ABSTRACT Growing environmental concerns associated with synthetic materials have intensified the demand for sustainable alternatives derived from renewable sources. In addition, the increasing global population has led to a surge in the demand for food products including juice, resulting in the generation of substantial quantities of byproducts, which are organic waste with the potential for valorization. This study investigated the bioconversion of carrot pomace (CP), waste generated in the juice industry, into fungal biomass to produce mycelium‐based foams. Filamentous fungus (Aspergillus oryzae) was cultivated on carrot pomace through a submerged process in a bubble column bioreactor. The analysis of the scanning electron microscopy (SEM) confirmed the presence of the fungal mycelium and CP residues in the material recovered from the bioreactor. This material was mixed with water, and the suspension was subjected to different grinding cycles in an ultrafine grinder, and mycelium‐based foams were then formed via freeze‐molding and freeze‐drying. The resulting foams exhibited an average density of 21.1 kg/m3, with compressive resistance values of 5.8 kPa at 10% deformation and 20.5 kPa at 30% deformation. These mechanical properties are comparable to those of commercial lightweight foams, as indicated by the Ashby material plot. These findings demonstrate the potential of mycelium‐based foams as an alternative to synthetic materials, contributing to waste valorization and development of environmentally friendly materials.
A new bio-based unsaturated polyester resin was blended with a bio-based reactive diluent and evaluated. Furan-based monomers were selected as the main monomers in both the resin and the bio-based reactive diluent to enhance thermomechanical properties and address solubility issues typically seen in bio-based resins and diluents. The resin was synthesized from 2,5-furan dicarboxylic acid, isosorbide, and glycerol, and the resulting polymer intermediate was then end-capped with methacrylic anhydride to introduce reactive sites for cross-linking reaction. The resin was then mixed with either different percentages of bio-based reactive diluent (2,5-bis(hydroxy-methyl) furan methacrylate) or with styrene to study the thermomechanical and rheological behavior of obtained resins. FT-IR, 13 C-NMR, and 1 H-NMR were used to determine the chemical structure of the bio-based reactive diluent. The thermomechanical properties of resin containing bio-based reactive diluent or styrene are characterized and compared by DMA, TGA, and DSC. The synthesized resin had good solubility in the bio-based reactive diluent but not in the styrene. The different mixtures of resin and bio-based reactive diluent showed glass transition temperatures ranging from 166 °C to 174 °C, which was higher than the commercial fossil-based unsaturated polyester resin used as a reference in this study. With thermal and mechanical properties comparable to commercial petroleum-based thermosets, these bio-based resins are promising candidates for high-performance composites, coatings, and other thermoset-based applications.
In this study, a bio-based resin containing glycerol, isosorbide, and 2,5-furan dicarboxylic acid was used to produce a glass fiber reinforced composite. The thermomechanical properties of the resin were examined through dynamic mechanical analysis, thermogravimetric analysis, and differential scanning calorimetry, and were compared with those of commercially available unsaturated polyester resin and epoxy resin. Glass fiber composites were prepared using the synthesized bio-based resin, commercial unsaturated polyester resin, and commercial epoxy resin. Tensile tests, flexural tests, and aging tests were performed on all three types of composites and the results were compared. The findings suggest that the bio-based resin exhibits superior thermomechanical properties compared to the commercial resins. Bio-based resin demonstrates a high storage modulus of 4807 MPa and a loss modulus of 72 MPa at 25 ℃, along with a high glass transition temperature of 173 ℃. The flexural and tensile properties of the bio-based resin were better than that of the commercial resins. The composite produced from bio-based resin shows a flexural strength of 334 MPa and a tensile strength of 256 MPa. Aging results indicate that the synthesized bio-based resin was fairly stable at elevated temperatures. The outcome of this work shows that the bio-based glass fiber reinforced composite is a promising composite for high temperature applications.
Citrus waste has been used as a source of bioplastics for research in different ways. Because the juice industry produces significant amounts of residue each year, it would be advantageous to use the byproducts in the creation of new materials. Researchers have long explored eco-friendly methods to convert citrus and other organic waste into polymers for producing biodegradable films. The goal of this study is to create biofilms from orange waste (OW) and ginger waste (GW) using an ultrafine grinder and study the films’ properties. Since pectin has the ability to gel, and because cellulosic fibers are strong, citrus waste has been studied for its potential to produce biofilms. After being washed, dried, and milled, orange and ginger waste was shaped into films using a casting process. Tensile testing was used to determine the mechanical properties of biofilms, while dynamic mechanical thermal analysis (DMTA), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) were used to determine their thermal properties. As the number of grinding cycles increased, the suspension’s viscosity increased from 29 mPa.s to 57 mPa.s for OW and from 217 mPa.s to 376 mPa.s for GW, while the particle size in the suspension significantly decreased. For OW and GW films, the highest tensile strength was 17 MPa and 15 MPa, respectively. The maximum strain obtained among all films was 4.8%. All the tested films were stable up to 150 °C, and maximum degradation occured after 300 °C.
The Current study aimed at valorizing carrot pomace (CP), an abundant waste from the juice industry. A water-soluble fraction of CP was separated from solid fraction of CP (SFCP) and employed as feedstock for producing fungal biomass (FB) in bench-scale bioreactors. FB combined with SFCP were used to develop mycelium-based papers (MBP) using the wet-laid method. The potential and capacity of FB, SFCP and MBP to remove dye (methylene blue) from wastewater was then investigated. The maximum achieved dye removal was 92% when using a mixture of SFCP and FB in their suspended forms. The MBP with the lowest density (549 kg/m3) reached 83% dye elimination. The findings of this study support the valorization of carrot pomace, through environmentally benign processes, to mycelium-based papers with potential application in wastewater treatment.
The manufacturing method influences the properties of the produced components. This work investigates the influence of manufacturing methods, such as fused deposition modeling (3D printing) and injection molding, on the water absorption and mechanical and thermal properties of the specimens produced from neat bio-based poly(lactic acid) (PLA) polymer and poly(lactic acid)/wood composites. Acrylonitrile butadiene styrene (ABS) acts as the reference material due to its low water absorption and good functional properties. The printing layer thickness is one of the factors that affects the properties of a 3D-printed specimen. The investigation includes two different layer thicknesses (0.2 mm and 0.3 mm) while maintaining uniform overall thickness of the specimens across two manufacturing methods. 3D-printed specimens absorb significantly higher amounts of water than the injection-molded specimens, and the increase in the layer thickness of the 3D-printed specimens contributes to further increased water absorption. However, the swelling due to water absorption in 3D-printed specimens decreases upon increased layer thickness. The tensile, flexural, and impact properties of all of the specimens decrease after water absorption, while the properties improve upon decreasing the layer thickness. Higher porosity upon increasing the layer thickness is the predominant factor. The results from dynamic mechanical analysis and microscopy validate the outcomes. The results from this experimental study highlight the limitations of additive manufacturing.
The manufacturing method influences the properties of the produced components. This work investigates the influence of manufacturing methods such as fused filament fabrication (3D printing) and injection molding on water absorption, mechanical and thermal properties of the specimens produced from neat biobased poly(lactic acid) (PLA) polymer and poly(lactic acid)/wood composites. Acrylonitrile butadiene styrene (ABS) acts as the reference material due to its low water absorption and good functional properties. The printing layer thickness is one of the factors that affects the properties of a 3D printed specimen. The investigation includes two different layer thicknesses (0.2 mm and 0.3 mm) while maintaining uniform overall thickness of the specimens across two manufacturing methods. 3D printed specimens absorb significantly higher amounts of water than the injection molded specimens, and the increase in the layer thickness of the 3D printed specimens contributes to further increased water absorption. However, the swelling due to water absorption in 3D printed specimens decreases on increased layer thickness. Tensile, flexural and impact properties of all the specimens decrease after water absorption while the properties improve on decreasing the layer thickness. Higher porosity on increasing the layer thickness is the predominant factor. The results from dynamic mechanical analysis and microscopy validate the outcomes.
Carrot pomace (CP) which is generated in a large volume in the juice production process, is rich in cellulose, hemicellulose, sugars, pectin, and minerals. However, in many previous investigations, only cellulose was purified and utilized while other components of CP were discarded as waste. Here, CP was valorized into fungal biomass and cellulose with the aim of utilizing all the CP components. Enzymatic pretreatments were applied to solubilize the digestible fraction of CP including hemicellulose, pectin, sucrose, and other sugars for fungal cultivation, while cellulose remained intact in the solid fraction. The dissolved fraction was utilized as a substrate for the cultivation of an edible fungus (Rhizopus delemar). Fungal cultivation was performed in shake flasks and bench-scale bioreactors. The highest fungal biomass concentration was obtained after pretreatment with invertase (5.01 g/L) after 72 h of cultivation (36 and 42% higher than the concentrations obtained after hemicellulase and pectinase treatments, respectively). Invertase pretreatment resulted in the hydrolysis of sucrose, which could then be taken up by the fungus. Carbohydrate analysis showed 28–33% glucan, 4.1–4.9% other polysaccharides, 0.01% lignin, and 2.7–7% ash in the CP residues after enzymatic pretreatment. Fourier transform infrared spectroscopy and thermogravimetric analysis also confirmed the presence of cellulose in this fraction. The obtained fungal biomass has a high potential for food or feed applications, or as a raw material for the development of biomaterials. Cellulose could be purified from the solid fraction and used for applications such as biobased-textiles or membranes for wastewater treatment, where pure cellulose is needed.
Unsaturated polyester resins, one of the most important thermosets, are invariably produced from oil-based monomers. Their application is limited in areas where high thermal stability is required due to their low T g . Besides, these resins contain 30–40% hazardous styrene as a reactive solvent. Therefore, developing bio-based solventless unsaturated polyester resin with medium to high thermomechanical properties compared to petrochemical-based counterparts is important. In order to achieve this, a series of branched bio-based unsaturated polyester resins were synthesized using bulk polymerization method in two steps. In the first step, four different intermediates were prepared by reacting glycerol (as a core molecule) with either isosorbide (diol), 1,3-propanediol (diol), 2,5-furandicarboxylic acid (saturated diacid), or adipic acid (saturated diacid). In the second step, the branched intermediate was end capped with methacrylic anhydride to introduce reactive sites for cross-linking on the branch ends. The chemical structure of the resins was characterized by 13 C-NMR. FT-IR confirmed the polycondensation reaction in the first step and the end functionalization of the resins with methacrylic anhydride in the second step. The effect of 2,5-furandicarboxylic acid and isosorbide on thermomechanical and thermal properties was investigated using dynamic mechanical analysis, differential scanning calorimetry, and thermo-gravimetric analysis. Results indicated that 2,5-furandicarboxylic acid based resins had superior thermomechanical properties compared to a commercial reference unsaturated polyester resin, making them promising resins for high-temperature composite applications. For example, the resin based on 2,5-furandicarboxylic acid and isosorbide and the resin based on 2,5-furandicarboxylic acid and 1,3-propanediol gave glass transition temperatures of 173 °C and 148 °C, respectively. Although the synthesized 2,5-furandicarboxylic acid based resins had higher viscosity (22.7 Pas) than conventional unsaturated polyester (0.4–0.5 Pas) at room temperature, preheated resins can be used for making high-temperature-tolerance fiber-reinforced composite.
Although structural polymers like epoxy are extensively used in marine applications over metallic structures, environmental water tends to ingress into this polymer which may affect its long-term durability. The extent of degradation caused by the absorbed water on polymeric composite's mechanical properties depends on the water diffusion mechanism, environmental temperature and subsequent reversible and irreversible chemical restructuring of the polymer. In this study, hydrothermal conditioning behavior of glass fiber reinforced epoxy (GE) composites with varying (0.1, 0.3, and 0.5) wt.% of pristine and functionalized carbon nanotubes (CNTs and FCNTs) was studied at 15 & DEG;C (Low-Temperature Hydrothermal Conditioning (LTHC)) and 50? (Elevated-Temperature Hydrothermal Conditioning (ETHC)) water baths. The changes in chemical bonding characteristics and glass transition temperature of GE composite due to above mentioned factors have been studied by Fourier transformed infrared spectroscopy and differential scanning calorimetry. The gravimetric analysis was employed to monitor the water uptake kinetics of the composites and flexural strength of conditioned composites after 50 days of conditioning and saturation was study to understand the effect of water sorption. Experimental results revealed that, FCNTs greatly hinders the water absorption through the interfaces at LTHC, as the equilibrium water content of 0.1FCNT-GE composite was similar to 9.5% and similar to 3.0% and Diffusion coefficient was similar to 60.0% and similar to 15.5% lower than the GE and 0.1CNT-GE composites, respectively at LTHC. At LTHC, the water saturated 0.1FCNT-GE composites exhibited superior flexural strength than GE and 0.1CNT-GE composites. At ETHC, generation of hygroscopic stresses and unfavorable stresses at the weak CNT/polymer interface adversely affected the 0.1CNT-GE composites water resistance compared to 0.1FCNT-GE composites with stronger FCNT/polymer interface. The extent of recovery in the flexural strength was evaluated by complete desorption of water-saturated specimens. Finally, a fractography study was conducted to understand the variation in the well-being of the glass fiber/polymer and nanotube/polymer interface due to mentioned varying factors.
The work demonstrates the utilization of fractionalized lignin from the black liquor of soda pulping for the development of starch-lignin biocomposites. The effect of ultrafine friction grinding on lignin particle size and properties of the biocomposites was investigated. Microscopic analysis and membrane filtration confirmed the reduction of lignin particle sizes down to micro and nanoparticles during the grinding process. Field Emission Scanning Electron Microscopy confirmed the compatibility between lignin particles and starch in the composites. The composite films were characterized for chemical structure, ultraviolet blocking, mechanical, and thermal properties. Additional grinding steps led to the reduction of large lignin particles and the produced particles were uniform. The formation of 7.7 to 11.3% lignin nanoparticles was confirmed in the two steps of membrane filtration. The highest tensile strain of the biocomposite films were 5.09 MPa, which displays a 40% improvement compared to starch films. Further, thermal stability of the composite films was better than that of starch films. The results from ultraviolet transmission showed that the composite films could act as an ultraviolet barrier in packaging applications.
Adipic acid was evaluated as a novel solvent for wet spinning of chitosan fibers. A solvent with two carboxyl groups could act as a physical crosslinker between the chitosan chains, resulting in improved properties of the fibers. The performance of adipic acid was compared with conventional solvents, i.e., lactic, citric, and acetic acids. Chitosan solutions were injected into a coagulation bath to form monofilaments. Sodium hydroxide (NaOH) and its mixture with ethanol (EtOH) were used as coagulation agents. Scanning electron microscopy confirmed the formation of uniform chitosan monofilaments with an even surface when using adipic acid as solvent. These monofilaments generally showed higher mechanical strength compared to that of monofilaments produced using conventional solvents. The highest Young’s modulus, 4.45 GPa, was recorded for adipic acid monofilaments coagulated in NaOH-EtOH. This monofilament also had a high tensile strength of 147.9 MPa. Furthermore, taking advantage of chitosan insolubility in sulfuric acid (H2SO4) at room temperature, chitosan fibers were successfully formed upon coagulation in H2SO4-EtOH. The dewatering of fibers using EtOH before drying resulted in a larger fiber diameter and lower mechanical strength. Adipic acid fibers made without dehydration illustrated 18% (for NaOH), 46% (for NaOH-EtOH), and 91% (for H2SO4-EtOH) higher tensile strength compared to those made with dehydration.
The purpose of this study was to investigate the influence of aging on the properties of high-density polyethylene (HDPE) reinforced with multi-wall carbon nanotubes (MWCNTs). Nanocomposites were prepared with nanotubes at 0, 1, 3, and 5 wt%. The long-term durability of the prepared materials was evaluated by thermo-oxidative aging test. Test bodies were aged at 110 degrees C for up to 10 weeks. The nanocomposites were characterized by differential scanning calometry, thermogravimetric analysis (TGA), C-13-NMR, elongation at break, and transmission electron microscopy. The aging mainly occurred on the surface of the samples and the neat HDPE showed a strong yellowing after the aging. A strong reduction in elongation at break was seen. For neat HDPE, the elongation at break was reduced from roughly 1400-25%. When HDPE was reinforced with the nanotubes, the reduction was less dramatic.
The poor adhesion between natural fibers and polymer matrix restricts the mechanical performance of natural fiber reinforced composites. Here, lignosulfonate was methacrylated and evaluated as a potential compatibilizer for flax fiber reinforced soybean-derived polyester thermosets. Significant improvement in both tensile and flexural properties of the fiber composites were achieved when the flax fiber mat was treated with methacrylated lignosulfonate solution. In particular, the flexural modulus and flexural strength more than doubled from 2.6 to 6.7 GPa and from 36 MPa to 76.8 MPa, respectively when the fibers were soaked in 5 wt % MLS solution. The SEM analysis revealed improved fiber-matrix interface and lower extent of fiber pull-out in the methacrylated lignosulfonate treated fiber composites, which correlates with the improved mechanical properties.
