Bio-Polyethylene and Polyethylene Biocomposites: An Alternative toward a Sustainable Future.

Polyethylene (PE), a highly prevalent non-biodegradable polymer in the field of plastics, presents a waste management issue. To alleviate this issue, bio-based PE (bio-PE), derived from renewable resources like corn and sugarcane, offers an environmentally friendly alternative. This review discusses various production methods of bio-PE, including fermentation, gasification, and catalytic conversion of biomass. Interestingly, the bio-PE production volumes and market are expanding due to the growing environmental concerns and regulatory pressures. Additionally, the production of PE and bio-PE biocomposites using agricultural waste as filler materials, highlights the growing demand for sustainable alternatives to conventional plastics. According to previous studies, addition of ≈50% defibrillated corn and abaca fibers into bio-PE matrix and a compatibilizer, results in the highest Young's modulus of 4.61 and 5.81 GPa, respectively. These biocomposites have potential applications in automotive, building construction, and furniture industries. Moreover, the advancement made in abiotic and biotic degradation of PE and PE biocomposites is elucidated to address their environmental impacts. Finally, the paper concludes with insights into the opportunities, challenges, and future perspectives in the sustainable production and utilization of PE and bio-PE biocomposites. In summary, production of PE and bio-PE biocomposites can contribute to a cleaner and sustainable future.

Thioxanthylium Cations: Highly Reversible Hydrochromic Mate-rials with Tunable Color and Moisture Sensitivity.

Hydrochromic materials, which change color in response to moisture, are highly sought-after due to some unique applications such as moisture detection, humidity monitoring, anti-counterfeiting, and sweat-pore mapping. We herein report a new thioxanthene-9-ols/thioxanthylium cations hydrochromic system. The hydrochromic thioxanthylium cations can be generated/regenerated by exposing a chemically stable thioxanthene-9-ol to trifluoroacetic acid (TFA). The intensely colored thioxanthylium cations can be chemically reverted to the colorless thioxanthene-9-ol. Interestingly, the conversion between thioxanthene-9-ol and its cation species was found to be highly reversible in most cases (up to 50 activation-deactivation cycles). The color and moisture-sensitivity of thioxanthylium cations were also validated to be tunable via functionalization of the thioxanthene core with different aliphatic and aromatic groups at its 9 or 2,7-positions. Finally, paper probes were prepared using solution-immersion and inkjet-printing techniques to demonstrate the system's potential applications in humidity sensing and anti-counterfeiting.

Electrospun PEO/PEG fibers as potential flexible phase change materials for thermal energy regulation.

Polyethylene glycol (PEG) is widely used as phase change materials (PCM) due to their versatile working temperature and high latent heat. However, the low molecular weight of PEG prevents from the formation of flexible microfibers, and the common leakage problem associated with solid-liquid PCM further hinders their applications in various fields. To address these challenges, polyethylene oxide (PEO) is incorporated as the supporting matrix for PEG, leading to a successful electrospinning of fibrous mats. Due to the similar chemical nature of both PEG and PEO, the blended composites show great compatibility and produce uniform electrospun fibers. The thermal properties of these fibers are characterized by DSC and TGA, and supercooling for the PEG(1050) component is effectively reduced by 75-85%. The morphology changes before and after leakage test are analyzed by SEM. Tensile and DMA tests show that the presence of PEG(1050) component contributes to plasticization effect, improving mechanical and thermomechanical strength. The ratio of PEO(600K):PEG(1050) at 7:3 affords the optimal performance with good chemical and form-stability, least shrinkage, and uniformity. These fibrous mats have potential applications in areas of food packaging, flexible wearable devices, or textiles to aid in thermal regulation.

Hydrolytic degradation and biodegradation of polylactic acid electrospun fibers.

Increased use of bioplastics, such as polylactic acid (PLA), helps in reducing greenhouse gas emissions, decreases energy consumption and lowers pollution, but its degradation efficiency has much room for improvement. The degradation rate of electrospun PLA fibers of varying diameters ranging from 0.15 to 1.33 µm is measured during hydrolytic degradation under different pH from 5.5 to 10, and during aerobic biodegradation in seawater supplemented with activated sewage sludge. In hydrolytic conditions, varying PLA fiber diameter had significant influence over percentage weight loss (W%L), where faster degradation was achieved for PLA fibers with smaller diameter. W%L was greatest for PLA-5 > PLA-12 > PLA-16 > PLA-20, with average W%L at 30.7%, 27.8%, 17.2% and 14.3% respectively. While different pH environment does not have a significant influence on PLA degradation, with W%L only slightly higher for basic environments. Similarly biodegradation displayed faster degradation for small diameter fibers with PLA-5 attaining the highest degree of biodegradation at 22.8% after 90 days. Hydrolytic degradation resulted in no significant structural change, while biodegradation resulted in significant hydroxyl end capping products on the PLA surface. Scanning electron microscopy (SEM) imaging of degraded PLA fibers showed a deteriorated morphology of PLA-5 and PLA-12 fibers with increased adhesion structures and irregularly shaped fibers, while a largely unmodified morphology for PLA-16 and PLA-20.

