Dissolution and Regeneration in Films of Natural Luffa in 1-butyl-3-methylimidazolium Chloride

Regenerated cellulose film was successfully prepared from natural luffa, a new cellulose raw material. A pretreatment of natural luffa was carried out by an alkali and hydrogen peroxide mixed solution. The dissolution process of the pretreated luffa in 1-butyl-3-methylimidazolium chloride ([BMIM]C1) was observed by polarized optical microscope. The structures and properties of the luffa films were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric (TGA), and porosity measurements. The results showed that the luffa fibers were transformed to fibrils after the pretreatment. [BMIM]Cl was a good non-derivatizing solvent for the luffa cellulose. The solution conditions were 80°C and 10 h for a 15% solution. After being regenerated, as films, from the luffa/[BMIM]Cl solution, the crystalline structure of the luffa film was transformed completely from cellulose I to cellulose II. The film showed the strong characteristic functional groups of cellulose in FTIR results. The surface of the film was smooth with a compact structure. The porosity of the film was 66.2% and the average pore size was 17.8 nm. It was thermally stabile up to 280°C.     

Effect of Individualized Cellulose Fibrils on Properties of Poly(Methyl Methacrylate) Composites

Cellulose fibrils were manufactured from flax fibers using chemical treatments followed by cryo-crushing and ultrasonication techniques. The fibrils, consisting mainly of cellulose free from lignin, pectin and hemicellulose, were exploited as a biofiller in preparing poly(methyl methacrylate) (PMMA) matrix composites. The effects of incorporating cellulose fibrils on the physical and mechanical properties of the polymer matrix were investigated. In particular, the influence of the fibrils on the thermal stability and degradation of the composites was studied by means of thermogravimetric analysis carried out in both inert and oxidative atmospheres. The runs performed under air flow revealed the efficiency of the cellulose fibrils in delaying the polymer decomposition during thermal oxidation. The weight loss was slowed down in the composites of all compositions and the temperature of degradation increased with increasing the amount of the fibrils. The combustion properties of the fibril-based composites were evaluated by means of pyrolysis combustion flow calorimetry. The addition of cellulose fibrils into the PMMA matrix resulted in a noticeable decrease of the primary combustion parameters.     

The Uniform Si-O Coating on Cotton Fibers by an Atmospheric Pressure Plasma Treatment

A uniform Si-O coating on cotton fabric was produced at atmospheric pressure by a plasma treatment. Before the plasma discharge, a pretreatment with hexamethyldisiloxane (HMDSO)-ethanol mixture solvents on the fabric was employed. The surface morphology and chemical structure of the plasma-treated fibers were analyzed by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray diffraction (XRD) analyses. The SEM results showed that a uniform, continuous film was formed on the cotton fiber surface. It was much rougher than the uncoated fiber. The FTIR results showed that the coatings contained most of the Si-O functional groups. These Si-O bonds, broken from the Si-O-Si functional groups by the plasma electron impact, had connected with the cellulose by chemical bonds of Si-O-Cellulose. XRD patterns revealed the existence of a crystalline structure within the thin coating film. The UV-vis transmission of the cotton textile was greatly reduced by such coatings.     

A Fluoropolymer Coating on Carbon Fibers Improves Their Adhesive Interaction with PTFE Matrix

Carbon fibers were treated in a HF glow discharge in tetrafluoroethylene and octafluorocyclobutane in order to improve their adhesion to poly(tetrafluoroethylene) matrix. As the result of the plasma treatment, a thin (20–140 nm) fluoropolymer coating was deposited onto the fiber surface. The structure of this coating was studied by means of IR spectroscopy, XPS, AFM and SEM techniques. The coating material appeared to be similar to PTFE in its chemical composition but distinguished by branched, partially crosslinked, amorphous structure and included unsaturated chemical bonds. The coating thickness of 70 nm was sufficient to effectively screen the field of molecular forces of the initial substrate, thus, decreasing the surface energy of the fibers and improving their compatibility with the PTFE matrix. The adhesive strength in the PTFE–carbon fiber systems, measured by means of the microbond test, more than doubled upon the plasma treatment (the local interfacial shear strength increased from 10.7 to 29.7 MPa, apparent IFSS from 4.3 to 7.8 MPa), and the interfacial frictional stress increased by 70%. The new composite material consisting of 20% short coated carbon fibers in the PTFE matrix showed better mechanical, thermal and tribological characteristics as compared with the composite reinforced with untreated fibers.     

