Ó Andrzej BUDKOWSKI (IF UJ)

http://www.if.uj.edu.pl/pl/ZINM/polyfilms/

30 h long course on ‘Macromolecules - polymer physics’.

Contents:

I. Polymer architecture, physical states, molecular weight.

I.1. Molecular architecture. Topological and chemical structure (homo-, co-polymers). Configurational (structural, sequential, stereo) isomerism (tacticity determination). Conformational isomerism (molecular flexibility, single/ double bond and rotational isomerism). Hierarchical polymer structure (configuration, conformation, aggregation, micro-morphology, morphology).

I.2. Polymer physical states. Physical states in condensed phases (glassy, elastic, plastic, molten) reflected by the modulus vs. temperature relation. Elastomer, thermoplastic, durplast. Physical states in (dilute, semi-dilute, concentrated, liquid-crystalline) solutions.

I.3. Molecular weight distribution and measurements. Number-, weight-, viscosity-average molecular weight. Polydispersity index. Membrane osmometry, light scattering, intrinsic viscosity. Gel chromatography and mass spectrometry.

II. Macromolecular size; chain conformations.

II.1. Ideal chain conformations. Ideal chain models: freely jointed chain model (Flory’s ratio, Kuhn segment). Radius of gyration. Distribution of end-to-end vectors. Free energy and elasticity.

II.2. Real chain conformations; conformational transitions of synthetic polymers. Conformation of isolated chain (in dilute solution): Excluded volume. Extended Flory model. Transitions globule - coil – swollen coil, observations and applications to wet nanotechnology. Transition helix-coil.

II.3 Conformational transitions of bio-molecules; chain size measurements. DNA denaturation. Formation of DNA globule. Protein de/re/naturation and re/folding. Conformation of non-izolated chains: Melts, semi-dilute solutions, pseudo-phase diagram. Macromolecular size determination from intrinsic viscosity (Mark-Houwink relation), light scattering (Guinier law, Zimm plot).

III. Chain dynamics and diffusion of individual macromolecules.

III.1. Dynamics of unentangled polymer. Diffusion mechanism for colloidal molecule and for polymer (differences). Rouse (melts) and Zimm (dilute solutions) models. Relaxation modes and sub-diffusion mechanism. Segment temporal regimes.

III.2. Dynamics of entangled polymer. Entanglement, tube (Edwards) and reptation (de Gennes) model. Sub-diffusion mechanisms and time regimes. Constraint release. Self-diffusion and tracer diffusion. Kinetic aspects of diffusion. Gel electrophoresis.

III.3. Time-temperature superposition; polymer reptation and visco-elasticity. Reptation and visco-elasticity reflected in the modulus vs. time relation. Temperature dependence of relaxation time, friction and diffusion coefficients. Time-temperature superposition.

IV. Macromolecular self-organization.

IV.1. Thermodynamics of polymer blends. Polymer macro- and mico-phases. Flory-Huggins lattice model and interaction parameter. Gibbs free energy of mixing and phase equilibrium and stability. Binodal, spinodal, critical point. Phase diagrams.

IV.2. Macro-phase separation of polmer blends. Ways to start phase separation. Two types of phase separation: Nucleation and growth. Spinodal decomposition and its 3 stages. Growing structural scale. Dynamic scaling.

IV.3. Micro-phase separation of block copolymers. Gibbs free energy of one-component system. Micro-phase morphology and diblock architecture, analogy to amphiphilic molecules. Order-disorder transition. Well-defined structural scale. Imposition of long-ranged order. Micro-phase morphology of triblocks. Nanotechnological applications.

V. Thermodynamics of mutual diffusion. Irreversible processes and Fick laws. Mutual diffusion vs. self-diffusion and tracer diffusion. Mutual diffusion: its thermodynamic acceleration, slowing-down, suppression, ’up-hill’ diffusion. Non-fickian concentration profiles.