OVERVIEW

Principles of Polymer Science (114422) is a 8 CFU class held in the first semester of the 1st year in the Sustainable Polymers and Process Chemistry MSc Course.

This class provides fundamental theoretical and practical knowledge on polymeric materials in solution, melt and solid state.

AIMS AND CONTENT

LEARNING OUTCOMES

Aim of this class is to provide the advanced knowledge (both theoretical and experimental) necessary for the study of macromolecules in the liquid and solid state, both in the amorphous and crystalline phase. The physico-chemical properties of polymeric materials and the structure-property relationships of macromolecules are discussed through the characterization of the molecular dimensions, the microstructure of the chains, the properties of the material. Theoretical concepts will be deepened by lab activities on characterization methods of polymers in solution, in the melt and solid state.

AIMS AND LEARNING OUTCOMES

Aim of this class is to provide fundamentals for advanced studies of macromolecules in solution, melt and solid state, both amorphous and semi-crystalline. Physical chemical properties of polymer materials as well as structure-property relations are discussed, focusing on characterization of molecular size, phase and kinetic transitions and melt/solid state material properties.

At the end of the class, students are expected to know:

- The concept of macromolecule, of molecular weight distribution and the meaning of the different molar mass averages;

- Thermodynamics principles governing the macromolecular state in solution, with particular emphasis on the Flory-Huggins and  Flory-Krigbaum models, the Theta temperature as well as the phase equilibria;

- The characteristics of the main techniques used for advanced characterization molar masses;

- To describe and discuss the correlation between size and structure of the polymer chains and their solution properties;

- Macromolecular properties in the (semi)crystalline state, melting (Tm), morphology, kinetics of crystallization, and connections with thermodynamic parameters;

- Properties of macromolecules in the amorphous state, in particular the glass transition temperature and its dependence on the molecular mass and on the polymer structure

- The working principles and application of the main techniques used for polymer characterization, including static light scattering, gel permeation chromatography, differential scanning calorimetry, wide-angle x-ray scattering, infra-red spectroscopy, polarized light microscopy, rotational rheometry and mechanical testing in uniaxial tension.

PREREQUISITES

Basic knowledge of polymer chemistry is required to efficiently follow the lectures of this teaching. For the students possessing a bachelor degree in Chemistry and Chemical Technology or Material Science from the University of Genova the prerequisites are given by the attendance of the teachings “Macromolecular Chemistry” or “Science and Technology of Polymeric Materials”. Students from abroad or from different bachelor courses must acquire this knowledge by independently deepen the topics on suggested studying material (for instance Introduction to Synthetic Polymers by, Ian M. CAMPBELL, Oxford University Press, 2000).

TEACHING METHODS

The teaching is organized in a series of lectures in the classroom by using powerpoint presentations (avilable to students through AulaWeb), for a total of about 32 hours. Following the classroom lectures there will be 9 laboratory practical lessons, for a total of about 36 hours. The students will be divided in small groups and will put into practice the theoretical knowledge gained in the first part of the teaching. Each laboratory activity will be introduced by a two hour lecture in the classroom (around 18 hours).

Lab attendance is compulsory. The exam is possible only after attending all lab experiences.

SYLLABUS/CONTENT

Classroom lectures:

1)   INTRODUCTION and CLASS PERSPECTIVE

1. Recalls on the Macromolecule concept
2. Recalls on Basic definition (monomer, polymer, copolymer,….)
3. Molecular Masses
4. Size and Shape
5. Configurations
6. Glass transition and melting temperatures

2) POLYMER SOLUTIONS

1. Thermodynamics of polymer solutions
2. Ideal mixtures of small molecules
3. Non-ideal  solutions
4. The Flory-Huggins theory
5. Mixing hentalpy
6. Free-energy mixing
7. Osmotic pressure
8. Limitations to Flory-Huggins model
9. Phase equilibria
10. Fractioning
11. Flory-Krigbaum Theory
12. Tetha temperature
13. Solution critical temperature
14. Solubility
15. Polymeric mixtures

3) POLYMER CHARACTERIZATION - MOLECULAR MASSES

1. Mn: ebullioscopy and cryoscopy, osmotic pressure, vapor pressure
2. Mw (Mz): Light scattering, refractive index change, small angle X-ray scattering, viscosity, GPC, MALDI-TOF.

4) POLYMER CHARACTERIZATION – CHAIN SIZE AND STRUCTURE

1. Average chain size
2. Freely Jointed Chain Model
3. Short chain interactions and chain stiffness
4. Treatment of Dilute Solution Data
5. NMR
6. IR
7. Thermal Analysis
8. X-ray Scattering

5) THE CRYSTALLINE STATE

1. Introduction
2. Crystallization mechanism
3. Temperature and crystal growth-rate
4. Fusion
5. Thermodynamical parametrs
6. Crystalline Arrangement of Polymers
7. Morphology and Kinetics
8. Special Macromolecules (block copoliyers, liquid crystals,...)

