Chitin nanofibrils (NCh, ∼10 nm lateral size) were produced under conditions that were less severe compared to those for other biomass-derived nanomaterials and used to formulate high internal phase Pickering emulsions (HIPPEs). Pre-emulsification followed by continuous oil feeding facilitated a “scaffold” with high elasticity, which arrested droplet mobility and coarsening, achieving edible oil-in-water emulsions with internal phase volume fraction as high as 88%. The high stabilization ability of rodlike NCh originated from the restricted coarsening, droplet breakage and coalescence upon emulsion formation. This was the result of (a) irreversible adsorption at the interface (wettability measurements by the captive bubble method) and (b) structuring in highly interconnected fibrillar networks in the continuous phase (rheology, cryo-SEM, and fluorescent microscopies). Because the surface energy of NCh can be tailored by pH (protonation of surface amino groups), emulsion formation was found to be pH-dependent. Emulsions produced at pH from 3 to 5 were most stable (at least for 3 weeks). Although at a higher pH NCh was dispersible and the three-phase contact angle indicated better interfacial wettability to the oil phase, the lower interdroplet repulsion caused coarsening at high oil loading. We further show the existence of a trade-off between NCh axial aspect and minimum NCh concentration to stabilize 88% oil-in-water HIPPEs: only 0.038 wt % (based on emulsion mass) NCh of high axial aspect was required compared to 0.064 wt % for the shorter one. The as-produced HIPPEs were easily textured by taking advantage of their elastic behavior and resilience to compositional changes. Hence, chitin-based HIPPEs were demonstrated as emulgel inks suitable for 3D printing (millimeter definition) via direct ink writing, e.g., for edible functional foods and ultralight solid foams displaying highly interconnected pores and for potential cell culturing applications.

We study the generation and decay of aqueous foams stabilized by sodium dodecyl sulfate (SDS) in the presence of unmodified cellulose nanofibrils (CNF). Together with the rheology of aqueous suspensions containing CNF and SDS, the interfacial/colloidal interactions are determined by quartz crystal microgravimetry with dissipation monitoring, surface plasmon resonance, and isothermal titration calorimetry. The results are used to explain the properties of the air/water interface (interfacial activity and dilatational moduli determined from oscillating air bubbles) and of the bulk (steady-state flow, oscillatory shear, and capillary thinning). These properties are finally correlated to the foamability and to the foam stability. The latter was studied as a function of time by monitoring the foam volume, the liquid fraction, and the bubble size distribution. The shear-thinning effect of CNF is found to facilitate foam formation at SDS concentrations above the critical micelle concentration (c SDS ≥ cmc). Compared with foams stabilized by pure SDS, the presence of CNF enhances the viscosity and elasticity of the continuous phase as well as of the air/water interface. The CNF-containing foams have higher liquid fractions, larger initial bubble sizes, and better stability. Due to charge screening effects caused by sodium counter ions and depletion attraction caused by SDS micelles, especially at high SDS concentrations, CNF forms aggregates in the Plateau borders and nodes of the foam, thus slowing down liquid drainage and bubble growth and improving foam stability. Overall, our findings advance the understanding of the role of CNF in foam generation and stabilization.

To better understand the complex system of wet foams in the presence of cellulosic fibers, we investigate bubble−surface interactions by following the effects of surface hydrophobicity and surface tension on the contact angle of captive bubbles. Bubbles are brought into contact with model silica and cellulose surfaces immersed in solutions of a foaming surfactant (sodium dodecyl sulfate) of different concentrations. It is observed that bubble attachment is controlled by surface wetting, but a significant scatter in the behavior occurs near the transition from partial to complete wetting. For chemically homogeneous silica surfaces, this transition during bubble attachment is described by the balance between the energy changes of the immersed surface and the frictional surface tension of the moving three-phase contact line. The situation is more complex with chemically heterogeneous, hydrophobic trimethylsilyl cellulose (TMSC). TMSC regeneration, which yields hydrophilic cellulose, causes a dramatic drop in the bubble contact angle. Moreover, a high interfacial tension is required to overcome the friction caused by microscopic (hydrophilic) pinning sites of the three-phase contact line during bubble attachment. A simple theoretical framework is introduced to explain our experimental observations.

The effects of wet-end additions of cationic starches and/or carboxymethyl cellulose (CMC) on paper properties was determined by papermaking trials. The aim of this study was to mitigate the distinctive decrease in strength and stiffness due to unrestrained drying by addition of wet-end additives, while maintaining the extraordinarily high stretch potential of papers after unrestrained drying. Addition of the different polysaccharides increased the tensile index and density of the paper. The largest incgtreases in tensile index and stiffness were seen when combining cationic starches with CMC. With certain combinations of cationic starch and CMC, it was possible to increase the tensile index and stiffness of the paper, while maintaining the high elongation at break after unrestrained drying. To complement the results from the papermaking trials, adsorption of cationic starches and CMC onto cellulose nanofibril model surfaces was studied by QCM-D and SPR techniques. The additives adsorbed onto cellulose surfaces as soft gels, containing a large amount of coupled water. Adsorption of soft and malleable polysaccharide layers in the fiber-fiber joints enhanced the paper properties significantly on a macroscopic level. The softest and most swollen polysaccharide layers resulted in the largest increases in tensile index and stiffness of paper ADDRESSES OF THE AUTHORS:

Tensile tests of individual bleached kraft pulp fibers and paper sheets of industrial origin were conducted in order to investigate the effect of refining and small-scale fiber deformations on the extensibility of fibers and paper. The shape of the tensile curves of most of the fibers was concave upward (i.e., increasing slope) and consisted of two or three phases suggesting that the fibrillar structure and disordered regions in the fiber wall were straightened out during straining. Only a few of the individual BSKP fiber tensile curves were apparently linear. Elongation of the individual kraft fibers varied from 8 to 32% and the average elongation was not increased by high consistency refining. Tensile test results of laboratory sheets made of the same BSKP pulp suggested that the fiber bonding not only governs paper strength, but also is highly relevant for the elongation of fiber networks. The key conclusion related to this investigation and freely dried sheets was that the increased network elongation and strength after refining is mainly due to increased inter-fiber bonding and a higher shrinkage tendency of the fiber network and not due to the increased elongation or strength of individual fibers.