HAC720C - Cours 1 & 2 - Introduction - 2021-2022

Matériaux inorganiques avancés
HAC720C
Responsables: Florence ROUESSAC & Umit DEMIRCI
Contact information:
04-67-14-91-59
Florence.Rouessac@umontpellier.fr
To know you better …
2
Course objectives:
Fundamentals
of
Inorganic Materials
3
Partie I : Généralités sur les matériaux inorganiques – Relations structure-propriétés
(F. Rouessac)
2 séances
Partie II : Les matériaux céramiques et leurs synthèses
Partie II-1 et II-2

4 séances
(F. Rouessac)
Partie II-3 2 séances (U. Demirci)
Partie III : Les verres et vitrocéramiques

(F. Rouessac)
2 séances
Partie IV : Les métaux (U. Demirci)
1 séance
Partie V – Matériaux inorganiques pour l’énergie
(U. Demirci)
3 séances
Au total Florence 11 séances (dont 1 en NPP) et Umit 8 séances comme initialement prévu
Modalities of knowledge control
Contrôle terminal
Note finale : Partie FR 60% de la note finale (partie UD 40 % )
5
Schedule: Vacances FR P2 CTM 6
FR4
FR 7
FR 7
FR5
FR1 FR 8
FR 8
FR2
Vacances
Vacances
FR3
FR P1 6
Cours en ligne
7
Bibliography
8
Introduction: description of the materials
Introduction
Definition:
These are solids, shaped and assembled for the manufacture of

macroscopic objects and having the required properties of use
(mechanical, electromagnetic, thermal, for nuclear, optics, etc...).
A distinction can be made between shaped materials (e.g. metals) and

consolidated materials (e.g. ceramics)
Ce sont des solides, façonnés et assemblés pour la fabrication d’objets macroscopiques et ayant les propriétés d’utilisation requises
(mécanique, électromagnétique, thermique, nucléaire, optique, etc...).
On peut distinguer les matériaux façonnés (p. ex., métaux) des matériaux consolidés (p. ex., céramique)
9
CLASSIFICATION OF MATERIALS
Introduction
Solid materials have been conveniently

grouped into three basic categories:
Metals,
Ceramics,
Polymers.
This scheme is based primarily on chemical

makeup and atomic structure. composition chimique et la structure atomique.
In addition, there are the composites, which

are engineered combinations of two or
more different materials.
… Another category is advanced materials
10
Wanted properties of materials
Introduction
 Mechanical properties: which reflect the behavior

of materials deformed by forces.
 Physical properties: which measure the behavior

of materials subjected to the action of temperature,
electric fields, magnetic fields or light
 Chemical properties: which characterize the

behavior of materials in a reactive environment
Propriétés mécaniques : qui reflètent le comportement des matériaux déformés par les
(corrosion, nuclear, ...). forces.
Propriétés physiques : qui mesurent le comportement des matériaux soumis à l’action de
la température, des champs électriques, des champs magnétiques ou de la lumière
Propriétés chimiques : qui caractérisent le comportement des matériaux dans un
environnement réactif (corrosion, nucléaire, ...).
11
In summary …
Introduction
The properties of the materials depend on:
•Properties of the constitutive solid phase (s).
•Microstructure (size, shape, orientation of the grains of

polycrystalline samples).
•The spatial distribution of the solid phases involved (case

of composites).
12
PART I
General information on inorganic materials
- Structure-property relationships -
13
Introduction
Introduction
It is not possible to predict all the properties of a crystalline solid from

its structure!
Part 1
But the knowledge of the structure on the atomic scale makes it

possible to understand and / or predict some of these properties.
The example of melting temperature:

A crystallized solid melts when the amplitude of the thermal vibrations of the atoms is
large enough for the crystalline edifice to collapse (it then reaches the order of
magnitude of the interatomic distances).
At a given temperature, this amplitude is all the smaller as the interatomic links which
oppose it are stronger.
 The higher the fusion temperature is, the more energetic the
interatomic bonds are.
14
Introduction
Relationship between melting temperature and nature of the chemical bond
Bonding Energies and Melting Temperatures for Various Substances

Part 1
 The classification by type of chemical bond is directly

correlated to the melting temperature scale.
15
Introduction
Part 1
Relationship between melting temperature and nature of the chemical bond
 The classification by type of chemical bond is directly

correlated to the melting temperature scale.
16
Introduction
Some solid properties
... depending on the type of dominant link

