Pii: S0032-3861(99)00830-7

High-energy mechanical milling has been performed on poly(methyl methacrylate) (PMMA) at ambient and cryogenic temperatures, as well as on polyisoprene (PI) and poly(ethylene-alt-propylene) (PEP) at cryogenic conditions only. Milling conducted at ambient temperature has a substantially greater impact on the molecular characteristics of PMMA than milling at cryogenic temperatures. An increase in the milling time is accompanied by substantial reductions in PMMA molecular weight and, hence, glass transition temperature and impact strength under both sets of experimental conditions. An unexpected trend identified here is that the PMMA molecular weight distribution initially broadens and subsequently narrows with increasing milling time. Solid-state mechanical milling promotes comparable decreases in molecular weight and glass transition temperature in PEP (at a slower rate relative to PMMA), but induces chemical crosslinking in PI, as confirmed by FTIR spectroscopy. Charlesby–Pinner analysis yields not only the degree of PI crosslinking, but also the relative crosslinking and scission rates of PI, during cryogenic milling. q 2000 Elsevier Science Ltd. All rights reserved.