980) – QD381K595
Rheology and Processing (specialized)
“Polymer and composite rheology” (Plastics Engineering, v.58) – R.K. Gupta (2002) - TA455 .P58 G88 (also electronic) – must be good, by fellow U. of D. grad.
“Physical chemistry of polymer rheology” – J. Furukawa (2003) - TP1120 .F87
“Engineering rheology” – R.I. Tanner (2000, 1985) - TP156 .R45 .T36
“The structure and rheology of complex fluids” – R.G. Larson (1999) - QD549.2 .C66 L37 – for the more mathematically inclined.
“Polymer processing : principles and design” – D.G. Baird (1998) - TP1180 .T5 B26
“Extrusion : the definitive processing guide and handbook” – H.F. Giles Jr. et al. (2005) - TP1175 .E9 G55 2005
“Injection molding handbook” - D.V. Rosato, ed. (2000) - TP1150 .I55; (1995) – TP1150.R67
“Fundamentals of polymer processing” – S. Middleman, Stanley (1977) - TP1087 .M5 – a classic
"Polymer Plastics Science and Technology - M.D. Baijal, Ed., SPE Monograph, Wiley, 1982
"Polymer Processing" - J.M. McKelvey, Wiley, 1962 – just about the first on the subject.
Advanced
“Principles of colloid and surface chemistry” – P.C. Hiemenz and R. Rajagopolan (1997) - QD549 .H53 – good text, level not too high.
“Physical chemistry of surfaces” A.W. Adamson and A.P. Gast (1997) - QD506 .A3 1997 (also electronic)
“Polymeric Systems (Advances in Chemical Physics, v. 94)” – I. Prigogine and S. Rice (1996) – QD453.A27 V.94 – for the more mathematically inclined
“The Mesoscopic Theory of Polymer Dynamics” – V.N. Pokrovskii (2000) – QD381.9 S65P63
“Diffusion in Polymers – Plastics Engineering Series, v. 32 – P. Neoogi, ed. (1996) – QD381.9 P45D53
“Mathematical modelling for polymer processing: polymerization, crystallization, manufacturing” – V. Capasso (2003) - TP156 .P6 M36
Polymer processing instabilities : control and understanding – S.G. Hatzikiriakos and K.B. Migler (2005) - TP1150 .P638
Standard Reference Works and Reference Websites
“Polymer handbook” (4th ed.) – J. Brandrup E.H. Immergut and E.A. Grulke, eds. (1999, 1989) - QD388 .P65
“Handbook of polymer synthesis” – H.R. Kricheldorf, O. Nuyken, G. Swift, eds. (2005) - TP1130 .H37
“CRC handbook of thermodynamic data of aqueous polymer solutions” – C. Wohlfarth (2004) QD381.9 .S65 W633
“CRC handbook of polymer-liquid interaction parameters and solubility parameters” – A.F. Barton (1991) – QD543.B22
“CRC handbook of thermodynamic data of polymer solutions at elevated pressures” – C. Wohlfarth (2005) - QD381.9 .S65 W636 "Physical Properties of Polymers" - J.E. Mark, A. Eisenberg, W.W. Graessley, L. Mandelkern, J.L. Koenig, ACS, 1984.
“Handbook of polymer-fibre composites” – F.R. Jones (1994) - TA 418 .9 C6 H343
“Handbook of applied polymer processing technology” - N.P. Cheremisinoff (1996, electronic)
“Handbook of polymer testing: physical methods” – R.P. Brown (1999) - TA455.P5 H352
“Handbook of polymer degradation” (2nd ed.) - S.H. Hamid, ed. (2000) - QD381.9 .D47 H36
“Modern Plastics Encyclopedia” (1994) - TP1110 .M62 1994 http://www.matweb.com/index.asp?ckck=1 http://www.scientificpolymer.com/index.asp http://www.polysciences.com/shop/ http://www.plasticsgeneral.com/BRAND-NAMES-LIST1.htm http://www.plasticsnet.com/content/homepage/default.asp?VNETCOOKIE=NO
Educational Websites
(1) http://www.chem.mtu.edu/~fmorriso/cm4650/selected_lecture_slides_rheology.html 1 = Intro., 2 = Vector review, 3 = Tensor notation, 5 = Tensor operations, 6 = Vector/tensor differential operations, 7 = Curvilinear coordinates, 8 = Derive continuity eqn., 9 = Derive momentum eqn., 10 = Derive stress tensor, 11 = Newtonian flow problems (no solutions, just setup), 13 = Shear and elongational flows (definition), 14 = Elongational flows, 15 = Measuring stress, 16 = Intro. to material functions; 17 = Creep; 18 = Material functions, oscillatory shear and elongational; 19, 20 = Steady shear flow; 21, 22 = Oscillatory shear; 23 = Large-strain shear; 24-29 = Simple constitutive models; 30-34 = More complex constitutive models.
(2) http://ocw.mit.edu/OcwWeb/Materials-Science-and-Engineering/3-064Polymer- EngineeringFall2003/CourseHome/index.htm - the entire 2003 Polymer Engineering class from MIT – notes somewhat sketchy.
