Dissolution and regeneration of cellulose in NaOH/thiourea aqueous solution

A novel cellulose solvent, 1.5 M NaOH/0.65 M thiourea aqueous solution, was used to dissolve cotton linters having a molecular weight of 10.1 × 10⁴ to prepare cellulose solution. Regenerated cellulose (RC) films were obtained from the cellulose solution by coagulating with sulfuric acid (H₂SO₄) aqueous solution with a concentration from 2 to 30 wt %. Solubility of cellulose, structure, and mechanical properties of the RC films were examined by infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, ¹³C NMR, and tensile tests. ¹³C NMR analysis indicated that the novel solvent of cellulose is a nonderivative aqueous solution system. The presence of thiourea enhanced significantly the solubility of cellulose in NaOH aqueous solution and reduced the formation of cellulose gel; as a result, thiourea prevented the association between cellulose molecules, leading to the solvation of cellulose. The RC film obtained by coagulating with 5 wt % H₂SO₄ aqueous solution for 5 min exhibited higher mechanical properties than that with other H₂SO₄ concentrations and a homogenous porous structure with a mean pore size of 186 nm for free surface in the wet state. The RC film plasticized with 10% glycerin for 5 min had a tensile strength of 107 MPa and breaking elongation of 10%, and about 1% glycerin in the RC film plays an important role in the enhancement of the mechanical properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1521–1529, 2002     

Effect of sodium hydroxide pre-treatment on the optical and structural properties of lyocell

Lyocell is a type of regenerated cellulose. Fibres spun from cellulose solution in N-methylmorpholine-N-oxide hydrate consist of crystalline cellulose II and amorphous cellulose. Lyocell fabrics were treated with aqueous sodium hydroxide solution (NaOH) to study the influence of alkali on optical and structural properties. It was observed that sodium hydroxide treatment causes the density, orientation and crystallinity of lyocell fibre to decrease with increasing sodium hydroxide concentration, a corresponding decrease in tensile strength is also observed. The greatest change in fibre properties occurs between 3.0 and 5.0 mol dm⁻³ NaOH. This is attributed to the onset of formation of Na-cellulose II at 3.0 mol dm⁻³ NaOH; a fully formed Na-cellulose II structure is expected above 6.8 mol dm⁻³ NaOH. Formation of Na-cellulose II causes plasticization of the lyocell fibres as both inter- and intra-molecular hydrogen bonds are broken by these higher sodium hydroxide concentrations.     

Behavior of cellulose in NaOH/Urea aqueous solution characterized by light scattering and viscometry

Cellulose was dissolved in 6 wt % NaOH/4 wt % urea aqueous solution, which was proven by a ¹³C NMR spectrum to be a direct solvent of cellulose rather than a derivative aqueous solution system. Dilute solution behavior of cellulose in a NaOH/urea aqueous solution system was examined by laser light scattering and viscometry. The Mark–Houwink equation for cellulose in 6 wt % NaOH/4 wt % urea aqueous solution at 25 °C was [η] = 2.45 × 10^?2 weight‐average molecular weight (M_w)^0.815 (mL g^?1) in the M_w region from 3.2 × 10⁴ to 12.9 × 10⁴. The persistence length (q), molar mass per unit contour length (M_L), and characteristic ratio (C_∞) of cellulose in the dilute solution were 6.0 nm, 350 nm^?1, and 20.9, respectively, which agreed with the Yamakawa–Fujii theory of the wormlike chain. The results indicated that the cellulose molecules exist as semiflexible chains in the aqueous solution and were more extended than in cadoxen. This work provided a novel, simple, and nonpollution solvent system that can be used to investigate the dilute solution properties and molecular weight of cellulose. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 347–353, 2004     

Dissolving of cellulose in PEG/NaOH aqueous solution

Here, a new solvent system for cellulose is reported. The solvent is a mixed aqueous solution of 1.0 wt.% poly(ethylene glycol) (PEG) and 9.0 wt.% of NaOH. Cellulose powder was added into the mixture at room temperature at first, and freezing it at −15 °C for 12 h following a thaw of the mixture at room temperature under strong stirring. There formed a clean solution of cellulose, and the optical microscopy was used to record the dissolving process. ¹³C-NMR, FT-IR, XRD, and intrinsic viscosity measurements revealed that there forms a homogeneous solution of cellulose in the new solvent system. The maximum solubility of cellulose with average molecular weight of 1.32 × 10⁵ g mol⁻¹ in the solvent system is 13 wt.%. The cellulose solution in the new solvent system is stable, even for 30 days storage at room temperature.     

