Biobased composites prepared by compression molding with a novel thermoset resin from soybean oil and a natural‐fiber reinforcement

Biobased composites were manufactured with a compression‐molding technique. Novel thermoset resins from soybean oil were used as a matrix, and flax fibers were used as reinforcements. The air‐laid fibers were stacked randomly, the woven fabrics were stacked crosswise (0/90°), and impregnation was performed manually. The fiber/resin ratio was 60 : 40. The prepared biobased composites were characterized by impact and flexural testing. Scanning electron microscopy of knife‐cut cross sections of the specimens was also done to investigate the fiber–matrix interface. Thermogravimetric analysis of the composites was carried out to provide indications of thermal stability. Three resins from soybean oil [methacrylated soybean oil, methacrylic anhydride modified soybean oil (MMSO), and acetic anhydride modified soybean oil] were used as matrices. The impact strength of the composites with MMSO resin reinforced with air‐laid flax fibers was 24 kJ/m², whereas that of the MMSO resin reinforced with woven flax fabric was between 24 and 29 kJ/m². The flexural strength of the MMSO resin reinforced with air‐laid flax fibers was between 83 and 118 MPa, and the flexural modulus was between 4 and 6 GPa, whereas the flexural strength of the MMSO resin reinforced with woven fabric was between 90 and 110 MPa, and the flexural modulus was between 4.87 and 6.1 GPa. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanical,thermal, and morphological properties of maleic anhydride‐g‐polypropylene compatibilized and chemically modified banana‐fiber‐reinforced polypropylene composites

Composites were prepared with chemically modified banana fibers in polypropylene (PP). The effects of 40‐mm fiber loading and resin modification on the physical, mechanical, thermal, and morphological properties of the composites were evaluated with scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Infrared (IR) spectroscopy, and so on. Maleic anhydride grafted polypropylene (MA‐g‐PP) compatibilizer was used to improve the fiber‐matrix adhesion. SEM studies carried out on fractured specimens indicated poor dispersion in the unmodified fiber composites and improved adhesion and uniform dispersion in the treated composites. A fiber loading of 15 vol % in the treated composites was optimum, with maximum mechanical properties and thermal stability evident. The composite with 5% MA‐g‐PP concentration at a 15% fiber volume showed an 80% increase in impact strength, a 48% increase in flexural strength, a 125% increase in flexural modulus, a 33% increase in tensile strength, and an 82% increase in tensile modulus, whereas the heat deflection temperature increased by 18°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermo‐mechanical behavior of polyamide 12—polyamide 66 recycled fiber composites

Postconsumed polyamide 66 (PA66) short fibers derived from carpets were utilized as reinforcement in a commercial polyamide (PA12) matrix at different concentrations, ranging from 10 wt% to 30 wt%, in order to evaluate the effect of PA66 content on the mechanical and dynamic behavior of the resulting materials. DSC tests revealed that both melting and crystallization behavior of PA12 matrix was slightly affected by the presence of the fibers, showing a somewhat nucleation effect of PA66. Quasi‐static tensile tests evidenced that the introduction of PA66 fibers provided a slight stiffening effect on the resulting composites, increasing the elastic modulus with the filler content, especially at testing temperatures above T_g. On the other hand, the presence of agglomerated fibers led to an embrittlement of polyamide composites, showing a significant reduction of the tensile properties at break increasing the PA66 fibers content. Tensile dynamic tests confirmed the stiffening effect provided by the recycled fibers, increasing both dynamic moduli (E′ and E″) with PA66 content over the whole range of considered temperatures. Glass transition temperature of PA12 was substantially increased by the presence of the fibers, while the coefficient of linear thermal expansion above T_g was progressively reduced with the filler content. Interestingly, isothermal creep compliance of the material above T_g was substantially reduced by the presence of PA66 fibers. Morphological analysis on the cryofractured surfaces revealed a quite good fiber‐matrix interfacial adhesion, with the presence of some nucleating phenomena on the pulled out surfaces. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Dynamic mechanical properties of oil palm microfibril‐reinforced natural rubber composites

