Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Chapter Outline: Ceramics

Chapter 12: Structure and Properties of

Ceramics

Crystal Structures
Silicate Ceramics
Imperfections in Ceramics
Carbon

Skip: 12.9 12.11

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Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Ceramics
keramikos - burnt stuff in Greek -
properties achieved through high-
temperature heat treatment (firing).
Usually metallic + non-metallic elements
Always composed of more than one
element (e.g., Al2O3, NaCl, SiC, SiO2)
Bonds are partially or totally ionic
Hard and brittle
Electrical and thermal insulators
Optically opaque, semi-transparent, or
transparent
Traditionally based on clay (china,
bricks, tiles, porcelain) and glasses
New ceramics for electronic,
computer, aerospace industries.

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Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Bonding in Ceramics (Chapter 2)

Electronegativity ability of atoms to accept

electrons (subshells with one electron - low
electronegativity; subshells with one missing
electron -high electronegativity).
Electronegativity increases from left to right.

Bonding is mixed:
ionic + covalent
Degree of ionic
depends on difference
in electronegativities
Cations(+); Anions(-)
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Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Crystal Structures: Predominantly Ionic

Crystal structure is defined by

Magnitude of electrical charge on each ion
Charge balance dictates chemical formula
(Ca2+ and F- form CaF2).
Relative sizes of cations and anions
Cations want maximum possible number of
anion nearest neighbors and vice-versa.

Ceramic crystal structures: anions surrounding a

cation are all in contact with it. For a specific
coordination number there is a critical or
minimum cation-anion radius ratio rC/rA for which
this contact can be maintained

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Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics
C.N. rC/rA Geometry

2 <0.155
The critical ratio
determined by
geometrical
3 0.155-0225
analysis

4 0.225-0.414

30

6 0.414-0.732
Cos 30= 0.866
= R/(r+R)

r/R = 0.155
8 0.732-1.0

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Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Crystal Structures
Rock Salt Structure
NaCl
rC = rNa = 0.102 nm, rA = rCl = 0.181 nm
rC/rA = 0.56
From table for stable geometries: C.N. = 6

Two interpenetrating FCC lattices

NaCl, MgO, LiF, FeO have this crystal structure
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Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Other crystal structures in ceramics

(will not be included in the test)
Cesium Chloride Structure:
rC = rCs = 0.170 nm, rA = rCl = 0.181 nm
rC/rA = 0.94
From table for stable geometries: C.N. = 8

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Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Other crystal structures in ceramics

(will not be included in the test)
Zinc Blende Structure: typical for compounds
where covalent bonding dominates. C.N. = 4

ZnS, ZnTe, SiC have this crystal structure

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 Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Other crystal structures in ceramics

(will not be included in the test)
Fluorite (CaF2):
rC = rCa = 0.100 nm, rA = rF = 0.133 nm
rC/rA = 0.75
From table for stable geometries: C.N. = 8

FCC structure with 3 atoms per lattice point

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 Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Density computation
(similar to Chapter 3.5 for metals)
= n(AC + AA) / (VcNA)
n: number of formula units in unit cell (all ions
included in chemical formula of compound =
formula unit)
AC: sum of atomic weights of cations
AA: sum of atomic weights of anions
Vc: volume of the unit cell
NA: Avogadros number,
6.0231023 (formula units)/mol

Example: NaCl
n = 4 in FCC lattice
AC = ANa = 22.99 g/mol
AA = ACl = 35.45 g/mol
Vc = a3 = (2rNa+2rCl)3 =
(20.10210-7 + 20.18110-7)3 cm3
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Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Silicate Ceramics
Mainly of silicon and oxygen, the two
most abundant elements in earths crust
(rocks, soils, clays, sand)
Basic building block: SiO44- tetrahedron
Si-O bonding is largely covalent, but
overall SiO4 block has charge of 4
Various silicate structures different
ways to arrange SiO4-4 blocks

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Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Silica = silicon dioxide = SiO2

Every oxygen shared by adjacent

tetrahedra
Silica is crystalline (quartz) or amorphous,
as in glass (fused or vitreous silica)

3D network of SiO4 tetrahedra in cristobalite

High melting temperature of 1710 C
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Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Window glasses
Common window glass is produced by adding
oxides (e.g. CaO, Na2O) whose cations are
incorporated within SiO4 network. The cations
break the tetrahedral network. Glasses melt at
lower temperature than pure amorphous SiO2.
Lower melting T makes it easier to form objects
(e.g, bottles). Some other oxides (TiO2, Al2O3)
substitute for silicon and become part of the
network

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 Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Imperfections in Ceramics (I)

