Adsorption and voltammetry of butyltin compounds

The adsorption of tributyltin onto materials commonly used for the construction of sampling and analytical equipment from aqueous solutions of varying ionic composition has been examined. The adsorption appears to be controlled by non-polar interactions between tributyltin and the surface involved. Since the speciation and hence polarity of tributyltin is affected by the ionic composition of the medium, the extent of adsorption is affected by the salinity and pH of a sample. The adsorption is rapid and, unless strategies are adopted to eliminate its effects, may render analytical results invalid. The electrochemistry of tributyltin, dibutyltin and monobutyltin, individually and in mixtures, has been investigated in aqueous media at mercury electrodes. The basic electrochemistry of each compound is summarised by the reaction BunSn (4-n)+ + (4-n)e- right left harpoons BunSn where n is the number of butyl groups attached to the tin atom. However, the electrochemistry of each compound is largely confined to the surface of the mercury electrode, and the simplicity of the above reaction is disrupted by polymerisation reactions and by butyl exchange processes occurring with the mercury electrode. When mixtures of butyltin compounds are present, the various processes that occur for each individual compound interfere with each other. A direct voltaminetric method for the determination of butyltin compounds in natural waters is therefore probably not possible.

Composition effects on ion transport in a polyelectrolyte gel with the addition of ion dissociators

The polymerization of lithium 2-acrylamido-2-methyl-1-propane sulphonic acid with N,N′-dimethylacrylamide has yielded polyelectrolyte gels which have the favourable property of being single ion conductors. The use of single ion conductors ensures that the transport number of lithium is close to unity. The mobility of the lithium ion is still quite low in these systems, resulting in low ionic conductivity. To increase ionic conductivity more charge carriers can be added however competing effects arise between increasing the number of charge carriers and decreasing the mobility of these charge carriers. In this paper the monomer ratio of the copolymer polyelectrolyte is varied to investigate the effect increasing the number of charge carriers has on the ionic conductivity and lithium ion and solvent diffusivity using pfg-NMR. Ion dissociators such as TiO₂ nano-particles and a zwitterionic compound based on 1-butylimidazolium-3-(N-butanesulfonate) have been added in an attempt to further increase the ionic conductivity of the system. It was found that the system with the highest ionic conductivity had the lowest solvent mobility in the presence of zwitterion. Without zwitterion the mobility of the solvent appears to determine the maximum ionic conductivity achievable.

Use of ionic liquids as electrolytes in electromechanical actuator systems based on inherently conducting polymers

The use of ionic liquids (ILs) as electrolytes for electromechanical actuators based on polypyrroles (PPy's) is described. The composition of the electrolytes has a significant effect on the electrochemical properties of the PPy actuator and subsequently on actuator performance, improving cycle life and strain generated. The actuator performance in ionic liquid electrolytes is significantly better than that in traditional organic and aqueous electrolytes.

Protic ionic liquids based on the dimeric and oligomeric anions: [(AcO)xHx−1]−

We describe a fluidity and conductivity study as a function of composition in N-methylpyrrolidine–acetic acid mixtures. The simple 1:1 acid–base mixture appears to form an ionic liquid, but its degree of ionicity is quite low and such liquids are better thought of as poorly dissociated mixtures of acid and base. The composition consisting of 3 moles acetic acid and 1 mole N-methylpyrrolidine is shown to form the highest ionicity mixture in this binary due to the presence of oligomeric anionic species [(AcO)_xH_x−1]− stabilised by hydrogen bonds. These oligomeric species, being weaker bases than the acetate anion, shift the proton transfer equilibrium towards formation of ionic species, thus generating a higher degree of ionicity than is present at the 1:1 composition. A Walden plot analysis, thermogravimetric behaviour and proton NMR data, as well as ab initio calculations of the oligomeric species, all support this conclusion.

Composition effects in polyetherurethane-based solid polymer electrolytes

Nuclear magnetic resonance spectroscopy (n.m.r.), dynamic mechanical thermal analysis (d.m.t.a.) and AC impedance techniques have been used in combination to probe the effect of electrolyte composition in an archetypal solid polymer electrolyte (SPE). A series of solid polymer electrolytes (SPEs) based on a urethane-crosslinked trifunctional poly(ethylene glycol) polymer host containing dissolved ionic species (LiClO₄ and LiCF₃SO₃) have been studied. D.m.t.a. has established that increasing LiClO₄ concentration causes a decrease in the polymer segmental mobility, owing to the formation of transient crosslinks via cation-polymer interaction. Investigation of the distribution of mechanical/structural relaxation times for the LiClO₄/polymer complex with d.m.t.a. reveals that increasing LiClO₄ concentration causes a slight broadening of the distribution, indicating a more heterogeneous environment. Results of n.m.r. ⁷Li T₁ and T₂ relaxation experiments support the idea that higher salt concentrations encourage ionic aggregation. This is of critical importance in determining the conductivity of the material since it affects the number of charge carriers available. Introduction of the plasticiser tetraglyme into the LiClO₄-based SPEs suppresses the glass transition temperature of the SPE, and causes a significant broadening of the relaxation time distribution (as measured by d.m.t.a.).

Polyelectrolyte-in-ionic-liquid electrolytes

Novel polymer electrolyte materials based on a polyelectrolyte-in-ionic-liquid principle are described. A combination of a lithium 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPSLi) and N,N′-dimethylacrylamide (DMMA) are miscible with the ionic liquid, 1-ethyl-3-methylimidazolium dicyanamide (EMIDCA). EMIDCA has remarkably high conductivity (≥ 2 · 10−2 S · cm−1) at room temperature and acts as a good solvating medium for the polyelectrolyte. At compositions of AMPSLi less than or equal to 75 mol-% in the copolymer (P(AMPSLi-co-DMAA)), the polyelectrolytes in EMIDCA are homogeneous, flexible elastomeric gel materials at 10 − 15 wt.-% of total polyelectrolyte. Conductivities higher than 8 · 10−3 S · cm−1 at 30 °C have been achieved. The effects of the monomer composition, polyelectrolyte concentration, temperature and lithium concentration on the ionic conductivity have been studied using thermal and conductivity analysis, and pulsed field gradient nuclear magnetic resonance techniques.

Potentiostatic control of ionic liquid surface film formation on ZE41 magnesium alloy

The generation of potentially corrosion-resistant films on light metal alloys of magnesium have been investigated. Magnesium alloy, ZE41 [Mg−Zn−Rare Earth (RE)-Zr, nominal composition 4 wt % Zn, 1.7 wt % RE (Ce), 0.6 wt % Zr, remaining balance, Mg], was exposed under potentiostatic control to the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate, denoted [P_6,6,6,14][DPP]. During exposure to this IL, a bias potential, shifted from open circuit, was applied to the ZE41 surface. Electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA) were used to monitor the evolution of film formation on the metal surface during exposure. The EIS data indicate that, of the four bias potentials examined, applying a potential of −200 mV versus OCP during the exposure period resulted in surface films of greatest resistance. Both EIS measurements and scanning electron microscopy (SEM) imaging indicate that these surfaces are substantially different to those formed without potential bias. Time of flight-secondary ion mass spectrometry (ToF-SIMS) elemental mapping of the films was utilized to ascertain the distribution of the ionic liquid cationic and anionic species relative to the microstructural surface features of ZE41 and indicated a more uniform distribution compared with the surface following exposure in the absence of a bias potential. Immersion of the treated ZE41 specimens in a chloride contaminated salt solution clearly indicated that the ionic liquid generated surface films offered significant protection against pitting corrosion, although the intermetallics were still insufficiently protected by the IL and hence favored intergranular corrosion processes.

Regenerated silk fibroin using protic ionic liquids solvents : towards an all-ionic-liquid process for producing silk with tunable properties

We have shown that protic ionic liquids, pILs, are effective coagulation solvents for the regenerated of silk fibroin, RSF. We show that the choice of pIL has a dramatic effect on the composition of the RSF. Additionally the use of pILs as the coagulator eliminates the need for volatile organic solvents in silk processing.

