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Following the circular bioeconomy concept, this work studies the potential of an industrial wastepaper residue as an alternative raw material for dissolving pulp‐grade production. Prehydrolysis‐kraft cooking (PHK), elemental chlorine‐free (ECF) bleaching, and acid‐washing treatments were applied to achieve that aim. Considering the high lignin and hemicellulose content of the raw material, it was submitted to PHK pulping to enhance its cellulose content by removing those components. This processing resulted in a remarkable increase of 84 % in pulp Fock reactivity (from 45.6 % to 84.1 %). The dissolution extension and time in solvent systems LiCl/DMAc and NMMO/H2O were discussed regarding the pulp physicochemical properties. The dissolving pulp produced under this work showed great potential as raw material for textile applications, particularly highlighting the innovative process developed to improve its solubility. [ABSTRACT FROM AUTHOR]

The pulp and paper industry is the largest industrial sector that converts wood‐based materials into fibre‐related products. It is common for pulp fibre plugs to develop within pipelines and equipment causing operational downtime, which ultimately requires the use of costly procedures for plug removal. In this study, a laboratory‐scale set‐up was developed to measure the breakup pressure of pre‐formed plugs to indicate the plug (fibre network) strength. A cupriethylenediamine (CED) solution was investigated with regards to its ability to decrease the plug strength. When the concentration of the CED solution is 0.1 M or lower, the plug breakup pressure increases due to fibre swelling. Conversely, when the CED concentration is 0.2 M or greater, the plug breakup pressure decreases significantly due to partial fibre dissolution. Cupriethylenediamine (CED), with its concentration of higher than 0.2 M, is effective in the removal of pulpfibre plugs. [ABSTRACT FROM AUTHOR]

In this research, we developed an efficient method for the fabrication of amorphous cellulosegraphene oxide composite. Amorphous cellulose (AC) and amorphous cellulose-graphene oxide (ACGO) beads were fabricated via H2SO4 gelatinization using eucalyptus paper as a raw material. The cellulose gel was droplet-extruded into deionized (DI) water and transformed to a solid bead via the water-regeneration process. Small AC and ACGO quasi-sphere beads with diameter of 2 mm were obtained. The semicrystalline eucalyptus cellulose was transformed into amorphous cellulose after the regeneration process. The entrapment of graphene oxide (GO) by the amorphous cellulose was confirmed by scanning electron microscopy (SEM), fourier-transform infrared (FTIR) and raman spectroscopies (Raman). The gelatinization and regeneration processes offered a simple and efficient methodology for AC and ACGO bead fabrication. [ABSTRACT FROM AUTHOR]

This paper reviews the preparation of hydrogel based on cellulose and its derivatives. Cellulose is the most abundant natural organic polymer on earth. To date, the exploitation of cellulose has been studied in various applications. However, cellulose has low solubility in water and most organic solvents. Thus, specific solvent systems such as NaOH/urea, NaOH/thiourea, lithium chloride, and ionic liquids need to be employed to vary cellulose application. The hydrogel is a 3D network structure that can retain a tremendous amount of water and highly dependent on the crosslinking property. It is important to use a compatible technique for a specific purpose. The paper discusses the materials and crosslinking techniques via chemical, physical, and polymerization, to produce hydrogels from dissolved cellulose and its derivatives.

Cellulose is a biopolymer with numerous advantages that make it an ecological, economical, and high-performing choice for various applications. To fully exploit the potential of cellulose, it is often necessary to dissolve it, which poses a current challenge. The aqueous zinc oxide/sodium hydroxide (ZnO/NaOH/Water) system is a preferred solvent for its rapid dissolution, non-toxicity, low cost, and environmentally friendly nature. In this context, the behavior of cellulose chains in the aqueous solution of ZnO/NaOH and the impact of temperature on the solubility of this polymer were examined through a molecular dynamics simulation. The analysis of the root means square deviation (RMSD), interaction energy, hydrogen bond curves, and radial distribution function revealed that cellulose is insoluble in the ZnO/NaOH solvent at room temperature (T = 298 K). Decreasing the temperature in the range of 273 K to 268 K led to a geometric deformation of cellulose chains, accompanied by a decrease in the number of interchain hydrogen bonds over the simulation time, thus confirming the solubility of cellulose in this system between T = 273 K and T = 268 K. [ABSTRACT FROM AUTHOR]