The dynamic mechanical properties of macro and microfibers of oil palm‐reinforced natural rubber (NR) composites were investigated as a function of fiber content, temperature, treatment, and frequency. By the incorporation of macrofiber to NR, the storage modulus (E') value increases while the damping factor (tan δ) shifts toward higher temperature region. As the fiber content increases the damping nature of the composite decreases because of the increased stiffness imparted by the natural fibers. By using the steam explosion method, the microfibrils were separated from the oil palm fibers. These fibers were subjected to treatments such as mercerization, benzoylation, and silane treatment. Resorcinol‐hexamethylenetetramine‐hydrated silica was also used as bonding agent to increase the fiber/matrix adhesion. The storage modulus value of untreated and treated microfibril‐reinforced composites was higher than that of macrofiber‐reinforced composites. The T_g value obtained for this microfibril‐reinforced composites were slightly higher than that of macrofiber‐reinforced composites. The activation energy for the relaxation processes in different composites was also calculated. The morphological studies using scanning electron microscopy of tensile fracture surfaces of treated and untreated composites indicated better fiber/matrix adhesion in the case of treated microfibril‐reinforced composites. Finally, attempts were made to correlate the experimental dynamic properties with the theoretical predictions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of poly(vinyl chloride)–continuous carbon fiber composites

In this article, we report on the preparation and characterization of novel poly(vinyl chloride) (PVC)–carbon fiber (CF) composites. We achieved the reinforcement of PVC matrices with different plasticizer contents using unidirectional continuous CFs by applying a warm press and a cylinder press for the preparation of the PVC–CF composites. We achieved considerable reinforcement of PVC even at a relatively low CF content; for example, the maximum stress (σ_max) of the PVC–CF composite at a 3% CF content was found to be 1.5–2 times higher than that of the PVC matrix. There were great differences among the Young's modulus values of the pure PVC and PVC–CF composites matrices. The absolute Young's modulus values were in the range 1100–1300 MPa at a 3% CF content; these values were almost independent of the plasticizer content. In addition, we found a linear relationship between σ_max and the CF content and also recognized a linear variation of the Young's modulus with the CF content. The adhesion of CF to the PVC matrix was strong in each case, as concluded from the strain–stress curves and the light microscopy and scanning electron microscopy investigations. The mechanical properties of the PVC–CF composites with randomly oriented short (10 mm) fibers were also investigated. At low deformations, the stiffness of the composites improved with increasing CF content. Dynamic mechanical analysis (DMA) was used to determine the glass‐transition temperature (T_g) of the PVC–CF composites. The high increase in the Young's modulus entailed only a mild T_g increase. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Soybean‐ and castor‐oil‐based thermosetting polymers: Mechanical properties

Maleic anhydride modified soybean‐ and castor‐oil‐based monomers, prepared via the malination of the alcoholysis products of the oils with various polyols, such as pentaerythritol, glycerol, and bisphenol A propoxylate, were copolymerized with styrene to give hard rigid plastics. These triglyceride‐based polymers exhibited a wide range of properties depending on their chemical structure. They exhibited flexural moduli in the 0.8–2.5 GPa range, flexural strength in the 32–112 MPa range, glass transition temperatures (T_g) ranging from 72 to 152°C, and surface hardness values in the 77–90 D range. The polymers prepared from castor oil exhibited significantly improved modulus, strength, and T_g values when compared with soybean‐oil‐based polymers. These novel castor and soybean‐oil‐based polymers show comparable properties to those of the high‐performance unsaturated polyester (UP) resins and show promise as an alternative to replace these petroleum‐based materials. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1497–1504, 2006     

Bio‐composites for structural applications: Poly‐l‐lactide reinforced with long sisal fiber bundles

Fully bio‐based and biodegradable composites were compression molded from unidirectionally aligned sisal fiber bundles and a polylactide polymer matrix (PLLA). Caustic soda treatment was employed to modify the strength of sisal fibers and to improve fiber to matrix adhesion. Mechanical properties of PLLA/sisal fiber composites improved with caustic soda treatment: the mean flexural strength and modulus increased from 279 MPa and 19.4 GPa respectively to 286 MPa and 22 GPa at a fiber volume fraction of V_f = 0.6. The glass transition temperature decreased with increasing fiber content in composites reinforced with untreated sisal fibers due to interfacial friction. The damping at the caustic soda‐treated fibers‐PLLA interface was reduced due to the presence of transcrystalline morphology at the fiber to matrix interface. It was demonstrated that high strength, high modulus sisal‐PLLA composites can be produced with effective stress transfer at well‐bonded fiber to matrix interfaces. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40999.     

