High-Quality Cellulosic Fibers Engineered from Cotton-Elastane Textile Waste.

Even small amounts of elastane in cotton-elastane blended textiles can prevent fiber-to-fiber recycling strategies in textile recycling. Herein, the selective separation of elastane from cotton blends was addressed by the aminolytic degradation of the synthetic component. Polar aprotic solvents were tested as elastane solvents, but side reactions impeded aminolysis with some of them. Aminolysis of elastane succeeded under mild conditions using dimethyl sulfoxide in combination with diethylenetriamine and 1,5-diazabicyclo[4.3.0]non-5-ene as a cleaving agent and catalyst, respectively. The analysis of the nitrogen content in the recovered cellulose fraction demonstrated that 2 h of reaction at 80 °C reduced the elastane content to values lower than 0.08%. The characterization of the recovered cellulose showed that the applied conditions did not affect the macromolecular properties of cellulose and maintained a cellulose I crystal structure. Degraded elastane products were recovered through precipitation with water. Finally, the cellulosic component was turned into new fibers by dry-jet wet spinning with excellent tensile properties.

Understanding the Dynamics of Cellulose Dissolved in an Ionic Liquid Solvent Under Shear and Extensional Flows.

Ionic liquids (ILs) hold great potential as solvents to dissolve, recycle, and regenerate cellulosic fabrics, but the dissolved cellulose material system requires greater study in conditions relevant to fiber spinning processes, especially characterization of nonlinear shear and extensional flows. To address this gap, we aimed to disentangle the effects of the temperature, cellulose concentration, and degree of polymerization (DOP) on the shear and extensional flows of cellulose dissolved in an IL. We have studied the behavior of cellulose from two sources, fabric and filter paper, dissolved in 1-ethyl-3-methylimidazolium acetate ([C2C1Im][OAc]) over a range of temperatures (25 to 80 °C) and concentrations (up to 4%) that cover both semidilute and entangled regimes. The linear viscoelastic (LVE) response was measured using small-amplitude oscillatory shear techniques, and the results were unified by reducing the temperature, concentration, and DOP onto a single master curve using time superposition techniques. The shear rheological data were further fitted to a fractional Maxwell liquid (FML) model and were found to satisfy the Cox-Merz rule within the measurement range. Meanwhile, the material response in the non-LVE (NLVE) regime at large strains and strain rates has special relevance for spinning processes. We quantified the NLVE behavior using steady shear flow tests alongside uniaxial extension using a customized capillary breakup extensional rheometer. The results for both shear and extensional NLVE responses were described by the Rolie-Poly model to account for flow-dependent relaxation times and nonmonotonic viscosity evolution with strain rates in an extensional flow, which primarily arise from complex polymer interactions at high concentrations. The physically interpretable model fitting parameters were further compared to describe differences in material response to different flow types at varying temperatures, concentrations, and DOP. Finally, the fitting parameters from the FML and Rolie-Poly models were connected under the same superposition framework to provide a comprehensive description within the wide measured parameter window for the flow and handling of cellulose in [C2C1Im][OAc] in both linear and nonlinear regimes.

Kinetic analysis of microwave-enhanced cellulose dissolution in ionic solvents.

Cellulose dissolution in mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate with dimethylsulfoxide, [C2C1Im][OAc] + DMSO, have been kinetically compared using conventional heating and microwave heating in a single-mode cavity with a semiconductor generator. Microwaves led to enhancements in the dissolution rate between 21 and 57% under different conditions of temperature and concentration of ionic liquid. Rate enhancement by microwaves prominently occurred at temperatures above 60 °C. Based on an Arrhenius plot and wide-band dielectric measurements we advance the hypothesis that the faster dissolution is caused by ionic motion induced by microwaves in the timescale of formation and breaking of hydrogen bonds between cellulose chains and acetate anions.

Strong Microheterogeneity in Novel Deep Eutectic Solvents.

With the increasing application of template assisted syntheses in deep eutectic solvents and successful application of hydrophobic deep eutectic solvents in extraction processes, where microheterogeneity plays a major role, suggestions for novel deep eutectic solvents which exhibit strong microheterogeneity are desirable. Therefore, classical molecular dynamics simulations were carried out on deep eutectic solvent systems constructed of choline chloride and some of its derivatives mixed with ethylene glycol in a molar composition of 1 : 2 since this is the optimal parent composition. The derivatives consisted of a series of elongated alkyl side chains and elongated alcohol side chains. Of these series only choline chloride ethylene glycol has been investigated experimentally, the other systems are suggested and theoretically investigated as possible target for synthesis. Our domain analysis supported by the clear distinction of polar and nonpolar parts from the electrostatic potentials reveals that strong microheterogeneity within these novel hypothetical deep eutectic solvents exists. Rather stretched than crumbled side chains maximize possible interaction sites for both polar and nonpolar parts which make the suggested compounds valuable objectives for experiments in order to exploit the microheterogeneity in deep eutectic solvents.

Rapid in situ quantification of rheo-optic evolution for cellulose spinning in ionic solvents.

It is critical to monitor the structural evolution of complex fluids for optimal manufacturing performance, including textile spinning. However, in situ measurements in a textile-spinning process suffer from the paucity of non-destructive instruments and interpretations of the measured data. In this work, kinetic and rheo-optic properties of a cellulose/ionic liquid solution are measured simultaneously while fibers are regenerated in aqueous media from a model wet-spinning process via a customized polarized microscope. This system enables to capture key geometrical and structural information of the fiber under spinning at varying draw ratios and residence time, including the flow kinematics extracted from feature tracking, and the flow-induced morphology and birefringent responses. A physics-oriented rheological model is applied to connect the kinematic and structural measurements in a wet-spinning process incorporating both shear and extensional flows. The birefringent responses of fibers under coagulation are compared with an orientation factor incorporated in the constitutive model, from which a superposed structure-optic relationship under varying spinning conditions is identified. Such structural characterizations inferred from the flow dynamics of spinning dopes exhibit strong connections with the mechanical properties of the fully-regenerated fibers, thus enabling to predict the spinning performance in a non-destructive protocol.