Response of Polypropylene Composites Reinforced with Natural Fibers: Impact Strength and Water-Uptake Behaviors.

Composites from polypropylene (PP) reinforced with hemp strands (HS) are prepared in the current work with the aim of deepening on the influence of this reinforcement on the impact performance of these specific composites. Despite all the research conducted in this field, the effect of this natural reinforcement on the absorbed energy during crack formation and propagation is not fully tackled in previous research works. From the methodology and samples' geometry, the results concluded that the quality of the interface has a noticeable role in the impact resistance of these materials. The interface strength, fiber dispersion and fiber pullout are the main contributors to crack formation, whereas fiber pullout is the main one responsible for crack propagation. Maximum values of absorbed energy were found for PP composites comprising 20-30 wt% of HS and 8 wt% of the coupling agent for the un-notched samples, whereas maximum absorbed energy values corresponded to PP composites with 40 wt% of HS and 4 wt% of coupling agent for the notched samples. The water-absorption behavior in different humid environments is also examined. From the kinetic study, the water diffusion followed a Fickean behavior showing low-diffusion coefficients, increasing with fiber content. This systematic investigation represents a contribution to the analysis of the potential of reinforcing conventional polymers with natural materials, as a strategy towards more sustainable development.

Behavior of the Flexural Strength of Hemp/Polypropylene Composites: Evaluation of the Intrinsic Flexural Strength of Untreated Hemp Strands.

The growing demand for plant fiber-reinforced composites offers new opportunities to compete against glass fiber (GF)-reinforced composites, but their performance must be assessed, revised, and improved as much as possible. This work reports on the production and the flexural strength of composites from polypropylene (PP) and hemp strands (20-50 wt.%), using maleic anhydride-grafted PP (MAPP) as a compatibilizer. A computational assessment of the reaction between cellulose and MAPP suggested the formation of only one ester bond per maleic anhydride unit as the most stable product. We determined the most favorable MAPP dosage to be 0.06 g per gram of fiber. The maximum enhancement in flexural strength that was attained with this proportion of MAPP was 148%, corresponding to the maximum fiber load. The modified rule of mixtures and the assumption of similar coupling factors for tensile and flexural strength allowed us to estimate the intrinsic flexural strength of hemp strands as 953 ± 116 MPa. While falling short of the values for sized GF (2415 MPa), the reinforcement efficiency parameter of the natural fibers (0.209) was found to be higher than that of GF (0.045).

Effective Tensile Strength Estimation of Natural Fibers through Micromechanical Models: The Case of Henequen Fiber Reinforced-PP Composites.

The performance of henequen fibers and polypropylene composites obtained by injection molding with and without coupling agent was evaluated. Henequen fibers are natural non-wood fibers mainly used in textile sector or in thermosetting matrix composites. In this work, henequen fibers have been used as a possible substitute reinforcement material for sized glass fibers. The surface charge density of the materials used was evaluated, as well as the morphology of the fibers inside the material. A significant reduction in the length of the fibers was observed as a consequence of the processing. The use of a 4% coupling agent based on fiber content was found to be effective in achieving significant improvements in the tensile strength of the composites in the reinforcement range studied. The influence of the aspect ratio on the coupling factor was determined, as well as the evaluation of the interface quality. The results obtained demonstrate the great potential of henequen fibers as reinforcement of composite materials, giving rise to strong interfaces with coupling. Finally, the comparison of henequen fiber composites with sized glass fiber composites showed that it is possible to substitute polypropylene composites with 20 wt.% glass fiber for 50 wt.% henequen fibers.

Effective Young's Modulus Estimation of Natural Fibers through Micromechanical Models: The Case of Henequen Fibers Reinforced-PP Composites.