Preparation and properties of bio‐based epoxy montomorillonite nanocomposites derived from polyglycerol polyglycidyl ether and ε‐polylysine

Glycerol polyglycidyl ether (GPE) and polyglycerol polyglycidyl ether (PGPE) were cured with ε‐poly(L ‐lysine) (PL) using epoxy/amine ratios of 1 : 1 and 2 : 1 to create bio‐based epoxy cross‐linked resins. When PGPE was used as an epoxy resin and the epoxy/amine ratio was 1 : 1, the cured neat resin showed the greatest glass transition temperature (T_g), as measured by differential scanning calorimetry. Next, the mixture of PGPE, PL, and montomorillonite (MMT) at an epoxy/amine ratio of 1 : 1 in water was dried and cured finally at 110°C to create PGPE‐PL/MMT composites. The X‐ray diffraction and transmission electron microscopy measurements revealed that the composites with MMT content 7–15 wt % were exfoliated nanocomposites and the composite with MMT content 20 wt % was an intercalated nanocomposite. The T_g and storage modulus at 50–100°C for the PGPE‐PL/MMT composites measured by DMA increased with increasing MMT content until 15 wt % and decreased at 20 wt %. The tensile strength and modulus of the PGPE‐PL/MMT composites (MMT content 15 wt %: 42 and 5300 MPa) were much greater than those of the cured PGPE‐PL resin (4 and 6 MPa). Aerobic biodegradability of the PGPE‐PL in an aqueous medium was ～ 4% after 90 days, and the PGPE‐PL/MMT nanocomposites with MMT content 7–15 wt % showed lower biodegradability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Dynamic mechanical properties of sisal fiber reinforced polyester composites fabricated by resin transfer molding

The dynamic mechanical properties of sisal fiber reinforced polyester composites fabricated by resin transfer molding (RTM) were investigated as a function of fiber content, frequency, and temperature. Investigation proved that at all temperature range the storage modulus (E′) value is maximum for the composites having fiber loading of 40 vol%. The loss modulus (E″) and damping peaks (tan δ) were lowered with increasing fiber content. The height of the damping peaks depends upon the fiber content and the fiber/matrix adhesion. The extent of the reinforcement was estimated from the experimental storage modulus, and it has been found that the effect of reinforcement is maximum at 40 vol% fiber content. As the fiber content increases the T_g from tan δ curve showed a positive shift. The loss modulus, storage modulus, and damping peaks were evaluated as a function of frequency. The activation energy for the glass transition increases upon the fiber content. Cole–Cole analysis was made to understand the phase behavior of the fiber reinforced composites. Finally, attempts were made to correlate the experimental dynamic properties with theoretical predictions. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Thermophysical properties of anhydride‐cured epoxy/nano‐clay composites

Polymer nano‐composites made with a matrix of anhydride‐cured diglycidyl ether of bisphenol A (DGEBA) and reinforced with organo‐montmorillonite clay were investigated. A sonication technique was used to process the epoxy/clay nano‐composites. The thermal properties of the nano‐composites were measured with dynamic mechanical analysis (DMA). The glass transition temperature T_g of the anhydride‐cured epoxy was higher than the room temperature (RT). For samples with 6.25 wt% (4.0 vol%) of clay, the storage modulus at 30°C and at (T_g + 15)°C was observed to increase 43% and 230%, respectively, relative to the value of unfilled epoxy. The clay reinforcing effect was evaluated using the Tandon‐Weng model for randomly oriented particulate filled composites. Transmission electron microscopy (TEM) examination of the nano‐composites prepared by sonication of clays in acetone showed well‐dispersed platelets in the nano‐composites. The clay nano‐platelets were observed to be well‐intercalated/expanded in the anhydride‐cured epoxy resin system. POLYM. COMPOS., 26:42–51, 2005. © 2004 Society of Plastics Engineers.     

Enhancement of the mechanical properties and interfacial interaction of a novel chitin‐fiber‐reinforced poly(ϵ‐caprolactone) composite by irradiation treatment

The effects of the fiber reinforcement of a novel bioabsorbable chitin‐fiber‐reinforced poly(?‐caprolactone) (PCL) composite were improved by irradiation treatment. The tensile strength and tensile modulus of the treated specimens were enhanced with respect to those of the untreated specimens. An increase in the fiber content (C_f) resulted in an increase in this enhancement tendency until C_f was 45%. A further increase in C_f increased the tensile modulus but decreased the strength. The flexural strength and flexural modulus were increased for the irradiation‐treated specimens in the same way as the tensile test. The microstructure of the tensile fracture showed an improvement in interfacial bonding for the irradiated specimens. The glass‐transition temperature (T_g) of the composite increased with an increase in C_f for the irradiation‐treated specimens, but there was no change in T_g for the untreated specimens with various values of C_f. This indicated that, for the composites with irradiation treatment, the fiber intensively affected the molecular segmental motion of PCL and thereby enhanced the interfacial interaction between the matrices and fibers. The same slope of the storage modulus (G′) versus the loss modulus (G″) for the irradiated specimens suggested an increase in the compatibility of the composite in comparison with the decrease in the slope with increasing C_f for the untreated specimens. All this demonstrated that there was some interfacial reaction between the fiber and matrix that resulted in the presence of an interfacial phase and improved the mechanical properties of the materials. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 486–492, 2002; DOI 10.1002/app.10149     

