SubjectsSubjects(version: 955)
Course, academic year 2019/2020
Physical Chemistry of Polymer Systems - AP403013
Title: Physical Chemistry of Polymer Systems
Guaranteed by: Department of Physical Chemistry (403)
Faculty: Faculty of Chemical Engineering
Actual: from 2019 to 2023
Semester: both
Points: 0
E-Credits: 0
Examination process:
Hours per week, examination: 2/1, other [HT]
Capacity: winter:unknown / unknown (unknown)
summer:unknown / unknown (unknown)
Min. number of students: unlimited
State of the course: taught
Language: English
Teaching methods: full-time
Teaching methods: full-time
Note: course is intended for doctoral students only
can be fulfilled in the future
you can enroll for the course in winter and in summer semester
Guarantor: Horský Jiří Ing. CSc.
Pientka Zbyněk RNDr. CSc.
Interchangeability : P403013
Examination dates   Schedule   
Annotation -
Both classic two-parameter and modern scaling theories of polymer systems are presented on the advanced level to Ph.D. students. Statistics of an ideal polymer chain, the effect of excluded volume on the polymer-coil dimensions, thermodynamics and flow of polymer solutions in various concentration regimes are explained. Thermodynamic, hydrodynamic, scattering and separation methods for investigation and characterization of polymer systems are described. Systems with specific interactions (e.g., polyelectrolytes) and advanced architecture (e.g., block copolymers, dendrimers) are also mentioned and their innovative potential is demonstrated.
Last update: Matějka Pavel (16.06.2019)
Aim of the course -

Students will be versed in thermodynamical and rheological models of polymer systems and will be able to use them for prediction and interpretation of phase and flow behavior. They will be able to choose a proper physico-chemical method for study and molecular characterization of polymer compounds and to evaluate its results.

Last update: Pátková Vlasta (16.11.2018)
Literature -

R: Rubinstein M., Colby R.H.: Polymer Physics. Oxford Univ. Press, 2004.

A: Kamide K., Dobashi T.: Physical Chemistry of Polymer Solutions. Theoretical Background. Elsevier Science 2000.

A: Teraoka, I.: Polymer solutions : an introduction to physical properties. Wiley-Interscience, 2002.

Last update: Řehák Karel (27.11.2018)
Learning resources -

Last update: Pátková Vlasta (16.11.2018)
Teaching methods -

Lectures (75 %) topical seminars (25 %).

Last update: Pátková Vlasta (16.11.2018)
Syllabus -

1 Polymer chain conformations and the description of polymer-coil dimensions - radius of gyration. Models of a polymer chain. An ideal chain – the random-walk model. The entropic elasticity of a polymer chain. Gibbs free energy of a polymer chain.

2. The effect of the segment excluded volume on the dimensions of a real chain. Mayer function. Expansion and collapse of a polymer coil in athermal and bad solvent. The deformation of a polymer coil - a tension blob.

3. Thermodynamics of polymer solutions. Flory-Huggins theory of the mixing Gibbs free energy. Derivatization of combinatorial entropy for mixing of small and large molecules on a lattice. Introduction of χ-parameter describing polymer-solvent interaction; mixing enthalpy.

4. Phase equilibria of polymer solutions; spinodale and binodale; lower and upper solution critical temperature. Effect of molar mass – theta temperature. Osmotic pressure of dilute solution: second virial coefficient, number-average molar mass.

5. Definitions of polymer-solution concentration regimes. Limiting concentration of semi-dilute solution. Scaling theory – thermal and correlation blobs. Dimensions of a polymer coil in concentrated solution and melt.

6. Elastic light scattering in polymer solutions. . Rayleig scattering of small particles. Scattering in a condense phase – concentration fluctuations. Scattering of medium sized particles; scattering vector, angle dependence of scattered intensity. Zimm diagram; mass average molar mass.

7. Elastic scattering of other types of radiation – neutrons, X-rays. Effect of wave-length on the scattering-vector value and dimensions of observable objects. Guinier approximation.

8. Dynamic light scattering, photon correlation spectroscopy. The relation for a monodisperse sample; the radius of the hydrodynamically equivalent sphere. Evaluation of the correlation function of disperse samples. Z-average diffusion coefficient. Zeta-potential measurements.

9. Polymer dynamics and macromolecular hydrodynamics. Gaussian chain – Rouse and Zimm models of polymer solution flow. Flory-Fox theory of hydrodynamical properties in good solvents. Mark-Houwink equation for the limiting viscosity number. Non-Newtonian behavior of polymer fluids. The validity region of the Rouse model. The reptation model of entangled polymer solutions and melts.

10. Molar-mass distribution of disperse polymers and experimental methods of their determination. Significance of the molar mass distribution in disperse polymers behavior. Size exclusion chromatography and its separation principle. Results evaluation – the transformation of a chromatogram to molar mass distribution. The calibration using polymer standards; principle of the universal calibration. Multidetector arrangement for direct molar mass determination.

11. Field flow fractionation – used forces, the role of diffusion, asymmetric flow field flow fractionation. MALDI-TOF mass spectrometry – movement of a charged particle in an electric field; the role of a matrix and an ionizationt agent in the desorption and ionization. Advantages and limitations of discussed method.

12. Weak and strong polyelectrolytes; the extended Hendersson-Haselbalch equation. Expansion of a polyelectrolyte moleculeů effect of the ionic strength. Charge distribution – Poisson-Boltzmann equation. Counter-ions condensation – Manning theory. Donnan equilibrium.

13. Branched polymers – types of branching, hyperbranched polymers, dendrimers. Kramer theorem – the radii of gyration of selected architectures. Contraction factors of hydrodynamic properties. Gels: functionality of a branching point; the gelation point; critical conversion - the Flory-Stockmayer equation. Gel deformation and swelling – the Flory-Rehner equation. Physical (thermoreversible) gels. Solubility of crystalline polymer.

14. Repetition

Last update: Pátková Vlasta (16.11.2018)
Entry requirements -

Knowledge of (i) fundamental thermodynamic terms and relations; (ii) types of polymer preparations, their chemical structures and specific properties.

Last update: Pátková Vlasta (16.11.2018)
Course completion requirements -

oral examination

Last update: Pátková Vlasta (16.11.2018)