One-Step Wet-Spinning of High-Energy Density Coaxial Fibrous Supercapacitors Based on In Situ Carbon-Modified Nitrogen-Doped MXene Nanosheets.

Fibrous supercapacitors (SCs) are emerging promising power sources for flexible/wearable electronics and have attracted an extensive amount of attention from researchers. However, the low energy density has always hindered their further development. Here, a coaxial fibrous SC (CFSC) was fabricated by one-step wet-spinning combined with an electrodeposition strategy. Benefiting from the large surface area and abundant pore structure of carbon-modified nitrogen-doped MXene nanosheets (NS), as well as the high conductivity of silver (Ag) NS, the electrolyte ion/electron transport paths are significantly improved. Furthermore, the distributed GO in the P(VDF-HFP) separator could form a high-speed continuous ion transport channel, thus enhancing the ionic conductivity. At a power density of 40-200 µW cm-2, the CFSC shows a high energy density of 0.7-3.39 µWh cm-2. The as-prepared CFSC also maintains an excellent capacitance retention rate of 90.3% even after 15 000 charge-discharge cycles. This work provides a general strategy for manufacturing high-performance, flexible, and wearable SCs.

Strategies for Making High-Performance Artificial Spider Silk Fibers.

Artificial spider silk is an attractive material for many technical applications since it is a biobased fiber that can be produced under ambient conditions but still outcompetes synthetic fibers (e.g., Kevlar) in terms of toughness. Industrial use of this material requires bulk-scale production of recombinant spider silk proteins in heterologous host and replication of the pristine fiber's mechanical properties. High molecular weight spider silk proteins can be spun into fibers with impressive mechanical properties, but the production levels are too low to allow commercialization of the material. Small spider silk proteins, on the other hand, can be produced at yields that are compatible with industrial use, but the mechanical properties of such fibers need to be improved. Here, the literature on wet-spinning of artificial spider silk fibers is summarized and analyzed with a focus on mechanical performance. Furthermore, several strategies for how to improve the properties of such fibers, including optimized protein composition, smarter spinning setups, innovative protein engineering, chemical and physical crosslinking as well as the incorporation of nanomaterials in composite fibers, are outlined and discussed.

Preparation and sensing performance of wet-spun fabric triboelectric nanogenerator for energy harvesting.

Flexible, wearable triboelectric nanogenerators (TENGs) monitoring human movement and health signals have received more attention recently. In particular, developing a flexible TENG combining stress, strain, electrical output performance and durability becomes the current research focus. Herein, a highly stretchable, self-powered coaxial yarn TENGs were manufactured using a low-cost, efficient continuous wet-spinning method. Carbon nanotube/conductive thermoplastic polyurethane (MWCNT/CTPU) and polyvinylidene fluoride-hexafluoropropylene were utilized for the coaxial fibers conductive layers and dielectric layers, respectively. Fibers were continuously collected over a length of 10 m. Excellent electrical output with an open-circuit voltage (Voc) of 11.4 V, short-circuit current (Isc) of 114.8 nA, and short-circuit transfer charge (Qsc) of 6.1 nC was achieved. In addition, fabric TENGs with different two and three dimensional structures were further prepared by the developed coaxial fibers. The corresponding electrical output properties and practical performance were discussed. Results showed that the four-layer three-dimensional angle interlocking structure exhibited the optimal performance with an open-circuit voltage (Voc) of 38.4 V, short-circuit current (Isc) of 451.5 nA, and short-circuit transfer charge (Qsc) of 23.1 nC.

Autonomous Electroluminescent Textile for Visual Interaction and Environmental Warning.

Visual interaction is a promising strategy for the externalized expression and transmission of information, having wide application prospects in wearable luminous textiles. Achieving an autonomous luminous display and dynamic light response to environmental stimuli is attractive but attracts little attention. Herein, we propose a liquid responsive structure based on alternating-current electroluminescent fibers and demonstrate conductive-liquid-bridging electroluminescent fabrics with high integration and personalized patterns. Impressively, our electroluminescent fibers and textiles could afford a sensitive response and high robustness to water, glycerol, ethanol, and sodium chloride solution. The final electroluminescent textiles show an excellent luminescence performance of 149.08 cd m-2. On the proof of concept, a rain-sensing umbrella, luminous sportswear, and liquid response glove are fabricated to demonstrate water detection, visual interaction, and environmental warning. The textile-type visualizing-responding strategy proposed in this work may open up new avenues for the application of ACEL devices in the field of visual interaction.

