Properties of regenerated cellulose films plasticized with α‐monoglycerides

Regenerated cellulose (RC) films were plasticized with glycerol, glycerin α‐monobutyrate, glycerin α‐monocaproate, glycerin α‐monocaprylate, and glycerin α‐monocaprate. The structure and properties of the films were investigated by using Fourier transform IR, wide‐angle X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy, and tensile tests. The experimental results showed that the addition of plasticizer enhanced the elongation at break, thermal stability, and crystallinity and lowered the tensile strength of the films. The formation of hydrogen bonds between the cellulose and plasticizers weakened the inter‐ and intra‐hydrogen bonds among cellulose molecules, leading to reduced tensile strength. These α‐monoglycerides have relatively good plasticizing effects. Compared with glycerol, the resistance against water washing of the synthesized compounds was significantly enhanced. With the increase of the carbochain length of the α‐monoglycerides, the plasticizing effect decreased but the resistance against water washing was enhanced. When the RC films were immersed in a 10% glycerin α‐monocaproate solution, the elongation at break increased to 15% and stayed at 14.8% after water washing. Glycerin α‐monocaproate might be better for plasticizing RC films than others. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3500–3505, 2003     

Novel regenerated cellulose fibers from rice straw

Regenerated cellulose fibers from rice straws with a diameter of 10 to 25 μm and initial modulus of 11 to 13 GPa were prepared by wet spinning in rice straw/N‐methylmorpholine‐N‐oxide (MMNO) solution. X‐ray diffraction analysis indicates that the rice straw regenerated fibers are classified as cellulose (II). This observation indicates a potential utility of rice straw as an alternative to wood pulp as a cellulose‐based fiber material. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1705–1708, 2001     

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     

离子液体法制备再生细菌纤维素纤维

以离子液体(氯化1-甲基-3-正丁基咪唑)溶解高聚合度细菌纤维素(BC),采用湿法纺丝制备再生细菌纤维素(RBC)初生纤维;通过红外光谱分析(FTIR)、广角X射线衍射(WAXD)分析、热失重(TG)分析、扫描电镜( SEM)、单丝强度拉伸等表征了RBC初生纤维的结构和性能.结果表明:该溶剂体系通过10 h的快速搅拌溶...     

Application of a linear synthetic polymer to improve the properties of cellulose fibers made by the NMMO process

Low‐molecular polyethylene (LMPE) as an internal flexibilizer was selected to improve the spinnability of cellulose solution in N‐methylmorpholine‐N‐oxide (NMMO). It is compatible with the conditions of cellulose dissolution and fiber spinning because of its chemical stability and melting point. In the course of rheological investigations, it was proven that this modification has a physical characteristic. Cross sections of the fibers reveal that cellulose–LMPE forms a two‐phase system with randomly distributed LMPE domains and a dominant skin‐core structure. The addition of 5% LMPE is enough to improve significantly the mechanical properties of the fibers. An increase of LMPE above 5% worsens these properties, because LMPE is not a fiber‐forming polymer. With the use of spinnerets with suitable dimensions, it is possible to obtain cellulose fibers with mechanical properties similar to those of synthetic fibers. The retention of water is lowered by the hydrophobic polyethylene polymer; however, it is high enough to retain the hydrophilic character of cellulose fibers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2762–2773, 2002; DOI 10.1002/app.10227     

Comparison of cellulose and chitin nanocrystals for reinforcing regenerated cellulose fibers

In this study, regenerated cellulose fibers reinforced by cellulose nanocrystals (CENC) and chitin nanocrystals (CHNC) were prepared by blending the nanocrystals suspensions with the cellulose solution in NaOH/urea/water solvent at room temperature. The effect of nanocrystals' addition on the properties of spinning dopes and regenerated fibers were investigated and compared. Results showed that the obtained CENC and CHNC had different dimensions, and both of them increased the viscosity and decreased the transparency of the spinning dopes. However, the dissolution state of cellulose was not changed. CHNC had a greater influence on the properties of spinning dopes, while CENC had more obvious effect on the performance of regenerated fibers. The CENC reinforced fibers showed a higher crystallinity index as compared to the CHNC reinforced fibers. The tensile strength of the regenerated fibers was evidently improved when 3 wt % CENC or 2 wt % CHNC were added, while the elongation at break of the fibers was slightly decreased with the increase of nanocrystals content. The morphology and thermal stability of the regenerated fibers was not affected by the addition of nanocrystals. This study suggested that the dimension, group and content of nanocrystals were important factors for the reinforcement of regenerated cellulose fibers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44880.     