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17
Introduction
1-1 Primary interatomic bonds
Ionic Bonding
An ionic bond is the bond caused by the transfer of one or more valence electrons (from
the outer electron layer) between one atom (donor) and another (recipient) atom.
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It corresponds to the electrostatic attraction between two ions of very different

electronegativities (found in compounds composed of both metallic and nonmetallic
elements).
 Ionic bonding is a strong bond (5 to 10 ev) and non directed

18
Introduction
Covalent Bonding
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 Strong (2 to 8 ev) and directed

19
Introduction
Metallic Bonding
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Electrostatic model
 strong bond (~ 4 eV ) and non directed
With this model, these valence electrons are not bound to any particular atom
in the solid and are more or less free to drift throughout the entire structure.
20
Introduction
1-1 Secondary bonding
van der Waals bonding
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Hydrogen bonding : a special type of secondary bonding
 Weak < 0.5 ev

21
Introduction
In summary …
ionique covalente métallique

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perte ou gain... partage... abandon...

... des électrons de valence
22
Partie
Part 11 Introduction
In summary …
23
Introduction
1-2 Crystalline defects - classification
- Point defects (dimensionless 0)

Vacancies
Part 11
Intrinsic or extrinsic point defects

Partie
Self-interstitials
Impurities in solids Extrinsic point defects
Substitution
- Linear defects (1D)
Edge dislocation
Screw dislocation
- Interfacial defects (2D)
Grain boundaries
External surfaces
Twin boundaries
- Bulk or volume defects– microstructure (3D)
-Atomic vibrations
24
Introduction
Point defects
Défauts ponctuels
…those associated with one or two atomic positions

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Comment:
The solid must contain defects in order to be thermodynamically

stable. All solids contain them, they can be organized and can even be
added!
Every crystal has a natural tendency to acquire punctual defects.
There are approximately 108 defect per mole of solid!
Cf. calculation : BUP 658 p 173-194 25

Introduction
Point defects
Lacunes
- The vacancies -
The simplest of the point defects is a vacant lattice site, one normally
occupied but from which an atom is missing
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Nv: number of vacancies (usually per

m 3)
Cas de l’aluminum QV:energy required for the formation of
a vacancy (J.mol-1)
26
Introduction
Point defects
Case of vacancies in ionic cristals
Cationic vacancies can be distinguished from anionic vacancies:

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A cationic vacancy is obtained by extracting a cation from the

volume and placing it on the surface.
An anionic vacancy is obtained by extracting an anion from the
volume to place it on the surface.
SCHOTTKY defects are site vacancies, formed in cation/anion pair.
 The overall stoichiometry of a solid is not affected

by the presence of Schottky defects.
27
Introduction
Point defects
- Self-interstitial defects-
There is an extra atom, of the same nature
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as the others but in a place which is not

foreseen for an atom.
- Impurities in solids -
Sometimes it can be forced in order to

change the properties of the material
(mechanical or electrical).
The addition of a big quantity of impurity
atoms results in the formation of a solid
solution. (depending on the kinds of impurity, their concentrations and T)
28
Introduction
Point defects
- Substitution -
Part 11
Impurity atoms replace or substitute for the host atoms

Partie
29
Introduction
Point defects
On parle de défauts de FRENKEL lorsqu’il y a association d’une lacune

et un interstice.
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30
Introduction
Point defects
• • • • • •
•
1 • •
•
•
•
•
•
•
•
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Exercice :
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• • • • •
• • •
2
• • •
• • • • • •
• • • • • •
• • • • •
•
3 • • • • •
• • • • •
• • • • • •
• • • 4 • •
• • • • • • •
• • • • •
• • • • • •
31
Introduction
Point defects
Impact of point defects on the properties of materials:

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 Properties related to transport phenomena
of material: diffusion through the vacancies
of electric charges: conduction in ionic solids
32
Introduction
Linear defects (1D)
 Linear defect: around which some of the atoms are
misaligned.
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Atoms are not necessarily present: dislocation

