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
Solidification G
G= H −T S

for T <T m in equilibrium G S <G L

entropy contribution decreases with T
Tm T
If there is no volume change and
no composition change

Energies per unit volume (volume contributions):

Δ GV =G S −G L =( H L − H S )−T (S S −S L )

Δ GV =Δ H V −T Δ S V

At small undercooling: Δ T =T m −T
Δ G V ∼Δ T →|Δ G V |=α Δ T
Solidification
Fluctuations in the liquid leads to the formation of tiny crystals
- let the small crystals be spheres with r radius
- due to the large surface fraction of the small crystals,
surface contribution becomes important in the energy balance
4π 3 2
Δ G (r )=Δ G V r + γ SL 4 π r
3

surface (free enthalpy) energy

of the solid-liquid interface
Solidification critical nucleus size
∗ 2 γ SL 2 γ SL
r = =
Δ G (r ) γ SL 4 π r
2
|Δ G V| α Δ T

energy barrier of nucleation

∗ 16 π γ 3SL 16 π γ 3SL
Δ G∗ r0 ΔG = 2
=
3|Δ G V | 3 α 2 (Δ T )2
Δ G (r ) r

4π 3 3 γ SL 3 ∗
Δ GV r r 0= = r
3 |Δ G V | 2

The G decreases if the crystalline nucleus larger than r ∗ ( γ SL , Δ G V )

where Δ G ∗ is the activation energy of the nucleation process

Δ G∗ and r ∗ decreases with increasing Δ T undercooling

Solidification
How large should be Δ T to get a stable nucleus from thermal
fluctuations? ΔTC

Stable nucleus can growth without the help of thermal fluctuations.

In thermal equilibrium, when N particles exist in a unit volume

( )
∗
∗ ΔG
N = N exp −
kT

For N*=1

( )
2 3
16 π γ 3SL ΔTC 16 π γ SL
ln N = =
3 α 2 (Δ T )2 kT Tm 2 2
3 α T m kT ln N
Solidification
Where alpha can be estimated
Δ GV =G S −G L =( H L − H S )−T (S S −S L )

T =T m →Δ G V =0 →( H L − H S )−T (S S −S L )

latent heat: LV =T m Δ S V

LV T m −T LV
Δ GV = LV −T = LV − = ΔT
Tm Tm Tm

LV
α=
Tm

( )
2 3
ΔTC 16 π γ SL 3
16 π γ SL T m
2
= ΔG =
∗
Tm 2
3 LV kT ln N 2
3 LV ( Δ T )
2
Solidification: Turnbull experiment
The surface energy is not known from theory, but it can be measured

Turnbull-experiment: solidification of high purity and extremely small

liquid droplets, i.e. micrometer size Hg droplets dispersed in oil
(no heterogeneous nucleation)

( )
ΔTC
Tm max
≈0.2 γ SL a 2≈0.4 LV a 3
Heterogeneous nucleation
Solid nucleus forms at the surface of a solid wall.

This is the typical nucleation process,

because it requires smaller activation energy
than homogeneous nucleation
(homogeneous nucleation occurs very rarely)
γ SL
γ LW γ LW =γ SW + γ SL cos Θ
solid liquid
γ SW wall
Δ G (r )= π r 3 Δ G V +r 2 γ SL f (Θ)
2Θ
(3 )
f (Θ)=(2−3 cos Θ+cos 3 Θ)<2
3
Interaction with the wall ∗ 4 π γ SL
ΔG = 2
f (Θ)
reduces activation energy 3 ΔG V
Heterogeneous nucleation
∗
Δ G (Θ)
The efficiency of the wall depends on
- chemical characteristics Δ G∗
- smoothness/roughness
- coherency
cos Θ
Θ=180 deg non-wetting (Turnbull experiment)
Θ=0 deg perfect wetting -1 0 1
(mostly the crystals of the liquid)

For small Δ G∗ the crystallization can start at small undercoolings

3/2
Toward small surface energies, undercooling decreases Δ T C ∼γ SL
Nucleation rate
Rate of the nucleation: I [number/(m3s)] I =ν N
Number of nuclei: N
Rate of attaching atoms: ν

( )
∗
∗ Δ G d
ν= N SL ε ν L exp −
kT

atoms at the surface of the critical nucleus

ε ratio of favored jumps, e.g. 1/6
ν L vibration frequency in liquid

( )
∗ ∗
∗ Δ G + Δ G d
I = N SL ε ν L N exp −
kT

I is very sensitive to the exponent,

the pre-exponential terms have only small effects.
 Nucleation rate
3 2 ∗
∗ 16 π γ SL T m Δ Gd
ln I =ln ( N SL ε ν L N )− −
2 2
3 L V (Δ T ) kT kT

