Core-spun carbon nanotube yarn supercapacitors for wearable electronic textiles

Linear (fiber or yarn) supercapacitors have demonstrated remarkable cyclic electrochemical performance as power source for wearable electronic textiles. The challenges are, first, to scale up the linear supercapacitors to a length that is suitable for textile manufacturing while their electrochemical performance is maintained or preferably further improved and, second, to develop practical, continuous production technology for these linear supercapacitors. Here, we present a core/sheath structured carbon nanotube yarn architecture and a method for one-step continuous spinning of the core/sheath yarn that can be made into long linear supercapacitors. In the core/sheath structured yarn, the carbon nanotubes form a thin surface layer around a highly conductive metal filament core, which serves as current collector so that charges produced on the active materials along the length of the supercapacitor are transported efficiently, resulting in significant improvement in electrochemical performance and scale up of the supercapacitor length. The long, strong, and flexible threadlike supercapacitor is suitable for production of large-size fabrics for wearable electronic applications.

Scaling up the production rate of nanofibers by needleless electrospinning from multiple ring

Mass production of nanofibers is crucial in both laboratory research and industry application of nanofibers. In this study, multiple ring spinnerets have been used to generate needleless electrospinning. Multiple polymer jets were produced from the top of each ring in the spinning process, resulting in thin and uniform nanofibers. Production rate of nanofibers increased gradually with the increase of the number of rings in the spinneret. Spinning performance of multiple ring electrospinning, namely the quality and production rate of the as-spun nanofibers, was dependent on experimental parameters like applied voltage and polymer concentration. Electric field analysis of multiple ring showed that high concentrated electric field was formed on the surface of each ring. Fiber diameter together with production rate of needleless electrospinning was dependent on the strength and distribution of the electric field of the spinneret. Needleless electrospinning from multiple ring can be further applied in both laboratory research and industry where large amount of nanofibers must be employed simultaneously. © 2014 The Korean Fiber Society and Springer Science+Business Media Dordrecht.

Effect of electrospinning parameters and polymer concentrations on mechanical-to-electrical energy conversion of randomly-oriented electrospun poly(vinylidene fluoride) nanofiber mats

Poly(vinylidene fluoride) (PVDF) nanofiber mats prepared by an electrospinning technique were used as an active layer for making mechanical-to-electric energy conversion devices. The effects of PVDF concentration and electrospinning parameters (e.g. applied voltage, spinning distance), as well as nanofiber mat thickness on the fiber diameter, PVDF β crystal phase content, and mechanical-to-electrical energy conversion properties of the electrospun PVDF nanofiber mats were examined. It was interesting to find that finer uniform PVDF fibers showed higher β crystal phase content and hence, the energy harvesting devices had higher electrical outputs, regardless of changing the electrospinning parameters and PVDF concentration. The voltage output always changed in the same trend to the change of current output whatever the change trend was caused by the operating parameters or polymer concentration. Both voltage and current output changes followed a similar trend to the change of the β crystal phase content in the nanofibers. The nanofiber mat thickness influenced the device electrical output, and the maximum output was found on the 70 μm thick nanofiber mat. These results suggest that uniform PVDF nanofibers with smaller diameters and high β crystal phase content facilitate mechanical-to-electric energy conversion. The understanding obtained from this study may benefit the development of novel piezoelectric nanofibrous materials and devices for various energy uses.

Comparison of various NMR methods for the indirect detection of nitrogen-14 nuclei via protons in solids

