A comparison of phosphorus and fluorine containing IL lubricants for steel on aluminium

Ionic liquids have been shown to be highly effective lubricants for a steel on aluminium system. This work shows that the chemistry of the anion and cation are critical in achieving maximum wear protection. The performance of the ILs containing a diphenylphosphate (DPP) anion all showed low wear, as did some of the tris(pentafluoroethyl)trifluorophosphate (FAP) and bis(trifluoromethanesulfonyl)amide (NTf2) anion containing ILs. However, in the case of the FAP and NTf2 based systems, a cation dependence was observed, with relatively poor wear resistance obtained in the case of an imidazolium FAP and two pyrrolidinium NTf2 salts, probably due to tribocorrosion caused by the fluorine reaction with the aluminium substrate. The systems exhibiting poor performance generally had a lower viscosity, which also impacts on their tribological properties. Those ILs that exhibited low wear were shown to have formed protective tribofilms on the aluminium alloy surface.

Tri-component bio-composite materials prepared using an eco-friendly processing route

We report on the blending of three natural polymers, raw cotton, silk and wool, using ionic liquids as the dissolving media. We find that with increased content of wool and silk the thermal degradation temperature of the new bio films increases. This is due to an increase in the hydrogen bond network between the blended polymers. We also investigated the role of the coagulating solvent by coagulating the bio films using water, methanol or isopropanol. Again, we find the coagulating solvent impacts the final properties of the bio films with water shown to coagulated films with the best material properties.

Preliminary investigations into triazole derived androgen receptor antagonists

A range of 1,4-substituted-1,2,3-N-phenyltriazoles were synthesized and evaluated as non-steroidal androgen receptor (AR) antagonists. The motivation for this study was to replace the N-phenyl amide portion of small molecule antiandrogens with a 1,2,3-triazole and determine effects, if any, on biological activity. The synthetic methodology presented herein is robust, high yielding and extremely rapid. Using this methodology a series of 17 N-aryl triazoles were synthesized from commercially available starting materials in less than 3h. After preliminary biological screening at 20 and 40 μM, the most promising three compounds were found to display IC50 values of 40-50 μM against androgen dependent (LNCaP) cells and serve as a starting point for further structure-activity investigations. All compounds in this work were the focus of an in silico study to dock the compounds into the human androgen receptor ligand binding domain (hARLBD) and compare their predicted binding affinity with known antiandrogens. A comparison of receptor-ligand interactions for the wild type and T877A mutant AR revealed two novel polar interactions. One with Q738 of the wild type site and the second with the mutated A877 residue.

Zn electrochemistry in 1-Ethyl-3-Methylimidazolium and N-Butyl-N-Methylpyrrolidinium Dicyanamides: promising new rechargeable Zn battery electrolytes

 We have studied both 1-ethyl-3-methylimidazolium (C2mim) and N-butyl-N-methylpyrrolidinium (C4mpyr) dicyanamide (dca) ionic liquids (ILs) containing 3 wt % H2O and 9 mol % Zn(dca)2 salt for their ability to support Zn0/2+ electrochemistry in the context of a rechargeable Zn battery. Despite the similarities of the two IL electrolyte systems [identical H2O and Zn(dca)2 contents], the system based on [C2mim] supported much higher current densities for Zn electrochemistry at greatly reduced overpotentials [−0.23 V vs. Zn pseudo-reference, 32 mA cm−2 (red) and 61 mA cm−2 (ox)] compared to the [C4mpyr]-based electrolyte [−0.84 V vs. Zn pseudo-reference, 8 mA cm−2 (red) and 15 mA cm−2 (ox)]. The overpotential for Zn deposition is reduced by 0.13 V on Zn metal surfaces compared to glassy carbon (GC), regardless of the electrolyte used. The morphologies of the Zn deposits on both GC and Zn surfaces were also studied. The Zn surfaces promote a deposition that displays a smooth morphology, resulting from an instantaneous nucleation mechanism demonstrated by chronoamperometric experiments. Finally, both [C2mim] and [C4mpyr] electrolytes were tested in symmetrical Zn|Zn cells, where it was determined that the [C2mim] system could sustain over 90 cycles at 0.1 mA cm−2, whereas the [C4mpyr] based system could only achieve 15 cycles at the more modest current density of 0.05 mA cm−2.