Chitin/cellulose blend fibers prepared by wet and dry‐wet spinning

We describe the wet and dry‐wet spinning of multifilament cellulosic composite fibers, namely chitin/cellulose fibers. The direct solution process for the two biopolymers based on an ionic liquid as solvent represents an environmentally friendly and alternative technology to the industrially applied viscose and lyocell process. Both cellulose and chitin possess good solubility in 1‐ethyl‐3‐methylimidazolium propionate ([C₂C₁Im][OPr]) and were spun into multifilament composite fibers. Moreover, for the first time, pure chitin multifilament fibers were obtained by dry‐wet spinning. The effect of chitin addition on the filament properties was investigated and evaluated by microscopic, spectroscopic, and mechanical analyses.     

Regioselective sulfation of trimethylsilyl cellulose using different SO3-complexes

Trimethylsilyl cellulose (DS_Si = 2.9) dissolved in dry tetrahydrofurane was reacted with SO₃-complexes of N,N-dimethylformamide, triethylamine, pyridine and ethyldiisopropylamine. Under the given reaction conditions, i.e. 25 °C, 24 h, 2.2 mol equivalent SO₃-complex, the SO₃ attacks the trimethylsilyl ether groups followed by the formation of sodium sulfate cellulose under sodium hydroxide work-up conditions. The regioselectivity of the sulfation is controlled by the complex partner of SO₃. Cellulose sulfates with preferred O-6 sulfation were obtained using SO₃-N,N-dimethylformamide. In case of SO₃-triethylamine, cellulose-2-sulfates could be prepared with good regioselectivity. Small residual amounts of silicon in the cellulose sulfates (0.1–0.2% w/w) can be quantified using inductively coupled plasma-optical emission spectroscopy (ICP-OES), and can be decreased up to 80% by heating (70 °C, 24 h) the polymers in vacuum.     

Dyeing behaviour of lyocell fabric: effect of NaOH pre-treatment

To understand the effect of alkali pre-treatment on the dyeing of lyocell fabrics, samples are pre-treated with 0.0–7.0 mol dm⁻³ NaOH using a pad-batch process and then dyed with different types of reactive dyes. Exhaustion, fixation, and visual colour strength (K/S values) are measured. It is observed that sodium hydroxide pre-treatment significantly improves the colour yield, exhaustion, and fixation for all dyes used. Highest K/S values are obtained when the fabrics are pre-treated with 2.0–2.5 mol dm⁻³ NaOH. Cross-sectional analysis shows that below this optimum concentration the core fibres in the yarn are not dyed; at optimum concentration all fibres in yarn cross-section are homogeneously dyed. Cross-sectional analysis shows that as the pre-treatment concentration of NaOH increases above 2.5 mol dm⁻³, the fibres change progressively from a circular to angular cross-section, forming a solid unit. The decrease in K/S above the treatment concentration of 2.5 mol dm⁻³, though the %E and %F remains almost constant, is attributed to the distribution of dye over a larger surface area of the outer fibres in the yarn cross section, forcing the K/S at λ_max to decrease. This paper was presented at the 2nd International Cellulose Conference, Tokyo, Japan, 24th October 2007.     