Strategies to Enhance the Electrochromic Properties of Conjugated Polymers Bearing Pyromellitic Diimide Acceptors.

A series of conjugated polymers bearing thiophene-based donors and pyromellitic diimide (PMDI) acceptor were prepared, and their electrochromic (EC) properties were studied via using fabricated thin-film EC devices. It was observed that structurally regular alternating polymers with fewer (1 and 2) thiophene donors do not exhibit any EC properties while increasing the number of donors eventually led to the emergence of orange-red-to-green colour switching. On this basis, two more random co-polymers containing higher donor-to-acceptor ratios were synthesized to further improve EC switching properties. The two polymers, which bear a PMDI-to-thiophene ratio of ca. 1 : 7 and 1 : 8, revealed orange red-to-blue colour switching and generally improved optical contrasts and switching speeds in both the visible and near infra-red (NIR) region. In addition, the subtle modulation of polymer colour and hue via variation of the number of thiophene donors was evident through colorimetric study. This work therefore demonstrates the potential and possibility of using the PMDI acceptor unit to construct EC-active conjugated polymers, and considerations for future tuning of colour and switching performances.

Ultra-high Performance Thermochromic Polymers via a Solid-solid Phase Transition Mechanism and Their Applications.

Thermochromic materials are substances that change colour in response to temperature variations. Today, sustainability concerns are the main drivers of thermochromic research, with smart, energy efficient windows being one of primary applications. While vanadium oxides and leuco dyes are traditionally the main thermochromic materials, hydrogels operating based on change of solvation have risen as some of the most promising materials due to their high optical transparency and good solar modulating abilities. In this work, a distinct mechanism for thermochromism arising from the crystalline solid to amorphous solid polymer transition, with a corresponding transition from an opaque state to a transparent state is disclosed. Both ultra-high optical transparency (Tlum up to 99%) and ultra-high solar modulation (ΔTsolar up to 87%) were observed. The transition temperature was tunable from 11 to 61 ͦ C by tuning the polymer structure. When incorporated into applications such as greenhouse materials and thermoelectric devices, significant performance enhancement was observed, due to the thermochromic material functioning as a thermal valve, speeding up solar heat absorbance while inhibiting the cooling process via its phase transition. This article is protected by copyright. All rights reserved.

Bio-Polypropylene and Polypropylene-based Biocomposites: Solutions for a Sustainable Future.

Polypropylene (PP) is among the most widely used commodity plastics in our everyday life due to its low cost, lightweight, easy processability, and exceptional chemical, thermo-mechanical characteristics. The growing awareness on energy and environmental crisis has driven global efforts for creating a circular economy via developing sustainable and eco-friendly alternatives to traditional plastics produced from fossil fuels for a variety of end-use applications. This review paper presents a brief outline of the emerging bio-based PP derived from renewable natural resources, covering its production routes, market analysis and potential utilizations. This contribution also provides a comprehensive review of the PP-based biocomposites produced with diverse green fillers generated from agro-industrial wastes, with particular emphasis on the structural modification, processing techniques, mechanical properties, and practical applications. Furthermore, given that the majority of PP products are currently destined for landfills, research progress on enhancing the degradation of PP and its biocomposites is also presented in light of the environmental concerns. Finally, a brief conclusion with discussions on challenges and future perspectives are provided.

Polylactic acid face masks: Are these the sustainable solutions in times of COVID-19 pandemic?