Exploring zinc coordination in novel zinc battery electrolytes

The coordination of zinc ions by tetraglyme has been investigated here to support the development of novel electrolytes for rechargeable zinc batteries. Zn(2+) reduction is electrochemically reversible from tetraglyme. The spectroscopic data, molar conductivity and thermal behavior as a function of zinc composition, between mole ratios [80 : 20] and [50 : 50] [tetraglyme : zinc chloride], all suggest that strong interactions take place between chloro-zinc complexes and tetraglyme. Varying the concentration of zinc chloride produces a range of zinc-chloro species (ZnClx)(2-x) in solution, which hinder full interaction between the zinc ion and tetraglyme. Both the [70 : 30] and [50 : 50] mixtures are promising electrolyte candidates for reversible zinc batteries, such as the zinc-air device.

An improved understanding of the dispersion of multi-walled carbon nanotubes in non-aqueous solvents

The homogeneous and stable dispersion of carbon nanotubes (CNTs) in solvents is often a prerequisite for their use in advanced materials. Dispersion procedures, reagent concentration as well as the interactions among reagent, defective CNTs and near-perfect CNTs will affect the resulting CNT dispersion properties. This study, for the first time, presents a detailed comparison between two different approaches for dispersing CNTs. The results enhance our understanding of the interactions between surfactant, defective CNTs and near-perfect CNTs and thus provide insight into the mechanism of CNT dispersion. Dispersions of "as-produced" short multi-walled carbon nanotubes (MWCNTs) in N,N-dimethylformamide were prepared by two different surfactant (Triton X-100) assisted methods: ultrasonication and ultrasonication followed by centrifugation, decanting the supernatant and redispersing the precipitate. Visual observation and UV-visible spectroscopy results showed that the latter method produce a more stable dispersion with higher MWCNT content compared to dispersions produced by ultrasonication alone. Transmission electron microscopy and Raman spectroscopic investigations revealed that the centrifugation/ decanting step removed highly defective nanotubes, amorphous carbon and excess surfactant from the readily re-dispersible near-perfect CNT precipitate. This is contrary to other published findings where the dispersed MWCNTs were found in the supernatant. Thermogravimetric analysis showed that 95 % of Triton X-100 was removed by centrifugation/decanting step, and the remainder of the Triton X-100 molecules is likely randomly adsorbed onto the MWCNT surface. Infrared spectral analysis suggests that the methylene groups of the polyoxyethylene (aliphatic ether) chains of the residual Triton X-100 molecules are interacting with the MWCNTs. © 2014 Springer Science+Business Media.

Study on nanocellulose by high pressure homogenization in homogeneous isolation

Nanocellulose from cotton cellulose was prepared by high pressure homogenization (HPH) in ionic liquids (1-butyl-3-methylimidazolium chloride ([Bmim]Cl). The nanocellulose possessed narrow particle size distribution, with diameter range of 10–20 nm. Weight average molecular weight (Mw) of nanocellulose treated by HPH was lower (173.8 kDa) than the one ILs treated cellulose (344.6 kDa). X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), and Solid-state CP/MAS 13C NMR measurements were employed to study the mechanism of structural changes, which suggested that network structure between cellulose chains were destructed by the shearing forces of HPH in combination with ionic liquids. The intermolecular and intra-molecular hydrogen bonds of cellulose were further destroyed, leading to the long cellulose molecular chains being collapsed into short chains. Therefore, the nanocellulose could provide desired properties, such as lower thermal stability and strong water holding capacity. Results indicated that it had great potential in the applications for packaging, medicines, cosmetics and tissue engineering.

