Microcrystalline cellulose as reactive reinforcing fillers for epoxidized soybean oil polymer composites

Microcrystalline cellulose (MCC) and its oxidized product dialdehyde cellulose (DAC) were introduced as the reinforcing filler in epoxidized soybean oil (ESO) thermosetting polymer. The composites comprising up to 25 wt % cellulose fillers were obtained via a solution casting. The reinforcing effects of the cellulose were evaluated by microstructure analysis, dynamic mechanical analysis, and tensile and thermal stability tests. The results showed that at the same filler concentration, DAC led to higher stretching strength, modulus, and break elongation than MCC. The 5 wt % DAC loading in ESO polymer exhibits the highest toughness and thermal stability due to the good dispersion and interfacial interaction between DAC and ESO polymer matrix. The increased storage modulus and glass transition temperature also indicate the cellulose fillers impart stiffness to the composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42488.     

Melt compounded nanocomposites with semi‐interpenetrated network structure based on natural rubber,polyethylene, and carrot nanofibers

The present study deals with the processing and characterization of cellulose nanocomposites natural rubber (NR), low‐density polyethylene (LDPE) reinforced with carrot nanofibers (CNF) with the semi‐interpenetrated network (S‐IPN) structure. The nanocomposites were compounded using a co‐rotating twin‐screw extruder where a master‐batch of NR and CNF was fed to the LDPE melt, and the NR phase was crosslinked with dicumyl peroxide. The prepared S‐IPN nanocomposites exhibited a significant improvement in tensile modulus and yield strength with 5 wt % CNF content. These improvements are due to a better phase dispersion in the S‐IPN nanocomposites compared with the normal blend materials, as demonstrated by optical microscopy, electron microscopy and ultraviolet–visible spectroscopy. The S‐IPN nanocomposite also displayed an improved crystallinity and higher thermal resistance compared with NR, CNF, and the normal blend materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45961.     

The aggregation structure regulation of lignin by chemical modification and its effect on the property of lignin/styrene–butadiene rubber composites

The aggregation structure of lignin in aqueous solution had an important effect on the dispersion of lignin and the properties of lignin/styrene–butadiene rubber (SBR) composites. This article revealed the relationship between aggregation structure and chemical structure of modified lignin. Unmodified lignin was amorphous; however, our results showed that aldehyde‐modified lignin was transformed into spherical aggregates, while propylene‐oxide‐modified lignin self‐aggregated into supramolecular domains. The relationships between aggregation structure, filler dispersion, filler–rubber interaction, and performance were also studied by investigating the microstructure, viscoelastic behavior, and mechanical properties of lignin/SBR composites. Meanwhile, a solution to improve the coprecipitation efficiency of lignin and SBR latex was proposed. In this article, epoxidized natural rubber (ENR) was also used as compatibilizer to improve the interfacial adhesion between polar lignin and nonpolar SBR. The results showed better lignin dispersion for the ENR‐containing rubber composites, as well as superior wet skid resistance and lower rolling resistance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45759.     

Graft copolymers of microcrystalline cellulose as reinforcing agent for elastomers based on natural rubber

In the present study, free radical graft copolymerization of acrylic monomers and microcrystalline cellulose (MCC) was applied to develop a biopolymer for natural rubber reinforcements. The copolymerization was carried out in aqueous media. Cerium ammonium nitrate was employed as the initiator in the presence of nitric acid. Acrylic monomers used in the copolymer synthesis were ethyl acrylate (EA) and butyl acrylate (BA). Effects of monomer concentration, initiator concentration, polymerization time, and polymerization temperature on the obtained graft copolymers were investigated. The graft parameters were obtained by thermal gravimetric analysis method. The obtained copolymers (MCC‐g‐PEA, MCC‐g‐PBA) were characterized by attenuated total reflection, wide‐angle X‐ray diffraction, field‐emission electron microscopy, and thermal gravimetric analysis. In comparison to native MCC, better thermal stability of graft copolymers were observed. In addition, the graft copolymers reinforced natural rubber composites were produced, and sulfur was used as the vulcanizing agent. Their vulcanization and mechanical properties were characterized. Comparing to the native MCC reinforced natural rubber composites, the copolymers reinforced natural rubber composites shows improved mechanical properties, indicating the copolymer's potential application as rubber reinforcements. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43087.     