In this study, Young's modulus of henequen fibers was estimated through micromechanical modeling of polypropylene (PP)-based composites, and further corroborated through a single filament tensile test after applying a correction method. PP and henequen strands, chopped to 1 mm length, were mixed in the presence of maleic anhydride grafted polypropylene (MAPP). A 4 wt.% of MAPP showed an effective enhancement of the interfacial adhesion. The composites were mold-injected into dog-bone specimens and tensile tested. The Young's modulus of the composites increased steadily and linearly up to 50 wt.% of fiber content from 1.5 to 6.4 GPa, corresponding to a 327% increase. Certainly, henequen fibers showed a comparable stiffening capacity of PP composites than glass fibers. The intrinsic Young's modulus of the fibers was predicted through well established models such as Hirsch or Tsai-Pagano, yielding average values of 30.5 and 34.6 GPa, respectively. The single filament test performed to henequen strands resulted in values between 16 and 27 GPa depending on the gauge length, although, after applying a correction method, a Young's modulus of 33.3 GPa was obtained. Overall, the present work presents the great potential for henequen fibers as PP reinforcement. Moreover, relationships between micromechanics models and filament testing to estimate Young's modulus of the fibers were explored.

Exploring the Potential of Cotton Industry Byproducts in the Plastic Composite Sector: Macro and Micromechanics Study of the Flexural Modulus.

The textile sector produces yearly great quantities of cotton byproducts, and the major part is either incinerated or landfilled, resulting in serious environmental risks. The use of such byproducts in the composite sector presents an attractive opportunity to valorize the residue, reduce its environmental impact, and decrease the pressure on natural and synthetic resources. In this work, composite materials based on polypropylene and dyed cotton byproducts from the textile industry were manufactured. The competitiveness of the resulting composites was evaluated from the analyses, at macro and micro scales, of the flexural modulus. It was observed that the presence of dyes in cotton fibers, also a byproduct from the production of denim items, notably favored the dispersion of the phases in comparison with other cellulose-rich fibers. Further, the presence of a coupling agent, in this case, maleic anhydride grafted polypropylene, enhanced the interfacial adhesion of the composite. As a result, the flexural modulus of the composite at 50 wt.% of cotton fibers enhanced by 272% the modulus of the matrix. From the micromechanics analysis, using the Hirsch model, the intrinsic flexural modulus of cotton fibers was set at 20.9 GPa. Other relevant micromechanics factors were studied to evaluate the contribution and efficiency of the fibers to the flexural modulus of the composite. Overall, the work sheds light on the potential of cotton industry byproducts to contribute to a circular economy.

Strong Polyamide-6 Nanocomposites with Cellulose Nanofibers Mediated by Green Solvent Mixtures.

Cellulose nanofiber (CNF) as a bio-based reinforcement has attracted tremendous interests in engineering polymer composites. This study developed a sustainable approach to reinforce polyamide-6 or nylon-6 (PA6) with CNFs through solvent casting in formic acid/water mixtures. The methodology provides an energy-efficient pathway towards well-dispersed high-CNF content PA6 biocomposites. Nanocomposite formulations up to 50 wt.% of CNFs were prepared, and excellent improvements in the tensile properties were observed, with an increase in the elastic modulus from 1.5 to 4.2 GPa, and in the tensile strength from 46.3 to 124 MPa. The experimental tensile values were compared with the analytical values obtained by micromechanical models. Fractured surfaces were observed using scanning electron microscopy to examine the interface morphology. FTIR revealed strong hydrogen bonding at the interface, and the thermal parameters were determined using TGA and DSC, where the nanocomposites' crystallinity tended to reduce with the increase in the CNF content. In addition, nanocomposites showed good thermomechanical stability for all formulations. Overall, this work provides a facile fabrication pathway for high-CNF content nanocomposites of PA6 for high-performance and advanced material applications.

High Performance PA 6/Cellulose Nanocomposites in the Interest of Industrial Scale Melt Processing.

