Part II – February 1968 - Papers - The 1967 Institute of Metals Lecture Spinodal Decomposition

The spinodal has long been regarded as a limit beyond which a homogeneous phase could no longer be metastable. But only recently has it become apparent that a phase beyond the spinodal would decompose by simple diffusional clustering mechanism quite different from the nucleation and growth mechanisms encountered for metastable phases. The theory of spinodal decomposition, which is based on the diffusion equation modified by thermodynamic requirements , is phenomenological, and each parameter can be measured by independent thermodynamic or diffusion experiments. The details of the theory have been carefully verified in a number of simple systems. It appears that the spinodal mechanism is commonly encountered in clustering reactions in solids and glasses. HISTORICAL INTRODUCTION The understanding of the earliest stages of precipitation in alloys has been the subject of three prior Institute of Metals Lectures. In 1932 Paul ~erica' reviewed the puzzling evidence that hardening of duralumin is completed before precipitation of CuAlz takes place and suggested that hardening occurs when the copper atoms "assemble in random groups on lattice positions of the duralumin, not of the CuAlz lattice". He called these random groups knots. This modification of his dispersion hardening theory seemed to fit all the facts, but Merica worried that the required diffusion "is just the reverse of what we deem normal; although quite spontaneous, it proceeds uphill, if you please". The reality of Merica's knots was quickly confirmed by Guinier's' and preston's3 X-ray work and these knots are today known as G.P. zones in their honor. Theoretical justification for uphill diffusion was also quickly provided by Becker and Dehlinger~ who noted that the diffusion coefficient could be negative in certain regions of phase diagrams. The boundaries of such regions could be described by a 90-year-old thermodynamic concept first described by ~ibbs' in 1877 as a limit of metastability for fluid phases, which by 1890 had received the name spinodal (see Appendix A). Spinodal in fluids is as old as nucleation theory. Both appear for the first time in the same paper by Gibbs who called the spinodal the limit of metastability. For the first 50 years, nucleation theory was forgotten and the spinodal was extensively treated in every good thermodynamics textbook.81Q The idea was simple and logical and it was accepted as part of a rigorous thermodynamic development of metastable phases, and for a while it was extensively investigated theoretically.