Physical Ceramics: Principles for Ceramic Science and Engineering

Chapter 2: Defects in Ceramics Pt. II

September/11/2012 Christian Arroyo Neshma Lpez Liliana Hernndez Wesley Cuadrado

Defect Association and Precipitation

Critical assumption
Concentration of defects is dilute so thermodynamic activity of the defects equals their concentration.

Consistent behavior with idealized point defect models. Heavily doped or nonstoichiometric ceramics have defects that become associated.

Factors affecting quasichemical equilibria

Concentration of defects. Charge of Defects. Dielectric properties of medium.

Dilute solutions (<1%).

Point Defect Association

Defects experience a binding energy between them. Electrically charged defects experience coulombic interactions.
Dimer (AlMg-VMg)

(V -VMg) occupy nearest neighbor sites on <100> and Z=6. Trivalent solutes
Vacancies introduced for charge compensation. Solute and vacancies associate.

Trimer (AlMg-VMg-AlMg)x

Point Defect Association

Dimer Point defect reaction: (AlMg+VMg)=(AlMgVMg) Equilibrium Constant: (AlMgVMg) = AlMg VMg =
~1

Trimer Point defect reaction: AlMg= [AlMg] + [(AlMgVMg)] Equilibrium Constant:

=
=

40

Extrinsic Potential
Changes in bulk defect structure cause changes in the sign and magnitude of this potential due to the fact that the origin of the surface charge is the equilibrium of surface ions with lattice defects. For a material in which Schottky defects dominate, the space charge potential changes when bulk concentrations of vacancies are altered by extrinsic solutes or nonstoichiometry.

Trivalent Substitutional Cation in MgO

Raise lattice concentration of vacancies

Potential :

Change in Surface Charge

Extrinsic Potential (Cont.)

The addition of extrinsic vacancies will result in the depopulation of anions from the surface, and the formation of a larger negative potential than the intrinsic case. Somewhere between the negative intrinsic potential and the positive extrinsic potential lies a point of zero potential known as the isoelectric point. Isoelectric Point dependent on:
Temperature Solute Concentration