Wet-spinning of PEDOT:PSS/Functionalized-SWNTs Composite: a Facile Route Toward Production of Strong and Highly Conducting Multifunctional Fibers

With the aim of fabricating multifunctional fibers with enhanced mechanical properties, electrical conductivity and electrochemical performance, we develop wet-spinning of composite formulation based on functionalized PEG-SWNT and PEDOT:PSS. The method of addition and loading are directly correlated to the quality and the ease of spinnability of the formulation and to the mechanical and electrical properties of the resultant fibers. Both the fiber modulus (Y) and strength (σ) scaled linearly with PEG-SWNT volume fraction (Vf). A remarkable reinforcement rate of dY/dVf = 417 GPa and dσ/dVf = 4 GPa were obtained when PEG-SWNTs at Vf ≤ 0.02. Further increase of PEG-SWNTs loading (i.e. up to Vf 0.12) resulted in further enhancements up to 22.8 GPa and 254 MPa in Modulus and ultimate stress, respectively. We also show the enhancement of electrochemical supercapacitor performance of composite fibers. These outstanding mechanical, electrical and electrochemical performances place these fibers among the best performing multifunctional composite fibers.

Scalable One-Step Wet-Spinning of Graphene Fibers and Yarns from Liquid Crystalline Dispersions of Graphene Oxide: Towards Multifunctional Textiles

Key points in the formation of liquid crystalline (LC) dispersions of graphene oxide (GO) and their processability via wet-spinning to produce long lengths of micrometer-dimensional fibers and yarns are addressed. Based on rheological and polarized optical microscopy investigations, a rational relation between GO sheet size and polydispersity, concentration, liquid crystallinity, and spinnability is proposed, leading to an understanding of lyotropic LC behavior and fiber spinnability. The knowledge gained from the straightforward formulation of LC GO “inks” in a range of processable concentrations enables the spinning of continuous conducting, strong, and robust fibers at concentrations as low as 0.075 wt%, eliminating the need for relatively concentrated spinning dope dispersions. The dilute LC GO dispersion is proven to be suitable for fiber spinning using a number of coagulation strategies, including non-solvent precipitation, dispersion destabilization, ionic cross-linking, and polyelectrolyte complexation. One-step continuous spinning of graphene fibers and yarns is introduced for the first time by in situ spinning of LC GO in basic coagulation baths (i.e., NaOH or KOH), eliminating the need for post-treatment processes. The thermal conductivity of these graphene fibers is found to be much higher than polycrystalline graphite and other types of 3D carbon based materials.

Exploiting high quality PEDOT:PSS–SWNT composite formulations for wet-spinning multifunctional fibers

In order to exploit the inherent properties of carbon nanotubes (CNT) in any polymer composite, systematic control of carbon nanotube loading and protocols that mitigate against CNT bundling are required. If such composites are to be rendered in fiber form via wet-spinning, then CNT bundling during the coagulation process must also be avoided. Here we have achieved this by utilizing highly exfoliated single walled carbon nanotubes (SWNT) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonicacid) (PEDOT:PSS) to obtain wet-spinnable composite formulations at various nanotube volume fractions (Vf). The addition of only 0.02 Vf of aggregate-free and individually dispersed SWNT resulted in a significant enhancement of modulus, tensile strength, electrical conductivity and two cell electrode specific capacitance of PEDOT:PSS–SWNT composite fibers to 5.2 GPa, 200 MPa, 450 S cm−1 and 59 F g−1 by the rate of dY/dVf = 89 GPa, dσ/dVf = 3.2 GPa, dS/dVf = 13 300 S cm−1 and 6 folds, respectively.

One-Step Wet-Spinning Process of Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate) Fibers and the Origin of Higher Electrical Conductivity

A simplified wet-spinning process for the production of continuous poly (3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) fibers is reported. Conductivity enhancement of PEDOT:PSS fibers up to 223 S cm−1 has been demonstrated when these fibers are exposed to ethylene glycol as a post-synthesis processing step. In a new spinning approach it is shown that by employing a spinning formulation consisting of an aqueous blend of PEDOT:PSS and poly(ethlylene glycol), the need for post-spinning treatment with ethylene glycol is eliminated. With this approach, 30-fold conductivity enhancements from 9 to 264 S cm−1 are achieved with respect to an untreated fiber. This one-step approach also demonstrates a significant enhancement in the redox properties of the fibers. These improvements are attributed to an improved molecular ordering of the PEDOT chains in the direction of the fiber axis and the consequential enrichment of linear (or expanded-coil like) conformation to preference bipolaronic electronic structures as evidenced by Raman spectroscopy, solid-state electron spin resonance (ESR) and in situ electrochemical ESR studies.

