School of Multidisciplinary Engineering
Center of Materials Engineering
Engineering Ceramics
Assignment on defect (worksheet 1)
Prepared by: Desalegn Shibesh
ID: GSR/9086/12
Submitted to: Anteneh Marelign (Ph. D.)
July 2020
Addis Ababa
Worksheet 1 Answers
#1) a reaction for the formation of Schottky defects in MO2.
Answers
Fundamental defect reactions for fully ionised point defects for oxides MaOb
General equation for Schottky defects ……………. (1)
Therefore for MO2, b=2 and a=1
2b/a=2*2/1=4 means ////
b/a=2/1=2
Now substitute the value of 2b/a and b/2 in to equation of (1)
Schottky defects in MO2: 0 (or Null) Vm''''+ 2Vo•• …….Ans
NB: “Null” indicate the reaction of defect from perfect crystal
#2 Schottky defect in Mg and a Schottky defect in MgO and the difference between them
Answers
For Mgo, b=1 and a=1
2b/a=2*1/1=2 means //
b/a=1/1=1
substitute the value of 2b/a and b/2 in to equation of (1)
Schottky defect in Mgo: 0 Vmg''+ Vo•• …………………………………. (i)
Schottky defect in Mg: 0 Vmg''+ 2h• ………………………………… (ii)
There is a difference between a Schottky defect in Mg and a Schottky defect in Mgo
because
Ans: in the Mgo reaction in equation (i) satisfies the mass, charge and site balance but in
Mg reaction in equation (ii) not satisfies the mass, charge and site balance. Therefore to
satisfy the balance doping two hole is necessary.
#3) a defect reaction for the formation of anion Frenkel defects in CaF2.
Answers
For MaOb, compound general equation for Frenkel defects defects:
…………………….(2)
Therefore for CaF2, b=2 and a=1
2b/a=2*2/1=4 means //// and ••••
Now substitute the value of 2b/a and b/2 in to equation of (2)
x x '''' ••••
Anion Frenkel defects in CaF2: Caca + Vi - Vca + Cai ……………………..Ans
#4) would you expect Frenkel defects to be more likely in Al or Al2O3? What factors do we need
to consider for answering this question?
Answers
Yes I expect Frenkel defects to be more likely in Al or Al2O3
Therefore for Al2O3, b=3 and a=2
2b/a=2*3/2=3 means /// and •••
Now substitute the value of 2b/a and b/2 in to equation of (2)
Frenkel defects Al2O3: AlAlx + Vix VAl'''+ Ali••• …………….(i)
AlAlx VAl'''+ 3h• …………………………………………(ii)
Ans: the factor consider Frenkel defects to be more likely in Al than Al2O3 is Frenkel defects
Al2O3 in the above reaction equation (i) satisfies balance of charge, mass and sit but Frenkel
defects Al equation (ii) not satisfies these balance. It has more chance to defect. Al2O3 is stable
#6) Write a defect reaction for the formation of fully ionized oxygen vacancies and electrons when
oxygen is lost in the reaction M2O3 = M2O3-x + x/2 O2(g).
Answers
The defect reaction of fully ionized oxygen vacancies and electrons when oxygen is lost in
the reaction M2O3 = M2O3-x + x/2 O2 (g):
3Vo•• +
6e• +3/2 O2 (g)……………………………………Ans
#7) Write a balanced defect reaction equation using the Kroger-Vink notation for substitution of
Ca2+ in CaF2 by Y3+.
Answers
The balanced defect reaction equation for substitution of Ca2+ in CaF2 by Y3+. Using the
Kroger-Vink notation is:
2Y3+ 2Yca•+ Vca'' ………………………………………………………………
Ans
#8) Write defect reactions for dissolution of CaO substitutionally into the anion-Frenkel
dominated Y2O3.
Answers
Defect reactions for dissolution of CaO substitutionally into the anion-Frenkel dominated
Y2O3:
2Cao 2Cay'+ 2Oox Vca•• ………………………………………………………………
Ans
#9)
Given case
An oxide which predominantly contains:
oxygen vacancies at reduced oxygen activities
Interstitial oxygen ions at high oxygen activities.
In an intermediate region the oxide is stoichiometric or close to stoichiometric.
Assumed that both the interstitial oxygen ions and the oxygen vacancies are doubly charged
Required
Draw a Brouwer diagram by showing all the necessary steps ?
Answers
Let us take some oxides with the fluorite structure exhibit such a defect structure, e.g.
Uo2±x.
Steps
………………………………………. (1)
………………………………………... (2)
……………………………………………………. (3)
…………………………………………... (4)
In these equilibria we have assumed small defect concentrations such that the
concentrations of normal lattice sites and empty interstitial sites have been assumed
constant and equal to unity and thus omitted from the expressions.
It should be noted that the defect equilibria are interrelated, and through a combination of
the equations it may be shown that:
.
Thus, only three out of the four equilibria are sufficient to describe the defect structure of
the oxide.
The full electro neutrality condition is given by
………………………………………………… (5)
At reduced oxygen activities
At large oxygen deficit the following approximation may be made
………………………………………………….. (6)
insert this into the appropriate equilibrium to find the concentrations of the dominating
defects :
………………………………………………… (7)
And then insert this into other equilibria to find the concentrations of the minority
defects.
By inserting the expression for the concentration of vacancies into the anion Frenkel
equilibrium, we obtain for the concentration of interstitials:
………………………………………………(8)
By inserting the expression for the concentration of electrons into the intrinsic electronic
equilibrium, we obtain for the concentration of holes:
At high oxygen activities.
For relatively large excess oxygen
……………………………………………… (10)
Analogous to the preceding case, derive the following relations:
………………………………………………………………………….(11)
…………………………………………………. (12)
……………………………….……………………….. (13)
Stoichiometric condition
At or close to stoichiometry two alternative limiting conditions must be considered,
namely dominance by intrinsic electronic ionization or by anion Frenkel disorder.
If intrinsic ionization of electrons predominates, and thus:
…………………………………………………(14)
The concentrations of electrons and electron holes (n and p) are then independent of
oxygen pressure.
The point defect concentrations are obtained by insertion of the expression for the
concentrations of the electronic defects into the appropriate equilibria, and we obtain:
……………………………………………………………….. (15)
…………………………......……………………………….. (16)
Figure 1 A Brouwer diagram illustrating stoichiometric condition, along with oxygen deficit and
excess.
#10)
Given
Repeat question 9 for the case where anion Frenkel predominates under the stoichiometric
condition.
Required
Draw a Brouwer diagram?
Answers
Anion Frenkel disorder predominates under stoichiometric conditions, and thus:
……………………………………. (17)
//
then [Oi ]iand [ Vo ] are independent of the partial pressure of oxygen, while the
concentrations of electronic defects are given by:
…………………………………………………….... (18)
…………………………………………………………... (19)
Figure 2: A Brouwer diagram illustrating anion Frenkel predominates under the
stoichiometric condition along with oxygen deficit and excess under