Point defects in ionic crystals are charged. Coulomb
forces are large. Any charge imbalance has a strong
tendency to balance itself. To maintain charge
neutrality several point defects can be occur:
Frenkel defect: a pair of cation (positive ion) vacancies
and a cation interstitial. Also be an anion (negative ion)
vacancy and anion interstitial. Anions are larger than
cations so not easy for an anion interstitial to form
Schottky defect is a pair of anion and cation vacancies

Schottky defect
Frenkel defect

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 Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Imperfections in Ceramics (II)

Frenkel and Schottky defects do not change ratio of
cations to anions compound is stoichiometric
Non-stoichiometry (composition deviates from the
one predicted by chemical formula) occurs when one
ion type can exist in two valence states, e.g. Fe2+, Fe3+
In FeO, Fe valence state is 2+.
Two Fe ions in 3+ state an Fe vacancy is required
to maintain charge neutrality
fewer Fe ions non-stoichiometry

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 Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Impurities in Ceramics
Impurity atoms can be substitutional or
interstitials
Substitutional: substitute for ions of like type
Interstitials: small compared to host structure
formation of anion interstitials is unlikely
Solubilities higher if ion radii and charges match
Incorporation of ion with different charge state
requires compensation by point defects

Interstitial impurity atom

Substitutional impurity ions

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Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Mechanical Properties of Ceramics

Brittle Fracture stress concentrators are
very important. (Chap. 8: measured
fracture strengths are much smaller
than theoretical due to stress risers)
Fracture strength greatly enhanced by
creating compressive stresses in the
surface region (similar to shot peening,
case hardening in metals, Chap. 8)

Compressive strength is typically ten

times the tensile strength Therefore
ceramics are good structural materials
under compression (e.g., bricks in
houses, stone blocks in the pyramids).

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Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Plastic Deformation in Ceramics

Crystalline ceramics: Slip (dislocation
motion) is difficult because ions of like
charge have to be brought close together
large barrier for dislocation motion
In ceramics with covalent bonding slip is
not easy (covalent bonds are strong)
ceramics are brittle.

Non-crystalline ceramic: no regular

crystalline structure no dislocations
or slip. Materials deform by viscous flow
(breaking and reforming bonds,
allowing ions/atoms to slide past each
other (like in a liquid)

Viscosity is a measure of glassy

materials resistance to deformation.
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Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Viscosity
Viscosity: measure of non-crystalline (glass
or liquid) resistance to deformation. High-
viscosity fluids resist flow; low-viscosity
fluids flow easily.
How readily a moving layer of molecules
drags adjacent layers of molecules along
determines its viscosity.
Units are Pa-s, or Poises (P) 1 P = 0.1 Pa-s
Viscosity of water at room temp is ~ 10-3 P
Viscosity of typical glass at room temp >>
1016 P

FA

dv dy dv dy

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Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Carbon
Carbon not a ceramic
Exists in various polymorphic forms: sp3 diamond
and amorphous carbon, sp2 graphite and
fullerenes/nanotubes, one dimensional sp carbon

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 Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Carbon: Diamond
Diamond-cubic structure
One of the strongest/hardest materials
High thermal conductivity (unlike ceramics)
Transparent in visible and infrared, high index
of refraction, looks nice, costs $$$
Semiconductor (can be doped to make
electronic devices)
Metastable (transforms to carbon when heated)

Hydrogenated diamond
{111} surface with the
dangling bonds or
radicals terminated by
hydrogen atoms

Diamond turning
into graphite at
elevated temperature

Figures from http://www.people.virginia.edu/~lz2n/Diamond.html

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Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Carbon: Graphite
Layered structure: Strong bonding within
planar layers. Weak, van der Waals bonding
between layers
Easy interplanar cleavage, applications as a
lubricant and for writing (pencils)
Good electrical conductor
Chemically stable even at high temperatures
Applications: furnaces, rocket nozzles, welding
electrodes

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 Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Carbon: buckyballs and nanotubes

Buckminsterfullerenes (buckyballs) + carbon
nanotubes expected to be important in future
nanotechnology applications (nanoscale materials,
sensors, machines, computers)

Carbon nanotube T-junction Nanotubes as reinforcing

fibers in nanocomposites

Nano-gear Nanotube holepunching/etching

Figures from http://www.nas.nasa.gov/Groups/SciTech/nano/

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Introduction to Materials Science, Chapter 12, Structure and Properties of Ceramics

Summary
Make sure you understand language and concepts:

Anion
Cation
Defect structure
Frenkel defect
Electroneutrality
Schottky defect
Stoichiometry
Viscosity

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