2a Am Fame Amis Microprop Djurado 2023-2024

Microstructures and Properties
2023 - 2024
Teaching team
Elisabeth DJURADO LEPMI

Arthur DESPRES SIMAP
Fabien VOLPI SIMAP
PHELMA / AMIS/FAME / 2023-2024

• Outlines
• Atomic bonds and related properties
2 lectures (ED-AD)
• Microstructure descriptors
• Microstructures – Mechanical properties 5 lectures (AD)
• Microstructures – Functional properties 5 lectures (ED + FV)
24 hours
PHELMA / AMIS/FAME / 2022-2023

EXAM
One exam 2h
50% Mechanical prop., 50% Functional prop.
With documents
December 2023
Atomic bonds and directly related properties
E. Djurado / A. Despres
elisabeth.djurado@lepmi.grenoble-inp.fr
arthur.despres@grenoble-inp.fr
2023 - 2024
Atomic bonds and related properties
• Outlines
1. Atomic structure
2. Types of atomic bonds
1. Covalent and Ionic
2. Metallic
3. Hydrogen and Van der Waals
3. Related properties
1. Elasticity
2. Thermal expansion
3. Melting temperature
1. Atomic structure
The arrangement of electrons around atoms correspond to precise rules
(quantum mechanics) leading to atomic orbitals where the energy and the
number of electrons are determined
• One nucleus
– protons : qp = +e = 1,60219.10-19 C, mp  1,67.10-27 kg
– neutrons : qn = 0, mn  1,67.10-27 kg
• Surrounded by electrons
– electrons : qe = -e, me  9,11.10-31 kg
• Atomic number Z
– number of protons = number of electrons
– atom electrically neutral
1. Atomic structure
1. Covalent
Sharing of electrons between two atoms
Strong and directional bonding
Pure covalent bonding: Coordination bonding:

Symmetrical sharing Non-Symmetrical
Diatomic gases (H2, N2, O2, …) ex :N + B → BN
Si, C
Covalent bonds:
ORBITALS, ELECTRONS
p
sp3 ORBITAL of C
Diamond
Ethane
2. Ionic
Cations + anions
Strong bonding but not directional
Ionic compounds:
hard,
High melting point,
de LiF à LiCl de 842 à 614°C
High boiling point,
de LiF à LiCl de 1676 à 1382°C
2. Ionic Cations are surrounded by anions and vice-versa

Ex: NaCl or CsCl structures (Matériaux, 1A)
3. Metallic
Electrostatic attraction between delocalized electrons (conduction electrons) and

charged metallic atoms
Strong, non directional
Simple and Compact structures

Excellent thermal and electrical conduction
4. Hydrogen
• Intermolecular bonding which is present in polymers

(strong bonding) and implying systematically an hydrogen
atom (e.g. O-H or N-H)
At the origin of 3D structure of

solid water (ice) H
Oxygen at the center of both
O tetrahedron and H tetrahedron O
5. Van der Waals weak bonding
Transient dipole Permanent dipole
(|Ecoh| some 0.1 to 0.5 eV)
(|Ecoh| some 0.01 to 0.2 eV) Large lattice parameter

Weak bonds
Due to dipolar attraction
Also important for polymers
E 2. Types of atomic bonds
Exercise Electrostatic Interaction
1 1 ei e j N
E =  = E cb
2 i =1, N ji 40 rij 2 Attraction → -
Ecb (pair of ions) Repulsion → +
2 2
1 e1 1 e1 nj
E cb =  
j 4 0 rj
=−
4 0 r
 Madelung constant  = − 
j rj / r
j: neighbour order
n j: number of jth neighbours
r: distance between 1st neighbours
rj: distance from jth neighbour to reference ion
3D Madelung Constant: solution limited to 4th neighbour
1er voisins : - 6 x (r/r)-1 -6
2ème voisins : + 12 x (√2r/r)-1 8,485
3ème voisins : - 8 x (√3r/r)-1 - 4,619
4ème voisins : + 6 x (2r/r)-1 3
= - 0,866 !!!
etc.
Na+
2
Cl- 1,95
1,9
1,85
valeur de alpha
1,8
+ + +
( −1 )( i + j + k )
=   = 1,74756...
1,75
1,7
i = − j = − k = − i + j +k
2 2 2
1,65 théorique
calcul
1,6
1,55
Exact solution: converges very slowly 1,5

0 5 10 15 20 25 30 35 40 45 50
rang considéré
Madelung constant values
NaCl CFC 1.74756

