Kinetic rates of thermal transformations and diffusion in polymer systems measured during sub-millisecond laser-induced heating.

Probing chemical reaction kinetics in the near-solid state (small molecules and polymers) is extremely challenging because of the restricted mobility of reactant species, the absence of suitable analytical probes, and most critically the limited temperature stability of the materials. By limiting temperature exposure to extremely short time frames (sub-millisecond), temperatures in excess of 800 °C can be accessed extending kinetic rate measurements many orders of magnitude. Here we demonstrate measurements on a model system, exploiting the advantages of thin-films, laser heating, and chemically amplified resists as an exquisite probe of chemical kinetic rates. Chemical reaction and acid diffusion rates were measured over 10 orders of magnitude, exposing unexpected and large changes in dynamics linked to critical mechanism shifts across temperature regimes. This new approach to the study of kinetics in near-solid state materials promises to substantially improve our understanding of processes active in a broad range of temperature-sensitive, low-mobility materials.

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