Radiation degradation of microcrystalline cellulose in solid status

Pulverization and degradation are important pretreatment procedures in producing bio‐ethanol from cellulose. In this study, microcrystalline cellulose (MCC), a pure α‐cellulose, was degraded by γ‐irradiation. The average degree of polymerization, content of reducing sugar, crystalline structure, and molecular structure were investigated to elucidate the radiation effect on the degradation of MCC. The results manifested that γ‐ray destroyed part of the chemical bond and hydrogen bond, leading to the degradation of cellulose and increasing of the reducing sugar content. According to the Fourier transform infrared result, radiation degradation led to the formation of reductive carbonyl group. Meanwhile, radiation had slight influence on the crystalline structures of MCC. Therefore, the radiation degradation procedure is expected to benefit the further proceedings such as ultrafine treatment and enzyme hydrolysis of cellulose. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dielectric behaviour of pure and nickel-doped cellulose acetate films

Pure and Ni (0·05%, 0·1% and 0·15%)-doped cellulose acetate (CA) films were formed on well-cleaned glass substrates using a solution growth technique. Metal–insulator–metal (MIM) sandwich structures of thin film capacitors were fabricated. Dielectric studies were carried out in the frequency range 1kHz to 10MHz in the temperature range 303–450K. The variation of capacitance and dielectric loss with temperature were studied at various frequencies. The variation of dielectric constants (ε′ and ε″) with frequency and temperature is discussed. An increase in capacitance with temperature was observed and this may be due to the chaotic oscillations of molecules in the polymer matrix. β (at lower temperature) and α (at higher temperature) relaxation loss peaks were observed. Doping results in the formation of charge transfer complexes/molecular aggregates in the polymer, which cause the shift of C_max value and the β and α relaxation loss peaks towards higher temperature. An appreciable dispersion of tan δ at lower frequency was noticed in all the samples studied. © 1998 SCI.     

Dielectric properties of amorphous cellulose acetate-butyrate polymer films

The dielectric constant, loss tangent and AC conductivity of solution grown cellulose acetate-butyrate films of 5μm thickness were studied as a function of temperature (300-450 K) in the frequency range 10 Hz-10 MHz. The decrease in dielectric constant was observed with the increase in frequency as well as with temperature. A loss peak was observed in the dielectric loss spectra and was identified as the β-relaxation peak. The frequency-dependent conductivity was also studied. The results were interpreted in terms of electronic conduction via hopping processes.     

过氧化氢氧化再生纤维素及其阻燃、吸附性能

以过氧化氢氧化再生纤维素(GC)制备羧基再生纤维素(OGC),表征OGC结构变化及其对阻燃和吸附性能影响机理。通过碱泡预处理能有效提高GC比表面积,增加反应效率,获得羧基含量达15.6%的OGC。FT-IR和¹³C NMR表征结果说明OGC葡萄糖基环上的C₆位伯羟基能被选择性氧化成羧基。随着羧基含量的提高,OGC无定形部分溶解而提高其结晶度,晶型则无显著变化,OGC的热分解温度下降,但是成炭率显著提高。当添加6.25%OGC为成炭剂用于环氧树脂膨胀型阻燃时,氧指数达到27.2,阻燃等级为V0。以火焰原子吸收分光光度法测定结果表明,当羧基含量为15.6%,OGC对铅和铜离子吸附量分别提高14倍和3.5倍,其原因在于氧化改性能显著提高OGC的比表面积和容积率,增加吸附容量。研究结果说明以过氧化氢氧化制备的OGC在阻燃成炭剂以及金属离子吸附领域中具有良好的应用前景。     

单壁碳纳米管/再生纤维素复合纤维的制备及性能

将经过酸化处理和十二烷基苯磺酸钠处理后的单壁碳纳米管(SWNTs)与离子液体和再生纤维素共混制得纺丝溶液,通过干湿法纺丝制得SWNTs/再生纤维素复合纤维.考察了SWNTs处理前后的结构及在离子液体中的分散性;研究了复合纤维的力学性能和热性能.结果表明:经酸化和功能化处理后的SWNTs的直径有所减小,SWNTs在离子液...     