The rheology and extrusion processing performance of wood/melamine composites

A modified melamine resin that exhibits both thermoplastic and thermoset behaviors was used as a matrix for wood plastic composites (WPCs). The thermoplastic melamine (TPM) resin exhibits a glass transition at approximately 34°C and continues to be thermally malleable until a crosslinking reaction develops with additional heating and an acid catalyst. Varying blends of TPM and wood flour were evaluated for their rheology and curing behavior using torque rheometry. WPC composites were manufactured with extrusion methods and final product properties determined. The torque rheometry results showed a highly dependent relationship of the curing behavior to the amount of wood flour utilized and temperature. Based upon the torque rheometry results, two extrusion platforms were developed to initiate the curing process; (1) cure within the die land and (2) post‐cure of the extrudate. The post‐cure procedure provided composites with higher mechanical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39858.     

Mechanical properties of natural carbon black reinforced polymer composites

This article describes the development of new carbon black material from agricultural waste (wood apple shells) by using pyrolysis method at various carbonization temperatures (400, 600, and 800°C) and used as reinforcement in polymer composites. The wood apple shell carbon black (WAS‐CB) particulates are characterized by proximate analysis, energy dispersive spectroscopy (EDS), and scanning electron microscope (SEM). Results showed that due to increases in carbonization temperature the percentage of carbon improved in the carbon black particles. Furthermore, various tests were performed to determine the effect of new carbon black material on the mechanical properties of composite at different filler loading. The results indicated that mechanical properties like tensile strength, tensile modulus, flexural strength, and flexural modulus are improved as the increase in the carbonization temperature and filler loading. The filler‐matrix bonding was analyzed by SEM. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41211.     

Poly(vinyl alcohol)/quaternized lignin composite absorbent: Synthesis,characterization and application for nitrate adsorption

A new poly(vinyl alcohol) (PVA)/quaternized lignin composite absorbent (PVA/QL) was synthesized from modified lignin and PVA, crosslinked by glutaraldehyde. As‐prepared absorbent was characterized by IR, DSC, SEM BET, and DMA. Effects of shaking time, absorbent dose, initial pH, and temperature on NO₃^? removal from aqueous solution by the absorbent were comprehensively investigated. The results show that the PVA/QL absorbent comprises quaternary ammonium groups in the form of ether bond. The composite absorbent exhibits remarkable network structure with large numbers of connected holes. The mechanical strength of the absorbent is enhanced by combining of PVA with modified lignin and crosslinkage of glutaraldehyde. The effect of pH on adsorption of NO₃^? is apparent and appropriate pH is 2.0. The adsorption process is endothermic, and determined to be consistent with the Langmuir isotherm. Furthermore, it is found that the quaternary ammonium structure and network structure in the surface of PVA/QL are the key factors to remove nitrate. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Processing–formulation–performance relationships of polypropylene/short flax fiber composites

This work is a comprehensive study of the effect of extrusion process parameters and formulation on the properties of polypropylene (PP)/short flax fiber composites. The parameters that were varied during the twin‐screw extrusion process were screw configuration, revolutions per minute (rpm), extrusion temperature, and flow rate. The effect of the feeding zone location of cellulosic fiber was also considered. This study investigates the effect of the formulation, cellulosic fiber content, the presence of a coupling agent, and of a reactive additive on composite performance. The composites were characterized in terms of morphology and microstructure, fiber length, rheological, thermal, and mechanical properties. Sensibility to humidity and recyclability were also considered. When compared with as‐received PP, the tensile strength of injection‐molded parts increased with cellulosic content by up to 40 vol %, and the tensile modulus increased 3.5 times when a combination of coupling and reactive agents was used. Exposed to controlled humidity of 50% during 1 year, these composites exhibited a very low level of humidity uptake around 0.85 wt %. The processability of these materials using a cast film line and the mechanical properties of extruded sheets are also presented. Furthermore, these materials demonstrate a good recyclability using injection molding by keeping the integrality of their mechanical properties after five reprocessing cycles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41528.     