Cellulose is the most abundant renewable resource which has found a diverse range of applications. Cellulose dissolution is a significant property for manufacturing man-made cellulosic fiber through viscose process. Crystalline microfibrillar structure and relatively high ordered packing of polymeric chains contribute to recalcitrance and poor reactivity of cellulose. One of the most common methods to improve cellulose dissolution is cellulase treatment. Herein, cellulase treatment at different doses was studied to explore the correlation of cellulose dissolution with crystallinity. Pulp showed improvement in Fock reactivity and other properties related to viscose application. But contrary to previous studies, cellulose crystallinity as determined by XRD and FTIR did not correlate with Fock reactivity at a higher dose of cellulase. The results indicated some complex mechanism to be involved between the cellulose dissolution and crystallinity than a simple negative correlation. Cellulase treatment at 150 HCU/g resulted in the upgraded pulp suitable for viscose application. [ABSTRACT FROM AUTHOR]

Dissolving pulps are used to manufacture various cellulose derived products through cellulose dissolution. Solubility of cellulose pulp has been claimed to be strongly dependent on the porosity development, the degree of polymerisation and the pulp viscosity. The removal of external cell walls has been proposed to have a key role in the pulp solubility. In this paper, the effect of the outermost surface layers on the solubility of a dissolving grade pulp was studied. Furthermore the effect of mechanical peeling and combined mechanical and enzymatic treatment on pulp solubility was compared. Based on the results combined mechanical and enzymatic treatment efficiently opens up the fibre structure and has a clear positive effect on the solubility of dissolving pulp. It seems that long fibre fraction is less accessible to solvent chemicals than the other pulp fractions. Mechanical peeling of outer fibre layers does not improve fibre dissolution to NaOH/ZnO. Thus, it seems that peeling alone is not a sufficient pre-treatment prior to dissolution. The results also revealed that the peeling treatment does not enhance the effects of enzymes as the studied mechanical treatment does. [ABSTRACT FROM AUTHOR]

Dissolving grade pulps are used as raw material for manufacture of regenerated cellulose fibres and their use is constantly growing. Despite intensive research, there is still a need to develop cellulose dissolution-regeneration processes that would be economically viable, fulfil the pre-conditions of sustainability and would be able to meet the strict product quality requirements. The basis for creation of such a process is in deep understanding of the biomass structure and factors affecting the cellulose modification and dissolution. In this paper, the effects of the mechanical and enzymatic pre-treatments on the pore structure and alkaline solubility of dissolving grade pulp are discussed. Formation of micro- and macropores in the pulp fibres during mechanical shredding was found to correlate with the susceptibility of the fibres to enzymatic hydrolysis. The fibre porosity development during the processing was studied by a modified solute exclusion approach, which revealed differences between the effect of mild enzyme or acid hydrolysis on the pore structure of fibres. The dissolution of the modified fibres in NaOH/ZnO was evaluated and found to correlate with overall pore volume and accessible surface area analysed by the modified solute exclusion method. [ABSTRACT FROM AUTHOR]

Abstract This paper reports on the effect of improved porous characteristics of cellulose on its solubility in DMAc/LiCl. The use of freeze-drying (FD) treatment led to higher surface area and void fraction of volume for high-molecular-weight (HMW) cotton cellulose (DP~5000). Improvement in porous characteristics of cellulose did not change the chemical and crystalline structures of cellulose, as compared to hot-drying (HD) treatment. However, significant improvement in the dissolution of FD-HMW cellulose in DMAc/LiCl was observed under relatively low temperature (80 °C). The relationship between the solubility and the porous characteristics of cellulose was discussed using Stokes-Einstein Equation and effective diffusion coefficient equation. It was concluded that the increase in the diffusion coefficient of the solvent and the improvement in the porous characteristics of cellulose played key roles to enhance the diffusion rate of the solvent through the cellulose molecular network. [ABSTRACT FROM AUTHOR]

The direct dissolution of cellulose offers a pathway to production of regenerated textile fibers. However, fiber production in the Lyocell process requires a high recyclability of the solvent. Some compounds from the class of ionic liquids (IL) may have higher dissolving capacities together with a higher thermal stability than the conventional N‐methylmorpholin‐N‐oxide (NMMO), which makes them more valuable in an industrial process. A promising representative of such an advanced solvent for Lyocell process, 7‐Methyl‐1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene acetate ([MTBDH][AcO]) was investigated in this study. A series of 21 consecutive cellulose dissolving and spinning trials via dry‐jet wet spinning was conducted with the same batch of solvent. In the spinning trials, the cellulose was regenerated into water consisting spinning bath. The solvent was recycled by removing the water from the spin bath via distillation in reduced pressure. Due these drastic changes in the water content of the IL during the whole process, the hydrolytic stability is an important aspect to assess the recyclability of the IL and viability of the whole process. The chemical composition of the IL was monitored by means of NMR spectroscopy. Although there was an increase of hydrolysis level of the solvent, cellulose could be dissolved constantly and spun to obtain staple fibers. The spinning behavior deteriorated slowly along the additional cycles, along with a measured increase in zero‐shear viscosity of the spinning dope. Nevertheless, the physical properties of the obtained fibers were barely influenced by the changes of the ionic liquid. [ABSTRACT FROM AUTHOR]