We present an experimental comparison of several through-space Hetero-nuclear Multiple-Quantum Correlation experiments, which allow the indirect observation of homo-nuclear single- (SQ) or double-quantum (DQ) ¹⁴N coherences via spy ¹H nuclei. These ¹H-{¹⁴N} D-HMQC sequences differ not only by the order of ¹⁴N coherences evolving during the indirect evolution, t1, but also by the radio-frequency (rf) scheme used to excite and reconvert these coherences under Magic-Angle Spinning (MAS). Here, the SQ coherences are created by the application of center-band frequency-selective pulses, i.e. long and low-power rectangular pulses at the ¹⁴N Larmor frequency, ν0(¹⁴N), whereas the DQ coherences are excited and reconverted using rf irradiation either at ν0(¹⁴N) or at the ¹⁴N overtone frequency, 2ν0(¹⁴N). The overtone excitation is achieved either by constant frequency rectangular pulses or by frequency-swept pulses, specifically Wide-band, Uniform-Rate, and Smooth-Truncation (WURST) pulse shapes. The present article compares the performances of four different ¹H-{¹⁴N} D-HMQC sequences, including those with ¹⁴N rectangular pulses at ν0(¹⁴N) for the indirect detection of homo-nuclear (i) ¹⁴N SQ or (ii) DQ coherences, as well as their overtone variants using (iii) rectangular or (iv) WURST pulses. The compared properties include: (i) the sensitivity, (ii) the spectral resolution in the ¹⁴N dimension, (iii) the rf requirements (power and pulse length), as well as the robustness to (iv) rf offset and (v) MAS frequency instabilities. Such experimental comparisons are carried out for γ-glycine and l-histidine.HCl monohydrate, which contain ¹⁴N sites subject to moderate quadrupole interactions. We demonstrate that the optimum choice of the ¹H-{¹⁴N} D-HMQC method depends on the experimental goal. When the sensitivity and/or the robustness to offset are the major concerns, the D-HMQC sequence allowing the indirect detection of ¹⁴N SQ coherences should be employed. Conversely, when the highest resolution and/or adjusted indirect spectral width are needed, overtone experiments are the method of choice. The overtone scheme using WURST pulses results in broader excitation bandwidths than that using rectangular pulses, at the expense of reduced sensitivity. Numerically exact simulations also show that the sensitivity of the overtone ¹H-{¹⁴N} D-HMQC experiment increases for larger quadrupole interactions.

Solid-state NMR as a probe of anion binding: molecular dynamics and associations in a [5]polynorbornane bisurea host complexed with terephthalate

A range of solid-state NMR techniques is used to characterise a molecular host:guest complex consisting of a [5]polynorbornane bisurea host binding a terephthalate dianion guest. Detailed information is obtained on the molecular dynamics and associations from the point of view of both the host and guest molecules. The formation of the complex in the solid state is confirmed using (1)H 2D exchange NMR, and the 180° flipping of the (2)H-labelled terephthalate guest and its eventual expulsion from the complex at elevated temperatures are quantified using variable-temperature (2)H spin-echo experiments. Two-dimensional (1)H-(13)C HETCOR spectra obtained under fast magic angle spinning conditions (60 kHz) show a high resolution despite the poor crystallinity of the solid complex, and clearly reveal changes in the rigidity of the host molecule when complexed. Short-range intra- and intermolecular (1)H-(1)H proximities are also detected using 2D SQ-DQ correlation methods, providing insight into the molecular packing in the solid phase.

Robust mechanical-to-electrical energy conversion from short-distance electrospun poly(vinylidene fluoride) fiber webs

Electrospun polyvinylidene fluoride (PVDF) nanofiber webs have shown great potential in making mechanical-to-electrical energy conversion devices. Previously, polyvinylidene fluoride (PVDF) nanofibers were produced either using near-field electrospinning (spinning distance < 1 cm) or conventional electrospinning (spinning distance > 8 cm). PVDF fibers produced by an electrospinning at a spinning distance between 1 and 8 cm (referred to as "short-distance" electrospinning in this paper) has received little attention. In this study, we have found that PVDF electrospun in such a distance range can still be fibers, although interfiber connection is formed throughout the web. The interconnected PVDF fibers can have a comparable β crystal phase content and mechanical-to-electrical energy conversion property to those produced by conventional electrospinning. However, the interfiber connection was found to considerably stabilize the fibrous structure during repeated compression and decompression for electrical conversion. More interestingly, the short-distance electrospun PVDF fiber webs have higher delamination resistance and tensile strength than those of PVDF nanofiber webs produced by conventional electrospinning. Short-distance electrospun PVDF nanofibers could be more suitable for the development of robust energy harvesters than conventionally electrospun PVDF nanofibers.

Weathering, fibre strength and colour properties of processed white cashmere

Weathering refers to the degradation of wool fibres that occur during growth from exposure of the fleece to sunlight, water and air. Weathering damage to Merino wool reduces quantities of fibre that are harvested, reduces length in both raw and processed wools, reduces spinning performance and dyeing outcomes. This work aimed to aimed to quantify if and to what extent weathering occurred in 38 lots of commercial dehaired white cashmere and cashmere top sourced from traditional and new origins of production and the extent of any association between weathering and tensile strength properties of the dehaired cashmere and cashmere top. The cashmere was tested for physical properties, bundle tenacity and extension, tristimulus values brightness (Y) and yellowness (Y-Z) and reflectance. Dye uptake was used as an index of weathering. Linear models, relating to weathering, bundle tenacity and Y-Z were fitted to origin and other objective measurements. Mean attributes (range) were: mean fibre diameter, 17.0 μm (13.5–21.3 μm); bundle tenacity of tops, 10.3 cN/tex (8.3–12.9 cN/tex), for dehaired fibre, 10.1 cN/tex (9.1–11.4 cN/tex). Stain uptake varied from 0.92 to 6.34 mg/g fibre indicating a six-fold variation in the extent of weathering. Both the extent of weathering and the bundle tenacity of commercial lots of cashmere were affected by the origin of the cashmere. Increased weathering reduced bundle tenacity, bundle extension, increased the yellowness and reduced reflectance of white cashmere. Bundle tenacity of cashmere declined as fibre diameter variability increased from 20 to 22.5%. For the samples tested, the cashmere from China, Mongolia, Afghanistan and Iran showed more weathering than cashmere from Australia, New Zealand and the USA. The differences in the extent of weathering and of bundle tenacity between cashmere from different origins were of commercial significance.

