Moisture uptake and resulting mechanical response of biobased composites. I. constituents

The mechanical properties of the biobased fiber and resins have been characterized and moisture influence on the behavior of these materials has been studied. Commercially available biobased thermoset resins (Tribest, EpoBioX, Palapreg, Envirez SA, and Envirez SB) and regenerated cellulose fibers (Cordenka) have been conditioned at different levels of relative humidity (as received, dried, 41, 70, and 90%) to obtain materials with different moisture content. The following properties of polymers were measured: tensile, flexural (3P‐bending), impact strength (unnotched Charpy), and fracture toughness (compact tension). The results of characterization of biobased thermosets were compared against data for epoxy Araldite LY556, which is used as reference resin. RCF bundles (with and without twist, extracted from fabric) as well as single fibers separated from these bundles were tested in tension. In general biobased resins performed well, moreover EpoBioX showed better properties than synthetic epoxy. POLYM. COMPOS., 35:1150–1159, 2014. © 2013 Society of Plastics Engineers     

Processing and mechanical properties of bio‐derived vinyl ester resin‐based composites

A “green” vinyl ester resin (GVER) is investigated for use in structural applications. The GVER was formulated using a monodisperse vinyl ester created via a novel synthetic route capable of using bio‐waste material from paper and biodiesel industries. The GVER was used either as a neat resin or as blended with a commercial vinyl ester resin. The processing viscosity and gel times are investigated. The GVER reaches a similar viscosity as the commercial resin with only half the styrene monomer content, thereby reducing the volatile organic compounds associated with manufacturing. Composites of the GVER matrix reinforced by carbon fabric were tested for their tensile and flexural properties. The mechanical performance of the GVER compares favorably with commercial resin and provide a route for composites manufacturing from sustainably sourced vinyl ester matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44642.     

An overview of luminescent bio‐based composites

The development of inorganic/organic composite materials represents a fast‐growing interdisciplinary area in materials science and engineering. In this topic, a key idea is the production of composites comprising biopolymers and functional inorganic phases that could replace conventional materials in several high‐technology applications. Following this concept, the use of different polymers from renewable sources, such as cellulose, starch, alginate, and chitosan, have gained great relevance because of their renewable nature, potential biocompatibility, and biodegradability, as well as specific physicochemical properties. The combination of these biopolymers with different fillers (including inorganic nanoparticles (NPs), clusters, or ions) allows the design of innovative bio‐based materials with specific and/or improved properties, namely, optical, mechanical, and barrier properties, luminescence, and biological properties (as antimicrobial activity and biocompatibility). This review will focus on the most important synthetic approaches, properties, and applications of luminescent bio‐based composites obtained by combining different biopolymers and fillers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41169.     

Palm‐based bio‐composites hybridized with kaolinite

This study described the mechanical and thermal properties of hybrid bio‐composites from oil palm empty fruit bunch (EFB) fibers and kaolinite. The polyurethane (PU) used as matrix is formed by reacting palm kernel oil (PKO)‐based polyester with crude isocyanate. The blending ratio of PU to EFB fibers was fixed at 35 : 65 and kaolinite was added at 0, 5, 10, 15, and 20% (by weight). The occurrence of chemical interactions between the hydroxyl terminals in both fillers and the PU system was determined via FTIR spectroscopy. Hybrid bio‐composites showed improved stiffness, strength, and better water resistance with the addition of kaolinite to an extent. At 15% of kaolinite loading, maximum flexural and impact strengths were observed. The interaction between kaolinite with PU matrix and EFB fibers enhanced the mechanical properties of the bio‐composites, which was justified from the FTIR spectrum. However, over‐packing of kaolinite was observed at 20% kaolinite loading, which ruptured the cellular walls and degraded strength of the bio‐composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Crystallization behavior and mechanical properties of bio‐based green composites based on poly(L‐lactide) and kenaf fiber

Bio‐based polymer composite was successfully fabricated from plant‐derived kenaf fiber (KF) and renewable resource‐based biodegradable polyester, poly(L ‐lactide) (PLLA), by melt‐mixing technique. The effect of the KF weight contents (0, 10, 20, and 30 wt %) on crystallization behavior, composite morphology, mechanical, and dynamic mechanical properties of PLLA/KF composites were investigated. It was found that the incorporation of KF significantly improves the crystallization rate and tensile and storage modulus. The crystallization of PLLA can be completed during the cooling process from the melt at 5°C/min with the addition of 10 wt % KF. It was also observed that the nucleation density increases dramatically and the spherulite size drops greatly in the isothermal crystallization with the presence of KF. In addition, with the incorporation of 30 wt % KF, the half times of isothermal crystallization at 120°C and 140°C were reduced to 46.5% and 28.1% of the pure PLLA, respectively. Moreover, the tensile and storage modulus of the composite are improved by 30% and 28%, respectively, by the reinforcement with 30% KF. Scanning electron microscopy observation also showed that the crystallization rate and mechanical properties could be further improved by optimizing the interfacial interaction and compatibility between the KF and PLLA matrix. Overall, it was concluded that the KF could be the potential and promising filler for PLLA to produce biodegradable composite materials, owing to its good ability to improve the mechanical properties as well as to accelerate the crystallization of PLLA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Bleached extruder chemi‐mechanical pulp fiber‐PLA composites: Comparison of mechanical,thermal, and rheological properties with those of wood flour‐PLA bio‐composites

An environmentally friendly bleached extruder chemi‐mechanical pulp fiber or wood flour was melt compounded with poly(lactic acid) (PLA) into a biocomposite and hot compression molded. The mechanical, thermal, and rheological properties were determined. The chemical composition, scanning electron microscopy, and Fourier transform infrared spectroscopy results showed that the hemicellulose in the pulp fiber raw material was almost completely removed after the pulp treatment. The mechanical tests indicated that the pulp fiber increased the tensile and flexural moduli and decreased the tensile, flexural, and impact strengths of the biocomposites. However, pulp fiber strongly reinforced the PLA matrix because the mechanical properties of pulp fiber‐PLA composites (especially the tensile and flexural strengths) were better than those of wood flour‐PLA composites. Differential scanning calorimetry analysis confirmed that both pulp fiber and wood flour accelerated the cold crystallization rate and increased the degree of crystallinity of PLA, and that this effect was greater with 40% pulp fiber. The addition of pulp fiber and wood flour modified the rheological behavior because the composite viscosity increased in the presence of fibers and decreased as the test frequency increased. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44241.     

Development and characterization of green composites from bio‐based polyethylene and peanut shell

In the present work, different compatibilizers, namely polyethylene‐graft‐maleic anhydride (PE‐g‐MA), polypropylene‐graft‐maleic anhydride (PP‐g‐MA), and polystyrene‐block‐poly(ethylene‐ran‐butylene)‐block‐polystyrene‐graft‐maleic anhydride (SEBS‐g‐MA) were used on green composites derived from biobased polyethylene and peanut shell (PNS) flour to improve particle–polymer interaction. Composites of high‐density polyethylene/peanut shell powder (HDPE/PNS) with 10 wt % PNS flour were compatibilized with 3 wt % of the abovementioned compatibilizers. As per the results, PP‐g‐MA copolymer lead to best optimized properties as evidenced by mechanical characterization. In addition, best particle–matrix interface interactions with PP‐g‐MA were observed by scanning electron microscopy (SEM). Subsequently HDPE/PNS composites with varying PNS flour content in the 5–30 wt % range with PP‐g‐MA compatibilizer were obtained by melt extrusion and compounding followed by injection molding and were characterized by mechanical, thermal, and morphological techniques. The results showed that PNS powder, leads to an increase in mechanical resistant properties (mainly, flexural modulus, and strength) while a decrease in mechanical ductile properties, that is, elongation at break and impact absorbed energy is observed with increasing PNS flour content. Furthermore, PNS flour provides an increase in thermal stability due to the natural antioxidant properties of PNS. In particular, composites containing 30 wt % PNS powder present a flexural strength 24% and a flexural modulus 72% higher than the unfilled polyethylene and the thermo‐oxidative onset degradation temperature is increased from 232 °C up to 254 °C thus indicating a marked thermal stabilization effect. Resultant composites can show a great deal of potential as base materials for wood plastic composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43940.     

