The effect of treatment temperature on corrosion resistance and hydrophilicity of an ionic liquid coating for mg-based stents

Mg alloys are attractive candidate materials for biodegradable stents. However, there are few commercially available Mg-based stents in clinical use because Mg alloys generally undergo rapid localized corrosion in the body. In this study, we report a new surface coating for Mg alloy AZ31 based on a low-toxicity ionic liquid (IL), tributyl(methyl)phosphonium diphenyl phosphate (P1,4,4,4 dpp), to control its corrosion rate. Emphasis is placed on the effect of treatment temperature. We showed that enhancing the treatment temperature provided remarkable improvements in the performances of both corrosion resistance and biocompatibility. Increasing treatment temperature resulted in a thicker (although still nanometer scale) and more homogeneous IL film on the surface. Scanning electron microscopy and optical profilometry observations showed that there were many large, deep pits formed on the surface of bare AZ31 after 2 h of immersion in simulated body fluid (SBF). The IL coating (particularly when formed at 100 °C for 1 h) significantly suppressed the formation of these pits on the surface, making corrosion occur more uniformly. The P1,4,4,4 dpp IL film formed at 100 °C was more hydrophilic than the bare AZ31 surface, which was believed to be beneficial for avoiding the deposition of the proteins and cells on the surface and therefore improving the biocompatibility of AZ31 in blood. The interaction mechanism between this IL and AZ31 was also investigated using ATR-FTIR, which showed that both anion and cation of this IL were present in the film, and there was a chemical interaction between dpp(-) anion and the surface of AZ31 during the film formation.

Electrochemical and physicochemical properties of small phosphonium cation ionic liquid electrolytes with high lithium salt content

Electrolytes of a room temperature ionic liquid (RTIL), trimethyl(isobutyl)phosphonium (P111i4) bis(fluorosulfonyl)imide (FSI) with a wide range of lithium bis(fluorosulfonyl)imide (LiFSI) salt concentrations (up to 3.8 mol kg−1 of salt in the RTIL) were characterised using a combination of techniques including viscosity, conductivity, differential scanning calorimetry (DSC), electrochemical impedance spectroscopy (EIS), nuclear magnetic resonance (NMR) and cyclic voltammetry (CV). We show that the FSI-based electrolyte containing a high salt concentration (e.g. 1:1 salt to IL molar ratio, equivalent to 3.2 mol kg−1 of LiFSI) displays unusual transport behavior with respect to lithium ion mobility and promising electrochemical behavior, despite an increase in viscosity. These electrolytes could compete with the more traditionally studied nitrogen-based ionic liquids (ILs) in lithium battery applications.

Biocompatible ionic liquid-biopolymer electrolyte-enabled thin and compact magnesium-air batteries.

With the surge of interest in miniaturized implanted medical devices (IMDs), implantable power sources with small dimensions and biocompatibility are in high demand. Implanted battery/supercapacitor devices are commonly packaged within a case that occupies a large volume, making miniaturization difficult. In this study, we demonstrate a polymer electrolyte-enabled biocompatible magnesium-air battery device with a total thickness of approximately 300 μm. It consists of a biocompatible polypyrrole-para(toluene sulfonic acid) cathode and a bioresorbable magnesium alloy anode. The biocompatible electrolyte used is made of choline nitrate (ionic liquid) embedded in a biopolymer, chitosan. This polymer electrolyte is mechanically robust and offers a high ionic conductivity of 8.9 × 10(-3) S cm(-1). The assembled battery delivers a maximum volumetric power density of 3.9 W L(-1), which is sufficient to drive some types of IMDs, such as cardiac pacemakers or biomonitoring systems. This miniaturized, biocompatible magnesium-air battery may pave the way to a future generation of implantable power sources.

A potential anti-corrosive ionic liquid coating for MG alloy AZ31 in simulated body fluids

Magnesium alloys are attractive materials for biomedical applications, due to their excellent biocompatibility. However, these alloys show fast corrosion rates in the body that limits their clinical applications. Low-toxic ionic liquid (IL) trimethyl(butyl)phosphonium diphenyl phosphate P1444dpp has been investigated to provide corrosion protection for magnesium alloy AZ31 in simulated body fluids (SBFs). This work reports a preliminary exploration of the influence of different treatment temperatures on the corrosion protection properties of IL films for the magnesium alloy AZ31 in SBFs. Results show that the IL treatment at room temperature did not bring significant improvement in the corrosion performance of the AZ31 in SBF. However, when the treatment temperature was increased to 75°C, the IL treatment resulted in a substantial reduction of the corrosion, in particular the reduction of localized pitting corrosion. The influence of ionic liquid treatment on the corrosion performance of the magnesium alloys AZ31 in SBFs has been investigated by electrochemical impedance spectroscopy (EIS) tests and immersion tests.

Characterization of the phase behaviour of a novel polymerizable lyotropic ionic liquid crystal

The development of new polymerizable lyotropic liquid crystals (LLCs) utilizing charged amphiphilic molecules such as those based on long chain imidazolium compounds, is a relatively new design direction for producing robust membranes with controllable nano-structures. Here we have developed a novel polymerizable ionic liquid based LLC, 1-hexadecyl-3-methylimidazolium acrylate (C16mimAcr), where the acrylate anion acts as the polymerizable moiety. The phase behaviour of the C16mimAcr upon the addition of water was characterized using small and wide angle X-ray scatterings, differential scanning calorimetry and polarized optical microscopy. We compare the phase behaviour of this new polymerizable LLC to that of the well known LLC chloride analogue, 1-hexadecyl-3-methylimidazolium chloride (C16mimCl). We find that the C16mimAcr system has a more complex phase behaviour compared to the C16mimCl system. Additional lyotropic liquid crystalline mesophases such as hexagonal phase (H1) and discontinuous cubic phase (I1) are observed at 20 °C for the acrylate system at 50 and 65 wt% water respectively. The appearance of the hexagonal phase (H1) and discontinuous cubic phase (I1) for the acrylate system is likely due to the strong hydrating nature of the acrylate anion, which increases the head group area. The formation of these additional mesophases seen for the acrylate system, especially the hexagonal phase (H1), coupled with the polymerization functionality offers great potential in the design of advanced membrane materials with selective and anisotropic transport properties.

Thermally flexible epoxy/cellulose blends mediated by an ionic liquid

Blends between the widely used thermoset resin, epoxy, and the most abundant organic material, natural cellulose are demonstrated for the first time. The blending modification induced by charge transfer complexes using a room temperature ionic liquid, leads to the formation of thermally flexible thermoset materials. The blend materials containing low concentrations of cellulose were optically transparent which indicates the miscibility at these compositions. We observed the existence of intermolecular hydrogen bonding between epoxy and cellulose in the presence of the ionic liquid, leading to partial miscibility between these two polymers. The addition of cellulose improves the tensile mechanical properties of epoxy. This study reveals the use of ionic liquids as a compatible processing medium to prepare epoxy thermosets modified with natural polymers.

Improved efficiency and stability of flexible dye sensitized solar cells on ITO/PEN substrates using an ionic liquid electrolyte

Flexible dye-sensitized solar cells (DSSCs) built on plastic substrates have attracted great interest as they are lightweight and can be roll-to-roll printed to accelerate production and reduce cost. However, plastic substrates such as PEN and PET are permeable to water, oxygen and volatile electrolyte solvents, which is detrimental to the cell stability. Therefore, to address this problem, in this work, an ionic liquid (IL) electrolyte is used to replace the volatile solvent electrolyte. The initial IL-based devices only achieved around 50% of the photovoltaic conversion efficiency of the cells using the solvent electrolyte. Current-voltage and electrochemical impedance spectroscopy (EIS) analysis of the cells in the dark indicated that this lower efficiency mainly originated from (i) a lack of blocking layer to reduce recombination, and (ii) a lower charge collection efficiency. To combat these problems, cells were developed using a 12 nm thick blocking layer, produced by atomic layer deposition, and 1 μm thick P25 TiO2 film sensitized with the hydrophobic MK-2 dye. These flexible DSSCs utilizing an IL electrolyte exhibit significantly improved efficiencies and a <10% drop in performance after 1000 h aging at 60°C under continuous light illumination.

Gelled ionic liquid sodium ion conductors for sodium batteries

Owing to the unique properties of certain Ionic liquids (ILs) as safe and green solvents, as well as the potential of sodium as an alternative to lithium as charge carriers, we investigate gel sodium electrolytes as safe, low cost and high performance materials with sufficient mechanical properties for application in sodium battery technologies. We investigate the effect of formation of two types of gel electrolytes on the properties of IL electrolytes known to support Na/Na⁺ electrochemistry. The ionic conductivity is only slightly decreased by 0.0005 and 0.0002 S cm^-1 in the case of 0.3 and 0.5 M NaNTf2 systems respectively as the physical properties transition from liquid to gel. We observed facile plating and stripping of Na metal around 0 V vs. Na/Na⁺ through the cyclic voltammetry. A wide-temperature range of the gelled IL state, of more than 100 K around room temperature, is achieved in the case of 0.3 and 0.5 M NaNTf2. We conclude that the formation of a gel does not significantly affect the liquid-like ion dynamics in these materials, as further evidenced by DSC and FTIR analysis.

Rapid and effective cuticle removal from wool fibers using ionic liquid

Wool fibers are composed of cuticle and cortex cells, which are of obvious differences in many properties. The development of methods to isolate the two kinds of cells can provide platform to elucidate the roles they play in the characteristics of wool fibers. Here we demonstrate the cuticle can be completely and rapidly removed from the wool fibers by the use of ionic liquids, with inner cortex intact. Confocal microscope, SEM and FTIR have been applied to study the wool fibers after cuticle removal. In contrast to the traditional/long physical or chemical separation routes (>14 h), our method is very rapid (<1 h). This work demonstrates the ability of ionic liquid as a novel, rapid and efficient media for cuticle/ cortex isolation.

Rechargeable Zn/PEDOT battery with an imidazolium-based ionic liquid as the electrolyte

 A non-aqueous secondary battery has been constructed by using Zn metal as the anode and chemically synthesised PEDOT as the cathode, with a 1-ethyl-3-methylimidazolium dicyanamide ionic liquid as the electrolyte, which avoids dendritic growth processes on the Zn surface upon charge/discharge cycling. The novel Zn/PEDOT rechargeable cell shows high efficiency and cycling ability, performing over 320 cycles with no indication of short circuit. Both the Zn and PEDOT surfaces showed minimal signs of degradation, suggesting that a Zn/PEDOT electrochemical device would be capable of extended cycle life under numerous charge/discharge cycles.

Film formation in trihexyl(tetradecyl)phosphonium diphenylphosphate ([P6,6,6,14][dpp]) ionic liquid on AA5083 aluminium alloy

Whilst ionic liquids (IL) have been shown to inhibit corrosion on some reactive metals and alloys by forming a surface film, e.g. Li and Mg, understanding of the interaction between ionic liquids and aluminium is lacking. This research study investigated the viability of film formation on AA5083 Aluminium Alloy by electrochemical treatments in the trihexyl(tetradecyl)phosphonium diphenylphosphate ([P6,6,6,14][dpp]) IL. Two-step anodic treatments were performed on AA5083 in the IL, followed by a comparison of the corrosion behaviour of the IL-treated samples with that of a control. It has been revealed that the two-step IL-treatment led to reduced current densities on AA5083 under cyclic voltammetry scan in the IL before and after the IL-treatment. Lower corrosion rates have been shown on all samples treated in IL at room temperature. Surface characterisation showed a non-uniform porous film on the 50°C IL-treated sample with a film thickness ranging between 37nm and 155nm. The IL-film enhanced the corrosion resistance of AA5083 by protecting the Al-matrix and Fe-rich intermetallic particles (IMPs). Although findings of this study suggest similar IL-film formation as that on Li and Mg, more research needs to be conducted to optimise the electrochemical treatment conditions and ultimately to develop a robust IL-film formation procedure for corrosion protection.

