Ceramics

Thermal
Coatings
 History and Background
• Applications date into antiquity - earthenware,
pottery, clay product, bricks, etc
• More modern uses: Transparent glass,
structural glass, refractories
• Advanced uses: Thermal barrier coatings,
structural ceramics, composite armor,
electronics, glass-ceramics
• Ceramics can be Amorphous or Crystalline
• Atomic structure contains strong Ionic Bonds
 What are they?
• A compound of metallic and nonmetallic
elements, for which the inter atomic
bonding is predominantly ionic.
• They tend to be oxides, carbides, etc of
metallic elements.
• The mechanical properties are usually good:
high strength, especially at elevated
temperature.
• However, they exhibit low to nil-ductility,
and have low fracture toughness.
 Crystalline Ceramics
• As with plastics, the amorphous ceramics
tend to be transparent
• The structural ceramics tend to be
crystalline and show greater strength, as
well as stability at high temperature
Structure Anion Packing Examples
AX FCC NaCl, MgO, FeO
AX Simple Cubic CsCl
AX FCC ZnS, SiC
AX2 Simple Cubic CaF2, UO2, ThO2
ABX3 FCC BaTiO3, SrZrO3
AB2X4 FCC MgAl2O4, FeAl2O4
 AX Structure - CsCl
• Cl-
Note: This is not
a BCC structure.

Cs+

Simple Cubic Crystal

AX Structure - NaCl

2- FCC
interpenetrating
lattices.
Try it!
Compute the theoretical density of Rock Salt based on its crystal structure.

Cl- For this NaCl structure, the

crystal lattice parameter is
Na+ a a= 2 ( r Na+ + r Cl -),
where r is ionic radius.

a M 4(A Na  A Cl )
 
V a3 NA
4 ions (22.99  35.45) g/mol

2[(0.102x10  7  0.181x10 7 )]cm3 (6.023x1023 )ions/mol
 2.14 g/cm3
(actual  2.16g/cm3 )
AX structure - Si C
Summary of most common
ceramic crystal structures
Silicate Ceramics

• Silica, SiO2
• Many
polymorphs:Qua
rtz
CrystobaliteTrid
ymite
• Low density:
Quartz: 2.65g/cm3
Crystalline Crystabolite
 Carbon
• Pure carbon has many polymorphs with
vastly varying properties. It also exists in
the amorphous state.
• Diamond: Is similar to ZnS in structure
• Graphite is considered to be a crystalline
ceramic
• Fullerenes, C60, are a newly discovered
polymorph - with interesting properties.
 Diamond
• AX type crystal structure similar
to that of ZnS.
• Each carbon atom is covalently bonded to four
other C atoms in a diamond-cubic crystal structure.
• The material is optically transparent and extremely
hard (hardest natural material known) and durable.
• In engineering applications, cruder or industrial
forms of diamond, that are much less expensive
than the gemstone forms, are used as abrasives,
indentors, and coatings (especially thin films) for a
variety of applications.
 Graphite
• Layers of hexagonally arranged and
covalently bonded C atoms.
• Between layers, weaker Van der Walls
bonds are active, giving easy slip
on the {0001} crystallographic planes.
• Excellent as a dry lubricant, relatively high strength at
elevated temperatures, high thermal and electrical
conductivity, low thermal expansion, resistance to
thermal shock, and good machinability.
• Usage: electrodes, heating elements, crucibles,
casting molds, rocket nozzles, and other applications.
 Fullerenes, C60
• Molecular form of carbon with a
hollow spherical structure resembling
a geodesic dome (soccer ball.)
• Called buckyballs after R. Buckminister
Fuller, who pioneered the geodesic dome.
Discovered in 1985 and have since been found to
occur naturally in several sources.
• In the solid crystalline state, C60 molecules pack
together in a FCC unit cell arrangement with a lattice
parameter a=1.41 nm.
• The pure solid material density is about 1.65 g/cm3 and
it is relatively soft and is non-conducting since it has no
free electrons.
 Properties of Buckyballs
• When alkali metal anions, most notably K+, are in the structure
(usually 3 per C60 molecule), the resulting molecular material
(K3C60) displays the characteristics of a metal. In fact, K 3C60 is
considered to be the first molecular metal ever encountered.
• K3C60 buckyballs and similar molecular materials become
super conducting (practically no electrical resistance) at about
18K (relatively high temperature for this phenomenon)
• Applications in low-power consumption, low-pollution,
magnetic-levitation and propulsion devices for mass transit
systems.
• Other synthetic ceramic materials have been developed that
display superconductivity at even higher temperatures (up to
100K) above the temperature of liquid nitrogen, a relatively
inexpensive and abundant coolant.
 Try It!
• Calcualte the theoretical density of
pure C60 based on a FCC unit cell
as shown:
a=1.41 nm