Wet-Spun Chitosan-Sodium Caseinate Fibers for Biomedicine: From Spinning Process to Physical Properties.

We designed and characterized chitosan-caseinate fibers processed through wet spinning for biomedical applications such as drug delivery from knitted medical devices. Sodium caseinate was either incorporated directly into the chitosan dope or allowed to diffuse into the chitosan hydrogel from a coagulation bath containing sodium caseinate and sodium hydroxide (NaOH). The latter route, where caseinate was incorporated in the neutralization bath, produced fibers with better mechanical properties for textile applications than those formed by the chitosan-caseinate mixed collodion route. The latter processing method consists of enriching a pre-formed chitosan hydrogel with caseinate, preserving the structure of the semicrystalline hydrogel without drastically affecting interactions involved in the chitosan self-assembly. Thus, dried fibers, after coagulation in a NaOH/sodium caseinate aqueous bath, exhibited preserved ultimate mechanical properties. The crystallinity ratio of chitosan was not significantly impacted by the presence of caseinate. However, when caseinate was incorporated into the chitosan dope, chitosan-caseinate fibers exhibited lower ultimate mechanical properties, possibly due to a lower entanglement density in the amorphous phase of the chitosan matrix. A standpoint is to optimize the chitosan-caseinate composition ratio and processing route to find a good compromise between the preservation of fiber mechanical properties and appropriate fiber composition for potential application in drug release.

Intrinsically Flexible Phase Change Fibers for Intelligent Thermal Regulation.

Owing to the significant latent heat generated at constant temperatures, phase change fibers (PCFs) have recently received much attention in the field of wearable thermal management. However, the phase change materials involved in the existing PCFs still experience a solid-liquid transition process, severely restricting their practicality as wearable thermal management materials. Herein, we, for the first time, developed intrinsically flexible PCFs (polyethylene glycol/4,4'-methylenebis(cyclohexyl isocyanate) fibers, PMFs) through polycondensation and wet-spinning process, exhibiting an inherent solid-solid phase transition property, adjustable phase transition behaviors, and outstanding knittability. The PMFs also present superior mechanical strength (28 MPa), washability (>100 cycles), thermal cycling stability (>2000 cycles), facile dyeability, and heat-induced recoverability, all of which are highly significant for practical wearable applications. Additionally, the PMFs can be easily recycled by directly dissolving them in solvents for reprocessing, revealing promising applications as sustainable materials for thermal management. Most importantly, the applicability of the PMFs was demonstrated by knitting them into permeable fabrics, which exhibit considerably improved thermal management performance compared with the cotton fabric. The PMFs offer great potential for intelligent thermal regulation in smart textiles and wearable electronics.

Continuous Wet Spinning of Regenerated Silk Fibers from Spinning Dopes Containing 4% Fibroin Protein.

The wet spinning of fibers from regenerated silk fibroin has long been a research goal. Due to the degradation of the molecular structure of the fibroin protein during the preparation of the regenerated silk fibroin solution, fibroin concentrations with at least 10% protein content are required to achieve sufficient viscosity for wet spinning. In this study, a spinning dope formulation of regenerated silk fibroin is presented that shows a rheological behavior similar to that of native silk fibroin isolated from the glands of B. mori silkworm larvae. In addition, we present a wet-spinning process that enables, for the first time, the continuous wet spinning of regenerated silk fibroin with only 4% fibroin protein content into an endless fiber. Furthermore, the tensile strength of these wet-spun regenerated silk fibroin fibers per percentage of fibroin is higher than that of all continuous spinning approaches applied to regenerated and native silk fibroin published so far.

Force-Induced Alignment of Nanofibrillated Bacterial Cellulose for the Enhancement of Cellulose Composite Macrofibers.

