A Novel Dry Chemical Path Way for Diene and Dienophile Surface Functionalization toward Thermally Responsive Metal–Polymer Adhesion

In this paper, we report a new and easily up-scalable dry chemical method to functionalize with diene and dienophile groups a large range of surfaces, such as metal, polymer, or glass, and we demonstrate the potentiality of this technique to realize thermally responsive adhesion between these materials. A complete and extensive surface chemistry analysis of the grafted surfaces, based on the deposition of an anhydride-rich thin plasma polymer layer by using an atmospheric pressure dielectric barrier discharge (DBD) plasma process, and its subsequent gas phase aminolysis reaction with specific diene or dienophile compound is discussed. The optimization of the assembling condition for these tailored surfaces has led to achieve a Diels-Alder adhesion force up to 0.6 N/mm at ambient temperature, which can be reduced by a factor of 50 when the retro Diels-Alder is ignited at a heating temperature around 200 °C. The study of the failure interface produced after peeling tests is presented and a mechanism of failure is proposed, based on forensic analyses involving surface analytical techniques such as XPS, ToF-SIMS, and SEM combined to AFM analyses for the retrieving of chemical and morphological information.