Chemical Sciences

GIANCARLO MASCI

The course aims to provide the Student with the basic knowledge of Macromolecular Science. Definitions and classifications of Macromolecules will be discussed as well as polymerization mechanisms and processes, their properties in solution, morphological aspects of the solid state, thermal behaviors, mechanical and rheological properties. The student will acquire skills regarding basic principles and terminology of Macromolecular Science, polymerization mechanisms and processes, the different types of polymer chains, macromolecular stereochemistry, their molecular weight characteristics (heterogeneity and distribution, methods of determination) and average size, thermodynamics of polymer solutions, the molten and solid state of polymeric materials, their crystallization, thermal and mechanical properties and elastic and viscoelastic rheological behaviors, as well as on classical thermodynamics and statistics of the ideal elastomer. Laboratory experiments are also planned to acquire further skills regarding the synthesis and characterization of polymers.


Finally, the students will gain ability to face challenges of the Chemical Industry of polymer materials thanks to their knowledge about correlations between structure and physical properties of polymers as well as will possess the necessary background to attend specialist courses to continue its academic formation.

Knowledge of the fundamental principles in polymeric materials science: structure, solution and solid state properties, main chemico-physical characterization techniques and polymerization methods.

Knowledge of fundamentals of mathematics, physics, organic and chemico-physical chemistry learned in the first two years of the chemical sciences bachelor.

Definitions and classifications. Natural and synthetic macromolecules. Homopolymers and copolymers.
Macromolecular classification as a function of their mechanical properties. Examples of polymer materials.
Configurational characteristics. Random flight chain. Gyration radius of macromolecules. Conformational characteristics and semiempirical calculations of the potential energy of a macromolecule. Different defects of the polymer chain. Different structures of proteins.
Outlines of polymer solution behaviour. Variation of mixing entropy of a polymer solution. Volume fractions. Flory temperature. Excluded volume concept for a polymer in solution.
Polymer molecular weights and their distribution. Determination of the polymer molecular weights: Number and weight average molecular weights. Dynamic and static light scattering. Z-average molecular weight. Viscosity average molecular weight. Mark-Houwink-Sakurada equation. Viscosity of polymers in solution. Newtonian, pseudoplastic, dilatant, thixotropic, rheopectic fluids. Overlap concentration. Gel Permeation Chromatography.
Morphological features of the polymer crystal. Fringed micelle model. Lamellar long spacing of polymer crystals. Chain folding. Kinetic theory of the polymer crystallization. Elongational force field influence on the polymer crystallization. Polymer crystallization from melt. Spherulites. Annealing process.
Thermal properties of polymers. First and second order thermodynamic transitions. Thomson-Gibbs equation. Melting temperature and polymer-structure correlations. Thermal transitions evidenced by the dynamo mechanical spectroscopy. Structure effects on the glass transition.
Polymer synthesis: mechanisms and processes. Step polymerizations: polycondensations, polyadditions, use of bifunctional monomers, polyfunctional monomers. Cross-linked, branched, star-polymers. Reaction mechanism, degree of conversion (p) and number average degree of polymerization (Xn), kinetics of polymerization. Chain polymerizations: Radicals, Initiation, Propagation, Termination, Structure of polymers from radical polymerization: head-to-tail and head-to-head structures, branching, stereo regularity, self-acceleration, inhibition and delay, Distribution of molecular weights, Effect of Temperature, Ionic polymerizations, living polymerizations. Cationic and anionic polymerization. Initiators, Monomers, Solvents. Controlled radical polymerizations. Coordination polymerization: stereo-control. Ziegler Natta and metallocene catalysts. Mechanism.
Polymers for special applications.
Data processing and interpretation of physical properties (mechanical and thermal properties, average molecular weight calculation). Laboratory practice: synthesis of polymers, preparation of hydrogels.

Adopted texts
- Ciardelli F., Farina M., Giusti P., Cesca S., Macromolecole. Scienza e Tecnologia Vol. I e II, Pacini Editore
- Guaita M., Ciardelli F., La Mantia F., Pedemonte E., Fondamenti di Scienza dei Polimeri, Pacini Editore
- Elias H. G., Macromolecules (4 volumi), 2009, Ed. Wiley (eBook Sapienza)
- Robert J. Young and Peter A. Lovell, Introduction to Polymers, 2011, CRC Press (eBook Sapienza).

Handbook of Polymers (Second Edition), edited by G. Wypych
ChemTec Publishing 2016
sapienza e-book
DOI https://doi.org/10.1016/B978-1-895198-92-8.50002-1

frontal lectures and laboratory experiments

Class attendance is optional. Attendance of laboratory exercises is mandatory.

Oral examination