CaF2 Cubique 2.51939
CdCl2 Hexagonal 2.244
MgF2 Tetragonal 2.381
ZnS (wurtzite) Hexagonal 1.64132
TiO2 (rutile) Tétragonal 2.408
Al2O3 Rhomboédrique 4.1719
? Rayon atomique diminue ? énergie d'ionisation augme nte ?
How determining bonding type?
Électronégativité augme nte ?
Groupe 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
ériode It depends on the atom link with own or foreign electrons→ Electronegativity
H He
1
2.1
Li Be B C N O F Ne
2
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Na Mg Al Si P S Cl Ar
3
0.9 1.2 1.5 1.8 2.1 2.5 3.0
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
4
0.8 1.0 1.3 1.5 1.6 1.6 1.5 1.8 1.9 1.8 1.9 1.6 1.6 1.8 2.0 2.4 2.8
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
5
0.8 1.0 1.2 1.4 1.6 1.8 1.9 2.2 2.2 2.2 1.9 1.7 1.7 1.8 1.9 2.1 2.5
Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
6 Lu
0.7 0.9 1.3 1.5 1.7 1.9 2.2 2.2 2.2 2.4 1.9 1.8 1.9 1.9 2.0 2.2
Fr Ra Lr Rf Db Sg Bh Hs Mt Ds Uuu Uub Uut Uuq Uup Uuh Uus Uuo
7
0.7 0.9
Pauling Electronegativity scale

χB
Ionic Covalent
Metal
Ionic
χA
Effect of A and B electronegativities on the A-B bonding type
Summary
Bond energy
(eV/at)
2-8
5 -10
0.01 – 0.3
ceramics
metals
polymers
Atomic bonds are not totally of one type
Three classes of materials

1. Bond energy
2. Elasticity
1. Bond energy
E
Repulsive energy

Pauli Principe
The bond energy (cohesion energy)
is the energy needed to build one
mole of solid from its gaseous 0
components.
Attractive energy
Cohesion energy
d
A B B
Equilibrium distance
E(d) shape:
* distance --> lattice parameter, density
* Depth --> cohesion energy
* curvature --> Young modulus E
--> Poisson ratio
* asymmetry: --> thermal dilatation
Atomic bonds and related properties
Exercise
E
Compute the values

corresponding to the two 0
arrows in the case of NaCl
Formation energy of NaCl : Hf = -98.3 kcal.mol-1

Vaporisation energy of Na : Hv = 26.1 kcal.mol-1,
Dissociation Energy of Cl2 : DCl2 = 57.8 kcal.mol-1
Ionisation energy of Na (Na→Na++e-) : INa = 118.4 kcal.mol-1,
Electronic affinity of Cl (Cl- → Cl+e-) ACl = 83.4 kcal.mol-1.
The diffraction angle of (100) planes is 2Θ =15.8° (λCu=0.154184 nm)
2. Elasticity
x
F Thomas YOUNG
z
y S (1773-1829, UK)
L L
- Young’s modulus, E
- Hooke’s law: Robert HOOKE
l
(1635-1703, UK)
F
 = E or =E
S l
2. Elasticity
When a stress is applied macroscopically to a material, the atomic
bonds react to these mechanical solicitations.
No stress Applied stress
k
E
a0
2. Elasticity
- Link between Young’s modulus and bond characteristics
Strong bonds (“deep” curves)
Large stiffness (large E values)
The Young's modulus will be all the higher as

the well of the potential will be pronounced
(to bring atoms closer to a given distance, ie
to deform the material of a given elastic
deformation). as much more energy (vertical
axis)
E polymers < E metals < E ceramics
2. Elasticity
- Link between Young’s modulus and bond characteristics
Strong bonds (“deep” curves)
Large stiffness (large E values)
Le module d'Young va être d'autant plus

élevé que le puits du potentiel sera prononcé
(pour rapprocher les atomes d'une distance
donnée c'est à dire pour déformer le
matériau d'une déformation élastique
donnée) il faudra apporter d'autant plus
d'énergie (axe vertical)
E polymères < E métaux < E céramiques
 Young modulus extraction
[Bailon]
U
A B
Distance to equilibrium Distance to equilibrium
r r
0 0
k B .Tm A
k B .Tm B
When do we reach the liquid state?

Easy Hyp: when the vibrations are big enough
In your opinion, do we have: TM(B) > TM(A) ou TM(B) < TM(A) ?

It can be assumed that the liquid state is reached when the position oscillations reach a defined value (red arrow)
2. Elasticity
2. Elasticity
- Poisson ratio
Siméon Denis POISSON

(1781-1840, France)
Traité de Mécanique (1811)
x
z
Unitary transverse contraction / unit axial elongation

(I draw according to Oy)
2. Elasticity
- Poisson ratio
VOLUME IS NOT CONSERVATIVE
Auxetic Material
2. Elasticity
- Young’s modulus
vs. density
Mike F. ASHBY
(1935-, UK)
Cambridge University
http://www-g.eng.cam.ac.uk/125/now/mfs/tutorial/non_IE/charts.html
ΔL
= αΔT
L0
kT 1 1
α 2  2
k E
kT
Vibrations around the equilibrium distance
Thermal activation
Asymetric potential
1 1
3. Thermal expansion α 2  2
k E
-1/2
Metallic
Covalent
Materials Ionic
Polymers
F. Lindemann:
melting occurs when Δa/a0  a few %
→ α .Tmelt= Cst
 ~ Cst/ Tmelt and  ~ 1/E2  Tmelt ~ E2  Tmelt/E2 ~ Cst

