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

Qin)

3. Structure and properties of liquid metals 2

3.1 Surface tension Liquid contains two parts: Inner bulk liquid and liquid surface, as illustrated in figure 1. Interaction forces acting on the atoms in the inner bulk of the liquid are balanced but in the surface of the liquid are unbalanced. In the later situation atoms are subject to an inward force. The liquid squeezes itself together until the lowest surface area is achieved. Finally, the inward force is balanced by the resistance of the liquid to compression. In terms of free energy, the inner bulk liquid possesses lower free energy density than that of the liquid surface. The liquid always tries to minimize the total free energy. For the aim of reducing free energy, liquid minimizes its surface area.

Bulk of liquid

Surface of liquid

Figure 1. Liquid: bulk and surface Surface tension is defined as the force along a line of unit length where the force is parallel to the surface but perpendicular to the line (Nm-1), or the quantity of work needed to be done in order to increase the surface area of one square meter (Jm-2). The surface tensions of some of liquid metals at their melting temperature are: Fe 1.872 Nm-1 Mn 1.09 Nm-1 Ni 1.778 Nm-1, Si 0.865 Nm-1 Cu 1.36 Nm-1 Zn 0.782 Nm-1,

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

3.2 Liquid-liquid interface When two liquid droplets of the same kind meet they will join together to form a bigger droplet to reduce the surface area. The process is called coalescence. A certain amount of energy is released in the coalescence. The energy of cohesion is defined when two bodies of the same liquid become joined by a boundary of unit area. The energy of adhesion is defined to two bodies of different liquids. As shown in figure 2, one has
A B Wadh = Wcoh + Wcoh AB = A + B AB

Figure 2. Liquid adhesion For two immiscible liquid mixtures, the minority phase formed the spherical shape and the majority takes the shape of the container. TIPS: For computer simulation of phase separation, 50/50 volume fractions are the absolute point to avoid. Sometimes, it could break the calculation. For experiments, 50/50 volume fractions bring out lots uncertainty. Interfacial energy can be modified by adding other chemical elements. For example, add other elements so that the interactions among particles around the interface area can be weaken so that the interfacial energy reduces. In nonmetallic materials, surfactant can substantially reduce interfacial energy between oil and water which makes oil extractions difficult. People uses the interfacial energy modification technique to make micelle.

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

It has been suggested recently that immiscible liquids can be glued by adding colloids to the interface so that phase separation can be prevented.

Figure 3. Colloid jamming at interface by Science 309, 2198 (2005)

3.3 Liquid-solid interface: Wetting and dewetting There are two different behaviors when put liquid in contacting with solid walls. In one case, liquid clumps up the solid wall and forms a concave (<90). Otherwise convex geometry obtains (>90). The contact angles for the two cases are demonstrated in figure 4. The first case is called wetting and the second is dewetting. Liquid mercury in copper wall shows wetting but in glass wall shows dewetting.

Figure 4. Contact angles for wetting and dewetting. The micromechanics for the wetting and dewetting are shown in Figure 5. At equilibrium, one has gs = ls + gl cos where ls , gl and gs are surface tension of solid-liquid, liquid-gas and solid-gas interfaces.

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

wetting

dewetting

Figure 5. Schematic diagram for mechanism of wetting and dewetting 3.3 Bubbles and droplets: Laplace law

P1 , r1

P1 , r1

P1 , r1

P2

Cylinder:

P 1P 2 =

1 1 + Saddle: P 1P 2 = r r 1 2
Sphere: P 1P 2 =
2 r

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

1/r
Figure 6. Laplace law 3.4 Surface tension in steel making a. Capillary in sand mold filling

Figure 7. Schematic mold demonstrating the occurrence of a filling pressure window for filling cylindrical mold cavities of radius R [2]

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

Liquid metal

Air

The critical pressure for cast and sand to stick together P = For steel, =2g/cm. =8g/cm3 we have [3] H, cm 10 100 2 0.08 0.8 p, kg/cm D, cm 0.1 0.01

4 = gH D

1000 8 0.001

10000 80 0.0001

b. Dendrites arm breaking and hot cracking

Figure 8. Breaking of dendrite arms.

f max =

2 D

For steel, =2Nm-1, D=4 nm, fmax=1 GPa

REFERENCES 1. Stratford et al., Science 309, 2198 (2005) 2. Hilden, Jon L. Capillarity in metal casting mold filling, PURDUE UNIVERSITY, 2001 3. 1985