Prof. Dr. Omar Azzaroni
Course: MACROMOLÉCULAS

Aims and objectives
The main goals of the course are: (a) to understand the physicochemical basis of macromolecular and polymeric materials, (b) to develop an understanding of the relationship between the chemical and physical properties of polymers and develop an understanding of structure-property
relationships, (c) to gain a knowledge of physical characterization methods used to characterize polymers and understand their molecular structure and architecture, and (d) to develop necessary experimental skills required for polymer synthesis and characterization, (e) to train students for a
future career in academia or industry, particularly in industries that manufacture, process, develop,and use polymeric materials.

Content

Synthetic Polymer Chemistry
Polymer structure. Classification of polymerization reactions. Preparation and characterization of the most important polymer types. Theory and practice of step growth polymerization, radical polymerization, ionic polymerization, ring-opening polymerization, polymerization by transition
metal catalysts, suspension and emulsion polymerization; group transfer polymerization; metathesis polymerization.

Physical Chemistry of Polymers
Main characteristics of macromolecular chains. Statistical thermodynamics, configuration and conformation of isolated polymer chains. The rotational isomeric state model. Thermodynamics and statistical mechanics of polymer solutions, scaling theory, single chain dynamics. Elasticity of
macromolecules and elasticity of elastomer materials. The glassy state and the glass transition of polymer materials. Viscoelasticity and rheology of polymers. Semicrystalline polymers and polymer crystallization.

Polymer Characterization
Characterization of polymers by up to fifteen methods, including spectroscopic (nuclear magnetic resonance, Raman, infrared), mechanical (tensile, dynamic mechanical, rheological), microscopic (electron and optical microscopy), physicochemical (intrinsic viscosity, differential scanning,
calorimetry, gel permeation chromatography) and scattering (light, x-rays). Molecular simulation techniques introduced. Lectures provide a state of-the- art description of these and additional polymer characterization methods.

Morphology of Polymers
Methods of structural characterization for important morphological classes of polymers. Overview of scattering physics leading to a discussion of specific techniques such as small and wide angle x-ray and transmission electron microscopy.

Polymeric Materials
Polymeric materials surveyed include mesophases, liquid crystalline polymers, polymer blends, block copolymers, and crystalline polymers forming lamellae or spherulites.

Specific learning outcomes of the course
At the end of this course, students will be able to:

  • Determine the parameters required to model a macromolecular chain by a freely-jointed chain model, a wormlike model, or a model of rotational isomeric states; explain using statistical physics how these parameters vary with molar mass, temperature or chemical nature of the repeating unit.
  • Describe phenomenologically the glass transition of polymers and the relaxation phenomena associated with it, on the basis of the notion of free volume. Use this approach to explain how the glass transition is sensitive to the temperature.
  • Describe the morphology of a semicrystalline polymer at different scales; state how this morphology controls the properties of the material; enumerate the parameters which control the melting temperature of a polymer.
  • Define and explain different concepts related to the molecular structure of polymers (topology, repeating units, configurational structures, average molecular weights and dispersity).
  • Describe and explain the mechanisms of the main methods of polymer synthesis : chain-reaction polymerizations (free radical polymerization, controlled radical polymerizations, coordinative polymerization and ionic polymerizations) and step-reaction polymerization;
    list and give the impact of the main parameters that govern the kinetics for each polymerization method ; establish relations between the polymerization method and the resulting molecular characteristics (architecture of the chain, regioselectivity, tacticity, molecular weight distribution) of the polymer chains.
  • Describe the structure of the main types of copolymers (random, alternating, graft and block copolymers) and discuss about the synthesis method and conditions in which each type of copolymer can be obtained; predict and justify the global composition of random copolymers based on the reactivity ratios of a given couple of monomers.
  • Describir la estructura de los principales tipos de copolímeros (en bloque, aleatorios, alternados, adicionados).
  • Select and describe an appropriated polymerization method of a given monomer in order to obtain a polymer with specific molecular characteristics.
  • Describe different polymerization processes (bulk polymerization, polymerization in solution, in suspension, in emulsion and interfacial polymerization) and state the advantages and drawbacks of each process.
  • Apply experimental techniques such as Raman spectroscopy, differential scanning calorimetry and rheology to polymer characterization.

Assessment

Written exam at the end of the course, comprising exercises and questions on the main concepts of the course. An oral exam may also be organized; this will be mentioned at the beginning of the course. The development of experimental skills will be assessed through the quality of the lab reports.

Teaching method

The course involves lectures, laboratory work and exercises done by the students. These exercises serve either to raise questions, or to solve particular issues. Practical classes will be also used to provide experience with relevant techniques and complement the theory presented in lectures. Concepts and notions will be introduced in lectures and tutorials and then investigated in laboratory experiments.

Bibliography

– “Polymer Chemistry: The Basic Concepts”, P.C. Hiemenz.
– “Polymer Physics”, M. Rubinstein, R.H. Colby.
– “Physical Chemistry of Macromolecules”, S.F. Sun.

Other information

This course requires having knowledge of physical chemistry and organic chemistry.

