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

Qin)

10. Thermodynamics of solidification 3

10.1 Thermodynamic driving force Molar Gibbs energy of solid and liquid phases in constant pressure isothermal system is expressed as GS = H S TS S (10.1) (10.2)

GL = H L TS L

The change of Gibbs energy around melting point is schematically demonstrated in figure 1. G

GS GL Tm T

Figure 1. Free energy vs temperature

When the system temperature is higher than melting temperature, the free energy of liquid is lower than that of solid and, therefore, liquid is stable. On the contrary when the system temperature is lower than the melting temperature, solid phase is stable. The difference between the free energies of solid and liquid is called thermodynamic driving force.

G = GS GL = ( H S H L ) T ( S S S L ) = H TS

(10.3)

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

When T is not far away from Tm, one can approximately have H = H m and

S = S m .

H m is melting enthalpy and S m is melting entropy. G = 0 at

melting point, one has

S m = H m / Tm
Insulting (10.4) and (10.3) has
H m T Tm

(10.4)

G =

(10.5)

When the system temperature is not near to melting temperature enough or when the heat capacities of solid and liquid are very different, Jones suggested the following correction

G =

H m T T + C p T T ln m Tm T

(10.6)

10.2 Effect of pressure on solidification The free energy of system takes the format of
F = U + PV TS

(10.7)

When the pressure changes the melting point of the system will change.

FL = VL P S L T FS = VS P S S T

(10.8) (10.9)

At the new melting point it has GL = GS or (VS VL )P = (S S S L )T . One has

T V T V = = m P S m H m

(10.10)

Equation (10.10) tells that for P > 0 , if V = VS VL < 0 then T > 0 , which means that the melting temperature will increase at higher pressure. Many

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

metallic materials are in this case. However, for the case of V > 0 for P > 0 , on has T < 0 , which means that the melting temperature will drop when the pressure increases if VS VL > 0 , examples are Sb, Bi, etc. Both cases are illustrated in figure 2.

T Tm+ Tm P

Tm Tm+ P+

P+ P

xB
Figure 2. Effect of pressure on melting point (a) T < 0 (b) T > 0

xB

Normally, it is very hard to use pressure to modify casting microstructure because the small melting temperature/pressure coefficient (~0.01 K/atm). However, the burst of bubbles in solidifying metal can generate very high pressure which increases melting temperature in dozens of degrees.

10.3 Effect of curvature on melting temperature When small solid particle forms in the liquid there is a pressure difference between the inside and outside of the particle. The outside is liquid metal. The pressure difference changes the melting point of solid particle. Equations (10.8) and (10.9) change into

FL = VL PL S L T FS = VS PS S S T
Using the relationship of that

(10.11) (10.12)

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

1 1 PS PL = r + r = 2 1 2
At melting point one has FS = FL , which gives

(10.13)

S L T = 2VS S S T
2VS 2TmVS = = d S H m

or

T =

(10.14)

Equation (10.14) shows that the melting temperature will drop because of curvature. The larger curvature has the lower melting temperature. That is why a certain undercooling is needed for solidification.

10.4 Magnetic contribution to thermodynamic properties For Fe, Ni, Co and their alloys the contribution of the magnetism to thermodynamic properties has to be taken into account. The magnetic contribution to the molar entropy in CALPHAD is expressed as
S mag = R ln( B0 + 1) f ( )

(10.15)

where B0 is the average magnetic moment per atom. = T / T * where T* is the critical temperature (the Curie temperature Tc for ferromagnetic materials or the Neel temperature TN for antiferromagnetic materials). f() is given by

where

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

p is a parameter which can be considered as the fraction of the magnetic enthalpy above the critical temperature, depends on the structure. P=0.4 for simple BCC_A2 and p=0.28 for other common phases. The magnetic contribution to the molar enthalpy is
H mag = RT ln( B0 + 1)h( )

(10.16)

where

The magnetic contribution to heat capacity is

mag Cp = R ln( B0 + 1)c( )

(10.17)

where

The magnetic contribution to Gibbs energy is

G mag = RT ln( B0 + 1) g ( )
where

(10.18)

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

Figure 3. Heat capacity of Co, Fe, and Ni

References 1. M.C. Flemings, Solidification processing, 1974. 2. N. Saunders and A.P. Miodownik, CALPHAD, 1998. 3. A.T. Dinsdale, CALPHAD 15 (1991) 317.