Durable and High-Performance Triboelectric Nanogenerator Based on an Inorganic Triboelectric Pair of Diamond-Like-Carbon and Glass.

The long-term durability of triboelectric nanogenerators (TENGs) remains a main challenge for practical applications because of inevitable material abrasion and wear, especially for sliding TENGs. Herein, an inorganic triboelectric pair composed of diamond-like carbon (DLC) and glass with excellent durability and triboelectric output for sliding-mode TENGs is proposed. This triboelectric pair possesses a low coefficient of friction and little abrasion and accordingly excellent durability (>500 000 cycles). Moreover, compared with the traditional copper-polytetrafluoroethylene (Cu-PTFE) TENG with maximum transferred charges of 50 nC, those of the DLC-glass TENG reaches 141 nC. Due to the low-friction and high hardness of the triboelectric pair, the output quickly recovers after simply cleaning wear debris. The DLC-glass TENG demonstrates an output power density of 530 mW m-2 and a fourfold faster capacitor charging speed than the Cu-PTFE TENG. Compared to the reported durable TENGs via structure optimization and interface lubrication, the DLC-glass TENG shows higher outputs and simpler structure. This DLC-glass pair structure is also introduced into a spherical TENG for blue energy harvesting with excellent durability. The inorganic triboelectric pair with excellent mechanical durability and electrical performance proposed in this work shows huge prospects for practical applications of TENGs.

Innovative Approaches for Manufacturing Epoxy-Modified Wood and Cellulose Fiber Composites: A Comparison between Injection Molding and 3D Printing.

The current study focused on improving the properties of polylactic acid (PLA) for wider application in load-bearing scenarios. Various methods were explored to optimize the interaction between PLA and natural fibers, particularly wood fibers (WFs). Alkalized and epoxy-impregnated WFs were evaluated against untreated WFs and cellulose fibers in both injection molding (IM) and fused deposition modeling (FDM). FTIR analysis revealed the removal of hemicellulose and lignin in alkalized WFs and uniform epoxy curing. Addition of fibers reduced PLA's thermal stability while acting as nucleating agents. Additionally, fibers augmented the storage modulus of biocomposites, with alkalized fibers exhibiting the highest tensile modulus in IM. FDM samples with a 0° raster angle showed superior impact resistance compared to IM counterparts. Moreover, raster angle significantly influenced FDM biocomposite properties, enhancing the tensile strength and modulus of untreated WF and cellulose fibers at 0°. Although FDM did not produce alkalized WF samples, epoxy impregnation emerged as a promising method for enhancing PLA/WF composite mechanical properties in the IM process, offering valuable insights for composite material development.

Ring-opening polymerization of emulsion-templated deep eutectic system monomer for macroporous polyesters with controlled degradability.

Biodegradable polyesters with interconnected macroporosity, such as poly(l-lactide) (PLLA) and poly(ε-caprolactone) (PCL), have gained significant importance in the fields of tissue engineering and separation. This study introduces functional macroinitiators, specifically polycaprolactone triol (PCLT) and polyethylene glycol (PEG), both OH-terminated, in the solventless ring-opening polymerization (ROP) of a liquid deep eutectic system monomer (DESm) composed of LLA and CL at a 30 : 70 molar ratio, respectively. The macroinitiators selectively initiate the organocatalyzed ROP of LLA in the DESm during the first polymerization stage, thereby modifying the PLLA architecture. This results in the formation of either branched or linear PLLA copolymers depending on the macroinitiator, PCLT and PEG, respectively. In the second stage, the ROP of the CL, which is a counterpart of the DESm, produces PCL that blends with the previously formed PLLA. The insights gained into the PLLA architectures during the first stage of the DESm ROP, along with the overall molecular weight and hydrophobicity of the resulting PLLA/PCL blend in bulk, were advantageously used to design polymerizable high internal phase emulsions (HIPEs) oil-in-DESm. By incorporating a liquid mixture of DESm and macroinitiators (PCLT or PEG), stable HIPE formulations were achieved. These emulsions sustained the efficient organocatalyzed ROP of the continuous phase at 37 °C with high conversions. The resulting polymer replicas of the HIPEs, characterized by macroporous and interconnected structures, were subjected to a degradation assay in PBS at pH 7.4 and 37 °C and remained mechanically stable for at least 30 days. Notably, they exhibited the capability to sorb crude oil in a proof-of-concept test, with a rate of 2 g g-1. The macroporous and interconnected features of the polyHIPEs, combined with their inherent degradation properties, position them as promising degradable polymeric sorbents for efficient separation of hydrophobic fluids from water.

Enzymatic Synthesis of Copolyesters with the Heteroaromatic Diol 3,4-Bis(hydroxymethyl)furan and Isomeric Dimethyl Furandicarboxylate Substitutions.

Polyesters from furandicarboxylic acid derivatives, i.e., dimethyl 2,5-furandicarboxylate (2,5-DMFDCA) and 2,4-DMFDCA, show interesting properties among bio-based polymers. Another potential heteroaromatic monomer, 3,4-bis(hydroxymethyl)furan (3,4-BHMF), is often overlooked but holds promise for biopolymer synthesis. Cleaning and greening synthetic procedures, i.e., enzymatic polymerization, offer sustainable pathways. This study explores the Candida antarctica lipase B (CALB)-catalyzed copolymerization of 3,4-BHMF with furan dicarboxylate isomers and aliphatic diols. The furanic copolyesters (co-FPEs) with higher polymerization degrees are obtained using 2,4-isomer, indicating CALB's preference. Material analysis revealed semicrystalline properties in all synthesized 2,5-FDCA-based co-FPEs, with multiple melting temperatures (Tm) from 53 to 124 °C and a glass-transition temperature (Tg) of 9-10 °C. 2,4-FDCA-based co-FPEs showed multiple Tm from 43 to 61 °C and Tg of -14 to 12 °C; one of them was amorphous. In addition, all co-FPEs showed a two-step decomposition profile, indicating aliphatic and semiaromatic segments in the polymer chains.

Effect of Polyelectrolyte Charge Density on the Linear Viscoelastic Behavior and Processing of Complex Coacervate Adhesives.

It is well-known that the phase behavior and physicochemical and adhesive properties of complex coacervates are readily tuneable with the salt concentration of the medium. For toxicity reasons, however, the maximum applicable salt concentration in biomedical applications is typically low. Consequently, other strategies must be implemented in order to optimize the properties of the resulting complex coacervates. In this work, the effect of the charge density of a strong polyanion on the properties of complex coacervates was studied. To control this charge density, statistical anionic/charge-neutral hydrophilic copolymers were synthesized by means of an elegant protection/deprotection strategy and subsequently complexed with a strong polycation. The resulting complexes were observed to have an increasing water content as well as faster relaxation dynamics, with either increasing salt concentration or decreasing charge density. Time-salt and time-salt-charge density superpositions could be performed and showed that the relaxation mechanism of the complex coacervates remained unchanged. When the charge density was decreased, lower salt concentration complexes became suitable for viscoelastic adhesion with improved injectability. Such complex coacervates are promising candidates for injectable biomedical adhesives.

Thiol-Ene Click Cross-linking of Starch Oleate Films for Enhanced Properties.

Biobased films were synthesized from starch oleate (DS = 2.2) cross-linked with polyethylene glycol with Mn = 2000 and 1000 g · mol-1, and ethylene glycol, all of which were esterified with either lipoic acid (LA) or 3-mercaptopropionic acid (MPA). Cross-linking was achieved through a UV-initiated thiol-ene click, and confirmed by Fourier transform infrared spectroscopy and rheometry. The films exhibit higher degradation temperatures, and an increased degree of crystallinity as cross-linker length increased. The introduction of MPA-based cross-linkers resulted in hydrophilic films, while the contact angle was barely affected by the addition of LA-based cross-linkers. A reduction in maximum strength upon introducing the cross-linkers was observed, while an increase in elongation was observed for most of the LA-based cross-linkers. Our results demonstrate the potential for tuning the mechanical and thermal properties of starch-based films through the cross-linker choice, with some formulations exhibiting increased flexibility that may be well suited for packaging applications.

Lipoic acid-based vitrimer-like elastomer.

Dynamic covalent networks (DCNs) are materials that feature reversible bond formation and breaking, allowing for self-healing and recyclability. To speed up the bond exchange, significant amounts of catalyst are used, which creates safety concerns. To tackle this issue, we report the synthesis of a lipoic acid-based vitrimer-like elastomer (LAVE) by combining (i) ring-opening polymerization (ROP) of lactones, (ii) lipoic acid modification of polylactones, and (iii) UV crosslinking. The melting temperature (Tm) of LAVE is below room temperature, which ensures the elastic properties of LAVE at service temperature. By carefully altering the network, it is possible to tune the Tm, as well as the mechanical strength and stretchability of the material. An increase in polylactone chain length in LAVE was found to increase strain at break from 25% to 180% and stress at break from 0.34 to 1.41 MPa. The material showed excellent network stability under cyclic strain loading, with no apparent hysteresis. The introduction of disulfide bonds allows the material to self-heal under UV exposure, extending its shelf life. Overall, this work presents an environmentally friendly approach for producing a sustainable elastomer that has potential for use in applications such as intelligent robots, smart wearable technology, and human-machine interfaces.

One-Pot Synthesis of Strong Anionic/Charge-Neutral Amphiphilic Block Copolymers.

Despite the ever more versatile polymerization techniques that are becoming available, the synthesis of macromolecules with tailored functionalities can remain a lengthy endeavor. This becomes more conspicuous when the implementation of incompatible chemistries (i.e., strong polyelectrolytes) within sequence-controlled polymers is desired, often requiring (i) polymerization, (ii) chain extension, and (iii) postpolymerization modification. Herein, we explore the production of strong anionic/charge-neutral block copolymers (BCPs) in a one-pot fashion. This straightforward three-step process includes the synthesis of a macroinitiator and chain extension via rapid and efficient photomediated atom transfer radical polymerization, followed by in situ deprotection to expose the polyanionic domains. The resulting BCPs, which are strong amphiphiles by nature, are capable of self-assembly in aqueous media, as evidenced by dynamic light scattering, small-angle X-ray scattering, ζ-potential measurements, and transmission electron microscopy. We further demonstrate the versatility of our methodology by producing several BCPs through sampling of a single reaction mixture, enabling the straightforward production of strong polymer amphiphiles.

Synthesis and Properties of Fully Biobased Crosslinked Starch Oleate Films.

Starch oleate (degree of substitution = 2.2) films were cast and crosslinked in the presence of air using UV curing (UVC) or heat curing (HC). A commercial photoinitiator (CPI, Irgacure 184) and a natural photoinitiator (NPI, a mixture of biobased 3-hydroxyflavone and n-phenylglycine) were used for UVC. No initiator was used during HC. Isothermal gravimetric analyses, Fourier Transform Infrared (FTIR) measurements, and gel content measurements revealed that all three methods were effective in crosslinking, with HC being the most efficient. All methods increased the maximum strengths of film, with HC causing the largest increase (from 4.14 to 7.37 MPa). This is consistent with a higher degree of crosslinking occurring with HC. DSC analyses showed that the Tg signal flattened as film crosslink densities increased, even disappearing in the case of HC and UVC with CPI. Thermal gravimetric analyses (TGA) indicated that films cured with NPI were least affected by degradation during curing. These results suggest that cured starch oleate films could be suitable for replacing the fossil-fuel-derived plastics currently used in mulch films or packaging applications.

Starch ester film properties: The role of the casting temperature and starch its molecular weight and amylose content.

