CODE 65191 ACADEMIC YEAR 2016/2017 CREDITS 4 cfu anno 2 SCIENZA E INGEGNERIA DEI MATERIALI 9017 (LM-53) - 6 cfu anno 1 SCIENZE CHIMICHE 9018 (LM-54) - SCIENTIFIC DISCIPLINARY SECTOR CHIM/03 LANGUAGE Italiano TEACHING LOCATION SEMESTER 1° Semester AIMS AND CONTENT LEARNING OUTCOMES Attainment of competences in the fields of crystal structure of solids (identification of symmetry elements, space group, etc. of a crystal structure; use of the International Tables of Crystallography, etc.) and correlation between crystal structure and bonding characteristics. Attainment of competences in the field of thermodynamic stability of solids, with reference to the crystal structure (thermodynamic modelling of the phases in mono- and multi-component systems), and use of software packages for the thermodynamic calculation of phase equilibria and phase diagrams of complex materials. TEACHING METHODS Lectures and practical exercises SYLLABUS/CONTENT Part 1 – Structure and bonding in crystalline solids (4 CFU) Crystal structure, elementary cell, lattice planes, etc.; point symmetry elements and operations; crystallographic point groups in 2D and 3D; stereographic representation; space symmetry elements and operations; Bravais lattices in 2D and 3D; space groups in 2D and 3D; use of the “International Tables for Crystallography”; standard description of a crystal structure according to the “Pearson's Handbook”; coordination, coordination histogram and polyhedra, atomic environments; close packed crystal structures described as stacking of close packed planes (triangular, hexagonal and Kagomé, etc.); interstitial sites and their coordination; detailed description of selected intermetallic structures (hcp, fcc, bcc, dhcp and related ordered structures, Laves phases, further structures such as -Mn, CrFe, Fe7W6, CaCu5, etc.; Laves principles, theories of Engel-Brewer and Altmann-Coulson-Hume-Rothery. Detailed description of selected tipically ionic structures (rock salt, sphalerite, wurtzite, fluorite, rutile, cristobalite, cuprite, spinel, perowskites, silicates, etc.); rationale of the ionic structures: ionic radii and Pauling rules; stability (Madelung energy, Born-Mayer and Kapustinskii equations, diagrams of Mooser-Pearson and Phillips-van Vechten, etc.). Description of selected covalent structures (diamond, graphite, etc.). Exercises: 1) Symmetry and space groups; 2) Closed packed structures and coordination; 3) Structure/bonding relations. The Ball&Sticks software and the “Pauling Files” database will be used. Parte 2 – Stabilità termodinamica dei sistemi eterogenei (2 CFU) Short overview on thermodynamics of heterogeneous systems (state variables and functions, extensive and intensive quantities, potentials, types of energy, characteristic equations, Gibbs-Duhem equation, phase rule, topology of the phase diagrams, ZPF lines, etc.) Thermodynamic modelling of the solid phases: a) pure elements (thermodynamic functions, temperature and pressure dependence, magnetic contribution, etc.); b) stoichiometric compounds (functions of formation, etc.); c) disordered solutions (ideal solutions, regular and subregular solutions, Bragg-William approximation, Redlich-Kister polynomials, etc.); d) ordered solutions (compound energy formalism, sublattice models for different phases and constituents, extrapolations to third- and higher-order systems, etc.). Thermodynamic modelling and crystal structure. The CALPHAD method for the calculation and prediction of phase equilibria and thermodynamic functions in multi-component systems: a) critical analysis of literature data; b) calculations based on existing databases; c) optimisation methodologies; d) extrapolation and prediction methodologies; e) application to alloy systems of technological interest. Exercises: 1) calculation of binary and ternary phase diagrams; 2) calculation of thermodynamic properties in binary and ternary systems; 3) application of the thermodynamic calculations to systems of technological interest. The Thermo-Calc software package will be used. RECOMMENDED READING/BIBLIOGRAPHY Antony R. West, Basic Solid State Chemistry, Wiley Ulrich Muller, Inorganic Structural Chemistry, Wiley Hans Lukas, Suzana G. Fries, Bo Sundman, Computational Thermodynamics - The Calphad Method, Cambridge University Press TEACHERS AND EXAM BOARD GABRIELE CACCIAMANI Ricevimento: Every day, on appointment. Exam Board GABRIELE CACCIAMANI (President) SERENA DE NEGRI SIMONA DELSANTE PAOLA RIANI ADRIANA SACCONE LESSONS Class schedule The timetable for this course is available here: Portale EasyAcademy EXAMS EXAM DESCRIPTION Evaluation of the exercise reports and final oral examination. Reports about the practical activity individually prepared by each student are assessed by the teacher. The average of the evaluations is considered in view of the final assessment. The oral examination is conducted by two teachers and it lasts not less than 30 minutes. Exam schedule Data appello Orario Luogo Degree type Note 12/06/2017 10:00 GENOVA Orale 28/06/2017 10:00 GENOVA Orale 10/07/2017 10:00 GENOVA Orale 11/09/2017 10:00 GENOVA Orale 09/10/2017 10:00 GENOVA Orale