3-1

Structure of Ceramics
! !

Ceramics have ionic or covalent bonding Crystal structure is strongly influenced by bonding This influences mechanical and physical properties. e.g.
! !

most ceramics are not electrical conductors; little ductility at room temperature

Introduction to Ceramics: 3: Bonding, structure and strength

3-2

Ionic Bonding
!

Crystals of opposite charged ions held together by nondirectional electrostatic forces Anions (-) are larger than Cations (+) Minimum energy anions and cations as close as possible with highest co-ordination number butAnions must not touch.

+ +

+ +

Introduction to Ceramics: 3: Bonding, structure and strength

3-3

Magnesium Oxide - Ideal Ionic Structure

MgO Ionic

Cubic 6:6 co-ordination Rock-salt structure

Oxygen Magnesium
Introduction to Ceramics: 3: Bonding, structure and strength

3-4

Covalent Bonding
!

Interatomic bonding occurs by shared electrons in orbitals of size and direction governed by quantum mechanics. Structures formed like scaffolds with fixed orientation at joints and fixed bond lengths.

C
104.28

C C C C C
Diamond [Silicon, Silicon carbide similar]

C C

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Silicon Carbide - Ideal Covalent Structure

SiC Covalent
[ This is SiC (cubic): the (hexagonal) forms are more common.

Silicon Carbon

Gallium arsenide etc. have the same structure ]

Introduction to Ceramics: 3: Bonding, structure and strength

3-6

Intermediate and Mixed Bonding

!

Ceramics can have structures intermediate to ionic and covalent and contain different sorts of bonds: e.g:
!

O Si O O

O Si O O Si O

Formula Unit

O O

silicate ceramics are made up of tetrahedral covalent SiO4 units (bonding >50% covalent) which share corners Pure SiO2 (quartz) is a network of these tetrahedral units clays, etc., contain silicate sheets linked by ionic forces

Shared Oxygen ions

2-D slice of quartz crystal showing linked tetrahedra

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Silicates
!

The SiO4 tetrahedron would be an ion if none of the O were shared (SiO4)4 -. Can get compounds such as Ca2SiO4 - calcium orthosilicate. Can form extended ions by sharing some of the O to make sheets or chains and satisfying the spare negative charge on each unattached O by the presence of balancing ions.

"

It is possible to share sufficient ions to make chains or sheets of silicates, e.g. MgSi2O5

Mg

Mg

Mg

Mg

Mg

Mg

Mg

Mg

Mg

Mg

Mg

Mg

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Natural Ceramics
!

Many natural ceramics are based on silicates Other oxides also form shared corner structures based on tetrahedra, octahedra or cube coordination Can form mixed oxides by sharing corners of different structural tetrahedra

These more complex materials can also contain balancing cations where there is no corner sharing Thus many chemical compositions can be accommodated in a range of mineral crystal structures

Introduction to Ceramics: 3: Bonding, structure and strength

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Structure of Glasses
!

Most important glasses are based on silica Structure is amorphous but the same joining rules apply as with silicates Structure is a random network of cornersharing tetrahedra

Other oxides can be admitted into the structure, obeying similar rules to in silicates Some oxides join in the network with their own co-ordination solids Others sit as discrete ions next to terminating oxygens

Introduction to Ceramics: 3: Bonding, structure and strength

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Structure of Glasses (2)

Other oxides can be incorporated into a glassy SiO2 network in several ways: Network formers are oxides which intrinsically form glassy structures Network modifiers terminate networks by requiring fewer oxygens to balance valency Network intermediates can join in glassy networks but cannot themselves form glasses

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Structure of Glasses
Can tune mechanical properties by varying composition. Other oxides can be incorporated into a glassy SiO2 network in several ways: Network modifiers: MgO, CaO, Na2O, K2O, PbO terminate networks by requiring fewer oxygens to balance valency Network formers: B2O3, P2O3 - oxides which intrinsically form glassy structures Network intermediates: B2O3, Al2O3, PbO can join in glassy networks but cannot themselves form glasses
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Modifiers
! !

