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Synthetic structural materials of high mechanical performance are typically either of large weight (for example, steels, and alloys) or involve complex manufacturing processes and thus have high cost or cause adverse environmental impact (for example, polymer-based and biomimetic composites). In this perspective, low-cost, abundant and nature-based materials, such as wood, represent particular interest provided they fulfill the requirements for advanced engineering structures and applications, especially when manufactured totally additive-free. Here, we report on a novel all-wood material concept based on delignification, partial surface dissolution using ionic liquid (IL) followed by densification resulting in a high-performance material. A delignification process using sodium chlorite in acetate buffer solution was applied to controllably delignify the entire bulk wooden material while retaining the highly beneficial structural directionality of wood. In a subsequent step, obtained delignified porous wood template was infiltrated with an IL 1-ethyl-3-methylimidazolium acetate, [EMIM]OAc and heat activated at 95 degrees C to partially dissolve the fiber surface. Afterward, treated wood was washed with water to remove IL and hot-pressed to gain a very compact cellulosic material with fused fibers while retaining unidirectional fiber orientation. The obtained cellulose materials were structurally, chemically, and mechanically characterized revealing superior tensile properties compared to native wood. Furthermore, suggested approach allows almost 8-fold tensile strength improvement in the direction perpendicular to fiber orientation, which is otherwise very challenging to achieve.

Ionic liquid solutions of cellulose or dopes can be spun into Lyocell-type textile fibers by dry-jet wet spinning. An extruded dope is drawn over an air gap into water, where the water hydrates the ionic liquid and cellulose is regenerated. Spinnability studies have concentrated on the deformation and failure modes in the air gap and thus the rheology of the unhydrated spinning dope. Herein, a breach in the bath, another failure mode, is discussed. Dopes are prepared from the good spinning solvents NMMO·H2O and [DBNH]OAc and the poor spinning solvents [emim]OAc and [TMGH]OAc. The diffusion constants for water diffusing inwards and for ionic liquid diffusing outwards the emerging filament are measured offline. The resiliences and strengths of cellulose–ionic liquid solutions with different hydration stoichiometries are measured by means of rheometry. By calculating the diffusion dynamics, the resilience distribution of the forming filament is simulated. Gel strength distribution accounts for the tendency of [emim]OAc dopes to undergo a telescope-type breach, whereas the gelatinous solution state of [TMGH]OAc dopes accounts for their poor spinnability.

Wood is not fully soluble in current non-derivatising direct-dissolution solvents, contrary to the many reports in the literature quoting wood 'dissolution' in ionic liquids. Herein, we demonstrate that the application of autohydrolysis, as a green and economical wood pre-treatment method, allows for a massive increase in solubility compared to untreated wood. This is demonstrated by the application of two derivitising methods (phosphitylation and acetylation), followed by NMR analysis, in the cellulose-dissolving ionic liquids 1-allyl-3-methylimidazolium chloride ([amim]Cl) and 1,5-diazabicyclo[4.3.0]non-5-enium acetate ([DBNH][OAc]. In addition, the non-derivitising tetrabutylphosphonium acetate ([P-4444][OAc]) : DMSO-d6 electrolyte also allowed for dissolution of the autohydrolysed wood samples. By combination of different particle sizes and P-factors (autohydrolysis intensity), it has been clearly demonstrated that the solubility of even wood chips can be drastically increased by application of autohydrolysis. The physiochemical factors affecting wood solubility after autohydrolysis are also discussed.

Novel methods for the fractionation of wood, as a major renewable chemical and material feedstock, are in demand. Ionic liquids, such as 1-ethyl-3-methylimidazolium acetate ([emim][OAc]), are promoted as potential media for these processes. However, the chemical stabilities of such ionic liquids are in question as they may have an effect on process sustainability or efficiency. With anion nucleophilicity and basicity being implicated more in ionic liquid reactivity, a rough scale of the relative reactivities for [emim]-based ionic liquids is demonstrated, based upon their TGA decomposition temperatures. These values are compared to the proton affinities for the anions of those ionic liquids, as a crude measure of nucleophilicity or basicity. The implications for the temperature-dependent chemical stability of imidazolium-based ionic liquids are discussed, in regard to their interactions with wood biopolymers. It is observed that for ionic liquids with less diffuse anions (more nucleophilic or basic), such as [emim][OAc], they unfortunately become more unstable. This is exhibited by a decrease in the thermal stability and an increase in the degree of interaction with the biomass, to the point of better solvation and even covalent interactions with dissolved components. The ab initio proton affinities, dipole moments, van der Waals surface area, and volumes, are presented for an extended series of anions, commonly used in ionic liquids.