(3) http://ocw.mit.edu/OcwWeb/Materials-Science-and-Engineering/3-91JMechanical- Behavior-of-PlasticsSpring2003/CourseHome/index.htm - the entire 2003 Mechanical Behavior of Plastics class from MIT – notes often sketchy.
(4) http://web.umr.edu/~wlf/ 1- The Museum – Historical Facts; 2 = Websites (mostly industrial); 3 = Intro. to MW’s and means of measurement; 4 = bulk poly. and bulk poly. properties (sketchy); 5 = solution poly. (sketchy); 6 = basics of coatings technology; 7 = spectroscopy (mostly links); 9 = fundamentals of adhesion; 10 = Mechanical Properties – good summary of basic elements, rubber elasticity eqn., superposition, WLF theory, regions of mechanical behavior of amorphous polymers; 11 = props. of some commercial polymers; 15 = some Math basics.
Index of movies on reptation, dynamics, processing.
(5) http://www.wtec.org/loyola/polymers/toc.htm - summary of composites manufacturing technology – long on text, short on pictures.
(6) http://www.engr.sjsu.edu/WofMatE/\ - good intro. summary on polymers and composites
(7) http://www.ch.ic.ac.uk/rzepa/mim/polymer/index.html - good structural pictures and shows reactions to make common polymers
(8) http://ull.chemistry.uakron.edu/biochem/ - an entire “Concepts in Biochemistry” course with lots of structures.
(9) http://www.chem.vt.edu/chem-ed/vt-chem-ed.html - the Chemistry Hypermedia project – something on everything, including something on every analytical technique imaginable.
(10) http://www.pslc.ws/mactest/maindir.htm 2 = basic polymer props., common polymers; 3 = basic concepts in polymer sci.; 4 = basic kinetics/reactor design; 5 = some basics of polymer charac.; 6 = intro. polymer processing; 7= how some polymers work
(11) http://plc.cwru.edu/tutorial/enhanced/main.htm - addition poly., MW averages, polymer structures, introduction to morphology, viscosity and thermal properties (DSC), introduction to applications of commercial polymers. Good viscosity lab.
- LCs introduction and phase transitions, basic optics, birefringence, applications, morphology, lyotropic and ferroelectric LCs.
- virtual labs on viscosity, MW distribution, LCs, birefringence, optics.
- a very good polymer glossary
(12) http://www.engin.umich.edu/~cre/ - Elements of Chemical Reaction Engineering, the wordwide standard text and website; sections on polymer kinetics, enzyme kinetics, polymerization reactors.
(13) http://kerouac.pharm.uky.edu/ASRG/HPLC/hplcmytry.html - HPLC guide
(14) http://www.chem.qmul.ac.uk/surfaces/scc/ - basic surface sci., some good material on surface spectroscopy
(15) http://macro.lsu.edu/CoreCourses/MSweb4/VirtualMacroBook.htm - Dr.Russo’s compilation of notes from all who have taught the CHEM 4010 and 4011 over many years.
(16) www.vilastic.com - see tech. notes on “A Structural View of Rheology” and “Rheological Parameters for Viscoelastic Materials”.
(17) http://ocw.mit.edu/OcwWeb/Materials-Science-and-Engineering/3-051JSpring- 2006/LectureNotes/index.htm - Spring 2006 notes for “Materials for Biomedical Applications” at MIT – some lectures very elegant.
(18) http://ocw.mit.edu/OcwWeb/Materials-Science-and-Engineering/3-012Fall- 2005/LectureNotes/index.htm - Fall 2005 notes for “Fundamentals of Materials Science” at MIT – some good, some not so good. Old Outline
