Thermoresponsive amphiphilic Pluronic F127 triblock copolymer solutions have been widely investigated in smart biomaterial applications due to the proximity of its critical gel temperature to human body temperature. Meanwhile, cellulose nanocrystals (CNCs) have quickly become the focus of many drug delivery and tissue engineering applications due to their biocompatibility, abundance, ability to conjugate with drug molecules, and superior rheological properties. Herein, we investigate the phase behavior and thermo-rheological properties of the composite hydrogels containing cellulose nanocrystals (up to 5% by weight) and the temperature responsive Pluronic F127. Our results revealed an unprecedented role of CNC network formation on micellization and gelation behavior of the triblock copolymer. Linear and nonlinear rheological analysis suggest that at low and moderate nanocrystal loadings (1–3% by weight), the composite gel remarkably becomes softer and deformable compared to the neat Pluronic F127 gels. The softening effect results from the disruption of the close packed micelles by the rodlike CNCs. At high concentrations, however, the nanocrystals form their own network and the micelles are trapped within the CNC meshes. As a result, the original (neat F127) hard-gel modulus is recovered at 4 to 5% nanocrystal loading, yet the composite gel is much more deformable (and tougher) in the presence of the CNC network. Our temperature sweep experiments show that the CNC addition up to 3% does not change the rapid thermal gelation of the F127 solutions; therefore, these composites are suitable for smart drug delivery systems. On the other hand, at higher CNC concentrations, abrupt viscosity transition is not observed, rather the composite gels smoothly thicken with temperature in contrast to thermal thinning of the aqueous neat CNC. Thus, they can be used as smartly adaptive biolubricants and bioviscostatic materials.

Cellulose nanocrystals (CNCs) have recently attracted wide interest due to their abundance, biocompatibility, and extraordinary physical properties. In particular, easy manipulation of their surface properties, hydrophilicity, and high aspect ratio make them ideal rheology modifiers; yet, the gelation mechanisms and microscopic origin of the complex rheological behavior in the presence of secondary components, such as polymers and surfactants, are far from well understood. In this work, we used light scattering, small-angle neutron scattering, and bulk rheology to study the phase behavior and mechanical behavior of aqueous CNC solutions in the presence of cationic 1-decyl trimethyl imidazolium chloride and 1-decyl trimethyl imidazolium ferric tetrachloride. The micelles of these surfactants form at similar cmc’s (about 50 mM) and adopt identical hydrodynamic sizes (on the order of a few nanometers) and prolate-shaped ellipsoids but vary in their intermicelle interactions (charged vs neutral), thus allowing us to clarify the unprecedented effect of the surfactant micelle charge on the gel behavior of the aqueous CNC–surfactant complexes. Our results show that the positively charged micelles greatly strengthen the gel network while excessive free micelles weaken the gels due to repulsive micelle–micelle interaction. In the meantime, analysis of the transition from linear to nonlinear deformation regimes suggests that the gels gradually become more fragile with surfactant concentrations due to electrostatic repulsion of the charged micelles. Such a surfactant concentration-dependent gel fragility was not observed in the presence of the neutral micelles. These results provide a great step further in our understanding of the phase behavior and rheology of complex CNC–surfactant mixtures and obtaining biocompatible hydrogels with tunable mechanical properties.