Physical properties of high Li-ion content N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide based ionic liquid electrolytes

Electrolytes based on bis(fluorosulfonyl)imide (FSI) with a range of LiFSI salt concentrations were characterized using physical property measurements, as well as NMR, FT-IR and Raman spectroscopy. Different from the behavior at lower concentrations, the FSI electrolyte containing 1 : 1 salt to IL mole ratio showed less deviation from the KCl line in the Walden plot, suggesting greater ionic dissociation. Diffusion measurements show higher mobility of lithium ions compared to the other ions, which suggests that the partial conductivity of Li(+) is higher at this higher composition. Changes in the FT-IR and Raman peaks indicate that the cis-FSI conformation is preferred with increasing Li salt concentration.

Novel Na+ Ion diffusion mechanism in mixed organic-inorganic ionic liquid electrolyte leading to high Na+ transference number and stable, high rate electrochemical cycling of sodium cells

Ambient temperature sodium batteries hold the promise of a new generation of high energy density, low-cost energy storage technologies. Particularly challenging in sodium electrochemistry is achieving high stability at high charge/discharge rates. We report here mixtures of inorganic/organic cation fluorosulfonamide (FSI) ionic liquids that exhibit unexpectedly high Na+ transference numbers due to a structural diffusion mechanism not previously observed in this type of electrolyte. The electrolyte can therefore support high current density cycling of sodium. We investigate the effect of NaFSI salt concentration in methylpropylpyrrolidinium (C3mpyr) FSI ionic liquid (IL) on the reversible plating and dissolution of sodium metal, both on a copper electrode and in a symmetric Na/Na metal cell. NaFSI is highly soluble in the IL allowing the preparation of mixtures that contain very high Na contents, greater than 3.2 mol/kg (50 mol %) at room temperature. Despite the fact that overall ion diffusivity decreases substantially with increasing alkali salt concentration, we have found that these high Na+ content electrolytes can support higher current densities (1 mA/cm2) and greater stability upon continued cycling. EIS measurements indicate that the interfacial impedance is decreased in the high concentration systems, which provides for a particularly low-resistance solid-electrolyte interphase (SEI), resulting in faster charge transfer at the interface. Na+ transference numbers determined by the Bruce-Vincent method increased substantially with increasing NaFSI content, approaching >0.3 at the saturation concentration limit which may explain the improved performance. NMR spectroscopy, PFG diffusion measurements, and molecular dynamics simulations reveal a changeover to a facile structural diffusion mechanism for sodium ion transport at high concentrations in these electrolytes.

Experimental investigation on CFRP-steel bond properties using ionic liquid

Solving the problem of pre mature debonding of CFRP retrofitted structure is a main concern for most of structural engineers nowadays. Reducing the brittleness of the bonding agent at the CFRP/concrete interface is a major factor to avoid this behaviour. In this research, the effect of modifying the bonding agent using different percentages of ionic liquid (IL) is investigated. This paper reports on an experimental investigation on the behaviour of modified epoxy resin with IL. Steel plates were used as hosting surface of the CFRP laminates, the laminates were attached to the steel surface using the IL modified epoxy. The shear mechanism at the interface of CFRP laminates to steel plates is discussed considering the relationship between the shear and the slip at the interface. The shear stress- displacement are traced for all specimens, the results are compared with control test prepared using unmodified epoxy. A 20% IL modified epoxy shows improved Behaviour. The improvement is with respect to ductility enhancement of the overall behaviour.

Reduction of oxygen in a trialkoxy ammonium-based ionic liquid and the role of water

The oxygen reduction reaction in a novel trialkoxy ammonium-based ionic liquid, N-ethyl-2-(2-methoxyethoxy)-N,N-bis(2-(2-methoxyethoxy)ethyl)ethan-1-aminium bis(trifluoromethylsulfonyl)imide, [N2(20201)(20201)(20201)] [NTf2] has been studied on glassy carbon and gold electrodes, showing faster electrokinetics on glass carbon because of weaker adsorption of the IL. This has been demonstrated by theoretical calculations and electrochemical studies. In the neat IL, the oxygen is reduced to superoxide (O2 -) through a one electron process; however, better performance is attained in the presence of water (42 mol%), in terms of current density, and onset potential of the reduction process via a reversible 2-electron process. Furthermore, a remarkable increase in cyclic coulombic efficiency is observed for the wet IL (66% in comparison with the neat IL (24%), showing the practicality of a reversible O2/H2O2 system for energy storage.