On an industrial scale, it is a challenge to achieve cellulose based nanocomposites due to dispersion issues and high process temperatures sensitivity. The current study describes methods to develop mechanically strong and thermally stable polyamide 6 (PA 6) and cellulose nanofibers (CNF) composites capable of tolerating high processing temperatures. With PA 6 being a very technical polymer matrix to be reinforced with CNF, good dispersion can be achieved with a high speed kinetic mixer and also shield the CNF from excess thermal degradation by implementing extremely short processing time. This paper presents an industrially feasible method to produce PA 6/CNF nanocomposites with high CNF composition processed by a high speed kinetic mixer (GELIMAT®) followed by compression molding to obtain a homogenous and thermally stable nanocomposites aimed at high performance applications. PA 6 was reinforced with three different wt % formulations (5, 15 and 25 wt %) of cellulose nanofibers. The resulting nanocomposites exhibited significant increase in Young's modulus and ultimate strength with CNF content, owing to the effective melt processing and the surface charge density of the CNF, which necessitated the dispersion. The thermal stability and polymer crystallinity with respect to CNF composition for the PA 6/CNF nanocomposites were examined by TGA and DSC analysis. Rheology studies indicated that viscosity of the composites increased with increase in CNF composition. Overall, this work demonstrates industrially viable manufacturing processes to fabricate high performance PA 6/CNF nanocomposites.

Bacterial Cellulose Network from Kombucha Fermentation Impregnated with Emulsion-Polymerized Poly(methyl methacrylate) to Form Nanocomposite.

The use of bio-based residues is one of the key indicators towards sustainable development goals. In this work, bacterial cellulose, a residue from the fermentation of kombucha tea, was tested as a reinforcing nanofiber network in an emulsion-polymerized poly(methyl methacrylate) (PMMA) matrix. The use of the nanofiber network is facilitating the formation of nanocomposites with well-dispersed nanofibers without using organic solvents or expensive methodologies. Moreover, the bacterial cellulose network structure can serve as a template for the emulsion polymerization of PMMA. The morphology, size, crystallinity, water uptake, and mechanical properties of the kombucha bacterial cellulose (KBC) network were studied. The results showed that KBC nanofibril diameters were ranging between 20-40 nm and the KBC was highly crystalline, >90%. The 3D network was lightweight and porous material, having a density of only 0.014 g/cm3. Furthermore, the compressed KBC network had very good mechanical properties, the E-modulus was 8 GPa, and the tensile strength was 172 MPa. The prepared nanocomposites with a KBC concentration of 8 wt.% were translucent with uniform structure confirmed with scanning electron microscopy study, and furthermore, the KBC network was homogeneously impregnated with the PMMA matrix. The mechanical testing of the nanocomposite showed high stiffness compared to the neat PMMA. A simple simulation of the tensile strength was used to understand the limited strain and strength given by the bacterial cellulose network. The excellent properties of the final material demonstrate the capability of a residue of kombucha fermentation as an excellent nanofiber template for use in polymer nanocomposites.

Stiffening Potential of Lignocellulosic Fibers in Fully Biobased Composites: The Case of Abaca Strands, Spruce TMP Fibers, Recycled Fibers from ONP, and Barley TMP Fibers.

Biocomposites are composite materials where at least the matrix or the reinforcement phases are obtained from natural and renewable resources. Natural fibers for composite preparation can be obtained from annual plants, wood, recycled products, or agroforestry waste. The present work selected abaca strands, spruce fibers, recycled fibers from old newspaper, and barley fibers as raw materials to produce biocomposites, in combination with a biobased polyethylene. One very important feature in material science and for industrial applications is knowing how a material will deform under load, and this characteristic is represented by Young's modulus. Therefore, in this work, the stiffness and deformation of the biocomposites were determined and evaluated using macromechanics and micromechanics analyses. Results were compared to those of conventional synthetic composites reinforced with glass fibers. From the micromechanics analysis, the intrinsic Young modulus of the reinforcements was obtained, as well as other micromechanics parameters such as the modulus efficiency and the length and orientation factors. Abaca strands accounted for the highest intrinsic modulus. One interesting outcome was that recycled fibers exhibited similar Young's moduli to wood fibers. Finally, agroforestry waste demonstrated the lowest stiffening potential. The study explores the opportunity of using different natural fibers when specific properties or applications are desired.

Effect of NaOH Treatment on the Flexural Modulus of Hemp Core Reinforced Composites and on the Intrinsic Flexural Moduli of the Fibers.