(1) Introduction - Polymer Types Fried 1.1-1.2; Rodriguez -- Ch.1; Billmayer -- 1A,1B; Hiemenz -- 1.1-1.3 (2) Bonding and Structure (11 pp. notes) Fried 1.1-1.2; Rodriguez -- 2.1-2.4; Billmayer -- 1C; Hiemenz -- 1.4-1.6 (3) Polymer Molecular Weights, Distributions (6 pp. notes + 11 pp. I.N. + HyukYu4 on common definitions) Fried 1.3; Rodriguez -- 6.1-6.3; Billmayer -- 1D; Hiemenz -- 1.7-1.8; Nauman -- 12.1 (4) Chain Growth (Addition) Polymerization – (17 pp. notes + 10 pp. I.N.) Fried 2.2; Rodriguez -- 4.1-4.4; Billmayer -- 3A-3D; Hiemenz -- 6.1-6.8; Nauman -- 12.1 (5) Step Polymerization – (8 pp. notes + 8 pp. I.N.) Fried - 2.1; Rodriguez - 4.6,4.7,4.9; Billmayer - 2A-2D; Hiemenz - Ch.5; Nauman -- 12.1 (6) Chain Growth Polymerization - Ionic and Coordination (10 pp.notes + 8 pp. I.N. ionic + 17 pp. I.N. coordination + Metallocene Review) Rodriguez -- 4.5; Billmayer -- 4A-4E; Hiemenz -- 6.10-6.11, 7.9-7.13; Gates -- Ch. 2 (7) Copolymerization (12 pp. notes + 15 pp. I.N.) Fried 2.5; Rodriguez -- 4.8; Billmayer -- 5A-5D; Hiemenz -- 7.1-7.8; Nauman -- 12.1 (8) Bulk, Solution Polymerization (11 pp. notes + 8 pp.handout + HyukYu2 on MWD distributions +HyukYu4 on moment generating functions and common prob. distributions) Fried 2.3; Rodriguez -- 5.1-5.3; Billmayer -- 6A; Froment -- Ch. 10; Nauman -- 12.3 (9) Suspension, Emulsion Polymerization (5 pp. notes) Rodriguez -- 5.4-5.6; Billmayer -- 6B-6C; Hiemenz -- 6.9; Froment -- Ch. 10; Gardon (1968) (10) Polymer Stabilization (5 pp. notes) Rodriguez -- 4.10, 11.1-11.5; Billmayer 6D (11) Statistical Mechanics of Solutions (4 pp. notes + 5 pp. handout + HyukYu5 on chain stats. + HyukYu6 on renormalized freely jointed chain stats.) Fried 3.1,7.2; Rodriguez -- 2.5, 7.2; Billmayer -- 7A-7C; Hiemenz -- 1.9-1.12; Richards -- Ch. 3 (12) Thermodynamics of Solutions (25 pp. notes + 8 pp. Tanford notes) Fried 3.2; Rodriguez -- 2.6; Billmayer – 7D-7E; Hiemenz -- 8.1-8.6; Richards -- Ch. 3 (13) Molecular Weight Measurement + Viscosity (8 pp. notes + 23 pp. P.R. on light scattering 17 pp. I.N. on rheometry) Fried 3.3; Rodriguez -- 6.4-6.7 + 7.1, 7.3-7.45; Billmayer -- 8A-8G; Hiemenz -- 8.7-8.13, 9.1- 9.5, 9.8-9.11, 10; Richards-- Ch. 4; Mark – Ch. 3. (14) Thermodynamics and Properties – Glasses (6 pp. notes + 17 pp. I.N. + 6 pp. P.R.) Fried 4.1-4.3; Rodriguez -- 3.1-3.3; Billmayer -- 11D; Hiemenz -- 4.1-4.2; 4.8-4.9; Mark -- Ch. 2; McKelvey -- Ch. 4 (15) Thermodynamics and Properties -- Crystalline State (17 pp. notes + 12 pp. P.R. + 13 pp. I.N.) Fried 4.1-4.3; Rodriguez -- 3.4-3.8; Billmayer -- 10A-10E, 12A-12B; Hiemenz -- 4.3-4.8; Mark -- Ch. 4; McKelvey -- Ch. 5 (16) Thermodynamics and Properties -- Rubbery State (7 pp. notes) Rodriguez -- 8.1-8.2; Billmayer -- 11B; Hiemenz -- 3.1-3.5; Mark -- Ch. 1 (17) Melts and Liquid Crystals (12 pp. notes + 3 pp.handout + 6 pp. P.R. on melts + 24 pp. I.N. on liquid crystals + 16 pp. P.R. on liquid crystals) Rodriguez -- 7.3-7.5; Billmayer -- 11A; Hiemenz -- 2.1-2.2; Mark -- Ch. 3; Richards -- Ch. 8 (18) Viscoelasticity, Mechanical Properties (22 pp. notes + 6 pp. handout + 11 pp. handout + 3 pp. handout + 13 pp. P.R. on visco./mech. Properties + 11 pp. I.N. on visco. + 49 pp. I.N. on mechanical properties + 41 pp. G.S. on both) Fried 4.4,7.3; Fried 5.1-5.2; Rodriguez -- 8.1, 8.3-8.10; Billmayer -- 11C, 11E, 12D; Hiemenz -- 3.6-3.12, 4.10-4.12; Mark -- Ch. 3; Baijal -- Ch. 8 (19) Non-Newtonian Rheology (21 pp. handouts + 41 pp. notes + 35 pp. from Dow Proc. Course + 20 pp. I.N. on fibers) Fried 11.1-11.4; Rodriguez -- 7.6-7.8; Hiemenz -- 2.3-2.14; Baijal -- Ch. 11; Denn -- Ch. 19 (20) Thermal, Electric and Ultimate Properties (17 pp. notes + 12 pp. Baijal notes + 16 pp. I.N. on thermal properties) Fried 4.3,5.1,12.3; Rodriguez -- Ch. 9; Billmayer -- 12C; Baijal -- Ch. 8 (21) Composites -- Properties and Manufacture (18 pp. notes + 10 pp. handouts) Rolston
Old Lab Experiments -- (1) Emulsion Polymerization of Vinyl Acetate (2) Osmotic Pressure and MW Measurement (3) Viscosity of Gels (4) Crystalline Structure Observation (5) Compositing in high shear mixer (6) Extrusion of commodity resin