Recent Developments in Synthesis, Properties, Applications and Recycling of Bio-Based Elastomers.

In 2021, global plastics production was 390.7 Mt; in 2022, it was 400.3 Mt, showing an increase of 2.4%, and this rising tendency will increase yearly. Of this data, less than 2% correspond to bio-based plastics. Currently, polymers, including elastomers, are non-recyclable and come from non-renewable sources. Additionally, most elastomers are thermosets, making them complex to recycle and reuse. It takes hundreds to thousands of years to decompose or biodegrade, contributing to plastic waste accumulation, nano and microplastic formation, and environmental pollution. Due to this, the synthesis of elastomers from natural and renewable resources has attracted the attention of researchers and industries. In this review paper, new methods and strategies are proposed for the preparation of bio-based elastomers. The main goals are the advances and improvements in the synthesis, properties, and applications of bio-based elastomers from natural and industrial rubbers, polyurethanes, polyesters, and polyethers, and an approach to their circular economy and sustainability. Olefin metathesis is proposed as a novel and sustainable method for the synthesis of bio-based elastomers, which allows for the depolymerization or degradation of rubbers with the use of essential oils, terpenes, fatty acids, and fatty alcohols from natural resources such as chain transfer agents (CTA) or donors of the terminal groups in the main chain, which allow for control of the molecular weights and functional groups, obtaining new compounds, oligomers, and bio-based elastomers with an added value for the application of new polymers and materials. This tendency contributes to the development of bio-based elastomers that can reduce carbon emissions, avoid cross-contamination from fossil fuels, and obtain a greener material with biodegradable and/or compostable behavior.

Recent developments in bio-based polyethylene: Degradation studies, waste management and recycling.

Nowadays, the tendency to replace conventional fossil-based plastics is increasing considerably; there is a growing trend towards alternatives that involve the development of plastic materials derived from renewable sources, which are compostable and biodegradable. Indeed, only 1.5 % of whole plastic production is part of the small bioplastics market, even when these materials with a partial or full composition from biomass are rapidly expanding. A very interesting field of investigation is currently being developed in which the disposal and processing of the final products are evaluated in terms of reducing environmental harm. This review presents a compilation of polyethylene (PE) types, their uses, and current problems in the waste management of PE and recycling. Particularly, this review is based on the capabilities to synthesize bio-based PE from natural and renewable sources as a replacement for the raw material derived from petroleum. In addition to recent studies in degradation on different types of PE with weight loss ranges from 1 to 47 %, the techniques used and the main changes observed after degradation. Finally, perspectives are presented in the manuscript about renewable and non-renewable polymers, depending on the non-degradable, biodegradable, and compostable behavior, including composting recent studies in PE. In addition, it contributes to the 3R approaches to responsible waste management of PE and advancement towards an environmentally friendly PE.

Experimental Analysis of Fiber Reinforcement Rings' Effect on Tensile and Flexural Properties of Onyx™-Kevlar® Composites Manufactured by Continuous Fiber Reinforcement.

Additive manufacturing of composite materials is progressing in the world of 3D printing technologies; composite materials allow the combination of the physical and mechanical properties of two or more constituents to create a new material that meets the required properties of several applications. In this research, the impact of adding Kevlar® reinforcement rings on the tensile and flexural properties of the Onyx™ (nylon with carbon fibers) matrix was analyzed. Parameters such as infill type, infill density and fiber volume percentage were controlled to determine the mechanical response in tensile and flexural tests of the additive manufactured composites. The tested composites showed an increment of four times the tensile modulus and 1.4 times the flexural modulus of pure Onyx™ matrix when compared with that of the Onyx™-Kevlar®. The experimental measurements demonstrated that Kevlar® reinforcement rings can increase the tensile and flexural modulus of Onyx™-Kevlar® composites using low fiber volume percentages (lower than 19% in both samples) and 50% of rectangular infill density. However, the appearance of some defects, such as delamination, was observed and should be further analyzed to obtain products that are errorless and can be reliable for real functions as in automotive or aeronautical industries.

Synthesis of Biobased Hydroxyl-Terminated Oligomers by Metathesis Degradation of Industrial Rubbers SBS and PB: Tailor-Made Unsaturated Diols and Polyols.

