1

MLE1101 Tutorial 6 - Suggested Solutions

1.






Using the above figure, calculate the critical radius ratio for octahedral coordination.

Solution:
From the triangle shown above in part (b),
( ) ( ) ( )
( )
2
2 2
2
2
2 2 2
2
2
0.414
0.414
r R R R
r R R
r R R
r R
r
R
+ = + (

+ =
+ =
=
=



2. Calculate the density in grams per cubic centimetre of CsI, which has the CsCl structure. Ionic
radii are Cs
+
= 0.165 nm and I
-
= 0.220 nm.

Solution:











For the CsCl structure, the ions touch each other across the cube diagonal. Let r = Cs
+
ion and
R = I
-
ion. Thus,
( ) 3 2 a r R = +
( )
8
2
0.165nm 0.220nm 0.445nm 4.45 10 cm
3
a

= + = =


(a) Octahedral coordination of
six anions (radii = R) around a
central cation of radius r.
(b) Horizontal section through
center of (a)
Cesium iodide
I
-
2

Since the unit cell of CsI contains one Cs
+
and one I
-
ion, its mass is
( ) ( )
22
unit cell
23
1Cs 132.9g/mol 1I 126.9g/mol
4.32 10 g
6.02 10 ions/mol
m
+

+
= =

The density is thus calculated as:
( )
22
3
3 3
8
4.32 10 g
4.90g /cm
4.45 10 cm
m m
v a

= = = =

3. Calculate the planar densities (of Co
2+
, O
2-
, Li
+
and Cl
-
) in ions per square nanometer on the
(111) and (110) planes for (a) CoO and (b) LiCl. Ionic radii are Co
2+
= 0.082 nm, O
2-
= 0.132
nm, Li
+
= 0.078 nm and Cl
-
= 0.181 nm.

Solution:
2
2
0.082
0.62
0.132
0.078
0.431
0.181
Co
O
Li
Cl
r
r
r
r
+

= =
= =

Since the radius ratio is between 0.414 and 0.732, both CoO and LiCl should have a
coordination number of 6, with the NaCl structure.

(a) For CoO, if we consider the O
2-
anions to be located at the FCC positions of a cubic
unit cell, then the (111) plane contains the equivalent of two anions.

1 1
6 2
3 anion 3 anion 2anions + =

The lattice constant,
( ) ( ) 2 2 0.082nm 0.132nm 0.428nm a r R = + = + =

Thus, area of the (111) plane is,

( )
( )
2
2
(111)
1 1 3 3
2 0.428nm 0.159nm
2 2 2 2
A bh a a
| |
= = = =
|
\ .


The planar density for the O
2-
anions then becomes,

2
2 2
planar
2
2(O ions)
12.6 O ions /nm
0.159nm

= =

The planar density of the Co
2+
cations is the same if we consider them to be located
at the FCC lattice points of the unit cell. Consequently,

2+ 2 2
planar
(CoO) 12.6 (Co or O )ions/nm

=

For the (110) plane, we have two ions contained within the plane. The area of the
plane is,
3


( )
( ) ( )
2
2
(110)
2 2 0.428nm 0.26nm A a a = = =

The (110) planar densities for CoO are,

( )
2 2
2 2 2
planar
2
2O 2Co
7.72 Co +7.72 O /nm
0.26nm

+
+
+
= =



(b) Similarly, for LiCl, the (111) planar densities are calculated as such:
( ) ( ) 2 2 0.078nm 0.181nm 0.518nm a r R = + = + =
( )
2
2
(111)
1 3
0.518nm 0.232nm
2 2
A bh = = =
2
planar
2
2(Cl ions)
8.6 Cl ions /nm
0.232nm

= =
2
planar
2
2(Li ions)
8.6 Li ions /nm
0.232nm

+
+
= =

For the (110) plane,
( )
2
2
(110)
2 0.518nm 0.38nm A = =
( )
2
planar
2
2Cl 2Li
5.26Cl 5.26Li /nm
0.38nm

+
+
+
= = +



4. Calculate the linear density of Ce
4+
and O
2-
in ions per nanometer in the [111] and [110]
directions for CeO
2
, which has the calcium fluorite structure. Ionic radii are Ce
4+
= 0.102 nm
and O
2-
= 0.132 nm.

Solution:
From the diagram,
( )
( )
( )
4 2
Ce O
4 2
Ce O
3
4
4 4
0.102nm 0.132nm
3 3
0.540nm
a r R
a r R
+
+
= +
= + = +
=





For the [111] direction:
(110) plane
4

( )
( )
4 2 4 2
4 2
1Ce 2O 1Ce 2O
3 3 0.540nm
1.07Ce 2.14O /nm
L
a

+ +
+
+ +
= =
= +


For the [110] direction,
( )
4 4
4
2Ce 2Ce
2.62 Ce /nm
2 2 0.540nm
L
a

+ +
+
= = =



5. What causes the lack of plasticity in crystalline ceramics?

Solution:
The lack of plasticity in crystalline ceramics is attributed to their ionic and covalent chemical
bonds.

In covalently bonded ceramics, the bonding between atoms is specific and directional.
Therefore, they will undergo brittle fracture as covalent bonds are broken without
subsequent reformation.

For ionic crystals, the slip of one plane of ions over another involves ions of different charges
coming into contact, and thus attractive and repulsive forces may be produced. For example,
in the NaCl-type structures (see figure below), slip on the {110} family of planes involves only
ions of unlike charges and hence the slip planes remain attracted to each other by
Coulombic forces during the slip process. In contrast, slip on the {100} family of planes is
rarely observed because ions of the same charges will repel each other when come into
contact. Hence, there are limited slip systems in ionically bonded ceramics which lead to the
lack of plasticity in ionically bonded ceramics.

Polycrystalline ionic ceramics show less plasticity than single crystals because the slip cannot
continue across the grain boundaries.












Top view of NaCl crystal structure
indicating (a) slip on the (110) plane and
in the [110] direction (line AA) and (b)
slip on the (100) plane in the [010]
direction (line BB).
5

6. Explain the plastic deformation mechanism for some single-crystal ionic solids such as NaCl
and MgO. What is the preferred slip system?

Solution:
For some single-crystal ionic solids, such as NaCl and MgO, compressive stresses at room
temperature cause considerable plastic deformation prior to fracture because planes of
oppositely charged ions can slip relative to each other. These slip planes, which maintain
their attraction through coulombic forces, typically prefer the {110} 110 < > slip system for
NaCl-type structures.


7. How do (a) porosity and (b) grain size affect the tensile strength of ceramic materials?

Solution:
(a) Pores serve as stress concentration points and induce cracks at lower threshold
values. They decrease the effective cross-sectional area for load distribution as well.
Consequently, as the porosity of a ceramic material increases, the material tensile
strength decreases.

(b) For a porosity-free ceramic, the flaw size, and thus the strength, is solely a function
of grain size; the finer the grain size, the smaller the flaws and the greater the
ceramic tensile strength.