Short sisal fiber reinforced polypropylene composites: the role of interface modification on ultimate properties

Sisal fibers have been used for the reinforcement of polypropylene matrix. The compatibilization between the hydrophilic cellulose fiber and hydrophobic PP has been achieved through treatment of cellulose fibers with sodium hydroxide, isocyanates, maleic anhydride modified polypropylene (MAPP), benzyl chloride and by using permanganate. Various fiber treatments enhanced the tensile properties of the composites considerably, but to varying degrees. The SEM photomicrographs of fracture surfaces of the treated composites clearly indicated the extent of fiber–matrix interface adhesion, fiber pullout and fiber surface topography. Surface fibrillation is found to occur during alkali treatment which improves interfacial adhesion between the fiber and PP matrix. The grafting of the fibers by MAPP enhances the tensile strength of the resulting composite. It has been found that the urethane derivative of polypropylene glycol and cardanol treatments reduced the hydrophilic nature of sisal fiber and thereby enhanced the tensile properties of the sisal–PP composites, as evident from the SEM photomicrographs of the fracture surface. The IR spectrum of the urethane derivative of polypropylene glycol gave evidence for the existence of a urethane linkage. Benzoylation of the fiber improves the adhesion of the fiber to the PP matrix. The benzoylated fiber was analyzed by IR spectroscopy. Experimental results indicated a better compatibility between benzoylated fiber and PP. The observed enhancement in tensile properties of permanganate-treated composites at a low concentration is due to the permanganate-induced grafting of PP on to sisal fibers. Among the various treatments, MAPP treatment gave superior mechanical properties. Finally, experimental results of the mechanical properties of the composite have been compared with theoretical predictions.     

Surface analysis of oxygen plasma treated poly(p-phenylene benzobisoxazole) fibers

The influence of oxygen plasma treatment on surface properties of poly(p-phenylene benzobisoxazole) (PBO) fibers and aging effect of the oxygen plasma modified PBO fiber surfaces were investigated by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and dynamic contact angle analysis (DCAA), respectively. The results indicated that the oxygen plasma treatment introduced some polar groups to PBO fiber surfaces, enhanced surface roughness and changed surface morphologies of PBO fibers by plasma etching and oxidative reactions. Surface wettability of PBO fibers may be significantly improved by increasing surface free energy of the fibers via oxygen plasma treatment. Aging effect of the oxygen plasma treated PBO fibers showed that the fiber surface wettability degraded in the first several days after the plasma treatment, and it was found to be changeless as the aging time continued as long as 30 days.     

Hydrolysis of Microcrystalline Cellulose to Produce Fermentable Monosaccharides by Plasma Acid

Plasma acid was obtained by treating distilled water with a dielectric barrier discharge (DBD) at atmospheric pressure. The tentative relationship between discharge conditions and pH value of the plasma acid was investigated. In order to optimize the hydrolysis conditions of microcrystalline cellulose with the plasma acid, an orthogonal experiment was carried out and the colorimetric determination of 3,5-dinitro-salicylic acid was applied to measure the concentration of total reduced sugar (TRS). The results showed that the pH value of the plasma acid was related to the discharge time. The acidity of the plasma acid was maintained for several hours and then faded gradually. The microcrystalline cellulose was hydrolyzed effectively by the plasma acid and the optimal hydrolysis conditions were as follows: pH 1.42 of the plasma acid, hydrolysis temperature of 80°C and hydrolysis time of 60 min. Under these conditions, the microcrystalline cellulose with polymerization degree of 200–300 was hydrolyzed completely to produce monosaccharides, including xylose and glucose with the mole ratio of 1:35, as shown by high-performance liquid chromatography (HPLC) analysis. Moreover, the hydrolysis of luffa cellulose with polymerization degree of 500–600 was also carried out. The luffa cellulose was hydrolyzed completely to produce monosaccharides including xylose, mannose and glucose with mole ratio of 6.7:1:218. Therefore, it could be concluded that the main hydrolysis product of both types of cellulose was glucose. The glucose yield of microcrystalline cellulose was 46%, whereas for luffa cellulose it was 41%. This method was an environmentally friendly and effective method to hydrolyze cellulose.     