This paper describes the potential of using hemp core waste in the composite industry. These lignocellulosic residues can be used to produce environmentally friendly and economically viable composites and improve the overall value chain of hemp production. To this purpose, hemp core residues were alkaline treated at different NaOH concentrations and then mechanically defibrated. Hemp core fibers were mixed with polypropylene and injection molded to obtain testing specimens. The effect of sodium hydroxide on the flexural modulus of composites was studied from macro and micro mechanical viewpoints. Results showed remarkable improvements in the flexural modulus due to the presence of hemp core fibers in the composites. At a 50 wt % of reinforcement content, increments around 239%, 250% and 257% were obtained for composites containing fibers treated at a 5, 7.5 and 10 wt % of NaOH, respectively. These results were comparable to those of wood composites, displaying the potential of hemp core residues. The intrinsic flexural modulus of the hemp core fibers was computed by means of micromechanical analysis and was calculated using the ratios between a fiber flexural modulus factor and a fiber tensile modulus factor. The results agreed with those obtained by using models such as Hirsch and Tsai-Pagano. Other micromechanical parameters were studied to fully understand the contribution of the phases. The relationship between the fibers' intrinsic flexural and Young's moduli was studied, and the differences between properties were attributed to stress distribution and materials' anisotropy.

Biocomposites from Rice Straw Nanofibers: Morphology, Thermal and Mechanical Properties.

Agricultural residues are major potential resources for biomass and for material production. In this work, rice straw residues were used to isolate cellulose nanofibers of different degree of oxidation. Firstly, bleached rice fibers were produced from the rice straw residues following chemical extraction and bleaching processes. Oxidation of rice fibers mediated by radical 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) at pH 10 was then applied to extract rice cellulose nanofibers, with diameters of 3-11 nm from morphological analysis. The strengthening capacity of rice nanofibers was tested by casting nanocomposite films with poly(vinyl alcohol) polymer. The same formulations with eucalyptus nanofibers were produced as comparison. Their thermal and mechanical performance was evaluated using thermogravimetry, differential scanning calorimetry, dynamic mechanical analysis and tensile testing. The glass transition of nanocomposites was shifted to higher temperatures with respect to the pure polymer by the addition of rice cellulose nanofibers. Rice nanofibers also acted as a nucleating agent for the polymer matrix. More flexible eucalyptus nanofibers did not show these two phenomena on the matrix. Instead, both types of nanofibers gave similar stiffening (as Young's modulus) to the matrix reinforced up to 5 wt.%. The ultimate tensile strength of nanocomposite films revealed significant enhancing capacity for rice nanofibers, although this effect was somehow higher for eucalyptus nanofibers.

Feasibility of Barley Straw Fibers as Reinforcement in Fully Biobased Polyethylene Composites: Macro and Micro Mechanics of the Flexural Strength.

Awareness on deforestation, forest degradation, and its impact on biodiversity and global warming, is giving rise to the use of alternative fiber sources in replacement of wood feedstock for some applications such as composite materials and energy production. In this category, barley straw is an important agricultural crop, due to its abundance and availability. In the current investigation, the residue was submitted to thermomechanical process for fiber extraction and individualization. The high content of holocellulose combined with their relatively high aspect ratio inspires the potential use of these fibers as reinforcement in plastic composites. Therefore, fully biobased composites were fabricated using barley fibers and a biobased polyethylene (BioPE) as polymer matrix. BioPE is completely biobased and 100% recyclable. As for material performance, the flexural properties of the materials were studied. A good dispersion of the reinforcement inside the plastic was achieved contributing to the elevate increments in the flexural strength. At a 45 wt.% of reinforcement, an increment in the flexural strength of about 147% was attained. The mean contribution of the fibers to the flexural strength was assessed by means of a fiber flexural strength factor, reaching a value of 91.4. The micromechanical analysis allowed the prediction of the intrinsic flexural strength of the fibers, arriving up to around 700 MPa, and coupling factors between 0.18 and 0.19, which are in line with other natural fiber composites. Overall, the investigation brightness on the potential use of barley straw residues as reinforcement in fully biobased polymer composites.

Valorization of Hemp Core Residues: Impact of NaOH Treatment on the Flexural Strength of PP Composites and Intrinsic Flexural Strength of Hemp Core Fibers.

