ABSTRACT
Cotton production is reaching a global limit, leading to a growing demand for bio-based textile fibers produced by other means. Textile fibers based on regenerated cellulose from wood holds great potential, but in order to produce fibers, the components need to be dissolved in suitable solvents. Furthermore, the dissolution process of cellulose is not yet fully understood. In this study, we investigated the dissolution state of microcrystalline cellulose in aqueous NaOH by using primarily scattering methods. Contrary to previous findings, this study indicated that cellulose concentrations of up to 2 wt % are completely molecularly dissolved in 8 wt % NaOH. Scattering data furthermore revealed the presence of semi-flexible cylinders with stiff segments. In order to improve the dissolution capability of NaOH, the effects of different additives have been of interest. In this study, scattering data indicated that the addition of ZnO decreased the formation of aggregates, while the addition of PEG did not improve the dissolution properties significantly, although preliminary NMR data did suggest a weak attraction between PEG and cellulose. Overall, this study sheds further light on the dissolution of cellulose in NaOH and highlights the use of scattering methods to assess solvent quality.
ABSTRACT
Certain ionic liquids are powerful cellulose solvents, but tend to be less effective when small-molecule hydrogen bond donors are present. This is generally attributed to competition with cellulose for hydrogen bonding opportunities to the anion of the ionic liquid. We show that the solubility of cellulose in dimethyl sulfoxide solutions of tetrabutylammonium acetate is less strongly affected by water than by ethanol on a molar basis, contrary to what can be expected based on hydrogen bond stoichiometry. Molecular dynamics simulations indicate that the higher tolerance to water is due to water-cellulose interactions that improves solvation of cellulose and, thereby, marginally favors dissolution. Through Kirkwood-Buff theory we show that water, but not ethanol, improves the solvent quality of DMSO and partly compensates for the loss of acetate-cellulose hydrogen bonds.
ABSTRACT
The inherent flammability of cellulosic fibers limits their use in some advanced applications. This work demonstrates for the first time the production of flame-retardant macroscopic fibers from wood-derived cellulose nanofibrils (CNF) and silica nanoparticles (SNP). The fibers are made by extrusion of aqueous suspensions of anionic CNF into a coagulation bath of cationic SNP at an acidic pH. As a result, the fibers with a CNF core and a SNP thin shell are produced through interfacial complexation. Silica-modified nanocellulose fibers with a diameter of ca. 15 µm, a titer of ca. 3 dtex and a tenacity of ca. 13 cN tex-1 are shown. The flame retardancy of the fibers is demonstrated, which is attributed to the capacity of SNP to promote char forming and heat insulation on the fiber surface.
ABSTRACT
Structured xylan-based hydrogels, reinforced with cellulose nanocrystals (CNCs), have successfully been prepared from water suspensions by cross-linking during freeze-casting. In order to induce cross-linking during the solidification/sublimation operation, xylan was first oxidized using sodium periodate to introduce dialdehydes. The oxidized xylan was then mixed with CNCs after which the suspension was frozen unidirectionally in order to control the ice crystal formation and by that the pore morphology of the material. Finally the ice crystal templates were removed by freeze-drying. During the freeze-casting process hemiacetal bonds are formed between the aldehyde groups and hydroxyl groups, either on other xylan molecules or on CNCs, which cross-links the system. The proposed cross-linking reaction was confirmed by using cross-polarization magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR) spectroscopy. The pore morphology of the obtained materials was analyzed by scanning electron microscopy (SEM). The materials were also tested for compressive strength properties, both in dry and water swollen state. All together this study describes a novel combined freeze-casting/cross-linking process which enables fabrication of nanoreinforced biopolymer-based hydrogels with controlled porosity and 3-D architecture.
Subject(s)
Cellulose/chemistry , Hydrogels/chemistry , Ice , Nanoparticles/chemistry , Xylans/chemistry , Freezing , Mechanical Phenomena , PorosityABSTRACT
This study presents results that show that the fine structure of arabinoxylan affects its interaction with cellulosic surfaces, an important understanding when designing and evaluating properties of xylan-cellulose-based materials. Arabinoxylan samples, with well-defined structures, were prepared from a wheat flour arabinoxylan with targeted enzymatic hydrolysis. Turbidity measurements and analyses using NMR diffusometry showed that the solubility and the hydrodynamic properties of arabinoxylan are determined not only by the degree of substitution but also by the substitution pattern. On the basis of results obtained from adsorption experiments on microcrystalline cellulose particles and on cellulosic model surfaces investigated with quartz crystal microbalance with dissipation monitoring, it was also found that arabinoxylan adsorbs irreversibly on cellulosic surfaces and that the adsorption characteristics, as well as the properties of the adsorbed layer, are controlled by the fine structure of the xylan molecule.