Bacterial cellulose, as an important renewable bioresource, exhibits excellent mechanical properties along with intrinsic biodegradability. It is expected to replace non-degradable plastics and reduce severe environmental pollution. In this study, using dry jet-wet spinning and stretching methods, we fabricate cellulose composite macrofibers using nanofibrillated bacterial cellulose (BCNFs) which were obtained by agitated fermentation. Ionic liquid (IL) was used as a solvent to perform wet spinning. In this process, force-induced alignment of BCNFs was applied to enhance the mechanical properties of the macrofibers. The results of scanning electron microscopy revealed the well-aligned structure of BCNF along the fiber axis. The fiber prepared with an extrusion rate of 30 m min-1 and a stretching ratio of 46% exhibited a strength of 174 MPa and a Young's modulus of 13.7 GPa. In addition, we investigated the co-spinning of carboxymethyl cellulose-containing BCNF with chitosan using IL as a "container", which indicated the compatibility of BCNFs with other polysaccharides. Recycling of the ionic liquid was also verified to validate the sustainability of our strategy. This study provides a scalable method to fabricate bacterial cellulose composite fibers, which can be applied in the textile or biomaterial industries with further functionalization.

The Size Effect of Silver Nanoparticles on Reinforcing the Mechanical Properties of Regenerated Fibers.

Regenerated silk fibroin (RSF), made from discarded silk cocoons, can be processed into regenerated silk fibers by a simple, inexpensive, and environmentally friendly wet-spinning process. However, the breaking strength and toughness of most RSF fibers are lower than those of natural silk. In this study, Ag nanoparticles (NPs) of different sizes were introduced into RSF to form RSF/AgNPs hybrid fibers by wet spinning. The effects of AgNPs of different sizes on the mechanical properties and structure of the hybrid fibers were investigated. The results demonstrated that the mechanical properties of hybrid fibers were significantly improved, especially the breaking strain, after the addition of four different sizes of AgNPs. With the reduction in AgNPs size (2-60 nm), the breaking strength and breaking strain of hybrid fibers tended to increase. The results showed that the hybrid fibers containing 2 nm AgNPs were remarkable, with excellent mechanical properties and toughness, and the breaking strain reached 138.27%, which was far greater than blank RSF fibers (15.02%) and even natural silk (about 21%). The S-FTIR and WAXD showed that, compared with the larger AgNPs, the smaller AgNPs contributed more to the formation of silk fibroin ß-sheet and crystallinity, and reduced the ß-crystallite size. This study is helpful to understand the relationship between the size of nanoparticles and the mechanical properties of hybrid fibers.

Controllable assembly of continuous hollow graphene fibers with robust mechanical performance and multifunctionalities.

Macroscopic conformation of individual graphene sheets serves as the backbone of translating their intrinsic merits towards multifunctional practical applications. However, controllable and continuous assemblies of graphene-based nanomaterials to create stable macroscopic structural components are always in face of great challenge. We have developed a scalable converging-flow assisted wet-spinning methodology for continuously fabricating hollow graphene fibers (HGFs, the newest variation of solid graphene fibers) with high quality. The degradable silk thread is selectively utilized as the continuous hollow structure former that holds the coaxially stacked graphene sheets aligned through the converging-flow modulating process. For the first time, we have created the longest freestanding HGF in length of 2.1 m. The continuous HGFs are in an average diameter of 180µm and with 4-8µm adjustable wall thicknesses. The optimal HGF demonstrates an average tensile strength of 300 MPa and modulus of 2.49 GPa (comparable to typical solid graphene fibers, but the highest among the reported HGFs in literature) and an exceptional failure elongation of 10.8%. Additionally, our continuous HGFs exhibit spontaneous resistive response to thermal and strain stimuli (in form of large deformations and human motions), offering great potential for developing multifunctional sensors. We envision that this work demonstrates an effective and well-controlled macroscopic assembly methodology for the scaled-up mass production of HGFs.

Toughening Wet-Spun Silk Fibers by Silk Nanofiber Templating.