The present work is focused on the synthesis of bio-based thermoset polymers and their thermo–oxidative ageing and biodegradability. Toward this aim, bio-based thermoset resins with different chemical architectures were synthesized from lactic acid by direct condensation with ethylene glycol, glycerol and pentaerythritol. The resulting branched molecules with chain lengths (n) of three were then end-functionalized with methacrylic anhydride. The chemical structures of the synthesized lactic acid derivatives were confirmed by proton nuclear magnetic resonance spectroscopy (1H-NMR) and Fourier transform infrared spectroscopy (FT–IR) before curing. To evaluate the effects of structure on their properties, the samples were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and the tensile testing. The samples went through thermo-oxidative ageing and biodegradation; and their effects were investigated. FT-IR and 1H-NMR results showed that three different bio-based resins were synthesized using polycondensation and end-functionalization. Lactic acid derivatives showed great potential to be used as matrixes in polymer composites. The glass transition temperature of the cured resins ranged between 44 and 52 °C. Pentaerythritol/lactic acid cured resin had the highest tensile modulus and it was the most thermally stable among all three resins. Degradative processes during ageing of the samples lead to the changes in chemical structures and the variations in Young’s modulus. Microscopic images showed the macro-scale surface degradation on a soil burial test.
ABSTRACTCarbon fiber (CF) modification by grafting of various graphene‐based nanofillers (GBN) by electrophoretic deposition (EPD) technique was proven to be a successful technique to enhance the out‐of‐plane performance of carbon fiber reinforced polymer (CFRP) composites. Graphene carboxyl (G‐COOH) grafting on carbon fiber by electrophoretic deposition (EPD) is a promising technique to improve the mechanical properties of CFRP composites. To our knowledge, there is a dearth of literature available on the effect of EPD process parameters on the mechanical behavior of modified CFRP composites. The aim of this study is to evaluate the effect of nanofiller concentration in the suspension, applied current, and the time of deposition during EPD on the mechanical behavior of nanophase CFRP composites, thus making it a novel work. With increasing concentration, interlaminar shear strength (ILSS) improved consistently and has shown a maximum enhancement of 24.7% than that of neat CFRP composite at 1.5 g/L nanofiller concentration, whereas flexural strength remained almost unaffected with varying concentration. On the contrary, variation of deposition current has affected the flexural strength but not ILSS. The maximum flexural strength was obtained at a deposition current of 5.0A with an improvement of 16.3% in comparison with neat CFRP samples. However, both flexural strength and ILSS of hybrid CFRP composites have shown improvement with increasing deposition time. At 60 min of deposition, ILSS and flexural strength have shown maximum improvements of 35.0 and 26.6%, respectively, when compared to control specimen. After evaluating the effect of process parameters future scope of the work involves the optimization of parameters for EPD of G‐COOH. Fractographic analysis of the fractured samples was performed using scanning electron microscope (SEM) to apprehend prominent failure mechanisms. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48925.
This chapter focuses on mechanical performance of biofibers such as flax, hemp, and sisal and their effect on mechanical performance when they are reinforced in thermoset and thermoplastic polymers. The aim of this chapter is to present an overview of the mechanical characterization of the biofibers and their corresponding composites. The mechanical characterization includes tensile, flexural, impact, compressive, shear, toughness, hardness, brittleness, ductility, creep, fatigue, and dynamic mechanical analyses. Detailed studies of each test have been widely reported and an overview is important to relate the studies. Studies pertaining to the topics are cited. The most common materials used in biocomposites are biofibers (also called natural fibers) and petroleum-based polymers such polypropylene. The use of renewable materials in biocomposites has increased in the past couple of decades owing to extensive research on cellulosic fibers and biopolymers based on starch or vegetable oil. Today, research is focused on reinforcing natural fibers in petroleum-based polymers. However, the emphasis is shifting toward the amount of renewable materials in biocomposites, which has led to the use of biopolymers instead of petroleum-based polymers in composites. The mechanical properties of some renewable resource-based composites are comparable to commercially available nonrenewable composites. Several plant biofibers have been reinforced in thermoplastics or thermosets to manufacture biocomposites because of their specific properties. The Young's modulus of commonly used biofibers such as hemp and flax could be over 50 GPa and therefore they could be good alternatives to glass fibers in several applications. The good mechanical properties of these biofibers influence the composites' mechanical performance when reinforced in polymers. It is important to understand the mechanical performance of these biofibers and biocomposites in a working environment. A detailed discussion about the mechanical performance of commonly used biofibers and composites is provided in this chapter.