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MECH 270

Material Science and Engineering

20. Structure of Ceramics


Chapter 12

Rick Holt

Queen’s University
KINGSTON, ONTARIO, CANADA.

Structures of Ceramics

• Bonding
• Crystal structures
• Point Defects

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RH80

Ceramic Bonding
• Bonding:
-- Mostly ionic, some covalent.
-- % ionic character increases with difference in
electronegativity.
• Large vs small ionic bond character:
CaF2: large
SiC: small

Adapted from Fig. 2.7, Callister 7e. (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.

Ceramic Crystal Structures

• ceramics that are predominantly ionic in nature


have crystal structures comprised of charged ions,
where positively-charged (metal) ions are called
cations, and negatively-charged (non-metal) ions
are called anions – the crystal structure for a given
ceramic depends upon two characteristics:

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Slide 3

RH80 ceramics typically contain two or more elements in a stoichiometric combination (eg. CaF2, SiO2), which
means that crystalline ceramics can have very complex crystal structures – furthermore, the
inter-atomic bonding in a ceramic can vary from purely ionic to totally covalent, depending upon the
electronegativities of the atoms involved
Richard Holt, 11/1/2007
Ceramic Crystal Structures

1. the magnitude of electrical charge on each


component ion, recognizing that the overall
structure must be electrically neutral
2. the relative size of the cation(s) and anion(s),
which determines the type of interstitial site(s)
for the cation(s) in an anion lattice

Crystal Structures

The common ceramics are oxides and chlorioes


– Oxygen and chlorine anions generally larger than metal
cations
– close packed anion in a lattice (usually FCC)
– Cations fill in the holes of the anion lattice

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Site Selection
Which sites will cations occupy?
1. Size of sites
– does the cation fit in the site
– Are the cations/anion distances minimized

2. Stoichiometry
– if all of one type of site is full the remainder
have to go into other types of sites.

1. Size - Stable structures:


--maximize the # of nearest oppositely charged neighbors.

Ionic Bonding & Structure


- - - - - -
+ + +
Adapted from Fig. 12.1,
Callister 7e.
- - - - - -
unstable stable stable

• Charge Neutrality: F-
--Net charge in the
CaF 2 : Ca 2+ +
structure must cation anions
be zero. F-

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

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Cation Site Size
• Determine minimum rcation/ranion for OH site
(C.N. = 6)

2ranion + 2rcation = 2a

a = 2ranion

2ranion + 2rcation = 2 2ranion

ranion + rcation = 2ranion rcation = ( 2 − 1)ranion

rcation
= 0 . 414
r anion

Coordination # and Ionic Radii


r cation
• Coordination # increases with r anion
Issue: How many anions can you
arrange around a cation? How close are they.
r cation Coord ZnS
r anion # (zincblende)
Adapted from Fig.
< 0.155 2 linear 12.4, Callister 7e.

0.155 - 0.225 3 triangular NaCl


(sodium
0.225 - 0.414 4 TD chloride)
Adapted from Fig. 12.2,
Callister 7e.

0.414 - 0.732 6 OH CsCl


(cesium
0.732 - 1.0 8 cubic chloride)
Adapted from Fig.
Adapted from Table 12.2, 12.3, Callister 7e.
Callister 7e.

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NaCL (Rock Salt) Structure
Example: NaCl (rock salt) structure

rNa = 0.102 nm

rCl = 0.181 nm

rNa/rCl = 0.564

∴ cations prefer OH sites

Adapted from Fig. 12.2,


Callister 7e.

MgO has the NaCl structure

O2- rO = 0.140 nm

Mg2+ rMg = 0.072 nm

rMg/rO = 0.514

∴ cations prefer OH sites

Adapted from Fig. 12.2,


Callister 7e.

So each oxygen has 6 neighboring Mg2+

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

rCs + 0 . 170
= = 0 . 939
rCl − 0 . 181

∴ Cations prefer cubic sites

So each Cs+ has 8 neighboring Cl-


Adapted from Fig. 12.3,
Callister 7e.

