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Lecture-7

Materials Science & Engineering


(ME 202)

Lecture By
Assistant Professor Maj(R) Athar Hameed
Mechanical Engineering Department
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HITEC University Taxila
MATERIAL SCIENCE AND ENGINEERING
Todays Topic

Ceramic Materials

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Ceramics Materials - Introduction
keramikos = burnt stuff
Metallic and Nonmetallic
Oxides, nitrides, and carbides, etc
Inter-atomic bonds are either
Totally ionic
Predominantly ionic
Covalent character
Long life
Great pyramids of Giza
5000 BC Pottery
Examples:- Glass, Clay, Refractory, Abrasives, Cement

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Ceramics Materials - Usage
In comparison with metals
Not tough
Corrosion resistant
Wear & decay resistant
Brittle
Properties
Optical transparency of Glass
Hydro-plasticity of Clays
Permanent magnetic and
ferroelectric behaviors
Used in applications tolerating
Compressive stress
High Temperature
Wear and corrosion

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Ceramics Materials - Usage
Oxides
Alumina, Al2O3 (spark plug insulators, grinding
wheels)
Magnesia, MgO (refractory linings of furnaces,
crucibles),
Zirconia, ZrO2 (piston caps, refractory lining of
glass tank furnaces), zirconia/alumina (grinding
media)
Spinels, M2+O.M23+O3 (ferrites, magnets,
transistors)
Fused silica glass a non-crystalline SiO2
(laboratory ware) 5
Ceramics Materials - Usage
Carbides
silicon carbide, SiC (chemical plant, crucibles)
Nitrides
Silicon nitride, Si3N4 (spouts for molten aluminium,
high-temperature bearings)
Boron nitride, BN (crucibles, grinding wheels for
high-strength steels)
Silicates porcelain (made from kaolinite with
chemical formula Al2Si2O5(OH)4 used for electrical
components), steatites (with chemical formula
Mg3(Si4O10)(OH)2 used for insulators), mullite (with
chemical formula 3Al2O3.2SiO2 used for refractories)
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Ceramics Materials - Usage
Sialons based on SiAlON and MSiAlON
where M = Li, Be, Mg, Ca, Sc, Y, rare earths (tool
inserts for high-speed cutting, extrusion dies, turbine
blades)
Glass-ceramics Pyroceram (magnesium
aluminosilicate glass for heat resistant purposes)

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Comparison of Materials
Property Ceramic Metal Polymer

Hardness Very High Low Very Low

Elastic modulus Very High High Low

Thermal expansion High Low Very Low

Wear resistance High Low Low

Corrosion resistance High Low Low

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Comparison of Materials
Property Ceramic Metal Polymer

Ductility Low High High

Density Low High Very Low

Electrical conductivity Depends High Low


on material

Thermal conductivity Depends High Low


on material

Magnetic Depends High Very Low


on material

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Ceramics Materials - Structures
Structures range from pure ionic to covalent bonding

Percent ionic character (%IC) of a bond between elements A and B


(A being the most electronegative) may be approximated by

XA and XB are the electronegativities for the respective elements

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Ceramics Materials - Structures

For atomic bonding predominantly ionic

Crystal structures - Electrically charged ions instead of atoms

Cations Positively Charged - Metallic

Anions Negatively Charged - Non metallic

Characteristics criteria

1. Charge magnitude

2. Relative size

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Ceramics Materials - Structures
Fulfilling First Criterion
Cations balanced by anions
Balanced formula
Example Calcium Fluoride; Ca2+ balanced by two F- = CaF2
Fulfilling second criterion
Smaller cations (rC ) / larger anions (rA) ; rC/rA < 1
Cation in contact with anion (CN) = Stable structures

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Ceramics Materials Structures
Min rC/rA for CN 3

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Ceramics Materials - Structures
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Ceramics Materials Crystal Structure - AX-Type

NaCl
CN 6
Interpenetrating FCC
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rC / rA = 0.414 and 0.732 for NaCl, MgO, MnS, LiF, and FeO
Ceramics Materials Crystal Structure - AX-Type

CsCl (used in the


preparation of
electrically
conducting glasses)
CN 8
Not a true BCC 23
Ceramics Materials Crystal Structure - AX-Type

ZnS (used in optics)


CN 4 (Tetrahedral)
Covalent bond
ZnTe, and SiC 24
Ceramics Materials Crystal Structure - AmXp-Type

CaF2 (brake
lining, and for
glass
manufacturing)
CN 8
ZrO2, UO2,
PuO2, and
ThO2 25
Ceramics Materials Crystal Structure - AmBnXp-Type

Barium Titanate BaTiO3 (a dielectric ceramic used for capacitors)


Perovskite crystal structure
Above 120C (248F), the crystal structure is cubic 26
Some Common Ceramic Crystal Structures

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Ceramic Crystal Structure Prediction
On the basis of ionic radii, what is predicted structure for FeO?

