4.1 Metalic Oxides 1

Slides are based in:
“Materials Science and Engineering. An

Introduction” William D. Callister Jr., David G.
Rethwish, John Wiley and Sons, 2018
Chapter 4: Imperfections in Solids
Chapter 7: Dislocations and Strengthening
Mechanisms
“Introduction to Materials Science for Engineers”

James F. Shackelford, Prentice Hall, 2015
Chapter 3: Crystalline Structure – Perfection
Ceramic structures
Ceramics
•Most ceramics are compounds between
nonmetallic and metallic elements
•Generally, have more complex crystal

structures than metals.
•The bonding in ceramics ranges from ionic to

covalent, but most are totally ionic or
predominantly ionic (with some covalent
character)
Ceramic crystal structures
•Most ceramic materials are made up of
ions.
•Metallic ions positively charged are
cations (smaller)
•Nonmetallic ions negatively charged are
anions (larger)
•Two main characteristics that influence

crystal structure:
• charge balance
• size of the ions
Cation/Anion Attraction
Cations tend to get surrounded by as many anions as
they can possibly fit.
Which one will be able to accommodate

more anions around?
+ +
The greater the difference

(i.e. the lower the RC/RA ratio)
the lower the coordination number
Cation/Anion Ratio
Coordination number can be correlated to the ratio of
the ionic radius of the cation, RC, to the ionic radius of
the anion, RA.
RC
Cation/ Anion Ratio :
RA
In-class Problem
Find the minimum cation/anion ratio, RC/RA,
for the coordination number 3:
AP = R A & AO = R A + R C
AP 3
= cos30°=
AO 2
AP RA 3
O = =
P AO R A + RC 2
30°
A RC 1- 3 2
P = = 0.155
RA 3 2
Coordination Numbers and Geometries
Not usual
Coordination Cation/Anion Coordination
Number Ratio (RC/RA) Geometry
2 <0.155

3 0.155 - 0.225

4 0.225 - 0.414

6 0.414 - 0.732
see table in textbook
8 0.732 - 1.0
Ionic radii for several cation and anions
(for a Coordination Numbers of 6)
AX Type Crystal Structures
A) Rock Salt Structure (NaCl, MgO, FeO)
Is this structure consistent
with the RC/RA and charge balance
criteria ?
Let’s determine the RC/RA ratio
for NaCl:
RNa/RCl =
NaCl = 0.102/0.181 =
= 0.563
Go to table
RNa/RCl = 0.563
Therefore,
Coordination
Number =
6
Balance of + and - ions in the unit cell ?
Number of cations= total 4
a) on the sides = 4 x ¼ = 1
b) on the bases = 8 x ¼ = 2
c) in the center = 1
Number of anions= total 4
a) on the corners = 8 x 1/8 = 1

NaCl b) on the faces = 6 x ½ = 3
Charge Balance  1 Na+ for each Cl _

Calculate density of MgO (Rock Salt)
mass of unit cell = 4 x m(Mg) + 4 x

m(O)
(4 x 24.3 + 4 x 16)/ 6 x 10 23 =
= 2.68 x 10-22 g
volume of unit cell = a3
MgO
What is a ?
Which ions are touching ?
Last O=
does
not touch
the other
anions
MgO
R(Mg2+) = 0.072 nm
Mg2+ only
R (O=) = 0.14 nm touches
the anions
Drawing at scale
Or
Mathematical solution
Calculate density of MgO (Rock Salt)
mass of unit cell = 4 x m(Mg) + 4 x m(O)
(4 x 24.3 + 4 x 16)/ 6 x 10 23 =
= 2.68 x 10-22 g
volume of unit cell = a3

What is a ?
Which ions are touching ?
= (2 RMg + 2 RO)3 = ( 2 (0.072 + 0.14))3 =
MgO = 7.62 x 10-23 cm3
density = 2.68 / 0.762 = 3.52 g/cm3

calc. 3.52 g/cm3  measured 3.59 g/cm3
B) Cesium Chloride Structure (note: this is not BCC)
Let’s determine the

RC/RA ratio:
RCs/RCl =
= 0.170/0.181 =
= 0.939
GO TO Table 13.2
Coordination Number =
8
How many Cs and Cl ions in the unit cell ?
Number of cations= total 1
in the center = 1
Number of anions= total 1
on the corners = 8 x 1/8 = 1
Charge Balance  1 Cs+ for each Cl _