Preparation and characterization of dense cellulose film for membrane application

Regenerated cellulose films were prepared with environmentally friendly process by utilized N‐methylmorpholine‐N‐oxide (NMMO)‐Cellulose system. To prepare a dense cellulose film for membrane application, some parameter process which influence porous forming such as cellulose DP, cellulose concentration, addition NMMO in coagulation bath, coagulation bath temperature, and drying condition were investigated. We resumed that the porosity and pore size of cellulose membrane decrease with lower cellulose DP, higher cellulose concentration, addition of NMMO in coagulation bath, applying room temperature in coagulation bath and drying, and applying vacuum on drying process resulted in membranes with porosity in range of 24–41% and pore size 13.4–20.2 nm. The main factor for controlling porosity and pore size of dense cellulose membrane was coagulation process condition especially addition of NMMO into coagulation bath. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

乙醇再生微晶纤维素的分级及其结构表征

在微晶纤维素（MCC）的Na OH/尿素溶液中加入不同质量的无水乙醇进行分级沉降，得到分级再生微晶纤维素。通过黏度法测定了再生微晶纤维素的聚合度，采用FTIR、XRD、XPS、TG和SEM对再生微晶纤维素的结构、结晶度、热稳定性和形貌进行了表征。结果表明，随着分级次数的增加，再生微晶纤维素的聚合度逐渐降低，3次分级后微晶纤维素的聚合度由MCC的203降至77；微晶纤维素形貌由表面光滑的棒状纤维结构变为粗糙多孔的结构；再生微晶纤维素的晶型由MCC的Ⅰ型转变为Ⅱ型，3次分级后微晶纤维素的结晶度由MCC的65.58%降至32.05%。分级再生微晶纤维素的自由羟基增加，参与成键的羟基减少；再生微晶纤维素的热稳定性随着分级次数的增加而降低，3次分级后初始分解温度由MCC的310℃降至257℃。     

Structure and properties of novel regenerated cellulose films prepared from cornhusk cellulose in room temperature ionic liquids

Cornhusk cellulose was regenerated using the ionic liquids viz., 1‐allyl‐3‐methylimidazolium chloride (AmimCl) and 1‐ethyl‐3‐methylimidazolium acetate (EmimAc). The cast cellulose films were characterized by FTIR, WAXD and SEM techniques. Their mechanical properties were also studied. These studies indicated that AmimCl and EmimAc are good solvents for the regeneration of cornhusk cellulose. The regenerated cornhusk cellulose (RCC) was found to be cellulose (II) with dense structure. The films cast from AmimCl exhibited good mechanical properties; the tensile modulus and strength were as high as 6 GPa and 120 MPa respectively, whereas these values for those films cast using EmimAc were found to be 4.1 GPa and 47 MPa respectively. Further, it was observed that after regeneration, the solvents could be effectively recycled. Thus a novel nonpolluting process of forming RCC films from agricultural waste was developed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Whitening regenerated cellulose fibers using fluorescent agent,surfactants, and salt—color indices measurements

The whitening efficiency of regenerated cellulose fibers using sodium 4,4′‐distyrylbiphenyl sulfonate in the presence of an anionic surfactant (sodium dodecylsulfate) and a cationic surfactant (dodecyl trimethyl ammonium chloride) and salt (NaCl) was determined by fluorescence spectroscopy and color index values (brightness, whiteness, and yellowness). Epifluorescence images gave an intense blue color with an apparent uniform emission distribution. In absence of salt, the whitening efficiency was higher for aqueous solutions containing cationic surfactant below critical micellar concentration (cmc). In presence of salt, whitening efficiency was higher for anionic surfactant and more important. The concentration of surfactant required for greater brightness, whiteness, and yellowness was lower than that required in absence of salt. These data were discussed by the decrease of the cmc and by the screening of the modified cellulose fibers by counter ions coming from the salt. The role of surfactants was explained by the admicelization during the sorption process. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and magnetic properties of Fe/Si/C/N ceramics derived from a polymeric precursor

Iron‐containing polysilazanes (PSZI) were prepared by the amine displacement reaction along with heat‐induced vinyl crosslinking reactions between Fe[N(SiMe₂Vi)₂]₃ (Vi = ? CH?CH₂) and polysilazane containing ? Si? Vi (PVSZ). The PSZIs were converted into magnetic ceramics by the pyrolysis in N₂. The ceramics produced were investigated by X‐ray diffraction, transmission electron microscope and vibrating sample magnetometer at room temperature. It was indicated that α‐Fe is the only magnetic crystalline embedded in the amorphous Si/C/N‐based matrix from 500 to 900°C. Moreover, the sample prepared at 500°C showed few hysteresis at room temperature, consistent with the behavior of superparamagnetic particles, which was confirmed by the zero‐field‐cooled and field‐cooled magnetization measurement. Additionally, the results indicated that the magnetic properties of the ceramics could be tuned by controlling the content of iron and the pyrolysis temperature. This flexibility may be advantageous for some particular magnetic materials applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation of polyimides derived from biphenyltetracarboxylic dianhydrides and aromatic diamines bearing alkylene spacers

