Phase Transformation Nucleation: There are two types of nucleation: Homogenous nucleation Heterogenous nucleation This distinction is made

based on the site at which nucleating events occur. Homogenous nucleation: In the homogenous type, nuclei of the new phase form unif ormly throughout the parent phase. Heterogenous nucleation: Nucleation on pre-existing surfaces is known as heterog enous nucleation. In the heterogenous type, nuclei form preferentially at struct ural inhomogenities, such as container surfaces, insoluble impurities, grain bou ndaries, dislocations and so on. Homogenous nucleation: In homogenous nucleation, the probability of nucleation o ccurring at any given site is identical to that at any other site within the vol ume of the parent phase. Homogenous nucleation in a liquid melt occurs when the metal itself provides the atoms needed to form a nuclei. When a pure liquid metal is cooled is cooled below its equilibrium freezing temp erature to a sufficient degree, many homogenous nuclei are created by slow-movin g atoms bonding together. Homogenous nucleation usually requires a considerable amount of undercooling, wh ich may be as much as several hundered Celsius for some metals. For a nucleus to be stable, so that it can grow into a crystal, it must reach a critical size. Embryo: A cluster of atoms bonded together that is less than the critical size i s called an embryo. An embryo is a tiny particle of solid that forms from the li quid as atoms cluster together. The embryo is unstable and may grow into a stabl e nucleus or redissolve. The formation of embryos is a statistical process. Many embryos form and redisso lve. Nucleus: A cluster of atoms bonded together that is larger than the critical siz e is called nucleus. Because of their instability, embryos are continuously being formed and redissol ved in the molten metal due to the agitation of atoms. When the solid particle is formed, a new interface is formed between the particl e and the liquid. Like all surfaces, this interface has a positive energy, which must be supplied during the transformation process. A tiny particle, has a large surface area to volume ratio and can therefore be u nstable. For a spherical particle of radius r (Surface area)Volume=((4r^2 ))/((4r^3)/3)=3/r As r0, this ratio can become very large and the energy of the surface can effecti vely prevent the formation of a tiny particle.

A particle is said to have nucleated, when it becomes stable and will not disapp ear due to thermal fluctuations. Once the particle has attained this stage, it can grow further with a continuous decrease in energy. The surface energy is no longer a dominant factor in the growth process. Energies involved in homogenous nucleation: In the homogenous nucleation of a solidifying pure metal, two kinds of energy ch anges must be considered: The volume (or bulk) free energy released by the liquid-to-solid transfo rmation The surface free energy required to form new solid surfaces of the solid ified particles. When the solid forms, a solid-liquid interface is created. A su rface free energy is associated with this interface. When a pure liquid metal is cooled below its equilibrium freezing temperature, t he driving energy for the liquid-to-solid transformation is the difference in th e volume (or bulk) free energy Gv of the liquid and that of the solid. If Gv is the change in free energy between the liquid and solid per unit volume o f metal, then the free energy change for a spherical nucleus of radius r is 4/3 r ^3 G _v since the volume of the sphere is 4/3 r^3. Gv is a negative quantity since energy is released by the liquid-to-solid transfo rmation. However, there is an opposing energy to the formation of embryos and nuclei, the energy required to form the surfaces of these particles. The energy required to create a surface for these spherical particles Gs is equal to the specific surface free energy of the particle, , times the area of the sur face of the sphere i.e., 4r^2 , where 4r^2 is the surface area of the sphere. The total free energy associated with the formation of an embryo or nucleus, is the sum of volume free energy and surface free energy. In equation form the tota l free energy change for the formation of a spherical embryo or nucleus of radiu s r formed in a freezing pure metal is G_T= 4/3 r^3 G GT R = Gv = _v+4r^2

= total free-energy change radius of embryo or nucleus = volume free energy specific surface free energy

Initially as the new phase particle starts to form, the energy of the system inc reases as the surface energy term is dominant. At the maximum, the variations wi th r of the surface energy and the volume free energy exactly balance each other . Thereafter, the variation in the volume term becomes dominant and as this term i s negative, there is a continuous decrease in the energy of the system. When r* reaches the critical value, GT has its maximum value of G*.