(which represent local distortions of the network).
Presumed existence in 1934 (Orowan, Polanyi, Taylor, Burgers)
- Edge Dislocation -
33
Introduction
Linear defects (1D)
- Edge Dislocation - Dislocation coin
Or Taylor-Orowan dislocation
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Propagation of the edge

dislocation under constraint.
34
Introduction
Linear defects (1D)
- Screw dislocation - Dislocation vis
Or Burgers dislocation
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Screw dislocation
The propagated distortion is the same in the both cases but the line
movement is different.
35
Introduction
Linear defects (1D)
Impact of linear defects on the properties of materials
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Deformation
The dislocation displacement determines the plasticity
(irreversible deformation, no time dependante)
 few damaging
exemple : shaping of metals and alloys: stamping steel
metal for automotive ...
Transport phenomena
Diffusion is easier along the dislocations than in the network: To
be avoided absolutely in the intrinsic semiconductors because they drop
their electrical resistivity.
36
Introduction
Interfacial defects (2D)
- External surface or free surface -
One of the most obvious boundaries is the external surface, along
which the crystal structure terminates.
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Surface atoms are not bonded to the maximum number of

nearest neighbors and are therefore in a higher energy state
than the atoms at interior positions.
The bonds of these surface atoms that are not satisfied give rise to a
surface energy. To reduce this energy, materials tend to minimize, if
at all possible, the total surface area. For example, liquids assume a
shape having a minimum area—the droplets become spherical.
this is not possible with solids, which are mechanically rigid !
cf. adsorption phenomena

37
Introduction
- Free surfaces - Surfaces libres
TLK Model
Terraces, Ledges, Kinks (terrasses, marches, décrochements)
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Chem. Comm., 588–589 (2003)

single crystals of (Ce0.5Zr0.5)O2
The Physical Chemistry of Solids -1992- Richard John

Borg,George Julian Dienes. 38
Introduction
- Grain boundary- Joint de grain
Boundary separating two small grains or crystals having different

crystallographic orientations in polycrystalline materials is called grain
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boundary.
It is a very fragile zone, because of the partial disorganization of atoms
approaching the two lattices of different orientation. They are more
chemically reactive than the grains themselves as a consequence of the
joint de
boundary energy. grain
10 m
grain = monocristal 39
Introduction
Joint de grain
- Grain boundaries-
When the difference in orientation between two neighboring crystals is

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small, the grain boundary may be described as a succession of edge

dislocations.
40
Introduction
- Grain boundary- Joint de grain
If the disorientation is important, only the atoms whose position is common to the
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networks of the two crystals remain at the interface.

Partie
• There are void spaces in the grain boundary with

respect to the bulk.
• The atoms of the grain boundary have fewer

neighbors than within the crystal.
It follows that:
• The diffusion is faster in the grain boundaries,

since there is more space to circulate;
•The energy of the atoms of the grain boundaries is

greater than that of the atoms within the crystal;
Grain boundary
with high • Grain boundaries are obstacles to movements of
desorder dislocations.
41
Introduction
- Twin Boundaries- mâcle
A twin boundary is a special type of grain boundary across which there is a

specific mirror lattice symmetry; that is, atoms on one side of the boundary are
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located in mirror image positions to those of the atoms on the other side.
42
Introduction
Impact of interfacial defects on the properties of materials

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- Places of rapid diffusion (conductivity, hot deformation,

precipitation ...)
- High Energy  High chemical reactivity, possible fragility,

cracking, corrosion…
- Resistance to plastic deformation (obstacle to movement of

dislocations)  hardness
 Lifespan under cyclic mechanical stresses ...
43
Bulk or volume defects– microstructure (3D)
Introduction
Other defects exist in all solid materials that are

much larger than those heretofore discussed.
They are introduced during processing and

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fabrication steps.
Exemples: pores, cracks, foreign inclusions, and

other phases…
44
Bulk or volume defects– microstructure (3D)
Introduction
Impact of volume defects

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• Loss of rigidity
• Weaknesses mechanically (concentrate stresses), rupture of

highly deformable materials
• Sensitivity to corrosion (pitting corrosion)
45
Introduction
Other imperfections: the phonons
Every atom in a solid material is vibrating very rapidly about its lattice
position (the amplitude of the vibrations increases with T).
Part 11
At room temperature, a typical vibrational frequency is on the order of

Partie
1013 vibrations per second, whereas the amplitude is a few

thousandths of a nanometer.
This leads to a disturbance of the regular arrangement of atoms in the
network.
Introduction
Other imperfections: the phonons
These vibrations are associated to quasi-particles which are called:

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phonons
Partie
These photons are associated as imperfections since they disturb the

periodicity of the crystal lattice.
But these are intrinsic perturbations and can not be eliminated!
Phonons are responsible for diffusion and limit the electrical conductivity
of a conductor.
Bilan anglais !
48
Introduction
Classes of inorganic materials
There are several methods for classifying materials, using different

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criteria such as their structure, properties, functions, or areas of use.

