Effect of vapor-phase glutaraldehyde crosslinking on electrospun starch fibers

In this work, we have proven that starch nanofibrous membranes with high tensile strength, water stability and non-cytotoxicity can be produced by electrospinning of starch solution and post-treatment with GTA in vapor phase. GTA vapor phase crosslinking plays a key role in forming water-stable nanofiber membrane and improving the mechanical properties. Comparing with non-crosslinked starch fibers, the crosslinked fibers are increased by nearly 10 times in tensile strength. The crosslinked starch fibrous membranes are non-cytotoxic. They may find applications in the fields of tissue engineering, pharmaceutical therapy and medical.

High rates of oxygen reduction over a vapor phase-polymerized PEDOT electrode

The air electrode, which reduces oxygen (O₂), is a critical component in energy generation and storage applications such as fuel cells and metal/air batteries. The highest current densities are achieved with platinum (Pt), but in addition to its cost and scarcity, Pt particles in composite electrodes tend to be inactivated by contact with carbon monoxide (CO) or by agglomeration. We describe an air electrode based on a porous material coated with poly(3,4-ethylenedioxythiophene) (PEDOT), which acts as an O₂ reduction catalyst. Continuous operation for 1500 hours was demonstrated without material degradation or deterioration in performance. O₂ conversion rates were comparable with those of Pt-catalyzed electrodes of the same geometry, and the electrode was not sensitive to CO. Operation was demonstrated as an air electrode and as a dissolved O₂ electrode in aqueous solution.

Stable deep doping of vapor-phase polymerized poly(3,4-ethylenedioxythiophene)/ionic liquid supercapacitors

Liquid-solution polymerization and vapor-phase polymerization (VPP) have been used to manufacture a series of chloride- and tosylate-doped poly(3,4-ethylenedioxythiophene) (PEDOT) carbon paper electrodes. The electrochemistry, specific capacitance, and specific charge were determined for single electrodes in 1-ethyl-3-methylimidazolium dicyanamide (emim dca) ionic liquid electrolyte. VPP-PEDOT exhibits outstanding properties with a specific capacitance higher than 300 F g(-1) , the highest value reported for a PEDOT-based conducting polymer, and doping levels as high as 0.7 charges per monomer were achieved. Furthermore, symmetric PEDOT supercapacitor cells with the emim dca electrolyte exhibited a high specific capacitance (76.4 F g(-1) ) and high specific energy (19.8 Wh kg(-1) ). A Ragone plot shows that the VPP-PEDOT cells combine the high specific power of conventional ("pure") capacitors with the high specific energy of batteries, a highly sought-after target for energy storage.

Conducting nylon, cotton and wool yarns by continuous vapor polymerization of pyrrole

Conductive textile yarns were prepared by a continuous vapor polymerization method; the application of polypyrrole by the continuous vapor polymerization method used is designed for the easy adaptation into industrial procedures. The resultant conductive yarns were examined by longitudinal and cross-sectional views, clearly showing the varying levels of penetration of the polymer into the yarn structure. It was found that for wool the optimum specific resistance was achieved by using the 400 TPM yarn with a FeCl3 solution concentration of 80 g/L FeCl3 to produce 1.69 Ω g/cm2. For cotton yarn, the optimum specific resistance of 1.53 Ω g/cm2 was obtained with 80 g/L of a FeCl3 solution.

The reduction of oxygen on iron(II) oxide/poly(3,4-ethylenedioxythiophene) composite thin film electrodes

© 2014 Elsevier Ltd. All rights reserved. Conducting polymers (CPs) are currently being investigated for use in many applications owing to their abilities to catalyze a wide range of electrochemical reactions and act as an effective electrode support for various inorganic and organic electrocatalyst materials. Here, we have found that the deposition of poly(3,4-ethylenedioxythiophene) (PEDOT) through the use of an established base-inhibited chemical vapor-phase polymerization (VPP) procedure using an iron(III) tosylate oxidant results in the co-deposition of electrocatalytic iron(II) oxide species within the film. The presence of these species accounts for the 2-electron reduction of hydrogen peroxide that occurs on these electrodes during the series 4-electron oxygen reduction reaction. Furthermore, this realization leads to the possibility of fabricating thin film inorganic/CP composites of various compositions through careful choice of oxidant in a facile, one-step process. A combination of in situ Raman (487.77 nm laser) and in situ UV-Vis spectroscopy was used to probe the oxidation state of PEDOT in the thin film composite electrodes while reducing oxygen in alkaline conditions. These measurements show that the 2-electron electroreduction of hydrogen peroxide (or HO2 -) occurs only on the iron(II) oxide species in a reaction that is facilitated by an effective electron transfer from the delocalized electron orbitals of the PEDOT matrix. This approach could potentially be used in situ to monitor the electrocatalyst/electrode interface quality of conducting polymer-supported electrocatalysts.

Frictional and tensile properties of conducting polymer coated wool and alpaca fibers

Wool and alpaca fibers were coated with polypyrrole by vapor-phase polymerisation method. The changes in frictional and tensile properties of the single fibers upon coating with the conductive polymer are presented. Coating a thin layer of polypyrrole on the alpaca and wool fibers results in a significant reduction in the fiber coefficient of friction, as the conducting polymer layer smooths the protruding edges of the fiber scales. It also reduces the directional friction effect of the fibers. Depending on the type of fiber, the coating may slightly enhance the tensile properties of the coated fibers.