Solution

Determine rC/rA

0.414 < 0.55 > 0.732 CN = 6

Rock salt type AX crystal structure

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Ceramic Density Computations

where
n = Number of ions in the unit cell
AC = Sum of atomic weights of all cations
AA = Sum of atomic weights of all anions
VC = Unit cell volume
NA = Avogadros number, 6.022x1023 ions/mol

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Ceramics Materials
Theoretical Density Calculation for NaCl

Previous slide

figure on the next slide


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Ceramics Materials
Theoretical Density Calculation for NaCl

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Imperfections in Ceramics Vacancy & Substitution

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Imperfections in Ceramics Vacancy & Substitution

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Imperfections in Ceramics Vacancy & Substitution

Same charge replacement


Maintenance of electro-neutrality
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Result - lattice defects
Imperfections in Ceramics - Porosity
Powder compaction
Pores generation
Heat treatment
Residual porosity
Load bearing
Stress concentrators

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Diffusion Process in Ceramics
Complicated phenomenon
Diffusive motion of opposite
charged ions
Vacancy of Pairs
Ion vacancy in non-stoichiometric
compounds containing
substitutional impurity ions having
different charge state than host ions
Transference of electrical charge
Movement of ions for maintenance
of charge neutrality
The rate of diffusion of these
electrically charged couples is
limited by the diffusion rate of the
slowest-moving species 36
Ceramics Phase Diagrams
Phase diagrams have been experimentally determined for a large
number of ceramic systems

For binary or two-component phase diagrams, it is frequently the


case that the two components are compounds that share a
common element, often oxygen

These diagrams may have configurations similar to metalmetal


systems, and interpreted in the same way

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Ceramics Phase Diagrams

The Al2O3Cr2O3 solid solution is a substitutional one in which Al3+ substitutes for
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3+
Cr , and vice versa.
Ceramics Phase Diagrams

MgO is virtually insoluble in Al2O3, mainly due to Mg2+


and Al3+ ions (0.072 versus 0.053 nm)
Ceramics Materials Plastic Deformation
Crystalline Ceramics
Dislocations movement
Slip systems in ionic bonds
Repulsive & slow
Slip systems in covalent
bonds Limited & complex
Non-Crystalline Ceramics
No dislocation movement
Viscous flow proportional to
temperature and applied
stress

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Ceramics Materials Brittle Fracture
No plastic deformation
Transgranular or intergranular crack growth
Moisture and contaminants in the atmosphere can introduce
surface cracks
Static fatigue, or delayed fracture mean slow propagation of cracks
under load
Conditions at crack tips tensile stress + atmospheric moisture
causes ionic bonds to rupture and growth of crack
Fracture strength depends upon:-
Presence of flaw capable to initiate crack
Probability of flaws depend upon size of specimen
No stress amplification under compression
Higher strength in compression than tension
Strength enhances by residual compressive stresses at surfaces 41
Ceramics Materials Hardness Tests
Difficult to measure
Cracks formation
Spherical indenters of Brinell & Rockwell
tests
Pyramidal indenters
Less brittle ceramics Vicker
Brittle ceramics Knoop
Increasing load decreases hardness
Ideal hardness test sufficiently large
Vickers indentations in Silicon Nitride
load without excessive cracks

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Ceramics Materials Hardness Tests

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Ceramics Materials Tensile Test
Constraints
Geometry
Grip
Ceramics fail after only about 0.1 % Strain
Transverse bending test
Flexural strength, modulus of rupture, fracture or bend strength
For rectangular cross-section

For circular cross-section

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Ceramics Materials Stress vs Strain

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Ceramics Materials Strength & Elasticity

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Ceramics Materials Creep

Compressive stress at
high temperature
Creep Tests
Temperature and
Stress level
Opposite figure
HIP SiC = Hot isostatic
pressed silicone
carbide
LVDT = Linear
variable differential
transducer

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Ceramics Materials - Magnetic Behavior
Ferromagnetism and Ferrimagnetism
MFe2O4, (M for metals)
Fe3O4, the mineral magnetite, sometimes called lodestone
Fe3O4 = Fe2+O2- & (Fe3+)2 (O2-)3, Fe ions +2 and +3 valence
states in the ratio of 1:2
Net spin magnetic moment for each Fe2+ and Fe3+ ion & O2-
magnetically neutral
Two positions for iron cations
CN 4 (tetrahedral)
CN 6 (octahedral)

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Tetrahedral & Octahedral Positions

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Tetrahedral & Octahedral Positions

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Spin Magnetic Moment Configuration for Fe2+ and Fe3+ ions in Fe3O4

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Ceramics Materials - Magnetic Behavior
Fe3+ in octahedral & in tetrahedral positions; Fe2+ in octahedral
positions
Aligned Fe3+spin moments in octahedral & tetrahedral but opposite
to each other
Anti-parallel coupling of adjacent Fe3+ cancels out with no
contribution
Fe2+ aligned in one direction; responsible for the net magnetization
Saturation magnetization = net spin magnetic moment x number of
Fe2+ ions
Examples: NiFe2O4 , (Mn, Mg)Fe2O4 , PbFe12O19 and BaFe12O19 etc

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Ceramics Materials - Electromagnetic Behavior

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Ceramics Materials - Electric Conduction
At room temperature
At relatively high temperature
Movement of anions and cations
Net movement of charged ions in addition to current
Migrations in opposite directions
Total conductivity = Electronic + ionic contributions
Increase of ionic contribution at high temperature

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Ceramics Materials - Electric Conduction

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MATERIAL SCIENCE AND ENGINEERING
Next Topic (Tentative)

Polymer Materials

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