Oleic acid and 10-undecenoic acid were used to esterify corn, tapioca, potato and a waxy potato starch, with a maximum degree of substitution of 2.4 and 1.9 respectively. The thermal and mechanical properties were investigated as a function of the amylopectin content and Mw of starch, and by the fatty acid type. All starch esters had an improved degradation temperature regardless of their botanical origin. While the Tg did increase with increasing amylopectin content and Mw, it decreased with increasing fatty acid chain length. Moreover, films with different optical appearances were obtained by varying the casting temperature. SEM and polarized light microscopy showed that films cast at 20 °C had porous open structures with internal stress, which was absent when cast at higher temperatures. Tensile test measurements revealed that films had a higher Young's modulus when containing starch with a higher Mw and amylopectin content. Besides that, starch oleate films were more ductile than starch 10-undecenoate films. In addition, all films were resistant to water at least up to one month, while some light-induced crosslinking took place. Finally, starch oleate films showed antibacterial properties against Escherichia coli, whereas native starch and starch 10-undecenoate did not.

Biobased Photopolymer Resin for 3D Printing Containing Dynamic Imine Bonds for Fast Reprocessability.

Acrylic photopolymer resins are widely used in stereolithographic 3D printing. However, the growing demand for such thermosetting resins is weighing on global issues such as waste management and fossil fuel consumption. Therefore, there is an increasing demand for reactive components that are biobased and enable recyclability of the resulting thermoset products. In this work, the synthesis of a photo-cross-linkable molecule containing dynamic imine bonds based on biobased vanillin and dimer fatty diamine is described. Using the biobased building blocks, formulations containing reactive diluent and a photoinitiator were prepared. The mixtures could be rapidly cross-linked under UV light, yielding vitrimers. Using digital light processing, 3D-printed parts were prepared, which were rigid, thermally stable, and reprocessed within 5 min at elevated temperature and pressure. The addition of a building block containing a higher concentration of imine bonds accelerated the stress relaxation and improved the mechanical rigidity of the vitrimers. This work will contribute to the development of biobased and recyclable 3D-printed resins to facilitate the transition to a circular economy.

Biobased 2,5-Bis(hydroxymethyl)furan as a Versatile Building Block for Sustainable Polymeric Materials.

Furanic polymers, currently mainly represented by polyethylene 2,5-furandicarboxylate (PEF), also known as polyethylene furanoate, have a fantastic potential to replace fossil-based polymers: for example, polyethylene terephthalate (PET). While 2,5-furandicarboxylic acid (FDCA), a precursor of PEF, and its derived polymers have been studied extensively, 2,5-bis(hydroxymethyl)furan (BHMF) has received relatively little attention so far. Similarly to FDCA, BHMF is a biobased platform chemical derived from renewable sources such as sugars. This review highlights different polymerization techniques for BHMF-based polyesters and addresses BHMF's relative instability during the synthesis of BHMF-derived polymers, including polycarbonates and polyurethanes. Furthermore, the degradability of furanic polyesters is discussed and BHMF's toxicity is briefly elaborated.

New insights in polydopamine formation via surface adsorption.

Polydopamine is a biomimetic self-adherent polymer, which can be easily deposited on a wide variety of materials. Despite the rapidly increasing interest in polydopamine-based coatings, the polymerization mechanism and the key intermediate species formed during the deposition process are still controversial. Herein, we report a systematic investigation of polydopamine formation on halloysite nanotubes; the negative charge and high surface area of halloysite nanotubes favour the capture of intermediates that are involved in polydopamine formation and decelerate the kinetics of the process, to unravel the various polymerization steps. Data from X-ray photoelectron and solid-state nuclear magnetic resonance spectroscopies demonstrate that in the initial stage of polydopamine deposition, oxidative coupling reaction of the dopaminechrome molecules is the main reaction pathway that leads to formation of polycatecholamine oligomers as an intermediate and the post cyclization of the linear oligomers occurs subsequently. Furthermore, TRIS molecules are incorporated into the initially formed oligomers.

Scalable and Degradable Dextrin-Based Elastomers for Wearable Touch Sensing.