Cotton fibre dissolution has been investigated using ionic liquids having a functionalized imidazolium cation. Two ionic liquids, 3-butyric acid-1-methyl imidazolium chloride [HOOC4MIM][Cl] (IL-acid) and 3-N,N-diethyl-butyramide-1-methyl imidazolium chloride [(Et)2NOC4MIM][Cl] (IL-amide), were synthesized by passing both through the intermediate 1-(3-Ethoxycarbonyl-propyl)-1-methyl imidazolium bromide. Their chemical structures were then confirmed using NMR and FTIR. 5 wt% cotton fibers have been completely dissolved in both synthesized ionic liquids in 3 h at room temperature. The regenerated cellulose with water, as an anti-solvent, was characterized using XRD, FTIR, TGA, and degree of polymerization (DP) methods. The FTIR and XRD results showed that no other chemical reaction occurred by both synthesized ILs other than the breakage of hydrogen bonds during the dissolution and regeneration processes. In addition, the regenerated cellulose had a reduced crystallinity and a structural transition from cellulose I to cellulose II. TGA results confirmed the low crystallinity of regenerated cellulose by demonstrating its low thermal stability compared to cotton fibers. Furthermore, the DP of cotton fibers was reduced from 805 ± 15 to 737 ± 12 and 765 ± 10 after regeneration from IL-acid and IL-amide, respectively, confirming partial cellulose network degradation. The IL-acid has an oily appearance and a viscosity (44 ± 5 mPa.s at 25 °C), allowing it to dissolve 14.5 wt% cotton fibers at 25 °C, IL-amide can only dissolve 5 wt% in 5 h at 25 °C due to its viscous nature. These results imply that the produced ionic liquids can be considered as competitive solvents for dissolving cellulose. [ABSTRACT FROM AUTHOR]

Cellulose is a readily available, renewable, and natural biomaterial that has the potential to replace synthetic fibres. However, their processing to shaped materials such as fibre or film is still complex and restricted due to its insolubility in most conventional solvents. Herein, we present the synthesis and cellulose dissolution characteristics of a new class of recyclable zwitterions composed of tethered N-oxyethylene substituted imidazolium cation and alkyl carboxylate anion. Investigations on cellulose dissolution showed that increasing the alkyl chain length of carboxylate anion and introduction of oxyethylene unit on imidazolium ring led to better cellulose dissolution ability, and up to 12% (w/w) cellulose could be dissolved in aqueous zwitterions at 105 °C. The thermal behavior of zwitterions and their cellulose solutions was characterized by TGA and found to be more stable than the NMMO and Lyocell solutions. Rheological characterization of cellulose solutions revealed viscoelastic behavior and zero shear viscosity of 6–12% (w/w) cellulose solution in hexanoate containing aqueous zwitterion was 555 to 5900 Pa.s at 120 °C. The characteristics of cellulose solution indicate its potential for processing to cellulose fibre by extrusion through a tiny spinneret. Physico-chemical analysis of regenerated cellulose indicates that zwitterions cause no adverse effect on cellulose structure and morphology during dissolution. The zwitterions are recovered after the cellulose regeneration process, and the recovery was found to be 99.6% after purification using the ion-exchange method. [ABSTRACT FROM AUTHOR]

Large amounts of textile waste are generated every year and disposed of through landfill or incineration, leading to numerous environmental and social issues. In this work, the dissolution of three typical waste cotton fabrics (t‐shirts, bed sheets and jeans) in NaOH/urea aqueous solution, H2SO4 aqueous solution, and LiCl/DMAc solution was investigated. Compared to different types of cotton fabrics, the effects of three solvents on the dissolution of fabrics were more obvious, leading to the significant changes in the structure and properties of regenerated cellulose films. Cotton fabrics (about 2%–5%) were rapidly dissolved (8 min) in H2SO4 and NaOH/urea solvents after acid pretreatment, while the dissolution in LiCl/DMAc solvent did not need any pretreatment, but a lower cellulose concentration (1%), higher dissolution temperature (80°C), and longer dissolution time (24 h) were required. The films produced from bed sheets in NaOH/urea solution exhibited the highest tensile strength, thermal stability, and water vapor barrier property. It was because of the stronger cellulose chain entanglement and hydrogen bonds induced by the higher cellulose concentration in NaOH/urea solution. Therefore, this work proves the feasibility to recycle waste cotton fabrics into biodegradable cellulose films, which can be potentially used in various food and agricultural applications. [ABSTRACT FROM AUTHOR]

The dissolution of cellulose is a critical step for the efficient utilization of this renewable resource as a starting material for high value-added chemical and biofuel production. In this study, three aprotic solvents were chosen to couple with three ionic liquids (ILs) as binary solvent systems for cellulose dissolution. The percentage of dissolved cellulose of each IL/co-solvent was evaluated and the crystallinity index (CrI) of the undissolved cellulose residues after dissolution were investigated by XRD. Dimethyl sulfoxide exhibited the most effective synergistic interaction with the ILs among three co-solvents for cellulose dissolution. In general, the higher percentage of dissolved cellulose of the IL/co-solvent binary system, the lower CrI value of the undissolved cellulose residue after dissolution. In addition, the dissolution of cellulosic materials with different crystallinity and degree of polymerization indicated that the crystallinity of a cellulosic material played a more dominating role than degree of polymerization in its dissolution process. The hydrogen bond basicity (β value) of selected IL/co-solvent binary system was also calculated. The results showed that the β value of a binary IL/co-solvent system exhibited different trend than neat IL in terms of the cellulose dissolution ability, which should be attributed to the co-solvent effect. [ABSTRACT FROM AUTHOR]

Cellulose, as the most abundant sustainable resource on earth, can be chemically transformed into a variety of biodegradable materials, which have been proposed as the ideal substitutes for plastic products. The first challenge for the fabrication of cellulose-based functional materials is the successful dissolution of cellulose by solvents. However, most existing cellulose solvents have environmental, economic, and other drawbacks that limit their further industrial applications. Research on developing novel solvent systems with "greener" and "cheaper" properties is needed to meet the challenges. [ABSTRACT FROM AUTHOR]

Lyocell fibers have received increased attention during the recent years. This is due to their high potential to satisfy the rising market demand for cellulose-based textiles in a sustainable way. Typically, this technology adopts a dry-jet wet spinning process, which offers regenerated cellulose fibers of excellent mechanical properties. Compared to the widely exploited viscose process, the lyocell technology fosters an eco-friendly process employing green direct solvents that can be fully recovered with low environmental impact. N-methylmorpholine N-oxide (NMMO) is a widely known direct solvent that has proven its success in commercializing the lyocell process. Its regenerated cellulose fibers exhibit higher tenacities and chain orientation compared to viscose fibers. Recently, protic superbase-based ionic liquids (ILs) have also been found to be suitable solvents for lyocell-type fiber spinning. Similar to NMMO, fibers of high mechanical properties can be spun from the cellulose-IL solutions at lower spinning temperatures. In this article, we study the different aspects of producing regenerated cellulose fibers using NMMO and relevant superbase-based ILs. The selected ILs are 1,5-diazabicyclo[4.3.0]non-5-ene-1-ium acetate ([DBNH]OAc), 7-methyl-1,5,7-triazabicyclo[4.4.0] dec-5-enium acetate ([mTBDH]OAc) and 1,8-diazabicyclo[5.4.0]undec-7-enium acetate ([DBUH]OAc). All ILs were used to dissolve a 13 wt% (PHK) cellulose pulp. The study covers the fiber spinning process, including the rheological characterization of the various cellulose solutions. Moreover, we discuss the properties of the produced fibers such as mechanical performance, macromolecular properties and morphology. [ABSTRACT FROM AUTHOR]

Cotton fibres of high Micronaire values are known to have inferior spinning performance. Either reduction of fibres' fineness or increase in tensile strength is generally expected to improve the spinnability of fibres. In this piece of research, the effects of alkali treatment at lower concentrations (0.75–2.25M) and higher temperatures (70–100 °C) on the cross-section of cotton fibre and on the tensile strength have been investigated. Observations were made using scanning electron microscopy (SEM) and single fibre tensile strength testing. It was found that the roundness of the fibre cross section was improved and the tensile strength of the fibres also increased after treatment with alkali at lower concentration (0.75 M) and relatively lower temperature (70 °C). It is proposed that such changes occurred due to possible cellulose dissolution/transformations. It was thus concluded that the alkali treatment of cotton fibres at lower concentrations (0.75 M) and 70 °C for a shorter period of time (45 mins) could lead to improvement in tensile strength and roundness of fibre cross-section, thereby improving micronaire. [ABSTRACT FROM AUTHOR]