Conducting polymer composite materials for hydrogen generation

A novel conducting polymer/non-conducting polymer composite (PEDOT/PEG), produced by vapor phase polymerization of PEDOT in the presence of PEG, shows stable electrocatalytic reduction of protons to hydrogen with conversion currents and over-potential comparable to platinum. The swelling of the composite by PEG and especially its ability to coordinate protons seems to be essential for the catalytic activity of the composite.

Unusual phase behaviour of the organic ionic plastic crystal N,N-dimethylpyrrolidinium tetrafluoroborate

Analysis of N,N-dimethylpyrrolidinium tetrafluoroborate by ¹H and ¹¹B NMR, Raman spectroscopy and powder XRD shows that this organic ionic plastic crystal material exhibits unusual phase behaviour. ¹H NMR analysis indicates that the mobility of the pyrrolidinium cation decreases when the material is heated into phase I, while the X-ray diffraction pattern changes from a simple, one peak structure in phase II to a more complex pattern in phase I. The possible origins of these unusual transitions are discussed.

New insights into the thermal behaviour of organic ionic plastic crystals: magnetic resonance imaging of polycrystalline morphology alterations induced by solid-solid phase transitions

Organic ionic plastic crystals (OIPCs) show strong potential as solid-state electrolytes for lithium battery applications, demonstrating promising electrochemical performance and eliminating the need for a volatile and flammable liquid electrolyte. The ionic conductivity (σ) in these systems has recently been shown to depend strongly on polycrystalline morphology, which is largely determined by the sample's thermal history. [K. Romanenko et al., J. Am. Chem. Soc., 2014, 136, 15638]. Tailoring this morphology could lead to conductivities sufficiently high for battery applications, so a more complete understanding of how phenomena such as solid-solid phase transitions can affect the sample morphology is of significant interest. Anisotropic relaxation of nuclear spin magnetisation provides a new MRI based approach for studies of polycrystalline materials at both a macroscopic and molecular level. In this contribution, morphology alterations induced by solid-solid phase transitions in triisobutyl(methyl)phosphonium bis(fluorosulfonyl)imide (P1444FSI) and diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate (P1224PF6) are examined using magnetic resonance imaging (MRI), alongside nuclear magnetic resonance (NMR) spectroscopy, diffusion measurements and conductivity data. These observations are linked to molecular dynamics and structural behaviour crucial for the conductive properties of OIPCs. A distinct correlation is established between the conductivity at a given temperature, σ(T), and the intensity of the narrow NMR signal that is attributed to a mobile fraction, fm(T), of ions in the OIPC. To explain these findings we propose an analogy with the well-studied relationship between permeability (k) and void fraction (θ) in porous media, with k(θ) commonly quantified by a power-law dependence that can also be employed to describe σ(fm).

A study of phase behavior and conductivity of mixtures of the organic ionic plastic crystal N-methyl-N-methyl-pyrrolidinium dicyanamide with sodium dicyanamide

We report on the thermal, structural and conductivity properties of the organic ionic plastic crystal (OIPC) N-methyl-N-methyl-pyrrolidinium dicyanamide [C1mpyr][N(CN)2] mixed with the sodium salt Na[N(CN)2]. The DSC thermal traces indicate that an isothermal transition, which may be a eutectic melting, occurs at ~ 89 °C, below which all compositions are entirely in the solid phase. At 20 mol% Na[N(CN)2], this transition is the final melt for this mixture, and a new liquidus peak grows beyond 20 mol% Na[N(CN)2]. The III- > II solid-solid phase transition continues to be evident at ~- 2 °C. The microstructure for all the mixtures indicated a phase separated morphology where precipitates can be clearly observed. Most likely, these precipitates consist of a Na-rich second phase. This was also suggested from the vibrational spectroscopy and the 23Na NMR spectra. The lower concentrations of Na[N(CN)2] present complex 23Na MAS spectra, suggesting more than one sodium ion environment is present in these mixtures consistent with complex phase behavior. Unlike other OIPCs where the ionic conductivity usually increases upon doping or mixing in a second component, the conductivity of these mixtures remains relatively constant and above 10- 4 S cm- 1 at ∼ 80 °C, even in the solid state. Such high conductivities suggest these materials may be promising to be used for all solid-state electrochemical devices.

Pulsed plasma polymerization of hexamethyldisiloxane onto wool : control of moisture vapor transmission rate and surface adhesion

A new fabric with potential in medical textiles has been developed by application of a surface coating on wool using pulsed plasma polymerization of HMDSO. This coating enabled a controllable MVTR and surface adhesion. MVTR in the range recommended for optimum wound healing was obtained by varying frequency, monomer pressure and deposition time. Lower surface adhesion was achieved. Peeling tests, contact angle measurements, SPM force curves and ATR FT-IR were used to characterize the surfaces for both wool and a PE model substrate. All these results were consistent with a decrease in surface energy after PP-HMDSO treatment. ATR FT-IR results showed a siloxane film with less organic Si(CH₃)_n groups and more SiOSi cross-links.