Defects in Ceramics

DEFECTs IN CERAMIC STRUCTURES

Point defects in ionic crystals are charged. The Coulombic forces that are generated due to
defects are very large and any charge imbalance has a strong tendency to balance itself,
electroneutrality. To maintain charge neutrality several point defects can be created at the same
time:

• Understand the structure of perfect crystals is so that we can begin to understand

imperfect crystals
• The interaction of defects is often most important
• For ceramics, a special example of such interactions occurs in grain growth.
• Grain-boundary movement in ceramics usually involves the movement of point defects.
• Ceramics usually have mixed bonding (combination of ionic and covalent bonding).
• So, defects, usually change the local distribution of charge or break bonds, depending on
predominant bond.
• Charge distribution can produce long-range effects. A broken covalent bond is known as
a dangling (unpaired electron) bond that also behaves like a localized charge.

TYPES OF POINT DEFECTS

• Defects are often classified in terms of a dimensionality.

• The different types of point defect that can occur in crystalline materials.

Vacancies:

• If an atom is not present on the site that it should occupy in a perfect crystal then a
vacancy is located at that site.
• A Schottky defect is a set of vacancies created by removing one atom for each atom in
the chemical formula. Thus, in a stoichiometric crystal such as MgO, we get a pair of
vacancies, one on the Mg sublattice and one on the O sublattice, as shown
• In spinel, a Schottky defect consists of seven vacancies.
FIGURE 11.1 Schematic of a Schottky defect drawn in 2D.

Interstitials:

• If an atom is present on any site that would be unoccupied in a perfect crystal then that
atom is an interstitial.
• A Frenkel defect is a vacancy + interstitial pair formed by removing an atom from its site
in the crystal structure and putting it into an interstice as
• Illustrated in Figure 11.2. Frenkel defects formed in Iodine-containing Ag-Br are essential
to the photographic Process

FIGURE 11.2 Schematic of a Frenkel defect

drawn in 2D
 • Frenkel Defect:
a cation is out of place. Anion interstitials are unlikely,
why?

• Schottky Defect :

- A paired set of cation and anion vacancies.

Equilibrium concentration of defects ~ exp Qp/kT

Misplaced atoms:

• If an atom is present on a crystal site that should be occupied by a different atom, that
atom is a misplaced atom and may be called an antisite defect.
• Antisite defects usually form in covalent ceramics such as AIN and SiC, but can also occur
in complex oxides that have several different types of cation, for example, spinels and
garnets.
 IMPURITIES

* Impurities must also satisfy charge balance

- Ex: NaCl Na+ cl-

Point Defects: Impurities

Stoichiometry

A state for ionic solids where there is an exact ratio of anions to cations defined by the chemical
formula unit.

— NaCl => anion to cation ratio is exactly 1:1

— Ca,F => 1:2, otherwise it is called non stoichiometry

— FeO => wustite, Fe2+ or Fe3+ may exist depending on temperature and O partial pressure. For
any Fe3+ there has to be an extra vacancy so that the charge neutrality is preserved... But then,
Fe,,.O for x <1...

Impurities in Ceramics

• Impurity atoms can exist as either substitutional or as interstitial solid solutions in

ceramics

— Substitutional ions substitute for ions of like type (anion to anion, cation to cation)

— Interstitial ions are small compared to host structure — formation of anion interstitials is

unlikely.
— Solubility is higher if ion radii and charges match closely.

— Incorporation of ion with different charge state requires compensation by point defects to
preserve charge neutrality.

Associated centers:

• When two-point defects interact so that they can be considered as a single defect they
are called an associated center.
• If more atoms are involved, a defect cluster or a defect complex.
• Exposing a material to ionizing radiation such as X-rays and y-rays can create large
numbers of defect clusters.

Solute (substitutional) atoms:

• in Cu alloys, we can add up to 30 at% Zn before the structure is changed.

• All Zn atoms sit on Cu sites so they substitute for the Cu and the crystal is said to be a solid
solution of Zn in Cu.

Electronic defects:

• Electrons and holes can both exist in ceramics.

