Gregory T. Schueneman

Site-Selective Modification of Cellulose Nanocrystals with Isophorone Diisocyanate and Formation of Polyurethane-CNC Composites

The unequal reactivity of the two isocyanate groups in an isophorone diisocyante (IPDI) monomer was exploited to yield modified cellulose nanocrystals (CNCs) with both urethane and isocyanate functionality. The chemical functionality of the modified CNCs was verified with ATR-FTIR analysis and elemental analysis. The selectivity for the secondary isocyanate group using dibutyl tin dilaurate (DBTDL) as the reaction catalyst was confirmed with (13)C NMR. The modified CNCs showed improvements in the onset of thermal degradation by 35 °C compared to the unmodified CNCs. Polyurethane composites based on IPDI and a trifunctional polyether alcohol were synthesized using unmodified (um-CNC) and modified CNCs (m-CNC). The degree of nanoparticle dispersion was qualitatively assessed with polarized optical microscopy. It was found that the modification step facilitated superior nanoparticle dispersion compared to the um-CNCs, which resulted in increases in the tensile strength and work of fracture of over 200% compared to the neat matrix without degradation of elongation at break.

Lignin-coated cellulose nanocrystals as promising nucleating agent for poly(lactic acid)

We report the effect of lignin-coated cellulose nanocrystals (L-CNCs) on the crystallization behavior of poly(lactic acid) (PLA). PLA/L-CNC nanocomposites were prepared by melt mixing, and the crystallization behavior of PLA was investigated using differential scanning calorimetry. Isothermal crystallization data were analyzed using Avrami and Lauritzen–Hoffman secondary nucleation theory, while the equilibrium melting temperature was determined using the nonlinear Hoffman–Weeks method. The lignin-coated cellulose nanocrystals acted as a nucleating agent and significantly increased the rate of crystallization and degree of crystallinity of PLA in PLA/L-CNC nanocomposites. The Avrami exponent, n, increased in the presence of L-CNCs, displaying a conversion from lamellar morphology to two-dimensional crystal growth. PLA/L-CNC nanocomposites also gave lower values of the nucleation parameters,

Rheological and Thermo-Mechanical Properties of Poly(lactic acid)/Lignin-Coated Cellulose Nanocrystal Composites

K_{\text{g}}

Exploiting colloidal interfaces to increase dispersion, performance, and pot-life in cellulose nanocrystal/waterborne epoxy composites

Kg and σe, due to a reduction in the activation energy for nucleation.