Regenerated silk fibers typically fall short of silkworm cocoon fibers in mechanical properties due to reduced fiber crystal structure and alignment. One approach to address this has been to employ inorganic materials as reinforcing agents. The present study avoids the need for synthetic additives, demonstrating the first use of exfoliated silk nanofibers to control silk solution crystallization, resulting in all-silk pseudocomposite fibers with remarkable mechanical properties. Incorporating only 0.06 wt% silk nanofibers led to a ≈44% increase in tensile strength (over 600 MPa) and ≈33% increase in toughness (over 200 kJ kg-1 ) compared with fibers without silk nanofibers. These remarkable properties can be attributed to nanofiber crystal seeding in conjunction with fiber draw. The crystallinity nearly doubled from ≈17% for fiber spun from pure silk solution to ≈30% for the silk nanofiber reinforced sample. The latter fiber also shows a high degree of crystal orientation with a Herman's orientation factor of 0.93, a value which approaches that of natural degummed B. mori silk cocoon fiber (0.96). This study provides a strong foundation to guide the development of simple, eco-friendly methods to spin regenerated silk with excellent properties and a hierarchical structure that mimics natural silk.

High-Performance Coaxial Asymmetry Fibrous Supercapacitors with a Poly(vinyl alcohol)-Montmorillonite Separator.

Fibrous supercapacitors have garnered great interest from researchers because of their large electrode/electrolyte interface area, short ion transport path, and high flexibility. However, obtaining a thin gel electrolyte interlayer with a high ion transport rate and uniform thickness is still challenging. Here, we proposed an efficient wet-spinning technique to fabricate uniform polyvinyl-montmorillonite tubular layers for the preparation of a high-performance coaxial asymmetry fibrous supercapacitor (AFSC). The coaxial AFSC shows ultrahigh energy densities in the range of 2.86-4.04 µW h cm-2 at power densities of 0.16-1.61 mW cm-2 while maintaining a long cycling life (94% retention even after 20 000 cycles). After charging at a constant voltage of 2.4 V for 30 s, the flexible watchband which is composed of three series-connected AFSCs could power a commercial electronic watch for more than 2 min. This work provides a universal strategy to fabricate high-performance and wearable energy storage devices.

Additive Manufacturing of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/Poly(D,L-lactide-co-glycolide) Biphasic Scaffolds for Bone Tissue Regeneration.

Polyhydroxyalkanoates are biopolyesters whose biocompatibility, biodegradability, environmental sustainability, processing versatility, and mechanical properties make them unique scaffolding polymer candidates for tissue engineering. The development of innovative biomaterials suitable for advanced Additive Manufacturing (AM) offers new opportunities for the fabrication of customizable tissue engineering scaffolds. In particular, the blending of polymers represents a useful strategy to develop AM scaffolding materials tailored to bone tissue engineering. In this study, scaffolds from polymeric blends consisting of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(D,L-lactide-co-glycolide) (PLGA) were fabricated employing a solution-extrusion AM technique, referred to as Computer-Aided Wet-Spinning (CAWS). The scaffold fibers were constituted by a biphasic system composed of a continuous PHBV matrix and a dispersed PLGA phase which established a microfibrillar morphology. The influence of the blend composition on the scaffold morphological, physicochemical, and biological properties was demonstrated by means of different characterization techniques. In particular, increasing the content of PLGA in the starting solution resulted in an increase in the pore size, the wettability, and the thermal stability of the scaffolds. Overall, in vitro biological experiments indicated the suitability of the scaffolds to support murine preosteoblast cell colonization and differentiation towards an osteoblastic phenotype, highlighting higher proliferation for scaffolds richer in PLGA.

Continuous Pilot-Scale Wet-Spinning of Biocompatible Chitin/Chitosan Multifilaments from an Aqueous KOH/Urea Solution.

