Moisture induced plasticity of amorphous cellulose films from ionic liquid

Amorphous cellulose films were created by regeneration from 1-Ethyl-3-methylimidazolium acetate (EmimAc) solutions. Their mechanical properties were analyzed as a function of water content. Cellulose with different molecular weights, i.e. microcrystalline cellulose (Avicel), Spruce cellulose and bacterial nanocellulose (BNC), were used for film preparation. All the regenerated films were free from EmimAc residues as shown by Fourier transform infrared spectroscopy (FTIR), amorphous as shown by wide angle X-ray spectroscopy (WAXS) and optical transparent. The equilibrium water content (w/w) was measured at different relative humidities. The plasticizing effect of water on the films was evidenced by both tensile tests and dynamical mechanical analysis (DMA) with humidity scans. The mechanical properties were clearly related to the proportional water uptake of the films. The sample with the longest cellulose chains, i.e. BNC, showed significantly larger elongation to brake at high moisture content which was owed to chain entanglements.     

Regenerated cellulose membrane prepared with ionic liquid 1‐butyl‐3‐methylimidazolium chloride as solvent using wheat straw

BACKGROUND: Currently, cellulose membranes are prepared by cellulose acetate hydrolysis or chemical derivatization dissolution and regeneration using cotton pulp or wood pulp. In this study, the concept ‘lignocelluloses biorefinery’ was used, and good quality long fiber was fractionated from wheat straw using clean technologies. The objective of this study is to develop wheat straw cellulose to prepare regenerated cellulose membrane with ionic liquid 1‐butyl‐3‐methylimidazolium chloride ([BMIM]Cl) as solvent. RESULTS: Wheat straw cellulose (WSC) fractionated from wheat straw contained 93.6% α‐cellulose and the degree of polymerization (DP) was 580. WSC was dissolved directly without derivatization in [BMIM]Cl. With increase in dissolving temperature, the DP of the regenerated cellulose dropped, which resulted in a decrease in the intensity of regenerated cellulose membrane. After regeneration in [BMIM]Cl, the WSC transformed from cellulose I to cellulose II, and the crystallinity of the regenerated cellulose was lower than the original cellulose. The regenerated WSC membrane had good mechanical performance and permeability, the tensile strength and breaking elongation were 170 MPa and 6.4%, respectively, the pure water flux was 238.9 L m^?2 h^?1 at 0.3 MPa pressure, and the rejection of BSA was stabilized at about 97%. CONCLUSION: Wheat straw cellulose fractionated from wheat straw satisfied the requirement to prepare regenerated cellulose membrane using ionic liquid [BMIM]Cl as solvent. Copyright © 2012 Society of Chemical Industry     

Drawing of self‐reinforced cellulose films

Self‐reinforced cellulose films were prepared by incomplete dissolution of commercial microcrystalline cellulose in LiCl/DMAc solvent and subsequent coagulation of regenerated cellulose in the presence of undissolved microcrystalline cellulose. By drawing in wet conditions and subsequent drying, preferred orientation was introduced into the self‐reinforced cellulose films, resulting in significantly improved tensile strength of up to 430 MPa and modulus of elasticity of up to 33 GPa. A linear relationship was observed between applied draw, and the orientation of cellulose in the films, and the measured elastic modulus and tensile strength, respectively. The optically transparent drawn films significantly surpass the strength and modulus of elasticity of current all‐bio‐based planar materials and may therefore present a bio‐degradable alternative to nonbio‐based materials with similar performance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2703–2708, 2007     

High‐strength regenerated cellulose fibers spun from 1‐butyl‐3‐methylimidazolium chloride solutions

High‐performance regenerated cellulose fibers were prepared from cellulose/1‐butyl‐3‐methylimidazolium chloride (BMIMCl) solutions via dry‐jet wet spinning. The spinnability of the solution was initially evaluated using the maximum winding speed of the solution spinning line under various ambient temperatures and relative humidities in the air gap. The subsequent spinning trials were conducted under various air gap conditions in a water coagulation bath. It was found that low temperature and low relative humidity in the air gap were important to obtain fibers with high tensile strength at a high draw ratio. From a 10 wt % cellulose/BMIMCl solution, regenerated fibers with tensile strength up to 886 MPa were prepared below 22 °C and relative humidity of 50%. High strengthening was also strongly linked with the fixation effect on fibers during washing and drying processes. Furthermore, an effective attempt to prepare higher performance fibers was conducted from a higher polymer concentration solution using a high molecular weight dissolving pulp. Eventually, fibers with a tensile strength of ～1 GPa and Young's modulus over 35 GPa were prepared. These tensile properties were ranked at the highest level for regenerated cellulose fibers prepared by an ionic liquid–based process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45551.     