Tetrahedral and Octahedral Sites
T site O site
Let’s visualize them
Tetrahedral
Octahedral
Simplifying Assumption
•Anions are the larger elements in crystal

•They can be packed in a high packing
factor arrangements (HCP or FCC)
•Cations can occupy interstitial positions,
according to their preferential coordination
number (most typical 4 and 6)
•Tetrahedral position has a coordination
number of 4
•Octahedral positions have coordination
number 6
FCC arrangement of anions
Let’s focus on the most highly packed plane (111)
Let’s focus on the most highly packed plane (111)
And now, on the following (111) plane
First layer of (111) plane
Add second layer of (111) plane
Find the Tetrahedral and Octahedral Sites

T site O site
O
Let’s try to develop the rock salt
structure based on this method
A) Find the
octahedral
positions in a FCC
unit cell
A) Find the
octahedral
positions in a FCC
unit cell
A) Find the
octahedral
positions in a FCC
unit cell
B) How many O
positions in the
unit cell?
12 x ¼ = 3
+
1 (center) = 4
Now, let’s find the tetrahedral positions
Now, let’s find the tetrahedral positions
How many T
positions in the
unit cell?
one in each
corner = 8
O positions, Anions and Cations
In unit cell:
O positions = 4
Anions = 4
In NaCl,:
Anions = Cations
Therefore
Occupancy of O sites = 100 %
O positions, Anions and Cations
In FCC unit cell:
T positions = 8
Anions = 4
In NaCl:
Anions = Cations
Therefore
Occupancy of T sites
=0%
Q: Why doesn’t Na go to the T sites ? C.N. = 4 vs 6
IMPORTANT !
In FCC arrangement of anions:
•a) the ratio O sites/anions = 1/1

•b) the ratio T sites/anions = 2/1
•The occupancy of T and O sites is

determined by:
• site preference (RC/RA)
• charge balance
In-class problem
•Assuming that the anions are arranged in an
FCC structure, determine the structure of Zinc
Sulfide (ZnS).
•Procedure:
a) obtain the (RC/RA) ratio and determine the
C.N. and whether it is a T or O site.
b) By looking at the charge balance, determine
the occupancy of O sites and T sites.
c) distribute the cations in the interstitial
positions, keeping them as far as possible
Result R(Zn2+) =
R(S=) =
0.074
0.184
Ratio = 0.40
range 0.225 - 0.414
C.N. = 4
T sites only
charge balance:
Anion/Cation = 1
Since T sites /anions = 2
cations/T sites = 1/2
50 % occupancy
Result
C.N. = 4
T sites only
charge balance:
Anion/Cation = 1
50 % occupancy
Please read:
“Materials Science and Engineering. An

Introduction” William D. Callister Jr., David G.
Rethwish, John Wiley and Sons, 2018
Chapter 12:
Structures and Properties of Ceramics
“Introduction to Materials Science for Engineers”

James F. Shackelford, Prentice Hall, 2015
Chapter 3: Crystalline Structure – Perfection
Ceramic structures

4.1 Metalic Oxides 1

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Slides are based in:

“Materials Science and Engineering. An

“Introduction to Materials Science for Engineers”

•Generally, have more complex crystal

•The bonding in ceramics ranges from ionic to

•Two main characteristics that influence

Which one will be able to accommodate

The greater the difference

Coordination Cation/Anion Coordination

Coordination Cation/Anion Coordination

Coordination Cation/Anion Coordination

Number of cations= total 4

Number of anions= total 4

a) on the corners = 8 x 1/8 = 1

Charge Balance  1 Na+ for each Cl _

mass of unit cell = 4 x m(Mg) + 4 x

volume of unit cell = a3

volume of unit cell = a3

MgO = 7.62 x 10-23 cm3

density = 2.68 / 0.762 = 3.52 g/cm3

Let’s determine the

Number of cations= total 1

Number of anions= total 1

on the corners = 8 x 1/8 = 1

Charge Balance  1 Cs+ for each Cl _

•Anions are the larger elements in crystal

Find the Tetrahedral and Octahedral Sites

•a) the ratio O sites/anions = 1/1

•The occupancy of T and O sites is

range 0.225 - 0.414

“Materials Science and Engineering. An

“Introduction to Materials Science for Engineers”

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