Unsaturated polyester resin (UPR) reinforced with flax fibers,untreated and cold He plasma-treated: thermal,mechanical and DMA studies

Hemp, jute, flax, bagasse, coconut and bamboo fibers are some of the natural fibers that have attracted attention for the preparation of composite materials because of their low cost compared with synthetics fibers (glass, carbon). The performance of a natural fiber as reinforcement in composite materials is linked to its ability in term of adhesion with the synthetic matrix. This depends mainly on the quality of the fiber surface. In order to improve this adhesion, a thin reactive coating is generally used. In this study, cold He plasma treatments have been carried out on reinforcing flax fiber. Composites with unsaturated polyester resin (UPR) have been used with untreated flax fibers and plasma-treated fibers. The data characterizing the thermal, mechanical (dynamic and static) will be presented in order to analyze the efficiency of the He plasma treatment on the composite performances.     

Effect of fiber surface treatments on the fiber–matrix interaction in banana fiber reinforced polyester composites

Cellulosic fibers have been used as cost-cutting fillers in plastic industry. Among the various factors, the final performance of the composite materials depends to a large extent on the adhesion between the polymer matrix and the reinforcement and therefore on the quality of the interface. To achieve optimum performance of the end product, sufficient interaction between the matrix resin and the cellulosic material is desired. This is often achieved by surface modification of the resin or the filler. Banana fiber, the cellulosic fibers obtained from the pseudo-stem of banana plant (Musa sepientum) is a bast fiber with relatively good mechanical properties. The fiber surface was modified chemically to bring about improved interfacial interaction between the fiber and the polyester matrix. Various silanes and alkali were used to modify the fiber surface. Modified surfaces were characterized by SEM and FTIR. The polarity parameters of the chemically modified fibers were investigated using the solvatochromic technique. The results were further confirmed by electrokinetic measurements. Chemical modification was found to have a profound effect on the fiber–matrix interactions. The improved fiber–matrix interaction is evident from the enhanced tensile and flexural properties. The lower impact properties of the treated composites compared to the untreated composites further point to the improved fiber–matrix adhesion. In order to know more about the fiber–matrix adhesion, fractured surfaces of the failed composites where further investigated by SEM. Of the various chemical treatments, simple alkali treatment with NaOH of 1% concentration was found to be the most effective. The fiber–matrix interactions were found to be dependent on the polarity of the modified fiber surface.     

Plasma treatment of carbon fibers: Non-equilibrium dynamic adsorption and its effect on the mechanical properties of RTM fabricated composites

The effect of oxygen plasma treatment on the non-equilibrium dynamic adsorption of the carbon fabric reinforcements in RTM process was studied. 5-Dimethylamino-1-naphthalene-sulfonylchloride (DNS-Cl) was attached to the curing agent to study the change of curing agent content in the epoxy resin matrix. Steady state fluorescence spectroscopy (FS) analysis was used to study this changes in the epoxy resin at the inlet and outlet of the RTM mould, and XPS was used to study the chemical changes on the carbon fiber surfaces introduced by plasma treatment. The interlaminar shear strength (ILSS) and flexural strength were also measured to study the effects of this non-equilibrium dynamic adsorption progress on the mechanical properties of the end products. FS analysis shows that the curing agent adsorbed onto the fiber surface preferentially for untreated carbon fiber, the curing agent content in the resin matrix maintain unchanged after plasma treatment for 3 min and 5 min, but after oxygen plasma treatment for 7 min, the epoxy resin adsorbed onto the fiber surface preferentially. XPS analysis indicated that the oxygen plasma treatment successfully increased some polar functional groups concentration on the carbon fiber surfaces, this changes on the carbon fiber surfaces can change the adsorption ability of carbon fiber to the resin and curing agent. The mechanical properties of the composites were correlated to this results.     