E (GPa)
Tm (°C)
Element Tm (°C)
Relations to give some evolutions….
…. Between mechanical / thermal properties
 .Tm ~ cste
Cohesive energy Melting point

Dilatation
coefficient
Young
E  Tm2
1
 modulus
E 2
4. Effect on functional properties
Microstructures & Properties
Effect on functional properties :

• Ionic conductivity
• Magnetism
PHELMA / AMIS-FAME / 2022-2023
Elisabeth.Djurado@lepmi.grenoble-inp.fr
Relations Microstructures - Properties in Materials / Materials Science and Engineering / PHELMA / Grenoble-INP / France
4. Effect on functional properties Electric / dielectric behaviors
Metallic bondings Covalent / Ionic bondings

- Conducting materials - Insulating materials
- Metals - Dielectrics and Semiconductors
• Large density of mobile electrons • Very low density of free electrons
(densities as large as 1023 cm-3 can
be reached) • An electric field can be applied within
the material
• No electric field can be established
within the metal • The applied electric field creates or
reorganises dipoles within the material
• An electric field can only appear at
the metal surfaces (skin effect) Exple : Electronic polarisation
• Under a time-varying electric field the

 
E =0
 
charges at the surfaces may or may E=0 E 0
not follow the electric field
+ - + -
P
 Electronic conductivity
 Electronic conductivity  Ionic conductivity
 Dielectric behaviour
4. Effect on functional properties Electrical conductivity
Electronic conductivity
(atomic bonding, impurities, temperature, size, defects) Materials Applications
-Semiconductors -Microelectronics
-Metals - Electrical energy transfer
Ionic conductivity Materials Applications

(atomic transport, point defects, temperature,dopant,nanometry)
-Ceramics -Energy storage
-Glasses - Sensors
-Polymers - Electrochromics
Solid electrolytes Molten salts
Aqueous or organic electrolytes
4. Effect on functional properties Electrical conductivity
J=E with  = en (in S/cm)

Density of electrical current
1
(Ohm law) =
 (Resistivity in Ohm.cm)
Electronic conductivity
The electron density is strongly influenced by the bonding type.
The electron mobility is influenced by collisions with :
phonons (~T-T0)
crystal defects (microstructure, dislocations,…)
impurities
Ionic conductivity
Point defect density

Point defect mobility influenced by :
Temperature
Microstructure (grain size, porosity, gb,...)
Partial pressure
Impurities
• Ionic conductivity
 (S.cm-1)
Super-conductors
106
Soft ionic crystals:
Metals 104 AgI
Glasses such as Li2S-P2S5-LiI
102 Refractory solids:
YSZ ( ZrO2-Y2O3), doped ThO2, CeO2
Semi-conductors bAl2O3 (11Al2O3-Na2O), NaSiCON
1
Molten salts
10-2
Aqueous or organic
10-4 electrolytes
10-6 Solid electrolytes
10-8
Insulators
Materials Applications
Pure Ionic conductivity
-Ceramics -Energy storage
-Glasses - Sensors 10-6 <  < 10-2 S.cm-1
from RT to 1200°C
-Polymers - Electrochromics
Material Science + Electrochemistry
• Ionic conductivity in oxide ceramics
Ionic conductivity results from intrinsic and extrinsic defects whose displacements occur in a
rigid matrix but which may be assisted by local deformations in case of organic polymers.
Intrinsic and extrinsic defects
A perfect crystal exists only at 0 K.

Thermal agitation generates intrinsic defects.
vibrations effect on thermal properties Energy
point defects effect on transport properties H
dislocations effect on mechanical properties
G= H-TS
Intrinsic point defects are a thermodynamic necessity
Ex: Schottky point defects % in NaCl crystal:

10-16 (300K) 10-8(700K) 10-4 (1100K) 0
-TS (S=k.lnw)
Point defects may also be created by « doping » with a dopant Defect %

Extrinsic point defects
Ex: Y2O3 doped ZrO2 solid solution
Point defects
Stoichiometric defects
Schottky defect Perfect crystal Frenkel defect
cationic vacancy
cationic vacancy
anionic vacancy
cationic interstitial
Kröger notation Intrinsic point defects
Example: a cationic Frenkel disorder Energy

M + empty band
M + X- M + X-
T=0K
X- M + X- M +
M + X- M + X- EF
X - full band
Energy
M + X - M++ X -
M+ . Conduction band
T>0K EF
X - +M + X - M +
M
M + X- X-
X-- valence band
, . ,
M x M .i + VM 0 h + e
M
The Kröger notation :

x effective charge : x (0)
species M . (+)
M , (-)
site q eff = q real – q site
• Ionic conductivity in solids
Microscopic description of mass transport in solids

Chemla’s experiment : 2 NaCl crystals in contact through a face covered by Cs137Cl film
and annealed for different durations at constant temperature.
Measured reactivity versus depth

 Concentration profile
Diffusion Diffusion
+
Migration
mobile species concentration gradient

Ionic transport driven by
applied electric field
• Ionic conductivity in solids
Mechanisms of atomic transport