 • They may be associated with particular ions, in which case they are simply charged point
defects.
• This leads to the topic of color centers, which color alkali halide crystals, amethyst,
diamond, etc.s

Kréger—Vink notation:

• Kréger—Vink notation to identify these different point defects

• This notation is completely general in that it can apply to any crystalline compound or
even to pure crystals.
• In this notation, structural elements are denoted as ScP

TABLE 11.2 The Kréger—Vink Notation for the Binary MX

Defect Notation Comments

Vacancy Vx V is also the chemical symbol for

the element vanadium: if there

is a possibility for confusion,

such as expressing a vacancy

on a vanadium site, then use

“Va” for the vacancy

Interstitial M; and X No “site”

Antisite atom My and Xi Usually in covalent solids

Associated defect (MiXm) Larger associations called “clusters”

Solute Sx Impurity substitution

Electron and hole e’ andh

Schottky (VuVx) Special associated defects

Frenkel (VaMi)
CREATION OF POINT DEFECTS IN CERAMICS:

• There are several ways that one can create point defects in ceramics.
• Point defects can be produced in nonstoichiometric oxides, such as ZnO, by heating in
either high or low pO,.
• In Nd-doped yttrium aluminum garnet (YAG)—the most widely used solid-state laser
crystal—the Nd Is incorporated into the YAG structure (it substitutes for Y3+ in small
amounts) when Nd2O3 is added to the YAG melt.
• A single crystal, which contains the Nd ions in solid solution, is pulled from the melt using
the Czochralski method.
• If a crystal is annealed at a sufficiently high temperature and for long enough, then the
equilibrium concentration of vacancies will increase.
• Abrupt quenching of the material can “freeze in” unusually high concentrations of point
defects.
• Vacancies, usually Schottky defects or Frenkel pairs, can be produced as a result of ion
bombardment in a process known as ion implantation. (single crystal MgO when it is
bombarded with high-energy Xe+ ions.)

Dislocations

Two vectors define the fundamental properties of any dislocation:

— The line direction

— The Burgers vector

• The glide plane of the dislocation is the plane that contains both vectors.
• Geometry - Burgers vector and line direction define the glide plane.
• Displacement - When a dislocation is present, atoms are displaced from their positions in
the perfect crystal; the material is strained so there must be a stress.
• Movement - Dislocations move and interact (they even intersect).
• Reacting - We generate dislocations, they multiply and combine (by intersecting).
• The dislocations in ceramics do not move as easily as those in metals and they are
usually not as numerous.
• There are two special types of dislocation.
- Edge dislocations
- Screw dislocations
 • Mixed dislocation

Burgers Vector and Circuit:

SUMMARY OF DISLOCATION PROPERTIES

• Dislocations cannot end inside the crystal lattice.

• Always assume that strains are so small that linear elasticity is a good approximation; so,
Hooke’s law holds.
• The displacement field for any dislocation falls off as r-1 as we move away from the
dislocation.
• The strain energy (or self-energy) of a dislocation actually depends on the character of
the dislocation, but set as E = αGb2, α ais ~0.5.
• Parallel dislocations repel one another if the angle between their Burgers vector is less
than 90°.
• A dislocation can always lower its strain energy by spreading its core or dissociating.
 • If dissociation occurs (forming identifiable partial dislocations) then this region is called a
stacking fault.
• Dislocations glide by the movement of kinks and climb by the movement of jogs. Since
climb requires changing the number of point defects (reacting or absorbing).

FIGURE 12.7 HRTEM of the core of dislocation in Al2O3

FIGURE 12.6 The intrinsic stacking fault in an FCC crystal

Fig 12.8 Diffraction contrast

from dislocation in Al2Os
Observing Dislocations

• We can view dislocations indirectly by etching the surface of a material. Where the
dislocation intersects the surface, it is preferentially etched creating a pit, which can easily
be seen optically.
• Using a transmission electron microscope, we can see the strain contrast that a
dislocation makes as it passes through a crystal, or at the atomic level we can see the
displacement of atomic columns due to the presence of a dislocation.

Optical etch pits in Silicon Carbide (Si-C) corresponding to the surface

intersection of pure edge dislocations having b= a/3 <11-20>and a line

direction of [0001], which is perpendicular to the etched surface.

