Graduate Institute of Ferrous Technology, POSTECH Rongshan Qin (R. S.

Qin)

13. Kinetics of solidification 3

13.1 Solid-liquid interface structure Solidification is by atom jumping from liquid into solid phases and attaching to the solid interface one by one. The easy that atom can attach themselves into growth solid interface depends on the interface structure. The interface structure is determined by thermodynamics of solidification.

Figure 1. Atomic interaction in cubic lattice Atom at interface possesses higher energy than at solid. The excess energy comes from the losing of the atom-atom interaction bond. The change of enthalpy in constant pressure solidification is expressed as
'H 'u  p 'V

(13.1)

In 'V

0 equation (13.1) reduces into 'H 'u

(13.2)

The heat of fusion 'H is the change of the internal energy caused by losing of the interaction bond from solid to liquid state. Suppose that an atom in solid has

Graduate Institute of Ferrous Technology, POSTECH Rongshan Qin (R. S. Qin)

totally m bonds, each bond is then with energy of 'H/m. The atom-atom bonds in cubic lattice are illustrated in figure 1.

For a perfect surface where all the possible atom positions are filled, the bonding 'H energy for an atom at interface is mI  mb  , where mI and mb are the number m of bond of an atom with neighbored-atoms at interface and bulk solid, respectively. For a non-perfect interface where only x fraction of atom positions 'H are occupied, the bonding energy for an atom at interface is mI x  mb  . The m difference between bonding energy at the perfect and fractal interfaces are
'H mI  mb   'H mI x  mb  m m 'H mI 1  x  m

Suppose there are N possible atom positions at preface interface, the total internl energy difference is given by
'u Nx 'H mI 1  x  2 m m N 'H I x1  x  2 m

(13.3)

The free energy change between the perfect and the fractal interfaces is given by
'F 'u  T'S

(13.4)

Where the entropy difference is known

'S

 NK  x ln x  (1  x) ln(1  x) 

(13.5)

At melting temperature T=Tm, insulting equations (13.3) and (13.5) into (13.4) gives
'F NKTm O x1  x   x ln x  (1  x) ln(1  x) 2

(13.6)

where O

'H mI KTm m

Graduate Institute of Ferrous Technology, POSTECH Rongshan Qin (R. S. Qin)

Equation (13.6) expresses the relationship between the free energy and the atom occupation ratio at interface. The right hand side of the equation (13.6) is plotted in figure 2.

Figure 2. Free energy at different O It can be found from figure 2 that the minimum free energy appears at x=0.5 when O d 2. The interface is called diffuse interface and is illustrated in figure 3.

Figure 3. Diffuse interface.

Graduate Institute of Ferrous Technology, POSTECH Rongshan Qin (R. S. Qin)

the O = 2 gives the entropy of fusion

'S m

mI / m depends on crystal structure and the surface orientation. For mI / m 0.5 ,

'H m Tm

OK

m mI

4K

(13.7)

which means that the diffuse interface is most stable when the molar entropy of fusion is 4R. Most of the metallic materials are with this condition. For O>5, the free energy is minimum when xo0 or xo1. The interface is flat. Most of organic materials are with this condition. Some materials such as Bi and Si are with 2<O<5. Interface structure is complicated. In diffuse interface, the transition from liquid to solid takes place over a number of atomic layers. Within the diffusion diffuse interface, ordering of atoms increases gradually with distance toward the fully crystalline side until essentially all the atoms are in their appropriate lattice site. There are lots positions for coming atoms to attach firmly on interface and crystal growth is considered continuously. The flat interface is atomically flat. The transition from liquid to solid takes place cross single atomic layer. The coming atoms can only attach to those step area otherwise the interaction is too loose, as illustrated in figure 4. Two-dimensional nucleation, screw dislocation and twin planes can form the steps.

Figure 4. Atom attachment

Graduate Institute of Ferrous Technology, POSTECH Rongshan Qin (R. S. Qin)

13.2 Continuous growth The solid growth must involve a net flux of atom across it. From transition state theory by Turnbull, the liquid-solid atomic flux rate is

Figure 5. Thermodynamic and kinetic barriers model.

J

'Gb A2 n1v1 exp  RT

(13.8)

where A2 is the fraction of atom sites on liquid able to receive atom from solid. n1 is the number of atoms per unit area on solid side adjacent to liquid. Q1 is the vibration frequency. The backward rate is
J

'Gb  'Gm A1n2v2 exp  RT

(13.9)

In equilibrium when 'Gm

0 , there is no flux, so that

A2 n1v1
The net flux is

A1n2v2

(13.10)

Graduate Institute of Ferrous Technology, POSTECH Rongshan Qin (R. S. Qin)

J J

'Gb 'Gm A1n2v2 exp  1  exp  RT RT

(13.11)

The interface velocity is given by

v

J

 Vm

NA

(13.12)

where Vm is molar volume and NA is Avogadros number. When the system is non-far from equilibrium, the interface velocity is v M'GmV (13.13)

where M is the interfacial mobility and is given by M

2 Vm A1n2v2 'Gb exp  N A RT RT

(13.14)

13.3 Lateral growth There are three lateral growth formats, as illustrated in figure 6.

(a)

Graduate Institute of Ferrous Technology, POSTECH Rongshan Qin (R. S. Qin)

(b)

(c ) Figure 6. (a) Growth by two-dimensional nucleation. (b). Growth by screw dislocation. (c). Growth by propagation of twin planes. References 1. M.C. Flemings, Solidification processing, 1974. 2. A. L. Greer, Kinetics, Cambridge.