Biobased hydroxyl-terminated polybutadiene (HTPB) was successfully synthesized in a one-pot reaction via metathesis degradation of industrial rubbers. Thus, polybutadiene (PB) and poly(styrene-butadiene-styrene) (SBS) were degraded via metathesis with high yields (>94%), using the fatty alcohol 10-undecen-1-ol as a chain transfer agent (CTA) and the second-generation Grubbs−Hoveyda catalyst. The identification of the hydroxyl groups (-OH) and the formation of biobased HTPB were verified by FT-IR and NMR. Likewise, the molecular weight and properties of the HTPB were controlled by changing the molar ratio of rubber to CTA ([C=C]/CTA) from 1:1 to 100:1, considering a constant molar ratio of the catalyst ([C=C]/Ru = 500:1). The number average molecular weight (Mn) ranged between 583 and 6580 g/mol and the decomposition temperatures between 134 and 220 °C. Moreover, the catalyst optimization study showed that at catalyst loadings as low as [C=C]/Ru = 5000:1, the theoretical molecular weight is in good agreement with the experimental molecular weight and the expected diols and polyols are formed. At higher ratios than those, the difference between theoretical and experimental molecular weight is wide, and there is no control over HTPB. Therefore, the rubber/CTA molar ratio and the amount of catalyst play an important role in PB degradation and HTPB synthesis. Biobased HTPB can be used to synthesize engineering design polymers, intermediates, fine chemicals, and in the polyurethane industry, and contribute to the development of environmentally friendly raw materials.

Estimation of the Effects of CO2 and Temperature on the Swelling of PS-CO2 Mixtures at Supercritical Conditions on Rheological Testing.

The use of supercritical CO2 as a blowing agent for polymeric foams instead of traditional blowing agents has been a trend in recent years. To achieve the final desired properties of the polymeric foams, the rheological behavior of the material needs to be reliable. The polymer swelling in the samples for rheological testing affects the results of the viscoelastic properties of the material. This study proposes a new testing methodology to control the accuracy and repeatability of the rheological characterization for PS-SCO2 samples. To develop this methodology, three polystyrene resins with different molecular weight distribution were studied at three temperatures (170, 185 and 200 °C) and three pressures (0.1 MPa, 6.89 MPa and 13.78 MPa). The CO2 concentration was estimated and used in the Sanchez-Lacombe Equation of State (SLEOS) to determine the polymer swelling, as it affects the dimensions of specimens tested in high-pressure rheometers. The correction factors provided a consistent trend in the viscosity with respect to temperature and a decrease of up to 50% in the standard deviation. The results of this study are crucial for an accurate measurement of viscoelastic properties by parallel-plate rheometry.

Effective Stiffness of Fused Deposition Modeling Infill Lattice Patterns Made of PLA-Wood Material.

Fused deposition modeling (FDM) uses lattice arrangements, known as infill, within the fabricated part. The mechanical properties of parts fabricated via FDM are dependent on these infill patterns, which make their study of great relevance. One of the advantages of FDM is the wide range of materials that can be employed using this technology. Among these, polylactic acid (PLA)-wood has been recently gaining attention as it has become commercially available. In this work, the stiffness of two different lattice structures fabricated from PLA-wood material using FDM are studied: hexagonal and star. Rectangular samples with four different infill densities made of PLA-wood material were fabricated via FDM. Samples were subjected to 3-point bending to characterize the effective stiffness and their sensitivity to shear deformation. Lattice beams proved to be more sensitive to shear deformations, as including the contribution of shear in the apparent stiffness of these arrangements leads to more accurate results. This was evaluated by comparing the effective Young's modulus characterized from 3-point bending using equations with and without shear inclusion. A longer separation between supports yielded closer results between both models (~41% for the longest separation tested). The effective stiffness as a function of the infill density of both topologies showed similar trends. However, the maximum difference obtained at low densities was the hexagonal topology that was ~60% stiffer, while the lowest difference was obtained at higher densities (star topology being stiffer by ~20%). Results for stiffness of PLA-wood samples were scattered. This was attributed to the defects at the lattice element level inherent to the material employed in this study, confirmed via micro-characterization.

Neural Network Direct Control with Online Learning for Shape Memory Alloy Manipulators.

New actuators and materials are constantly incorporated into industrial processes, and additional challenges are posed by their complex behavior. Nonlinear hysteresis is commonly found in shape memory alloys, and the inclusion of a suitable hysteresis model in the control system allows the controller to achieve a better performance, although a major drawback is that each system responds in a unique way. In this work, a neural network direct control, with online learning, is developed for position control of shape memory alloy manipulators. Neural network weight coefficients are updated online by using the actuator position data while the controller is applied to the system, without previous training of the neural network weights, nor the inclusion of a hysteresis model. A real-time, low computational cost control system was implemented; experimental evaluation was performed on a 1-DOF manipulator system actuated by a shape memory alloy wire. Test results verified the effectiveness of the proposed control scheme to control the system angular position, compensating for the hysteretic behavior of the shape memory alloy actuator. Using a learning algorithm with a sine wave as reference signal, a maximum static error of 0.83° was achieved when validated against several set-points within the possible range.