Properties of electropolymerized polycarboxyphenylmethacrylamide matrices/graphite fiber composites: Crosslinking effect

Imide formation from -CONH and -COOH functional groups of 2-carboxyphenylmethacrylamide (2-CPM), 4-carboxyphenylmethacrylamide (4-CPM), 4-carboxyphenyl methacrylamide/methylmethacrylate (4-CPM/MMA) and 4-carboxyphenylmethacrylamide/N-phenylmalemide (4-CPM/NPMI) electropolymerized matrices was investigated. It was found that 2-CPM polymers undergo intramolecular imidization and anhydride formation, which result in a small amount of crosslinked network. On the other hand, the thermally cured 4-CPM polymer demonstrates a significant increase in gel fraction. T_g and dynamic storage modulus, owing to crosslinked network formation. T_gs of 4-CPM/MMA and 4-CPM/NPMI composites measured by thermomechanical analysis after thermal heating were increased and were correlated very well with the preheating time. The 4-CPM/MMA composites with a particle crosslinking (T_g increased to 245°C) maintained a higher Izod impact strength than a typical epoxy composite (200 kJ/m² vs. 100 kJ/m²). Upon heating to promote crosslinking, a lower shear strength (65 MPa) of a 4-CPM/MMA composite increased to a strength of 78 MPa, close to the 80 MPa of an epoxy composite at 67% fiber volume fraction. A lower water absorption of around 1% was associated with the increased crosslinking. The mechanical properties of the 4-CPM/NPMI composites showed a similar trend upon preheating.     

Fabrication and characterization of electrospun polybutadiene fibers crosslinked by UV irradiation

Crosslinked electrospun polybutadiene (BR) fibers were made using electrospinning and UV curing methods. The crosslinked BR fibers were obtained by irradiating UV light on the electrospun BR fibers containing a photoinitiator and a crosslinker. Although uncrosslinked electrospun BR fibers did not retain the fiber morphology at room temperature due to a cold flow resulting from the very low glass transition temperature (T_g) of BR (below ?80°C), the crosslinked electrospun BR fibers retained the fiber morphology. The crosslink density increased with increase of the content of crosslinking agent. The crosslinked BR fibers had higher T_g than the raw BR. Tensile strength, modulus, and elongation at break of the electrospun BR fiber mats increased with increase of the crosslinker content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2233–2337, 2006     

Addition‐cure‐type phenolic resin based on alder‐ene reaction: Synthesis and laminate composite properties

A maleimide‐functional phenolic resin was reactively blended with an allyl‐functional novolac in varying proportions. The two polymers were coreacted by an addition mechanism through Alder‐ene and Wagner–Jauregg reactions to form a crosslinked network system. The cure characterization was done by differential scanning calorimetry and dynamic mechanical analysis. The system underwent a multistep curing process over a temperature range of 110–270°C. Although the cure profiles were independent of the composition, the presence of maleimide led to a reduced isothermal gel time of the blend. Increasing the allylphenol content decreased the crosslinking in the cured matrix, leading to enhanced toughness and improved resin‐dominant mechanical properties of the resultant silica laminate composites. Changing the reinforcement from silica to glass resulted in further amelioration of the resin‐reinforcement interaction, but the resin‐dominant properties of the composite remained unaltered. Increasing the maleimide content resulted in enhanced thermal stability. Integrating both the reactive groups in a single polymer and its curing led to enhanced thermal stability and T_g, but to decreased mechanical properties of the laminate composites. This can be attributed to a brittle matrix resulting from enhanced crosslinking facilitated by interaction of the reactive groups located on the polymer of an identical backbone structure. The cured polymers showed a T_g in the range of 170–190°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 737–749, 2001     

High‐performance polymeric materials with greatly improved mechanical and thermal properties from cyanate ester/benzoxazine resin reinforced by silane‐treated basalt fibers

This present article investigates the effect of silane‐treated basalt fibers (TBFs) on the morphological, mechanical and thermal properties of cyanate ester/benzoxazine (CE/BOZ) resin composites. The characterization was made using a scanning electron microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), flexural test, impact strength (IS) test, microhardness test, dynamic scanning calorimetry, and thermogravimetric analysis. The mechanical test results inferred the distinctive improvements in the values of the flexural strength and modulus, IS, and microhardness of the CE/BOZ composites. The thermal stabilities in terms of the T_g, T_5%, T_10%, and T_HRI were appreciably improved and were higher than those of the pure CE/BOZ resin. Data from the SEM and FTIR tests ascertained the good dispersion and adhesion between the TBFs and the resin matrix, which might be behind the significant enhancement in the ultimate performances of the composites, with respect to the distinguished properties of BFs. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46283.     

