Spinodal decomposition

Spinodal decomposition is a mechanism for the rapid unmixing of a mixture of liquids or solids from one thermodynamic phase to form two coexisting phases. As an example, consider a hot mixture of water and an oil. At high temperatures the oil and the water may mix to form a single thermodynamic phase in which water molecules are surrounded by oil molecules and vice versa. The mixture is then suddenly cooled to a temperature at which thermodynamic equilibrium favours an oil-rich phase coexisting with a water-rich phase. Spinodal decomposition then occurs when the mixture is such that there is essentially no barrier to nucleation of the new oil-rich and water-rich phases. In other words, the oil and water molecules immediately start to cluster together into microscopic water-rich and oil-rich clusters throughout the liquid. These clusters then rapidly grow and coalesce until there is a single macroscopic oil-rich cluster, the oil-rich phase, and a single water-rich cluster, the water-rich phase.

Spinodal decomposition can be contrasted with nucleation and growth. There the initial formation of the microscopic clusters involves a large free energy barrier, and so can be very slow, and may occur as little as once in the initial phase, not throughout the phase, as happens in spinodal decomposition.

Spinodal decomposition is of interest for two primary reasons. In the first place, it is one of the few phase transition in solids for which there is a complete quantitative theory. The reason for this is the inherent simplicity of the reaction. Since there is no thermodynamic barrier to the reaction inside of the spinodal region, the decomposition is determined solely by diffusion. Thus, it can be treated purely as a diffusional problem, and many of the characteristics of the decomposition can be described by an approximate analytical solution to the general diffusion equation.

In contrast, theories of nucleation and growth have to invoke the thermodynamics of fluctuations. The diffusional problem involved in the growth of the nucleus is far more difficult to solve because it is unrealistic to linearize the diffusion equation.

From a more practical standpoint, spinodal decomposition provides a means of producing a very finely dispersed microstructure that can significantly enhance the physical properties of the material.

In the early 1940s, Bradley reported the observation of sidebands around the Bragg peaks of the X-ray diffraction pattern from a Cu-Ni-Fe alloy that had been quenched and then annealed inside the miscibility gap. Further observations on the same alloy were made by Daniel and Lipson, who demonstrated that the sidebands could be explained by a periodic modulation of composition in the <100> directions. From the spacing of the sidebands, they were able to determine the wavelength of the modulation, which was of the order of 100 angstroms.

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