The global massive consumption of disposable face masks driven by the ongoing COVID-19 pandemic has emerged as a blooming disaster to both the land and marine environment that might last for generations. Growing public concerns have been raised over the management and control of this new form of plastic pollution, and one of the proposed sustainable solution is to use renewable and/or biodegradable resources to develop mask materials in order to minimize their environmental impacts. As a representative biodegradable polymer, polylactic acid (PLA) has been proposed as a promising candidate to produce non-woven face masks instead of those fossil-based polymers. To further explore the feasibility of this alternative mask material, the present work aims to study both the hydrolytic and bio-degradation behaviors of pure PLA-derived 3-ply disposable face masks at ambient temperature. Hydrolytic degradability was investigated at different pH conditions of 2, 7 and 13 with the whole piece of face mask soaked for regular timed intervals up to 8 weeks. Weight loss study showed neutral and acidic conditions had minimal effect on PLA masks, but rapid degradation occurred under basic conditions in the first week with a sharp 25% decrease in weight that slowly tapered off, coupled with solution pH dropping from 13 to 9.6. This trend was supported by mechanical property, bacterial filtration efficiency (BFE) and particulate filtration efficiency (PFE) studies. Masks soaked in basic conditions had their modulus and tensile strength dropped by more than 50% after 8 weeks where the middle layer reached 68% and 90% respectively just after 48 h, and BFE and PFE decreased by 14% and 43% respectively after 4 weeks, which was much more significant than those in neutral and acidic conditions. Base degradation was also supported by nuclear magnetic resonance (NMR) and fourier transform infrared (FTIR), which disclosed that only the middle layer undergo major degradation with random chain scission and cleavage of enol or enolate chain ends, while outer and inner layers were much less affected. Scanning electron microscopy (SEM) attributed this observation to thinner PLA fibers for the middle layer of 3-7 µm diameter, which on average is 3 times smaller. This degradation was further supported by gel permeation chromatography (GPC) which saw an increase in lower molecular weight fragment Mw ~ 800 Da with soaking duration. The biodegradation behavior was studied under OECD 301F specification in sewage sludge environment. Similarly, degradation to the middle meltblown layer was more extensive, where the average weight loss and carbon loss was 25.8% and 25.7% respectively, double that of outer/inner spunbond layer. The results showed that the face masks did not completely disintegrate after 8 weeks, but small solubilized fragments of PLA formed in the biodegradation process can be completely mineralized into carbon dioxide without generation of secondary microplastic pollution in the environment. PLA masks are therefore a slightly greener option to consider in times of a pandemic that the world was caught unprepared; however future research on masks could be geared towards a higher degradability material that fully breaks down into non-harmful components while maintaining durability, filtration and protection properties for users.

Bottom-Up Engineering Strategies for High-Performance Thermoelectric Materials.

The recent advancements in thermoelectric materials are largely credited to two factors, namely established physical theories and advanced materials engineering methods. The developments in the physical theories have come a long way from the "phonon glass electron crystal" paradigm to the more recent band convergence and nanostructuring, which consequently results in drastic improvement in the thermoelectric figure of merit value. On the other hand, the progresses in materials fabrication methods and processing technologies have enabled the discovery of new physical mechanisms, hence further facilitating the emergence of high-performance thermoelectric materials. In recent years, many comprehensive review articles are focused on various aspects of thermoelectrics ranging from thermoelectric materials, physical mechanisms and materials process techniques in particular with emphasis on solid state reactions. While bottom-up approaches to obtain thermoelectric materials have widely been employed in thermoelectrics, comprehensive reviews on summarizing such methods are still rare. In this review, we will outline a variety of bottom-up strategies for preparing high-performance thermoelectric materials. In addition, state-of-art, challenges and future opportunities in this domain will be commented.

Improved Alignment of PEDOT:PSS Induced by in-situ Crystallization of "Green" Dimethylsulfone Molecules to Enhance the Polymer Thermoelectric Performance.

Dimethylsulfone (DMSO2), a small organic molecule, was observed to induce the alignment of poly(3,4-ethylenedioxythiophene): poly(4-styrenesulfonate) (PEDOT:PSS) via in-situ crystallization in PEDOT:PSS mixture, which was verified by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and atomic force microscopy (AFM). A chemically stable dopant, DMSO2, remarkably raised the electrical conductivity of the PEDOT:PSS film, which was fabricated from pre-mixed solution of PEDOT:PSS and DMSO2, up to 1080 S/cm, and more importantly, such a PEDOT:PSS film showed a long-term humidity stability and it retained near 90% electric conductivity after 60 days, suggesting DMSO2 is promising for an eco-friendly alternative to replace dimethyl sulfoxide (DMSO), ethylene glycol (EG) and various acids dopants that have been widely employed to dope and post-treat PEDOT:PSS. Pairwise interaction energies and free energy of solvation between PEDOT:PSS and DMSO2 were calculated by first-principles and molecular mechanics, respectively, revealing the mechanism of DMSO2 in enhancing the electrical conductivity.