Influence of finishing oil on structure and properties of multi-filament fibers from cellulose dope in NaOH/urea aqueous solution

Cellulose multi-filament fibers have been spun successfully on a pilot plant scale, from a cellulose dope in 7 wt% NaOH/12 wt% urea aqueous solution pre-cooled to −12 °C. Coagulation was accomplished in a bath with 10 wt% H₂SO₄/12 wt% Na₂SO₄ and then 5 wt% H₂SO₄ aqueous solution. By using different finishing oil, including H₂O, 4% glycerol aqueous solution, 2% polyvinyl alcohol (PVA) aqueous solution, 2% polyethylene glycol octyl phenylether (OP) aqueous solution, mobol and 2%glycerol/1%PVA/1%OP aqueous solution (PGO), we prepared six kinds of the cellulose multi-filaments, with tensile strength of 1.7–2.1 cN/dtex. Their structure and properties were investigated with scanning electron microscope (SEM), ¹³C NMR solid state, wide-angle X-ray diffraction (WAXD) and tensile testing. The cellulose fibers treated with PGO possessed higher mechanical properties and better surface structure than others. Interestingly, although the orientation of the cellulose multi-filaments is relatively low, the tensile strength of the single-fiber was similar to that of Lyocell. It was worth noting that the dyeability of the multi-filament fibers was superior to viscose rayon.     

Dilute solution properties of cellulose in LiOH/urea aqueous system

Cellulose was dissolved rapidly in 4.6 wt % LiOH/15 wt % urea aqueous solution and precooled to –10 °C to create a colorless transparent solution. ¹³C‐NMR spectrum proved that it is a direct solvent for cellulose rather than a derivative aqueous solution system. The result from transmission electron microscope showed a good dispersion of the cellulose molecules in the dilute solution at molecular level. Weight‐average molecular weight (M_w), root mean square radius of gyration (〈s²〉_z^1/2), and intrinsic viscosity ([η]) of cellulose in LiOH/urea aqueous solution were examined with laser light scattering and viscometry. The Mark–Houwink equation for cellulose in 4.6 wt % LiOH/15 wt % urea aqueous solution was established to be [η] = 3.72 × 10^?2 M in the M_w region from 2.7 × 10⁴ to 4.12 × 10⁵. The persistence length (q), molar mass per unit contour length (M_L), and characteristic ratio (C_∞) of cellulose in the dilute solution were given as 6.1 nm, 358 nm^?1, and 20.8, respectively. The experimental data of the molecular parameters of cellulose agreed with the Yamakawa–Fujii theory of the worm‐like chain, indicating that the LiOH/urea aqueous solution was a desirable solvent system of cellulose. The results revealed that the cellulose exists as semistiff‐chains in the LiOH/urea aqueous solution. The cellulose solution was stable during measurement and storage stage. This work provided a new colorless, easy‐to‐prepare, and nontoxic solvent system that can be used with facilities to investigate the chain conformation and molecular weight of cellulose. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3093–3101, 2006     

Multi-length scale wear damage mechanisms of ultra-high molecular weight polyethylene nanocomposites

Ultra-high molecular weight polyethylene (UHMWPE) is reinforced with 1–3 wt % sliver (Ag) nanoparticles and zinc oxide (ZnO) micro-rods, and tensile strength as well as wear resistance of the samples is evaluated. Tensile strength was observed to increase with Ag and ZnO reinforcement up to 18% for 1 wt % ZnO and 1 wt % Ag, but in case of 3 wt % ZnO and 3 wt % Ag + 3 wt % ZnO, it decreases marginally by 4% when compared with neat polymer. The sliding wear rate for 1 wt % Ag + 1 wt % ZnO and 3 wt % Ag + 3 wt % ZnO decreases from 9.54 × 10⁻⁵ mm³ (neat polymer) to 7.49 × 10⁻⁵ mm³ and 5.65 × 10⁻⁵mm³, respectively, showing the synergistic effect of Ag and ZnO reinforcement. In scratch testing, minimum damage is obtained in 1 wt % ZnO reinforced polymer. On one hand, where micro-scratch damage is resisted by harder ZnO, whereas on the other hand, pin on disc wear (repeated surface damage) is protected by softer Ag tribolayer. The improved tensile strength (up to 9.7%) and wear resistance with synergistic addition of Ag and ZnO (both 1 wt %) opens a window in the development of bearing surface biomaterials providing improved longevity and durability, thus, may reduce the chances of revision surgery.     