1 - direct exchange: not probable in iono-covalent binary compounds (distortions, local repulsions)
Observed in complex ternary compounds when jump is performed between sites of closed charge
(cations in Oh and Td in spinels)
2 - indirect exchange (cycle) : derives from N°1. It implies a cooperative displacement few probable
of several species
3 - vacancy mechanism: the displacement is performed from a normal site to a vacant

neigbouring one (in a crystal with predominant Schottky type defect)
4 - direct interstitial: where one atom goes from a lattice interstitial site to a next empty interstitial one
5 - indirect interstitial: an interstitial atom drives out an atom, which is in a normal site, into a free
neighbour interstitial one (Ag+ in halides)
6 - cooperative exchange
Atomic jumps in solids
• Typical ionic crystals : alkali halides, eg NaCl
Mechanism
Na+ ion moves to an adjacent vacant cation site and then leaves its own site vacant.
Cations are usually more mobile than anions.
Cation vacancies = Main current carriers in NaCl
Magnitude of NaCl conductivity depends on the number of

cation vacancies which are related:
- to the thermal history of the crystal
Energy H
G= H-TS
Migration of cation -TS (S=k.lnw)

vacancies (Na+) in NaCl Defect %
Ex: Schottky punctual defects % in NaCl crystal:
10-16 (300K) 10-8(700K) 10-4 (1100K)
- to the purity of the crystal (extrinsic defects)

In the case of CaCl2 main impurity in NaCl
CaNa● + VNa’ (CaNa●, VNa’)X
to preserve charge balance

At low temperature (e.g. 25°C), extrinsic 

Number of thermally intrinsic vacancies is very small
Parallel lines are related to different amounts of dopant
Usual expression of temperature dependence of ionic conductivity

(Arrhenius equation)
σ=Aexp −E 
 RT 
E: activation energy
R: gas constant
Depends only on the cation mobility  T: absolute temperature
( RT )
A: pre-exponential factor contains several constants
 =0exp −Em
(vibrational frequency of the potentially mobile ions)
Em: activation energy for migration of cation vacancies
( = n e  )
i
i i i
ni=number of charge carriers
ei=their charge
 = ne0exp −RT
Em ( )
Pathway
Relations Microstructures - Properties in Materials / Materials Science and Engineering / PHELMA / Grenoble-INP / France for Na+ migration in NaCl
At higher temperature, thermally-induced vacancy concentration is

greater than vacancy concentration associated with the dopant.
Number of cationic vacancies, n, is temperature dependent

 - Ef 
n = N x constant x exp 
 2RT 
Ef
with = activation energy for formation of one mole of
2 cation vacancies (half the energy required to form
one mole of Schottky defects)
 − Em 
 = 0exp 
 RT 
 − Em   − Ef 
 = N x constant x e x μ0  RT   2RT 
exp  exp
 
 Em + E f / 2 
Usual expression (Arrhenius diagram) σ = A exp -  
 RT 
• Typical solid electrolytes : doped Zr02 (or CeO2)
Fluorite structure
Zr or Ce
Oxygen vacancy
Y or Gd
O Zr or Ce
Zr1-xM3+xO2-x/2 Y2O3  2Y’Zr + 3OxO + VO••
The high T ZrO2 stabilized by Y2O3 (8YSZ = Yttria-stabilised Zirconia 8%)
Electric field
ZrO 8 cube
Y 3+
Zr 4+
O2-
 SOFC cells
Oxygen vacancy
Influence of dopant nature and concentration
Zr1-xM3+xO2-x/2 Y2O3  2Y’Zr + 3OxO + VO••
0,18
0,16 850 °C Defect pairs

Sc2O3
2Y’Zr + VO••
0,14
0,12
= (2YZr-VO)x
-1
 / S.cm
0,10
0,08
0,06 Y2O3
0,04
• ordering of vacancies
0,02 or
2 4 6 8 10 12 • formation of a
Mole % M2O3-Zr02 superstructure within the
anion sublattice
ZrO2-Sc2O3
Best  for ZrO2-Sc2O3 Weak stability with time
rZr4+ = 0.80Å rSc3+ = 0.81Å High cost (4000 €/kg)
Influence of dopant nature (charge and radius) for a same vacancy cc of oxide ions
Max of ionic conductivity when the ionic radii of the dopant cation
(•) 3YbTZP (■) 3YTZP (▲) 3GdTZP et () 3SmTZP
is closed to the host one. 0,5
0
(ZrO2)1-x(Y2O3)x ,( x =0.03)
log ( T (S.cm-1.K))
-0,5
Tetragonal zirconia
-1
-1,5
Zr4+ Sc3+ Yb3+ Y3 Gd3+ Sm3
+ +
-2
0.084 nm 0.098 nm 0.102 0.106 nm
0.087 nm nm 0.109
nm -2,5
High stress in Sm/TZP compensated by a larger

association between VO.. and R’Zr cationic defects in order -3 1 1,2 1,4 1,6 1,8
to minimize the free energy 3
1/T / 10 (K )
-1
Arrhenius diagrams of bulk ceramics

