Environmentally friendly wood plastic composites (WPC) with biobased high density polyethylene (BioHDPE) as the polymer matrix and hemp, flax and jute short fibers as natural reinforcements, were melt-compounded using twin-screw extrusion and shaped into pieces by injection molding. Polyethylene-graft-maleic anhydride (PE-g-MA) was added at two parts per hundred resin to the WPC during the extrusion process in order to reduce the lack in compatibility between the lignocellulosic fibers and the non-polar polymer matrix. The results revealed a remarkable improvement of the mechanical properties with the combination of natural fibers, along with PE-g-MA, highly improved stiffness and mechanical properties of neat BioHDPE. Particularly, hemp fiber drastically increased the Young’s modulus and impact strength of BioHDPE. Thermal analysis revealed a slight improvement in thermal stability with the addition of the three lignocellulosic fibers, increasing both melting and degradation temperatures. The incorporation of the fibers also increased water absorption due to their lignocellulosic nature, which drastically improved the polarity of the composite. Finally, fire behavior properties were also improved in terms of flame duration, thanks to the ability of the fibers to form char protective barriers that isolate the material from oxygen and volatiles.
The main objective of the work reported here was the analysis and evaluation of halloysite nanotubes (HNTs) as natural flame retardancy filler in partially biobased polyamide 610 (PA610), with 63% of carbon from natural sources. HNTs are naturally occurring clays with a nanotube-like shape. PA610 compounds containing 10%, 20%, and 30% HNT were obtained in a twin-screw co-rotating extruder. The resulting blends were injection molded to create standard samples for fire testing. The incorporation of the HNTs in the PA610 matrix leads to a reduction both in the optical density and a significant reduction in the number of toxic gases emitted during combustion. This improvement in fire properties is relevant in applications where fire safety is required. With regard to calorimetric cone results, the incorporation of 30% HNTs achieved a significant reduction in terms of the peak values obtained of the heat released rate (HRR), changing from 743 kW/m2 to about 580 kW/m2 and directly modifying the shape of the characteristic curve. This improvement in the heat released has produced a delay in the mass transfer of the volatile decomposition products, which are entrapped inside the HNTs’ lumen, making it difficult for the sample to burn. However, in relation to the ignition time of the samples (TTI), the incorporation of HNTs reduces the ignition start time about 20 s. The results indicate that it is possible to obtain polymer formulations with a high renewable content such as PA610, and a natural occurring inorganic filler in the form of a nanotube, i.e., HNTs, with good flame retardancy properties in terms of toxicity, optical density and UL94 test.
In this work, green composites have been developed and characterized using a bio-based polymeric matrix such as BioPBSA and the introduction of 30 wt.% short hemp fibers as a natural reinforcement to obtain materials with maximum environmental efficiency. In order to increase the interfacial adhesion between the matrix and the fiber to obtain better properties in the composites, a reactive extrusion process has been carried out. On the one hand, different additives derived from bio-based itaconic acid have been added to the BioPBSA/HEMP composite, such as dibutyl itaconate (DBI) and a copolymer of PBSA grafted with itaconic acid (PBSA-g-IA). On the other hand, a different copolymer of PBSA grafted with maleic anhydride (PBSA-g-MA) was also tested. The resulting composites have been processed by injection-molding to obtain different samples which were evaluated in terms of mechanical, thermal, chemical, dynamic-mechanical, morphological and wettability and color properties. In relation to the mechanical properties, the incorporation of hemp fibers resulted in an increase in the stiffness of the base polymer. The tensile modulus of pure BioPBSA increased from 281 MPa to 3482 MPa with 30% fiber. The addition of DBI shows a remarkable improvement in the ductility of the composites, while copolymers with IA and MA, generate mechanically balanced composites. In terms of thermal properties, the incorporation of hemp fiber and compatibilizing agents led to a reduction in thermal stability. However, from the point of view of thermomechanical properties, a clear increase in rigidity is achieved throughout the temperature range studied. As far as the color of the samples is concerned, the incorporation of hemp generates a typical color, while the incorporation of the compatibilizing agents does not modify this color excessively. Finally, the introduction of lignocellulosic fibers greatly affects water absorption and contact angle, although the use of additives helped to mitigate this effect.
Biobased HDPE (bioHDPE) was melt-compounded with different percentages (2.5 to 40.0 wt.%) of short hemp fibers (HF) as a natural reinforcement to obtain environmentally friendly wood plastic composites (WPC). These WPC were melt-compounded using a twin-screw extrusion and shaped into standard samples by injection molding. To improve the poor compatibility between the high non-polar BioHDPE matrix and the highly hydrophilic lignocellulosic fibers, a malleated copolymer, namely, polyethylene-graft-maleic anhydride (PE-g-MA), was used. The addition of short hemp fibers provided a remarkable increase in the stiffness that, in combination with PE-g-MA, led to good mechanical performance. In particular, 40 wt.% HF drastically increased the Young’s modulus and impact strength of BioHDPE, reaching values of 5275 MPa and 3.6 kJ/m2, respectively, which are very interesting values compared to neat bioHDPE of 826 MPa and 2.0 kJ/m2. These results were corroborated by dynamic mechanical thermal analysis (DMTA) results, which revealed a clear increasing tendency on stiffness with increasing the fiber loading over the whole temperature range. The crystal structure was not altered by the introduction of the natural fibers as could be seen in the XRD patterns in which mainly the heights of the main peaks changed, and only small peaks associated with the presence of the fiber appeared. Analysis of the thermal properties of the composites showed that no differences in melting temperature occurred and the non-isothermal crystallization process was satisfactorily described from the combined Avrami and Ozawa model. As for the thermal degradation, the introduction of HF resulted in the polymer degradation taking place at a higher temperature. As for the change in color of the injected samples, it was observed that the increase in fiber generated a clear modification in the final shades of the pieces, reaching colors very similar to dark woods for percentages higher than 20% HF. Finally, the incorporation of an increasing percentage of fibers also increased water absorption due to its lignocellulosic nature in a linear way, which drastically improved the polarity of the composite
Bio-based polyamide 1010 was melt-compounded with different percentages (2.5 to 10.0 wt.%) of expandable graphite (EGr) as an environmentally friendly solution to improve the flame retardancy properties. The mechanical, morphological, thermal and fire retardancy properties (among others) are analysed. The novelty of the article lies in the use of fully removable polyamide. The effect of the incorporation of EGr in the properties of this polymer was analysed and characterised. The incorporation of EGr into the PA1010 matrix led to very promising results. Mechanically, the EGr provided increased stiffness and a tensile strength up to 7.5 wt.%, verifying good mechanical performance. The DMTA results also show how the incorporation of EGr in the PA1010 matrix clearly increases the stiffness of the composites over the entire temperature range analysed. In terms of physical properties, water absorption of PA1010 was reduced particularly in the 10% EGr, which reduces the water absorption of PA1010 by 20%. In terms of flame retardant properties, with the incorporation of EGr, a significant reduction in the heat release rate (HRR) values as the concentration of the additive increases and a reduction in the maximum peak heat release rate (pHRR) can be observed for all compounds. In particular, it goes from 934 kW/m2 for neat polyamide to a value of 374 kW/m2 with 10% EGr. Finally, an improvement in the UL-94 rating of the 7.5 and 10% EGr composites was also observed, going from V-2 in the PA to V-1 in these composites.
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