Correction for 'Cellulose regeneration and spinnability from ionic liquids' by Lauri K. J. Hauru et al., Soft Matter, 2016, 12, 1487-1495.

Composite fibres that contain cellulose and lignin were produced from ionic liquid solutions by dry-jet wet spinning. Eucalyptus dissolving pulp and organosolv/kraft lignin blends in different ratios were dissolved in the ionic liquid 1,5-diazabicyclo[4.3.0]non-5-enium acetate to prepare a spinning dope from which composite fibres were spun successfully. The composite fibres had a high strength with slightly decreasing values for fibres with an increasing share of lignin, which is because of the reduction in crystallinity. The total orientation of composite fibres and SEM images show morphological changes caused by the presence of lignin. The hydrophobic contribution of lignin reduced the vapour adsorption in the fibre. Thermogravimetric analysis curves of the composite fibres reveal the positive effect of the lignin on the carbonisation yield. Finally, the composite fibre was found to be a potential raw material for textile manufacturing and as a precursor for carbon fibre production.

The constant worldwide increase in consumption of goods will also affect the textile market. The demand for cellulosic textile fibers is predicted to increase at such a rate that by 2030 there will be a considerable shortage, estimated at ~15 million tons annually. Currently, man-made cellulosic fibers are produced commercially via the viscose and Lyocell™ processes. Ionic liquids (ILs) have been proposed as alternative solvents to circumvent certain problems associated with these existing processes. We first provide a comprehensive review of the progress in fiber spinning based on ILs over the last decade. A summary of the reports on the preparation of pure cellulosic and composite fibers is complemented by an overview of the rheological characteristics and thermal degradation of cellulose–IL solutions. In the second part, we present a non-imidazolium-based ionic liquid, 1,5-diazabicyclo[4.3.0]non-5-enium acetate, as an excellent solvent for cellulose fiber spinning. The use of moderate process temperatures in this process avoids the otherwise extensive cellulose degradation. The structural and morphological properties of the spun fibers are described, as determined by WAXS, birefringence, and SEM measurements. Mechanical properties are also reported. Further, the suitability of the spun fibers to produce yarns for various textile applications is discussed.

Considerable growth is expected in the production of man-made cellulose textile fibers, which are commercially produced either via derivatization to form cellulose xanthate (viscose) or via direct dissolution in N-methylmorpholine N-oxide (Lyocell). In the study at hand, cellulosic fibers are spun from a solution in the ionic liquid [DBNH] [OAc] into water, resulting in properties equal or better than Lyocell (tensile strength 37 cN tex−1 or 550 MPa). Spinning stability is explored, and the effects of extrusion velocity, draw ratio, spinneret aspect ratio and bath temperature on mechanical properties and orientation are discussed. With the given set-up, tenacities and moduli are improved with higher draw ratios, while elongation at break, the ratio of wet to dry strength, modulus of resilience and birefringence depend little on draw ratio or extrusion velocity, elastic limit not at all. We find the process robust and simple, with stretching to a draw ratio of 5 effecting most improvement, explained by the orientation of amorphous domains along the fiber axis.

Ionic liquid-cosolvent systems have been proposed as selective solvent media for lignocellulosic materials. We present the ionic liquid-aided fractionation of silver birch (Betula pendula) combined with an autohydrolysis pretreatment. Contrary to untreated birchwood meal, autohydrolyzed birchwood meal reveals quantitative dissolution in 1-ethyl-3-methylimidazolium acetate and distinct separation into the individual wood polymers upon regeneration in acetone/water. The process yields two main fractions, a cellulose-rich precipitate with a residual lignin content of 13–15% and another virtually pure lignin fraction. No cellulose yield loss is observed during the ionic liquid processing step. A comprehensive mass balance of the process, including insoluble material, wash waters, and soluble residues, is provided. The product fractions are characterised for their chemical compositions, molar mass distributions and structural characteristics by Klason lignin and sugar analysis, 13C NMR, GPC and WAXS. The study investigates the effects of wood particle size and autohydrolysis intensity on fractionation efficiency and selectivity.

