Renewable resources as reinforcement of polymeric matrices: composites based on phenolic thermosets and chemically modified sisal fibers

Lignocellulosic materials can significantly contribute to the development of composites, since it is possible to chemically and/or physically modify their main components, cellulose, hemicelluloses and lignin. This may result in materials more stable and with more uniform properties. It has previously been shown that chemically modified sisal fibers by ClO(2) oxidation and reaction with FA and PFA presented a thin coating layer of PFA on their surface. FA and PFA were chosen as reagents because these alcohols can be obtained from renewable sources. In the present work, the effects of the polymeric coating layer as coupling agent in phenolic/sisal fibers composites were studied. For a more detailed characterization of the fibers, IGC was used to evaluate the changes that occurred at the sisal fibers surface after the chemical modifications. The dispersive and acid-base properties of untreated and treated sisal fibers surfaces were determined. Biodegradation experiments were also carried out. In a complementary study, another PFA modification was made on sisal fibers, using K2Cr2O(7) as oxidizing agent. In this case the oxidation effects involve mainly the cellulose polymer instead of lignin, as observed when the oxidation was carried out with ClO(2). The SEM images showed that the oxidation of sisal fibers followed by reaction with FA or PFA favored the fiber/phenolic matrix interaction at the interface. However, because the fibers were partially degraded by the chemical treatment, the impact strength of the sisal-reinforced composites decreased. By contrast, the chemical modification of fibers led to an increase of the water diffusion coefficient and to a decrease of the water absorption of the composites reinforced with modified fibers. The latter property is very important for certain applications, such as in the automotive industry.     

Thermoset matrix reinforced with sisal fibers: Effect of the cure cycle on the properties of the biobased composite

Thermoset phenolic composites reinforced with sisal fibers were prepared to optimize the cure step. In the present study, processing parameters such as pressure, temperature, and time interval were varied to control the vaporization of the water generated as a byproduct during the crosslinking reaction. These molecules can vaporize forming voids, which in turn affect the final material properties. The set of results on impact strength revealed that the application of higher pressure before the gel point of the phenolic matrix produced composites with better properties. The SEM images showed that the cure cycle corresponding to the application of higher values of molding pressure at the gel point of the phenolic resin led to the reduction of voids in the matrix. In addition, the increase in the molding pressure during the cure step increased the resin interdiffusion. Better filling of the fiber channels decreased the possibility of water molecules diffusing through the internal spaces of the fibers. These molecules then diffused mainly through the bulk of the thermoset matrix, which led to a decrease in the water diffusion coefficient (D) at all three temperatures (25, 55 and 70 °C) considered in the experiments.     

Enzyme degradability of benzylated sisal and its self‐reinforced composites

To produce natural polymer based composite materials, sisal fibers were slightly benzylated and then molded into sheets. Because the modified skin portions of the fibers acquired certain thermoplasticity and the unmodified core parts remain constant, the resultant composites fall into the category of self‐reinforced ones. The present article is devoted to the evaluation of the materials biodegradability with the help of cellulase. It was found that the inherent biodegradability of plant fibers is still associated with the benzylated sisal and the molded composites, as characterized by structural variation, weight loss and deterioration of mechanical performance of the materials. Reaction temperature and time, pH value of the enzyme solution, and dosage of the enzyme had significant influences on the decomposition behavior of the materials. In principle, the enzymolysis of sisal and its self‐reinforced composites is a diffusion‐controlled process. Due to the insusceptibility of lignin to cellulase and the hindrance of it to the cellulase solution, the degradation rates of the materials are gradually slowed down with an increase in time. Copyright © 2003 John Wiley & Sons, Ltd.     

Improvement in mechanical and thermal properties of polylactic acid biocomposites due to the addition of hybrid sisal fibers and diatomite particles

Hybrid sisal fibers (HSFs) were made by mixing untreated sisal fibers with alkali-treated sisal fibers (ASFs), and the HSFs were blended with polylactic acid (PLA) matrix. Then the diatomite particles were added into the PLA/HSFs composite to make PLA/HSFs/diatomite composite. The effect of these two fillers on mechanical and thermal properties was investigated. The results showed that the reinforcing effect of HSFs was better than ASFs. Mechanical and thermal properties (especially the impact strength and crystallinity) of PLA/HSFs were higher than that of PLA/ASFs. The addition of diatomite further improved the mechanical and thermal properties of PLA composites.     

Mechanical and thermal characterization of sisal fiber reinforced polylactic acid composites

The advantages of green composites are including, but not limited to their environmental friendly nature, lightweight, reduction of production energy and costs, and recyclability. This work focuses on the mechanical, thermal, and dynamic mechanical properties of biocomposites. For that purpose, biosourced polymers were used, namely polylactic acid (PLA) and sisal fiber, and biocomposites were extruded and then injection molded with different contents of sisal fibers (5%, 10%, 15%). The results show that the increase of the rate of reinforcement improves the mechanical and dynamic mechanical properties of the biocomposites made. By the increase of the sisal fiber content, the degree of crystallinity of the matrix was increased from 47% to 61%, as sisal fibers were acted as a nucleating agent for the PLA.     

Thermal characterization and electrical properties of Fe-modified cellulose long fibers and micro crystalline cellulose

Thermal properties of polylactic acid (PLA) filled with Fe-modified cellulose long fibers (CLF) and microcrystalline cellulose (MCC) were studied using thermo gravimetric analysis (TG), differential scanning calorimetry, and dynamic mechanical analysis (DMA). The Fe-modified CLFs and MCCs were compared with unmodified samples to study the effect of modification with Fe on electrical conductivity. Results from TG showed that the degradation temperature was higher for all composites when compared to the pure PLA and that the PLA composites filled with unmodified celluloses resulted in the best thermal stability. No comparable difference was found in glass transition temperature (T _g) and melting temperature (T _m) between pure PLA and Fe-modified and unmodified CLF- and MCC-based PLA biocomposites. DMA results showed that the storage modulus in glassy state was increased for the biocomposites when compared to pure PLA. The results obtained from a femtostat showed that electrical conductivity of Fe-modified CLF and MCC samples were higher than that of unmodified samples, thus indicating that the prepared biocomposites have potential uses where conductive biopolymers are needed. These modified fibers can also be tailored for fiber orientation in a matrix when subjected to a magnetic field.     

Facile extraction,processing and characterization of biorenewable sisal fibers for multifunctional applications

Synthetic fibers based materials have replaced most of the traditional metallic/ceramic materials for a number of applications owing to their enormous properties such as light weight, specific strength and modulus to name a few. Unfortunately, the traditional synthetic fibers are not desired from the health and environmental point of view. So, in this work, we have carried out the isolation, processing and characterization of cellulosic sisal fibers. These fibers were extracted for the first time by a simple and new unique mechanical extraction technique without affecting the quality of fibers. Subsequently these cellulosic sisal fibers were thoroughly characterized for their physicochemical, microstructure and mechanical properties. These fibers were then converted into fine textured sisal textile yarn made out of 3–6 sisal fibers in continuous operation and used for the preparation of new green materials. Different properties of fine textured sisal textile and the impact of sisal fine textile on the physical, microstructural, thermal and mechanical characteristics of the green materials were studied and discussed in detail.     

Preparation and adsorption of novel cellulosic fibers modified by β‐cyclodextrin

Novel cellulosic fibers modified by β‐cyclodextrin (CFEC) were prepared for adsorption for heavy metal ions like copper (II) and organic dye like neutral red from their aqueous solutions. The modified cellulosic fibers gave higher copper ion adsorption, and showed copper ion uptake values of 6.24 mg/g at 293°C, as against no adsorption for unmodified cellulosic fibers. Adsorption isotherm model indicated the adsorption of the novel modified fibers for heavy metal ions best fitted for Langmiur model. The adsorption was an exothermic reaction, and the reaction caloric was 6.295 kJ/mol. Copper ions could form a 7:4 complex with β‐cyclodextrin (β‐CD). The novel modified cellulosic fibers could also form inclusion complexes with neutral red via β‐CD molecules. In addition, it was found that the novel modified cellulosic fibers had nearly the same mechanical and thermal properties as the unmodified cellulosic fibers because the modification did not destroy the main chain of cellulose molecules. Copyright © 2008 John Wiley & Sons, Ltd.     

Modification of renewable resources—lignin—by three chemical methods and its applications to polyurethane foams

To improve the economic viability of polymer from renewable resources, a value‐added lignin polymer is increasingly important. The lignin was successfully modified by three chemical methods: hydroxymethylation, epoxidation, and phenolation. Through these methods, the percentage of impurity had decreased, and the number of phenolic hydroxyl groups of lignin had dramatically increased, particularly by phenolation, reaching 9.41%, nearly three times higher than that in the unmodified one. Meanwhile, we added different amounts of modified lignin into polyurethane foams, and the results showed that 1 wt% modified lignin could not only increase the decomposition temperature of the foam material but also remarkably improve its mechanical properties. The optimum reaction time was 4 hr, and the reaction temperature was 80°C for blends. Copyright © 2014 John Wiley & Sons, Ltd.     

Studies on the cellulose-binding domains adsorption to cellulose

Cellulose-binding domains (CBD) are modular peptides, present in many glycanases, which anchor these enzymes to the substrate. In this work, the effect of CBD adsorption on the surface properties of a model cellulose, Whatman CF11, was studied. The methods applied include inverse gas chromatography (IGC), ESCA, X-ray diffraction, and scanning electron microscopy (SEM). The CBD partition affinity (0.85 L/g) was calculated from adsorption isotherms. However, true adsorption equilibrium does not exist, since CBDs are apparently irreversibly adsorbed to the fibers. Both IGC and ESCA showed that fibers with adsorbed CBD have a lower acidic character and also a slightly higher affinity toward aliphatic molecules. This may however be a consequence of an increased surface area, a hypothesis that is supported by microscopic observations. The crystallinity index was not affected by CBD treatment.     

Preparation of PA6/nano titanium dioxide (TiO2) composites and their spinnability

In this work, surface modification technique with coupling agents and anchoring polymerization was adopted to tailor the surface properties of nanoscaled titanium dioxide (TiO₂). Ethyl glycol sols with TiO₂ were prepared in order to simulate the dispersibility of differently modified TiO₂ in a molten polyamide 6 (PA6) matrix. The modified TiO₂ were melt compounded with PA6 and composites and fibers were prepared. The average filler diameter of 47 nm (in composites) and 44 nm (in fibers) indicated homogeneous dispersion of TiO₂ in the matrix, whereas unmodified TiO₂ showed agglomerated structures in the PA6 matrix. The mechanical properties of the composite fibers were improved as compared to pure PA6 fibers and composite fibers with unmodified TiO₂.     

Microstructure and surface properties of fibrous and ground cellulosic substrates

Cotton and linen fibers were ground in a ball-mill, and the effect of grinding on the microstructure and surface properties of the fibers was determined by combining a couple of simple tests with powerful techniques of surface and structure analysis. Results clearly proved that the effect of grinding on cotton fiber was much less severe than on linen. For both fibers, the degree of polymerization reduced (by 14.5% and 30.5% for cotton and linen, respectively) with a simultaneous increase in copper number. The increased water sorption capacity of the ground substrates was in good agreement with the X-ray results, which proved a less perfect crystalline structure in the ground samples. Data from XPS and SEM-EDS methods revealed that the concentration of oxygen atoms (bonded especially in acetal and/or carbonyl groups) on the ground surfaces increased significantly, resulting in an increase in oxygen/carbon atomic ratio (XPS data: from 0.11 to 0.14 and from 0.16 to 0.29 for cotton and linen, respectively). Although grinding created new surfaces rich in O atoms, the probable higher energy of the surface could not be measured by IGC, most likely due to the limited adsorption of the n-alkane probes on the less perfect crystalline surfaces.     

Investigation into the interactions between filler and elastomers used for tyre production

An investigation in the interactions between silica and elastomers used in the production of tyre treads was carried out. To achieve some knowledge on the interactions between reinforcing agent and elastomers, which are fundamental in determining the rubber reinforcement, inverse gas chromatography (IGC) at infinite dilution was used to evaluate surface properties of both unmodified and modified silica and to calculate the adsorption free energy and enthalpy of low molecular weight analogues of elastomers. The predictions derived from the thermodynamic study were compared with some of the results obtained by a morphological analysis of silica-filled compounds carried out by transmission electron microscopy (TEM) and automated image analysis (AIA).     

Carbon-13 NMR spectroscopic studies on chemically modified and unmodified synthetic and natural humic acids

Carbon-13 cross-polarization magic-angle spinning nuclear magnetic resonance spectroscopy ((13)C-CP/MAS-NMR) was applied to study the chemical modification process of humic acids (HA) with diazomethane and the subsequent alkaline hydrolysis of the methylated HA. This modification process results in HA with selectively blocked phenolic OH groups, which can be used for metal ion binding studies with humic substances. Different chemically modified and unmodified natural and synthetic HA with carbon-13 of natural abundance were investigated. In addition, carbon-13 labeled modified synthetic HA, that were synthesized with [(13)C]diazomethane as methylation reagent, were studied to confirm the assumed modification process and to determine the type of functional groups that have the highest affinity for methylation with diazomethane. The results of the NMR studies with carbon-13 labeled modified HA show that predominantly carboxyl and phenolic OH groups are methylated with diazomethane resulting in methyl ester and methyl ether groups, respectively. Due to the alkaline treatment of the methylated HA, the methyl esters of carboxyl groups are hydrolyzed, whereas methyl ethers of phenolic OH groups remain unchanged, which results in modified HA with blocked phenolic OH groups. From the spectra of the modified and unmodified HA with carbon-13 of natural abundance it can be concluded that the applied preparative modification procedure causes only the desired structural changes in HA.     

The effect of plasma treatment on the mechanical behavior of UHMWPE fiber–reinforced thermoplastic HDPE composite

Ultra‐high‐molecular‐weight polyethylene (UHMWPE) fibers have been modified by plasma treatment to increase adhesion in high‐density polyethylene (HDPE) matrices. Results showed that surface roughness predominates for modified UHMWPE fibers, indicating that the plasma treatment favors the interaction with HDPE. Unmodified HDPE composite samples gave a lower interlaminar shear strength than did the samples that were incorporated with UHMWPE. The addition of unmodified UHMWPE fibers to the neat HDPE significantly increases interlaminar shear strengths of composites, up to 20 vol%. The oxygen concentration increased from 16.16 %to 21.99%, and the ratio of oxygen to carbon atoms increased significantly from 0.194 to 0.284 after oxygen plasma treatment for 5 minutes with a power of 300 W.     

A study of the surface properties of cotton fibers by inverse gas chromatography

In the present study, the potential relationships between the microstructure and the surface properties of different cotton fibers are analyzed by inverse gas chromatography (IGC) at infinite dilution. By measuring the retention time of polar and nonpolar gaseous probes into a column containing the fibers, surface characteristics of these fibers, in particular the dispersive component of their surface energy and their surface morphological index, were determined. It is clearly shown that the presence of natural waxes on cotton fibers plays a major role on their thermodynamic surface properties, affecting the surface energy and the acid-base character as well as the morphological aspects of such fibers. Finally, it appeared that IGC is a well appropriate method for the evaluation of the surface characteristics of cotton fibers.     

Braking Performance of an Organic Brake Pad Based on a Chemically Modified Phenolic Resin Binder

An organic brake pad for railroad passenger-coach braking was prepared using a chemically modified phenolic resin (PF), that was designed and manufactured in our laboratory. The braking performance of the pad was investigated on a full-scale test bench. For comparison, a brake pad based on straight PF was also prepared and investigated. The results showed that the modified PF pad possessed much higher impact strength, and better braking stability and wear resistance than the straight PF pad. It is thought that the better overall properties of the modified PF pad resulted from the changes in chemical structure of the resin during the frictional process and the strong interreaction of the modified resin binder with the hybrid fibers.     

STUDIES ON THE PREPARATION OF ZINC-CONTAINING ACTIVATED CARBON FIBERS AND THEIR ANTIBACTERIAL ACTIVITY

1. INTRODUCTION Microbial pollution will bring about various problems in industry and other vital fields, such as causing decomposing of materials, harming people抯 health. In order to reduce these problems, new antibacterial materials have been demanded. Recently, much attention has been paid to inorganic materials including zinc oxide [1~4]. These inorganic antibacterial materials are now substituting for organic materials to avoid releasing noxious organic molecules harmful to humans;…     

Sisal fibers coated with conducting polyaniline: Property and structural studies

Sisal (Agave sisalana) fiber was extracted by manual process. These fibers were subjected to surface coating with conducting polyaniline, through in situ oxidative polymerization. The polyaniline modified sisal fibers were characterized by thermal, spectroscopic and microscopic techniques. It was shown that the fiber was coated with polyaniline through in situ oxidative polymerization and the latter had a smoothing effect on the surface as compared to uncoated sisal fiber. Besides, it was confirmed that polyaniline was deposited in conductive form of emeraldine salt. This in turn verified the introduction of active functionalities to the system, which is helpful to tune up surface chemistry of polyaniline for water treatment applications.