Site Selection
2. Stoichiometry
– If all of one type of site is full the remainder have
to go into other types of sites.

Ex: FCC unit cell has 4 OH and 8 TD sites.

If for a specific ceramic each unit cell has 6


cations and the cations prefer OH sites
4 in OH
2 in TD

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AX2 Crystal Structures
Fluorite structure

• Calcium Fluorite (CaF2)


•rCa = -.10 nm
•rF = 0.13 nm
•rCa/rF = 0.752

• cations in cubic sites

• UO2, ThO2, ZrO2, CeO2


Adapted from Fig. 12.5,
Callister 7e.

ABX3 Crystal Structures

• Perovskite

Ex: complex oxide


BaTiO3
Adapted from Fig. 12.6,
Callister 7e.

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RH81

Silicate Ceramics
Most common elements on earth are Si & O
– rSi = 0.04
– rO = -.14
– rSi/rO = 0.286 → cations prefer TD
Si4+

O2-

Adapted from Figs.


12.9-10, Callister 7e.
crystobalite

• SiO2 (silica) structures are quartz, crystobalite, &


tridymite
• The strong Si-O bond leads to a strong, high melting
material (1710ºC)

Amorphous Silica
• Silica gels - amorphous SiO2
– Si4+ and O2- not in well-ordered lattice
– Charge balanced by H+ (to form
OH-) at “dangling” bonds
• very high surface area > 200 m2/g
– SiO2 is quite stable, therefore unreactive
• makes good catalyst support

Adapted from Fig.


12.11, Callister 7e.

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Slide 17

RH81 another common class of ceramics is the family of silicate ceramics, composed primarily of silicon and
oxygen – given that Si and O are the two most abundant elements in the earth’s crust, the majority of
soils, rocks, clays, and sand can be classified as silicates – silicon dioxide (SiO2), also called silica, is the
simplest silicate – as is the case with many ceramic materials, silica has three polymorphic crystalline
forms: quartz, cristabolite, and tridymite

Most crystalline ceramics contain very complex 3-D arrangements, such as the cristobalite unit cell
shown here.
Richard Holt, 11/1/2007
Silica Glass
• Dense form of amorphous silica
– Charge imbalance corrected with “counter
cations” such as Na+
– Borosilicate glass is the pyrex glass used in
labs
• better temperature stability & less brittle than sodium
glass

Defects in Ceramic Structures


• Frenkel Defect
--a cation is out of place.
• Shottky Defect
--a paired set of cation and anion vacancies.
Shottky
Defect: Adapted from Fig. 12.21, Callister 7e.
(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 − Q D / kT

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Impurities
• Impurities must also satisfy charge balance = Electroneutrality
• Ex: NaCl Na + Cl -
cation
• Substitutional cation impurity vacancy
Ca 2+
Na +
Na +
Ca 2+
initial geometry Ca 2+ impurity resulting geometry

• Substitutional anion impurity an ion vacancy


O 2-

Cl - Cl -
initial geometry O 2- impurity resulting geometry

Diffusion
• Because of the point defect structures than
must have a charge balance diffusion is
more complicated in ceramics that in metals
• e.g., the two vacant cites of a Shottky defect
must stay close together

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Ceramic Phase Diagrams
often part of a three component system such as Mg-Al-O can be treated as a
two component system if two ceramics are taken as end points

MgO-Al2O3 diagram:

Adapted from Fig.


12.25, Callister 7e.

Summary

• Ceramic materials have covalent & ionic bonding.


• Structures of ionic ceramics are based on:
-- charge neutrality
-- minimizing cation-anion distance
-- maximizing # of nearest oppositely charged neighbors.
• Structures may be predicted based on:
-- ratio of the cation and anion radii.
• Defects
-- must preserve charge neutrality
-- have a concentration that varies exponentially w/T.

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