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02 Ikatan Atom Keramik PDF
02 Ikatan Atom Keramik PDF
CERAMIC
Chapter 12 - 1
Chapter 12 - 2
Figure 1.7 Periodic table with ceramic compounds indicated by a combination of one or more
metallic elements (in light color) with one or more nonmetallic elements (in dark color). Note
that elements silicon (Si) and germanium (Ge) are included with the metals in this figure but
were not included in the periodic table shown in Figure 1.4. They are included here because,
in elemental form, Si and Ge behave as semiconductors (Figure 1.16). Elemental tin (Sn) can
be either a metal or a semiconductor, depending on its crystalline structure.
Nonmetallic ceramic forming
Metallic Elements elements
Ceramics are usually oxides. However, silicon nitride (Si3N4) is an important nonoxide ceramic
used in a variety of structural applications. Some ceramics are chemical compounds made up
of one of the five nonmetallic materials, C, N, O, P or S, shaded with dark blue color in figure
1.7. Very many variety of ceramic materials can be formed.
(C, N, P, S are forming none-oxide ceramics with metallic elements.)
(Now, Si and Ge are included as metallic elements in this classification, because they formChapter 12 -
ceramics.)
Atomic Bonding in Ceramics
Bonding:
-- Can be ionic and/or covalent in character.
-- % ionic character increases with difference in
electronegativity of atoms.
Degree of ionic character may be large or small:
CaF2: large
SiC: small
Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by
Cornell University.) Chapter 12 - 4
IONIC BONDING
Occurs between + and - ions.
Requires electron transfer.
Large difference in electronegativity required.
Example: NaCl
Chapter 12 - 8
Characteristics of Ionic Bonding
Chapter 12 -
EXAMPLES: IONIC BONDING
Predominant bonding in Ceramics
NaCl
MgO
H He
2.1 CaF2 -
Li Be O F Ne
1.0 1.5 CsCl 3.5 4.0 -
Na Mg Cl Ar
0.9 1.2 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
Example: CH4
C: has 4 valence e,
needs 4 more
H: has 1 valence e,
needs 1 more
Electronegativities
are comparable.
Chapter 12 - 10
Characteristics of Covalent Bonding
Chapter 12 -
EXAMPLES: COVALENT BONDING
H2O
column IVA
H2 F2
C(diamond)
H He
2.1
SiC - Cl2
Li Be C O F Ne
1.0 1.5 2.5 2.0 4.0 -
Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -
K Ca Ti Cr Fe Ni Zn Ga Ge As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 1.6 1.8 2.0 2.8 -
Rb Sr Sn I Xe
0.8 1.0 1.8 2.5 -
Cs Ba Pb At Rn
0.7 0.9 1.8 2.2 -
Fr Ra
0.7 0.9
Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is GaAs
adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright
1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.
Chapter 12 - 11
fig_12_26
Chapter 12 - 12
CERAMIC CRYSTAL STRUCTURES
16.03.2015 13
Ceramic Crystal Structures
Oxide structures
oxygen anions larger than metal cations
close packed oxygen in a lattice (usually FCC)
cations fit into interstitial sites among oxygen ions
Chapter 12 - 14
Factors that Determine Crystal Structure
1. Relative sizes of ions Formation of stable structures:
--maximize the # of oppositely charged ion neighbors.
- - - - - -
+ + +
Adapted from Fig. 12.1,
Callister & Rethwisch 8e.
- - - - - -
unstable stable stable
2. Maintenance of
Charge Neutrality : F-
CaF 2 : Ca 2+ +
--Net charge in ceramic
cation anions
should be zero.
--Reflected in chemical F-
formula:
A m Xp
m, p values to achieve charge neutrality
Chapter 12 - 15
Coordination # and Ionic Radii
r cation
Coordination # increases with r
anion
To form a stable structure, how many anions can
surround around a cation?
r cation Coord ZnS
r anion # (zinc blende)
Adapted from Fig. 12.4,
< 0.155 2 linear Callister & Rethwisch 8e.
a = 2ranion
2ranion 2rcation = 2 2ranion
rcation
= 2 1 = 0.414
ranion
Chapter 12 - 18
Chapter 12 - 19
Chapter 12 - 20
Bond Hybridization
Bond Hybridization is possible when there is significant
covalent bonding
hybrid electron orbitals form
For example for SiC
XSi = 1.8 and XC = 2.5
Chapter 12 - 21
Example Problem: Predicting the Crystal
Structure of FeO
On the basis of ionic radii, what crystal structure
would you predict for FeO?
Cation Ionic radius (nm) Answer:
Al 3+ 0.053 rcation 0.077
=
Fe 2+ 0.077 ranion 0.140
Fe 3+ 0.069 = 0.550
Ca 2+ 0.100
based on this ratio,
-- coord # = 6 because
Anion
0.414 < 0.550 < 0.732
O2- 0.140
-- crystal structure is NaCl
Cl - 0.181
Data from Table 12.3,
F- 0.133 Callister & Rethwisch 8e.
Chapter 12 - 22
Rock Salt Structure
Same concepts can be applied to ionic solids in general.
Example: NaCl (rock salt) structure
rNa = 0.102 nm
rCl = 0.181 nm
rNa/rCl = 0.564
Chapter 12 - 23
MgO and FeO
MgO and FeO also have the NaCl structure
O2- rO = 0.140 nm
rMg/rO = 0.514
Chapter 12 - 24
EXAMPLE OF CRYSTAL STRUCTURE
16.03.2015
EXAMPLE OF CRYSTAL STRUCTURE
16.03.2015
AX Crystal Structures
AXType Crystal Structures include NaCl, CsCl, and zinc blende
rCs 0.170
= = 0.939
rCl 0.181
Chapter 12 - 27
AX2 Crystal Structures
Fluorite structure
Antifluorite structure
positions of cations and
anions reversed
Chapter 12 - 28
ABX3 Crystal Structures
Perovskite structure
Chapter 12 - 29
VMSE: Ceramic Crystal Structures
Chapter 12 - 30
Density Computations for Ceramics
n(AC AA )
=
VC N A
Avogadros number
Volume of unit cell
Chapter 12 - 31
Chapter 12 - 32
Chapter 12 - 33
Silicate Ceramics
Most common elements on earth are Si & O
Si4+
O2-
Quartz is crystalline
Na +
SiO2:
Si 4+
O2 -
(soda glass)
Adapted from Fig. 12.11,
Callister & Rethwisch 8e.
Chapter 12 - 37
Layered Silicates
Layered silicates (e.g., clays, mica, talc)
SiO4 tetrahedra connected
together to form 2-D plane
Chapter 12 - 38
Layered Silicates (cont.)
Kaolinite clay alternates (Si2O5)2- layer with Al2(OH)42+
layer
Chapter 12 - 40
Polymorphic Forms of Carbon (cont)
Graphite
layered structure parallel hexagonal arrays of
carbon atoms
Chapter 12 - 42
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
O2-
Cl - Cl -
without impurity O2- impurity with impurity Chapter 12 - 43
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 - 44
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
Chapter 12 - 45
Chapter 12 - 46
Chapter 12 - 47
Chapter 12 - 48
Chapter 12 - 49