Elastomer-based wearables can improve people's lives; however, frictional wear caused by manipulation may pose significant concerns regarding their durability and sustainability. To address the aforementioned issue, a new class of advanced scalable supersoft elastic transparent material (ASSETm) is reported, which offers a unique combination of scalability (20 g scale), stretchability (up to 235%), and enzymatic degradability (up to 65% in 30 days). The key feature of our design is to render native dextrin hydrophobic, which turns it into a macroinitiator for bulk ring-opening polymerization. Based on ASSETm, a self-powered touch sensor (ASSETm-TS) for touch sensing and non-contact approaching detection, possessing excellent electrical potential (up to 65 V) and rapid response time (60 ms), is fabricated. This work is a step toward developing sustainable soft electronic systems, and ASSETm's tunability enables further improvement of electrical outputs, enhancing human-interactive applications.

Kármán Vortex Street Driven Membrane Triboelectric Nanogenerator for Enhanced Ultra-Low Speed Wind Energy Harvesting and Active Gas Flow Sensing.

Wind energy harvesting and sensing have a huge prospect in constructing self-powered sensor nodes, but the energy transducing efficiency at low and ultra-low wind speeds is still limited. Herein, we proposed a Kármán vortex street driven membrane triboelectric nanogenerator (KVSM-TENG) for ultra-low speed wind energy harvesting and flow sensing. By introducing Kármán vortex in the KVSM-TENG, the cut-in wind speed of the KVSM-TENG decreased from 1 to 0.52 m/s that is the lowest cut-in wind speed in current TENGs. The instantaneous output density of the KVSM-TENG significantly increased by 1000 times and 2.65 times at the inlet wind speeds of 1 and 2 m/s, respectively. In addition, with the excellent energy transducing performance at the ultra-low speed range, the KVSM-TENG was successfully demonstrated to detect a weak leakage of gas pipeline (∼0.6 m/s) for alarming with high sensitivity. The interaction mechanism between the vortex and KVSM-TENG was systematically investigated. Through the simulation and experimental validation, the enhancement mechanism of vortex dependence on the cylinder diameter and placement location of KVSM-TENG was investigated in detail. The influence of parameters such as membrane length, width, thickness, and electrode gap on the performance of the KVSM-TENG was systematically studied. This work not only provided an ingenious strategy for ultra-low speed wind energy harvesting but also demonstrates the promising prospects for monitoring the air flow in the natural gas exploitation and transportation.

Strong Anionic/Charge-Neutral Block Copolymers from Cu(0)-Mediated Reversible Deactivation Radical Polymerization.

Despite recent developments in controlled polymerization techniques, the straightforward synthesis of block copolymers that feature both strong anionic and charge-neutral segments remains a difficult endeavor. In particular, solubility issues may arise during the direct synthesis of strong amphiphiles and typical postpolymerization deprotection often requires harsh conditions. To overcome these challenges, we employed Cu(0)-mediated reversible deactivation radical polymerization (Cu(0)-RDRP) on a hydrophobic isobutoxy-protected 3-sulfopropyl acrylate. Cu(0)-RDRP enables the rapid synthesis of the polymer, reaching high conversions and low dispersities while using a single solvent system and low amounts of copper species. These macromolecules are straightforward to characterize and can subsequently be deprotected in a mild yet highly efficient fashion to expose their strongly charged nature. Furthermore, a protected sulfonate segment could be grown from a variety of charge-neutral macroinitiators to produce, after the use of the same deprotection chemistry, a library of amphiphilic, double-hydrophilic as well as thermoresponsive block copolymers (BCPs). The ability of these various BCPs to self-assemble in aqueous media was further studied by dynamic light scattering, ζ-potential measurements as well as atomic force and electron microscopy.

A more efficient synthesis and properties of saturated and unsaturated starch esters.