Hemp core is a lignocellulosic residue in the production chain of hemp strands. Huge amounts of hemp core are gathered annually in Europe (43,000 tons) with no major application end. Such lignocellulosic wastes have potential as filling or reinforcing material to replace synthetic fibers and wood fibers in polymer composites. In this study, hemp core biomass was treated under different NaOH concentrations and then defibrated by means of Sprout Waldron equipment to obtain single fibers. Polypropylene matrix was reinforced up to 50 wt.% and the resulting hemp core fibers and the flexural properties were investigated. The results show that the flexural strength of composites increased with the intensity of NaOH treatment. The effect of NaOH was attributed to the removal of extractives and lignin in the fiber cell wall leading to improved interfacial adhesion characteristics. Besides, a methodology was established for the estimation of the intrinsic flexural strength of hemp core fibers. The intrinsic flexural strength of hemp core fibers was calculated to be 940 MPa for fibers treated at 10 wt.% of NaOH. In addition, a relationship between the lignin content and the intrinsic strength of the fibers was established.

Influence of lignin content on the intrinsic modulus of natural fibers and on the stiffness of composite materials.

Agricultural wastes are an alternative to the use of wood in plastic composites, thanks to their abundance, easy availability and other environmental and economic advantages. Agricultural wastes can be processed to obtain lignocellulosic fibers of different compositions that will allow better performance of their composites and the final desired residues' valorization. In this context, the current investigation aims at the management of corn stover wastes to be applied as reinforcement of polypropylene (PP). Four types of lignocellulosic fibers were obtained by submitting the wastes to mechanical, thermomechanical, semi-chemical or chemical processes. Corn fibers were characterized in terms of chemical composition, morphology and mechanical properties. In addition, PP was reinforced with corn fibers and the composites' stiffness evaluated. An assessment of the influence of the fiber composition on the mechanical performance of the composites is conducted. It is observed the key role of lignin content on the intrinsic modulus of the reinforcing fibers, which directly affected the final stiffness of composites. The best performance was achieved for an optimal kappa number between 40 and 50, corresponding to the semi-chemical fibers. The intrinsic modulus of the fibers, as well as the efficiency factor, length and orientation factors in composites were determined via micromechanical models.

Xyloglucan coating for enhanced strength and toughness in wood fibre networks.

In recent times, cellulosic materials are witnessing strong interest from both industry and academia for their ability to progress in high-value products with green stamp. Besides the renewability and biodegradability appeal, exceptional properties such as mechanical strength together with toughness are pursued. In the present work, wood fibre networks from eucalyptus Kraft pulp fibres and cellulose nanofibres are combined to produce nanostructured composite networks with outstanding mechanical behaviour. For this purpose, xyloglucan (XG) polymer is adsorbed on cellulose nanofibres (CNF) forming core-shell CNF fibrils in hydrocolloidal suspension which is used to dramatically strengthen wood fibre networks. TEMPO-CNF at two different oxidation levels were coated with XG. The exceptional Young's modulus and tensile strength found for fibre networks with only 10 wt% CNF was attributed to the fibre-fibre bond strength with better homogeneous stress distribution at the micro/nano scale. The production, mechanical characterization and structure analysis of such bionanocomposites is here presented.

Biobased Composites from Biobased-Polyethylene and Barley Thermomechanical Fibers: Micromechanics of Composites.

The cultivation of cereals like rye, barley, oats, or wheat generates large quantities of agroforestry residues, which reaches values of around 2066 million metric tons/year. Barley straw alone represents 53%. In this work, barley straw is recommended for the production of composite materials in order to add value to this agricultural waste. First of all, thermomechanical (TMP) fibers from barley straw are produced and later used to reinforce bio-polyethylene (BioPE) matrix. TMP barley fibers were chemically and morphologically characterized. Later, composites with optimal amounts of coupling agent and fiber content ranging from 15 to 45 wt % were prepared. The mechanical results showed the strengthening and stiffening capacity of the TMP barley fibers. Finally, a micromechanical analysis is applied to evaluate the quality of the interface and to distinguish how the interface and the fiber morphology contributes to the final properties of these composite materials.

Explorative Study on the Use of Curauá Reinforced Polypropylene Composites for the Automotive Industry.

