September 8-13, 2019
Bio-nanocomposites with superior mechanical, transport and flame-retardant properties can be produced from the combination of biopolymers and silicate nanoclay platelets, such as montmorillonite (MMT) [1,2,4]. The highly ordered nanostructure observed in such systems is often compared to natural ones, such as in the brick-and-mortar arrangement of aragonite plates in nacreous materials . Previous work on nacre-mimetic alginate/MMT nanocomposites has shown good compatibility between the biopolymer and inorganic filler and a dependence on MMT concentration to the level of alignment . In this study, we investigate the effect of gelation on the orientation of nanoparticles and its impact on clay stacking and effective aspect ratio. Thermo-reversible gelling biopolymers, i.e. gelatin and carrageenan, were used as matrices to induce early gelation; and compared to sodium alginate (late gelling reaction). Self-supporting bio-nanocomposite films based on gelatin or carrageenan, with a wide range of Na-montmorillonite concentration – up to 80 wt.% MMT – were successfully prepared by solvent casting. The obtained films display a highly aligned nacre-like structure (Fig. 1). To investigate the effect of MMT ordering on the mechanical properties, we have analyzed the obtained films with dynamic mechanical thermal analysis. The bio-nanocomposite films display exceptional mechanical properties, with storage modulus as high as 33 GPa (carrageenan/MMT); and high reinforcement depending on MMT concentration (Fig. 2). At remarkably high inorganic fraction, 80 wt.% MMT, early gelling biopolymers showed a continued increase in material reinforcement, whereas late gelation shows a slight decrease. This suggests that early gelling might reduce restacking of MMT platelets, thus, improving the effective aspect ratio of the filler. The highly ordered structure observed in the gelatin 80 wt.% MMT composite was also reflected in its high heat distortion temperature, implying lower oxygen diffusivity. To better understand the influence of gelation and MMT addition on the mechanical properties, we further applied a conventional composite theory (Halpin-Tsai model), which considers the individual contributions of filler, such as the level of alignment, aspect ratio, volume fraction, and the modulus of the MMT platelets.
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Suellen Pereira Espindola, Ben Norder, Jure Zlopasa, and Stephen J. Picken, "Structure-property relations of highly ordered bio-nanocomposites" in "Nature-Inspired Engineering", Marc-Olivier Coppens, University College London, United Kingdom Bharat Bhushan, Ohio State University, USA Eds, ECI Symposium Series, (2019). https://dc.engconfintl.org/nature_inspired/33