蔗渣纤维素在离子液体中的溶解与再生

以蔗渣纤维素为原料,在1-烯丙基-3-甲基咪唑氯盐([Amim]Cl)离子液体中,制备出蔗渣纤维素再生膜。通过偏光显微镜观察了蔗渣纤维素的溶解过程,采用红外光谱、扫描电镜、X射线衍射、热重及力学性能等分析测试手段,对蔗渣纤维素及再生膜进行表征,结果表明:未经活化的蔗渣纤维素可快速、直接溶解在离子液体中,再生前后蔗渣纤维素发生了从纤维素Ⅰ到纤维素Ⅱ的晶型转变,蔗渣纤维素再生膜具有致密的结构,热力学稳定性达到292℃,拉伸强度高达144MPa。     

Wet spun fibers from solutions of cellulose in an ionic liquid with suspended carbon nanoparticles

Wet spun fibers from solutions of dissolving pulp in 1‐ethyl‐3‐methylimidazolium acetate (EmimAc) with up to 50 wt % (based on cellulose) suspended carbon black and graphene nanoplatelets particles were studied. Carbon fillers were dispersed by simple shearing in a Couette type mixer and the resulting spin dope was extruded into a hot water coagulation bath from a single hole spinneret. Microstructure, mechanical properties, and electrical conductivity were assessed as a function of filler loading and discussed in comparison to melt spun fibers with similar fillers. The coagulation process and subsequent drying of wet spun fibers was found to produce a significant microporosity, more so the higher the filler loading. The electrical percolation threshold was quite high in the wet spun fibers and relatively modest values of conductivity were obtained with regard to the high filler loadings. Carbon black was found to be superior to graphene nanoplatelets. This was related to flow‐induced orientation effects. The mechanical properties of the carbon‐filled fibers were found to be similar or lower compared to the pure cellulose fibers because of low interfacial interactions and formation of microporosity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41417.     

Transparent,flexible, and high‐strength regenerated cellulose/saponite nanocomposite films with high gas barrier properties

Regenerated cellulose‐saponite nanocomposite films were prepared from LiOH/urea solutions, and exhibited high optical transparency and flexibility. The saponite platelets formed intercalated nanolayered structures in the composites. The longitudinal directions of both the cellulose II crystallites and the saponite platelets were preferentially oriented parallel to the film surface in the composites. The good nanodispersibility and high orientation of the saponite platelets in the composite films resulted in high mechanical strength, high Young's modulus, and good thermal dimensional stabilities, and gas barrier properties in the composites, compared with a reference cellulose film. Moreover, the tensile strength and Young's modulus of the composite film reached 241 MPa and 7.7 GPa, respectively, when a simple drawing process was applied to the wet composite film; this is probably owing to the improvement in the orientation of the cellulose II crystallites and saponite platelets in the composites. The composite films also showed high toughness and ductility. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3168–3174, 2013     

Structure and properties of cellulose nanocomposite films containing melamine formaldehyde

Films of high Young's modulus and low density are of interest for application as loudspeaker membranes. In the present study nanocomposite films were prepared from microfibrillated cellulose (MFC) and from MFC in combination with melamine formaldehyde (MF). The prepared materials were studied with respect to structure as well as physical and mechanical properties. Studies in SEM and calculation of porosity showed that these materials have a dense paper‐like structure. The moisture sorption isotherms were measured and showed that moisture content decreased in the presence of MF. Mechanical properties were studied by dynamical mechanical thermal measurements as well as by tensile tests. Cellulose films showed an average Young's modulus of 14 GPa while the nanocomposites showed an average Young's modulus as high as 16.6 GPa and average tensile strength as high as 142 MPa. By controlling composition and structure, the range of properties of these materials can extend the property range available for existing materials. The combination of comparatively high mechanical damping and high sound propagation velocity is of technical interest. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Influence of water on phase transition and rheological behavior of cellulose/ionic liquid/water ternary systems