In this work, several kinds of quaternary ammonium-based room-temperature ionic liquids (QA RTILs) are synthesized by alkylation and ion-exchange reactions for the rapid dissolution of cellulose. The applications of cellulose materials have been limited due to their poor solubility in conventional organic solvents, because of a high degree of structural regularity and a large number of hydrogen bonds. The prepared ionic liquids were identified by nuclear magnetic resonance, elemental analysis, and liquid chromatography-mass spectrometry. The results indicated that N,N,N-triethylhexan-1-aminium acetate (N6222OAc), tetrahexylammonium acetate (N6666OAc), and N,N,N,N′,N′,N′-hexaethyldecane-1,10-diaminium acetate (C10(N222OAc)2) exhibited good cellulose-dissolution without any pretreatment. The regenerated cellulose films with a low degree of crystallization of the cellulose II phase were also prepared easily in this process using N6222OAc due to its polar and small cation. These QA RTILs can be used as non-derivatizing solvents for cellulose and can also be easily recycled because of their thermostable and nonvolatile properties. [ABSTRACT FROM AUTHOR]

It is essential for textile manufacturing industries to invent new resources, composites and industrial technologies, which are environmentally acceptable and can fulfill the consumer necessities. Therefore, in the recent years, large number of research is focused on optimizing and modifying the fibre manufacturing processes. The recent advances in technology have allowed modifying these processes through various techniques and novel raw materials/additives to manufacture the fibres. Among the various fibre regeneration processes, the NMMO based lyocell process has numerous advantages over conventional rayon fibres and it has great potential to fulfil the environmental and customer requirements. The present review delivers a complete account of all the six types of cellulose regeneration processes namely viscose, cellulose acetate, cuprammonium, LiCl/DMAc as well as lyocell processes based on ionic liquid or NMMO. Additionally, the review considers latest developments with process technology, cellulose swelling and dissolution phenomena, factors affecting the lyocell process and future prospects of the lyocell fibres. [ABSTRACT FROM AUTHOR]

Abstract: The transesterification reaction between cellulose and vinyl esters is regarded as a clean and facile strategy for the tunable synthesis of cellulose esters. In this study, a series of cellulose esters with degrees of substitution from 0.58 to 3.0 have been prepared successfully under mild conditions without adding any external catalysts when cellulose was dissolved in the 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)/DMSO/CO2 solvent system and then followed by adding equimolar amounts of long chain fatty, aromatic, branched and steric vinyl esters. The optimization study of different reaction parameters like reaction time, temperature and amounts of substrates demonstrates that the reaction can proceed smoothly even at room temperature. This is evidenced by a cellulose benzoate with a DS of 2.6 obtained when the reaction is performed at 25 °C in 4 h. The as-prepared cellulose esters structure has been confirmed by 1H NMR, 13C NMR and FTIR, and material thermal properties were evaluated by DSC and TGA for an in-depth understanding the relationship between the cellulose esters structure and properties. It is believed that the DBU not only acts as a reagent for the CO2-derivative dissolution of cellulose in DMSO, but also acts as an in situ organocatalyst for the subsequent transesterification reaction.Graphical abstract: Cellulose esters have been prepared successfully at low temperature using long chain fatty acids, aromatic, branched and steric vinyl esters as acyl donors in the DMSO/DBU/CO2 solvents system, and the DBU not only acts as reagents for the CO2-derivative dissolution of cellulose in DMSO, acts as an organocatalyst for the subsequent derivatisation. [ABSTRACT FROM AUTHOR]

High cellulose solubility is an essential to successful production of regenerated cellulose, from which hydrogels can be produced. Additionally, some pretreatment usually facilitates cellulose solubility. Bleached cellulose pulp from kenaf core (BK), consisting of lignin (0.3%), hemicellulose (5.2%) and ash (0%), was treated with an electron beam irradiation (EBI) at 10, 30, 50 and 70 kGy. The BK and irradiated bleached cellulose pulp (IK) were then dissolved in either sodium hydroxide/urea or lithium hydroxide/urea solvents which subsequently crosslinked with epichlorohydrin (ECH) solution to stabilize the formation of regenerated cellulose hydrogels. The amount of α-cellulose component in IK samples decreased as much as 38% and caused the viscosity average molecular weight (Mv) and degree of polymerization of IK samples to be reduced significantly by 84 and 87%, respectively. This resulted in an increase in cellulose solubility (up to 30%) for the IK samples in both solvent systems. However, this treatment resulted in a reduction in the overall cellulose fibre strength. X-ray diffraction of the hydrogels showed a transformation from cellulose I to amorphous cellulose. These hydrogels exhibited a higher degree of swelling, transparency and porosity compared to hydrogels prepared from non-irradiated pulp. [ABSTRACT FROM AUTHOR]