Four series of aromatic polyimides (PIs V–VIII) composed of biphenyltetracarboxylic dianhydrides (BPDAs) and aromatic diamines bearing alkylene spacers were prepared by two methods. Most polymers could be readily prepared in a one‐step method for the combination of a‐BPDA with α,ω‐bis(3‐aminophenoxy)alkanes, a‐BPDA with α,ω‐bis(4‐aminophenoxy)alkanes, and s‐BPDA with α,ω‐bis(3‐aminophenoxy)alkanes. However, the polymerization of s‐BPDA with α,ω‐bis(4‐aminophenoxy)alkanes gave powders. On the other hand, all four monomer combinations afforded the desired polyamic acid solution in a two‐step method. These polymer solutions could be cast into tough and flexible films, which were characterized by their inherent viscosity, differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical spectrometry measurements. The glass transition temperatures (T_gs) of the polymers were in the range of 110–240°C, but they were not clearly defined for PIs VIII and VI. The 5% weight loss temperatures were around 450°C for all prepared PIs. For PI VIII an “odd–even” behavior of the tensile properties of the films was detected, corresponding to the reported behavior of the melting temperatures. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2404–2413, 1999     

Homogeneous graft copolymerization of acrylonitrile onto high α‐cellulose in a dimethyl acetamide and lithium chloride solvent system

Homogeneous graft copolymerization of acrylonitrile (AN) monomer onto high α‐cellulose was investigated in a lithium chloride/N,N‐dimethyl acetamide (DMAc/LiCl) solvent system. Benzoyl peroxide (BPO) and azobisisobutyronitrile (AIBN) were used as radical initiators. By varying temperature, time, and monomer concentrations in grafting reactions, the optimum conditions for both initiator systems were fixed. The graft yield for the AN–BPO system was higher than that for the AN–AIBN system. The optimum conditions of reactions were at temperatures of 70 and 60°C with initiator concentrations of 0.4% (0.36 mmol) and 2% (1.24 mmol) for the AN–AIBN and AN–BPO systems, respectively, at a monomer concentration of 5% (14.1 mmol) solution. The number of grafts per cellulose chain was in the range from 2.2 to 1.1 for AN–BPO and 0.5 to 2.1 for the AN–AIBN system. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 630–637, 2003     

Physical properties of lyocell fibers spun from different solution‐dope phases

The hydration number (n) of NMMO hydrates has a significant effect on the rheological properties and phase of the cellulose solutions in the hydrates. The physical properties of the lyocell fibers spun from the cellulose solutions in NMMO hydrates with different values of n were investigated relative to the phase of the solution dope. NMMO hydrate with n = 1.1 could not fully dissolve cellulose, resulting in a heterogeneous solution. NMMO hydrate with n = 0.72 produced a mesophase solution that exhibited a good spinnability. When NMMO hydrates with n = 0.72 and 1.0 were used, the lyocell fiber spun from 15 wt % solution dope gave higher tensile strength than that spun from 12 wt % solution dope. NMMO hydrate with n = 1.0 produced a lyocell fiber whose tensile strength was slightly affected by spin–draw ratio but the tensile strength of the lyocell fiber prepared from NMMO hydrate with n = 0.72 was monotonically increased with increasing spin–draw ratio. Further, the latter gave higher birefringence. The lyocell fiber spun from 15 wt % solution in NMMO hydrate with n = 0.72 produced finely fibrillated structures. When treated with sonic wave the lyocell fiber prepared from 15 wt % cellulose (DP_w 940) solution in NMMO hydrate with n = 0.72 yielded the most serious fibrillation on the fiber surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 981–989, 2002     

Preparation and properties of castor oil‐based polyurethane/α‐zirconium phosphate composite films

Novel castor oil‐based polyurethane/α‐zirconium phosphate (PU/α‐ZrP) composite films with different α‐ZrP loading (0–1.6 wt %) and different NCO/OH molar ratios were synthesized by a solution casting method. The characteristic properties of the PU/α‐ZrP composite films were examined by Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and tensile testing. The results from Fourier transform infrared spectroscopy indicated that strong intermolecular hydrogen bonding formed between α‐ZrP and PU, XRD and SEM results revealed that the α‐ZrP particles were uniformly distributed in the PU matrix at low loading, and obvious aggregation existed at high loading. Because of hydrogen bonding interactions, the maximum values of tensile strength were obtained with 0.6 wt % α‐ZrP loading and 1.5 of NCO/OH molar ratio in the matrix. Evidence proved that the induced α‐ZrP used as a new filler material can affect considerably the mechanical and thermal properties of the composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011