Ultrasound-Assisted Surface-Modification of Wood Particulates for Improved Wood/Plastic Composites

The combined effects of alkali and ultrasound treatment of wood flour on the mechanical properties of polypropylene-based wood/plastic composites (WPCs) were examined. FT-IR measurements confirmed that the alkali treatment removed both hemicellulose and lignin from the wood, and there was an increase in the number of hydroxyl groups on the cellulose surface. This process was promoted by ultrasound treatment. Mechanical testing of injection-molded WPC samples revealed that alkali treatment improved both composite strength and modulus when polypropylene grafted with maleic acid was used as a coupling agent. The strength increase is due to improved adhesion between the fiber and matrix, while improved modulus is due to the removal of lignin and hemicellulose that are not as stiff as cellulose. Polarized optical microscopy showed the presence of well-defined polymer crystals on the surface of the modified wood, and this is also responsible for the improved mechanical properties. It is conclusively demonstrated that the combination of chemical treatment of wood and ultrasound assistance is more effective in improving the mechanical properties of the composites than the use of chemical treatment alone.     

Upgrading poly(butylene succinate)/wood fiber composites by esterified lignin

Aliphatic chains were introduced into the macromolecule of kraft lignin using aliphatic chlorides as esterification reagents. The hydrophobicity of esterified lignin (EL) was enhanced as compared to the original lignin. EL was further used as a macromolecular coupling agent in poly(butylene succinate)/chemi-thermomechanical pulp fiber composites. As a result, the composites with enhanced mechanical performance were obtained, and the tensile strength, impact strength, and bending strength were increased by 25.1, 22.4, and 19.3%, respectively, under 2 wt% EL-treatment (synthesized by palmitoyl chloride, –COCl/–OH = 1.5:1) in comparison with those of the specimen without any coupling agent treatment. Furthermore, the composite prepared with EL-treated fibers shows significant lower water absorption ratio than that of untreated one. A significant increase in storage modulus (E′) was observed upon the incorporation of treated fibers. Furthermore, the improved interfacial bonding between treated fibers and matrix was verified by SEM images. The shear viscosity of composite was increased by the incorporation of EL, but in general, the rheological behaviors of composites are not significantly changed.     

热处理竹材的化学成分傅里叶变换红外光谱分析

化学热处理是实现可再生木质生物能源中纤维素高效利用及半纤维素糖化转换的关键步骤。通过预处理过程可以快速去除难溶木质素,实现细胞壁中半纤维素的物理化分离,使得植物细胞壁中化学成分发生变化,从而增加木质纤维素的产出量。以硫酸(H₂SO₄)、稀碱(NaOH)及甘油(glycerol)为预处理介质,采用不同的热处理温度(硫酸(H₂SO₄)、稀碱(NaOH)热处理温度为117和135 ℃;甘油(glycerol)热处理温度为117 ℃)),对竹材处理前后的主要化学组分进行对比分析,并通过傅里叶变换红外光谱进一步证实化学热处理前后竹材化学组分的变化,以获得不同的化学热处理介入下竹材化学成分转换的主要变化规律和机理。结果表明：热化学处理后竹材的纤维素产出量明显增加。纤维素得率及木质素的去除率在不同的处理介质条件下的变化规律为,稀碱(NaOH)处理效果优于稀酸(H₂SO₄)和甘油(glycerol);此外,在相同介质条件下135 ℃热处理效果比117 ℃热处理效果显著。对于不同处理条件的半纤维素的降解程度大小变化结果与此相同。通过红外光谱分析可知,热处理后纤维素环状C-O-C不对称伸缩振动峰出现峰值分解,半纤维素的红外吸收特征峰出现明显陡降变化,木质素苯环特征吸收峰明显减弱,证明纤维素产出量明显增加,半纤维素降解趋势明显,木质素去除效果良好。傅里叶红外变换光谱分析结果与标准测定结果一致。     

