Course information

The aim of the course is to understand and quantify the thermal, rheological and mechanical properties of polymers, their solutions and mixtures based on the chemical composition and architecture of macromolecular chains. Introduction: Reminder of basic structural features and properties of polymers. Chemical constitution and architecture of macromolecules. Six main families of polymers. Molecular weight distributions. Conformations of polymer chains: Statistical description. Simple models for linear chains experiencing local interactions along their backbones: freely jointed, freely rotating, wormlike (Porod-Kratky) chain. Quantities characteristic of the spatial extent of a chain: end-to-end distance and its distribution, radius of gyration. Quantities characteristic of the conformational stiffness of a chain: characteristic ratio, Kuhn segment length, persistence length. Random walks and Self-Avoiding walks. Excluded volume effect. Swelling of chains in good solvents. Theta conditions. Thermodynamics of polymer solutions: Flory-Huggins theory: free energy of mixing. The chi interaction parameter. Osmotic pressure of polymer solutions. Daoud-Jannink diagram and Scaling of chain dimensions in solution. UCST and LCST. Systems with Binodals, Monotectic points and Eutectic points. Binary and ternary phase diagrams of polymer solutions and blends. Flory theory for rod polymer – solvent systems. Dilute polymer solution dynamics: Friction coefficient and viscosity. Intrinsic viscosity and its calculation based on the Einstein equation. Mark-Houwink equation and its use in the determination of molecular weights. Polymer networks: Types of networks and their topological characteristics. Thermodynamics of elastic deformation. Entropic and energetic contribution to the elastic response. Ideal elastomers. Swelling of polymer networks in solvents. Gels and their applications. Linear viscoelasticity models. Boltzmann superposition principle. Entanglements and their consequences for rheological properties. Reptation model and its scaling predictions for the dependence of diffusivity and viscosity on molecular weight. Glassy polymers: Phenomenology of the glass transition. Kauzmann temperature. Experimental determination of the glass temperature. Free volume theories. Williams-Landel-Ferry (WLF) equation and time-temperature superposition principle. Mechanical properties of glassy polymers. Plasticization.