Catalogo dei Corsi di studio

The course target is to provide the student with basic knowledge of macromolecular science. Definitions and classifications of polymers will be illustrated as well as polymerization mechanisms and processes. In addition, properties of polymer solutions, morphological aspects of solid state and thermal, mechanical, rheological, electrical behaviour of polymer materials will be also studied. The course includes some numerical exercises and laboratory experiences.
The student will achieve knowledge on basic principles of the Macromolecular Science and right terminology of the discipline. In particular, he will be provided with right skills about polymerization mechanisms and processes, molecular weight characteristics, macromolecular stereochemistry, thermodynamics of polymer solutions, polymer crystallization, rheological and mechanical as well as thermal and electrical properties of polymer materials. The laboratory exercises will allow the student to also acquire skills concerning the synthesis and physical characterization of some polymers of industrial interest. In addition, laboratory activity reports will be drawn up and discussed to develop critical and analytical skills.
Finally, the student 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.

Programme

Definitions and classifications. Natural and synthetic macromolecules. Omopolymers 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. Z-average molecular weight. Viscosity average molecular weight. Mark-Houwink-Sakurada equation. Gel Permeation Chromatography.
Morphological features of the polymer crystal. Fringed micelle model. Lamellar long spacing of polymer cristals. Chain folding. Kinetic theory of the polymer crystallization. Elongational force field influence on the polymer crystallization. Polymer crystallization from melt. Spherulites. Annealing process. Roe experiment.
Thermal properties of polymers. First and second order thermodynamic transitions. Thomson-Gibbs equation. Melting temperature and polymer-structure correlations. Thermal transitions evidenced by the dynamomechanical spectroscopy. Structure effects on the glass transition.
Rheologial and mechanical properties of polymers. Stress-strain diagrams of different materials. Viscous behaviour of polymer materials. WLF equation. Rubber elasticity.
The electrical behaviour of polymers. Inorganic and organic semiconductors. Polyacetylene synthesis and doping.
Polymerization reactions. Mechanism and processes of polymerization. Polymerization kinetic.
Numerical exercises on the determination of molecular weights, polymerization average grade, polymerization yield, polydispersity index of condensation and chain polymers.

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
Helias H. G., Macromolecules, J. Wiley
Billmayer F. W., Textbook of Polymer Science, Interscience Publishers, New York, London
W. Hellerich, G. Harsch, S. Haenle, Prontuario delle Materie Plastiche, Tecniche Nuove
Flory P. J., Principles of Polymer Chemistry, Cornell University Press
Young R. J., Lovell P. A., Introduction to Polymers, CRC Press

Study modes

lectures and classroom exercise lectures

Exam modes

Written examination plus oral examination to increase the mark

Exam reservation date start	Exam reservation date end	Exam date
01/01/2022	14/01/2022	20/01/2022
25/05/2022	09/06/2022	14/06/2022
23/06/2022	06/07/2022	12/07/2022
18/08/2022	01/09/2022	06/09/2022
01/09/2022	16/09/2022	22/09/2022

Programme

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.
Numerical exercises.

Adopted texts

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).

Bibliography

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

Study modes

frontal lectures and numerical exercises

Exam modes

Written examination and oral examination

Exam reservation date start	Exam reservation date end	Exam date
06/01/2021	09/06/2022	14/06/2022
06/01/2021	08/07/2022	13/07/2022
06/01/2021	02/09/2022	07/09/2022
06/01/2021	16/09/2022	21/09/2022
06/01/2021	03/11/2022	09/11/2022
06/01/2021	19/01/2023	24/01/2023