The significant effect of the phase composition on the oxygen reduction reaction activity of a layered oxide cathode

Layered oxides of Sr4Fe4Co2O13 (SFC2) which contains alternating perovskite oxide octahedral and polyhedral oxide double layers are attractive for their mixed ionic and electronic conducting and oxygen reduction reaction properties. In this work, we used the EDTA–citrate synthesis technique to prepare SFC2 and vary the calcination temperature between 900 and 1100 _C to obtain SFC2, containing different phase content of perovskite (denoted as SFC-P) and (Fe,Co) layered oxide phases (SFC-L). Rietveld refinements show that the SFC-P phase content increased from _39 wt% to _50 wt% and _61 wt% as the calcination temperature increased from 900 _C (SFC2-900) to 1000 _C (SFC2-1000) and 1050 _C (SFC2-1050). At 1100 _C (SFC2-1100), SFC-P became the dominant phase. The oxygen transport properties (e.g. oxygen chemical diffusion coefficient and oxygen permeability), electrical conductivity and oxygen reduction reaction activity is enhanced in the order of SFC2-1000, SFC2-1100 and SFC2-1050. The trend established here therefore negates the hypothesis that the perovskite phase content correlates with the oxygen transport property enhancement. The results suggest instead that there is an optimum composition value (e.g. 61 wt% of SFC-L for SFC2-1050 in this work) on which synergistic effects take place between the SFC-P and SFC-L phase.

Effect of solvent on ionic liquid dissolved regenerated antheraea assamensis silk fibroin

We report on the dissolution of semi-domestic silk type Antheraea assamensis using ionic liquids. We investigated the impact of different coagulating solvents, including isopropanol and water on the structure and the morphology of the regenerated silk. We found that the water regenerated silk film showed a high β-sheet content and a native silk-like XRD pattern.

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.

Oxygen reduction reaction in ionic liquids: an overview

The oxygen reduction reaction has been the subject of intensive research during decades due to their importance in life processes such as biological respiration, and also as a cathodic process in energy storage devices (e.g. fuel cells and air batteries). Detailed reviews on the oxygen reduction reaction in aqueous and non-aqueous media are available in the literature but it is lacking in the case of ionic liquids. Therefore a comprehensive review on the oxygen reduction reaction (ORR) in ionic liquids is described in this chapter in order to compile the state of the art from a fundamental point of view and improve the current knowledge towards not only fundamental but also practical applications. The oxygen reduction reaction mechanism in neat imidazolium, pyrrolidinium, quaternary ammonium, and phosphonium-based ionic liquids, which mainly undergo one-electron pathway leading to the generation of superoxide anion (O2•-), is the main topic of this chapter. The reversibility of the O2/O2•- redox couple is highly dependent on the composition of the ionic liquid, as an example superoxide is more stable in the presence of aliphatic and alicyclic cations than in the presence of aromatic rings. Furthermore, the influence of protic and aprotic additives in the ORR mechanism is also explained in this chapter together with the influence in electrochemical parameters such as formal potential, E0'.

Formation of dynamic duolayer systems at the air/water interface by using non-ionic hydrophilic polymers

The inclusion of a water-soluble polymer, poly(vinyl pyrrolidone) (PVP), into a surface active film composition before application to the water surface leads to the formation of a dynamic duolayer; a novel surface film system. This duolayer shows improved surface viscosity over the monolayer compound alone, while the addition of polymer maintains other film properties such as evaporation control and equilibrium spreading pressure. Brewster Angle Microscopy shows that the duolayer film undergoes a different formation mechanism upon film compression, and the resultant surface pressure/area isotherm is different at lower surface pressures indicating the PVP is present on the water surface at these pressures and squeezed out to the water subphase at higher pressures. The addition of water-soluble polymers to form a dynamic duolayer provides a unique way to produce defect-free and tightly packed films while polymer is associated with the film. This finding provides new knowledge for the design of surface films with improved properties with potential applications in many areas.

Duolayers at the air/water interface: improved lifetime through ionic interactions

Ionic interactions to stabilize Langmuir films at the air/water interface have been used to develop improved duolayer films. Two-component mixtures of octadecanoic (stearic) acid and poly(diallyldimethylammonium chloride) (polyDADMAC) with different ratios were prepared and applied to the water surface. Surface pressure isotherm cycles demonstrated a significant improvement in film stability with the inclusion of the polymer. Viscoelastic properties were measured using canal viscometry and oscillating barriers, with both methods showing that the optimum ratio for improved properties was four octadecanoic acid molecules to one DADMAC unit (1:0.25). At this ratio it is expected multiple strong ionic interactions are formed along each polymer chain. Brewster angle microscopy showed decreased domain size with increased ratios of polyDADMAC, indicating that the polymer is interspersed across the surface. This new method to stabilize and increase the viscoelastic properties of charged monolayer films, using a premixed composition, will have application in areas such as water evaporation mitigation, optical devices, and foaming.