STRUKTUR KRISTAL

KERAMIK

Chapter 12 - 1
 EXAMPLE OF CRYSTAL STRUCTURE

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 TYPE AX : Rock Salt Structure
Same concepts can be applied to ionic solids in general.
Example: NaCl (rock salt) structure  1 anion (Cl-) dan 1 kation (Na+)

rNa = 0.102 nm

rCl = 0.181 nm

rNa/rCl = 0.564

C.N = 6  octahedral

Adapted from Fig. 12.2,

Callister & Rethwisch 8e.
Chapter 12 - 3
TYPE AX : Rock Salt Structure
MgO and FeO also have the NaCl structure

O2- rO = 0.140 nm

Mg2+ rMg = 0.072 nm

rMg/rO = 0.514

 cations prefer octahedral sites

Adapted from Fig. 12.2,

Callister & Rethwisch 8e.

So each Mg2+ (or Fe2+) has 6 neighbor oxygen atoms

Chapter 12 - 4
 EXAMPLE OF CRYSTAL STRUCTURE

Rock salt structure(AX)(NaCl ) Fluorite structure(AX2)(CaF2)

Perovskite structure(ABX3)(BaTiO3) Spinel structure(AB2X4)(MgAl2O4)

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23.03.2015
 AX Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc blende

Cesium Chloride structure:

rCs  0.170
  0.939
rCl  0.181

 Since 0.732 < 0.939 < 1.0,

cubic sites preferred

Adapted from Fig. 12.3,

So each Cs+ has 8 neighbor Cl-
Callister & Rethwisch 8e.

Chapter 12 - 6
 AX Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc blende
Zinc Blende structure:

Adapted from Fig. 12.3,

Callister & Rethwisch 8e.

Chapter 12 - 7
 AX2 Crystal Structures
Fluorite structure

• Calcium Fluorite (CaF2)

• C.N = 8
• Cations in cubic sites

• UO2, ThO2, ZrO2, CeO2

• Antifluorite structure –
Adapted from Fig. 12.5,
positions of cations and
Callister & Rethwisch 8e. anions reversed
Chapter 12 - 8
 ABX3 Crystal Structures
• Perovskite structure

Ex: complex oxide

BaTiO3

pada T= 120 oC, struktur

kristal cubic

Adapted from Fig. 12.6,

Callister & Rethwisch 8e.

Chapter 12 - 9
VMSE: Ceramic Crystal Structures

Chapter 12 - 10
 Density Computations for Ceramics

Number of formula units/unit cell

n(AC  AA )

VC N A
Avogadro’s number
Volume of unit cell

AC = sum of atomic weights of all cations in formula unit

AA = sum of atomic weights of all anions in formula unit



Chapter 12 - 11
 Silicate Ceramics
Most common elements on earth are Si & O

Si4+

O2-

Adapted from Figs.

12.9-10, Callister &
Rethwisch 8e
crystobalite

• SiO2 (silica) polymorphic forms are quartz,

crystobalite, & tridymite
• The strong Si-O bonds lead to a high melting
temperature (1710ºC) for this material
Chapter 12 - 12
 Silicates
Bonding of adjacent SiO44- accomplished by the
sharing of common corners, edges, or faces

Adapted from Fig.

12.12, Callister &
Rethwisch 8e.
Mg2SiO4 Ca2MgSi2O7

Presence of cations such as Ca2+, Mg2+, & Al3+

1. maintain charge neutrality, and
2. ionically bond SiO44- to one another
Chapter 12 - 13
 Glass Structure
• Basic Unit: Glass is noncrystalline (amorphous)
4- • Fused silica is SiO2 to which no
Si0 4 tetrahedron impurities have been added
Si 4+ • Other common glasses contain
O2 - impurity ions such as Na+, Ca2+,
Al3+, and B3+

• Quartz is crystalline Na +
SiO2: Si 4+

O2-

(soda glass)
Adapted from Fig. 12.11,
Callister & Rethwisch 8e.

Chapter 12 - 14
 Layered Silicates
• Layered silicates (e.g., clays, mica, talc)
– SiO4 tetrahedra connected
together to form 2-D plane

• A net negative charge is associated

with each (Si2O5)2- unit
• Negative charge balanced by
adjacent plane rich in positively
charged cations

Adapted from Fig.

12.13, Callister &
Rethwisch 8e.

Chapter 12 - 15
 Layered Silicates (cont.)
• Kaolinite clay alternates (Si2O5)2- layer with Al2(OH)42+
layer

Adapted from Fig. 12.14,

Callister & Rethwisch 8e.

Note: Adjacent sheets of this type are loosely bound to

one another by van der Waal’s forces.
Chapter 12 - 16
 Polymorphic Forms of Carbon
Diamond
– tetrahedral bonding of
carbon
• hardest material known
• very high thermal
conductivity
– large single crystals –
gem stones
– small crystals – used to
grind/cut other materials
– diamond thin films
Adapted from Fig. 12.15,
• hard surface coatings – Callister & Rethwisch 8e.
used for cutting tools,
medical devices, etc.

Chapter 12 - 17
Polymorphic Forms of Carbon (cont)
Graphite
– layered structure – parallel hexagonal arrays of
carbon atoms

Adapted from Fig.

12.17, Callister &
Rethwisch 8e.

– weak van der Waal’s forces between layers

– planes slide easily over one another -- good
lubricant
Chapter 12 - 18
 Polymorphic Forms of Carbon (cont)
Fullerenes and Nanotubes
• Fullerenes – spherical cluster of 60 carbon atoms, C60
– Like a soccer ball
• Carbon nanotubes – sheet of graphite rolled into a tube
– Ends capped with fullerene hemispheres

Adapted from Figs.

12.18 & 12.19, Callister
& Rethwisch 8e.

Chapter 12 - 19
 Imperfections in Ceramics
• Electroneutrality (charge balance) must be maintained
when impurities are present
• Ex: NaCl Na + Cl -
cation
• Substitutional cation impurity vacancy
Ca 2+
Na +
Na +
Ca 2+
without impurity Ca 2+ impurity with impurity
• Substitutional anion impurity an ion vacancy
O 2-

Cl - Cl -
without impurity O 2- impurity with impurity
Chapter 12 - 20
 Point Defects in Ceramics (i)
• Vacancies
-- vacancies exist in ceramics for both cations and anions
• Interstitials
-- interstitials exist for cations
-- interstitials are not normally observed for anions because anions
are large relative to the interstitial sites

Cation
Interstitial
Cation
Vacancy
Adapted from Fig. 12.20, Callister
& Rethwisch 8e. (Fig. 12.20 is
from W.G. Moffatt, G.W. Pearsall,
and J. Wulff, The Structure and
Properties of Materials, Vol. 1,
Structure, John Wiley and Sons,
Inc., p. 78.)
Anion
Chapter 12 - 21
Vacancy
 Point Defects in Ceramics (ii)
• Frenkel Defect
-- a cation vacancy-cation interstitial pair.
• Shottky Defect
-- a paired set of cation and anion vacancies.
Shottky
Defect: Adapted from Fig.12.21, Callister
& Rethwisch 8e. (Fig. 12.21 is
from W.G. Moffatt, G.W. Pearsall,
and J. Wulff, The Structure and
Properties of Materials, Vol. 1,
Structure, John Wiley and Sons,
Inc., p. 78.)
Frenkel
Defect

• Equilibrium concentration of defects  e QD /kT

Chapter 12 - 22
Chapter 12 - 23
Chapter 12 - 24
Chapter 12 - 25
Chapter 12 - 26