Biobased circular materials are alternatives to fossil-based engineering plastics, but simple and material-efficient synthetic routes are needed for industrial scalability. Here, a series of ...lignin-based vitrimers built on dynamic acetal covalent networks with a gel content exceeding 95% were successfully prepared in a one-pot, thermally activated, and catalyst-free “click” addition of softwood kraft lignin (SKL) to poly(ethylene glycol) divinyl ether (PDV). The variation of the content of lignin from 28 to 50 wt % was used to demonstrate that the mechanical properties of the vitrimers can be widely tuned in a facile way. The lowest lignin content (28 wt %) showed a tensile strength of 3.3 MPa with 35% elongation at break, while the corresponding values were 50.9 MPa and 1.0% for the vitrimer containing 50 wt % of lignin. These lignin-based vitrimers also exhibited excellent performance as recoverable adhesives for different substrates such as aluminum and wood, with a lap shear test strength of 6.0 and 2.6 MPa, respectively. In addition, recyclability of the vitrimer adhesives showed preservation of the adhesion performance exceeding 90%, indicating a promising potential for their use in sustainable circular materials.
Synthetic polymers are indispensable in many different applications, but there is a growing need for green processes and natural surfactants for emulsion polymerization. The use of solid particles to ...stabilize Pickering emulsions is a particularly attractive avenue, but oxygen sensitivity has remained a formidable challenge in controlled polymerization reactions. Here we show that lignin nanoparticles (LNPs) coated with chitosan and glucose oxidase (GOx) enable efficient stabilization of Pickering emulsion and in situ enzymatic degassing of single electron transfer-living radical polymerization (SET-LRP) without extraneous hydrogen peroxide scavengers. The resulting latex dispersions can be purified by aqueous extraction or used to obtain polymer nanocomposites containing uniformly dispersed LNPs. The polymers exhibit high chain-end fidelity that allows for production of a series of well-defined block copolymers as a viable route to more complex architectures.
Brittleness has hindered commercialization of cellulose nanofibril (CNF) films. The use of synthetic polymers and plasticizers is a known detour that impairs biodegradability and carbon footprint of ...the product. Herein, we utilize a variety of softwood Kraft lignin morphologies to obtain strong and ductile CNF nanocomposite films. An optimum 10 wt % content of colloidal lignin particles (CLPs) produced films with nearly double the toughness compared to a CNF film without lignin. CLPs rendered the films waterproof, provided antioxidant activity and UV-shielding with better visible light transmittance than obtained with irregular lignin aggregates. We conclude based on electron microscopy, dynamic water sorption analysis, and tp-DSC that homogeneously distributed CLPs act as ball bearing lubricating and stress transferring agents in the CNF matrix. Overall, our results open new avenues for the utilization of lignin nanoparticles in biopolymer composites equipped with versatile functionalities for applications in food packaging, water purification, and biomedicine.
The commercial breakthrough of Li‐ion batteries (LIBs) in the 1990s irrevocably shaped today's energy storage landscape, but the disposed batteries represent a growing hazard to the environment. One ...may initially assume that recycling processes are commendable technologies to ensure a counterbalance to LIBs manufacturing. However, the question remains whether current state‐of‐the‐art in LIBs recycling technologies can be considered as green. This problem is due to the application of toxic chemicals or the in situ generation of harmful substances during the recycling process. Besides the potential toxicity, current solutions are accompanied with intense energy consumption, causing carbon dioxide emissions, in disagreement with the circular economy principles. This review provides a critical assessment of both published research articles and patents to derive a broad picture on the sustainability of LIBs recycling technologies. Although the efficiency of industrially applied recycling technologies can exhibit a high overall efficiency, their general process design is generally based on waste reduction and downcycling. Contrariwise, sustainable recycling of LIBs should rely on circular processes ensuring upcycling of all materials toward zero waste and minimized energy utilization. Current solutions and expected development in LIBs recycling are presented, ranging from dismantling over components separation to application of bioderived materials.
Current recycling technologies of used Li‐ion batteries (LIBs) cannot be considered as green technologies due to their sole focus on waste minimalization. This review provides a critical assessment of recent progress in LIBs recycling with an emphasis on sustainable processes, which are designed toward zero waste, minimized energy consumption, and circular materials management.
