Shape-memory poly(isocyanurate−urethane) (PIR−PUR) aerogels are low-density monolithic nanoporous solids that remember and return to their permanent shape through a heating actuation step. Herein, through structural design at the macro scale, the shape-memory response is augmented with an auxetic effect manifested by a negative Poisson's ratio of approximately −0.8 at 15% compressive strain. Thus, auxetic shape-memory PIR−PUR monoliths experience volume contraction upon compression at a temperature above the glass transition temperature of the base polymer (T g ≈ 30 °C), and they can be stowed indefinitely in that temporary shape by cooling below T g . By heating back above T g , the compressed/shrunk form expands back to their original shape/ size. This technology is relevant to a broad range of industries spanning the commercial, aeronautical, and aerospace sectors. The materials are referred to as meta-aerogels, and their potential applications include minimally invasive medical devices, soft robotics, and situations where volume is at a premium, as for example for storage of deployable space structures and planetary habitats during transport to the point of service.
Tetrahydroquinazoline (THQ) was designed as an all-nitrogen analogue of main-stream benzoxazine monomers. THQ solutions in DMF gelled at 100 °C via HCl-catalyzed ring-opening polymerization to polybenzodiazine (PBDAZ) wet gels, which were dried in an autoclave with supercritical fluid CO 2 to aerogels. These as-prepared PBDAZ-100 aerogels undergo ring-fusion aromatization at 240 °C under O 2 . This oxidized form is referred to as PBDAZ-240. Chemical identification of PBDAZ-100 and PBDAZ-240 relied on consideration of all nine possible polymerization pathways, in combination with elemental analysis, infrared and solid-state 13 C NMR spectroscopy, and 15 N NMR spectroscopy of aerogels from the selectively 15 N-enriched THQ monomer. Fully oxidized PBDAZ-240 aerogels were carbonized at 800 °C under Ar to carbon aerogels with 61% w/w yield and with retention of the nanomorphology of the parent PBDAZ-100 aerogels. Direct pyrolysis of PBDAZ-100 at 800 °C, i.e., without prior oxidation, resulted in only 40% w/w yield and complete loss of the fine nanostructure. The evolution of PBDAZ-240 aerogels along pyrolysis toward carbonization was monitored using progressively higher pyrolysis temperatures from 300 to 800 °C under Ar. Aerogels received at 600 and 800 °C (referred to as PBDAZ-600 and PBDAZ-800, respectively) had relatively high surface areas (432 and 346 m 2 g −1 , respectively), a significant portion of which (79% in both materials) was assigned to micropores. The new polymer aerogels, together with polybenzoxazine aerogels, comprise a suitable basis set for comparing N-rich versus O-rich porous carbons as adsorbers.
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