SURFACES:

• A surface is just the interface between a solid (or liquid) and a gas or vacuum.
• Surface of a material, or any interface between materials, is a region of excess energy
relative to the bulk or matrix.
 • To maintain the lowest total energy for the system, the configuration of the surface
adapts itself to minimize this excess energy.
• Impurities or dopants that lower the surface energy tend to concentrate in the surface.
• Similarly, defects will move to the interface if by segregating there they lower the overall
energy of the system even if it raises the interfacial energy.
• Surface will tend to orient parallel to certain crystallographic planes that have a lower
energy.
• The surface energy can be intentionally lowered using a wetting agent or a (liquid or solid)
surfactant.
• For example, the interfacial energy of liquid Ni in contact with Al2O3 can be changed by
the presence of Ti at the surface.
• The Ti is strongly attracted to the oxide interface because of its high chemical reactivity
with oxygen.

CERAMIC SURFACES

• The surface is particularly important for ceramics because, are often using powders at
some stage of processing
• Surface area-to-volume ratio is larger for powders than bulk materials.
• Many uses of ceramics rely on their inertness or reactivity, but nanoparticles of “inert”
ceramics can be very reactive, partly because of this enhanced ratio.
• Failure of a ceramic usually occurs first at the surface.
• Catalysis is enabled at the surface.
• Sintering, the most important processing route for ceramic materials, is the process of
joining two surfaces together.

Interfaces

• Crystalline solids usually consist of a large number of Randomly oriented grains separated
by grain boundaries (GBs)
• Each grain is a single crystal and contains many of the defects already described.
• A GB is defined as the surface between any two grains that have the same crystal
structure and composition.
• Many GBs, but not all, can be modeled as arrays of dislocations.
• The grains are related to one another by a rotation axis and meet on a plane, which may
be curved
 • The rotation axis is fixed only for a given boundary and is not unique, even for that
boundary; there are different ways to form the same GB.
• Considering two identical grains.
• Fix one grain and rotate the other about any axis.
• Cut each crystal parallel to a particular flat plane (to keep it simple) in space and join the
grains at this plane.
• This plane is the GB. Then allow the atoms to relax to a low-energy configuration (which
may not be the minimum energy).
• The conventional approach is to consider four types of GB based on the symmetry
operation used to create them:

— twist,

— tilt,

— mixed, &

— twin.

LOW-ANGLE GBs:

• Low-angle GBs contain arrays of dislocations.

• In its simplest form, the structure of the twist boundary consists of two sets of orthogonal
screw dislocations as shown in Figure (a) and (b).
• Schematics show the structure before and after relaxation to form the screw dislocations.
• Figure (c) shows how dislocations in a twist boundary might be seen emerging at the
surface; you can see that part of the grain is physically twisted relative to the other
because of the screw dislocations.
FIGURE Schematics of a low-angle twist GB. (a) Before and (b) after local

atomic relaxations. (c) The twist when the GB emerges at the surface.

FIGURE Schematics of low-angle tilt GBs

(a) Symmetric; (b) asymmetric.

HIGH-ANGLE GBs:

• When ø is >10°, the interface is referred to as a high-angle GB.

For certain
orientations, a
fraction of the points
in each lattice will be
common to both
lattices. This fraction

FIGURE 14.14
Schematics of the
[001] E -5 tilt GB In
NIO; only the lower
one Is actually
possible.

TWIN BOUNDARIES

• As in metals, twin boundaries are common in many ceramic materials including MgO,
spinel, Al2O3 , Fe2O3, the rare earth oxides, quartz, Si, and, of course, the new high-Tc
superconductors.
 • Some special twin relationships observed in minerals are illustrated schematically in
Figure.
• The observation of so many twin boundaries is interesting because they are found to facet
parallel to low-index planes in at least one grain.
• interfaces can accommodate impurity ions, and this can lead to the phenomenon of
chemical twinning, wherein apparently different crystal structures can be related to one
another by the periodic repetition of a pair of twin interfaces.

Phase Boundaries:

• In ceramic materials, as in other materials systems, interfaces are the most important
region of the material because that is where most of the action takes place.
• Phase boundaries are particularly important because they are the interfaces between
dissimilar phases.
• Phase transformations take place by the movement of PBs.
• Growing one material on a different material generates a PB (a heterojunction).
• Bonding one material to another generates a PB.
• Most commercial and natural ceramics contain two ormore phases and thus many PBs.