Preparation and characteristic of a sodium alginate/carboxymethylated bacterial cellulose composite with a crosslinking semi‐interpenetrating network

A novel ionic crosslinking sodium alginate (SA)/carboxymethylated bacterial cellulose (CM‐BC) composite with a semi‐interpenetrating polymer network (semi‐IPN) structure was developed in this study. The composite was prepared through the blending of an SA gel with CM‐BC then crosslinking by Ca²⁺ followed by a freeze‐drying process. Scanning electron microscopy showed the composite matrix organized in a three‐dimensional network of CM‐BC interpenetrated against SA molecular chains with a quantity of calcium alginate microspheres upon the surface. The swelling ratios of the composite were enhanced by 183, 198, and 212% with the supplementation of CM‐BC weight fractions of 25, 50, and 75%, respectively; the swelling ratios changed with changing pH. The tensile modulus, tensile strength, and elongation at break of SA were enhanced by 165, 152, and 188%, respectively, with the addition of 50 wt % CM‐BC. This study demonstrated that the semi‐IPN structure dramatically changed the swelling and mechanical properties of the composite, and the semi‐IPN will be a promising candidate for biomedical applications such as wound dressings and skin tissue engineering. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39848.     

Torrefied biomass‐polypropylene composites

Torrefied almond shells and wood chips were incorporated into polypropylene as fillers to produce torrefied biomass‐polymer composites. The composites were prepared by extrusion and injection molding. Response surface methodology was used to examine the effects of filler concentration, filler size, and lignin factor (relative lignin to cellulose concentration) on the material properties of the composites. The heat distortion temperatures, thermal properties, and tensile properties of the composites were characterized by thermomechanical analysis, differential scanning calorimetry, and tensile tests, respectively. The torrefied biomass composites had heat distortion temperatures of 8–24°C higher than that of neat polypropylene. This was due to the torrefied biomass restricting mobility of polypropylene chains, leading to higher temperatures for deformation. The incorporation of torrefied biomass generally resulted in an increase in glass transition temperature, but did not affect melting temperature. Also, the composites had lower tensile strength and elongation at break values than those of neat polypropylene, indicating weak adhesion between torrefied biomass and polypropylene. However, scanning electron microscopy results did indicate some adhesion between torrefied biomass and polypropylene. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41582.     

Novel CNC/silica hybrid as potential reinforcing filler for natural rubber compounds

This work describes the development of a low-density, renewable, and high reinforcing filler for natural rubber (NR) compounds. The cellulose nanocrystal (CNC)-based hybrid filler was synthesized by decorating the surface of CNCs with silica using a simple and efficient coprecipitation method. The properties of the prepared hybrid were investigated by field emission scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, nitrogen physisorption measurements, and Thermogravimetric analysis. Then, the prepared hybrid was incorporated in NR using two different approaches, namely, dry mixing and coprecipitation. The dynamic and tensile mechanical properties of the hybrid/NR compounds were evaluated indicating that: the coprecipitation method was found much more effective for homogeneous dispersion and the CNC/silica hybrid provided quite higher reinforcement to NR than reference silica; however, much lower density of the final compounds was obtained. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48332.     

Toward green three‐phase composites with enhanced dielectric permittivity

This work aims to investigate the dielectric potential of microcrystalline cellulose, a green biosourced material, as a third constituent in the three‐phase composites based on ethylene vinyl acetate‐vinyl ester of versatic acid (EVA‐VeoVa) terpolymer and BaTiO₃. For that, new green three‐phase composites were prepared using an economic and green process, with simple implementation at room temperature and using water as a solvent. Compared with the binary composite EVA‐VeoVa/BaTiO₃, the three‐phase composite EVA‐VeoVa/BaTiO₃/microcrystalline cellulose showed an improvement of the BaTiO₃ particles dispersion, enhanced relative permittivity, and reduced dielectric loss, which explains the significance of this study. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46147.     