These volume, surface, and total free energy contributions are plotted schematic ally as a function of nucleus radius

The curve corresponding to the term 4/3 r^3 G _v (which is negative) decrease s with the third power of r. The curve corresponding to 4r^2 (energy values are positive) and increase with the square of the radius. The curve associated with the sum of the two terms G_T= 4/3 r^3 G _v+4r^2 first increases, passes through a maximum and finally decreas When the solid is very small, with the radius less than the critical rad ius for nucleation (r*), further growth causes the free energy to increase. The critical radius (r*) is the minimum size of the crystal that must be formed by atoms clustering together in the liquid before the solid particle is stable and begins to grow. If by any chance, an embryo forms that has a radius larger than (r*), further gr owth causes the total free energy to decrease. The new solid is stable and sustainable since nucleation has occurred and the gr owth of the particle which is now called a nucleus begins. At the thermodynamic melting or freezing temperatures, the probability of formin g stable sustainable nuclei is extremely small. Therefore, solidification does not begin at the thermodynamic melting or freezin g temperature. If the temperature continues to decrease below the equilibrium freezing temperat ure, the liquid phase that should have transformed into a solid becomes increasi ngly unstable thermodynamically. Because the temperature of the liquid is now below the equilibrium freezing temp erature, the liquid is considered to be undercooled. Undercooling: Undercooling (T) is the difference between the equilibrium freezing temperature and the actual temperature of the liquid. As the extent of undercooling increases, the thermodynamic driving force for the formation of the solid phase from the liquid overtakes the resistance to create a solid-liquid interface. Homogenous nucleation: As liquid cools to temperatures below the equilibrium fre ezing temperature, two factors combine to favor nucleation. First, since atoms are losing their thermal energy, the probability of f orming clusters to form larger embryos increases. Second, the larger free energy difference between the liquid and solid r educes the critical size (r*) of the nucleus Homogenous nucleation occurs when the undercooling becomes large enough to cause the formation of a stable nucleus. A critical free energy G* occurs at the critical radius and consequently at the m aximum of the curve. This G* corresponds to an activation free energy, which is the free energy requir ed for the formation of a stable nucleus. Equivalently it may be considered an e nergy barrier to the nucleation process.

A relationship among the size of the critical nucleus, surface free energy, and volume free energy for the solidification of a pure metal can be obtained by dif ferentiating equation G_T= 4/3 r^3 G _v+4r^2

The differential of the total free energy G_T with respect to r is zero when r = r*. This is because the total free energy of the nucleus plot is then at a maxim um and its slope d(G_T )/dr=0 i.e. d(G_T )/dr=d/dr (4/3 r^3 G 12/3 r* ^2 G_V+8*=0

_v+4r^2 )

Therefore r^*=-2/(G_V ) Substituting r^*=-2/(G_V ) in the equation G_T= 4/3 r^3 G _v+4r^2 gives the following expression for G* G ^*=(16^3)/(3(G _V )^2 )

It can be shown that G_V is a function of temperature as G ^*=(H_f (T_m-T))/T_m

Where H_f is the latent heat of fusion (i.e., the heat given up during solidifica tion) and Tm and T are the temperature in Kelvin. Substitution of this expressio n in the expressions for r* and G* gives r^*=(-(2T_m)/H and G ^*=((16^3 T_m^2)/(3H _f^2 )) 1/(T_m-T)^2 _f )(1/(T_m-T))

From the equation for r*, as undercooling increases i.e. Tm T increases, the cri tical radius required for nucleation (r*) decreases. From the above two equations, both the critical radius r* and the activation fre e energy G* decrease as the temperature increases. Physically, this means that with a lowering of temperature at temperatures below the equilibrium solidification temperature Tm, nucleation occurs more readily. Next, the number of stable nuclei n* (having radii greater than r*) is a functio n of temperature as n^*=K_1 exp(-G ^*/kT) In the above equation the constant K1 is related to the total number of nuclei i n solid phase. As the temperature is lowered below Tm (melting/freezing temperature), the expon ential term in the above equation also decreases and therefore the magnitude of n* increases. Assumptions made: A spherical shape was assumed for nuclei. However, the treatment may be

applied to any shape with the same final result. This treatment may also be applied to other types of transformation in a ddition to solidification such as (solid-vapor, solid-solid etc.,). In these cas es, the magnitudes of Gv and , in addition to diffusion rates of atomic species wi ll be different among the different transformation types. Further in solid-solid transformations, there may be volume changes due to the formation of new phases.

Heterogeneous nucleation: In heterogeneous nucleation, the probability of nucleation occurring at certain preferred sites in the assembly is much greater than at other sites. uring solidification of a liquid, inclusions of foreign particles in the liquid and the walls of the container holding the liquid provide preferred nucleation sites. In solid-solid transformations, foreign inclusions, grain boundaries, interfaces , stacking faults and dislocations can provide sites for preferred nucleation. Nucleation in solids is almost always of heterogeneous character and one speaks of heterogeneous nucleation. The reason for prevalence of heterogeneous nucleation in solids is that the Gibb s energy barrier for nucleation at defects in the microstructure of the material , as grain boundaries, stacking faults, dislocations and (condensed) vacancies, can be smaller than for nucleation in the defect-free remainder of the matrix. Heterogeneous nucleation is nucleation that occurs in a liquid on the surfaces o f its container, insoluble impurities, and other structural material that the lo wer the critical free energy required to form a stable nucleus. This may be obvious: the reduction in the matrix of grain-boundary area, stackin g fault area, dislocation line length, etc. upon occupation of grain boundaries, stacking faults and dislocations, etc. by the developing precipitates releases grain-boundary, stacking fault, dislocation strain, etc. energy, and thereby G* b ecomes reduced. Although the levels of supercooling for homogenous nucleation may be significant (on occasion several hundred degrees), in practical situations they are often o n the order of only several degrees Celsius.

