Materials Physics II

Contents:
1. Diffusion and concentration dependent diffusion
2. Role of crystal defects in diffusion
3. Solidification of pure materials: nucleation and crystal growth
4. Solidification of solid solutions and eutectic phase mixtures
5. Precipitation
6. Metastable phases and spinodal decomposition
7. Solid solution hardening
8. Plastic deformation of multicomponent systems
9. Diffusion free phase transformations
10. Ceramics, covalent (ionic) crystals and glasses
11. Composites
Hardening of crystalline materials

Hardening: dislocation motion is impeded, therefore plastic

deformation or yielding requires larger stress

Alloying leads to hardening in case of the following objects

●
Atoms in the solid solution
●
Particles of a second phase
●
Ordered regions
●
Phase mixtures
Generally, hardening is due to the heterogeneities in the matrix
Solid solution hardening
Solid solution hardening is due to inhomogeneities at atomic scale

Important features in solid solution hardening:

●
Crystal structure of the host matrix
- Peiers stress is small (fcc,hcp): 2D dislocation motion
- Peiers stress is large (bcc, diamond): kink motion in 1D
●
Distribution of the solute atoms
Number of obstacles, N0 increases with the concentration
Dislocation – solute atom interaction T<Tm/2
●
Type of the solute atoms
- substitutional
- interstitial
Solid solution hardening
Description of solute hardening
1) Interaction of a single dislocation with one solute atom
2) Interaction of many solute atoms and one flexible dislocation
3) Thermal activation
Solid solution hardening
I. Interaction between solute atoms and dislocations

a) Size effect
Elastic deformation fields interact
Solute atoms have different atomic volume (ΔV≠0)
Substitutional solute atoms have spherical dilatational centre

It interacts only with the hydrostatic stress component

1−ν
E k =Δ V⋅σ⋅3
1+ ν
 Fx
Solid solution hardening
For a straight edge dislocation
x
near the solute atom σ xx +σ yy +σ zz G b 1+ ν sin α
σ= =
3 3 π 1−ν r
G b sin α
E k= π ΔV
r
F x =− ( )
∂ Ek
∂x
Gb 2x z
=− π
( x2+ z2)
2
Δ V
interaction force
(divergent?)

In fcc metals: F max ≈G b 2 δ

δ=
1 ∂a
a ∂c( )
For screw dislocations there is no first order
size effect if the dilatation field is spherical, Δ V =3 Ω δ
because hydrostatic stress component
atomic volume
is zero: σ=0
Solid solution hardening

In bcc metals: the interstitial atoms has a tetragonal deformation field

( )
ε11 0 0
ε= 0 ε 22 0 → E k =−∑ εik σ ikscrew Ω→
i,k
0 0 ε33

2ε11−ε 33
→ F max ≈G b
3

For example: α-Fe with C atom ε11=0.38 ε 22=−0.03

In general, interstitial atoms can increase the hardness strongly,

ε11 −ε33
because for interstitials sometimes → ≈0.3
3
while for substitutional solid solution →δ⩽0.15 (Hume-Rothery)
Solid solution hardening
1
In second order the size effect E k∼ 2
r
This leads to an interaction between also screw dislocations and
the substitutional solid solution

b) Modulus effect: in the environment of a solute atom

the elastic moduli of the material is different η= ( )
1 ∂G
G ∂c
(it can reach 20)
For edge dislocations:
G b2 Ω η
E k= 2
8 π (1−ν) r
2 2 F x =−( )
∂ Ek
=
G b2 Ω η 2x
∂ x z 8 π (1−ν) ( x + z )
2 2 2 2 2
ΔV

For screw dislocations:

2
Gb Ωη
E k= 2 2
8π r
Solid solution hardening
c) Electronic interaction: short range interaction, probably it is
negligible in metals (ionic crystals)

d) Chemical interaction:
in a stacking fault fcc hcp
the solute solubility is different,
therefore solute atom concentration can be higher
this is the so called Suzuki atmosphere
 Yield strength of solid solutions
1) Dilute solid solutions (Friedel-Fleischer model)

w≪l

distance of the average

interaction distance of
solute atoms
l2
x=R−√ R −l
2 2
x≈
2R
( )
1/ 3
2T b
dislocations 2 l=
T average b cτ
have curvature τ= concentration c≈
due to stress Rb lx
Dislocations make contact with new solute atoms due to the stress dependent
curvature. This effect reduces the length and leads to a stress dependent length. l =l ( τ)
3/2
F max 1/ 2
F =τ l b F max =τ b l ( τ c ) τc = 2 1 /2
c
b (2 T )
Yield strength of solid solutions
Combined size and modulus effect
G 3/ 2 1/2
τ c = ε c + τ 00
Z

|η|
ε=|η' −α δ| η' =η/(1+ )
2
Z =760 screw
α= +3
±16 edge

Works well in dilute alloys e.g. for Fe-(C) c<10-4

Yield strength of solid solutions
2) Extended obstacles: (Mott and Nabarro 1948, Labusch 1972)
dislocation interacts with a group of obstacles (solute atoms) and
not with a single solute atom.