Thermoplastic composites of polyamide‐12 reinforced by cellulose nanofibers with cationic surface modification

Cellulose nanofibers (CNFs) have many useful properties, including high strength and low thermal expansion, and are also environmentally friendly, readily renewable, safe, and biodegradable. The focus of this study was the development of lightweight thermoplastic polymer composites with good mechanical properties based on the incorporation of CNFs that have undergone surface pretreatment with a cationic reagent. The polyamide (PA12) was mixed with surface‐treated CNFs using a twin screw extruder and the resulting pellets were injection molded. The Izod impact strength without notch of CNF‐based composites exceeded that of composites incorporating organophilic montmorillonite (OMMT), a representative nanocomposite material. When the Izod impact test without notch, the impact hammer was stopped by the specimen with incorporation of surface treated CNF. Furthermore, the bending modulus and strength were equal to or greater than that of OMMT composites. The heat distortion temperature was improved as 33°C from neat PA12, and moreover improved as 29°C from OMMT composites. Cationic pretreatment of the CNF surfaces was found to increase the dispersion of the fibers and also to greatly improve the mechanical and thermal properties of the composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40920.     

Asolectin from soybeans as a natural compatibilizer for cellulose‐reinforced biocomposites from tung oil

The free radical copolymerization of tung oil, divinylbenzene, and n‐butyl methacrylate results in bio‐based thermosetting polymers with tunable properties. Biocomposites have been obtained by the reinforcement of such bio‐based resins with α‐cellulose. Asolectin from soybeans consists of a mixture of natural, polyunsaturated phospholipids. Because of its long, unsaturated fatty acid chains, and the presence of phosphate and ammonium groups, asolectin from soybeans is a good candidate for acting as a natural compatibilizer between the hydrophobic matrix and the hydrophilic reinforcement. In the current work, we investigate the changes in properties resulting from the addition of asolectin to a tung oil‐based polymer reinforced with α‐cellulose. An evaluation of the cure‐kinetics of the tung oil‐based resin has been conducted by dielectric analysis (DEA), and the final biocomposites have been thoroughly characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), Soxhlet extraction, and scanning electron microscopy (SEM). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41833.     

Performance of nylon 6 composites reinforced with modified agave fiber: Structural,morphological, and mechanical features

Nylon 6 (Ny6) composites reinforced with treated agave fiber (AF) at different concentrations (5–20 wt%) were achieved by melt mixing process at 250°C, without the addition of any compatibilizing or coupling agents, and characterized in terms of their structural, morphological, and mechanical properties. The alkaline-ultrasound (NaOH-U) treatment in AF resulted in the removal of the low thermal stability components (pectin and hemicellulose), concentrating the cellulose fraction, and favoring the crystallinity percentages (X_c) of the Ny/AF composites. Moreover, the interfacial interactions between functional groups of agave fiber and Ny6 resulted in the increase Young's modulus (18.8%), flexural strength (11.3%), and density (3.7%). These findings could be useful when looking for potential applications in the mobility industry.     

Aramid nanofiber reinforced nitrile rubber assisted by cellulose nanocrystals

A fiber-reinforced rubber composite was prepared by mixing aramid nanofibers (ANF) suspension and nitrile rubber (NBR) latex. The effects of ANF content and corresponding surface modification on the microstructure, vulcanization performance, processing and mechanical properties of composite materials, were systematically investigated. We found that, compared with commonly used short-cut aramid fibers, ANF fillers tend to form a stronger filling network within NBR matrix, resulting in a pronounced Payne effect. By improving the interfacial adhesion via dopamine (DA) coating onto ANF surface, the tensile strength can be further enhanced as expected. Besides, to eliminate the detriment of mechanical performance due to residual sodium polyacrylate in the course of flocculation, cellulose nanocrystal (CNC) was adopted to serve as a thickener during solution mixing. The incorporation of CNC can significantly improve the mechanical properties, which identifies a synergistic reinforcement effect arising from the cooperation of two types of fillers.     