Green synthesis of room temperature ionic liquids (RTILs), are presented as friendly and challenging solvents for the effective dissolution of oil palm-lignocellulosic biomass. A series of Bronsted acidic-ionic liquids were prepared by the direct neutralization of diethyl dimethyl ammonium hydroxide with several (economical and environmental friendly) Bronsted acids as RTILs. The structural and physicochemical characterization was performed by applying various techniques as Fourier transform infrared (FT-IR), nuclear magnetic resonance (NMR), thermo gravimetric analysis (TGA), differential scanning calorimetry (DSC), zeta-nanosizer and dynamic light scattering (DLS) respectively, to state the effect of anion on the extended cellulose dissolution capabilities of the synthesized RTILs under mild conditions. As a polysaccharide solvent, diethyl dimethyl ammonium phosphate (A1P) showed the extreme capability to extract 65 % of cellulose from biomass without any pretreatment for 30 min. The present study could be a significant step toward the synthesis of efficient RTILs and generating upgraded cellulose for Hi-tech engineered composites and energy concerns. [ABSTRACT FROM AUTHOR]

Rheological properties of microcrystalline and kraft cellulose dissolved in lithium chloride/ N, N-dimethylacetamide solutions were characterized using an advanced rheometer. First, the effect of LiCl on the viscosity of DMAc (8%) at various temperatures was evaluated. Then the shear rheology of cellulose/DMAc/LiCl solutions was studied in a range of concentrations (0.25-2 wt%) and temperatures (25-80 °C). The solutions of kraft cellulose/LiCl/DMAc behave as non-Newtonian liquids and its viscosity is dependent on the shear rate. The Newtonian flow was recorded for the microcrystalline cellulose/LiCl/DMAc solutions. The viscosity values of these solutions were analyzed in detail for viscosity-concentration and viscosity-temperature. The viscosity of the solutions increased with the increase in solution concentration. The heightening of the solution temperature reduced the viscosity of the solutions. The activation energy of the dissolved kraft cellulose was calculated from the Arrhenius approximation within a concentration range of 0.25-2 wt%, and then compared with that of the microcrystalline cellulose. [ABSTRACT FROM AUTHOR]

Cellulose is the most abundant natural polymer on the earth, and effective solvents are essential for its wide application. Among various solvents such as alkali/urea or ionic liquids, cations all play a very important role on the cellulose dissolution. In this work, the influence of cation on the cellulose dissolution in alkali/urea via a cooling process was investigated with a combination of MD simulation and experiments, including differential scanning calorimetry (DSC) and NMR diffusometry (PFG-SE NMR). The results of DSC proved that the dissolution of cellulose in both solvents was a process within a temperature range, starting at above 0 °C and completing at low temperature (−5 °C for LiOH/urea and −20 °C for NaOH/urea), indicating the necessity of low temperature for the cellulose dissolution. Molecular dynamic (MD) simulation suggested that the electrostatic force between OH and cellulose dominated the inter-molecular interactions. In our findings, Li could penetrate closer to cellulose, and displayed stronger electrostatic interaction with the biomacromolecule than Na, thus possessed a greater 'stabilizing' effect on the OH/cellulose interaction. PFG-SE NMR demonstrated a more significant binding fraction of Li than Na to cellulose, which was consistent with MD. These results indicated that the direct interactions existed between the cations and cellulose, and Li exhibited stronger interaction with cellulose, leading to stronger dissolving power. [ABSTRACT FROM AUTHOR]

Dissolution of cellulose from various sources (microcrystalline cellulose and different dissolving grade pulp fibers) is investigated in solvent systems based on triethyl( n-octyl)ammonium chloride (N2228Cl). Clear cellulose solutions are obtained with N2228Cl in a variety of solvents, e.g., dimethyl sulfoxide, N,N-dimethylacetamide, and acetone. It is possible to prepare clear cellulose solutions from pulp fibers with concentrations up to 15 wt%. However, it is found that the cellulose is degraded, especially when neat (i.e., molten) N2228Cl is used as a solvent. The present work includes comprehensive rheological characterization of the cellulose solutions, both with shear and extensional rheology. In most cases, the viscosity values are low (complex viscosities below 100 Pa s for 5-10 wt% dissolved cellulose), and the solutions show more Newtonian than viscoelastic behavior. [ABSTRACT FROM AUTHOR]

We have found that the dissolution of cellulose in the binary mixed solvent tetrabutylammonium acetate/dimethyl sulfoxide follows a previously overlooked near-stoichiometric relationship such that one dissolved acetate ion is able to dissolve an amount of cellulose corresponding to about one glucose residue. The structure and dynamics of the resulting cellulose solutions were investigated using small-angle X-ray scattering (SAXS) and nuclear magnetic resonance techniques as well as molecular dynamics simulation. This yielded a detailed picture of the dissolution mechanism in which acetate ions form hydrogen bonds to cellulose and causes a diffuse solvation sheath of bulky tetrabutylammonium counterions to form. In turn, this leads to a steric repulsion that helps to keep the cellulose chains apart. Structural similarities to previously investigated cellulose solutions in aqueous tetrabutylammonium hydroxide were revealed by SAXS measurement. To what extent this corresponds to similarities in dissolution mechanism is discussed. [ABSTRACT FROM AUTHOR]

