SPRING 2007

 

CSI 612 / PHYS 780:

PHYSICAL CHEMISTRY OF SOLIDS

 

Robinson Hall, Room A206, Friday, 16:30-19:10

Instructor: Y. Mishin, ymishin@gmu.edu, http://physics.gmu.edu/~ymishin/

 

Prerequisites: MATH 113, 114, 213; PHYS 260 or 266, CHEM 331 and 332, PHYS 780/SCI 685, or permission of the instructor.

 

 

Course description: An advanced course of physical chemistry for graduate students with emphasis on solid state materials. It covers advanced and rigorous thermodynamics, kinetics, atomic diffusion, and solid-state reactions in different classes of materials, including metals, ionic crystals, and semiconductors. Applications to technologically important solid-state reactions, such as metal oxidation, solid solution decomposition, diffusion controlled phase growth, discontinuous precipitation, and others will be demonstrated.

 

 

Lecture Content:

  • Lecture 1: Introduction. Review of theory of crystal vibrations in the harmonic approximations. Vibration density states. Phonons.
  • Lecture 2: Review of statistical mechanics and simple applications (molecules in a gas, harmonic solids, etc.).
  • Lecture 3: Principles of thermodynamics: an axiomatic approach.
  • Lecture 4: Thermodynamics functions and relations between them. Absolute calculations of thermodynamic functions. Thermodynamic functions of harmonic solids.
  • Lecture 5: Applications of thermodynamic functions. Phase equilibrium and phase stability. Solid-sold and solid-gas equilibrium. Phase diagrams of unary systems.
  • Lecture 6-7: Thermodynamics of multi-component systems. Chemical potentials. Gibbs phase rule. Solid solution models. Phase diagrams.
  • Lecture 8: Chemical thermodynamics. Gas reactions. Reactions involving solid phases. Applications to metallurgical reactions.
  • Lecture 9: Thermodynamics of surfaces and interfaces. Curved interfaces, capillarity (Gibbs-Thomson) effect in phase equilibrium, size effect in phase transformations. Equilibrium shape of crystals, contact angles and wetting.
  • Lecture 10: Thermodynamics of adsorption and segregation. The Gibbs adsorption equation and its applications. Relations between excess quantities. Atomistic models of segregation/adsorption.
  • Lecture 11: Thermodynamics and statistical mechanics of point defects in solids. Configuration and vibration effects. Defect complexes is ionic solids.
  • Lecture 12: Diffusion in solids: phenomenology and continuum theory. Diffusion-controlled reactions.
  • Lecture 13: Atomistic theory of diffusion: mechanisms, transition state theory, Nernst-Einstein equation and application to ionic conductivity.
  • Lecture 14: Oxidation of metals as a case study of sold-state reactions: atomic mechanisms and kinetics of the oxide scale growth. Other solid-state reactions: internal oxidation of alloys, discontinuous precipitation reactions, classical theory of heterogeneous nucleation.

 

Homework: A typical weekly assignment includes 3-4 problems

 

Project: A literature overview of a particular physical chemistry or materials science problem. Each student makes a literature search, writes a 10-15 page overview paper, and gives a Power Point presentation to the class. Typical project topics: Experimental measurements of thermodynamic activity in alloys, Experimental measurements of alloy phase diagrams, Atomistic methods of phase diagram calculation, Biography and legacy of J.W. Gibbs, The Gibbs Paradox: history and resolution, Isotope effect in diffusion, Diffusion mechanisms in amorphous solids, Thermodynamics and kinetics of phase coarsening, High-pressure behavior of solids and applications to geosciences, Surface stress in solids, etc.

 

Exams: A midterm and final exams each include 5-6 problems on the level of homework assignments. Students are allowed to use class notes but not textbooks


Grades:

  • Homework assignments (20%)
  • Mid-term exam (20%)
  • Term project including an oral presentation (20%)
  • Final exam (30%)
  • Class participation and discussion (10%)

Recommended Texts:

The course is largely based on notes of the instructor, supplemented by several texts:

·         R.J. Borg and G.J. Dienes: The Physical Chemistry of Solids (Academic Press, 1992) ISBN 0-12-118420-X

·         R. T. DeHoff: Thermodynamics in Materials Science (Boca Raton: CRC/Taylor & Francis, 2006) ISBN 0849340659

·         J. Philibert: Atom Movements. Diffusion and Mass Transport in Solids (Le Editions de Physique, 1991) ISBN 2-86883-161-3

·         R. W. Balluffi, S. M. Allen and W. C. Carter: Kinetics of Materials (Wiley, 2005) ISBN 13 978-0-471-24689-3

 

COURSE MATERIAL
(authorized access only)