Wet-spinning of multifunctional graphene fibers using graphene oxide liquid crystals

The recent discovery of liquid crystalline (LC) behavior of graphene oxide (GO) dispersions in various organic, and aqueous media brings added control to the assembly of larger structures using the chemical process approach.[1-3] The LC state can be used to direct the ordered assembly of nanocomponents in macroscopic structures via simple methods like wet-spinning. [3] Here, we developed a scaleable fabrication route to produce graphene fibers via a facile continuoes wetspinning methode. We develop solid understanding in the required criteria to correlate processability with LC behavior, aspect ratio and the dispersion concentration to provide a viable platform for spinning of LC GO. We demonstrate a striking result that highlits the importance of GO sheet size and polydispersity in generating wetspinnable LC GO dispersions from very low spinning dope concentrations (as low as 0.075 wt. %). The new knowledge gained through rheological investigations provides a sound explanation as to why continuous spinning of binder-free GO fibers is enabled by the LC behavior at this very low concentration.

Understanding key wet spinning parameters in an ionic liquid spun regenerated cellulosic fibre

The use of ionic liquid solvents for thespinning of regenerated cellulose fibres has thepotential to produce both technical and textile graderegenerated cellulose fibres. When spinning fibres,many parameters impact the material properties of thespun fibre. In this study, key wet spinning parametershave been investigated for the development of regeneratedcellulose fibres from ionic liquid solutions. Thecoagulation and associated diffusion equilibrium werecalculated for two imidazolium-based ILs, and it wasfound that the anion largely influenced the coagulationkinetics. This was likely due to the associationbetween the anion of the IL and cellulose. Theorientation of the polymer chains is known to influencethe mechanical properties greatly; previously, hotstretching was used to orientate cellulose acetate. Herewe investigated this influence on the mechanicalproperties of regenerated cellulose fibres by applying apost stretch at different stretch ratios.

A facile approach to spinning multifunctional conductive elastomer fibres with nanocarbon fillers

Electrically conductive elastomeric fibres prepared using a wet-spinning process are promising materials for intelligent textiles, in particular as a strain sensing component of the fabric. However, these fibres, when reinforced with conducting fillers, typically result in a compromise between mechanical and electrical properties and, ultimately, in the strain sensing functionality. Here we investigate the wet-spinning of polyurethane (PU) fibres with a range of conducting fillers such as carbon black (CB), single-walled carbon nanotubes (SWCNTs), and chemically converted graphene. We show that the electrical and mechanical properties of the composite fibres were strongly dependent on the aspect ratio of the filler and the interaction between the filler and the elastomer. The high aspect ratio SWCNT filler resulted in fibres with the highest electrical properties and reinforcement, while the fibres produced from the low aspect ratio CB had the highest stretchability. Furthermore, PU/SWCNT fibres presented the largest sensing range (up to 60% applied strain) and the most consistent and stable cyclic sensing behaviour. This work provides an understanding of the important factors that influence the production of conductive elastomer fibres by wet-spinning, which can be woven or knitted into textiles for the development of wearable strain sensors.

Elastic conducting carbon nanotube-laden SIBS fibers

We report a facile method to produce elastic conducting fibers using a continuous flow wet-spinning approach. The spun fibers were highly stretchable, similar to the elastomeric polymer used.

Highly Stretchable Conducting SIBS-P3HT Fibers

Poly(styrene-β-isobutylene-β-styrene)-poly(3-hexylthiophene) (SIBS-P3HT) conducting composite fibers are successfully produced using a continuous flow approach. Composite fibers are stiffer than SIBS fibers and able to withstand strains of up 975% before breaking. These composite fibers exhibit interesting reversible mechanical and electrical characteristics, which are applied to demonstrate their strain gauging capabilities. This will facilitate their potential applications in strain sensing or elastic electrodes. Here, the fabrication and characterization of highly stretchable electrically conducting SIBS-P3HT fibers using a solvent/non-solvent wet-spinning technique is reported. This fabrication method combines the processability of conducting SIBS-P3HT blends with wet-spinning, resulting in fibers that could be easily spun up to several meters long. The resulting composite fiber materials exhibit an increased stiffness (higher Young’s modulus) but lower ductility compared to SIBS fibers. The fibers’ reversible mechanical and electrical characteristics are applied to demonstrate their strain gauging capabilities.