The influence of water content on liquid crystalline (LC) gel formation and the rheological behavior of a ternary microcrystalline cellulose (MCC)/1‐ehtyl‐3‐methylimidazolium acetate (EmimAc)/water system was investigated using polarized optical microscopy (POM) and rheometry. POM indicated that the distinct water content range for forming a fully anisotropic LC gel with 14 wt % MCC was 4–10 wt %. Adding water to the MCC/EmimAc system resulted in enhanced complex viscosity and storage and loss moduli, and ultimately LC gel formation. Comparison of creep compliance vs. time revealed that the system without water showed representative viscoelastic behavior, while the time dependence of creep compliance disappeared as the water content increased, suggesting elastic‐solid behavior. Additionally, hydrogen bonding between cellulose and EmimAc weakened as water content increased, whereas the intra‐ and intermolecular hydrogen bonds of cellulose became stronger because of strong self‐association. This strong bonding caused aggregation, chain entanglement, and self‐supporting LC gel network formation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44658.     

Recent advances in regenerated cellulose materials

The dual threats of the depletion of nonrenewable energy and environmental pollution caused by petroleum-based polymers motivate utilization of naturally occurring polymers to create new materials. Cellulose, as the most abundant natural polymer on earth, has attracted attention due to its renewability, wide availability, low-cost, biocompatibility and biodegradability, etc. Regenerated cellulose may be constructed simply via physical dissolution and regeneration, an environmentally friendly process avoiding the consuming of chemicals since most of the reagents (solvents, coagulant, etc.) may be recycled and reused. “Green” solvents and techniques for the preparation of the environmentally friendly regenerated cellulose materials have been developed successfully, showing great potentials in the fields of polymer science and technology.In this article, the widely used non-derivatizing cellulose solvents are summarized, including their dissolution mechanisms. Regenerated cellulose materials with different functions and properties have been designed and fabricated in different forms, such as filaments, films/membranes, microspheres/beads, hydrogels/aerogels and bioplastics, etc., to meet various demands. The concept of regeneration through a physical process is illustrated, and a number of novel regenerated cellulose materials are introduced for wide applications in textiles, packaging, biomedicine, water treatment, optical/electrical devices, agriculture and food, etc. The methodology of material processing and the resultant properties and functions are also covered in this review, with emphasis on the neat regenerated cellulose materials and the composite materials. The 277 references cited concerning the direct preparation of cellulose materials via physical dissolution and regeneration are representative of the wide impact and benefits of the regenerated cellulose materials to society.     

Structure and thermomechanical properties of stretched cellulose films

Regenerated and stretched cellulose films were investigated for structure and thermomechanical properties as a potential packaging material. Cellulose films were cast from lithium chloride/N, N‐dimethylacetamide and were stretched up to 30% in a dynamic mechanical analyzer sample holder. Wide‐angle X‐ray diffraction analysis indicated that the orientation factor was significantly increased due to stretching. In addition, the stretched films have a higher resistance to the thermal decomposition from thermo gravimetric analysis. The increased orientation of cellulose crystalline structure by the stretching process also increased the storage modulus of cellulose films characterized by dynamic mechanical analysis, which suggest that mechanical properties of cellulose films could be tuned during the stretching process. The α₂ and α₁ relaxations were found at 240 and 300°C, respectively, which are attributed to the micro‐Brownian motion of segments in amorphous region, and activation energies for relaxations were determined with the stretching levels. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

功能性再生纤维素复合膜的制备及性能研究进展

纤维素是自然界中储量最大的天然高分子化合物,被认为是未来能源和化工的主要原料。然而,天然纤维素聚合度高、结晶度高的特性,使其难以溶于常规溶剂,极大限制了纤维素的应用。近年来,人们发现了多种新型纤维素溶剂体系,本文简要介绍了基于新型纤维素溶剂体系制备而来的再生纤维素膜以及一系列功能性再生纤维素基有机/无机复合膜材料。通过新型纤维素溶剂体系溶解再生得到的再生纤维素基复合膜在多孔性、热稳定性、强度等性能方面得到一定程度的改善,有望应用于包装、污水处理、传感器、生物医学等领域。本文基于再生纤维素膜及其复合膜材料的最新研究进展,对今后发展的热点方向进行了展望,旨在为纤维素溶解和功能性再生纤维素新材料的开发提供参考。     

