(1001)

Homework 3 - Solution
1. The cubic-to-tetragonal phase transformation of perovskites is critically important to their application and varies widely among the perovskites of different compositions. Given that the ionic radii of Ba2+, Ca2+, and Sr2+ are 0.135, 0.1, and 0.118 nm, respectively, list these three perovskites by their Curie point (Tc) from high to low. Briefly explain why Tc changes with the radii of the cations. Solution: (a) Tc from high to low is BaTiO3 > SrTiO3 > CaTiO3 (b) The lattice parameter increases with the A-site cation; therefore, the Ti4+ ions would have a greater freedom to change from cubic to tetragonal phase at a higher temperature, resulting in a higher curie temperature. 2. Uses Google or any other search engines to find any ferroelectric (or piezoelectric, pyroelectric) ceramics. Describe in short about its composition, structure, property, and particular applications. Solution: You may find many interesting perovskite-structured oxide ceramics with functional optical/electrical/mechanical/magnetic properties that are of practical use owing to their structure and composition from search engines such as Google or open web information such as Wikipedia.

3. Write down possible defect reactions and their corresponding mass equilibrium constants for (i) Oxygen from atmosphere going interstitial (ii) Schottky defect in M2O3 (iii) Metal loss from ZnO (iv) Frenkel defect in Al2O3 (v) Dissolution of MgO in Al2O3 (vi) Dissolution of Li2O in NiO Solution:

ii) null 2VM 3VO

K S [VM ]2 [VO ]3

4. Calculate the equilibrium number of Schottky defects per mole in an MO oxide at 1000K in a ceramic solid for which the enthalpy for defect formation of cations is 2 eV. Assume that the vibrational contribution to the entropy can be neglected. Solution: The intrinsic vacancy concentration at 1000K is given by n/N = [VM]=[VO..]=exp[-2/(2x8.62x10-5x1000)]=9.16x10-6 Note that this n/N is the number fraction of defects n relative to the number of possible sites N. This fraction could be expressed in concentration units of atomic fraction in an elemental solid, or cation fraction, or mole fraction. For example, if there is one mole of the material, the equilibrium number of defects per mole is then 9.16x10-6 x 6 x 1023 = 5.5 x 1018

5. Same as the Prob. 2 but now the oxide has a stoichiometry of MO2. Calculate the equilibrium number of Schottky defects per mole for both cations and anions. Solution: For cations: 5.5x1018. For anions: 11x1018.

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