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M.A.N.I.T., Bhopal
Contents
Solidification of Metals Cooling Curves
Solidification of Metals
Solidification of Metals
1. During solidification, the liquid changes in to solid during cooling. 2. The energy of liquid is less than that of the solid above the melting point. Hence liquid is stable above the melting point. 3. Below the melting point, the energy of liquid becomes more than that of the solid. 4. Hence below the melting point, the solid becomes more stable than the liquid. 5. Therefore at the melting point, liquid gets converted in to solid during cooling. 6. This transformation of liquid into solid below melting point is known as solidification.
Solidification of Metals
1. Thermodynamically, both liquid and solid have equal energy at melting point and therefore both are equally stable at melting point. 2. Therefore, no solidification or melting will take place at the melting point. Liquid will remain liquid and solid will remain solid. 3. Some under-cooling will be essential for solidification. 4. This transformation occurs by nucleation and growth.
Cooling Curve
Cooling Curve
A cooling curve is a graphical plot of the changes in temperature with time for a material over the entire temperature range through which it cools.
Cooling Curve
Then these temperatures are used for the construction of the phase diagrams
Undercooling during
Series of cooling curves for different alloys in a completely soluble system. The dotted lines indicate the form of the phase diagram
Homogeneous Nucleation
Homogeneous Nucleation Formation of a critically sized solid from the liquid by clustering together of a large number of atoms at a high undercooling (without an external interface).
Solidification of Metals
The transformation temperature, as shown on the equilibrium diagram, represents the point at which the free energy of the solid phase is equal to that of the liquid phase. Thus, we may consider the transition, as given in a phase diagram, to occur when the free energy change, GV , is infinitesimally small and negative, i.e. when a small but positive driving force exists.
(a) Effect of nucleus size on the free energy of nucleus formation. (b) Effect of undercooling on the rate of precipitation.
Homogeneous Nucleation
Quantitatively, since Gv depends on the volume of the nucleus and GS is proportional to its surface area, we can write for a spherical nucleus of radius r G = (4 r3 /3) Gv + 4 r2 where Gv is the bulk free energy change involved in the formation of the nucleus of unit volume and is the surface energy of unit area.
The probability of an atom having sufficient energy to jump the barrier is given, from the MaxwellBoltzmann distribution law, as proportional to exp [Q/kT] where k is Boltzmanns constant, T is the temperature and Q is usually expressed as the energy per atom in electron volts.1 The rate of reaction is given by Rate = A exp [- Q/kT] where A is a constant
The surface energy factor is not strongly dependent on temperature, but the greater the degree of undercooling or supersaturation, the greater is the release of chemical free energy and the smaller the critical nucleus size and energy of nucleation. This can be shown analytically since Gv = H - TS, and at T = Te, Gv = 0, so that H = Te S. It therefore follows that Gv =(Te -T) S = TS and because Gv is proportional to T, then W is proportional to S3 / T2
Heterogeneous Nucleation
Heterogeneous Nucleation Formation of a critically sized solid from the liquid on an impurity surface. heterogeneous nucleation occurs in a liquid on the surface of its container, insoluble impurities and other structural materials that lower the critical free energy required to form a stable nucleus
Heterogeneous Transformation
In practice, homogeneous nucleation rarely takes place and heterogeneous nucleation occurs either on the mould walls or on insoluble impurity particles. A reduction in the interfacial energy would facilitate nucleation at small values of T. This occurs at a mould wall or pre-existing solid particle
Ingot Structure
Al ingot
L: 35wt%Ni
35
24
120 0
A B C D36 E
a (solid)
110 0 20 30
35 C0
40
50
wt% Ni
Dendrites
In metals, the crystals that form in the liquid during freezing generally follow a pattern consisting of a main branch with many appendages. A crystal with this morphology slightly resembles a pine tree and is called a dendrite, which means branching. The formation of dendrites occurs because crystals grow in defined planes due to the crystal lattice they create. The figure to the right shows how a cubic crystal can grow in a melt in three dimensions, which correspond to the six faces of the cube. For clarity of illustration, the adding of unit cells with continued solidification from the six faces is shown simply as lines. Secondary dendrite arms branch off the primary arm, and tertiary arms off the secondary arms and etcetera.
Dendrites
Dendrites
During freezing of a polycrystalline material, many dendritic crystals form and grow until they eventually become large enough to impinge upon each other. Eventually, the interdendriticspaces between the dendrite arms crystallize to yield a more regular crystal. The original dendritic pattern may not be apparent when examining the microstructure of a material. However, dendrites can often be seen in solidification voids that sometimes occur in castings or welds, as shown in the next slide..
Dendrites
Computer simulated image of dendritic growth using a cellular automata technique. Notice the branching on the dendrites. Photograph courtesy of the Institute of Materials, based on the work of U. Dilthey, V. Pavlik and T. Reichel, Mathematical Modelling of Weld Phenomena III, eds H. Cerjak and H. Bhadeshia, Institute of Materials, 1997.
Steady-state patterns formed at the crystalmelt interface of a binary alloy of succinonitrile and coumarin 152 during directional solidification.
(A) Time evolution of the interface morphology for SCN/rhodamine 6G at constant pulling speed V (V = 3.11 m/s, G = 2.8 K/cm, C = 0.325 wt%).
Shrinkage
Most materials contract or shrink during solidification and cooling. Shrinkage is the result of:
Contraction of the liquid as it cools prior to its solidification Contraction during phase change from a liquid to solid Contraction of the solid as it continues to cool to ambient temperature.
Shrinkage can sometimes cause cracking to occur in component as it solidifies. Since the coolest area of a volume of liquid is where it contacts a mold or die, solidification usually begins first at this surface. As the crystals grow inward, the material continues to shrink. If the solid surface is too rigid and will not deform to accommodate the internal shrinkage, the stresses can become high enough to exceed the tensile strength of the material and cause a crack to form. Shrinkage cavitation sometimes occurs because as a material solidifies inward, shrinkage occurred to such an extent that there is not enough atoms present to fill the available space and a void is left.