Crystal Structures of simple

compounds
Structures of ceramic materials (ionic/covalen
How do they differ from that of metals?
amic materials are inorganic, non-metallic solids
are made up of a combination of metallic and nonmetallic elements .

What are the factors determining the structure

Ceramics?

What are the different possible structures for

Ceramics?

1
 CERAMIC BONDING
• Bonding:
--Mostly ionic, some covalent.
--% ionic character increases with difference in
electronegativity.
• Large vs small ionic bond character:

H
2.1
CaF 2: large He
-
Li C F
1.0
Be
1.5 SiC: small 2.5 4.0
Ne
-
Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -
K Ca Ti Cr Fe Ni Zn As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 2.0 2.8 -
Rb Sr I Xe
0.8 1.0 2.5 -
Cs Ba At Rn
0.7 0.9 2.2 -
Fr Ra
0.7 0.9 Table of Electronegativities 2
 IONIC BONDING & STRUCTURE
• Charge Neutrality: F-
--Net charge in the CaF : Ca2+ +
2 cation anions
structure should
be zero. F-

A mXp
--General form:
m, p determined by charge neutrality

• Stable structures:--maximize the # of

nearest
oppositely charged neighbors.
- - - - - -
+ + +
- - - - - -
unstable stable stable 3
 COORDINATION # AND IONIC
RADII rcation
Coordination # increases with
ranion
Issue: How many anions can you
arrange around a cation?
rcation ZnS
Coord #
ranion (zincblende)
< .155 2

.155-.225 3 NaCl
(sodium
.225-.414 4 chloride)

.414-.732 6
CsCl
(cesium
.732-1.0 8 chloride)
4
Minimum r+/r_ required for coordination of 3:
Common Ceramic crystal structures

Structure Structure Anion Co- Anion Example

Name Type Packing ordination
no: Cation
Sodium AX FCC 6 6 Nacl,
Chloride MgO,Feo
Cesium AX Simple 8 8 CsCl
Chloride Cubic
Zinc AX2 Simple 8 4 CaF2, ZnS
blende Cubic
Zinc Blende Structure
 EX: PREDICTING STRUCTURE OF
FeO
n the basis of ionic radii, what crystal structur
ould you predict for FeO?
Cation Ionic radius (nm) • Answer:
Al 3+ 0.053
rcation 0.077
2+ 0.077 
Fe r
anion 0.140
Fe 3+ 0.069 0.550
Ca2+ 0.100
based on this ratio,
--coord # = 6
Anion
--structure = NaCl
O2- 0.140
Cl- 0.181
F- 0.133 5
 AmXp STRUCTURES
rcation 0.100
• Consider CaF2 : r  0.8
anion 0.133
• Based on this ratio, coord # = 8 and structure = CsCl.
• Result: CsCl structure w/only half the cation sites
occupied.

• Only half the cation sites

are occupied since
#Ca2+ ions = 1/2 # F- ions.

6
CARBON
•Exists in various polymorphic forms as well as in
amorphous state
•Does not fall into either metal, ceramic or polymer
categories.
•Graphite is sometimes classified as Ceramic and
Diamond structure is similar to Zinc blende
Diamond:
•Metastable carbon polymorph at room
temperature and pressure.
•Variant of Zinc blende structure where C atoms
occupy both Zn and S positions.
•Same structure is found in Germanium, Silicon
and gray tin.
X-Ray Diffraction:

•Experimental method for determination of crystal

structures.
•Produced lot of Nobel prizes: Max Von Laue
(1914) to Venkatraman Ramakrishnan (2009)
•Recall diffraction grating experiment in Optics
lab: spacing between slits comparable to
wavelength of visible light.
•For crystals we have to use x-rays since the length
scales are very small
•Beam of x-rays incident on a crystal forces the
electrons oscillate.
•Oscillating electrons are a a source of EM waves
of same frequency.
•Waves reinforce constructively in certain
directions
Actually what is happening is diffraction, but it is
visualized as reflection from atomic planes.
Condition for constructive interference:

n 2d sin 
As sin ≤ 1, we conclude
n ≤ 2d
Which is why you can’t use visible light!
How do we relate d (interplanar spacing) to
interatomic distances?
Recall that the Fraunhofer diffraction pattern is a
Fourier transform.
X-rays interact with the electrons, hence the
diffraction pattern is the Fourier transform of the
electron density.
For cubic systems:
More complicated
relations for other
crystal systems

h, k and l are integers

From above equation it is seen that d for (200) is
half of the d value for (100) plane. Therefore…
Second order maximum for (100) will coincide with
first order maximum for (200).
Hence no need to worry about n. Set it equal to 1!
In order to increase the probability that crystals
with the right orientation for Bragg reflection are
available, following procedures are followed:
1.Powder technique: Monochromatic x-ray beam,
crystals in powder form
2.Laue technique: Stationary Single crystal (fixed
, White radiation
3.Rotating crystal method: Rotating crystal,
monochromatic x-ray beam. Bragg condition
satisfied for some orientation.
Powder method:
Widely used. Cylindrical camera (Debye-Scherrer)
Powder photograph:
Typical exposure: few hours

Distance between corresponding arcs = S = 4R

ntensity can be recorded in a Diffractometer:
uses counter in place of film
Diffractometer
Symmetry determination from Laue Method
Structure Determination of Monoatomic cubic
crystals:

2
sin  
2

4a 2
h 2 2
k l 2

Distinction between lattices of cubic system
possible as all combinations of (h2+ k2 + l2) do not
occur for all systems.

Eg: In BCC (100) reflection is absent.

 If 1 and 3 are in phase, 2
1
2 will be out of phase and it
will lead to exact
3 cancellation

BCC
 Extinction Rules for cubic crystals
Crystal Allowed reflections

SC All values of (h2+k2+l2)

BCC Even values of (h+k+l)

FCC When h,k and l are all odd or

all even

DC When h,k and l are all odd or

all even, (h+k+l) should be
divisble by four
Allowed values of (h2+k2+l2)

SC 1:2:3:4:5:6:8…
BCC 1:2:3:4:5:6:7…
FCC 3:4:8:11:12
DC 3:8:11:16
Comparison of observed sin2 with above is
sufficient to identify crystal structure.
Example
From a powder camera of diameter 114.6 mm,
using an x-ray beam of wavelength 1.54Å, the
following S values in mm are obtained for a
material:
86, 100,148, 180,188,232 and 272
Determine the structure and the lattice parameter
of the material.
Sol: The Bragg angles in degrees are:
21.5 25 37 45 47 58 68
The sin2 values are:
0.1343 0.1786 0.3621 0.4999 0.5348 0.7191 0.8596
What are the corresponding hkl values?
How to find out?
Divide all the sin2 values by the least sin2 value.
We get:
1.0000 1.3297 2.6964 3.7225 3.9821 5.3544 6.4005
But these have to be integers. Multiply by some number so
that all of them become integers.
3.0000 3.9890 8.0891 11.1674 11.9464 16.0632 19.2014
3 4 8 11 12 16 19
Therefore: FCC
Lattice parameter = 3.62Å calculated from the highest Bragg angle
Why highest?
Scanning Tunneling Microscope image of a Platinum
surface: Note the shape of the atoms and the regularity of
their positions: