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Nucleation and growth kinetics

Homogeneous nucleation Critical radius, nucleation rate Heterogeneous nucleation Nucleation in melting and boiling Growth mechanisms Rate of a phase transformation

Reading: Chapters 4.1and 4.2 of Porter and Easterling,

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Nucleation and growth - the main mechanism of phase transformations in materials


2 X B

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

Kinetics of phase transformations


Phase transformations involve change in structure and (for multi-phase systems) composition rearrangement and redistribution of atoms via diffusion is required. The process of phase transformation usually involves: Nucleation of the new phase(s) - formation of stable small particles (nuclei) of the new phase(s). Nuclei are often formed at grain boundaries and other defects. Growth of the new phase(s) at the expense of the

original phase(s).
S-shape curve: percent of material transformed vs. the logarithm of time.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

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

liquid solid homogeneous nucleation

liquid solid heterogeneous nucleation

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Homogeneous nucleation 1 supercooled liquid 2 liquid solid

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

Reminder: Driving force for solidification (Gv)


When a liquid is cooled below the melting temperature, there is a driving force for solidification, Gv = GvL - GvS
L * L GL = H T Sv v v S * S GS = H T Sv v v G v = H v - T*Sv

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

Origin of the interfacial energy (SL)


Consider a solid-liquid interface. Depending on the type of material and crystallographic orientation of the interface, the interface can be atomically flat (smooth, faceted) or rough (diffuse).

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

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

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

Temperature of unstable equilibrium of a solid cluster of radius r* with undercooled liquid.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

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

Both r* and G* decrease with increasing undercooling

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

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

Both r* and G* decrease with increasing undercooling


MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

MD simulation of laser melting of nanocrystalline Au


Lin, Leveugle, Bringa, Zhigilei, J. Phys. Chem. C 114, 5686, 2010

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

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Laser melting of single crystal Au film

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

Tm = 963 K 100 200 300 400 500

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.

Laser melting of nanocrystalline Au film 45 J/m2

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.

Melting of nanocrystalline film (melted regions are blanked)

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

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Unstable equilibrium between a crystalline cluster of radius r and undercooled liquid

2 SL 1 T = Tm 1 H m r
*
6000

Number of atoms in the crystalline cluster

835 K 5000 820 K 841 K

4000

T* 845 K
845 K

3000 844 K 2000 850 K

847 K 843 K

840 K

1000

50

100

150

200

250

300

MSE 3050, Phase Diagrams and Kinetics, Time Leonid (ps) Zhigilei

Critical undercooling temperature of a crystalline cluster surrounded by undercooled liquid

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

equation and the rate of homogeneous nucleation is


* G & ~ exp N d kT

nuclei per m3 per s

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:

* Q G & ~ exp d exp N kT kT

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Rate of homogeneous nucleation


* Q G & ~ exp d exp N kT kT

Qd exp kT

G * exp kT

& N
Temperature

Tm

G* > Qd

exp G* kT << exp( Qd kT) exp G* kT > exp( Qd kT)

G* is too high - nucleation is suppressed

G * Q d

G*~ 1/T2 decreases with T sharp rise of homogeneous nucleation (diffusion is still active)

exp( Qd kT) too small low atomic mobility


suppresses the nucleation rate
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

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

where A has a relatively weak dependence on temperature (as compared to T2)


& N

very strong temperature dependence!


There is critical undercooling for homogeneous nucleation Tcr there are virtually no nuclei until Tcr is reached, and there is an explosive nucleation at Tcr.

Tcr

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Heterogeneous nucleation

liquid supercooled liquid solid

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

How about the out-of-plane component of the liquidvapor surface tension?


LS = SV + LV cos() = 90 LS = SV

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

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

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 ( )

S ( ) = (2 + cos )(1 cos ) /4

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Heterogeneous nucleation
G
het r

4 = - r 3 G 3

+ 4 r 2 SL S ( ) = G

hom r

S ( )

where S ( ) = (2 + cos )(1 cos )2 /4 1 At r = r*

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

Active nucleation starts

cr T het

cr T hom

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Heterogeneous Nucleation

2 SL r = G v
*

* het

= S ( )G

* hom
2

if = 10 o

S ( ) = (2 + cos )(1 cos ) /4 10 - 4

G * hom G * het

r*

heterogeneous nucleation starts at a lower undercooling


& N
hom

G * hom ~ exp kT

& N

& het N

& hom N

& het N

G * het ~ exp kT

& het >> N & hom N


MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Nucleation of melting For solid/liquid/vapor interfaces, often

Solid-Vapor > Solid-Liquid + Liquid-Vapor


In this case, no superheating is required for nucleation of the liquid and surface melting can take place below Tm. (remember our discussion of the paper on ice skating) Melting starts from free surfaces.

Melting of small atomic clusters, a cross-section through the center of the cluster is shown (simulations by J. Sethna, Cornell University)

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

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.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

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

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Growth: Temperature dependence


In multi-component systems, non-congruent phase transformations typically involve long-range diffusion of components necessary for achieving the equilibrium phase composition. The atomic rearrangements necessary for growth of a onecomponent phase or growth in a congruent phase transformation also involve thermally-activated elementary processes (diffusion). When growth is diffusion controlled, it slow down with decreasing temperature.

Ed D = D 0 exp RT

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Rate of phase transformations


Total rate of a phase transformation induced by cooling is a product of the nucleation rate (driving force increases

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

Growth mechanisms directional dependence


The shape of a growing crystal can be affected by the fact that different crystal faces have different growth rates. Close-packed low-energy faces tend to grow slower and, as a result, they are the ones that are mostly present in a growing crystallite.

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.

Growth instabilities, dendrites


Material and heat diffusion limits the rate at which a crystal can grow, often greatly affecting the shape of the growing crystals. An example is the Mullins-Sekerka instability. Consider a flat solid surface growing into a supersaturated vapor. If a small bump appears on the surface, then the bump sticks out farther into the supersaturated medium, and hence tends to grow faster than the surrounding surface. supersaturated vapor crystal

As a result the flat growth is unstable, and a crystal tend to grow into more complex shapes, e.g. snowflakes

MSE 3050, Phase Diagrams and Kinetics,http://www.its.caltech.edu/~atomic/snowcrystals/ Leonid Zhigilei

Patterns of snow crystals: A letter from the sky

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

Two-dimensional ice dendrites on windows

by Harry Bhadeshia

by Nadezhda Bulgakova
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Water dendrites in ice

http://www.msm.cam.ac.uk/

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Crystal growth and heat flow during solidification Thermal dendrites

Bragard et al., Interfacial Science 10, 121, 2002

microstructure of a metal ingot


MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei http://www.msm.cam.ac.uk/phase-trans/

Crystal growth and heat flow during solidification Thermal dendrites

liquid metal

cold mould heat flow What are the processes leading to the formation of the microstructure schematically shown in this figure?

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

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