MCG 2361 Engineering Materials II: Lecture 3: Ceramics: Introduction & Structure (2/2)

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MCG 2361
Engineering Materials II
Lecture 3: Ceramics: introduction & structure (2/2)

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Ceramics: review
Ceramics are generally crystalline structures.
The most prevalent type of chemical bond between the constituents of

ceramics is the ionic bond.
Ionic bond: bond between a metal element and a non-metal element.
… metal: easily gives away valence electrons

… non metal: easily accepts electron on free energy levels.
Ionic
The two ions (one positive: metal – cation & one negative: non metal
- anion) created in the process attract one another (Coulomb
attraction) and reach a stable configuration (of their electrons).
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Ceramics: review
Ionic bond…
The ionic bond is not oriented, so in a stable structure each type A

atom (say a metal) can only have type B atoms (say a non metal) as
immediate neighbours, and that in all directions.
Attraction energies associates to this type

of bond are very high, which explains
some physical properties of
ceramics such as their
high melting
temperatures
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Ceramics: review
Ionic bond…

Electrons are strongly associated with

the atoms that they link, and notably
with non-metal atoms that strongly
Attract them so as to complete
their incomplete energy levels.
Thermal and electrical conductivity

values for ceramics are therefore
generally very low.
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Ceramics: review
Ionic bond…

Example of industrial ceramic material

where strong bonds are essentially
ionic:
MgO
Magnesium oxide.
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Ceramics: review
Chemical bonds that unit the atoms in such materials sometimes have
a covalent character.
Covalent bond: bond between two atoms that have partly complete
valences; by sharing free electrons on these valences and by sharing
them between the two atoms,
a complete configuration is
obtained.
The covalent bond is oriented and

defined between specific atoms.
Ex.: SiC silicon carbide

GaAs gallium arsenide
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Ceramics: review
ionic covalent metallic
loss or gain sharing... loss...

... of valence electrons
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Ceramics: review
Most of the time, the bonds that unite atoms into molecules of ceramic
material are partly covalent and partly ionic.
If we consider the two (…there can be more!) constituents of a

ceramic on the periodic table of elements,
a wider separation of their positions, both horizontal and vertical,

between the lower left and the upper upper right corner =
= greater difference in electro-negativity between the atoms =

stronger ionic character to the bond.
Capability to accept electrons !
Sharing of atoms on external valences.
Alternatively, if the positions on the table are close one to another, the
degree of covalence is high.
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Ceramics: review
Important note:
- in reality, bonds are ionocovalent (more or less ionic or
covalent)
Pure covalent bond H H

Ionocovalent bond H Cl
Pure Ionic Na Cl
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Ceramics: review
In summary...
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Ceramics: review
Most of the time, the bonds that unite atoms into molecules of ceramic
material are partly covalent and partly ionic.
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Ceramics: structures
What determines the structure of molecules:
- Stoichiometry → molecules must be electrically neutral

- Configuration → must be such that, taking into account the
‘dimensions’ of atoms, these must be in stable
contact
→ this is how the coordination number is defined:
number of anions in direct contact with a
given cation (in 3D, not simply in 2D !!)
Stable Stable Unstable

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Neutral atoms that have gained an electron are called anions, and they are much larger than their respective
atoms. As an additional electron occupies an outer orbital, there is increased electron-electron repulsion (and
hence, increased shielding) which pushes the electrons further apart.
positive: cation one negative: anion
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15

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Crystalline structures: Structures AX
→ Same number of anions (A)

and cations (X)
There are many types of AX structures !
Type 1: Coordination number 4

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Structure AX type 1 – coordination number 4
Industrial example:
SiC – Silicon carbide

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Industrial example:
SiC – Silicon carbide silicon carbide polytypes
Cubic Hexagonal Hexagonal

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SiC Nano flower bouquet
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Industrial example:
SiC – Silicon carbide
- Very good mechanical properties:

E ≅ 450 GPa
σult ≅ 500 MPa
- Low density: ρ = 3.21 g/cc
- Excellent resistance to high temperatures;
- Excellent resistance to corrosion;
- Excellent resistance to thermal shocks;
- One of the hardest materials around.
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Industrial example:
SiC – silicon carbide
Applications:
Parts and surface coatings: aviation, chemical and nuclear industry,

machinery, engines, valves, bearings, cutting tools, abrasives, cutters,
composite reinforcement fibres for aerospace, …
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Industrial example:

…electronics…
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Industrial example:

Telescope mirror
for Herschel space
telescope,
launched by EADS
in 2007.
Powder (sintering)
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Equivalent to two face centred cubic
Industrial example: structures merged one into another.
MgO – magnesium oxide
As simple crystal:
Substrate for
semi-conductors
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Industrial example:
MgO – magnesium oxide
As simple crystal:
High temperature ‘windows’
Melting point
2800 °C
Young’s modulus (E)
249 GPa
Ultimate strength
138 MPa
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Industrial example:
MgO - magnesium oxide
Careful!
Note: A given chemistry and a

given structure do not mean
that you end up with the
exact same thing !!
→ Be careful with what you

buy / specifiy !!
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Example… not really industrial:
MgO - magnesium oxide
As a powder:
Active ingredient in
milk of magnesia !
(a common component of antacids and laxatives)
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MgO - magnesium oxide, applications…
Refractory Used in the manufacturing of steel –

thermal insulating plates (50% of all uses)
Steels Used in some spring steels and steels for
high-voltage transformers
Car batteries Used in cell separators
Chemical industry Used as intermediate in many industrial
chemical reactions & processes
Electricity production MgO is an additive to fuel that neutralises
corrosive combustion products
Concrete floors Improves wear resistance
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MgO - magnesium oxide, applications…
Brakes MgO used in friction surfaces

Water treatment Neutralises heavy metals
- Fertilisers
- Glass production
- Leather tanning
- Pulp & paper industry
- Plastics (PP, neoprene, ABS, UP, epoxy, etc.),
- Pigments
- Pesticides
- Sugar refining
- Additives in lubricants,
- Etc etc etc
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Industrial example:
FeO – iron oxide
= rust !
- Used in numerous
industrial colorants
- Used as a catalyst
- Ferrite-based magnets (ferrimagnetic)

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Industrial example:
FeO – iron oxide
- Ferrite-based magnets (ferrimagnetic)

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‘Industrial’ example:
CsCl – caesium chloride

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‘Industrial’ example:
CsCl – caesium chloride
- Genetic processes: separation of DNA and RNA
- Detection and measurement of radiations (137CsCl or 131CsCl)
- Catalysts for industrial chemical reactions
- Plasma physics: electricity generation, electronics, optical

fibres.
- Cancer therapies. (When enriched in radioisotopes, such as

137CsCl or 131CsCl)
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Crystalline structures: Structures AmXp

→ Different numbers of anions (A) and cations (X)
Example: CaF2 , calcium fluoride

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Crystalline structures: Structures AmXp

→ Different numbers of anions (A) and cations (X)
Example: BaTiO3 , barium titanate

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Special case: C carbon → diamond (crystal)

graphite (superimposed planes)
fullerenes (tubes, balls, …’nano’)
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Fullerene: Buckminster Fuller

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C60 C70
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Montréal biosphere
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Ceramics: properties
- Thermal resistance → thermal screens

- Hardness → cutting tools
- Electical insulators → electrical equipment
- Chemical resistance → beakers, etc.
- Young’s modulus generally high…