Laser surface treatment of regenerated cellulose fiber

Effects of the excimer laser irradiation on regenerated cellulose fibers were investigated. The surface structure change was remarkable only when the ArF laser was applied. Small pores and fibrils were observed on the fiber surface at the high fluence irradiation. In some cases, several cracks were observed inside the fiber. The fiber structure change was strongly dependent on fluence and number of pulses. XPS analysis indicated an increase of carbonyl groups and removal of CO and CO₂ on the fiber surface. Concerning the fiber properties, the tensile strength lowered, and the moisture content was improved a little. Those property changes could be explained by the breakage of intermolecular hydrogen bonding and that of the main chain of the cellulose molecule. Increase of specific surface area and chemical structure change suggest that irradiated fiber can be applied as a component for soft composite materials.     

Pretreatment combining ultrasound and sodium percarbonate under mild conditions for efficient degradation of corn stover

Ultrasound (US) can be used to disrupt microcrystalline cellulose to give nanofibers via ultrasonic cavitation. Sodium percarbonate (SP), consisting of sodium carbonate and hydrogen peroxide, generates highly reactive radicals, which cause oxidative delignification. Here, we describe a novel pretreatment technique using a combination of US and SP (US–SP) for the efficient saccharification of cellulose and hemicellulose in lignocellulosic corn stover. Although US–SP pretreatment was conducted under mild condition (i.e., at room temperature and atmospheric pressure), the pretreatment greatly increased lignin removal and cellulose digestibility. We also determined the optimum US–SP treatment conditions, such as ultrasonic power output, pretreatment time, pretreatment temperature, and SP concentration for an efficient cellulose saccharification. Moreover, xylose could be effectively recovered from US–SP pretreated biomass without the formation of microbial inhibitor furfural.     

Kenaf/polypropylene biocomposites: effects of electron beam irradiation and alkali treatment on kenaf natural fibers

Thermal and dynamic mechanical properties of kenaf natural fiber reinforced polypropylene (PP) biocomposites were examined to compare the effects of natural fiber treatment by electron beam irradiation (EBI) and alkalization. The alpha cellulose contents, the functional groups on the surfaces and the thermal stability of the untreated and treated kenaf fibers were studied. Kenaf fiber/polypropylene(PP) biocomposites were fabricated by means of a compression molding technique using chopped kenaf fibers treated with electron beam (EB) dosages of 100, 200, 500 kGy or with NaOH concentrations of 2, 5, 10 wt%, respectively. The thermal stability, the dynamic mechanical and the interfacial properties of untreated and treated kenaf/PP biocomposites were also investigated through a thermogravimetric analysis, a dynamic mechanical analysis and a fractographic observation, respectively. The results show that the characteristics of kenaf fibers and biocomposites depended on the different treatment level with the EB dosages or on the NaOH concentrations used. In this study, the modification of kenaf fiber surfaces at 200 kGy EBI and treatment with 5 wt% NaOH was most effective for improving the performance of kenaf/PP biocomposites. This study suggests that EBI can be used for modification of natural fiber as an environmentally friendly process and contribute to an improvement in the performances of kenaf/PP biocomposites.     

Atmospheric air-plasma treatment of polyester fiber to improve the performance of nanoemulsion silicone

Influence of atmospheric air plasma treatment on performance of nanoemulsion silicone softener on polyethylene terephthalate fibers was investigated by the use of fourier transform infrared spectroscopy (FTIR), bending lengths (BL), wrinkle recovery angles (WRA), fiber friction coefficient analysis (FFCA), moisture absorbency (MA), scanning electron microscopy (SEM) and reflectance spectroscopy (RS). Results indicated that the plasma pretreatment modifies the surface of fibers and increases the reactivity of substrate toward nanoemulsion silicone. Moisture regain and microscopic tests showed that the combination of plasma and silicone treatments on polyethylene terephthalate can decrease moisture absorption due to uniform coating of silicone emulsion on surface of fibers.     