Properties of bio‐based polymer nylon 11 reinforced with short carbon fiber composites

In this work, micro‐composite materials were produced by incorporating 3‐mm long reclaimed short carbon fibers into bio‐based nylon 11 via melt compounding. A systematic fiber length distribution analysis was performed after the masterbatching, compounding and an injection moulding processes using optical microscopy images. It was found that the large majority of the fibers were within the 200–300 μm in length range after the injection moulding process. The mechanical (flexural and tensile), thermo‐mechanical, and creep properties of the injection moulded materials are reported. We found that an enhancement in flexural and Young's modulus of 25% and 14%, respectively, could be attained with 2 wt% carbon fiber loading whilst no significant drawback on the ductility and toughness of the matrix was observed. The creep resistance and recovery of the nylon 11, tested using dynamic mechanical thermal analysis at room temperature and 65°C, was significantly improved by up to 30% and 14%, respectively, after loading with carbon fiber. This work provides an insight into the property improvement of the bio‐based polymer nylon 11 using a small amount of a reclaimed engineered material. POLYM. COMPOS., 36:668–674, 2015. © 2014 Society of Plastics Engineers     

Development of water‐blown bio‐based thermoplastic polyurethane foams using bio‐derived chain extender

Water‐blown bio‐based thermoplastic polyurethane (TPU) formulations were developed to fulfill the requirements of the reactive rotational molding/foaming process. They were prepared using synthetic and bio‐based chain extenders. Foams were prepared by stirring polyether polyol (macrodiol), chain extender (diol), surfactant (silicone oil), chemical blowing agent (distilled water), catalyst, and diisocyanate. The concentration of chain extender, blowing agent, and surfactant were varied and their effects on foaming kinetics, physical, mechanical, and morphological properties of foams were investigated. Density, compressive strength, and modulus of foams decrease with increasing blowing agent concentration and increase with increasing chain extender concentration, but are not significantly affected by changes in surfactant concentration. The foam glass‐transition temperatures increase with increasing blowing agent and chain extender concentrations. The foam cell size slightly increases with increasing blowing agent content and decreases upon surfactant addition (without any dependence on concentration), whereas chain extender concentration has no effect on cell size. Bio‐based 1,3‐propanediol can be used successfully for the preparation TPU foams without sacrificing any properties. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Lipid‐derived monomer and corresponding bio‐based nanocomposites

Fatty acid based monomer and corresponding hybrid polymer layered silicate nanocomposites have successfully been prepared by using in situ polymerizations. The hybrid materials were prepared by adding different ratios of nanoclay during free radical homopolymerization of 2‐(acryloyloxy)ethyl stearate (AOES) monomer and copolymerization of AOES with styrene. AOES monomer was synthesized by treating stearic acid with 2‐hydroxyethyl acrylate. The formation of AOES monomer, homopolymer and copolymer was confirmed by ¹H NMR spectroscopic analysis. Further analysis and characterization of the nanocomposites were carried out by XRD, transmission electron microscopy, AFM and attenuated total reflectance Fourier transform infrared spectroscopy. TGA of the polymer nanocomposites was also carried out to evaluate their thermal stability, while flammability tests were conducted to investigate the effect of layered silicate on flame retardancy. Nanofiller addition into the polymer matrix substantially improved the thermal properties and fire retardancy of the composites. © 2016 Society of Chemical Industry     

Structure and mechanical properties of polysulfone‐based in situ composites

Composites based on the polysulfone of bisfenol A (PSF) and a liquid‐crystalline copolyester (Rodrun 5000) were obtained by two processing methods, (1) direct injection moulding (DI) and (2) extrusion followed by injection moulding (PI), across the whole composition range. The blends were immiscible and showed two pure amorphous phases. The inferior mechanical properties of PI blends, and their more difficult processing, meant that the PI procedure is not suitable in these blends. The generally linear relationship of the Young's modulus of the DI blends is due to the counteracting effects of the large orientation of the skin and its low thickness. The improvement in notched impact strength of PSF on the addition of small amounts of LCP indicated an important reduction in its notch sensibility. The tensile strength behaviour was close to linearity, with the exception of the 20/80 blend in which it was synergistic. This had been seen in previous thermoplastic/LCP blends, and depicts a behaviour reminiscent of rubber‐toughened blends. Copyright © 2004 Society of Chemical Industry     

Rheological and mechanical characterization of polypropylene‐based wood plastic composites

The aim of this article is to investigate the influence of filler content and temperature on the rheological, mechanical, and thermal properties of wood flour polypropylene composites (WPCs). Testing WPCs at high temperatures and percentages of filler is extremely challenging because of reduced linear viscoelastic region, high viscosity, and degradation. In this work, a complete characterization of WPCs with different filler percentages (0–70 wt%) has been made. Rheological tests are performed at 170°C for the WPCs and in the 170–200°C range for neat polypropylene. A single master curve is obtained using two shift factors that can be described by a modified Eilers model and a Williams‐Landel‐Ferry equation. This master curve, fitted with a Carreau‐Yasuda model, can be very useful for predicting the viscosity of WPCs at temperatures that are typically used during processing and for any percentage of filler. POLYM. COMPOS., 37:3460–3473, 2016. © 2015 Society of Plastics Engineers     

Development and physico‐mechanical behavior of LDPE–sisal prepreg‐based composites

Low‐density polyethylene (LDPE)‐coated sisal fiber prepreg was prepared by using solution coating process. These coated fiber prepregs were consolidated to make composites having different weight fraction of sisal fibers in a hot compression‐molding machine. This experimental study reveals that higher loading of sisal fiber up to 57wt% in LDPE–sisal composites is possible by this technique. Mechanical and abrasive wear characteristics of these composites were determined. The tensile strength of composites increased with the increase in sisal fiber concentration. Coating thickness of LDPE was varied by changing the viscosity of LDPE–xylene solution that manifested to different weight fraction of fiber in sisal–LDPE composites. Mechanical, dynamic mechanical, and abrasive wear characteristics of these composites were determined. The tensile strength and modulus of sisal composites reached to 17.4 and 265 MPa, respectively, as compared to 7.1 and 33MPa of LDPE. Storage modulus of sisal composites LD57 reached to 2.7 × 10⁹ MPa at 40°C as compared to 8.1 × 10⁸ MPa of LDPE. Abrasive wear properties of LDPE and its composites were determined under multi‐pass mode; pure LDPE showed minimum specific wear rate. The specific wear rate of composites decreased with the sliding distance. Increase of coated sisal fiber content increased the specific wear rate at all the sliding distances, which has been explained on the basis of worn surface microstructures observed by using SEM. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Flame retardancy and mechanical properties of pet‐based composites containing phosphorus and boron‐based additives

Flame retardancy of poly(ethylene terephthalate), PET, was improved using different flame retardant additives such as triphenylphosphate, triphenylphosphine oxide, zinc borate, and boron phosphate (BP). Composites were prepared using a twin screw extruder and subsequently injection molded for characterization purposes. The flame retardancy of the composites was determined by the limiting oxygen index (LOI) test. Smoke emission during fire was also evaluated in terms of percent light transmittance. Thermal stability and tensile properties of PET‐based composites were compared with PET through TGA and tensile test, respectively. The LOI of the flame retardant composites increased from 21% of neat PET, up to 36% with the addition of 5% BP and 5% triphenyl phosphate to the matrix. Regarding the smoke density analysis, BP was determined as an effective smoke suppressant for PET. Enhanced tensile properties were obtained for the flame retardant PET‐based composites with respect to PET. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42016.     

Recent advances in bio‐sourced polymeric carbohydrate/nanotube composites

Nanotubes (NTs), especially carbon nanotubes (CNTs), have attracted much attention in recent years because of their large specific surface area, and their outstanding mechanical, thermal, and electrical properties. In this review we emphasize the development of fascinating properties of polymeric carbohydrate/CNT composites, particularly in terms of their mechanical and conductivity properties and potential applications. Many methods used to modify CNTs during preparation of polymeric carbohydrate/CNT composites are presented. Moreover, we also discuss the enhanced mechanical and electrical effectiveness when hybrid CNTs or halloysite nanotubes were incorporated into different carbohydrate polymer matrices. Finally, we give a future outlook for the development of polymeric carbohydrate/CNT composites as potential alternative materials for various applications including sensors, electroactive paper, electrodes, sorbents for environmental remediation, packaging film, specialty textile, and biomedical devices. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40359.     