Conducting gel-fibres based on carrageenan, chitosan and carbon nanotubes

A simple continuous flow wet-spinning method for assembling fibres consisting of two oppositely charged biopolymers (chitosan and carrageenan) and carbon nanotubes is reported. It was observed that the order in which the biopolymers are added, i.e. spinning chitosan into one of the carrageenans (or vice versa), affects the fibre composition as well as the resulting electrical and mechanical properties. The addition of carbon nanotubes into the fibres was found to improve Young's modulus values coupled with a significant improvement in the electrical conductivity by up to 6 orders of magnitude.

Mechanical Reinforcement of Continuous Flow Spun Polyelectrolyte Complex Fibers

A simple continuous flow wet-spinning method to achieve mechanical reinforcement of the two oppositely charged biopolymers chitosan and gellan gum is described. The mechanical properties of these biopolymers are influenced by the order of addition. Using a facile method for mechanical reinforcement of gellan gum/chitosan fibers resulted in increases in Young's modulus, tensile strength, and toughness. Spinning gellan gum into chitosan resulted in the strongest fibers. We show that our fibers can provide a mechanical alternative for bio-fibers without the need of cross-linking. It is demonstrated that the fibers become ionically conducting in the presence of water vapor.

Strain-responsive polyurethane/PEDOT:PSS elastomeric composite fibers with high electrical conductivity

It is a challenge to retain the high stretchability of an elastomer when used in polymer composites. Likewise, the high conductivity of organic conductors is typically compromised when used as filler in composite systems. Here, it is possible to achieve elastomeric fiber composites with high electrical conductivity at relatively low loading of the conductor and, more importantly, to attain mechanical properties that are useful in strain-sensing applications. The preparation of homogenous composite formulations from polyurethane (PU) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) that are also processable by fiber wet-spinning techniques are systematically evaluated. With increasing PEDOT:PSS loading in the fiber composites, the Young's modulus increases exponentially and the yield stress increases linearly. A model describing the effects of the reversible and irreversible deformations as a result of the re-arrangement of PEDOT:PSS filler networks within PU and how this relates to the electromechanical properties of the fibers during the tensile and cyclic stretching is presented. Conducting elastomeric fibers based on a composite of polyurethane (PU) and PEDOT:PSS, produced by a wet-spinning method, have high electrical conductivity and stretchability. These fibers can sense large strains by changes in resistance. The PU/PEDOT:PSS fiber is optimized to achieve the best strain sensing. PU/PEDOT:PSS fibers can be produced on a large scale and integrated into conventional textiles by weaving or knitting. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Knitted strain sensor textiles of highly conductive all-polymeric fibers

A scaled-up fiber wet-spinning production of electrically conductive and highly stretchable PU/PEDOT:PSS fibers is demonstrated for the first time. The PU/PEDOT:PSS fibers possess the mechanical properties appropriate for knitting various textile structures. The knitted textiles exhibit strain sensing properties that were dependent upon the number of PU/PEDOT:PSS fibers used in knitting. The knitted textiles show sensitivity (as measured by the gauge factor) that increases with the number of PU/PEDOT:PSS fibers deployed. A highly stable sensor response was observed when four PU/PEDOT:PSS fibers were co-knitted with a commercial Spandex yarn. The knitted textile sensor can distinguish different magnitudes of applied strain with cyclically repeatable sensor responses at applied strains of up to 160%. When used in conjunction with a commercial wireless transmitter, the knitted textile responded well to the magnitude of bending deformations, demonstrating potential for remote strain sensing applications. The feasibility of an all-polymeric knitted textile wearable strain sensor was demonstrated in a knee sleeve prototype with application in personal training and rehabilitation following injury.

Compositional effects of large graphene oxide sheets on the spinnability and properties of polyurethane composite fibers

Recent advances in wearable electronics, technical textiles, and wearable strain sensing devices have resulted in extensive research on stretchable electrically conductive fibers. Addressing these areas require the development of efficient fiber processing methodologies that do not compromise the mechanical properties of the polymer (typically an elastomer) when nanomaterials are added as conductive fillers. It is highly desirable that the addition of conductive fillers provides not only electrical conductivity, but that these fillers also enhance the stiffness, strength, stretchability, and toughness of the polymer. Here, the compatibility of polyurethane (PU) and graphene oxide (GO) is utilized for the study of the properties of elastomeric conductive fibers prepared by wet-spinning. The GO-reinforced PU fibers demonstrate outstanding mechanical properties with a 200-fold and a threefold enhancement in Young's modulus and toughness, respectively. Postspinning thermal annealing of the fibers results in electrically conductive fibers with a low percolation threshold (≈0.37 wt% GO). An investigation into optimized fiber's electromechanical behavior reveals linear strain sensing abilities up to 70%. Results presented here provide practical insights on how to simultaneously maintain or improve electrical, mechanical, and electromechanical properties in conductive elastomer fibers.