This work presents a series of starch esters synthesized via 1,5,7-triazabicyclo[4.4.0]-dec-5-ene (TBD) catalyzed transesterifications in dimethyl sulfoxide (DMSO). The reaction was performed with saturated and unsaturated fatty acids (8, 11, and 18 carbon atoms). The degree of substitution (DS) was raised by purging the reaction flask with nitrogen instead of simply performing the reaction under a nitrogen atmosphere. The increase of DS was most obvious for long-chain fatty acids, as an almost complete DS was observed for starch stearate (2.8) and starch oleate (2.7). The products were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and X-ray diffraction. Starch esters from unsaturated fatty acids have a lower Tg than their saturated analogues. Moreover, contact angle and moisture uptake measurements showed increased hydrophobicity for all starch esters in comparison to pristine starch. Our results show a more efficient method for synthesizing a biobased material that steers into the direction of a material that could replace conventional plastics.

Influence of different ester side groups in polymers on the vapor phase infiltration with trimethyl aluminum.

The vapor phase infiltration (VPI) process of trimethyl aluminum (TMA) into poly(4-acetoxystyrene) (POAcSt), poly(nonyl methacrylate) (PNMA) and poly(tert-butyl methacrylate) (PtBMA) is reported. Depth-profiling X-ray photoelectron spectroscopy (XPS) measurements are used for the first time for VPI based hybrid materials to determine the aluminum content over the polymer film thickness. An understanding of the reaction mechanism on the interaction of TMA infiltrating into the different polymers was obtained through infrared (IR) spectroscopy supported by density functional theory (DFT) studies. It is shown that the loading with aluminum is highly dependent on the respective ester side group of the used polymer, which is observed to be the reactive site for TMA during the infiltration. IR spectroscopy hints that the infiltration is incomplete for POAcSt and PNMA, as indicated by the characteristic vibration bands of the aluminum coordination to the carbonyl groups within the polymers. In this context, two different reaction pathways are discussed. One deals with the formation of an acetal, the other is characterized by the release of a leaving group. Both were found to be in direct concurrence dependent on the polymer side group as revealed by DFT calculations of the IR spectra, as well as the reaction energies of two possible reaction paths. From this study, one can infer that the degree of infiltration in a VPI process strongly depends on the polymer side groups, which facilitates the choice of the polymer for targeted applications.

Enzymatic Synthesis of Muconic Acid-Based Polymers: Trans, Trans-Dimethyl Muconate and Trans, ß-Dimethyl Hydromuconate.

The vast majority of commodity polymers are acquired from petrochemical feedstock, and these resources will plausibly be depleted within the next 100 years. Therefore, the utilization of carbon-neutral renewable resources for the production of polymers is crucial in modern green chemistry. Herein, we report an eco-friendly strategy that uses enzyme catalysis to design biobased unsaturated (co)polyesters from muconic acid derivatives. This method is an attractive pathway for the production of well-defined unsaturated polyesters with minimum side reactions. A suite of characterization techniques was performed to probe the reaction mechanism and properties of the obtained polyesters. It is rationalized that the alkene functionality of the muconate monomers plays an important role in the enzyme catalysis mechanism. The rendered polyesters possessed excellent thermal stabilities and unreacted alkene functionality that can consecutively undergo chain extension, copolymerization, or act as an anchor for other functional groups. These properties open new avenues in the fields of unsaturated polyester resins and photosensitive coatings.

Physicochemical properties of heat-moisture treated, sodium stearate complexed starch: The effect of sodium stearate concentration.

Amylose­sodium stearate (SS) complexes (2, 5 and 8%) in heat-moisture treated potato starch (HPS) were evaluated for their physicochemical properties. Based on the DSC thermograms, the amylose - SS complexes were successfully formed with high thermal stability, indicated by a melt temperature (Tpeak) of ≥ 112 °C for type I and ≥125 °C for type II complexes. Addition of 2% SS resulted in a single endothermal peak of the complexes, while 5 and 8% led to the formation of type I and II complexes with much higher enthalpy (ΔH) values. The XRD curve confirmed that the complexes were successfully formed. The pasting temperature increased from 66 °C for native to 91 °C for HPS145 complexed starch with 5% SS. Furthermore, the swelling power could be largely decreased, and the granular structure preserved. In addition, the inclusion complexation with SS on (HPS) succesfully improved the cook stabiliy.