New Polyurethane‐based magnetostrictive composites: Dynamical mechanical properties

Polyurethane‐based magnetostrictive composites containing between 30 and 70 wt% Terfenol‐D have been prepared in order to obtain better and tailored dynamic‐mechanical properties. The thermal and mechanical properties of polyurethanes with different chemical compositions were first analyzed to determine the most adequate one to prepare the composite materials. Calorimetric analysis indicates that the amount of crystallites increased in presence of Terfenol‐D. Dynamic‐mechanical properties have also been determined for the chosen composite, showing that the damping peak at glass transition increased by the addition of the magnetostrictive material while it became simultaneously broader. However, the storage modulus showed a drop with the increase in the filler content from 2200 MPa for pure polyurethane to 400 MPa for polyurethane with 60 %wt Terfenol‐D. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers     

Strong and super tough: Layered ceramic‐polymer composites with bio‐inspired morphology

Bio‐inspired layered ceramic‐polymer composites with high strength and toughness were prepared from sintered aluminum oxide ceramic sheets and cationically curing epoxy resins toughened with poly(ε‐caprolactone) (PCL). The architecture of the composite is inspired by nacre but is arranged on a larger scale. Ceramic sheets with a nominal thickness of 250 μm were assembled into composite plates by adhesive layers with a nominal thickness of 20 μm. Before the manufacturing of the composites, the stress‐strain properties of the polymer component were tailored by the variation in the PCL content between 0 and 39 wt%. For composites with 4 and 15 ceramic layers, the bending strengths achieved 327 MPa and 376 MPa, which are higher than that of pure ceramic sheets. Moreover, composites with 15 ceramic layers show a 16 times higher toughness compared to that of the pure ceramic sheets. The results indicate that the toughness of the layered composites increases significantly with the number of layers. Inspired by the geometrical ratio of the natural sheet composite nacre, we have achieved a similar strength but a 2 times higher toughness than nacre by only adding up to 6 vol% of the polymer.     

Preparation and thermal properties of bio‐based gallic acid epoxy/carbon nanotubes composites by cationic ring‐opening reaction

In order to prepare the bio‐based polymeric materials, a gallic acid epoxy resin (GA‐ER) is synthesized by using biodegradable gallic acid, and the nanocomposites of GA‐ER/glycidyl methacrylate (GMA)/multiwalled carbon nanotubes (MWCNTs) were prepared by dual hybrid cationic ring‐opening reaction. Differential scanning calorimetry (DSC) results show that the curing reaction temperature of the nanocomposites is between 150 and 225°C. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results suggest that MWCNTs are homodispersing in the GA‐ER/GMA matrix when the MWCNTs content is not more than 1.0 wt%. The glass transition temperature of the nanocomposite with 0.5 wt% MWCNTs is 9.3°C higher than that of pure resin system. The initial thermal degradation temperature and degradation activation energies E_a of the nanocomposite with 1.0 wt% MWCNTs is 10°C and 68.6 kJ/mol higher than that the pure resin system, respectively. POLYM. COMPOS., 37:3093–3102, 2016. © 2015 Society of Plastics Engineers     

Research progress on bio‐based thermosetting resins

Compared with the rapid progress on bio‐based thermoplastics, research on bio‐based thermosetting resins should have attracted much more attention, considering that they will have a bright future. In this paper, the current research progress on bio‐based thermosetting resins is reviewed. We pay special attention to the synthesis and investigation of properties of epoxies and unsaturated polyesters derived from renewable plant oil, cardanol, rosin acid, lignin, glycerol, gallic acid, furan, isosorbide, itaconic acid, etc. This mini review gives an overall perspective for bio‐based thermosets.© 2015 Society of Chemical Industry