Structure and properties of blend membranes prepared from cellulose and alginate in NaOH/urea aqueous solution

Regenerated cellulose (RC)/alginic acid (AL) blend membranes were satisfactorily prepared from 6 wt % NaOH/4 wt % urea aqueous solution by coagulating with 5 wt % CaCl₂ aqueous solution, and then treated with 3 wt % HCl. Morphology, crystallinity, mechanical properties, and thermal stability of the membranes were investigated by scanning electron microscopy (SEM), IR and UV spectroscopes, X‐ray diffraction, tensile tests, and thermogravimetric analysis (TGA). The RC/AL blends were miscible in all weight ratios of cellulose to alginate. The membranes have homogeneous mesh structures, and the mesh sizes of the blend membranes (200–2000 nm) significantly increased with increasing alginate content. The crystalline state of the AL membrane prepared from 6 wt % NaOH/4 wt % urea aqueous solution was broken completely, and the crystallinity of the blend membranes decreased with an increase of AL. Comparing with AL membranes, the tensile strength and breaking elongation of the blend membranes were obviously improved in dry and wet states. Therefore, the RC/AL blends offer a promising way of alginate as separate and functional materials used in the wet state. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 451–458, 2001     

Evolution of the precipitation kinetics,morphologies, permeation performances,and crystallization behaviors of polyvinylidenefluoride (PVDF) hollow fiber membrane by adding different molecular weight polyvinylpyrrolidone (PVP)

Polyvinylidenefluoride (PVDF) hollow fiber membranes were fabricated by wet spinning (wet/wet) and dry‐jet wet spinning (dry/wet; 3 cm air gap) processes with four types of polyvinylpyrrolidone (PVP) of different molecular weight as additives. Evolution of the precipitation kinetics, morphologies, permeation performances, and crystallization behaviors of the as‐spun PVDF membranes were investigated. The PVDF membranes were well characterized by numerous state‐of‐the‐art analytical techniques: scanning electron microscopy (SEM), X‐ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and attenuated total reflectance fourier Transform Infrared (FTIR‐ATR) and elucidated accompanying with its precipitation kinetics obtained by light transmittance measurements. The precipitation kinetics results confirm that four PVDF/PVP/NMP dopes experience instantaneous demixing mechanism and the precipitation rate decreases as PVP molecular weight increases. Little peaks are found in the precipitation curves of the PVDF dopes containing PVP of low molecular weight. The SEM images indicate that the middle sponge‐like layer sandwiched by double finger‐like layers becomes thinner for the special precipitation behaviors. Visible large pores exist in the internal surfaces of the PVDF membranes spun by both wet/wet and dry/wet spinning processes. The increase in PVP molecular weight restricts the formation of large pores in the internal surfaces of the PVDF membranes for the increase in dope viscosity. The pure water permeability (PWP) of the as‐spun PVDF membranes increases initially and then decreases as PVP molecular weight increases. The largest PWP flux of 316.7 L m^?2 h^?1 bar^?1 is obtained for the PVDF membrane containing PVP K25 by wet/wet spinning process. The rejections for bovine serum albumin (BSA) by the as‐spun PVDF membranes range from 35.4 to 82.9%. It illustrates that typical PVDF ultrafiltration membranes were obtained in this research. The melting temperature(T_m) of the PVDF hollow fiber membranes decreases with the increase in the PVP molecular weight as a whole. IR spectra and XRD patterns verify the exclusive formation of β crystalline phase structure in the as‐spun PVDF membranes. Copyright © 2010 John Wiley & Sons, Ltd.     

Structure and properties of the regenerated cellulose membranes prepared from cellulose carbamate in NaOH/ZnO aqueous solution

Regenerated cellulose (RC) membranes were prepared from cellulose carbamate—NaOH/ZnO aqueous solutions by coagulating with H₂SO₄ solution. Structure, morphology and properties of the membranes were investigated by using scanning electron micrograph (SEM), X-ray diffraction, Fourier transform infrared spectroscopy, flow rate method, and tensile testing. The results from SEM and water permeability revealed that the pore size and water permeability of the membranes in wet state changed drastically as a function of the concentration of H₂SO₄ and coagulation temperature, whereas they hardly changed with the coagulation time. RC membranes coagulated with the relatively dilute H₂SO₄ solution at relatively low temperature exhibited better mechanical properties. This work provided a promising way to prepare cellulose membranes with different pore sizes and good physical properties.     