Partie
But the classification between big families of materials depends in large

part on the type of bond between the atoms.
For inorganic materials:

 Three classes are distinguished
-the conductors,
- the semiconductors,
- the insulators.
49
The various possible electron band structures in solids
Introduction
energy
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conductor insulator semiconductor
The energy corresponding to the highest filled state at 0 K is called the Fermi energy Ef
50
Introduction
 The insulators:
Also called dielectrics
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-The width of the band gap in covalent and ionic solids is too large to allow
free electrons to move under the action of an electric field.
- The ionic materials have their complete valence layer, which increases the
energy required for an electron to pass from the valence band to the
conduction band.
Materials with ionic bounding are good

electrical insulators
51
Introduction
 The insulators:
What is the order of magnitude of electrical resistivity ?

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a) Between 108 and 1016 W.m
b) Between 10-8 and 10-16 W.m-1
c) Between 1 and 102 W.m
d) Between 10-3 and 0 W.m-1
order of magnitude of electrical resistivity r : 108 à 1016 W.m 52

Introduction
 The electrical conductors:

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For metals there are vacant energy states adjacent

to the highest filled state at Ef. Generally, the energy
provided by an electric field is sufficient to excite large
numbers of electrons into these conducting states.
No Band Gap
53
Introduction
 The electrical conductors:

What is the order of magnitude of electrical resistivity ?
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a) Between 108 à 1016 W.m-1
b) r < 10-10 W.m-1
c) Between 1 et 102 W.m
d) r < 10-6 W.m
order of magnitude of electrical resistivity r < 10-6 W.m

54
Introduction
 The semiconductors:
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To become free, therefore,

electrons must be promoted across
the energy band gap and into empty states at the bottom of the conduction band.
This is possible only by supplying to an electron the difference in energy between
these two states, which is approximately equal to the band gap energy Eg.
 Increasing the temperature of an insulator results in an increase

in the thermal energy that is available for electron excitation. Thus, more
electrons are promoted into the conduction band, which gives rise to an
enhanced conductivity
order of magnitude of electrical resistivity r ?

between insulators and conductors !
55
Introduction
Reminder on the properties of materials
1- Mechanical properties
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56
Introduction
Young’s modulus or the modulus of elasticity (Rigidité)
The stiffness of the solid is its resistance to elastic deformation. It

Part 11
is often represented by the Young's modulus

Partie
(E, unit: Pa ) also called modulus of elasticity.

where  is the stress on the body, and  is the
strain
contrainte 
Module d' Young E  
déformatio n 
force F (l  l0 )
  
cross sectional area A l0
Its value is proportional to the intensity of the atomic bonds.
The elastic deformation is a reversible deformation: the medium returns to its

initial state when the constraints applied are eliminated.
57
Introduction
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58
Hardness
Introduction
Dureté
Definition :
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Measure of the resistance of a material to permanent (plastic) local

deformation and is often measured by forcing a chosen solid into the
surface of the material to be tested (unit: MPa)
The hardness is an anisotropic quantity, varying with the

crystallographic directions. It is difficult to use as an absolute
characteristic.
There is an apparent hardness of certain aggregates: red ocher can

be scratched by the nail, but is formed of fine grains of hematite
scratching the glass.
The texture can also give a false result. For example, if the structure
is fine-grained, it is possible to confuse a scratch and the grabbing of
small grains.
59
Introduction
A scale of hardness: the Mohs scale

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(1773 -1839)
Scale with 10 classes of relative

hardness, based on the scratch
resistance of different materials, talc and
diamond being the extremes.
60
Introduction
The scale is not linear.
It is necessary to distinguish toughness and hardness: the diamond