Effect of dimethyl sulfoxide on synthesis of thermoplastic cellulose‐Graft‐poly(l‐lactide) copolymer using ionic liquid as reaction media

In this study, ring‐opening graft polymerization of l ‐lactide onto cellulose was carried out homogeneously in ionic liquid (IL)/dimethyl sulfoxide (DMSO) co‐solvent as a reaction media. Through the effective control of high viscosity and steric hindrance caused by the interaction between the IL and the hydroxyl group of cellulose by adding DMSO as a co‐solvent, cellulose‐graft‐poly(l ‐lactide) (Cell‐g‐PLLA) copolymer with higher substitution efficiency was successfully prepared, at relatively low concentration of l ‐lactide. The maximum values of molar substitution, degree of lactyl substitution, and degree of polymerization of poly(l ‐lactide) in the copolymer were 3.76, 1.74, and 2.16, respectively, determined by ¹H‐NMR. The prepared cell‐g‐PLLA copolymers showed thermal plasticization with a glass transition temperature of 155°C. In addition, the thermal processibility could be improved as the amount of grafted PLLA in the copolymer increased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41331.     

Fabrication of natural cellulose microspheres via electrospraying from NaOH/Urea aqueous system

Regenerated cellulose microspheres (RCM) with controllable sizes and architectures are prepared via electrospraying from environmental‐friendly NaOH/Urea aqueous system. The particle size and shape of RCM is mainly dependent on the interplay among the electrical force, surface tension, and viscous force. Particle size can be reduced to a certain extent by increasing voltage and decreasing surface tension, electrode spacing, solution concentration, degree of polymerization, and flow rate. The deformation of droplets, which is peculiarly prone to occur for low viscosity and long electrode spacing, results in elongated spheres, tear‐shaped particles, wedge‐shaped particles, and banding shaped particles besides micorspheres. The sophericity and uniformity of particles generally become worse as a result of the deformation of droplets. RCM possess good porosity and large specific surface area after regeneration. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40656.     

In situ dispersion and compatibilization of lignin/epoxidized natural rubber composites: reactivity,morphology and property

Lignin, a naturally occurring polymer, was viewed as a potential substitute of carbon black for reinforcing rubber materials. However, it shows no reinforcing effect if directly mixed with rubber. In this study, lignin was in situ dispersed at submicrometer size and highly compatible with epoxidized natural rubber (ENR) by using a high‐temperature dynamic heat treatment (HTDHT). Rheology analysis indicated that the ring opening reaction between lignin and ENR occurred at 160°C or above, which was further confirmed by infrared spectroscopy. Due to the consumption of acidic groups of lignin by ENR, the retardant vulcanization effect of lignin was weakened. Morphology observation and dynamic mechanical analysis demonstrated the perfect lignin dispersion and the strong interactions between lignin and ENR. The mechanical properties of the lignin/ENR composites were significantly improved by using HTDHT. Compared to the directly mixed rubber composites, the tensile strength and tear strength of the heat treated rubber composites filled with 40 phr lignin were increased by 114% and 23%, respectively. Especially, the 300% modulus of the heat treated rubber composite was increased by ca. 400%. X‐ray diffraction results indicated that the reinforcement of the composites originated from the presence of lignin rather than the strain‐induced crystallization of ENR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42044.     

Effect of irradiation on the composition and thermal properties of softwood kraft lignin and styrene grafted lignin

Lignin is an abundant, underutilized natural resource that has potential to be used as a biomaterial but is currently hampered in its use by not being uniform in structure and composition and is thermally unstable due to phenolic group. To address these issues and modify its thermal properties, softwood kraft lignin was modified using γ‐irradiation at low doses with and without styrene present and characterized. Irradiation of kraft lignin alone with γ‐radiation shows an initial decrease in molecular weight due to chain scission up to about 10 kGy followed by an increase in molecular weight due to crosslinking. NMR results indicate a decrease of about 15% in the OH content of the lignin with 30 kGy irradiation. Thermal properties such as T_g, free volume and ΔC_p follow accordingly. Irradiation at very low dosages was determined to facilitate the grafting of styrene monomer to lignin, decreasing the OH content by 23%. This effect increased the hydrophobicity of the material, depressed the value of T_g, increased the ΔC_p, increased the mobility in the liquid state, and made the material more thermally stable relative to the lignin alone, thus improving its processability at high temperatures. Both the irradiation of lignin alone and the grafting of styrene to lignin increased the yield of mass during pyrolysis and the activation energy for mass loss relative to untreated lignin alone. This work has demonstrated that the application of low dosages of γ‐irradiation is a promising method to attach functional molecules onto lignin for use in various applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39743.