Edge-On (Cellulose II) and Face-On (Cellulose I) Adsorption of Cellulose Nanocrystals at the Oil-Water Interface: A Combined Entropic and Enthalpic Process.

Nanocelluloses can be used to stabilize oil-water surfaces, forming so-called Pickering emulsions. In this work, we compare the organization of native and mercerized cellulose nanocrystals (CNC-I and CNC-II) adsorbed on the surface of hexadecane droplets dispersed in water at different CNC concentrations. Both types of CNCs have an elongated particle morphology and form a layer strongly adsorbed at the interface. However, while the layer thickness formed with CNC-I is independent of the concentration at 7 nm, CNC-II forms a layer ranging from 9 to 14 nm thick with increasing concentration, as determined using small-angle neutron scattering with contrast-matched experiments. Molecular dynamics (MD) simulations showed a preferred interacting crystallographic plane for both crystalline allomorphs that exposes the CH groups (100 and 010) and is therefore considered hydrophobic. Furthermore, this study suggests that whatever the allomorph, the migration of CNCs to the oil-water interface is spontaneous and irreversible and is driven by both enthalpic and entropic processes.

Chitin Pickering Emulsion for Oil Inclusion in Composite Films.

A film containing a stable and well-dispersed hydrophobic phase in a surfactant-free bio-based hydrophilic matrix is proposed. In this study, an aqueous suspension of rod-like chitin nanocrystals (ChiNCs), mixed with paraffin oil, form an oil-in-water Pickering emulsion with a droplet diameter of 3 µm. These emulsions mixed with a 5 wt% starch solution formed homogeneous composite films by solvent casting. Various amounts of emulsion were incorporated, leading to self-supported films with a volume of oil as high as 45 vol%, with less than 1% of ChiNCs. This model inclusion system leads to droplets homogeneously dispersed throughout the composite films, as revealed by microscopy (SEM and CLSM) with mechanical properties controlled by the matrix. Finally, the droplets were easily released from the matrix by enzymatic hydrolysis. This easy-to-implement transparent film proved to be a good candidate when it is desirable to disperse a poor water-soluble component in a hydrophilic edible matrix.

Thermal Superinsulating Materials Made from Nanofibrillated Cellulose-Stabilized Pickering Emulsions.

Thermal superinsulating properties of biobased materials are investigated via the structuration of aerogels through a biphasic system. Highly stable Pickering emulsions are produced using TEMPO-oxidized cellulose nanofibrils (NFC) adsorbed at an oil/water interface. NFCs form an entangled system of clusters of droplets that lead to excellent mechanical properties. The emulsions produced are strong gels that are further used as template to form aerogels. The freeze-dried emulsions result in porous bioaerogels with extremely low densities (0.012-0.030 g/cm3). We describe a hierarchical morphology with three levels of porosity: an alveolar organization of larger macropores due to ice crystals, spherical smaller macropores induced by the emulsion template, and mesoporous domains localized at the pore walls level. The low-density bioaerogels have compression moduli as high as 1.5 MPa and can be deformed up to 60% strain before the structure collapse. NFC aerogels have thermal superinsulating properties; the lowest thermal conductivity obtained is 0.018 W/(m·K). In the context of the development of sustainable materials, we demonstrate that NFC-stabilized Pickering emulsions are excellent templates to produce fully biobased, mechanically strong thermal superinsulating materials.

Design of Pickering Micro- and Nanoemulsions Based on the Structural Characteristics of Nanocelluloses.

The development of biobased materials with lower environmental impact has seen an increased interest these last years. In this area, nanocelluloses have shown a particular interest in research and industries. Cellulose nanocrystals (CNC) and cellulose nanofibrils (CNF) are both known to stabilize oil-water interfaces, forming the so-called Pickering emulsions which are surfactant-free, highly stable emulsions armored by a layer of solid particles. This work describes the emulsion's characteristics and properties according to particle size, shape and surface chemistry in order to produce controlled micro- and nanoemulsions stabilized by nanocelluloses. For this purpose, four nanocelluloses which vary in source, length, width, and surface charge density were used. Isolated droplets were produced by CNCs and interconnected droplets by CNFs that led to distinct drop size (micro- and nanosized), organization of nanoparticles at the surface of the droplets, stability, and mechanical properties through rheological measurements. This work gives a precise description of the resulting emulsions and shows the ability to produce nanosized droplets for CNC and TEMPO oxidized CNF but not for the less fibrillated CNF using HP-homogenizer. Individual noncreaming droplets with average diameters as low as 350 nm were achieved for cotton CNCs and TEMPO oxidized CNFs.

Spray freeze-dried nanofibrillated cellulose aerogels with thermal superinsulating properties.

Nanofibrillated cellulose (NFC) aerogels were prepared by spray freeze-drying (SFD). Their structural, mechanical and thermal insulation properties were compared to those of NFC aerogels prepared by conventional freeze-drying (CFD). The purpose of this investigation is to develop superinsulating bioaerogels by reducing their pore size. Severe reduction of the aerogel pore size and skeleton architecture were observed by SEM, aerogels prepared by SFD method show a fibril skeleton morphology, which defines a mesoporous structure. BET analyses confirm the appearance of a new organization structure with pores of nanometric sizes. As a consequence, the thermal insulation properties were significantly improved for SFD materials compared to CFD aerogel, reaching values of thermal conductivity as low as 0.018W/(mK). Moreover, NFC aerogels have a thermal conductivity below that of air in ambient conditions, making them one of the best cellulose based thermal superinsulating material.