Thermomechanical characteristics of benzoxazine–urethane copolymers and their carbon fiber‐reinforced composites

Copolymers of polybenzoxazine (BA‐a) and urethane elastomer (PU) with three different structures of isocyanates [i.e., toluene diisocyanate (TDI), diphenylmethane diisocyanate, and isophorone diisocyanate], were examined. The experimental results reveal that the enhancement in glass transition temperature (T_g) of BA‐a/PU copolymers was clearly observed [i.e., T_g of the BA‐a/PU copolymers in 60 : 40 BA‐a : PU system for all isocyanate types (T_g beyond 230°C) was higher than those of the parent resins (165°C for BA‐a and ?70°C for PU)]. It was reported that the degradation temperature increased from 321°C to about 330°C with increasing urethane content. Furthermore, the flexural strength synergism was found at the BA‐a : PU ratio of 90 : 10 for all types of isocyanates. The effect of urethane prepolymer based on TDI rendered the highest T_g, flexural modulus, and flexural strength of the copolymers among the three isocyanates used. The preferable isocyanate of the binary systems for making high processable carbon fiber composites was based on TDI. The flexural strength of the carbon fiber‐reinforced BA‐a : PU based on TDI at 80 wt % of the fiber in cross‐ply orientation provided relatively high values of about 490 MPa. The flexural modulus slightly decreased from 51 GPa for polybenzoxazine to 48 GPa in the 60 : 40 BA‐a : PU system. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of varying fiber lengths on mechanical,thermal, and morphological properties of MA‐g‐PP compatibilized and chemically modified short pineapple leaf fiber reinforced polypropylene composites

Environmentally benign, low cost and abundantly available short pineapple leaf fibers (PALF), found mostly in the Tropical rain forest climates are ideal materials for manufacture of thermoplastic polymer‐matrix composites. Here, mechanical and thermal properties of composites of maleic anhydride grafted polypropylene (MA‐g‐PP) and chemically modified short PALF are studied as a function of different fiber lengths at 10 vol % fibers loading with fiber orientation in the longitudinal direction. The effects of fiber lengths and fiber loading on the morphological properties are assessed via observations by scanning electron microscopy. Fiber length of 6 mm oriented longitudinally at 10 vol % fibers loading in PP is the optimum and recommended composition, where 73% increase in impact properties, 37% increase in the flexural modulus, 33% increase in flexural strength, and 14% increase in vicat softening temperature are observed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly(lactic acid)/Phormium tenax composites: Morphology and thermo‐mechanical behavior

Composites of Phormium tenax fibers in a poly(lactic acid) matrix with fiber content of up to 40 wt%, produced by injection molding and twin screw compounding, were characterized by scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis, and mechanical tests (static and dynamic). Thermal analysis showed that cold‐crystallization peak shifted to lower temperatures with increasing fiber content, confirming that the addition of Phormium fiber has the effect of promoting crystallinity. Dynamic mechanical analysis (DMA) results showed that the addition of Phormium fiber did not affect significantly the T_g of the polymer and the area under the tan δ decreased with the addition of Phormium fiber. Tensile modulus has been consistently increased by reinforcing the composite with growing amounts of fibers, whilst the effect on tensile strength is less evident. SEM micrographs of fracture surfaces allowed highlighting failure modes of the composites, which included a diffuse presence of fiber pull‐out and debonding. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Effects of fiber composition and graft‐copoly(ethylene/maleic anhydride) on thermoplastic natural rubber composites reinforced by aramid fiber

Thermoplastic natural rubber (TPNR) composites of natural rubber and high‐density polyethylene at a ratio of 70/30 were prepared by melt blending with aramid fibers using an internal mixer. The fiber loadings were varied from 0 to 30% for systems with and without graft‐copoly(ethylene/maleic anhydride) (PE‐g‐MA) as a compatibilizer to study the variation of mechanical and dynamic mechanical properties. The tensile strength, modulus, hardness, and storage modulus improved with fiber loadings for both systems. The interaction between the matrix and fiber had also improved with the addition of PE‐g‐MA. Nevertheless, different behavior was observed in tan δ peak. The tan δ peak decreased with the increment of Twaron composition in the system with PE‐g‐MA and increased in the system without PE‐g‐MA. The results showed the importance of PE‐g‐MA in the system in improving the mechanical properties of Twaron–TPNR composite. POLYM. COMPOS., 27:395–401, 2006. © 2006 Society of Plastics Engineers