The automotive industry is under a growing volume of regulations regarding environmental impact and component recycling. Nowadays, glass fiber-based composites are commodities in the automotive industry, but show limitations when recycled. Thus, attention is being devoted to alternative reinforcements like natural fibers. Curauá (Curacao, Ananas erectifolius) is reported in the literature as a promising source of natural fiber prone to be used as composite reinforcement. Nonetheless, one important challenge is to obtain properly dispersed materials, especially when the percentages of reinforcements are higher than 30 wt %. In this work, composite materials with curauá fiber contents ranging from 20 wt % to 50 wt % showed a linear positive evolution of its tensile strength and Young's modulus against reinforcement content. This is an indication of good reinforcement dispersion and of favorable stress transfer at the fiber-matrix interphase. A car door handle was used as a test case to assess the suitability of curauá-based composites to replace glass fiber-reinforced composites. The mechanical analysis and a preliminary lifecycle analysis are performed to prove such ability.

Modeling the Stiffness of Coupled and Uncoupled Recycled Cotton Fibers Reinforced Polypropylene Composites.

The stiffness of a composite material is mainly affected by the nature of its phases and its contents, the dispersion of the reinforcement, as well as the morphology and mean orientation of such reinforcement. In this paper, recovered dyed cotton fibers from textile industry were used as reinforcement for a polypropylene matrix. The specific dye seems to decrease the hydrophilicity of the fibers and to increase its chemical compatibility with the matrix. The results showed a linear evolution of the Young's moduli of the composites against the reinforcement contents, although the slope of the regression line was found to be lower than that for other natural strand reinforced polypropylene composites. This was blamed on a growing difficulty to disperse the reinforcements when its content increased. The micromechanics analysis returned a value for the intrinsic Young's modulus of the cotton fibers that doubled previously published values. The use of two different micromechanics models allowed evaluating the impact of the morphology of the fibers on the Young's modulus of a composite.

Smart nanopaper based on cellulose nanofibers with hybrid PEDOT:PSS/polypyrrole for energy storage devices.

In the current work, flexible, lightweight, and strong conductive nanopapers based on cellulose nanofibers (CNFs) with poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) and/or polypyrrole (PPy) were prepared by following a mixing and in situ chemical polymerization method. A successful homogeneous coating of PEDOT:PSS on cellulose nanofibers occurred by means hydrogen-bonding interactions between the hydroxyl functionalized CNF and the electronically charged PEDOT:PSS, as shown by FTIR spectra. The electrical conductivity and the specific capacitance of CNF-PEDOT:PSS nanopapers were 2.58Scm-1 and 6.21Fg-1, respectively. Further coating of PPy produced a substantial improvement on the electrical conductivity (10.55Scm-1) and the specific capacitance (315.5Fg-1) of the resulting CNF-PEDOT:PSS-PPy nanopaper. A synergistic phenomenon between both conductive polymers supported the high electrical conductivity and specific capacitance of the ternary formulation. Moreover, CNF-PEDOT:PSS-PPy nanopaper showed higher mechanical properties and it was more flexible than the nanopaper containing only polypyrrole conducting polymer (CNF-PPy). It is concluded that the good mechanical, electrical and electrochemical properties of the ternary formulation can apply for smart nanopaper in flexible electronics and energy storage devices.

Strong and electrically conductive nanopaper from cellulose nanofibers and polypyrrole.

In this work, we prepare cellulose nanopapers of high mechanical performance and with the electrical conductivity of a semiconductor. Cellulose nanofibers (CNF) from bleached softwood pulp were coated with polypyrrole (PPy) via in situ chemical polymerization, in presence of iron chloride (III) as oxidant agent. The structure and morphology of nanopapers were studied, as well as their thermal, mechanical and conductive properties. Nanopaper from pure CNF exhibited a very high tensile response (224MPa tensile strength and 14.5GPa elastic modulus). The addition of up to maximum 20% of polypyrrole gave CNF/PPy nanopapers of high flexibility and still good mechanical properties (94MPa strength and 8.8GPa modulus). The electrical conductivity of the resulting CNF/PPy nanopaper was of 5.2 10(-2)Scm(-1), with a specific capacitance of 7.4Fg(-1). The final materials are strong and conductive nanopapers that can find application as biodegradable flexible thin-film transistor (TFT) or as flexible biosensor.