Discontinuous reactions are solid state moving boundary phase transitions characterised by a discontinuous or abrupt change in orientation and composition between the matrix phases in the reactant and product aggregate across the migrating boundary or reaction front that provides a short circuit path of diffusion. The reactions include discontinuous precipitation, discontinuous coarsening, discontinuous dissolution, and diffusion induced grain boundary migration. All these reactions may account for a substantial change in microstructure, composition, and material properties, and hence, deserve adequate scientific attention for a better understanding. The present review provides a comprehensive discussion on the current status of understanding about nucleation and growth mechanisms, genesis and driving force, product morphology and distribution, kinetic growth models, and related experimental techniques, and above all, the unresolved questions concerning these discontinuous reactions. In addition, ...

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Discontinuous reactions in solids

Diffusion induced grain boundary migration

On the driving force for diffusion induced grain boundary migration

The analytical electron microscope (AEM) was used to examine the microstructure of type 316LN stainless steel alloys which had been annealed for 50 to 300 hours in the temperature range 600 to 700 °C. The M23C6 carbide chemistry and distribution are described as a function of heat treatment.X-ray spectroscopy in the AEM revealed significant chromium depletion at grain boundaries in the vicinity of carbides for samples aged at 50 and 100 hours at 650 °C and 100 and 300 hours at 700 °C, with lower grain boundary chromium values observed at 650 °C than at 700 °C. The width of the chromium depleted zone normal to the grain boundaries increased with increasing annealing time and/or temperature. Measurements of chromium concentration along the grain boundaries away from a carbide were made after aging at 700 °C for 100 hours, and the chromium level rose steadily until the bulk value was reached at a distance of ~3μm from the carbide. The width of the chromium depleted zone normal to the boundaries in the same sample was an order of magnitude less. Some molybdenum depletion was also found at the grain boundaries, and the Mo-depletion profiles were in form and extent similar to the chromium results. Simple thermodynamic models were used to calculate the equilibrium value of chromium at the carbide-matrix interface, and the chromium distribution along and normal to the grain boundaries. The results of these models agreed well with the AEM results, and the agreement can be improved by considering the effect of electron probe configuration on the AEM measurements. The calculated thermodynamic data and the AEM results were related to the corrosion behavior of the alloys. The occurrence of severe asymmetries in some concentration profiles normal to the grain boundaries, which increased with increasing annealing temperature or time, was shown to be due to boundary movement during the discontinuous precipitation of M23C6 carbides.

Chromium depletion in the vicinity of carbides in sensitized austenitic stainless steels

Grain-boundary precipitation in Allvac 718Plus

The morphology of cellular precipitation in a Cu-9.5 at. pet In alloy has been investigated by light and electron microscopy. Both cellular and general precipitation were observed to occur simultaneously in quenched and aged alloys while only cellular precipitation was observed to occur in isothermally aged alloys. Because of the presence of wide, solute rich, precipitate free zones in the vicinity of grain boundaries in the quenched and aged alloys, the early development of cellular precipitation was found to be identical for both types of heat treatment. From light and electron microscopy observations of the early stages of cellular precipitation a mechanism for the formation of cells was developed. At the start of aging, the unoccupied grain boundary begins to migrate under the influence of grain boundary migration forces as if it were in a single phase alloy. As the boundary migrates, solute segregates along it to form allotriomorphs which pin the boundary. The boundary continues to migrate and bows between the simultaneously forming allotriomorphs. With further aging, the allotriomorphs lengthen following the bowing boundary and the allotriomorphs become the initial precipitate lamellae of the developing cell as a steady-state lamellar structure develops. Assuming that the critical step in the development of a cell is the ability of the boundary to bow between the initial allotriomorphs, a criterion for the occurrence of cellular precipitation was developed.

R. A. Fournelle

Papers

The genesis of the cellular precipitation reaction