The amphiphilicity of solvent systems is realized for adjusting the dissolution of natural cellulose by making use of tetra-butylammonium hydroxide (TBAH) as an example. TBAH aqueous solution is found to have an obvious effect on adjusting its amphiphilicity, along with a flexible concentration ranging from 40 to 60 wt% for dissolving cellulose. With a suitable amphiphilic property, cellulose can be dissolved by a TBAH aqueous system . The experimental results demonstrate that with the introduction of urea (more than 0.2:1, w:v) into a TBAH aqueous system, the dissolution process of cellulose can be dramatically promoted, leading to a transparent solution of cellulose. Herein, a complex solvent of TBAH/urea has been proposed for mild and effective dissolution of cellulose under ambient conditions. In the TBAH/urea complex solvent, the structure of the hybrid hydrate of TBAH and urea formed. Urea served as a hydrophobic contributor adjusting the amphiphilicity of the solvent system, allowing interfacial resistance between the amphiphilic crystal surfaces of the natural cellulose and solvent to be reduced. After that, the crystal of natural cellulose could be fully infiltrated and subsequently dissolved by the TBAH/urea aqueous solvent. The performances of the aqueous solvent and ambient temperature dissolution make aqueous TBAH/urea a potential and green solvent of cellulose for broad applications, such as composites, films or wet spinning of cellulose, in laboratories or industries. [ABSTRACT FROM AUTHOR]

Chitosan is a widely used biopolymer with very attractive properties. However, to compensate for the deficiencies in the application of this bio-macromolecule, many studies have been performed on the preparation of chitosan blends with various polymers, such as cellulose, which is abundant and unique with a tough bio-structure. Because of the different dissolution conditions of chitosan and cellulose, an acceptable industrial and environmentally friendly process to prepare a monotonous cellulose-chitosan composite film has not been achieved yet. Therefore, as an alternative approach, nanochitosan (Nano-CS) particles were synthesized and blended with a cellulose matrix, which was dissolved using ionic liquid. Atomic force microscope and field emission scanning electron microscope (FESEM) images demonstrated that the most frequent size of Nano-CS particles was in the 10-60 nm range. FESEM nano-graphs evidenced monotonous distribution of Nano-CS particles through the produced nano-biocomposite films. X-ray diffractograms indicated that following the dissolution process of cellulose a less ordered cellulose matrix or one with less crystallite sizes was formed. Meanwhile, following the addition of certain amounts of Nano-CS, the mechanical properties were improved. Also, optical analysis exhibited proper transparency of the biocomposite films (≈80 %) in the range of visible wavelengths (400-700 nm). [ABSTRACT FROM AUTHOR]

As a result of the constantly growing demand for textile fibres interest in utilising cellulose pulps for manufacturing regenerated cellulose fibres is growing. One promising water-based process for the manufacture of regenerated cellulosic products is the Biocelsol process based on an NaOH/ZnO solvent system. The drawback of the Biocelsol process is the need for pre-treatment of the pulp, i.e. long mechanical pre-treatment (up to 5 h) followed by a 2-3-h enzymatic hydrolysis utilising a rather high amount of cellulolytic enzymes. In this work more efficient conditions to carry out the pre-treatment of cellulose pulp prior to dissolution into NaOH/ZnO are presented. Based on the results, cellulase treatment, when carried out in an extruder, can be used to effectively open up and fibrillate the fibres without completely destroying the fibre structure. The molar mass of the pulp treated enzymatically in an extruder was 14 % lower as compared to the state-of-the-art-treated cellulose. As a consequence, the alkaline solutions prepared from the pulp treated enzymatically in an extruder had clearly lower dope viscosities regarding the cellulose content than the solutions prepared from the state-of-the-art-treated pulp. This enabled increasing the cellulose content in the dope up to 7 % (w/w) without increasing the dope viscosity. [ABSTRACT FROM AUTHOR]

Subcritical and supercritical water are known to dissolve crystalline cellulose, offering a simple way to produce low molar mass cellulose which precipitates at ambient temperatures. However, the yield of precipitate is limited by concomitant degradation reactions. In this study, the formation of cellulose precipitate from six different microcrystalline celluloses (MCC) was investigated in 0.2 s treatments at 250-380 °C. The results were elucidated with a simple two-step kinetic model. The maximum yield of cellulose precipitate depended on the choice of starting material, which had a more important role than the optimized treatment time or temperature. Wood-derived MCCs dissolved faster and resulted in a higher yield of precipitate than those prepared from cotton linter. The highest yield of precipitate, 68 %, was recovered from a MCC prepared from mercerized prehydrolysis hardwood Kraft pulp. The high yield of precipitate could not be attributed to any single factor but in general the wood-derived MCCs had a smaller particle size, smaller crystallite dimensions, and lower molar mass than their cotton-derived equivalents. The analysis of molar mass distributions indicated heterogeneous dissolution mechanism at 250 and 320 °C whereas at 380 °C the cellulose crystallites were subjected to random chain cleavage. [ABSTRACT FROM AUTHOR]

