Nanocomposite Foams with Balanced Mechanical Properties and Energy Return from EVA and CNT for the Midsole of Sports Footwear Application.

Polymer foam that provides good support with high energy return (low energy loss) is desirable for sport footwear to improve running performance. Ethylene-vinyl acetate copolymer (EVA) foam is commonly used in the midsole of running shoes. However, EVA foam exhibits low mechanical properties. Conventional mineral fillers are usually employed to improve EVA's mechanical performance, but the energy return is sacrificed. Here, we produced nanocomposite foams from EVA and multi-walled carbon nanotubes (CNT) using a chemical foaming process. Two kinds of CNT derived from the upcycling of commodity plastics were prepared through a catalytic chemical vapor deposition process and used as reinforcing and nucleating agents. Our results show that EVA foam incorporated with oxygenated CNT (O-CNT) demonstrated a more pronounced improvement of physical, mechanical, and dynamic impact response properties than acid-purified CNT (A-CNT). When CNT with weight percentage as low as 0.5 wt% was added to the nanocomposites, the physical properties, abrasion resistance, compressive strength, dynamic stiffness, and rebound performance of the EVA foams were improved significantly. Unlike the conventional EVA formulation filled with talc mineral fillers, the incorporation of CNT does not compromise the energy return of the EVA foam. From the long-cycle dynamic fatigue test, the CNT/EVA foam displays greater properties retention as compared to the talc/EVA foam. This work demonstrates a good balanced of mechanical-energy return properties of EVA nanocomposite foam with very low CNT content, which presents promising opportunities for lightweight-high rebound midsoles for running shoes.

Extrusion Based 3D Printing of Sustainable Biocomposites from Biocarbon and Poly(trimethylene terephthalate).

Three-dimensional (3D) printing manufactures intricate computer aided designs without time and resource spent for mold creation. The rapid growth of this industry has led to its extensive use in the automotive, biomedical, and electrical industries. In this work, biobased poly(trimethylene terephthalate) (PTT) blends were combined with pyrolyzed biomass to create sustainable and novel printing materials. The Miscanthus biocarbon (BC), generated from pyrolysis at 650 °C, was combined with an optimized PTT blend at 5 and 10 wt % to generate filaments for extrusion 3D printing. Samples were printed and analyzed according to their thermal, mechanical, and morphological properties. Although there were no significant differences seen in the mechanical properties between the two BC composites, the optimal quantity of BC was 5 wt % based upon dimensional stability, ease of printing, and surface finish. These printable materials show great promise for implementation into customizable, non-structural components in the electrical and automotive industries.

Lignin derived nano-biocarbon and its deposition on polyurethane foam for wastewater dye adsorption.

Historically, lignin has been produced as a waste by-product in industrial processes. In this study, lignosulfonate nanoparticles were fabricated and freeze-dried for use as a precursor material for carbonization. The use of the carbonized lignins for the adsorption of textile effluent as a value-added application is demonstrated. Characterization of the as received lignin (LN) and the developed nano-based freeze-dried lignin (NFLN) were performed prior to and after carbonization at 600, 750, 900 and 1050 °C. Using probe sonication, lignosulfonates were broken down into nanoparticles with lower weight-average molecular weight as verified by dynamic and static light scattering techniques. The difference between the LN and the NFLN was determined to be primarily morphological as the sonication and freeze-drying process imparted a platelet-like shape to the NFLN biocarbons and an increased surface area, while the remaining functionality was similar. The adsorption behaviour of methylene blue (MB), a synthetic cationic dye, was investigated using adsorption isotherm and kinetic models, with the NFLN exhibiting a maximum adsorption capacity of 109.77 mg/g. Overall, electrostatic attraction and hydrogen bonding contribute significantly to the MB adsorption. Further preliminary work was also performed demonstrating the coating of polyurethane foam for the adsorption of MB. These renewable biocarbons show promising properties for use as additive in adsorbent, coating, pigment or as a filler in polymer composite applications.

Flame synthesis of carbon nanoparticles from corn oil as a highly effective cationic dye adsorbent.

Carbon nanoparticles (CNP) were synthesized through flame deposition method from a sustainable corn oil precursor. The morphology, particle size, surface chemistry, thermal stability, and zeta potential of the CNP were characterized. The batch adsorption of a cationic dye, methylene blue (MB), by the CNP at various concentrations, pH, and temperatures was evaluated to investigate the CNP's efficacy in industrial wastewater treatment applications. Results revealed the excellent adsorption of MB onto the CNP. The experimental data were then fitted into isotherm models, kinetic models, and thermodynamic models, and the model parameters, constants, Gibb free energy, enthalpy, and entropy were calculated and discussed. Hydrogen bonding and strong electrostatic interaction were the main adsorption mechanism for MB adsorption by the CNP. The CNP exhibited a maximum adsorption capacity of 138.89 mg/g, indicating superior adsorption of MB dye without the need for any further purification and activation steps. The adsorption efficiency did not compromise as the solution temperature increased up to 60 °C, and it can further be enhanced under alkaline conditions. To simulate the practical and industrial use of the developed CNP in textile effluent treatment, successful experiments were conducted in continuous flow adsorption by allowing concentrated MB solution to flow through a designed fixed bed purification system with a CNP filter bed.

Underutilized Agricultural Co-Product as a Sustainable Biofiller for Polyamide 6,6: Effect of Carbonization Temperature.

Polyamide 6,6 (PA66)-based biocomposites with low-cost carbonaceous natural fibers (i.e., soy hulls, co-product from soybean industry) were prepared through twin-screw extrusion and injection molding. The soy hull natural fiber was pyrolyzed at two different temperatures (500 °C and 900 °C denoted as BioC500 and BioC900 respectively) to obtain different types of biocarbons. The BioC500 preserved a higher number of functional groups as compared to BioC900. Higher graphitic carbon content was observed on the BioC900 than BioC500 as evident in Raman spectroscopy. Both biocarbons interact with the PA66 backbone through hydrogen bonding in different ways. BioC900 has a greater interaction with N-H stretching, while BioC500 interacts strongly with the amide I (C=O stretching) linkage. The BioC500 interrupts the crystallite growth of PA66 due to strong bond connection while the BioC900 promotes heterogeneous crystallization. Dynamic mechanical analysis shows that both biocarbons result in an increasing storage modulus and glass transition temperature with increasing content in the BioC/PA66 biocomposites over PA66. Rheological analysis shows that the incorporation of BioC900 results in decreasing melt viscosity of PA66, while the incorporation of BioC500 results in increasing the melt viscosity of PA66 due to greater filler-matrix adhesion. This study shows that pyrolyzed soy hull natural fiber can be processed effectively with a high temperature (>270 °C) engineering plastic for biocomposites fabrication with no degradation issues.

Studies on durability of sustainable biobased composites: a review.

Global concerns over environmental issues have led to a tremendous growth in sustainable materials emerging from biobased plastics and their composites (biocomposites). This class of materials can be an alternative to traditional composite materials to reduce the carbon footprint and strain on the environment. Many studies and reviews have been focused on enhancing the mechanical performance of biocomposites with the aim for them to compete with traditional composites and expand their applications. However, the current scientific knowledge relating to the long-term durability performance of biocomposites is very limited in open access literature. Studies of the effects of different aging mechanisms when subjected to different service conditions and environments on the biocomposites' behaviours are needed. This review provides a focused discussion on the overview of the long-term durability performance and degradation behaviour under various aging environments (thermo-oxidative aging, accelerated weathering (ultraviolet aging), hydrolytic degradation, fatigue and creep, etc.) of the commercially important biobased-composites for the first time. Future perspectives and methods to improve the durability performance of biocomposites are also discussed in this review.

Strategy To Improve Printability of Renewable Resource-Based Engineering Plastic Tailored for FDM Applications.

This work features the first-time use of poly(trimethylene terephthalate) (PTT), a biobased engineering thermoplastic, for fused deposition modeling (FDM) applications. Additives such as chain extenders (CEs) and impact modifiers are traditionally used to improve the processability of polymers for injection molding; as a proof of concept for their use in FDM, the same strategies were applied to PTT to improve its printability. The filament processing conditions and printing parameters were optimized to generate complete, warpage-free samples. The blends were characterized through physical, thermal, viscoelastic, and morphological analyses. In the optimal blend (90 wt % PTT, 10 wt % impact modifier, and 0.5 phr CE), the filament diameter was improved by ∼150%, the size of the spherulites significantly decreased to 5% of the ∼26 µm spherulite size found in neat PTT, and the melt flow index decreased to ∼4.7 g/10 min. From this blend, FDM samples with a high impact performance of ∼61 J/m were obtained, which are comparable to other conventional FDM thermoplastics. The ability to print complete and warpage-free samples from this blend suggests a new filament feedstock material for industrial and home-use FDM applications. This paper discusses methods to improve hard-to-print polymers and presents the improved printability of PTT as proof of these methods' effectiveness.

Novel sustainable biobased flame retardant from functionalized vegetable oil for enhanced flame retardancy of engineering plastic.

The flame retardancy of an engineering plastic, poly(butylene terephthalate) (PBT), with a biobased flame retardant (FR) made from phosphorylated linseed oil (PLO) and phosphorylated downstream corn oil (PCO) was studied. Different phosphorus moieties were incorporated into the vegetable oil backbone through a ring-opening reaction. The chemical structure of the phosphorylated oil was confirmed by Fourier-transform infrared (FTIR) and nuclear resonance magnetic (NMR) spectroscopy. It was found that the incorporation of only 7.5 wt% of PLO was sufficient to change the UL-94 fire class of PBT from non-rating to V-0. The flame-retardancy mechanism of the PBT/PLO blends was evaluated from TGA-FTIR analysis. The combined effects of the gas phase mechanism and the dripping tendency of the blends aided to retard the flame propagation effectively. As the synthesized PLO and PCO contained high free fatty acids, the acid-ester exchange reaction occurred in the blends to form oligomers during the ignition. As a result, the blend dripped immediately and the drips carried all the heat to prevent fire. This work suggests that this sustainable biobased FR could be a desirable alternative to halogen-based FRs for PBT and other engineering polymers to develop more environmentally friendly FR products for various future applications.

Tuning the compatibility to achieve toughened biobased poly(lactic acid)/poly(butylene terephthalate) blends.

A series of sustainable biobased polymer blends from poly(lactic acid) (PLA) and poly(butylene terephthalate) (PBT) were fabricated and characterized. These blends are engineered to achieve optimal mechanical properties and toughness with a reactive epoxidized styrene-acrylic copolymer (ESAC) compatibilizer, and an ethylene-n-butyl-acrylate-co-glycidyl methacrylate (EBA-GMA) elastomer-based compatibilizer. The results showed that the tensile strength, modulus, flexural strength and modulus of the PBT increase, while the elongation at break and notched impact strength decrease after blending with the biopolymer PLA. The full co-continuity of PLA in PBT was confirmed at a 50/50 wt% blend ratio. The droplet size of the PLA was reduced and the distinct phases of the blends were gradually diminished with the increasing content of the ESAC compatibilizer. The increase in the complex viscosity of the blends was due to the formation of PLA-g-PBT copolymers in the blend after addition of reactive compatibilizers. The incorporation of both compatibilizers in the blends led to superior notched impact strength in comparison to only a single compatibilizer used in the blends. The synergistic effect of both compatibilizers effectively reduces the PLA droplet size and improves the dispersion of PLA in PBT as evidenced by atomic force microscopy (AFM) topography observations. The high toughness of the blends corresponds to the formation of effective EBA-GMA structures and enhanced interfacial compatibilization due to the synergistic effect of the compatibilizers.