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is hard but not tough: it breaks easily thanks to its octahedral cleavage.
Mesurements:
The hardness is measured by the imprint left by a penetrator in a material

under a given force. There are different tests according to the shape of
the penetrator and the nature of the measurement of the impression
(surface or depth).
In all cases, the hardness is given in mega Pascal (MPa): It is the
ratio of a force in Newton (N) to a surface calculated in square millimeters
(mm2).
61
Introduction
Hardness indenters
F [kgf]
D [mm]
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The use of the Brinell scale is standardized by the International Organization for Standardization
(ISO), the European Committee for Standardization (CEN) and ASTM International.
62
Introduction
Exercice :
• What type of
hardness is
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measured on this
apparatus?
HBS 5/750/20 Test :
The 3 numbers indicate the conditions of the test:

-the first gives the diameter of the ball (in mm).
-The second indicates the value of the force (in N)
multiplied by a proportionality factor 0.102 (kgf).
-The third digit gives the charge holding time (in
seconds).
Calculate the hardness

63
Introduction
Exercice : • What type of hardness is measured on this apparatus?

Brinell Hardness
Test HBS 5/750/20. 1kgf = 9.81 N
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The 3 numbers indicate the conditions of the test:

-the first gives the diameter of the ball (in mm).
-The second indicates the value of the force (in N) multiplied by
a proportionality factor 0.102 (kgf).
-The third digit gives the charge holding time (in seconds).
• Calculate the hardness: 2F

HB 
D ( D  D2  d 2 )
2  750
HB 
  5(5  52  2 2 )
H B  230MPa
64
Introduction
Some Brinell hardness values

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Material Brinell Hardness

Softwood ~1 HB
Hardwood ~7 HB
Aluminium ~15 HB
Copper ~35 HB
Soft steel ~120 HB
Stainless steel ~250 HB
Soda-lime Glass ~550 HB
Tool steel 650 to 700 HB
65
Introduction
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66
2- Electrical properties
Electrical conductivity
Introduction
 (Ω.m)-1 (is used to specify the electrical character of a material. It is the

reciprocal of the resistivity:

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  ne ee
Partie
e 
E
Where
ne, the number of free electrons per unit volume,
e, the charge of one mole the electron,
e , the mobility of electrons
 , the instantaneous velocity under an electric field E.
Generally, the resistivity r (Ω.m) is measured insted of the conductivity.

The electrical conductivity depends strongly on the temperature.
Pouillet’s law :
l
Rr
S
R resistance (Ohm), r resistivity, l the length (m) and S the section (m²) of the material
67
Introduction
Conductivity in ionic materials is due to ion displacement
(Reminder: the width of the band gap is too high to allow an electron to pass to the
conduction band)
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The mobility of the ions is given by the following equation: ZeD

 
kT
D is the diffusion constante , Z is the number of electrons lost or accepted, e is the charge
of the electron (ev), k is the Boltzmann’s constant (8,63. 10-5 eV/K) and T the temperature
(K).
Vacancies and impurities increase the conductivity of ionic solids. The

vacancies are necessary for diffusion and their number increases with
temperature. The impurities can also diffuse through the material and thus help to
transport current.
 Ionic materials generally remain poor electrical conductors.
68
Introduction
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69
Introduction
Effect of impureties
Effet de la température
Liaisons métalliques Liaisons ioniques
r r
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effet moins marqué

que pour les métaux
T T
Effet des impuretés
Liaisons ioniques
métal avec défauts
r r
pures
métal pur
avec
impuretés
T T
It is possible to control the electrical resistivity of a material by controlling the

number of free electrons or by controlling the mobility of these electrons in the
material.
-Electron mobility is an important factor in metals, depending on the type of

bond, defects and microstructure.
- The number of electrons is a determining factor in semiconductors.

70
Introduction
The mobility of electrons is a function of the drift velocity (average electron velocity
. Following multiple collisions, the
in the direction of the force imposed by the applied field)
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electrons lose their kinetic energy which is transformed into phonons.
Under the effect of thermal agitation, the electrons regain a kinetic

energy but the direction they pursue is random.
In a perfect crystal at 0 K there are directions according to which an

electron can move without colliding with the atoms.
When T  in the solid, there is a thermal agitation which disturbs the

order. The atoms vibrating around an equilibrium position then reduce the
mean free path and the mobility of the free electron:
 The electrical resistivity of the material increases with T

71
Introduction
Mobility of electrons - effect of temperature

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 The presence of defects and impurities contributes to the decrease in

electron mobility and conductivity.
 The presence of irregularity in the lattice contributes to the decrease

in electron mobility and conductivity
 The resistivity is higher for alloys than for metals

72
3- Thermal properties
Introduction
The thermal conductivity and heat diffusivity in a material are

important physical properties in its application. These properties depend
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on the structure of the material.