Different acid-base conjugates were made by combining a range of bases and superbases with acetic and propionic acid. Only the combinations that contained superbases were capable of dissolving cellulose. Proton affinities were calculated for the bases. A range, within which cellulose dissolution occurred, when combined with acetic or propionic acid, was defined for further use. This was above a proton affinity value of about 240 kcal mol(-1) at the MP2/6-311+G(d,p)//MP2/ 6-311+G(d,p) ab initio level. Understanding dissolution allowed us to determine that cation acidity contributed considerably to the ability of ionic liquids to dissolve cellulose and not just the basicity of the anion. By XRD analyses of suitable crystals, hydrogen bonding interactions between anion and cation were found to be the dominant interactions in the crystalline state. From determination of viscosities of these conjugates over a temperature range, certain structures were found to have as low a viscosity as 1-ethyl-3-methylimidazolium acetate, which was reflected in their high rate of cellulose dissolution but not necessarily the quantitative solubility of cellulose in those ionic liquids. 1,5-Diazabicyclo[4.3.0]non-5-enium propionate, which is one of the best structures for cellulose dissolution, was then distilled using laboratory equipment to demonstrate its recyclability.

The ionic liquids 1-ethyl-3-methylimidazolium acetate [emim]OAc, N,N,N,N-tetramethylguanidium propionate [TMGH]EtCO(2), and N,N,N,N-tetramethylguanidium acetate [TMGH]OAc, and the traditional cellulose solvent N-methylmorpholine N-oxide NMMO were characterized for their Kamlet-Taft (KT) values at several water contents and temperatures. For the ionic liquids and NMMO, thresholds of regeneration of cellulose solutions by water were determined using nephelometry and rheometry. Regeneration from wet IL was found to be asymmetric compared to dissolution into wet IL. KT parameters were found to remain almost constant at temperatures, between 20-100 °C, even at different water contents. Among the KT parameters, the β value was found to change most drastically, with an almost linear decrease upon addition of water. The ability of the mixtures to dissolve cellulose was best explained by the difference β-α (net basicity), rather than β alone. Regeneration of cellulose starts at thresholds values of approximately β0.8 (β-α0.35) and displayed four phases.

A series of novel ionic liquids comprising two asymmetric phosphate-derived anions, namely dimethyl phosphorothioate and dimethyl phosphoroselenoate, and several imidazolium and non-imidazolium-based cations was prepared via a facile synthetic route. Thermal degradation was studied by dynamic thermogravimetric analysis (TGA) revealing a slightly higher stability of the imidazolium ionic liquids and an overall low thermal stability for the phosphoroselenoate salts. Long-term moisture sorption analysis showed correlation with the polarity of the cation and differences in absorption and desorption kinetics. Finally, a Eucalyptus globulus kraft paper grade pulp was dissolved and subsequently regenerated to assess the degradation of the various molecular weight fractions by size exclusion chromatography. In addition, pre-extracted xylan was subjected to the same dissolution procedure to examine the degradation of low-molecular weight components in more detail.

In this study, we investigate the “chemical welding” of paper with the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc) using a two-step process. First, the IL is transported into the structure of the paper as a water solution. Then, partial dissolution is achieved by activation with heat (80–95 °C), where the water evaporates and the surfaces of the fibres partially dissolve. The activated paper is washed with water to remove IL, and dried to fuse fibre surfaces into each other. The “chemically welded” paper structure has both elevated dry and wet strength. The treatment conditions can be adjusted to produce both paper-like materials and films. The most severe treatment conditions produce films that are fully transparent and their oxygen and grease barrier properties are excellent. As an all-cellulose material, the “chemically welded” paper is fully biodegradable and is a potential alternative to fossil fuel-based plastics.