Effect of chemical modifications of the pineapple leaf fiber surfaces on the interfacial and mechanical properties of laminated biocomposites

Natural fiber reinforced renewable resource based laminated composites were prepared from biodegradable poly(lactic acid) (PLA) and untreated or surface-treated pineapple leaf fibers (PALF) by compression molding using the film stacking method. The objective of this study was to determine the effects of surface treatment of PALF on the performance of the fiber-reinforced composites. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) were used to aid in the analysis. The mechanical properties of the PLA laminated composites were improved significantly after chemical treatment. It was found that both silane- and alkali-treated fiber reinforced composites offered superior mechanical properties compared to untreated fiber reinforced composites. The effects of temperature on the viscoelastic properties of composites were studied by dynamic mechanical analysis (DMA). From the DMA results, incorporation of the PALF fibers resulted in a considerable increase of the storage modulus (stiffness) values. The heat defection temperature (HDT) of the PALF fiber reinforced PLA laminated composites was significantly higher than the HDT of the neat PLA resin. The differential scanning calorimeter (DSC) results suggest that surface treatment of PALF affects the crystallization properties of the PLA matrix. Additionally, scanning electron microscopy (SEM) was used to investigate the distribution of PLA within the fiber network. SEM photographs of fiber surface and fracture surfaces of composites clearly indicated the extent of fiber–matrix interface adhesion. It was found that the interfacial properties between the reinforcing PALF fibers and the surrounding matrix of the laminated composite are very important to the performance of the composite materials and PALF fibers are good candidates for the reinforcement fiber of high performance laminated biodegradable biocomposites.     

Plasma-polymerized organosilicones as engineered interlayers in glass fiber/polyester composites

The plasma polymerization technique was used to surface modify glass fibers in order to form a strong but tough link between the glass fiber and the polyester matrix, and enable an efficient stress transfer from the polymer matrix to the fiber. Plasma polymer films of hexamethyldisiloxane, vinyltriethoxysilane, and tetravinylsilane in a mixture with oxygen gas were engineered as compatible interlayers for the glass fiber/polyester composite. The interlayers of controlled physico-chemical properties were tailored using the deposition conditions with regard to the elemental composition, chemical structure, and Young's modulus in order to improve adhesion bonding at the interlayer/glass and polyester/interlayer interfaces and tune the cross-linking of the plasma polymer. The optimized interlayer enabled a 6.5-fold increase of the short-beam strength compared to the untreated fibers. The short-beam strength of GF/polyester composite with the pp-TVS/O₂ interlayer was 32% higher than that with industrial sizing developed for fiber-reinforced composites with a polyester matrix.     

Effects of γ-ray radiation grafting on aramid fibers and its composites

Armos fiber was modified by Co⁶⁰ γ-ray radiation in the different concentrations’ mixtures of phenol-formaldehyde and ethanol. Interlaminar shear strength (ILSS) was examined to characterize the effects of the treatment upon the interfacial bonding properties of Armos fibers/epoxy resin composites. The results showed that the ILSS of the composite, whose fibers were treated by 500 kGy radiation in 1.5 wt% PF, was improved by 25.4%. Nanoindentation technique analysis showed that the nanohardnesses of the various phases (the fiber, the interface and the matrix) in the composite, whose fibers were treated, were correspondingly higher than those in the composite, whose fibers were untreated. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR) spectrum confirmed the increase in the polar groups at the fibers’ surface. Atomic force microscopy (AFM) results revealed that the surface of the fibers treated was rougher than that of the fibers untreated. The wettability of the fibers’ surface was also enhanced by the treatment. The conclusion that γ-ray irradiation grafting significantly improved the surface properties of Armos fibers could be drawn.