Equilibrium state is determined by the minimum of the

dislocation line tension + interaction energy

4/3
F max 2/3
τc = K 1/ 2
c
T

G 4/3 2 / 3
τc = ∗
ε c + τ 00 ∗
Z =550
Z
Yield strength of solid solutions
Experimental validation (How to sum the size and modulus effects?):
Friedel-Fleischer Mott-Nabarro-Labusch
G 3/ 2 1/2 G 4/3 2 / 3
τc = ε c + τ 00 τ c = ∗ ε c + τ 00 compression
Z Z
ε=|η' −α δ|
|η| slip plane
η' =η/(1+ )
2
α= +3 screw
±16 edge tension
Z =760 Z ∗=550
Basic question: How to take into account
the different solute atoms at the
Jax-Kratochvil-Haasen opposite sides of an edge dislocation?
ε0=|η'|+α|δ| If |η'|≈16|δ| →ε0
ε: |η' +16 δ|+|η' −16 δ|
ε1 = If |η'|≫16|δ| or 16|δ|≫|η'|→ε1
2 ctrue
If ε0 : α=16 and c=
2
Yield strength of solid solutions

Cu alloys
Au alloys Ag alloys

Au, Ag and Cu-based solid solutions

for screw (α=3) and edge (α=16) dislocations
Mott-Nabarro-Labusch model
Yield strength of solid solutions

Based on the experiments

●
In typical fcc solid solutions the Mott-Nabarro-Labusch
model works well
●
Hardening is caused primarily
by the effect of edge dislocations
●
Both the size and modulus effects
are important in the interaction

size effect: Au-(Ag, Zn, Cd)

modulus effect Au-(Ga)

CRSS in Au alloys
in JKH model
 Materials Physics II
Contents:
1. Diffusion and concentration dependent diffusion
2. Role of crystal defects in diffusion
3. Solidification of pure materials: nucleation and crystal growth
4. Solidification of solid solutions and eutectic phase mixtures
5. Precipitation
6. Metastable phases and spinodal decomposition
7. Solid solution hardening
8. Plastic deformation of multicomponent systems
9. Diffusion free phase transformations
10. Ceramics, covalent (ionic) crystals and glasses
11. Composites
Plastic deformation in multicomponent systems

Preparation of multicomponent systems

●
Casting
●
Heat treatment
●
Internal oxidation
●
Artificial mixing

What is too complicated: n>2 phase systems

What we could discuss: n=2 phase systems
composites (particles in matrix)
two separate phases: eutectic, eutectoid systems
two phases as two kinds of particles
What we will discuss: particles in a homogeneous matrix
precipitates (α→α+β)
f <10 % r , l ≈1−5⋅10 2 nm
dispersions (e.g. oxides)
Plastic deformation in multicomponent systems

Shear stress necessary for plastic deformation

−4
well heat treated pure metal τ /G∼10
−3
solid solution τ /G∼10
particle containing alloy τ /G∼10−2

Particles will change both

- the yield stress
- the strain hardening
Important parameters determine the strength of the material:
- particles strength
- contact surface between the particle and the matrix
Special cases to be discussed:
- hard particles with incoherent contact surface
- particles with fully coherent contact surface
Plastic deformation in multicomponent systems
I. Yield strength
1) one dislocation and one obstacle
2a) sum of several obstacles and one dislocation
2b) all the dislocations
Interactions:
●
different elastic moduli
●
different lattice parameters
●
stacking fault energy particles
as strong
●
chemical obstacles
●
ordering, etc ...
Problems:
●
common effect of two or more interactions solute atoms
as weak
●
common effect of different obstacles obstacles
Linear summation for many weak and few strong obstacles works
Investigation of single crystals is preferred
Orowan stress
Hard particles with incoherent contact surface
Microscopic description: one dislocation and one (two) obstacle

D bending out of a dislocation

Rg=
2 between two obstacles

2T it requires a shear stress, because of

τ=
Db the T line tension of the dislocation

Gb
2
Gb
T= τ=
2 D

Orowan (1948)

Loop formation at critical position

Al2O3 particles in Cu-Zn alloy
 Orowan stress
Modification to the Orowan stress
E = E (θ)
2
d E (θ)
T (θ)=E (θ)+ 2
dθ tangent

Differential equation to the shape of the bent out dislocation

When the dislocation surpass the obstacles?

Ashby dipole criterion (1968)

in the critical position, the 1 and 2
dislocation segments are parallel
1 Gb x
x1.5 τ edge= ln
for isotropic 2π D r0
materials 1 Gb x
τ screw = ln
2 π(1−ν) D r0
Orowan stress
But this is not the critical position
F =2 E cos(Φ)
because the interaction of the
bent out dislocation lines should be
taken into account

[( ( ) )]
2
Gb x D
E (Φ)= ln 1+ −1 sin Φ
4π r0 x

4πF
2
Gb Effect of dipole force
Orowan stress
Orowan stress

for spherical particles with R radius: 1

D
=
√
f 1
2 R

Averaging for macroscopic sample

Gb ln (1.57 R / r 0 )
Δ σ=0.85
2 π √ 1−ν D−1.57 R

√ f Gb ln (1.57 R / r 0 )
Δ σ=0.85
2 2 π √ 1−ν R(1−1.57 √ f / 2)
Cut through process
Coherent particles
Microscopic description: one dislocation and one obstacle

When K particle strength is F =2 T cos ϕ

smaller than Orowan stress
∗
K < 2 T cos ϕ
particle will be cut through
τ crit l b= K
Particles in Al-Ni-Cr alloy

( )
1/ 2
Friedel: 1 1 F
=
l D 2T

averaging for l length

( )
3/ 2
K 2T K
Δ σ= =
l b D b 2T
Cut through process
Particle strength determined cut through force via Γ surface energy

( )
2
Rπ R
K dx=Γ dx
2
for spherical particles f ≈2
D

√ ( )
3/2
2T f K
Δ σ=
Rb 2 2T

( ) ( )
1/2
Γ
3/ 2
f R
Δ σ=1.44 G ⋅
Gb b

T
f R
Δ σ cut through ≈const .

Δ σ Orowan ≈const . √ f
T √ if K ∼R

R
Hardening processes
Experiments:

Δ σ cut through ≈const .

T
√ f R
T
Δ σ Orowan ≈const .
R
√ f
Hardening processes