Plastic deformation and heat-enabled structural recovery of monolithic silica aerogels

Abstract Drying shrinkage during ambient pressure drying of silica gels is made reversible by preventing condensation reactions of surface silanol groups via surface modification. This partial recovery of the gel volume and structure is referred to as the spring-back effect (SBE) and enables the production of monolithic silica aerogels by evaporative drying. The SBE is sometimes completed by annealing at mild temperatures. Similarities between drying-related deformations and deformations induced by mechanical stimuli suggest analogous underlying mechanisms. While the causes of drying shrinkage are relatively well-known, it remains unclear how the relaxation of the structure by drying and annealing occurs across the different length scales. Here we show a complete structural recovery of silica aerogels at the macro- and nano-scale enabled by annealing. We propose that residual deformations after drying and mechanical compression are caused by the entanglement of silica clusters that can be unraveled by annealing at 230 °C. The deformation under loading is interpreted as two different re-arrangement mechanisms for dry and annealed gels, by the sliding of the silica clusters along the loading direction and by the compression of large pores beyond the fractal structure, respectively. Our results demonstrate how the shape and structure of silica aerogels can be restored and controlled by thermal activation, broadening the various applications of these materials. We also emphasize how tuning silica gels to promote a two-step SBE by annealing can pave the way toward the production of larger monolithic aerogels by APD. Graphical Abstract