Influence of molecular weight and rheological behavior on electrospinning cellulose nanofibers from ionic liquids

Dissolving pulp was depolymerized with 2.5M HCl into cellulose fractions with decreasing molecular weight relative to acid treatment time. The cellulose fractions were dissolved at various concentrations in the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate (EmimAc) with co‐solvent DMSO at ratio 1 : 1 (w/w) and electrospun. Size exclusion chromatography was used to evaluate the molecular weight distributions and the rheological properties were characterized with a cone‐and‐plate rheometer. Scanning electron microscope was used to evaluate the fiber morphology, and thereby spinnability. Zero shear viscosity as a function of cellulose concentration show that all the solutions in this study are in the entangled semi‐dilute regime; where the polymer concentration is large enough for significant overlap necessary for chain entanglement. However, within the intervals studied, neither cellulose concentration nor molecular weight seems to be decisive for if a solution can be electrospun into fibers or not. It is rather the viscosity of the solution that is decisive for electrospinnability, even though the solution is in the entangled semi‐dilute regime. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2303–2310, 2013     

Thermomechanical properties of poly(lactic acid) films reinforced with hydroxyapatite and regenerated cellulose microfibers

Novel composite films constituted of poly(lactic acid) (PLA), hydroxyapatite (HAp), and two types of regenerated cellulose fillers—particulate and fibrous type—were produced by melt extrusion in a twin‐screw micro‐compounder. The effect of the film composition on the tensile and dynamic mechanical behavior and the HAp dispersion in the PLA matrix were investigated thoroughly. Appearance of crazed regions and prevention of HAp aggregation in the PLA matrix were elucidated in the composites with up to 15 wt % particulate cellulose content, which was the main reason for only slight reduction in the tensile properties, and consequently trivial degradation of their pre‐failure energy absorption as compared to neat PLA films. Superior dynamical energy storage capacities were obtained for the particulate cellulose modified composites, while their fibrous counterparts had not as good properties. Additionally, the anisotropic mechanical behavior obtained for the extruded composites should be favorable for use as biomaterials aimed at bone tissue engineering applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40911.     

Effects of plasticization conditions on the structures and properties of cellulose packaging films from ionic liquid [BMIM]Cl

By using natural softwood pulp with higher degree of polymerization (DP = 1460) as cellulose source, 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) ionic liquid as solvent and glycerol as plasticizer, a novel cellulose packaging film was prepared. The effects of plasticization conditions on the structures, mechanical properties, permeability for oxygen and water vapor were measured by Wide-angle X-ray scattering, thermogravimetric analysis, scanning electron microscopy (SEM), and other techniques. The investigations suggested that the glycerol concentration and plasticizing time had great effect on the properties of the regenerated cellulose films. The crystal transformation of cellulose I to cellulose II occurred during the dissolution and regeneration process, combining with the decrease of thermal stability. The tensile strength decreased rapidly with the addition of glycerol and prolongation of plasticizing time. However, elongation at break of the regenerated cellulose films increased at first and then decreased with increasing of glycerol concentration and plasticizing time. The morphologies for the fracture surface obtained from SEM images showed transformation of typical brittle fracture to plastic deformation with increasing of glycerol concentrations. It was also found that both water vapor permeability and oxygen permeability of the regenerated cellulose films decreased slowly with increasing of glycerol concentrations and plasticizing time, but water vapor permeability and oxygen permeability presented an almost opposite trend. The films prepared by using ionic liquid technology would be used in food packaging or other fields as a kind of green packaging material. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Chemical modification of cellulose acetate by allylation and crosslinking with siloxane derivatives

A new pathway to cellulose–siloxane hybrid materials was investigated. Allylated cellulose was prepared by chemical modification of cellulose acetate using three different procedures and was crosslinked afterwards by hydrosilylation in the presence of Karstedt's catalyst. Poly[dimethyl(methyl‐H)siloxane] with 25 mol% Si? H side groups and 1,1,3,3‐tetramethyldisiloxane were used as crosslinking agents in different ratios as regards the unsaturated component. The occurrence of the reaction was verified using Fourier transform infrared spectrometry following the reduction until disappearance of bands corresponding to Si? H and C?C bonds with the formation of new Si? C bonds that led to the crosslinking of the cellulose derivative. The reaction products were processed as films that were insoluble in common solvents. Surface (static contact angle, water vapour sorption capacity and swelling in various solvents), mechanical and thermal properties of the networks processed as films were investigated and the results were correlated with the reactant ratios. The crosslinking density was determined based on differential scanning calorimetry data. Copyright © 2012 Society of Chemical Industry     

