Tunable Aggregation and Gelation of Thermoresponsive Suspensions of Polymer-Grafted Cellulose Nanocrystals.
The colloidal stability together with the tunable aggregation and viscoelastic properties of thermoresponsive polymer-grafted cellulose nanocrystals (CNCs) were investigated. TEMPO oxidation of CNCs followed by peptidic coupling in water were used to covalently graft thermosensitive Jeffamine polyetheramine M2005 chains onto the surface of CNCs. The resulting polymer-decorated particles (M2005-g-CNCs) exhibited new colloidal properties, by their ability to perfectly redisperse in water and organic solvents such as toluene, dichloromethane or DMF after freeze-drying. In addition, they presented an enhanced thermal stability when compared to that of sulfated or TEMPO-oxidized CNCs. Dynamic light scattering experiments were used to demonstrate that the thermally induced aggregation of M2005-g-CNCs was fully reversible and reproducible over many temperature cycles and that, most interestingly, the aggregation number could be tuned by varying the ionic strength and/or the pH of the medium, making the suspension multiresponsive. This property arises from the variations of the sign (attractive or repulsive) and the range of the different types (entropic, electrostatic, hydrophobic) of interaction forces between the thermosensitive polymer-decorated nanoparticles. The variation of the viscoelastic properties of M2005-g-CNCs suspensions as a function of temperature, probed by oscillatory rheology measurements of more concentrated suspensions, revealed a reversible temperature-triggered liquid-to-gel transition. Such enhanced functionalities pave the way to the design of advanced CNC-based materials benefiting both from the intrinsic characteristics of these biosourced particles and the new properties imparted by the stimuli-sensitive grafted chains.
Université Grenoble Alpes , Centre de Recherches sur les Macromolécules Végétales (CERMAV), F-38000 Grenoble, France.|CNRS, CERMAV, F-38000 Grenoble, France.
Firas
F
Azzam
Université Grenoble Alpes , Centre de Recherches sur les Macromolécules Végétales (CERMAV), F-38000 Grenoble, France.|CNRS, CERMAV, F-38000 Grenoble, France.
Eder
E
Siqueira
Université Grenoble Alpes , Centre de Recherches sur les Macromolécules Végétales (CERMAV), F-38000 Grenoble, France.|CNRS, CERMAV, F-38000 Grenoble, France.
Sébastien
S
Fort
Université Grenoble Alpes , Centre de Recherches sur les Macromolécules Végétales (CERMAV), F-38000 Grenoble, France.|CNRS, CERMAV, F-38000 Grenoble, France.|Université Grenoble Alpes , Laboratoire Rhéologie et Procédés (LRP), F-38000 Grenoble, France.|CNRS, LRP, F-38000 Grenoble, France.
Roumaïssa
R
Hassaini
Université Grenoble Alpes , Laboratoire Rhéologie et Procédés (LRP), F-38000 Grenoble, France.|CNRS, LRP, F-38000 Grenoble, France.
Frédéric
F
Pignon
Université Grenoble Alpes , Centre de Recherches sur les Macromolécules Végétales (CERMAV), F-38000 Grenoble, France.|CNRS, CERMAV, F-38000 Grenoble, France.
Christophe
C
Travelet
Université Grenoble Alpes , Centre de Recherches sur les Macromolécules Végétales (CERMAV), F-38000 Grenoble, France.|CNRS, CERMAV, F-38000 Grenoble, France.
Jean-Luc
JL
Putaux
Université Grenoble Alpes , Centre de Recherches sur les Macromolécules Végétales (CERMAV), F-38000 Grenoble, France.|CNRS, CERMAV, F-38000 Grenoble, France.
Bruno
B
Jean
D002482:Cellulose / Q000737:chemistry*; D005782:Gels / Q000737:chemistry*; D057927:Hydrophobic and Hydrophilic Interactions; D053758:Nanoparticles / Q000737:chemistry*; D009994:Osmolar Concentration; D011108:Polymers / Q000737:chemistry*; D013535:Suspensions; D013696:Temperature; D014867:Water / Q000737:chemistry*
D005782:Gels; D011108:Polymers; D013535:Suspensions; D014867:Water; D002482:Cellulose