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Homogeneous nucleation Critical radius, nucleation rate Heterogeneous nucleation Nucleation in melting and boiling Growth mechanisms Rate of a phase transformation
X0 B
1 X B
B atoms
2 X B
X0 B
1 X B
B atoms
2 X B
X0 B
1 X B
spatial coordinate
liquid solid
T
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
original phase(s).
S-shape curve: percent of material transformed vs. the logarithm of time.
Nucleation
Nucleation can be Heterogeneous the new phase appears on the walls of the container, at impurity particles, etc. Homogeneous solid nuclei spontaneously appear within the undercooled phase. Lets consider solidification of a liquid phase undercooled below the melting temperature as a simple example of a phase transformation.
supercooled liquid
Is the transition from undercooled liquid to a solid spherical particle in the liquid a spontaneous one? That is, does the Gibbs free energy decreases?
The formation of a solid nucleus leads to a Gibbs free energy change of G = G2 - G1 = -VS (GvL GvS) + ASLSL negative below Tm VS volume of the solid sphere ASL solid/liquid interfacial area SL solid/liquid interfacial energy always positive
Gv = GvL GvS is the difference between free energies per unit volume of solid and liquid at T < Tm, GvS < GvL solid is the equilibrium phase
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
At temperature T*
Gv G T T* Tm GvS GvL
At temperature Tm
m G v = H m v - Tm Sv = 0
Sm v
H m v = Tm
For small undercooling T we can assume that Hv and Sv are independent of temperature (neglect the difference in Cp between liquid and solid) m m
* G v H m T v
H v H v T = Tm Tm
At any temperature below Tm there is a driving force for solidification. The liquid solidify at T < Tm. If energy is added/removed quickly, the system can be significantly undercooled or (supercooled). As we will see, the contribution of interfacial energy (SL) results in a kinetic barrier for the phase transformation.
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
liquid solid
liquid solid
H
HS v - Tm SS v
interface
HL v
- TS
- Tm S L v
G
GS v
SL
GL v
spatial coordinate
Homogeneous nucleation
G = G2 - G1 = -VS Gv + ASLSL For a spherical nucleus with radius r:
4 G r = - r 3 G v + 4 r 2 SL 3
G
4 VS = r 3 3 A SL = 4 r 2
interfacial energy ~ r2
r*
G
volume energy ~ r3 For nucleus with a radius r > r*, the Gibbs free energy will decrease if the nucleus grows. r* is the critical nucleus size, G* is the nucleation barrier.
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
Homogeneous nucleation
At r = r*
d G dr
SL
= -4 r 2 G
+ 8 r SL = 0
SL 3
r* =
2 G
16 G = 2 3(G v )
*
( )
2 SL = r*
r = r*
GvS T T* Tm GvL
Homogeneous nucleation
r* = 2 G
SL
16 G = 2 3(G v )
*
( )
SL 3
The difference between the Gibbs free energy of liquid and solid (also called driving force for the phase transformation) is proportional to the undercooling below the melting temperature, T = Tm T: H m T G v = Tm where Hm is the latent heat of melting (or fusion) Therefore:
SL 2 Tm * r = H m
1 T
16 SL 3 T 2 m = 3 H 2 m
( (
1 (T )2
Homogeneous nucleation
G
G
* 2 * G 1
r2* r1*
G
T2 < T1 < Tm
2 SL Tm r = H m
*
1 T
16 SL 3 T 2 m = 3 H 2 m
( (
1 (T )2
laser pulse
laser pulse
20 nm Au films irradiated with 200 fs laser pulse Model: ~500,000 atoms, nanocrystalline sample has 31 grains, average grain diameter is 8 nm
45 J/m2
20 ps
1.2
200 ps
6000
Te
1.15 1.1
5000
Temperature (K)
4000
T/Tm
1.05 1
3000
0.95 0
2000
Time (ps)
Fabs = 45 J/m
500 ps
1000
Tl
0 100 200 300 400 500
Time (ps)
Melting starts at free surfaces of the free-standing film, two melting fronts propagate from the surfaces, temperature drops (energy goes into HmVl). Melting stops when T approaches MSE 3050, Phase Diagrams and temperature Kinetics, LeonidT Zhigilei the equilibrium melting m.
20 ps
1.1
50 ps
1.05
T/Tm
Tm = 963 K
0.95
100 ps
0.9 0
100
200
300
400
500
Time (ps)
Melting starts at grain boundaries, temperature drops (energy goes into HmVl). Melting continues even after T drops below the equilibrium melting temperature Tm at ~30 ps and the last MSE 3050, Phase Diagrams and Kinetics, crystalline region disappears at Leonid ~250 Zhigilei ps.
50 ps
100 ps
The continuation of the melting process below Tm can be explained based on the nucleation theory
4 3 G r = r G v + 4 r 2 SL 3
2 SL 2 SL Tm r* = = G v H m 1 T
critical radius at T
2 SL 1 * T = Tm 1 H m r
temperature of the equilibrium between the cluster of size r and the surrounding liquid
2 SL 1 T = Tm 1 H m r
*
6000
4000
T* 845 K
845 K
847 K 843 K
840 K
1000
50
100
150
200
250
300
MSE 3050, Phase Diagrams and Kinetics, Time Leonid (ps) Zhigilei
2 SL 1 T = Tm 1 H m r
*
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
Homogeneous nucleation
There is an energy barrier of G* for formation of a solid nucleus of critical size r*. The probability of energy fluctuation of size G* is given by the Arrhenius
where d is the frequency with which atoms from liquid attach to the solid nucleus. The rearrangement of atoms needed for joining the solid nucleus typically follows the same temperature dependence as the diffusion coefficient:
Qd d ~ exp kT
Therefore:
Qd exp kT
G * exp kT
& N
Temperature
Tm
G* > Qd
G * Q d
G*~ 1/T2 decreases with T sharp rise of homogeneous nucleation (diffusion is still active)
Rate of Homogeneous Nucleation In many phase transformations, it is difficult to achieve the level of undercooling that would suppress nucleation due to the drop in the atomic mobility (regime 3 in the previous slide). The nucleation typically happens in regime 2 and is defined by the probability of energy fluctuation sufficient to overcome the activation barrier G*r:
* G & ~ exp N kT
* r
1 (T )2
Using
16 SL 3 T 2 m = 3 H m 2 v
( ) ( )
A & N = I 0 exp (T )2
Tcr
Heterogeneous nucleation
the new phase appears on the walls of the container, at impurity particles, grain boundaries, etc. Lets consider a simple example of heterogeneous nucleation of a nucleus of the shape of a spherical cap on a wall of a container. Three interfacial energies: LC liquid container interface, LS liquid-solid interface, SC solid-container interface.
liquid
solid nucleus SC LS
LC
Balancing the interfacial tensions in the plane of the container wall gives LC = SC + LS cos() and the wetting angle is defined by cos() = (LC - SC)/ LS
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
The out-of-plane component of the liquid-vapor surface tension is expected to be balanced by the elastic response of the solid, but theoretical analysis is not straightforward due to an apparent divergence of stress at the contact line. See [Physical Review Letters 106, 186103, 2011] for extracurricular reading
Heterogeneous Nucleation
liquid
solid nucleus SC LS
LC
The formation of the nucleus leads to a Gibbs free energy change of Grhet = -VS Gv + ASLSL + ASCSC - ASCLC VS = r3 (2 + cos()) (1 cos())2/3 ASL = 2 r2 (1 cos()) One can show that and ASC = r2 sin2()
het r
4 = - r 3 G 3
+ 4 r 2 SL S ( ) = G
2
hom r
S ( )
Heterogeneous nucleation
G
het r
4 = - r 3 G 3
+ 4 r 2 SL S ( ) = G
hom r
S ( )
d G r = - 4 r 2 G dr
G
* het
+ 8 r SL S ( ) = 0
2 SL r = G v
*
16 SL = S ( ) = S ( )G 2 3 (G v )
( )
* hom
G*
* het
G * hom
cr T het
cr T hom
Heterogeneous Nucleation
2 SL r = G v
*
* het
= S ( )G
* hom
2
if = 10 o
G * hom G * het
r*
G * hom ~ exp kT
& N
& het N
& hom N
& het N
G * het ~ exp kT
Melting of small atomic clusters, a cross-section through the center of the cluster is shown (simulations by J. Sethna, Cornell University)
Growth mechanisms The next step after the nucleation is growth. Atomically rough (diffuse) interfaces migrate by continuous growth, whereas atomically flat interfaces migrate by ledge formation and lateral growth.
liquid
liquid
solid
solid
The rate of the continuous growth (typical for metals) is typically controlled by heat transfer to the interfacial region for pure materials and by solute diffusion for alloys. Growth in the case of atomically flat interfaces can proceed from existing interfacial steps (e.g. due to the screw dislocations or twin boundaries) or by surface nucleation and lateral growth of 2D islands.
Growth mechanisms
Smooth solid-liquid interfaces typically advance by the lateral growth of ledges. Ledges can result from surface nucleation or from dislocations that is intersecting the interface.
Spiral growth on dislocations AFM images of growing crystal of KDP (potassium dihydrogen phosphate) by De Yoreo and
Land, LLNL and Malkin and Kuznetsov, University of California
Ed D = D 0 exp RT
with undercooling but diffusion needed for atomic rearrangement slows down with T decrease) and
growth rate (diffusion controlled - slows down with T decrease). overall transformation rate growth rate
nucleation rate
temperature
Tm
high T (close to Tm): low nucleation and high growth rates coarse microstructure with large grains low T (strong undercooling): high nucleation and low growth rates fine structure with small grains
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
For example, water ice I(h) has hexagonal crystal symmetry that is reflected in the symmetry of snow crystals. The growth rate is fast parallel to the basal {0001} and prism {1010} faces. As a result, very small snow crystals have shape of hexagonal prisms. As they grow, growth instabilities result in more complex shapes of larger snow crystals.
MSE 3050, Phase Diagrams and Kinetics, Leonid P. V. Hobbs, Zhigilei Ice Physics, Oxford Univ. Press, Oxford, 1974.
As a result the flat growth is unstable, and a crystal tend to grow into more complex shapes, e.g. snowflakes
Nakaya diagram: The shape of snow crystals depends on the temperature and humidity of the atmosphere in which they have grown. Vertical axis shows the density of water vapor in excess of saturation with respect to ice. The black curve shows the saturation with respect to liquid water as a function of temperature. Physics Today, Dec. 2007, pp. 70-71, 2007
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei http://www.lowtem.hokudai.ac.jp/ptdice/english/aletter.html
by Harry Bhadeshia
by Nadezhda Bulgakova
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei
http://www.msm.cam.ac.uk/
liquid metal
cold mould heat flow What are the processes leading to the formation of the microstructure schematically shown in this figure?
Summary Make sure you understand language and concepts: Homogeneous nucleation Interfacial energy Critical radius, nucleation rate Heterogeneous nucleation Temperature dependence homogeneous and heterogeneous nucleation rates Nucleation in melting and boiling Nucleation in solidification Growth mechanisms Rate of a phase transformation Growth instabilities, dendrites
H. Imai and Y. Oaki, MRS Bulletin 35, February issue, 138-144 (2010)
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei