MSE 260

 Energetics of Macro/Nanoscale Materials
Term Offered: Spring
Text(s): Introduction to the Thermodynamics of Materials, D.R. Gaskell, McGraw-Hill, 4th edition (required). Additional lecture notes/handouts will be supplied throughout the course.
Instructor(s): Professor Peter Davies, Room 200 LRSM, davies@lrsm.upenn.edu, 898-1013
Prerequisite(s): Prerequisite: Chem. 102 or equivalent
Grading: 1. Homework problems
2. Quizzes over each chapter
3. Two hourly exams and one final exam.
Course Home Page URL:  
Course Description: Basic principles of chemical thermodynamics as applied to macro and nano-sized materials. This course will cover the fundamentals of classical thermodynamics as applied to the calculation and prediction of phase stability, chemical reactivity and synthesis of materials systems. The size-dependent properties of nano-sized systems will be explored through the incorporation of the thermodynamic properties of surfaces. The prediction of the phase stability of two and three component systems will be illustrated through the calculation and interpretation of phase diagrams for metallic, semiconductor, inorganic, polymeric and surfactant systems.
Course Outline: 1. Fundamental Principles and Laws of Thermodynamics. Review of 1st law of thermodynamics: state functions; path independence, heat and work, internal energy, enthalpy, heat capacity. Types of paths: adiabatic, isothermal, isochoric, isobaric (G2). 2nd law: reversibility; entropy; equilibrium, calculation of entropy changes, entropy and disorder. (G3 &4). Third Law: free energy, standard states, utilizing experimental data to calculate enthalpy, entropy, and free energy changes in macro-scale systems (G5). 2 weeks
2. Phase equilibrium in a one-component system. Vapor pressure, co-existence of phases, chemical potential. 1 component phase diagrams. G7 1/2 week.
3. Reaction equilibrium in gaseous systems. Standard state for a gas, partial pressure, free energy of mixing, chemical potential. Reaction equilibria; equilibrium constant; meaning of standard free energy change. Balance between chemical stability and entropy of mixing. G11 1/2 week
4. Heterogeneous equilibria. Standard state for solids and liquids, reaction equilibria for metal/metal oxide systems. Ellingham diagrams. Multiple oxidation states in transition metal oxide systems. Application to growth of thin film heterostructures G12. 1 week
5. Thermodynamics of condensed solutions. Raoult's law; ideal solutions, activity, chemical potential, free energy of mixing in solid solutions, meaning of random mixing. Non-ideal solutions; activity coefficient, excess free energy of mixing, enthalpy of mixing. Mixing models for binary systems; regular solution model, interaction parameter, stability of inorganic solid solutions; relation of mixing energetics to crystal structure. Mixing in polymer solutions, Flory-Huggins model. G9 2 weeks
6. Size dependent properties of nano-crystals. Surface tension, surface free energy, Kelvin effect. Variation of melting point and solid state phase transitions with particle size in the nano-regime. Stabilization of "metastable systems". Increased solubility of nano particles, Ostwald ripening. 1.5 weeks
7. Phase stability in two-component systems. Free-energy - composition relationships; immiscibility in the solid state, common tangents. Solid-liquid equilibria, Calculation of phase diagrams for ideal solid-liquid co-existence. (G 10) Non-ideal systems; eutectic systems, peritectic systems. Free energy of mixing curves, activity-composition relations. (G 13) Effect of size dependence on phase stability in the nano-regime. 2 weeks
8. Binary and Ternary Phase Diagrams. Cooling curves in binary systems, reading complex diagrams, intermediate compounds, congruent and incongruent melting. Phase stabilities in oxide, semi-conductor, polymer and surfactant systems. Ternary systems; representing compositions, simple equilibria in the solid and liquid state. 2.5 weeks

Course Objectives:

1. To provide an understanding of the classical thermodynamic approach to the energetics of complex systems.
2. To provide a foundation for the application of the principles of thermodynamics
3. To provide a consistent picture of thermodynamics concepts when applied to phase equilibria
4. To provide an understanding of the effect of the size dependence on the stability and chemical reactivity of materials systems.
5. To provide the background for other courses in the curriculum
Course Outcomes:

1. Predict chemical reactivity and equilibrium of nano and macro-scale materials at varying temperatures and pressures.
2. Understand key factors affecting the phase diagrams of one, two and three component materials systems.
3. Interpret and read the phase diagrams of hard and soft materials.
4. Understand thermodynamics for advanced courses: thin film growth, kinetics, materials synthesis, and stability/properties of nano-scale materials.

 


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