Charged Cellulose Nanocrystals Research Articles

Electric Interfacial Layer of Modified Cellulose Nanocrystals in Aqueous Electrolyte Solution: Predictions by the Molecular Theory of Solvation

The X-ray crystal structure-based models of Iα cellulose nanocrystals (CNC), both pristine and containing surface sulfate groups with negative charge 0-0.34 e/nm(2) produced by sulfuric acid hydrolysis of softwood pulp, feature a highly polarized "crystal-like" charge distribution. We perform sampling using molecular dynamics (MD) of the structural relaxation of neutral pristine and negatively charged sulfated CNC of various lengths in explicit water solvent and then employ the statistical mechanical 3D-RISM-KH molecular theory of solvation to evaluate the solvation structure and thermodynamics of the relaxed CNC in ambient aqueous NaCl solution at a concentration of 0.0-0.25 mol/kg. The MD sampling induces a right-hand twist in CNC and rearranges its initially ordered structure with a macrodipole of high-density charges at the opposite faces into small local spots of alternating charge at each face. This surface charge rearrangement observed for both neutral and charged CNC significantly affects the distribution of ions around CNC in aqueous electrolyte solution. The solvation free energy (SFE) of charged sulfated CNC has a minimum at a particular electrolyte concentration depending on the surface charge density, whereas the SFE of neutral CNC increases linearly with NaCl concentration. The SFE contribution from Na(+) counterions exhibits behavior similar to the NaCl concentration dependence of the whole SFE. An analysis of the 3D maps of Na(+) density distributions shows that these model CNC particles exhibit the behavior of charged nanocolloids in aqueous electrolyte solution: an increase in electrolyte concentration shrinks the electric interfacial layer and weakens the effective repulsion between charged CNC particles. The 3D-RISM-KH method readily treats solvent and electrolyte of a given nature and concentration to predict effective interactions between CNC particles in electrolyte solution. We provide CNC structural models and a modeling procedure for studies of effective interactions and the formation of ordered phases of CNC suspensions in electrolyte solution.

Influence of Charge Density and Ionic Strength on the Aggregation Process of Cellulose Nanocrystals in Aqueous Suspension, as Revealed by Small-Angle Neutron Scattering

Aggregation of rodlike colloidal particles is investigated here through the aggregation process by either increasing ionic strength or decreasing surface charge density of cellulose nanocrystals (CNCs). The form factor of the nanoparticles is characterized up to the Guinier plateau using small-angle neutron scattering (SANS) extended to very small scattering vector Q. Ionic strength, above the threshold of screening charges, brings aggregative conditions that induced fractal organizations for both charged and uncharged CNCs. These two structures display respective fractal dimensions of 2.1 for charged CNCs at high ionic strength and 2.3 for desulfated CNCs over more than a decade of the scattering vector Q, irrespective of salinity, revealing a denser structuration for neutral particles. This is discussed in the framework of aggregation of rodlike particles with an aspect ratio higher than 8. Furthermore, dilution of the rod gel led to disentanglement of the network of fractal aggregates with a subsequent macroscopic sedimentation of the suspensions, with a characteristic time that depends upon the ionic strength and surface charge density. It revealed a threshold independent of salt content around 2.5 g/L and the metastable out-of-equilibrium character of CNC suspensions.

Preparation and stabilization of d-limonene Pickering emulsions by cellulose nanocrystals

The aim of this study was to investigate d-limonene Pickering emulsion stabilized by cellulose nanocrystals (CNCs) and factors that may affect its properties. CNCs were prepared by ammonium persulfate hydrolysis of corncob cellulose, and d-limonene Pickering emulsions were generated by ultrasonic homogenizing method. The morphology and size of the prepared emulsions with different CNCs concentrations were studied by optical microscopy and laser light diffraction. In addition, factors that may affect the stability of emulsions such as ionic concentration, pH and temperature were also studied. As indicated by the experiment data, when temperature rose, the stability to of emulsions would be increased, and the stability of emulsions was reduced with low pH or high salt concentration due to electrostatic screening of the negatively charged CNC particles. In conclusion, high stability of d-limonene Pickering emulsions could be obtained by CNCs.

Nanoporous membranes with cellulose nanocrystals as functional entity in chitosan: Removal of dyes from water

Fully biobased composite membranes for water purification were fabricated with cellulose nanocrystals (CNCs) as functional entities in chitosan matrix via freeze-drying process followed by compacting. The chitosan (10wt%) bound the CNCs in a stable and nanoporous membrane structure with thickness of 250–270μm, which was further stabilized by cross-linking with gluteraldehyde vapors. Scanning electron microscopy (SEM) studies revealed well-individualized CNCs embedded in a matrix of chitosan. Brunauer, Emmett and Teller (BET) measurements showed that the membranes were nanoporous with pores in the range of 13–10nm. In spite of the low water flux (64Lm−2h−1), the membranes successfully removed 98%, 84% and 70% respectively of positively charged dyes like Victoria Blue 2B, Methyl Violet 2B and Rhodamine 6G, after a contact time of 24h. The removal of dyes was expected to be driven by the electrostatic attraction between negatively charged CNCs and the positively charged dyes.