6) THE AMORPHOUS STATE

1. The Amorphous State
2. The Glassy State
3. Relaxation Processes in the Glassy State
4. Glass Transition Region, the Glass Transition Temperature
5. Tg determination
6. Chain Flexibility
7. Steric Effects
8. Configurational Effects
9. Effect of Cross-Links on Tg
10. Theoretical Treatments
11. The Free-Volume Theory
12. Gibbs–Di Marzio Thermodynamic Theory (mention)
13. Adam–Gibbs Theory (mention)
14. Dependence of Tg on Molar Mass
15. Structural Relaxation and Physical Aging

Practical laboratory activities:

1) POLYMER CHARACTERIZATION - MOLECULAR MASSES

1. Static light scattering of polyethyleneoxide/water solutions

2. Gel Permeation Chromatography of polyethyleneoxide

2) THE CRYSTALLINE STATE

3. Differential scanning calorimetry: non-isothermal crystallization of polylactide, isothermal crystallization kinetics and Avrami equation

4. Polarized optical microscopy: spherulitic growth kinetics as a function of temperature, Hoffman-Weeks extrapolations to determine the equilibrium melting temperature

5. Index of crystallinity via wide-angle X-ray diffraction

6. Infrared spectroscopy of polyethylene: effect of polymer density and of chain orientation

3) THE AMORPHOUS STATE

7. Glass transition: effect of chain constitution and molecular mass

8. Viscosity of polyethyleneoxide melt: effect of temperature and molecular mass

4) THE SOLID STATE

9. Mechanical properties of semi-crystalline polymers in tensile test at constant rate and in creep tests: effect of crystallinity and kinetics of plastic deformation

RECOMMENDED READING/BIBLIOGRAPHY

I.M.G. Cowie, “Polymers: Chemistry & Physics of Modern Materials”, Blakie and Son Ltd, Glasgow (1991).

S. Koltzenburg, M. Maskos, O. Nuyken, “Polymer Chemistry”, Springer-Verlag Berlin-Heidelberg (2017).

P. Flory “Principles of Polymer Chemistry”, Cornell University Press, Itacha 1953

U.W. Gedde, “POLYMER PHYSICS”, Kluwer Academic Publishers, Dordrecht 2001

W.D. Callister Jr. and I.D.G. Rethwisch, “Materials Science and Engineering”, J. Wiley and Sons, Hoboken (NJ) (2015)

Additional notes and bibliography can be provided to worker-students and unpaired students in order to fulfill specific requirements

TEACHERS AND EXAM BOARD

Exam Board

DAVIDE COMORETTO (President)

DARIO CAVALLO

LESSONS

LESSONS START

The class schedule is available at  https://easyacademy.unige.it/portalestudenti/

Class schedule

The timetable for this course is available here: Portale EasyAcademy

EXAMS

EXAM DESCRIPTION

The oral exam consists in a discussion covering the topics presented during lessons, including lab activities. The exam will start with the discussion of one laboratory experience selected by the student among those carried out (up to 10/30). Then, one or more theoretical questions will follow. The student must show to have understood main physical/chemical/technological fundamentals related to the topics and to use the suitable technical vocabulary including ability to answer questions (up to 20/30).

Lab attendance is compulsory. The exam is possible only after attending all lab experiences.

For students with disabilities or with SLD, the assessment method will comply with the UNIGE rules summarized in https://unige.it/disabilita-dsa.

Students have to book in advance an appointment for the exam with teachers.

In case of emergency and only according to specific indications by the University of Genoa, the assessment method for the exam might be changed, including the possibility of an online procedure.

ASSESSMENT METHODS

The aim of the exam is to verify the achievement of the intended learning objectives both for the theoretical and labs topics. If these objectives are not met, the student will be encouraged to further study the topics, with the support of the teacher’s explanations, and attempt the exam again. During the laboratory classes, teachers will assess the extent of students' participation and their capability in conducting experimental work. The exam will ascertain whether the student has attained an adequate level of knowledge on the class topics, with particular reference to polymer physico-chemical properties in various states and their means of characterization.

FURTHER INFORMATION

For any other information, students are invited to directly contact teachers by email (davide.comoretto@unige.it; dario.cavallo@unige.it, telephone (0103538736/8744; 010/3536086) or visiting them in their offices/labs.

Attending lectures is strongly recommended in order to familiarize yourself with the examination procedure, as the lectures are always accompanied by concrete examples industrially relevant.

Lab attendence is compulsory.

Agenda 2030 - Sustainable Development Goals

Quality education (4)

Gender equality (5)

Industry, Innovation, and Infrastructure (9)

Sustainable Cities and Communities (11)

Responsible consumption and production (12)

Climate action (13)

Students who have valid certification of physical or learning disabilities on file with the University and who wish to discuss possible accommodations or other circumstances regarding lectures, coursework and exams, should speak both with the instructor and with Professor Sergio Di Domizio (sergio.didomizio@unige.it), the Department’s disability liaison.