Indicators of defects.
Heat spreads through different mechanisms:
* Convection
* Diffusion
* Radiation
In solids heat propagates without the flow of matter by diffusion of heat

carriers such as phonons, electrons or photons (They only play a role at
high temperature T>800°C).
73
Introduction
The thermal conductivity k is related to the electrical conductivity (motion of

charge carriers) and to the structure of the material itself (vibrations of the
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atoms).
In a solid, the vibrations of the atoms are not random and independent of each
other but correspond to eigen modes of vibration: the phonons.
These phonons correspond to waves which can propagate in the material, if its
structure is periodic. This contribution will be more important in a crystal,
ordered, than in a glass, disordered.
The thermal conductivity can thus be written as the sum of two contributions:
ke : charge carriers (electrons or holes)
k  ke  k p kp : the lattice vibration (phonons)
[W.m-1.K-1]
74
Introduction
Thermal conductivity of some materials
Tamb
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Air : ~10-2 W.m-1.K-1

75
Introduction
Part 11
 In the case of materials with ionic or covalent bonds and

Partie
amorphous materials, the contribution of free electrons is very low and

the thermal conductivity is due essentially to the thermal agitation of the
atoms which increases with temperature
 Thermal insulators are materials that contain many obstacles that

reduce or prevent the propagation of phonons and electrons.
76
Introduction
Thermal expansion
Most solid materials expand upon heating and contract when cooled. The
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change in length with temperature for a solid material may be expressed

as follows, where  is the linear coefficient of thermal expansion:
l f  l0
  is given in K-1
l0 (T f  T0 )
where l0 and lf represent, respectively, initial and final lengths with the
temperature change from T0 to Tf.
If the material is anisotropic or not, the coefficient of thermal expansion

varies or not according to the direction of measurement.
77
Introduction
Within the same class, for

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example metals, it varies

little, but when changing to
another class, ceramics or
polymers,  changes by
several orders of
magnitude.
BUP - Vol. 106 pp 77- 92 Janvier 2012 78

Partie
79
Introduction
Relationship between coefficient of dilation and melting temperature

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 The higher the melting point of a material, the lower

its coefficient of thermal expansion.
80
Introduction
Importance of dilation
Part of an expansion joint between the road and a concrete bridge

(length 620m).
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As the deck is located in the air it is subjected to temperature variations

greater than the road located on the ground hence the necessity of the
joints.
81
Introduction
Heat Capacity
Heat capacity indicates a material’s ability to absorb heat from the

external surroundings; it represents the amount of energy required to
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produce a unit temperature rise.

where dQ is the energy required to
dQ produce a dT temperature change.
C Typically, heat capacity is specified per
dT mole of material (J/mol.K, or cal/mol.K).
In general, specific heat is more often used in engineering than thermal

capacity.
Heat capacity
Specific heat  c 
atomic weight
82
4- Optical properties
Introduction
The optical phenomena that occur within solid materials involve

interactions between the electromagnetic radiation and atoms, ions, and/or
electrons. Two of the most important of these interactions are electronic
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polarization and electron energy transitions.

When light proceeds from one medium into another (e.g., from air into a
solid substance), several things happen
The intensity I0 of the beam incident to the

surface of the solid medium must equal the
sum of the intensities of the transmitted,
absorbed, and reflected beams, denoted as
IT, IA, and IR, respectively
I0 = IT + IA + IR
A solid is transparent if it transmits visible light with low absorption. A solid

is opaque if the light radiation is not transmitted.
83
Introduction
For the visible range of frequencies, the electric field interacts with
the electron cloud surrounding each atom within its path in such a
Part 11
Partie
way as to induce electronic polarization or to shift the electron cloud

relative to the nucleus of the atom with each change in direction of
electric field component.
Two consequences of this polarization are as follows:
- some of the radiation energy may be absorbed (absorption)
- light waves are decreased in velocity as they pass through the
medium. The second consequence is manifested as refraction.
84
Introduction
For metals:
If a wave (from radio waves, through infrared and the visible, and into about the middle of the
ultraviolet radiation) strikes those electrons near to the Fermi level, surface can
Part 11
Partie
absorb the photons, as plenty of empty energy states lie nearby.