Sorption of dyes on cellulose II: effect of alkali treatment of fibre and dye structure

Cellulose is a linear 1,4-β-glucan polymer where the units are able to form highly ordered structures, as a result of extensive interaction through intra- and intermolecular hydrogen bonding of the three hydroxyl groups in each cellulose unit. Alkali has a substantial influence on morphological, molecular and supramolecular properties of cellulose II polymer fibres causing changes in crystallinity. Lyocell fibres pre-treated with 0.0, 2.0, and 4.0 mol dm⁻³ aqueous NaOH solution were dyed with hydrolyzed reactive dyes that had different molecular shapes and sizes. Overall exhaustion (q _e), value of K, and −ΔG increased for lyocell samples pre-treated with aqueous NaOH solution in the following order: 2.0 > 4.0 > 0.0 mol dm⁻³ NaOH. The same trends were observed for colour strength (K/S) values of the dyeings. Pre-treatment of lyocell with 2.0 mol dm⁻³ NaOH creates the substrate that achieves the most thermodynamically favourable system for sorption of hydrolyzed reactive dyes, as at this concentration crystallinity decreases (with respect to 0.0 mol dm⁻³ NaOH treated lyocell) to afford higher sorption; however, at higher alkali concentrations the macro-sorbent forms a compacted unit that limits diffusion within the sorbent interior. Molecular size of the sorbate dye has a significant effect on the sorption process: for the largest dye structure the sorption isotherm is most closely correlated to a Langmuir isotherm; as the size of the dye decreases correlation to a Langmuir isotherm is observed, but with good correlation to the Freundlich isotherm; as the size of the dye is decreased further sorption is more typical of a Freundlich isotherm.     

Hybrid electrospun nonwovens from chitosan/cellulose acetate

Co-mixtures of chitosan (CS) and cellulose acetate (CA) were electrospun into fibrous webs from a binary co-solvent containing 70:30 trifluoroacetic acid (TFA): methylene chloride (DCM). Fibrous webs were produced from CS/CA in ratios (wt%) of 20:80, 40:60, 50:50 and 60:40. As determined by SEM analysis, 12% polymer solutions of CS/CA 60:40 produced structures with uniform bead free fibre morphologies with an average fibre diameter of 458 nm. FTIR-spectroscopy confirmed the presence of CS in the as-spun fibres in the form of chitosan-amine trifluoroacetate salts (NH₃ ⁺CF₃COO⁻). Uniform mixing of the CS and CA components was confirmed by DSC analyses. Alkaline neutralisation of the chitosan amine salts was explored as a means of increasing wet stability. The as-spun fibres were found to be relatively unstable in aqueous medium due to the solubility of the chitosan amine salts. Alkaline post-neutralisation was evaluated as means of minimising weight loss and maximising retention of fibrous structure.     

Flame retardant activity of SiO2-coated regenerated cellulose fibres

An alternative route to lower the flammability of viscose fibres is presented. Instead of adding a flame retardant to the viscose dope chemically, we have grown a layer of silica (SiO₂) on the surface of a regenerated cellulose fibre via a sol-gel process. One set of samples was used as-received, while the other was pre-treated in an 18% NaOH solution, giving a rough, etched surface to the fibre. The different surface morphology of both fibre types triggered a different growth of silica layers. On an untreated fibre, silica formed a 300-400 nm thick surface layer containing a high density of cracks and holes. Conversely, on a NaOH pre-treated fibre, the silica layer intruded into fibre interior, adhered more tightly to the fibre structure and formed an almost defect-free, thin (100 nm) layer on the outer fibre surface. This type of silica layer increased the temperature at which the fibre started to decompose by 20 °C. It also hindered significantly the flow of oxygen to the generated volatiles during the thermal decomposition, and increased the temperature of glowing combustion of the residual char; the temperature of the corresponding exothermic peaks increased by ca. 20 °C and 40 °C. In contrast, the thermal effects of silica coatings that grew on an untreated fibre were much smaller.     