Programme

Definitions and classifications of macromolecules
Configurational characteristics of polymer chains. Definition of Polydispersity, Monomer (monomer unit), Repetitive unit, Degree of polymerization, Oligomers, Telomers, Telechelic Polymers, Polyelectrolytes, Macroions and Macroradicals.
Types of macromolecules.
Synthetic polymers and natural polymers. Homopolymers and copolymers: linear homopolymers, linear alternating copolymers, linear block copolymers, linear statistical copolymers. Branched polymers; Cross-linked polymers; Ladder polymers; Comb polymers; Dendrimers.
Classification according to mechanical properties. Examples of types of polymeric materials.
Configurational characteristics of polymer chains.
Polymers containing double bonds in the repeating unit; Polymers containing asymmetric carbon atoms in the repeating unit; Taxia: Isotactic polymers; Syndiotactic polymers; Ditactic polymers; Erythro-di-isotactic polymers; Threo-di-isotactic polymers; Erythro-di-syndiotactic polymers; Threo-didiotactic polymers.
Conformational characteristics of polymer chains.
The model of the freely articulated chain (the random flight chain): Case of the chain with constrained link angle, Case of the chain with constrained internal rotation angle; The characteristic ratio; The radius of gyration. Conformers or Rotamers or Conformational Isomers; Conformational degrees of freedom; Possible conformations; Semiempirical calculations of potential energy for the determination of possible conformations; Torsional energy, Van der Waals energy, Colombian energy, Hydrogen bonding energy; The coefficients of the potential functions; Potential energy map of n-butane; Potential energy map of polyethylene. Examples of catastrophic conformational transitions. Types of defects in the polymer chain; Reticular defects in PE; The various types of protein structure: primary, secondary, tertiary and quaternary structure.
Mechanisms and processes of synthesis of polymers.
Step Polymerizations: polycondensations, polyadditions, Use of bifunctional monomers, polyfunctional monomers and obtaining of cross-linked, branched, star polymers; reaction mechanism; Conversion degree (p) and numerical mean degree (Xn); Polymerization kinetics.
Chain Polymerizations: Radicals, Initiation, Propagation, Termination; Structure of free radical polymerization polymers: head-tail and head-head concatenations, ramifications, stereoregularity; Self-acceleration phenomenon; Inhibition and Delay; Distribution of molecular weights; Effect of Temperature; Ionic Polymerizations (Cationic, Anionic): Initiators, Monomers, Solvents; Ex. Of polymerization; Stereospecific (coordination) polymerizations Ziegler Natta: Mechanism; Notes on polymerization processes.
Notes on the behavior of polymers in solution.
References to ideal solutions; References to regular solutions; Polymer solutions; Change in entropy of mixing; Volume fractions; Flory temperature; The volume excluded.
Molecular weights, their distribution and techniques for their determination.
Number average molecular weight; Analytical techniques for Mn determination. Weight average molecular weight, Mw measurement techniques: Diffusion of light, Case of light diffusion in a gas, Case of light diffusion in a solution with point particles, Debye's equation, Case of light diffusion in a solution with non-point particles, Zimm Plot. Ultracentrifugation, average molecular weight z, sedimentation rate. Viscosimetric mean molecular weight, Huggins and Kramer equations, Mark-Houwink-Sakurada equation. Gel Permeation Chromatography, GPC Average Molecular Weight.
Morphological aspects related to the solid state of polymeric materials.
The fringed micelles model. The crystalline structure of polymers. Single crystals; The Long Spacing; Types of folds; The sectorization. Kinetic theory of crystallization of polymers. Solution crystallization under the effect of elongational force fields. Crystallization from the melt: The spherulites. Annealing, Roe's experiments.
Thermal behavior of polymeric materials.
Thermal transitions of polymeric materials: 1st order thermodynamic transitions; Determination of the thermodynamic or equilibrium melting temperature; Causes of the widening of the melting peak; Dependence of Tm on the heating rate; Thomson-Gibbs equation; Tm-structure correlations; The variation of entropy upon fusion; 2nd order thermodynamic transitions; The glass transition; Objections to the thermodynamic nature of Tg. Amorphous in semicrystalline polymers; The rigid amorphous. The transitions highlighted by dynamo-mechanical spectroscopy. Boyer's and Shatzki's mechanisms.
Effects of the chemical structure, of polarity of molecular weight and of cross-linking on Tg.
Mechanical and rheological properties of materials.
Types of material behavior; Types of stresses; Types of measures. Stress-strain diagram; Characteristics of stress-strain curves; Stress-strain curves of fibers; Stress-strain curves of PVC and PET. Deformations and free energy. Viscous Flow: Dynamic and Kinematic Viscosity, Newtonian Behavior, Pseudoplastic Behavior, Dilating Behavior, Plastic Behavior, Time-Dependent Behaviors, Measurement Techniques; Dependence of viscosity on molecular weight, Dependence of viscosity on ramifications and polydispersity, Dependence of viscosity on temperature; WLF equation. Dynamo-mechanical technique and complex module. Elastomers, The typical behavior of elastomers, Stress-strain curve of the elastomer, Elasticity of entropy
Electrical behavior of polymeric materials and notes on characteristics of polymers including high performance ones.
Conductive polymers; Polyenes; The theory of bands; Fermi's free electron gas; The energy levels; The Fermi level; The electrical conductivity; Band occupation and forbidden energy gap in different materials; Insulators, semiconductors and conductors; Intrinsic and extrinsic semiconductors; type "n" and “P” type doping; Comparison between inorganic semiconductors and polymeric semiconductors; Types of conductive polymers; Synthesis of Polyacetylene; The isomers of PA; PA isomerization; Morphological aspects of the PA; Change in the conductivity of the PA by doping; Doping agents; Possible applications of conductive polymers. Notes on the characteristics and application importance of polymers including high-performance ones.
Numerical and laboratory exercises
• Numerical exercises to determine the molecular weight, degree of polymerization, yield, polydispersity index of polymers obtained by step and chain polymerization.
• Laboratory practice: Synthesis of polyamides, polyesters or vinyl polymers of industrial interest
• Characterization of mechanical and thermal properties of polymeric materials

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
Helias H. G., Macromolecules, J. Wiley
Billmayer F. W., Textbook of Polymer Science, Interscience Publishers, New York, London
W. Hellerich, G. Harsch, S. Haenle, Prontuario delle Materie Plastiche, Tecniche Nuove
Flory P. J., Principles of Polymer Chemistry, Cornell University Press
Young R. J., Lovell P. A., Introduction to Polymers, CRC Press

Exam modes

Written and oral examination

Exam reservation date start	Exam reservation date end	Exam date
15/05/2022	14/06/2022	15/06/2022
15/05/2022	13/07/2022	14/07/2022
15/05/2022	06/09/2022	07/09/2022
15/05/2022	20/09/2022	21/09/2022
15/05/2022	15/11/2022	16/11/2022
15/05/2022	11/01/2023	12/01/2023