Prof. Dr. Omar Azzaroni
Course: ADVANCED SPECTROSCOPIES (Techniques for physicochemical characterization of materials)

Aims and objectives

Knowledge of the various techniques and instruments needed to analyze and characterize materials is extremely important as these techniques form the foundation of the investigation of different kinds of materials in both a research and industrial environment. The student needs to know the types of techniques that are available, and the types of information that can be obtained from each technique.

This course will introduce many routine and advanced techniques used to analyze and characterize materials. It will also focus on the interpretation of analysis results, as well as the planning and execution of practical assignments. The course will allow students to become familiar with the techniques, instruments and experimental approaches that are available, in order to apply this knowledge to solving real research or practical problems.

Content

Characterization of materials at the micrometer, nanometer and atomic/molecular scale using microscopy, scattering and spectroscopic techniques:

  • Dynamic light scattering (DLS)
  • Surface plasmon resonance spectroscopy (SPR)
  • Fourier transform infrared spectroscopy (FTIR)
  • Raman spectroscopy
  • Small- and wide angle X-ray scattering (SAXS and WAXS)
  • X-ray reflectivity (XRR)
  • Grazing-incidence small-angle X-ray scattering (GISAXS)
  • Thermogravimetric analysis (TGA)
  • Differential scanning calorimetry (DSC)
  • Quartz crystal microbalance (QCM)
  • Physisorption analysis
  • Fluorescence spectroscopy
  • Spectroscopic ellipsometry
  • Scanning electron microscopy (SEM)
  • Transmission electron microscopy (TEM)

Specific learning outcomes of the course

At the end of this course, students will be able to:

  • Describe the analytical techniques including the principles behind these techniques.
  • Read and interpret the results of the various techniques.
  • Provide critical analysis of experimental information.
  • Evaluate the uncertainty of observations and results from the different methods.
  • Assess which methods of characterization are appropriate for different material problems.
  • Plan an approach to solve a particular problem, including what technique you will need to use to get the required information, what information you will need and a strategy for getting the required information.
  • Show a basic understanding and knowledge of how to operate the various instruments used in the course.

Assessment

Written exam at the end of the course, comprising questions on the main concepts of the course. An oral exam may also be organized; this will be mentioned at the beginning of the course. The development of experimental skills will be assessed through the quality of the lab reports.

Teaching method

This course will be based on lectures, practical work and assignments. We will also be reading and analyzing scientific papers to get a better idea of how the various techniques can be used. You will also be asked to prepare and present mini lectures in class on some techniques and report back on your work.

Other information

This course requires having knowledge of physics (optics, electricity and magnetism) and physical chemistry.

One of the main missions of the Soft Matter Laboratory (SML) is to educate by creating an atmosphere that stimulates, supports and encourages the professional development of its graduate students. The first essential step towards this goal is to sharpen the thinking processes, the practical
skills and the creativity of our students.

The SML offers a unique environment for PhD education in soft matter science – one that is large enough to boast world-class research facilities, but is small enough to give each student individualized attention.

Our lab members combine their individual expertise to deliver a comprehensive training programme and a wide choice of research projects from across the full range of soft matter science.

The doctoral program of the SML is dedicated to meeting the educational needs of its graduate students, to providing learning opportunities in soft matter research, to assisting the local industry in developing new soft-matter based materials and technologies and tackling challenging technical
problems, and to enhancing the country´s innovation capacity. To this end, we are committed to produce highly skilled professionals with high-level technical skills, intellectual rigor, strong critical thinking and problem solving capabilities, excellent communication skills, and flexibility.

Key features of our PhD training program include:

  • Research projects that span chemistry, physics biology and materials science.
  • Strong interaction with industry (research training via industry-oriented PhD projects).
  • A considerable breadth of academic knowledge and experience.
  • State-of- the-art experimental facilities.
  • Transferable, soft skills training (oral and written communication, time management, problem solving, decision making and teamwork, among others).
  • A visit to an overseas academic laboratory to foster international experiences during the doctoral study.

The thrust of our doctoral program is to educate by active participation. Students engage in their research under the guidance and supervision of a SML member. The current state of soft matter science is revealed to students through formal courses, seminars, independent reading and daily
interactions.

Research in the SML is mostly focused on the rational design, synthesis, characterization and application of novel soft matter-based functional materials. Within this framework, self-motivated and talented people at all levels (postdoctoral scholars, graduate students, or undergraduate
students) with background/interest in organic and polymer synthesis, materials science and physical chemistry are welcome to contact us and explore the possibility of joining our laboratory.

PhD candidates can directly apply for available PhD projects in the Soft Matter Laboratory:

“Synthesis, Self-Assembly and Characterization of Supramacromolecular Electroactive Materials for Energy Storage Applications”. Contact: Dr. Waldemar Marmisollé

“Molecular Design, Synthesis and Characterization of Amphiphilic Macromolecules for Industrial Applications” Contact: Dr. Juan Martín Giussi

“Nanostructured Interfaces Displaying Hierarchical Functional Domains”. Contact: Dr. Omar Azzaroni

“Design, Characterization and Applications of Biomimetic Nanodevices Based on Solid-State Nanopores” Contact: Dr. Omar Azzaroni