M 4(60)(12.011)
  7 3
V (1.41x10 ) N A
 1.71g/cm3
(actual  1.65g/cm ) 3
 Defects in Crystalline Ceramics
• Vacancy
• Interstitial
• Dislocation
• Grain Boundary

Cation Interstitial
Anion Vacancy
Cation Vacancy

Schotky Defect Electro-

Frenkel Defect neutrality
 Mechanical Properties
• Brittle Materials, hard to perform a Tension Test.
• Flexural Test (Bend) is often substituted.
• Obtain Flexural Strength (Modulus of Rupture),
Stiffness (Modulus of Elasticity), and Ductility.
• Strength is often good, Stiffness my be high, but
Ductility and affected properties are poor.
• In crystalline ceramics, dislocation motion is
difficult because of the need to maintain electro-
neutrality. Consequently plastic deformation is
restricted.
Flexural Test Configuration
P P

b
d

a a
X-Section

Four point bend fixture

Rectangular: Circular:
6P a 32Pa
   
mr mr
b d2  D3
 Stress-Strain Behaviour
300

Aluminum Oxide

200
Bending Stress, MPa

100

Soda-Lime Glass

0
0.0000 0.0002 0.0004 0.0006 0.0008 0.0010

Bending Strain
Mechanical Properties of Various Ceramics

a Sintered with about 5% porosity

Hardness of Ceramics
Relative Hardness

B4C, SiC
WC, Al2O3

Glass
Effect of Porosity on Stiffness

E  E o (1  1.9P  0.9P ) 2

Where Eo is the theoretical modulus of elasticity with no

porosity, and P is the volume fraction of porosity.
Effect of Porosity on Strength

   e  nP
mr o
Where o is the theoretical modulus of rupture with no
porosity, P is the volume fraction of porosity, and n is an
empirical material constant
Fracture Toughness

Fracture Toughness (MPam)

 Amorphous Ceramics - Glasses
(Na20, Ca0, K2O, etc)
• The viscosity of the material at ambient temperature is
relatively high, but as the temperature increases there is a
continuous decrease in viscosity.
• When the viscosity has decreased to the point that the
ceramic is a fluid, it is considered to have melted.
• At ambient temperature while it is still solid, it is said to be in
the “glassy” condition.
• There is no distinct melting temperature (T m) for these
materials as there is with the crystalline materials.
• The glass transition temperature, Tg, is used to define the
temperature below which the material is a “solid” and
defines a practical upper limit on service temperature.
 Specific volume of
amorphous and crystalline
ceramics.
Liquid

supercooled
liquid

glass Crystalization

Crystaline
solid

Tg Tm TEMPERATURE
 Viscous Behaviour in
Amorphous Ceramics
F 
  ; 
A dv / dy

= shear stress

 = viscosity of
material

• Plastic deformation does not occur by dislocation motion in

amorphous or non-crystalline ceramics, such as glass.
•Deformation is by viscous flow: rate of deformation proportional
to applied stress.
 Ceramic Phase Diagrams

• Note: They are similar to metal alloy systems - except the

temperatures are generally higher.
Binary Eutectic Ceramic Alloy

Spinel