Abstract:The renewability, biocompatibility and mechanical properties of cellulose nanocrystals (CNCs) have made them an attractive material for numerous composite, biomedical and rheological applications. However, for CNCs to shift from laboratory curiosity to commercial applications, researchers must transition from CNCs extracted at the bench scale to material produced at an industrial scale. There are a number of companies currently producing kilogram to ton per day quantities of sulfuric acid-hydrolyzed CNCs, as well as other nanocelluloses, as described herein.With the recent intensification of industrially produced CNCs, the variety of cellulose sources, hydrolysis methods and purification procedures, characterization of these materials becomes critical. This has further been justified by the past two decades of research which demonstrate that CNC stability and behaviour is highly dependent on surface chemistry, surface charge density and particle size. This work outlines key test methods that should be employed to characterize these properties to ensure a "known" starting material and consistent performance.Of the sulfuric acid-extracted CNCs examined, industrially produced material compared well with laboratory-made CNCs, exhibiting similar charge density, colloidal and thermal stability, crystallinity, morphology and self-assembly behaviour. In addition, it was observed that further purification of CNCs, using Soxhlet extraction in ethanol, had minimal impact on nanoparticle properties and is unlikely to be necessary for many applications. Overall the current standing of industrially produced CNCs is positive suggesting that the evolution to commercial scale applications will not be hindered by CNC production.

No abstract

The production of well-dispersed reinforced polymer nanocomposites has been limited due to poor understanding of the interactions between components. Measuring the cohesive particle-particle interactions and the adhesive particlepolymer interactions is challenging due to nanoscale dimensions and poor colloidal stability of nanoparticles in many solvents. We demonstrate a new cohesive interaction measurement method using cellulose nanocrystals (CNCs) as a model system; CNCs have recently gained attention in the composites community due to their mechanical strength and renewable nature. Multi-wavelength surface plasmon resonance spectroscopy (SPR) was used to monitor the swelling of CNC thin films to elucidate the primary forces between CNCs. This was achieved by measuring swelling in situ in water, acetone, methanol, acetonitrile, isopropanol, and ethanol and relating the degree of swelling to solvent properties. Films swelled the most in water where we estimate 1.2-1.6 nm spacings between CNCs (or 4-6 molecular layers of water).Furthermore, a correlation was found between film swelling and the solvent's Hildebrand solubility parameter (R 2 =0.9068). The hydrogen bonding component of the solubility parameters was more closely linked to swelling than the polar or dispersive components. The films remained intact in all solvents, and using DLVO theory we have identified van der Waals forces as the main cohesive interaction between CNCs. The trends observed suggest that solvents (and polymers) alone are not sufficient to overcome CNC-CNC cohesion and that external energy is required to break CNC agglomerates. This work not only demonstrates that SPR can be used as a tool to measure cohesive particle-particle interactions but additionally advances our fundamental understanding of CNC interactions which is necessary for the design of cellulose nanocomposites.

A model describing the kinetics of bulk styrene polymerization through bifunctional initiators has been developed. The diffusion-controlled propagation and termination reactions at high monomer conversions are modeled with the free volume theory for polymer solutions. Three different commercially available bifunctional initiators were experimentally evaluated for a wide range of polymerization conditions to study the effect of the reaction rate on the molecular weight and molecular weight distribution. The model predictions for the same polymerization conditions show excellent agreement with the experimental data, for the whole range of conversions, for both reaction rate and molecular weight distribution development, under all the conditions tested. It is demonstrated throughout this study that high molecular weights, very high reaction rates, and narrow molecular weight distributions can be achieved simultaneously by using bifunctional initiators. A comparison between monofunctionally initiated systems with the bifunctionally initiated ones shows that shortcycle reactions with reductions in polymerization time of up to 75% may be achieved with the bifunctional initiators for a wider range of conditions without significantly affecting the molecular weight and molecular weight distribution of the final product.

SYNOPSISThe plasticizing effect of n-pentane on the rate of bulk free radical polymerization of styrene and molecular weight distribution development has been modeled on the basis of the free volume theory for both monofunctional and bifunctional initiation. A strong decrease in the reaction rate in the late stages of the polymerization, due to the displacement of the onset of the gel effect, has been observed for both types of initiation. This decrease in the polymerization rate limited the terminal conversion to values well below 100% for monofunctional initiation. However, in bifunctionally initiated polymerization, terminal conversions close to 100% were obtained in spite of the decrease in reaction rate. Contrary to what was expected, the molecular weight distribution obtained at terminal conversion was almost completely insensitive to these changes in polymerization rate. This phenomenon is explained in terms of limited transfer to monomer reactions when n-pentane is present in the system. In suspension polymerization, the limiting conversion and plasticizing effects of n -pentane in monofunctionally initiated systems, caused enhanced coalescence leading to suspension set-up. In bifunctionally initiated systems this enhanced coalescence was completely overcome by the short duration of the particle growth stage, owing to high polymerization rates, and stable suspensions were achieved. For these systems the particle size distributions obtained were similar to that of suspension polystyrene without n-pentane.

No abstract

No abstract

This work explores cellulose nanocrystal (CNC) thin films (<50 nm) and particle-particle interactions by investigating film swelling in aqueous solutions with varying ionic strength (1-100 mM). CNC film hydration was monitored in situ via surface plasmon resonance, and the kinetics of liquid uptake were quantified. The contribution of electrostatic double-layer forces to film swelling was elucidated by using CNCs with different surface charges (anionic sulfate half ester groups, high and low surface charge density, and cationic trimethylammonium groups). Total water uptake in the thin films was found to be independent of ionic strength and surface chemistry, suggesting that in the aggregated state van der Waals forces dominate over double-layer forces to hold the films together. However, the rate of swelling varied significantly. The water uptake followed Fickian behavior, and the measured diffusion constants decreased with the ionic strength gradient between the film and the solution. This work highlights that nanoparticle interactions and dispersion are highly dependent on the state of particle aggregation and that the rate of water uptake in aggregates and thin films can be tailored based on surface chemistry and solution ionic strength.