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.

'Laser chemistry' synthesis, physicochemical properties, and chemical processing of nanostructured carbon foams

Laser ablation of selected coordination complexes can lead to the production of metal-carbon hybrid materials, whose composition and structure can be tailored by suitably choosing the chemical composition of the irradiated targets. This 'laser chemistry' approach, initially applied by our group to the synthesis of P-containing nanostructured carbon foams (NCFs) from triphenylphosphine-based Au and Cu compounds, is broadened in this study to the production of other metal-NCFs and P-free NCFs. Thus, our results show that P-free coordination compounds and commercial organic precursors can act as efficient carbon source for the growth of NCFs. Physicochemical characterization reveals that NCFs are low-density mesoporous materials with relatively low specific surface areas and thermally stable in air up to around 600°C. Moreover, NCFs disperse well in a variety of solvents and can be successfully chemically processed to enable their handling and provide NCF-containing biocomposite fibers by a wet-chemical spinning process. These promising results may open new and interesting avenues toward the use of NCFs for technological applications.

Influence of processing conditions on polymorphic behavior, crystallinity, and morphology of electrospun poly(VInylidene fluoride) nanofibers

The polymorphism and crystallinity of poly(vinylidene fluoride) (PVDF) membranes, made from electrospinning of the PVDF in pure N,N-dimethylformamide (DMF) and DMF/acetone mixture solutions are studied. Influence of the processing and solution parameters such as flow rate, applied voltage, solvent system, and mixture ratio, on nanofiber morphology, total crystallinity, and crystal phase content of the nanofibers are investigated using scanning electron microscopy, wide-angle X-ray scattering, differential scanning calorimetric, and Fourier transform infrared spectroscopy. The results show that solutions of 20% w/w PVDF in two solvent systems of DMF and DMF/acetone (with volume ratios of 3/1 and 1/1) are electrospinnable; however, using DMF/acetone volume ratio of 1/3 led to blockage of the needle and spinning process was stopped. Very high fraction of β-phase (∼79%-85%) was obtained for investigated nanofiber, while degree of crystallinity increased to 59% which is quite high due to the strong influence of electrospinning on ordering the microstructure. Interestingly, ultrafine fibers with the diameter of 12 and 15 nm were obtained in this work. Uniform and bead free nanofiber was formed when a certain amount of acetone was added in to the electrospinning solution.

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.

Towards the knittability of graphene oxide fibres

Recent developments in graphene oxide fibre (GO) processing include exciting demonstrations of hand woven textile structures. However, it is uncertain whether the fibres produced can meet the processing requirements of conventional textile manufacturing. This work reports for the first time the production of highly flexible and tough GO fibres that can be knitted using textile machinery. The GO fibres are made by using a dry-jet wet-spinning method, which allows drawing of the spinning solution (the GO dispersion) in several stages of the fibre spinning process. The coagulation composition and spinning conditions are evaluated in detail, which led to the production of densely packed fibres with near-circular cross-sections and highly ordered GO domains. The results are knittable GO fibres with Young's modulus of ~7.9 GPa, tensile strength of ~135.8 MPa, breaking strain of ~5.9%, and toughness of ~5.7 MJ m(-3). The combination of suitable spinning method, coagulation composition, and spinning conditions led to GO fibres with remarkable toughness; the key factor in their successful knitting. This work highlights important progress in realising the full potential of GO fibres as a new class of textile.

Development of a novel cellulose/duck feather composite fibre regenerated in ionic liquid

By blending cellulose and duck feather in the common solvent 1-allyl-3-methylimidazoloium chloride, a regenerated composite fibre has been developed with improved fibres over regenerated cellulose fibres (RCF). The mechanical properties of composite fibre was shown to be better than RCF with a 63.7% improvement in tensile strain. Here, we thoroughly characterise the composite fibre and show that the composite fibre has many advantages over RCFs both from a spinning perspective and as a regenerated fibre.