Early Evidence
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.
The growth of a composition modulation in an initially homogeneous alloy implies uphill diffusion, or a negative diffusion coefficient. Becker and Dehlinger had already predicted a negative diffusivity inside the spinodal region of a binary system. But their treatments could not account for the growth of a modulation of particular wavelength, such as was observed in the Cu-Ni-Fe alloy. In fact, any model based on Fick's law yields a physically unacceptable solution when the diffusion coefficient is negative.
The first explanation of the periodicity was given by Mats Hillert in his 1955 Doctoral Dissertation at MIT. Starting with a regular solution model, he derived a flux equation for one-dimensional diffusion on a discrete lattice. This equation differed from the usual one by the inclusion of a term which allowed for the effect on the driving force of the interfacial energy between adjacent interatomic planes that differed in composition. Hillert solved the flux equation numerically and found that inside the spinodal it yielded a periodic variation of composition with distance. Furthermore, the wavelength of the modulation was of the same order as that observed in the Cu-Ni-Fe alloys.
A more flexible continuum model was subsequently developed by John W. Cahn, who included the effects of coherency strains as well as the gradient energy term. The strains are significant in that they dictate the ultimate morphology of the decomposition in anisotropic materials.
Read more about this topic: Spinodal Decomposition
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