However, the electrons can just as easily fall back to the lower levels
originally occupied, and the photons are re-emitted.
Each electron becomes an electromagnetic wave emitter (with the same  as
the incident wave, all these waves form the reflected wave where all the incident energy is found).
Nothing can penetrate the metal: it is opaque.

The electrons of the metal bond are responsible for the
reflectance and opacity of metals.
 metal is shiny (brightness)

85
Introduction
For metals:
Part 11
Partie
86
Introduction
In an insulator, this phenomenon does not occur since there is

no free electron: the covalent or ionic crystal can therefore be
Part 11
transparent. It is the case of diamond, many oxides, salts, organic

Partie
crystals ...
In the case of a semiconductor, portion of the incident wave is

absorbed to pass an electron from the valence band to the conduction
band.
Things are actually more complex: some electrons function as oscillators

set in vibration by the exciting electromagnetic wave if its frequency is
close. Certain wavelengths are thus selectively absorbed: the crystal
then appears colored.
87
Partie
88
Introduction
5- Propriétés magnétiques
Pourquoi étudier les propriétés magnétiques

des matériaux ?
Partie 1
Le magnétisme est un phénomène en vertu duquel certains matériaux en attirent

ou en repoussent d'autres. La compréhension des mécanismes du magnétisme
permet de modifier les propriétés magnétiques permanentes de certains
matériaux.
89
Introduction
Partie 1
Le fer, la magnétite, certains aciers sont des

exemples bien connus de matériaux magnétiques,
mais on oublie souvent que tous les matériaux
réagissent plus ou moins à la présence d'un champ
magnétique !
90
Introduction
Les dipôles magnétiques
Quand des particules électriquement chargées se déplacent, elles engendrent autour

Partie 1
d'elles des forces magnétiques qui peuvent s'ajouter à des forces électrostatiques. On
appelle champ magnétique l'ensemble des forces magnétiques qui se manifestent dans
un espace déterminé. On représente ce champ par un ensemble de courbes, appelées
lignes de force, qui indiquent la répartition des forces et leur direction d'action.
Les matériaux magnétiques contiennent des dipôles magnétiques qui réagissent

à l'application d'un champ magnétique, comme les dipôles électriques
réagissent à l'application d'un champ électrique !

91
Introduction
D’où viennent les moments magnétiques???

Partie 1
De l’atome et en particulier des électrons !
Chaque électron d'un atome engendre deux moments magnétiques
orbital spin
Le moment magnétique résultant d'un atome est la somme vectorielle de tous ses moments
magnétiques !
92
Introduction
On range les matériaux en trois classes : les diamagnétiques, les paramagnétiques et

les ferromagnétiques.
Partie 1
Pour « compliquer » les choses, certains matériaux présentent une forme particulière
de ferromagnétisme : les antiferromagnétiques et les ferrimagnétiques.
A RETENIR !
Tous les matériaux présentent au moins une forme de magnétisme et, quand on leur
applique un champ magnétique, leur comportement dépend de la réaction de leurs
dipôles magnétiques, au niveau atomique ou électronique.
93
Introduction
Diamagnétisme
Partie 1
C’est un phénomène de très faible intensité. Il disparaît dès que le champ magnétique
extérieur cesse d'agir. En I'absence de champ magnétique extérieur, ces matériaux ne
présentent aucune aimantation à l'échelle macroscopique !
94
Introduction
Paramagnétisme
Chaque atome de certains matériaux solides possède un moment magnétique dipolaire
Partie 1
permanent parce que la somme des moments magnétiques orbitaux et de spin de ses
électrons est différente de zéro. En I'absence de champ magnétique extérieur, ces
matériaux ne présentent aucune aimantation à l'échelle macroscopique, car les dipôles
magnétiques de leurs atomes sont orientés au hasard ! Un champ magnétique extérieur
va les orienter.
95
Introduction
Ferromagnétisme
Certains métaux ou alliages possèdent un moment magnétique permanent et présentent