The reason for this is that the activation energy (i.e. energy barrier) for nucl eation G ^*=(16^3)/(3(G _V )^2 ) is lowered when nuclei form on pre-existing surfaces or i es, since the surface free energy is reduced. This is because; it is easier for nucleation to occur at surfaces and interfaces than at other sites. This type of nucleation is known as heterogenous nucleatio n. Except in controlled laboratory experiments, homogenous nucleation never occurs in liquids. Instead, impurities in contact with the liquid, either suspended in the liquid o r on the walls of the container that holds the liquid, provide a surface on whic h a surface on which the solid can form.

Now a radius of curvature greater than the critical radius is achieved with very little total surface area between the solid and liquid. Relatively, few atoms m ust cluster together to produce a solid particle that has the required radius of curvature. Much less undercooling is required to achieve the critical size, so nucleation o ccurs more rapidly. Nucleation on pre-existing conditions is known as heterogeno us nucleation. For heterogeneous nucleation to take place, The solid nucleating agent (impurity solid or container) must be wetted by the liquid metal. Liquid should solidify easily on the nucleating agent. Figure shows a nucleating agent (impurity solid or container) that is wetted by the solidifying liquid, creating a low contact angle between the solid metal and the nucleating agent. Heterogeneous nucleation takes place on the nucleation agent because the surface free energy to form a stable nucleus is lower on this material than in the pure liquid itself (homogenous nucleation). Since the surface energy is lower for heterogeneous nucleation, the total free e nergy change for the formation of a stable nucleus will be lower and the critica l size of the nucleus will be smaller. Therefore, a much smaller amount of undercooling is required to form a stable nu cleus produced by heterogeneous nucleation. Using the same procedure, for homogenous nucleation, similar expressions for r* and G* can be derived as r^*=-(2_SL)/(G_V ) G ^*=(16_SL^3)/(3(G _V )^2 ) S()

Where S()=2-3cos +(cos )^3 The S() term of the above equation is a function only of (i.e. the shape of the n ucleus), which will have a numerical value between zero and unity. S() is depende nt only on i.e., the shape of the nucleus. It is therefore referred to as shape factor. The activation energy barrier for heterogeneous nucleation is smaller than the h omogenous barrier by an value corresponding to this S() function or G_het^*=G_hom^* S() This lower G* for hetereogenous nucleation implies that a smaller energy must be overcome during the nucleation process (than the homogenous nucleation) and ther efore heterogenous nucleation occurs more rapidly. The rate of nucleation or nucleation rate (the number of nuclei formed per unit time) is a function of temperature. Prior to solidification, there is no nucleat ion. At temperatures, above the freezing point, the rate of nucleation is zero. As temperature drops, the driving force for nucleation increases; however as the temperature decreases, atomic diffusion becomes slower, hence slowing the nucle ation process.

Therefore, a typical rate of nucleation reaches a maximum at some temperature be low the transformational temperature. In heterogeneous nucleation, the rate of nucleation is dictated by the concentra tion of the nucleating agents. Growth: The growth step in a phase transformation begins once an embryo has exceeded the critical size r*, and has become the stable nucleus. It is important to understand that nucleation will continue to occur simultaneou sly with the growth of the new phase particles; however, it is important to note that nucleation cannot occur in regions that have already transformed to the ne w phase. The growth process will cease in any region where particles of the new phase mee t, since the transformation will have reached completion. Particle growth occurs by long-range atomic diffusion, which normally involves s everal steps for example, diffusion through the parent phase, across the phase b oundary, and then into the nucleus. Consequently, the growth rate G is determined by the rate of diffusion, and its temperature dependence is the same as for diffusion coefficient. (G =Cexp(-Q/kT) ) Where Q is the activation energy and C a pre-exponential are independent of temp erature. The overall transformation rate is equal to some product of N and G . The general shape of the overall transformation rate is the same as for the nucl eation rate, in that it has a peak or maximum that has been shifted upward relat ive to the N curve. Transformation rate vs temperature curve: The size of the product phase particles will depend on transformation te mperature. Transformations that occur at temperatures near to Tm, corresponding to low nucleation and high growth rates, few nuclei form that grow rapidly. Thus th e resulting microstructure will consist of few and relatively large phase partic les (e.g., coarse grains). For transformations at lower temperatures, nucleation rates are high and growth rates are low, which result in many small particles (e.g., small grains) .