The rapid coagulation of NaOH-based cellulose solution during the wet spinning process leads to a low stretching ratio and, consequently, the low mechanical properties of the fibres. The aim of this work was to slow down the coagulation by replacing the sulphuric acid spin bath with an acetic acid bath. The spin dope was prepared by dissolving the enzyme-treated dissolving pulp in aqueous sodium zincate using a freezing-thawing method. The optimal zinc oxide and sodium hydroxide concentrations were studied first. The most thermally stable cellulose solution contained 6.5 wt% NaOH and 1.3 wt% ZnO with 6 wt% enzyme-treated dissolving pulp. The spin dope was prepared accordingly. Coagulation of the cellulose solution slowed down in the acetic acid bath, resulting in a significantly higher stretching ratio for the fibres than with the sulphuric acid bath. However, the acetic acid spun fibres shrunk strongly during drying, and the possibly aligned order of the molecular chains due to the high stretch was partly lost. As a consequence, the high stretch was not transferred to high tenacity of the fibres in this study. However, the result suggests attractive potential to develop processing conditions to increase fibre tenacity. [ABSTRACT FROM AUTHOR]

The dissolution of different cellulose pulps from different sources such as wood, bamboo and ramie pulp in 7 wt% NaOH/12 wt% urea aqueous solution was investigated in the present article, as well as the structure and properties of the resultant regenerated films. All of the cellulose samples with molecular weight below 1.2 × 10 could be quickly and completely dissolved in NaOH/urea aqueous solution precooled to −12.5 °C in 2 min, regardless of the cellulose source, indicating the universality of cellulose dissolution in NaOH/urea solvent. The resultant cellulose solutions exhibited similar rheological behaviors, indicating a similar solution procedure of cellulose in NaOH/urea. These regenerated cellulose films exhibited similar structures and morphologies according to the results of the scanning electron microscope, X-ray diffraction and Fourier transform infrared spectroscopy analyses, indicating a microporous structure with a pore diameter ranging from 100 to 300 nm, as well as a complete transition from cellulose I to cellulose II after the dissolution and regeneration process. Furthermore, all of the films had good mechanical properties and light transmittance as a result of the homogeneous structure. In view of the results mentioned above, the NaOH/urea solvent system displayed a strong cellulose dissolving capacity, exhibiting great potential for the further development and comprehensive utilization of cellulose from agricultural and forestry wastes. It is capable of increasing the applications of cellulose and has potential for further development. [ABSTRACT FROM AUTHOR]

Ionic liquids (ILs) and deep eutectic solvents (DESs) are the two most widely used neoteric solvents. Recently, our group described how the simple addition of acetic acid (AcOH) to 1-Ethyl-3-methylimidazolium chloride (EMIMCl) could promote the transition from the original IL to an eutectic mixture of EMIMCl and AcOH. Herein, we studied how cellulose regeneration and EMIMCl recovery from EMIMCl solutions of cellulose could be benefited by the significant differences existing between EMIMCl- and EMIMCl·AcOH-based mixtures and the easy switching from one to the other. Finally, we also demonstrated that the transition could also be accomplished by addition of acetic anhydride and water so that the process could be eventually useful for the achievement of highly acetylated cellulose. [ABSTRACT FROM AUTHOR]

Three alkaline mixtures (NaOH/thiourea, NaOH/urea/thiourea, NaOH/urea/ZnO) and sulfuric acid were used at low temperatures as cellulose solvents, and their cellulose solubility and films' physical properties for bleached chemical wood pulps and cotton linter were compared. Their degree of polymerization (DP) was controlled to 600–800 before dissolution. Among the alkaline solvents, NaOH/urea/ZnO gave the film the highest tensile strength and stretch. When compared to sulfuric acid, NaOH/urea/ZnO gave lower strength properties but higher crystallinity indices in the films. While alkaline solvents could not dissolve the high DP cellulose (DP ~ 2000), sulfuric acid could dissolve the high DP cellulose at below zero Celsius temperature, and the strength properties of the films were not much different from that of the low DP one. It appeared that the low-temperature sulfuric acid treatment did away with the cellulose's DP controlling stage; it decreased cellulose DP very quickly for the high-DP cellulose at the initial stage, and as soon as the cellulose DP reached a DP low enough for dissolution, it began to dissolve the cellulose to result in stable cellulose solution. [ABSTRACT FROM AUTHOR]