A Rapid Process for Producing Cellulose Multi‐Filament Fibers from a NaOH/Thiourea Solvent System

Summary: Cellulose was dissolved rapidly in 9.5 wt.‐% NaOH and 4.5 wt.‐% thiourea aqueous solution pre‐cooled to −5 °C to prepare a transparent solution. Novel cellulose multi‐filament fibers were spun successfully, for the first time, from the cellulose dope on an extended laboratory scale. The results from ¹³C NMR, scanning electron microscopy and wide angle X‐ray diffraction (WAXD) patterns indicated that the fibers exhibited cellulose II character and possessed a circular cross‐section and smooth surface. The tensile strength of the novel fibers reached 1.9–2.2 cN · dtex⁻¹. 2D WAXD and SAXS patterns revealed that, with a drawing progress, the orientation factor increased and mechanical properties were improved.

SEM micrographs of the novel multi‐filament fibers spun from cellulose solution in a NaOH/thiourea aqueous system pre‐cooled to −5 °C on an extended laboratory scale.     

Attenuated total reflectance Fourier-transform Infrared spectroscopy analysis of crystallinity changes in lyocell following continuous treatment with sodium hydroxide

Cellulose is a linear 1,4-β-glucan polymer where the units are able to form highly ordered structures, as a result of extensive interaction through intra- and intermolecular hydrogen bonding of the three hydroxyl groups in each cellulose unit. Alkali has a substantial influence on morphological, molecular and supramolecular properties of cellulose II polymer fibres causing changes in crystallinity. These physical changes were observed herein using ATR-FTIR spectroscopy, following continuous treatment of the cellulose II fabrics with aqueous sodium hydroxide solution under varying condition parameters. Post-treatment, maxima for total crystallinity index and lateral order index, and minima for hydrogen bond intensity, were observed at concentrations of 3.3 and 4.5 mol dm⁻³ NaOH, when treated at 25 °C and 40 °C, respectively. Under these treatment conditions, it is proposed that maximum molecular reorganisation occurs in the amorphous and quasi-crystalline phases of the cellulose II polymer.     

Modification of Tencel with Treatment of Ferric Sodium Tartrate Complex Solution I. Effect of Treatment Condition

Partial dissolution of cellulose by ferric sodium tartrate complex (FeTNa) solution was examined as refining treatment of the organic-solvent spun cellulose fiber (Tencel). The treatment conditions were discussed in terms of solvent strength, temperature, duration of the treatment, and free NaOH concentration by measuring the weight loss, crystallinity, and tenacity of the resultant yarns. For improving fibrillation resistance, the optimized solution of the FeTNa complex was composed of 1–1.5M FeCl₃ with 20% excess sodium tartrate and 1 N free NaOH, and the duration of the treatment was 60 min at 20°C. The loss in weight and tenacity could be maintained as low as 5% and 30–40%, respectively, by the optimized conditions. The resulting yarn showed significantly improved fibrillation resistance.     

Dissolution of Cellulose in Aqueous NaOH Solutions

Dissolution of a number of cellulose samples in aqueous NaOH was investigated with respect to the influence of molecular weight, crystalline form and the degree of crystallinity of the source samples. A procedure for dissolving microcrystalline cellulose was developed and optimized, and then applied to other cellulose samples of different crystalline forms, crystallinity indices and molecular weights. The optimum conditions involved swelling cellulose in 8–9 wt % NaOH and then freezing it into a solid mass by holding it at –20°C. This was followed by thawing the frozen mass at room temperature and diluting with water to 5% NaOH. All samples prepared from microcrystalline cellulose were completely dissolved in the NaOH solution by this procedure. All regenerated celluloses having either cellulose II or an amorphous structure prepared from linter cellulose and kraft pulps were also essentially dissolved in the aqueous NaOH by this process. The original linter cellulose, its mercerized form and cellulose III samples prepared from it had limited solubility values of only 26–37%, when the same procedure was applied. The differences in the solubility of the celluloses investigated have been interpreted in terms of the degrees to which some long-range orders present in solid cellulose samples have been disrupted in the course of pre- treatments.