→ very high ultimate strength in compression
→ very high ultimate resistance in shear
→ in tension: depends on presence of cracks!
- BRITTLE !
→ therefore, design as a function of ultimate strength !
… and leave some margin (safety factor) because of the statistical

nature of the mechanical properties of these materials and of the
size of possible defects.
Ceramics: properties 43
Statistical Nature of Fracture

ln(xy) = y ∙ ln(x) ln(x / y) = ln(x) - ln(y) ln(1)=0

Testing properties of brittle materials
(a) The bend test often used for measuring the strength of
brittle materials, and (b) the deflection δ obtained by bending
Testing properties of brittle materials
Three point Four point

Four point test preferred to three point test for brittle materials because
there is a large region under constant stress. (In 3-point test, the largest
defect might not be exactly at the point of maximum stress).
Ceramics: Questions 51
1. Give the 4 main types of bonds in materials

2. Give an example of a purely covalent ceramic and a purely ionic
ceramic.
3. What is an ionocovalent ceramic? What does it mean in terms of the
sharing of electrons between elements? Give an example of
ionocovalent ceramic.
4. What type of bond is created between elements with a large difference
in electro-negativity?
5. What is the coordination number?
6. Give an example of a material with a coordination number of 4,6 and
8.
7. Why do brittle materials have a wide range of fracture strengths?
8. What does the Weibull modulus represent? Give an approximate value
for the Weibull modulus of a brittle ceramic and a ductile metal.
9. If I measure the tensile strength of a ceramic in compression, 3pt
bending, 4 pt bending and in tension I find that
σf (compression)> σf (3pt) > σf (4pt) > σf (tension)
Explain why.

MCG 2361 Engineering Materials II: Lecture 3: Ceramics: Introduction & Structure (2/2)

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1

Lecture 3: Ceramics: introduction & structure (2/2)

Ceramics are generally crystalline structures.

The most prevalent type of chemical bond between the constituents of

Ionic bond: bond between a metal element and a non-metal element.

… metal: easily gives away valence electrons

Ceramics are generally crystalline structures.

The ionic bond is not oriented, so in a stable structure each type A

Attraction energies associates to this type

Ceramics are generally crystalline structures.

The ionic bond is not oriented, so in a stable structure each type A

Electrons are strongly associated with

Thermal and electrical conductivity

Ceramics are generally crystalline structures.

The ionic bond is not oriented, so in a stable structure each type A

Example of industrial ceramic material

Ceramics are generally crystalline structures.

The covalent bond is oriented and

Ex.: SiC silicon carbide

ionic covalent metallic

loss or gain sharing... loss...

If we consider the two (…there can be more!) constituents of a

a wider separation of their positions, both horizontal and vertical,

= greater difference in electro-negativity between the atoms =

Pure covalent bond H H

Ceramics are generally crystalline structures.

What determines the structure of molecules:

- Stoichiometry → molecules must be electrically neutral

Stable Stable Unstable

What determines the structure of molecules:

What determines the structure of molecules:

Crystalline structures: Structures AX

→ Same number of anions (A)

There are many types of AX structures !

Type 1: Coordination number 4

Type 2: Coordination number 6

Type 3: Coordination number 8

Structure AX type 1 – coordination number 4

SiC – Silicon carbide

Structure AX type 1 – coordination number 4

SiC – Silicon carbide silicon carbide polytypes

Cubic Hexagonal Hexagonal

Structure AX type 1 – coordination number 4

Structure AX type 1 – coordination number 4

SiC – Silicon carbide

- Very good mechanical properties:

Structure AX type 1 – coordination number 4

SiC – silicon carbide

Parts and surface coatings: aviation, chemical and nuclear industry,

Structure AX type 1 – coordination number 4

SiC – silicon carbide

Structure AX type 1 – coordination number 4

SiC – silicon carbide

Structure AX type 2 – coordination number 6

MgO – magnesium oxide

Structure AX type 2 – coordination number 6

MgO – magnesium oxide

High temperature ‘windows’

Structure AX type 2 – coordination number 6

MgO - magnesium oxide

Note: A given chemistry and a

→ Be careful with what you

Structure AX type 2 – coordination number 6