This is small at Tm

Nucleation rate can not be measured

directly, only through thermal or
dimensional changes of the material

This nucleation model approximates only

the real nucleation process

Surface energy can be determined

from the slope, it is approx. 200mJ/m2
Nucleation rate
For large undercooling, the rate decreases due to the diffusion term.
The liquids can not be undercooled so much.
Glass formation in some alloys

TTT (Temperature-Time-Transformation) diagram with C curve

C curve
Crystal growth from liquid
Atomic mechanisms are less known, e.g. atomic motions
between the ordered crystal and the disordered liquid

Surface roughness

γ SL=h SL −Ts SL

- enthalpy (h) dominated:

atomic smooth surface, crystal shape
- entropy (s) dominated:
rough, disordered surface, isotropic shape
Crystal growth from liquid
Crystal growth along screw dislocations whiskers
It is important for small undercoolings Δ T ∼v

See e.g. https://youtu.be/6tpnKQzHruA

Crystal growth along a screw dislocation in AFM
Crystal growth from liquid

Temperature gradient also determines the shape

of the solidification front

Surface stability:

surface moves Δx during Δt time

kS ( )
∂T
∂x S
Δ t = LV Δ x + k L ( ) Δt
∂T
∂x L

equation for heat transport near the solidification front

Crystal growth from liquid
fluctuation: surface moves forward locally
T

Tm

kS ( )
∂T
∂x S
Δ t = LV Δ x + k L ( ) Δt
∂T
∂x L

decreases increases
more heat moves to the surface, flat surface is stable
Crystal growth from liquid
Undercooled liquid, solidification occurs at Tm

kS ( )
∂T
∂x S
Δ t = LV Δ x + k L ( ) Δt
∂T
∂x L

Therefore negative heat gradient forms in the liquid

[
LV Δ x= k S ( ) ∂T
∂x S
|( ) |]
+k L
∂T
∂x L
Δt k L≫ k S

|( ) | increases
∂T
∂x L
heat is removed from the solidification front,
therefore smooth surface becomes unstable

Dendrites and secondary dendrites grow in specific crystallographic

directions, e.g. <1010> for hexagonal and <100> for cubic crystals
Crystal growth from liquid
Dendritic crystal growth

dendrites

See e.g.
https://youtu.be/S07fPo45BvM
 Δ T =T i −T ∞
Δ T 0 =T m −T ∞
Rate of dendrite growth
heat transport in the solid is neglected, k L ≫ k S
while heat transport in the liquid determines V

V=
Δ x k L ∂T
=
Δ t LV ∂ x ( ) L

heat transport increases for small r

∂T ΔT ∂T ΔT ϕ≈1.0
∼ =ϕ
∂x r ∂x r
but dendrites with small r solidify below Tm
therefore undercooling is smaller for them

Δ T (r )=Δ T 0 ( 1−
r∗
r ) r=r ∗ →Δ T =0

kL ΔT kL ΔT0
( )
∗
r
V =ϕ =ϕ 1−
LV r LV r r
Rate of dendrite growth

V (r )=ϕ
kL ΔT
LV r
=ϕ
kL ΔT 0
LV r
1−
r(
r∗
)
velocity curve with a maximum
V max =V (2 r ∗ )

- for r ≫ 2 r ∗ heat gradient decreases for larger dendrite sizes

- for r <2 r ∗ surface energy will reduce the growth rate

- dendrites with r=2 r ∗ grow fastest (this is the most probable size)
- secondary dendrites grow if r >2 r ∗
∗
- spacing of the dendrite arms is about 4 r (from experiments)
- rate of crystallization can be estimated from it
Methods for single crystal preparation
Single crystals for basic research, Si technology, magnetic storage, …
Single crystals can be grown by
- controlled heterogeneous nucleation
- adjusting the rate of crystal growth

Bridgman method:

Crystal grows from a seed,

by slowly pulling the conical crucible
with the solidifying molten material
out from the furnace
Methods for single crystal preparation
Czochralski method

Pulling an oriented crystal seed

from the melt by rotating it

See e.g: https://www.youtube.com/

watch?v=XbBc4ByimY8

Solidification by normal freezing

Zone refining method