Stress-Transfer in Anisotropic and Environmentally Adaptive Cellulose Whisker Nanocomposites

Abstract

Quantitative insights into the stress-transfer mechanisms that determine the mechanical properties of tunicate cellulose whisker/poly(vinyl acetate) nanocomposites were gained by Raman spectroscopy. The extent of stresstransfer is influenced by local orientation (or anisotropy) of the whiskers, which in turn is governed by the processing conditions used to fabricate the nanocomposites. Solution-cast materials display no microscopic anisotropy, while samples that were cast and subsequently compression molded contain both isotropic regions as well as domains of locally oriented whiskers. Polarized optical microscopy showed these regions to have dimensions in the hundreds of μm. Polarized Raman spectroscopy of the 1095 cm -1 Raman band, associated with C-O ring stretching of the cellulose backbone, was used to quantify the local orientation of the cellulose whiskers. Clear and discernible shifts of this Raman band upon uniaxial deformation of nanocomposite films were further used to determine the level of stress experienced by the cellulose whiskers, ultimately reflecting the levels of stress-transfer predominantly between the poly(vinyl acetate) matrix and the tunicate whiskers, but also between the whiskers within the network. In the isotropic regions, where whiskers form a percolating network, the observed Raman shift rate with respect to strain is smaller than in the regions where the whiskers are uniaxially orientated. The Raman shift is strongly affected by the presence of water, leading to a lack of stress-transfer when the samples are fully hydrated, which is clearly detected by the Raman technique. Heating of the nanocomposites above the glass transition temperature of the poly(vinyl acetate) matrix also reduces the stress experienced by the individual whiskers.

Cross-Linked Bacterial Cellulose Networks Using Glyoxalization

“…It was noted that the shift in this band is higher in magnitude for dry networks compared to wet samples, in agreement with previous work on wet cellulose nanowhisker-based composite materials 38 . Figure 8a reports the detailed positions of the Raman band initially located at 1095 cm -1 as a function of strain for dry unmodified and glyoxalized BC networks.…”

Mechanically adaptive nanocomposites for neural interfacing

“…Quantitative insights into the stress-transfer mechanisms that determine the fi lms stiffness were gained by Raman spectroscopy. 90 A diagnostic Raman band, associated with the C-O ring stretching of the cellulose backbone, was used to quantify the local orientation of and the level of stress experienced by the cellulose whiskers. It was shown that the extent of stress-transfer is infl uenced by local orientation and connectivity of the cellulose whiskers; these features are governed by the processing conditions used to fabricate the materials.…”

Development of a stimuli-responsive polymer nanocomposite toward biologically optimized, MEMS-based neural probes

“…The fixed mechanical properties of typical materials used in micromachined Si, polyimide, or parylene neural probes cannot be optimized for both brain penetration and long-term deployment. Thus PVAc-TW, and the new class of mechanically adaptive polymer nanocomposites that it represents [8,25,26], provides a potential advantage over conventional polymers for penetrating probe-based neural interfacing in that the nanocomposite is sufficiently rigid for probe insertion, but upon deployment absorbs biological fluids, becoming much more pliable to better mechanically match brain tissue. Fabrication of neural probes from such polymers will enable researchers to evaluate the role that mechanics plays in long-term neural recording.…”