Partie 1
une très forte aimantation. Le moment magnétique permanent des matériaux

ferromagnétiques résulte des moments magnétiques de spin engendrés par leurs
électrons, dont la somme n'est pas nulle. Les moments orbitaux contribuent également
mais dans une moindre mesure. En plus les atomes adjacents d'un matériau
ferromagnétique interagissent par paires pour produire des moments de spin dont la
somme contribue à leur alignement, même en l'absence de champ extérieur.
96
Introduction
Partie 1
Résumé de quelques propriétés
97
Introduction
Partie 1
Résumé de quelques propriétés
98
Introduction
Partie 1
Matériaux céramiques
99
Introduction
Conclusion
 Effect of the nature of the chemical bonds involved on the intrinsic

properties of the solid (ex.:Young modulus, melting temperature, , depend on
interatomic binding forces)
Part 11
Partie
 If we want to modify the properties of materials, it is only possible to

play on extrinsic properties.
* Intrinsic properties
- difficult to modify
- depend on the type of chemical bond and the atomic
architecture
- vary continuously depending on the composition
100
Introduction
Conclusion – part 1
* Extrinsic Properties
- depend on the defects included in the material and on the

Part 11
microstructure;
Partie
-vary considerably depending on the composition and the treatments

applied to it (thermal or mechanical).
exemples: conductivity, elastic limit, tensile strength, elongation
at break, toughness, hardness, etc…
Mechanisms of modification of mechanical properties

- Variation of composition;
- Modification of the microstructure (grain size);
- Mechanical treatments (hardening, lamination, ...);
- Thermal treatments (cooling and heating).
101

HAC720C - Cours 1 & 2 - Introduction - 2021-2022

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Matériaux inorganiques avancés

Responsables: Florence ROUESSAC & Umit DEMIRCI

Partie II : Les matériaux céramiques et leurs synthèses

Partie II-1 et II-2

Partie II-3 2 séances (U. Demirci)

Partie III : Les verres et vitrocéramiques

Partie IV : Les métaux (U. Demirci)

Partie V – Matériaux inorganiques pour l’énergie

Note finale : Partie FR 60% de la note finale (partie UD 40 % )

These are solids, shaped and assembled for the manufacture of

A distinction can be made between shaped materials (e.g. metals) and

Solid materials have been conveniently

This scheme is based primarily on chemical

In addition, there are the composites, which

 Mechanical properties: which reflect the behavior

 Physical properties: which measure the behavior

 Chemical properties: which characterize the

The properties of the materials depend on:

•Properties of the constitutive solid phase (s).

•Microstructure (size, shape, orientation of the grains of

•The spatial distribution of the solid phases involved (case

General information on inorganic materials

It is not possible to predict all the properties of a crystalline solid from

But the knowledge of the structure on the atomic scale makes it

The example of melting temperature:

Bonding Energies and Melting Temperatures for Various Substances

 The classification by type of chemical bond is directly

 The classification by type of chemical bond is directly

... depending on the type of dominant link

It corresponds to the electrostatic attraction between two ions of very different

 Ionic bonding is a strong bond (5 to 10 ev) and non directed

 Strong (2 to 8 ev) and directed

 strong bond (~ 4 eV ) and non directed

Hydrogen bonding : a special type of secondary bonding

 Weak < 0.5 ev

ionique covalente métallique

perte ou gain... partage... abandon...

- Point defects (dimensionless 0)

Intrinsic or extrinsic point defects

…those associated with one or two atomic positions

The solid must contain defects in order to be thermodynamically

Every crystal has a natural tendency to acquire punctual defects.

There are approximately 108 defect per mole of solid!

Cf. calculation : BUP 658 p 173-194 25

Nv: number of vacancies (usually per

Cationic vacancies can be distinguished from anionic vacancies:

A cationic vacancy is obtained by extracting a cation from the

SCHOTTKY defects are site vacancies, formed in cation/anion pair.

 The overall stoichiometry of a solid is not affected

as the others but in a place which is not

Sometimes it can be forced in order to

Impurity atoms replace or substitute for the host atoms

On parle de défauts de FRENKEL lorsqu’il y a association d’une lacune

Impact of point defects on the properties of materials:

 Properties related to transport phenomena

of material: diffusion through the vacancies

of electric charges: conduction in ionic solids

Atoms are not necessarily present: dislocation

Presumed existence in 1934 (Orowan, Polanyi, Taylor, Burgers)

Propagation of the edge

Surface atoms are not bonded to the maximum number of

this is not possible with solids, which are mechanically rigid !

cf. adsorption phenomena