Structure of Ionic Solids and Ceramics

ESO205: Nature & Properties of Materials Instructor: Dr. Anish Upadhyaya

 IONIC BONDING & STRUCTURE
• Charge Neutrality:
-- Net charge in the F-
CaF 2 : Ca 2+ +
structure should cation anions
be zero.
F-
--General form:
Am Xp
m, p determined by charge neutrality
• Stable structures:
--maximize the # of nearest oppositely charged neighbors.
- - - - - -
+ + +
- - - - - -
unstable stable stable
 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
Cs Cl
(cesium
.732-1.0 8 chloride)
 EXAMPLE:
PREDICTING STRUCTURE OF FeO
• On the basis of ionic radii, what crystal structure
can be predicted for FeO?
Cation Ionic radius (nm) • Answer:
Al 3+ 0.053 r cation 0.077
Fe 2+ 0.077 
r anion 0.140
Fe 3+ 0.069  0.550
Ca 2+ 0.100
based on this ratio,
Anion --coord # = 6
O 2- 0.140 --structure = NaCl
Cl - 0.181
F-
Data from Table
0.133 12.3, Callister 6e.
Illustration
CsCl
 STRUCTURE OF COMPOUNDS: NaCl

• Compounds: Often have similar close-packed str

• Structure of NaCl
• Identify Close-packed directions
NaCl Unit Cell
NaCl Structure
CaF2
ZnS
Perovskite Structure- BaTiO3
Perovskite

BaTiO3
MgO
Ice
TiO2 UO2
Ceramic Crystal Structure
Crystalline and Non-Crystalline SiO2
 GLASS STRUCTURE
• Basic Unit: • Glass is amorphous
4- • Amorphous structure
Si0 4 tetrahedron
occurs by adding impurities
Si 4+ (Na+,Mg2+,Ca2+, Al3+)
O 2- • Impurities:
interfere with formation of
• Quartz is crystalline crystalline structure.
SiO2: Na +
Si 4+
O 2-

(soda glass)
-quartz cristobalite
Crystalline SiO2 (Cristobalite)
 FEATURES OF A SLIP
Shear
• Clay is inexpensive
• Adding water to clay
--allows material to shear easily charge
along weak van der Waals bonds neutral
--enables extrusion
--enables slip casting

• Structure of Kaolinite Clay: weak van

der Waals
bonding
4+
charge Si
3+
neutral Al
-
(W.E. Hauth, "Crystal Chemistry of OH
Ceramics", American Ceramic 2-
O
Society Bulletin, Vol. 30 (4), 1951, p.
140.)
Shear
 SUMMARY

• Ceramic materials have mostly covalent & some

ionic bonding.

• Structures are based on:

--charge neutrality
-- maximizing # of nearest oppositely charged neighbors.

• Structures may be predicted based on:

--ratio of the cation and anion radii.
Diamond Cubic Structure Graphite Fullerene
Supplemental Slides