Modifiers terminate networks They reduce the mean number of atoms in a chain The covalent Si-O-Si bond has a rotational degree of freedom, thus adding modifiers reduces the total structure rigidity They result in lower melting points (good for processing) and lower elastic moduli.

+ -

+ -

+ -

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Ceramic Phase Diagrams

Mullite (3Al2O3.2SiO2)

Phase diagrams are used to understand the evolution of microstructure much as in metals. However: ! Diffusion is much slower than in metals so equilibrium is rarely reached; ! Phase diagrams are often simplified by using compounds rather than elements.

Al2O3

2000 Temperature (C) 1800 1600 1400 1200 1000 0 SiO2

Liquid

20

40

60

80

wt% Al2O3
Cristobalite (SiO2) Tridymite (SiO2))

100 Al2O3

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Traditional Ceramic Microstructure

Porcelain electrical insulator ! Note complex microstructure with evidence of:
!

largely unmolten phases (Flint SiO2) melting and liquid phase sintering new phases crystallising in frozen melt

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Mechanical Properties
!

Plastic flow by dislocation motion is very difficult in covalent and ionic materials
! !

High yield stress and hardness Very limited plastic flow at crack tips low fracture toughness

Compression: strong (high yield stress); may flow or propagate shear cracks (crushing). Tension: weak (low toughness); always fail by brittle fracture Highly resistant to wear and erosion (compression loading phenomena)

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Dislocations In Ionic Solids

!

+ + + + -

+ + + +

+ + + + -

+ + + +

+ + + + -

+ + + +

+ + + + -

+ + + +

Po

ss

+ + + + -

ib

le

Ionic structures are usually fairly close packed Slip direction and slip plane are constrained by charge e.g. cannot bring like charged ions in contact Dislocation motion is possible but difficult because slip is not on the most close packed planes Often only a limited number of slip systems due to low symmetry of crystal structures
!

+ + + +

Impossible

need 5 for full plasticity in polycrystals

Dislocation motion can be easier at high temperatures

!

easier flow on normal slip systems, new systems may begin to operate.

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Dislocations In Covalent Solids

!

! !

The rigid bond network in covalent solids is very resistant to deformation Dislocations have very high energies Dislocation motion is difficult as bonds must be broken and remade, and bond angle distorted. Very low dislocation mobilities except at very high temperatures (> 0.5 Tm or higher)

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Ceramics: Defect Controlled Strength

Tensile fracture stress F is controlled by the defects present either from fabrication or from damage
Porosity defect in poorlysintered alumina

F =

K Ic

50m

KIc Fracture toughness geometrical factor (~1) a size of biggest crack under stress
Introduction to Ceramics: 3: Bonding, structure and strength

Cross-section through thermallyshocked alumina bar (4mm x 4mm) Dye-penetrant test shows cracks

3 - 19

Toughness, Crack Size and Strength

Tough Metal Example KIc
(MPam1/2)

Brittle Metal Cast Iron 20 13 mm 510 m

Typical Ceramic Alumina, SiC 4 510 m 20 m

Brittle Ceramic Glass, Silicon 1 32 m 1.2 m

Good steel 100 320 mm 13 mm

a for F = 100 MPa a for F = 500 MPa

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Defect-controlled Strength
!

! !

One large crack will lead to failure

Must make ceramics defect free and avoid damage in service

!

Or make tougher ceramic?? even boosting KIc to 15 or 20 MPam1/2 would be useful

In practice, this is dealt with statistically (see later)

Density of cracks

For ceramics, the strength controlling defects can be a few microns or tens of microns in size Below limit of detection of (most) NDT techniques Weakest link problem

When is density low enough that you are sure there are no cracks of this size present ?

Crack size

Introduction to Ceramics: 3: Bonding, structure and strength