Chitin is a promising natural polymer with great potential as a biomedical, hygiene, absorbent, and food-packing material. Producing chitin multifilament and assembling them into textiles is an efficient way of preparing these materials, with wet-spinning a major method used to produce man-made fibers. Unfortunately, dissolving chitin, producing a stable and suitable chitin dope, and ensuring filament strength are the main obstacles to the production of chitin multifilament. Based on recent research into chitin dissolution, solution properties, and high-strength chitin-based materials, chitin multifilament wet-spinning is no longer only a hypothetical strategy. Here, a pilot-scale wet-spinning method is introduced that overcomes the abovementioned limitations. A stable chitin spinning dope is prepared by dissolution and aging in an aqueous KOH/urea solution. A chitin multifilament is prepared by wet-spinning using a pilot-scale wet-spinning apparatus and aqueous alcohol/salt coagulation. After deacetylation, the chitosan multifilament possesses a dense structure and low crystallinity, but excellent mechanical properties. The chitin/chitosan multifilaments exhibit excellent cytocompatibilities and have promising prospects in biomedical applications. The method developed in this work provides a new approach for the pilot-scale wet-spinning of chitin/chitosan multifilaments.

Flexible Cyclic-Poly(phthalaldehyde)/Poly(ε-caprolactone) Blend Fibers with Fast Daylight-Triggered Transience.

Cyclic-poly(phthalaldehyde) (cPPHA) exhibits photo-triggerable depolymerization on-demand for applications like the photolithography of microfabricated electronics. However, cPPHA is inherently brittle and thermally sensitive; both of these properties limit its usefulness as an engineering plastic. Prior to this report, small molecule plasticizers are added to cPPHA-based films to make the polymer more flexible. But plasticizers can eventually leach out of cPPHA, then leaving it increasingly more brittle throughout product lifetime. In this research, a new approach to fabricating flexible cPPHA blends for use as spun fibers is achieved through the incorporation of poly (ε-caprolactone) (PCL) by a modified wet spinning method. Among blend compositions, the 50/50 cPPHA/PCL fiber shows fast transience (<50 s) in response to daylight while retaining the flexibility of PCL and mechanical properties of an elastomer (i.e., tensile strength of ≈8 MPa, Young's modulus of ≈118 MPa, and elongation at break of ≈190%). Embedding 2 wt% gold nanoparticles to cPPHA can further improve the transience rate of fibers comprising less than 50% cPPHA. These flexible, daylight-triggerable cPPHA/PCL fibers can be applied to an extensive range of applications, such as wearable electronics, intelligent textiles, and zero waste packaging for which modest mechanical performance and fast transience are desired.

Hierarchically Porous Silk/Activated-Carbon Composite Fibres for Adsorption and Repellence of Volatile Organic Compounds.

Fabrics comprised of porous fibres could provide effective passive protection against chemical and biological (CB) threats whilst maintaining high air permeability (breathability). Here, we fabricate hierarchically porous fibres consisting of regenerated silk fibroin (RSF) and activated-carbon (AC) prepared through two fibre spinning techniques in combination with ice-templating-namely cryogenic solution blow spinning (Cryo-SBS) and cryogenic wet-spinning (Cryo-WS). The Cryo-WS RSF fibres had exceptionally small macropores (as low as 0.1 µm) and high specific surface areas (SSAs) of up to 79 m2·g-1. The incorporation of AC could further increase the SSA to 210 m2·g-1 (25 wt.% loading) whilst also increasing adsorption capacity for volatile organic compounds (VOCs).

Bioinspired and Mechanically Strong Fibers Based on Engineered Non-Spider Chimeric Proteins.

Silk-protein-based fibers have attracted considerable interest due to their low weight and extraordinary mechanical properties. Most studies on fibrous proteins focus on the recombinant spidroins, but these fibers exhibit moderate mechanical performance. Thus, the development of alternative structural proteins for the construction of robust fibers is an attractive goal. Herein, we report a class of biological fibers produced using a designed chimeric protein, which consists of the sequences of a cationic elastin-like polypeptide and a squid ring teeth protein. Remarkably, the chimeric protein fibers exhibit a breaking strength up to about 630 MPa and a corresponding toughness as high as about 130 MJ m-3 , making them superior to many recombinant spider silks and even comparable to some native counterparts. Therefore, this strategy is a novel concept for exploring bioinspired ultrastrong protein materials through the development of new types of structural chimeric proteins.

