No abstract

Polyimide (PI) aerogels are highly porous solids having low density, high porosity and low thermal conductivity with good mechanical properties. They are ideal for various applications including use in antenna and insulation such as inflatable decelerators used in entry, decent and landing operations. Recently, attention has been focused on stimuli responsive materials such as cellulose nano crystals (CNCs). CNCs are environmentally friendly, bio-renewable, commonly found in plants and the dermis of sea tunicates, and potentially low cost. This study is to examine the effects of CNC on the polyimide aerogels. The CNC used in this project are extracted from mantle of a sea creature called tunicates. A series of polyimide cellulose nanocrystal composite aerogels has been fabricated having 0-13 wt of CNC. Results will be discussed.

Inspired by the ability of the sea cucumber to (reversibly) increase the stiffness of its dermis upon exposure to a stimulus, we herein report a stimuli-responsive nanocomposite that can reversibly increase its stiffness upon exposure to warm water. Nanocomposites composed of cellulose nanocrystals (CNCs) that are grafted with a lower critical solution temperature (LCST) polymer embedded within a poly(vinyl acetate) (PVAc) matrix show a dramatic increase in modulus, for example, from 1 to 350 MPa upon exposure to warm water, the hypothesis being that grafting the polymers from the CNCs disrupts the interactions between the nanofibers and minimizes the mechanical reinforcement of the film. However, exposure to water above the LCST leads to the collapse of the polymer chains and subsequent stiffening of the nanocomposite as a result of the enhanced CNC interactions. Backing up this hypothesis are energy conserving dissipative particle dynamics (EDPD) simulations which show that the attractive interactions between CNCs are switched on upon the temperature-induced collapse of the grafted polymer chains, resulting in the formation of a percolating reinforcing network.

A series of strong, rebondable polydisulfide nanocomposite adhesive films have been prepared via the oxidation of a thiol-endcapped semicrystalline oligomer with varying amounts of thiol-functionalized cellulose nanocrystals (CNC-SH). The nanocomposites are designed to have two temperature-sensitive components: (1) the melting of the semicrystalline phase at ca. 70 °C and (2) the inherent dynamic behavior of the disulfide bonds at ca. 150 °C. The utility of these adhesives was demonstrated on different bonding substrates (hydrophilic glass slides and metal), and their bonding at both 80 and 150 °C was examined. In all cases, stronger bonding was achieved at temperatures where the disulfide bonds are dynamic. For high surface energy substrates, such as hydrophilic glass or metal, the adhesive shear strength increases with CNC-SH content, with the 30 wt % CNC-SH composites exhibiting adhesive shear strengths of 50 and 23 MPa for hydrophilic glass and metal, respectively. The effects of contact pressure and time of bonding were also investigated. It was found that ca. 20-30 min bonding time was required to reach maximum adhesion, with adhesives containing higher wt % CNCs requiring longer bonding times. Furthermore, it was found that, in general, an increase in contact pressure results in an increase in the shear strength of the adhesive. The rebonding of the adhesives was demonstrated with little-to-no loss in adhesive shear strength. In addition, the 30 wt % nanocomposite adhesive was compared to some common commercially available adhesives and showed significantly stronger shear strengths when bonded to metal.

An electrochemical process has been used to compact cellulose nanocrystals (CNC) and access aligned micron-sized CNC fibers. Placing a current across aqueous solutions of carboxylic acid functionalized CNCs (t-CNC-COOH) or carboxylic acid/primary amine functionalized CNCs (t-CNC-COOH-NH) creates a pH gradient between the electrodes, which results in the migration and concentration of the CNC fibers at their isoelectric point. By matching the carboxylic acid/amine ratio of CNCs and collagen (ca. 30:70 carboxylic acid:amine ratio), it is possible to coelectrocompact both nanofibers and access aligned nanocomposite fibers. t-CNC-COOH-NH/collagen fibers showed a maximum increase in mechanical properties at 5 wt % of t-CNC-COOH-NH. Compared to collagen/CNC films which have no alignment in the plane of the films, the tensile properties of the aligned fibers show a significant enhancement in the wet mechanical properties (40 MPa vs 230 MPa) for the 5 wt % of t-CNC-COOH-NH/collagen films and fiber, respectively.