|
1. Polymerization |
||
|
8/29/02 |
Thursday |
Introduction: Types of polymers, nomenclature, molecular weight, degree of polymerization, molecular weight distribution. |
|
9/3/02 |
Tuesday |
Step growth polymerization, practical examples: polyamides, polyesters, polyethers, polycarbonates. |
|
9/5/02 |
Thursday |
Extent of reaction, statistics of step growth polymerization. Molecular weight and distribution. |
|
9/10/02* |
Tuesday |
Chain growth polymerization. Active ends: radicals, anions, cations. Kinetics of radical polymerization. |
|
9/12/02* |
Thursday |
Chain transfer. Molecular weight control. Effects of temperature in free radical polymerization. Ceiling temperature |
|
9/17/02 |
Tuesday |
Anionic polymerization, "living" polymers, block copolymerization. Model topological polymers. |
|
9/19/02 |
Thursday
|
Non-linear polymerization, gelation, statistics of network formation. Examples of network forming polymerizations. Crosslinking and the statistics of gelation by crosslinking. |
|
2. Polymer Chain Architecture |
||
|
9/24/02 |
Tuesday |
Isomerization. Structural isomers. Stereoisomers, Fisher projections. Isotactic, syndiotactic, atactic vinyl polymers. Effects of temperature, coordination polymerization. Diene polymers: structural (cis and trans) and stereo isomers. Conformers. |
|
9/26/02 |
Thursday |
Rotation about sigma-bonds, Newman projections, staggered, eclipsed, gauche and trans. Freely jointed chains model. Random walk, RMS end-to-end vector, radius of gyration. |
|
10/1/02 |
Tuesday |
Equivalent chain, equivalent random link. Real chains, freely rotating chain, rotational isomeric state models. Excluded volume. |
|
3. Polymer Microstructure |
||
|
10/3/02* |
Thursday |
Structure of amorphous polymers. Small angle neutron scattering. Semicrystalline polymers. Liquid crystalline polymers. |
|
10/8/02 [Prelim] |
Tuesday |
Crystallinity: Methods of measuring. Waxs, DSC, density, IR. Effects of chain architecture on crystallinity, Tm. Polymer crystal structures and chain packing. |
|
10/10/02 |
Thursday |
Crystal morphology: extended chain, fringed micelle and folded chain lamellar crystals. Fold surface and tie molecule controversies. Single crystals, spherulites, "shish-kebabs", row structures. |
|
Fall Break |
||
|
10/17/02 |
Thursday |
Thermodynamics of melting. Kinetics of crystallization, Avrami-Johnson-Mehl equation. Kinetic theory of chain folding. |
|
4. Glass transitions |
||
|
10/22/02 |
Tuesday |
Phenomenology. V, H, S, Cp vs. T. Rate effects, physical aging. G, ho. Free volume theory of Tg. Kauzmann paradox, configurational entropy (Gibbs-DiMarzio) theory of Tg. |
|
10/24/02 |
Thursday |
Effect of molecular variables on Tg. Chain stiffness, flexible side chains, diluents, molecular weight, crosslinking. |
|
5. Viscoelasticity |
||
|
10/29/02 |
Tuesday |
Linear viscoelasticity. Spring and dashpot models: Voigt and Maxwell models. Standard linear solid. Spectrum of relaxation times. Effects of stress and strain history. |
|
10/31/02 |
Thursday |
Boltzmann superposition principle. Dynamic mechanical spectroscopy. Complex moduli and compliances, tan d. Time-temperature superposition. |
|
11/5/02
|
Tuesday
|
Shift factor aT. WLF eq'n. Relaxation in crystalline polymers. Sub-Tg relaxations. Origins in molecular motions. Super-Tg relaxations: Disentanglement, Rouse model, reptation, tube models. Diffusion of polymer chains. Evidence for reptation, constraint release. Effects of molecular weight, topology. |
|
6. Polymer Thermodynamics |
||
|
11/7/02 |
Thursday |
Quasilattice model: comparison of entropy of mixing of polymer chains with that of small molecules. Flory parameter, c. Polymer blends, phase diagrams, UCST, LCST, block copolymers. |
|
11/12/02 [Prelim] |
Tuesday |
Polymer-small molecule solutions. Virial expansion, theta temperature, colligative properties, osmotic pressure. |
|
7. Measurement of molecular weight and polydispersity |
|
|
|
11/14/02 |
Thursday |
Weight average molecular weight, light scattering, Zimm plot. Number average molecular weight. |
|
11/19/02 |
Tuesday |
End group analysis, osmometry. Gel permeation chromatography. Dilute solution viscometry. |
|
8. Rubber elasticity |
||
|
11/21/02 |
Thursday |
Entropy of a stretched chain. Gaussian statistics. Entropy and free energy of a deformed network. |
|
11/26/02 |
Tuesday |
Effects of entanglements, dangling ends, loops, reinforcing particles (carbon black). Strain induced crystallization. |
|
Thanksgiving |
||
|
9. Plastic deformation and molecular orientation |
||
|
12/3/02 |
Tuesday |
Plastic instabilities, necking and cold drawing. Yielding behavior. Effects of entanglements and crosslinks. |
|
12/5/02 |
Thursday |
Cold drawing of crystalline polymers. High modulus fibers by drawing, extrusion, gel drawing, structure of ultraoriented fibers. Crazing and fracture of glassy polymers. Molecular network effects on crazing. |