Recombinant Silk Fiber Properties Correlate to Prefibrillar Self-Assembly.

Spider silks are desirable materials with mechanical properties superior to most synthetic materials coupled with biodegradability and biocompatibility. In order to replicate natural silk properties using recombinant spider silk proteins (spidroins) and wet-spinning methods, the focus to date has typically been on modifying protein sequence, protein size, and spinning conditions. Here, an alternative approach is demonstrated. Namely, using the same ≈57 kDa recombinant aciniform silk protein with a consistent wet-spinning protocol, fiber mechanical properties are shown to significantly differ as a function of the solvent used to dissolve the protein at high concentration (the "spinning dope" solution). A fluorinated acid/alcohol/water dope leads to drastic improvement in fibrillar extensibility and, correspondingly, toughness compared to fibers produced using a previously developed fluorinated alcohol/water dope. To understand the underlying cause for these mechanical differences, morphology and structure of the two classes of silk fiber are compared, with features tracing back to dope-state protein structuring and preassembly. Specifically, distinct classes of spidroin nanoparticles appear to form in each dope prior to fiber spinning and these preassembled states are, in turn, linked to fiber morphology, structure, and mechanical properties. Tailoring of dope-state spidroin nanoparticle assembly, thus, appears a promising strategy to modulate fibrillar silk properties.

Highly Conductive Ti3 C2 Tx MXene Hybrid Fibers for Flexible and Elastic Fiber-Shaped Supercapacitors.

Fiber-shaped supercapacitors (FSCs) are promising energy storage solutions for powering miniaturized or wearable electronics. However, the scalable fabrication of fiber electrodes with high electrical conductivity and excellent energy storage performance for use in FSCs remains a challenge. Here, an easily scalable one-step wet-spinning approach is reported to fabricate highly conductive fibers using hybrid formulations of Ti3 C2 Tx MXene nanosheets and poly(3,4-ethylenedioxythiophene):polystyrene sulfonate. This approach produces fibers with a record conductivity of ≈1489 S cm-1 , which is about five times higher than other reported Ti3 C2 Tx MXene-based fibers (up to ≈290 S cm-1 ). The hybrid fiber at ≈70 wt% MXene shows a high volumetric capacitance (≈614.5 F cm-3 at 5 mV s-1 ) and an excellent rate performance (≈375.2 F cm-3 at 1000 mV s-1 ). When assembled into a free-standing FSC, the energy and power densities of the device reach ≈7.13 Wh cm-3 and ≈8249 mW cm-3 , respectively. The excellent strength and flexibility of the hybrid fibers allow them to be wrapped on a silicone elastomer fiber to achieve an elastic FSC with 96% capacitance retention when cyclically stretched to 100% strain. This work demonstrates the potential of MXene-based fiber electrodes and their scalable production for fiber-based energy storage applications.

Boosting Lithium Storage Properties of MOF Derivatives through a Wet-Spinning Assembled Fiber Strategy.

Graphene composite fibers are of great importance in constructing electrode materials with high flexibility and conductivity for energy storage and electronic devices. Integration of multifunctional metal-organic frameworks (MOFs) into graphene fiber scaffolds enables novel functions and enhanced physical/chemical properties. The close-packed and aligned graphene sheets along with the porous MOF-derived structures can achieve excellent lithium storage performance through synergetic effects. In this work, a facile and general strategy is demonstrated for the preparation of MOF/graphene oxide (GO) fibers, which serve as precursors for the subsequent preparation of porous metal oxide/reduced graphene oxide (rGO) composite fibers. The obtained composites, for example, porous Fe2 O3 /rGO and Co3 O4 /rGO fibers, possess unique features of MOF-derived porous structures and excellent electrical conductivity. When tested as anode materials for lithium-ion batteries in coin cells, the MOF/GO fiber-derived porous metal oxide/rGO composite fibers exhibited high specific capacity, excellent rate capability and cycling performance. Moreover, a flexible fiber battery was fabricated based on the Fe2 O3 /rGO composite fiber, which demonstrates its potential application for flexible electronic devices.