J.A. Kilner, Solid State Ionics 8 (1983) 201 Boulc’h F., et al.
J.E. Bauerle, J. Hrizo, J. Phys. Chem. Solids 30 (1969) 565 Solid State Ionics 154-155 (2002) 143-150.
• Effect of the microstructure size at the nano-scale
Comparison of electrical conductivities of YSZ as thin films for different

grain sizes
"Electrical conductivity of nanocrystalline ceria and zirconia thin
films", I. Kosacki, T. Suzuki, V. Petrovsky, H.U Anderson, Solid
State Ionics 136-137 (2000) pp. 1225-1233
• Effect of the microstructure size at the nano-scale
Consisted in crystallites structuraly ordered and atoms localized at interfaces which are structuraly
disordered being classified in between crystalline and amorphous classes
Sketches of solids (a) crystalline (with vacancy), (b) nanocrystalline, (c) amorphous
0,05 % 4% 35
%
1
60 nm
mm
6 nm
S/V
For a compact stacking of zirconia spheres

Applications
[Electrochimie des solides, Deportes et al, pug]
Applications
SOLID OXIDE FUEL CELLS (SOFC)
. .
M
e- e-
O 2-
H2
O2
a) b)
H2O
a) 1/2 O2 + 2e - O 2- (cathode)
b) O 2-
+ H2 H2O + 2 e- (anode)
G
1/2 O 2 + H 2 H 2O 2 F E = G
Anode Cermet
EEC program ~ 200 kW (1997) Ni-(ZrO 2-Y2O3)
Solid Electrolyte
(ZrO2-Y2O3)
H2O
H2
Bipolar Plate :
Cr-Ni, SiC
Cathode
La1-xSrxMnO3
[Electrochimie des solides, Deportes et al, pug]
O2Materials / Materials Science and Engineering / PHELMA / Grenoble-INP / France
Relations Microstructures - Properties in
Microstructures & Properties
Effect on functional properties :

• Magnetism
PHELMA / AMIS-FAME / 2022-2023
Elisabeth.Djurado@lepmi.grenoble-inp.fr
• Magnetic properties
- Spin dipolar momentum

- Behaviour of substances in a magnetic field
- Influence of temperature: Curie and Curie-Weiss Laws
- Mechanisms of ferro- and antiferromagnetic ordering, superexchange
- Magnetic domains – Hysteresis loop
Application - Induction furnaces – soft magnetic materials
- Magnetocrystalline Anisotropy
Application: electric transformer
-Ferrimagnetism
Application to magnetite Fe3O4
- Hard magnetic materials (permanent magnets)
Each ion which contains single electron, (unpaired d and f electrons, usually located on metal
cations - transition metals, lanthanides-) is characterized by a resulting magnetic moment,
mainly due to the coupling of electron spin with its kinetic moment (electron orbital motion).
If we consider only the spin contribution, the projected magnetic moment for an ion in the
quantification direction is :
n with g~2 is the Landé g-factor (gyromagnetic ratio), B=9.2740154 10-24 A.m-2
 z = g  B n: number of non-apparied electrons (1B=eh/4me)
2
In a crystal, the magnetic moments can be oriented in 4 fondamental arrangements:
Ferromagnetism Antiferromagnetism Ferrimagnetism Paramagnetism
These arrangements are stable only below a certain temperature

Tc: Curie T (Ferromagnetism)
TN: Néel T (Antiferro-,Ferrimagnetism)
Behaviour of substances in a magnetic field
Materials may be classified by their response to externally applied magnetic

fields as diamagnetic, paramagnetic, or ferromagnetic. These magnetic
responses differ greatly in strength.
Diamagnetism is a property of all materials and opposes applied magnetic

fields, but is very weak.
Low intensity
Paramagnetism, when present, is stronger than diamagnetism and produces

magnetization in the direction of the applied field, and proportional to the
applied field (it is the situation where unpaired electrons arranged at random in the
material show some tendency to align themselves in a magnetic field).
Ferromagnetic effects are very large, producing magnetizations sometimes

orders of magnitude greater than the applied field and are much larger than
either diamagnetic or paramagnetic effects (in ferromagnetic materials, a
spontaneous parallel alignment of magnetic dipoles occurs due to cooperative
interactions between spins on neighbouring ions in the crystal structure)
Behaviour of substances in a magnetic field
H: Magnetic field (A/m)

B=H+4I B: Magnetic induction (density of lines of force in the sample)
(T = 1Wb/m2)
P = B/H = 1 + 4  
I: Magnetic moment of the sample per unit volume
P: Permeability Wb/(A.m) c: Molar susceptibility

c=  F/d  : Susceptibility = I F: formula weight
d: density of the sample
H
Different kinds of magnetic behaviour vs P,  , c , T, field dependence
Behaviour of substances in a magnetic field H
Diamagnetic substances experience a slight repulsion

by H
Paramagnetic substances are attracted by H
PARAMAGNETIC substances are attracted to a magnetic field (P>1,  and c are positive)
DIAMAGNETIC substances experience a slight repulsion (P<1,  and c are small and slightly
negative)
FERROMAGNETIC substances are strongly attracted to a magnetic field (P>>1, large values of 
and c )
ANTIFERROMAGNETIC substances (P>1,  and c are positive and comparable to or less than those for
paramagnetic substances)
Effects of temperature: Curie and Curie-Weiss Laws
Curie Law
c = C/T
where C=Curie constant
(for paramagnetic compounds, especially at high T)
A better fit to experimental data is provided by the Curie-Weiss Law:

(for ferro- and anti-ferromagnetic compounds,
Curie-Weiss Law
c = C/T+q Curie/Curie-Weiss Laws)
where q=Weiss constant
Influence of temperature: Curie and Curie-Weiss Laws
For ferro- and antiferromagnetic substances
Structural disorder when T
Curie-Weiss Law
T
TC
C
Variation of BS for Fe versus T
Case of Gd 289K, Co 1403K, Ni 631K
When T , a decrease of antiparallel ordering

with an increase in the number of ‘disordered’ electron spins
TN Case of MnO, FeO,NiO, MnS, CrSb, FeCO3, MnF2
Temperature dependence of the magnetic susceptibility for

Relations(a) paramagnetic,
Microstructures (b) ferromagnetic
- Properties in Materials / Materials Science and and (c) / antiferromagnetic
Engineering materials
PHELMA / Grenoble-INP / France
Mechanisms of ferro- and antiferromagnetic ordering, superexchange
NiO Ni2+ d8 in octahedron
t2g6 eg2
• Magnetic properties Magnetic domains
In a ferromagnetic material: spontaneous orientation of atomic magnetic dipoles even without an exterior
magnetic field.
Magnetic domains: In each domain all the spins are aligned parallel.
Different domains have different orientations
Bloch wall
a) Magnetic domains (Weiss domains) in a ferromagnetic material

b) Orientation change of magnetic dipoles through a bloch wall.
In a polycrystalline sample, grain boundaries = Bloch walls
In a single-crystalline sample, several magnetic domains can exist with their own orientation and Bloch walls.
Without exterior magnetic field, the vectoriel sum of magnetic orientations of domains being zero,
no spontaneous magnetization
• Magnetic properties Magnetic domain walls
The border between domains of opposing magnetization cannot be sharp or sudden,

As this would imply a great cost in exchange energy.
In those regions, a compromise results: the energy minimization is achieved by
the existence of a layer in which the magnetization orientation varies gradually.
Such region is called a domain wall (Bloch wall).
• Magnetic properties Magnetic domains

Ferromagnetic single-crystal
Mean magnetic induction B of a ferromagnetic material strongly depends on the orientation of magnetic
domains versus H.
Mean orientation of domains = zero At a limit, for a critical HS,

one unic ferromagnetic domain
Magnetic domains which orientation with same orientation of H.
is close to the H one mainly increase. Maximum value of B: BS called
Shifts of Bloch walls Induction at saturation
• Magnetic properties Hysteresis loop

B vs H with BS, Br, HC
Ferromagnetic material
Saturation magnetization, BS
OA: curve of 1st aimantation

or curve of magnetization
DEFA: way of field is changed

and H intensity is increased.
AB: Intensity of H is decreased towards 0,

magnetic domains appear again but the shift of Bloch walls is not instantaneous, Br remanent induction.
BC: An opposite way of H is applied with comparison with the one for the 1st magnetization in order
to get B equal to 0 corresponding to the coercitive field, HC.
CD: When
Relations H intensity
Microstructures is increased,
- Properties B reaches
in Materials / Materials Science andagain the/ PHELMA
Engineering maximum value/ France
/ Grenoble-INP BS.
Ferromagnetic material
The area of the hysteresis loop represents

the energy used per unit volume of the material to reorientate the magnetic moments
of domains and to displace the Bloch walls during a complete cycle of varied exterior H.
Dissipation of energy as heat.
Application of this phenomenon: possibility to heat or melt some materials,

conductor of electricity, submitted to cyclic variations of an intense magnetic
field .
• Magnetic properties Application
Let us consider an electrical conductor in an alternative magnetic field H produced by a solenoid.

In this field, the free electrons are moved (Lenz’s law) and inside the material, internal electrical currents appear,
Foucault currents,
which produced magnetic field in the opposite way of the exterior magnetic field avoiding this last one to go inside
the material.
The material is heated consequently to Joule effect due to these currents (up to the melting point).
Appearance of Foucault current, iF, in an electrical conductor

in an alternative magnetic field H produced by a solenoid
Skin effect: usually these currents are established close to the surface of the conductor
this thickness is lower as far as the frequency of the exterior field is high
Induction Furnaces (thermal treatments for steel pieces in surface)
Lenz's Law
In 1834, Russian physicist Heinrich Lenz discovered the directional relationships between
induced magnetic fields, voltage, and current when a conductor is passed within the lines of
force of a magnetic field. Lenz's law states:
"An induced electromotive force generates a current that induces a counter magnetic
field that opposes the magnetic field generating the current."
• Influence of the microstructure: Magnetocrystalline Anisotropy