Photonic crystals are optical materials that are often fabricated by assembly of particles into periodically arranged structures. However, assembly of lignin nanoparticles has been limited due to ...lacking methods and incomplete understanding of the interparticle forces and packing mechanisms. Here we show a centrifugation-assisted fabrication of photonic crystals with rainbow structural colors emitted from the structure covering the entire visible spectrum. Our results show that centrifugation is crucial for the formation of lignin photonic crystals, because assembly of lignin nanoparticles without centrifugation assistance leads to the formation of stripe patterns rather than photonic crystals. We further prove that the functions of centrifugation are to classify lignin nanoparticles according to their particle size and produce monodispersed particle layers that display gradient colors from red to violet. The different layers of lignin nanoparticles were assembled in a way that created semi-closed packing structures, which gave rise to coherent scattering. The diameter of the lignin nanoparticles in each color layer is smaller than that predicted by a modified Bragg's equation. In situ optical microscope images provided additional evidence on the importance of dynamic rearrangement of lignin nanoparticles during their assembly into semi-closed packing structures. The preparation of lignin nanoparticles combined with the methodology for their classification and assembly pave the way for sustainable photonic crystals.
Conspectus The increasing demand for polymeric materials derived from petroleum resources, along with rising concerns about climate change and global plastic pollution, has driven the development of ...biobased polymeric materials. Lignin, which is the second most abundant biomacromolecule after cellulose, represents a promising renewable raw material source for the preparation of advanced materials. The lucrative properties of lignin include its high carbon content (>60 atom %), high thermal stability, biodegradability, antioxidant activity, absorbance of ultraviolet radiation, and slower biodegradability compared to other wood components. Moreover, the advent of lignin nanoparticles (LNPs) over the last ten years has circumvented many well-known shortcomings of technical lignins, such as heterogeneity and poor compatibility with polymers, thereby unlocking the great potential of lignin for the development of advanced functional materials. LNPs stand out owing to their well-defined spherical shape and excellent colloidal stability, which is due to the electrostatic repulsion forces of carboxylic acid and phenolic hydroxyl groups enriched on their surface. These forces prevent their aggregation in aqueous dispersions (pH 3–9) and provide a high surface area to mass ratio that has been exploited to adsorb positively charged compounds such as enzymes or polymers. Consequently, it is not surprising that LNPs have become a prominent player in applied research in areas such as biocatalysis and polymeric composites, among others. However, like all ventures of life, LNPs also face certain challenges that limit their potential end-uses. Solvent instability remains the most challenging aspect due to the tendency of these particles to dissolve or aggregate in organic solvents and basic or acidic pH, thus limiting the window for their chemical functionalization and applications. In addition, the need for organic solvent during their preparation, the poor miscibility with hydrophobic polymeric matrices, and the nascent phase regarding their use in smart materials have been identified as important challenges that need to be addressed. In this Account, we recapitulate our efforts over the past years to overcome the main limitations mentioned above. We begin with a brief introduction to the fundamentals of LNPs and a detailed discussion of their associated challenges. We then highlight our work on: (i) Preparation of lignin-based nanocomposites with improved properties through a controlled dispersion of LNPs within a hydrophobic polymeric matrix, (ii) Stabilization of LNPs via covalent (intraparticle cross-linking) and noncovalent (hydration barrier) approaches, (iii) The development of an organic-solvent-free method for the production of LNPs, and (iv) The development of LNPs toward smart materials with high lignin content. Finally, we also offer our perspectives on this rapidly growing field.
Lignin is one the most fascinating natural polymers due to its complex aromatic‐aliphatic structure. Phenolic hydroxyl and carboxyl groups along with other functional groups provide technical lignins ...with reactivity and amphiphilic character. Many different lignins have been used as functional agents to facilitate the synthesis and stabilization of inorganic materials. Herein, the use of lignin in the synthesis and chemistry of inorganic materials in selected applications with relevance to sustainable energy and environmental fields is reviewed. In essence, the combination of lignin and inorganic materials creates an interface between soft and hard materials. In many cases it is either this interface or the external lignin surface that provides functionality to the hybrid and composite materials. This Minireview closes with an overview on future directions for this research field that bridges inorganic and lignin materials for a more sustainable future.
Lignin–inorganic hybrid materials: Lignin can provide reactive phenolic interfaces to inorganic materials. It is often this interface or external surface that brings synergic effects and completely new functionality useful in applications. This Minireview takes a critical look at the most intriguing examples of lignin–inorganic hybrids, composites, and other materials from the viewpoint of materials chemistry.
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