Impact of non‐solvent on regeneration of cellulose dissolved in 1‐(carboxymethyl)pyridinium chloride ionic liquid

Cellulose dissolved in ionic liquid (1‐(carboxymethyl)pyridinium chloride)/water (60/40 w/w) mixture is regenerated in various non‐solvents, namely water, ethanol, methanol and acetone, to gain more insight into the contribution of non‐solvent medium to the morphology of regenerated cellulose. To this end, the initial and regenerated celluloses were characterized with respect to crystallinity, thermal stability, chemical structure and surface morphology using wide‐angle X‐ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. According to the results, regardless of non‐solvent type, all regenerated samples have the same chemical structure and lower crystallinity in comparison to the initial cellulose, making them a promising candidate for efficient biofuel production based on enzymatic hydrolysis of cellulose. The reduction in crystallinity of regenerated samples is explained based on the potential of the non‐solvent to break the hydrogen bonds between cellulose chains and ionic liquid molecules as well as the affinity of water and non‐solvent which can be evaluated based on Hansen solubility parameter. The latter also determines the phase‐separation mechanism during the regeneration process, which in turn affects surface morphology of the regenerated cellulose. The pivotal effect of regenerated cellulose crystallinity on its thermal stability is also demonstrated. Regenerated cellulose with lower crystallinity is more susceptible to molecular rearrangement during heating and hence exhibits enhanced thermal stability. © 2019 Society of Chemical Industry     

Chemical‐vapor‐sensitive materials based on a multiwalled carbon nanotube/hydroxyl propyl methylcellulose/cellulose composite

A type of chemical vapor‐sensing material made from multiwalled carbon nanotubes/hydroxyl propyl methyl cellulose/cellulose composite films were prepared in the room‐temperature ionic liquid 1‐butyl‐3‐methylimidazolium chloride ([BMIm]Cl). A typical negative vapor coefficient was observed when the film was placed in polar organic solvents, such as methanol and ethanol. The sensitivity of the film to vapors increased significantly with increasing temperature. Interestingly, the resistance of the films increased almost linearly with decreasing vacuum, and the changes in resistance with the vacuum show good repeatability. The surface morphology, thermostability, and stress–strain properties of the composite films were analyzed with scanning electron microscopy, thermogravimetric analysis, and an electrical universal testing machine, respectively. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41639.     

新型溶剂法制备再生纤维素纤维研究进展

再生纤维素纤维以可再生、可生物降解的天然纤维素为原料,它的研究和开发对充分利用纤维素资源和促进纤维行业的可持续发展具有重要意义.离子液体和碱溶液溶剂体系对纤维素具有独特的溶解性能,为再生纤维素纤维的制备提供了新方法.这种新型的再生纤维素纤维具有制备过程简单、对环境无污染、纤维力学性能优异或生产成本低等优点,发展前景十分广阔.综述了离子液体法和碱溶液法再生纤维素纤维的最新研究进展,包括溶剂种类及其溶解能力、纤维素原料的性质与选择、纤维的制备方法和力学性能等,同时归纳和对比了各因素对新型再生纤维素纤维力学性能的影响.最后展望了两种新型再生纤维素纤维存在的挑战、未来发展趋势和工业化前景.     

Preparation and characterization of cellulose carbamate membrane with high strength and transparency

In this study, cellulose carbamate was synthesized from alkali cellulose and urea by a low-cost solid–liquid phase method. Cellulose carbamate was dissolved in cuprammonium solution to form a regenerated cellulose membrane with high strength and high transparency. The mass fraction of cellulose dissolved was greatly increased (up to 17%), and the thermal stability of cellulose was retained. The surface of the membrane is compact and there are regular microchannels in it. The factors influencing the transparency and mechanical properties of regenerated cellulose membrane were discussed by the range analysis of orthogonal experiment. The light transmittance is 95.50%, the breaking strength is 98.35 MPa, the elongation at break is 21.74%. The ability of heat preservation and moisture preservation of regenerated cellulose membrane was tested, and the effect was close to that of conventional polyethylene membrane. The membrane material has broad application prospects in packaging, food preservation, agriculture, and other fields.