In many cases, the magnetization of a material, M(H) under an applied magnetic
field (H) depends on the direction in which the field is applied.
This anisotropy results from factors which can be intrinsic, relative to the crystalline
state of the material, or extrinsic, such as the shape of the sample or internal strain.
We can always associate with each of these factors, a contribution to the total
energy of the system: the anisotropy energy.
The atomic wave functions of the magnetic ions, which involve d electrons in
transition metals and f electrons in rare-earth, are usually not spherical. This leads
to a preferential accomodation of the charge under the influence of the local electric
crystal field at the site of the magnetic ion.
The interaction of the orbitals charge

with the local electric field influences
H the orientation of the magnetic
moment.

In a crystal, there are directions along which the magnetic moments align preferably:
easy axis of magnetization.
Other directions, along which the alignement requires more energy: hard axis of magnetization
The electron spins feel this anisotropy through the spin-orbit atomic interaction.
For the material, the associated energy is called magnetocrystalline energy.
Depending on the crystal symmetry, one can have one or more anisotropy axis.
Fe Ni Co

Fe single crystal
• Influence of the microstructure: Magnetocrystalline Anisotropy - Application

Fe: (low cost, availability) as nucleus for electric transformers
-should be easily magnetized and demagnetized (AC current and magnetic field) to follow the
variations of H, Hc has to be as low as possible
-the hysteresis cycle should be very thin to decrease the energy losses dissipated as heat.
-the value of Bs has to be as high as possible in order to canalize the lines of H towards the
secondary rolling-up of the transformer.
Fe-Si
In order to increase Bs along <001>,

Thermal treatment after hammer-hardening (écrouissage) to obtain large grain microstructure
which mean orientation <001> is in the direction of the laminate.
• Magnetic properties Hc has to be as low as possible

Bs has to be as high as possible
When an exterior field varies, no opposition to the displacement of Bloch walls and
to the reorientation of magnetic domains.
In a ferro-magnetic material, the obstacles are : gb, solute atoms, dislocations,
precipitates and other phases
Ferrimagnetic materials: spontaneous magnetization
Ferrimagnetism
Oxides
Spinel – MgAl2O4, Fe3O4, …
Normal: [A]tet [B2]oct O4, g=0

Inverse: [B]tet [A, B]oct O4, g=1
Random: [B0.67 A0.33]tet [A0.67 B1.33]oct O4, g = 0.67
g is the fraction of A cations in the octahedral site
• Magnetic properties Oxides
Spinel structure
The spinel structure (sometimes called garnet structure) is named

after the mineral spinel (MgAl2O4); the general composition is AB2O4.
It is essentially cubic, with the O 2-ions forming a fcc lattice.

FERRIMAGNETISM: Application to magnetite Fe3O4
In physics, a ferrimagnetic material is one in which the magnetic moment of the atoms
on different sublattices are opposed, as in antiferromagnetism; however, in ferrimagnetic
materials, the opposing moments are unequal and a spontaneous magnetization
remains. This happens when the sublattices consist of different materials or ions (such
as Fe2+ and Fe3+).
Ferrimagnetic ordering
Some ferrimagnetic materials are YIG (yttrium iron garnet) and ferrites composed of iron oxides
and other elements such as aluminum, cobalt, nickel, manganese and zinc.
Theoretical aimantation A
A= M z (A.m-1)
V
MZ : Resulting magnetic moment
V: cell volume
a = 8.3939Å, cell parameter
FERRIMAGNETISM: Application to magnetite Fe3O4

A = 509 kA.m-1
magnetite Fe3O4
Fe tetrahedral Fe octahedral
site site
• Magnetic properties Ferrites
On a technological point of view,

Ferrites, which are characterized by ionic bondings, are bad electricity conductor
(insulators)
When ferrites are under alternative variations of high magnetic fields, the energy
(determined by the area of the hysteresis loop) is dissipated as heat but their insulating
nature avoids
-the appearance of Foucault currents,
-heating from Joule effect.
By substituting Fe2+ in ferrites (Td) by:

-Ni2+ in NiO.Fe2O3, susceptibility is decreased because Ni2+<Fe2+
- Zn2+ in ZnO.Fe2O3, susceptibility is increased while Zn2+=0 but
equilibrium of Fe3+ ions in Td and Oh sites
By changing the nature of ions in ferrites, many combinations
soft Magnetic materials hard

• SOFT Magnetic materials
Selection criteria of soft magnetic materials

- Narrow hysteresis loop (low Hc)
- Large saturation induction BS and magnetic susceptibility
Applications
-Transformators
- Inductances of precision of electronic circuits
- Magnetic screens
91
• SOFT Magnetic materials
Magnetic memories in data processing
Disk with static heads
MAGNETIC DISK
Samsung Memory
92
http://perso.wanadoo.fr/daniel.robert9/Digit/Digit_12T.html#MAGNÉTIQUES http://informatique.kelkok.fr
• Magnetic properties Hard magnetic materials

