Memory effect on ion beam-induced depolymerization of PMMA

Recently a new ion beam-induced phenomenology - depolymerization of macromolecular target - has been found and studied in our laboratory. This has been observed in poly(methylmethacrylate) (PMMA) using He+ 300 keV ion beam, in a temperature range much lower than that required for thermal depolymerization. Here we report an in situ monitoring of PMMA depolymerization performed by mass spectrometry. We have found that at a given temperature the monomer flux due to depolymerization of the bombarded polymer is much more intense when the temperature is quenched, with respect to the same temperature during heating. The results have been rationalized by using an accurate model that involves initiation and propagation kinetics followed by the diffusion process. The use of the model allowed us to exclude any influence of transport properties of PMMA on this effect but indicates that the hysteresis phenomenon detected at macroscopic level has a microscopic counterpart linked to the chemical yields of the depolymerization kinetics. (C) 2001 Elsevier Science B.V. All rights reserved.