STRUKTUR KRISTAL

KERAMIK

Chapter 12 - 1

EXAMPL O CRYSTA STRUCTU

E
F L
RE

23.03.2015

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
O2Mg2+

rO = 0.140 nm
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

EXAMPL O CRYSTA STRUCTU

E
F L
RE

Rock salt structure(AX)(NaCl )

Fluorite structure(AX2)(CaF2)

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

http://www.eng.uwo.ca/es021/ES021b_2007/Lecture%20Notes/Chap%2012-13%20SN%20-%20Ceramics.pdf

23.03.2015

AX Crystal Structures
AXType Crystal Structures include NaCl, CsCl, and zinc blende
Cesium Chloride structure:

Cs

Cl

0.170

0.939
0.181

Since 0.732 < 0.939 < 1.0,

cubic sites preferred
Adapted from Fig. 12.3,
Callister & Rethwisch
8e.

So each Cs+ has 8 neighbor Cl-

Chapter 12 - 6

AX Crystal Structures
AXType 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 (CaF )

2
C.N = 8
Cations in cubic sites

UO ThO , ZrO , CeO

2,
2
2
2

Adapted from Fig. 12.5,

Callister & Rethwisch
8e.

Antifluorite structure
positions of cations and
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

Avogadros number

Volume of unit cell

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

AA =

Chapter 12 - 11

Silicate Ceramics
Most common elements on earth are Si & O

Si4+
O2Adapted from Figs.
12.9-10, Callister &
Rethwisch 8e

crystobalite

SiO (silica) polymorphic forms are quartz,

2
crystobalite, & tridymite
The strong Si-O bonds lead to a high melting
temperature (1710C) 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 SiO4 4- to one another
Chapter 12 - 13

Glass Structure
Basic Unit:

Glass is noncrystalline (amorphous)

Fused silica is SiO to which no

4-

Si0 4 tetrahedron
Si 4+
O2-

Quartz is crystalline
SiO2:

impurities have been added

Other common glasses contain
impurity ions such as Na+, Ca2+,
Al3+, and 3+
B
Na +
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

adjacentcharge
plane balanced
rich in positively
Negative
by
charged cations

Adapted from Fig.

12.13, Callister &
Rethwisch 8e.
Chapter 12 - 15

Layered Silicates (cont.)

Kaolinite clay alternates (Si O )22 5
layer

layer with Al (OH) 2+

2
4

Adapted from Fig. 12.14,

Callister & Rethwisch
8e.

Note: Adjacent sheets of this type are loosely bound to

one another by van der Waals 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
hard surface coatings
used for cutting tools,
medical devices, etc.

Adapted from Fig. 12.15,

Callister & Rethwisch
8e.

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 Waals 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, C
60
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 Substitutional cation impurity

cation
vacancy

Ca 2+

Na +
without impurity

Na +
Ca 2+ impurity

Substitutional anion impurity

Ca 2+

with impurity
an ion vacancy

O 2-

without impurity

Cl -

Cl -

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

Anion
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.)
Chapter 12 21

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

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Chapter 12 - 24

Chapter 12 - 25

Chapter 12 - 26