- when the magnetic field produced by the material is high and stable in time and not perturbated by an exterior
field,
- used in permanent magnets,
- should have high values of remanence and coercitive field.
The figure of merit for a permanent magnet is basically the energy product BrHc (or density of specific energy).
To increase it, one needs mechanisms that pin the domain wall motion and therefore the presence of defects or
inhomogeneities is important. This is favoured by the presence of several phases in the material and a small grain
microstructure.
X-ray composition micrograph of a sintered

Nd2Fe14B magnet
Calculation of the merit factor BH.
For a Bx value, BH product = Surface of the rectangle
BxCHxO.
The presence of defects or
impurities pins the motion of the
Bloch wall.
This requires higher energy
(higher field) to overcome this
effect.
Larger hysteresis
loop implies a large
Narrow hysteresis loop implies a amount of dissipated
small amount of dissipated energy in energy in reversing
reversing the magnetization the magnetization
VARIATION IN HYSTERESIS CURVES

From SOFT to HARD magnetic materials
Desirable for transformer and motor Desirable for

cores to minimize the energy permanent magnets
dissipation with the alterning fields and memory devices
associated with AC electrical
applications
• Magnetic properties Hard magnetic materials
Typical properties for several hard magnetic materials
Introduction of Cr
W or Co increases Hc
2 phases
Hard materials are not easily demagnetized: used as permanent magnets

• Hard magnetic materials
Applications
Hard magnetic materials are used when the magnetic field generated by the
material has to stay stable with time . It has to be high even in presence of
exterior parasite magnetic field
- Permanent magnets
- Lifting magnets
- Loudspeaker core
- Low power electric motors
- The magnetic lenses (for cathode ray tubes)
96
• Hard magnetic materials
Some examples
– Electromagnets
MOORING ELECTRO-MAGNETS 97
http://www.afcan.org/dossiers_techniques/amarrage.html
• Hard magnetic materials Electromagnets
They allow the lifting of objects made of magnetic metal (ferrous)
Often specific, always very powerful, for intensive use.
Magnetic suction cups
98
http://www.kuhnke.fr/pages/kuhnke4.htm

2a Am Fame Amis Microprop Djurado 2023-2024

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Microstructures and Properties

Elisabeth DJURADO LEPMI

PHELMA / AMIS/FAME / 2023-2024

• Microstructures – Mechanical properties 5 lectures (AD)

• Microstructures – Functional properties 5 lectures (ED + FV)

PHELMA / AMIS/FAME / 2022-2023

Atomic bonds and directly related properties

Sharing of electrons between two atoms

Strong and directional bonding

Pure covalent bonding: Coordination bonding:

Strong bonding but not directional

2. Ionic Cations are surrounded by anions and vice-versa

Electrostatic attraction between delocalized electrons (conduction electrons) and

Simple and Compact structures

• Intermolecular bonding which is present in polymers

At the origin of 3D structure of

5. Van der Waals weak bonding

Transient dipole Permanent dipole

(|Ecoh| some 0.1 to 0.5 eV)

(|Ecoh| some 0.01 to 0.2 eV) Large lattice parameter

Exercise Electrostatic Interaction

1er voisins : - 6 x (r/r)-1 -6

2ème voisins : + 12 x (√2r/r)-1 8,485

3ème voisins : - 8 x (√3r/r)-1 - 4,619

4ème voisins : + 6 x (2r/r)-1 3

Exact solution: converges very slowly 1,5

Madelung constant values

NaCl CFC 1.74756

Pauling Electronegativity scale

Atomic bonds are not totally of one type

Three classes of materials

Compute the values

Formation energy of NaCl : Hf = -98.3 kcal.mol-1

No stress Applied stress

The Young's modulus will be all the higher as

Le module d'Young va être d'autant plus

Distance to equilibrium Distance to equilibrium

When do we reach the liquid state?

In your opinion, do we have: TM(B) > TM(A) ou TM(B) < TM(A) ?

Siméon Denis POISSON

Unitary transverse contraction / unit axial elongation

 ~ Cst/ Tmelt and  ~ 1/E2  Tmelt ~ E2  Tmelt/E2 ~ Cst

Cohesive energy Melting point

Microstructures & Properties

Effect on functional properties :

PHELMA / AMIS-FAME / 2022-2023

Metallic bondings Covalent / Ionic bondings

• Under a time-varying electric field the

Ionic conductivity Materials Applications

Solid electrolytes Molten salts

Aqueous or organic electrolytes

J=E with  = en (in S/cm)

Point defect density

Material Science + Electrochemistry

Intrinsic and extrinsic defects

A perfect crystal exists only at 0 K.

Ex: Schottky point defects % in NaCl crystal:

Point defects may also be created by « doping » with a dopant Defect %

Schottky defect Perfect crystal Frenkel defect

Example: a cationic Frenkel disorder Energy

The Kröger notation :

Microscopic description of mass transport in solids

Measured reactivity versus depth

mobile species concentration gradient