The Influence of water and metal salt on the transport and structural properties of 1-Octyl-3-methylimidazolium Chloride

The addition of diluents to ionic liquids (ILs) has recently been shown to enhance the transport properties of ILs. In the context of electrolyte design, this enhancement allows the realisation of IL-based electrolytes for metal-air batteries and other storage devices. It is likely that diluent addition not only impacts the viscosity of the IL, but also the ion-ion interactions and structure. Here, we investigate the nano-structured 1-methyl-3-octylimidazolium chloride (OMImCl) with varying water concentrations in the presence of two metal salts, zinc chloride and magnesium chloride. We find that the choice of metal salt has a significant impact on the structure and transport properties of the system; this is explained by the water structuring and destructing properties of the metal salt.

Ductile thermoset polymers via controlling network flexibility

We report the design and synthesis of a polymer structure from a cross-linkable epoxy-ionic liquid system which behaves like a hard and brittle epoxy thermoset, perfectly ductile thermoplastic and an elastomer, all depending on controllable network compositions.

Evaluation of electrochemical methods for determination of the seebeck coefficient of redox electrolytes

Recent advances in thermoelectrochemical cells, which are being developed for harvesting low grade waste heat, have shown the promise of cobalt bipyridyl salts as the active redox couple. The Seebeck coefficient, Se, of a redox couple determines the open circuit voltage achievable, for a given temperature gradient, across the thermoelectrochemical cell. Thus, the accurate determination of this thermodynamic parameter is key to the development and study of new redox electrolytes. Further, techniques for accurate determination of Se using only one half of the redox couple reduces the synthetic requirements. Here, we compare three different experimental techniques for measuring Se of a cobalt tris(bipyridyl) redox couple in ionic liquid electrolytes. The use of temperature dependent cyclic voltammetry (CV) in isothermal and non-isothermal cells was investigated in depth, and the Se values compared to those from thermo-electromotive force measurements. Within experimental error, the Se values derived from CV methods were found to be in accordance with those obtained from electromotive force (emf) measurements. The applicability of cyclic voltammetry techniques for determining Se when employing only one part of the redox couple was demonstrated.

Síntese e caracterização do líquido iônico tetrafluoroborato de 1-metil-3-(2,6-(S)-dimetiloct-2-eno)-imidazol como eletrólito para produção de hidrogênio via eletrólise da água

Ionic liquids (ILs) are organic compounds liquid at room temperature, good electrical conductors, with the potential to form as a means for electrolyte on electrolysis of water, in which the electrodes would not be subjected to such extreme conditions demanding chemistry [1]. This paper describes the synthesis, characterization and study of the feasibility of ionic liquid ionic liquid 1-methyl-3(2,6-(S)-dimethyloct-2-ene)-imidazole tetrafluoroborate (MDI-BF4) as electrolyte to produce hydrogen through electrolysis of water. The MDI-BF4 synthesized was characterized by thermal methods of analysis (Thermogravimetric Analysis - TG and Differential Scanning Calorimetry - DSC), mid-infrared spectroscopy with Fourier transform by method of attenuated total reflectance (FTIR-ATR), nuclear magnetic resonance spectroscopy of hydrogen (NMR 1H) and cyclic voltammetry (CV). Where thermal methods were used to calculate the yield of the synthesis of MDI-BF4 which was 88.84%, characterized infrared spectroscopy functional groups of the compound and the binding B-F 1053 cm-1; the NMR 1H analyzed and compared with literature data defines the structure of MDI-BF4 and the current density achieved by MDI-BF4 in the voltammogram shows that the LI can conduct electrical current indicating that the MDI-BF4 is a good electrolyte, and that their behavior does not change with the increasing concentration of water

Estudo do equilíbrio líquido-vapor do sistema água+etanol+líquido iônico visando a separação do álcool anidro

Anhydrous ethanol is used in chemical, pharmaceutical and fuel industries. However, current processes for obtaining it involve high cost, high energy demand and use of toxic and pollutant solvents. This problem occurs due to the formation of an azeotropic mixture of ethanol + water, which does not allow the complete separation by conventional methods such as simple distillation. As an alternative to currently used processes, this study proposes the use of ionic liquids as solvents in extractive distillation. These are organic salts which are liquids at low temperatures (under 373,15 K). They exhibit characteristics such as low volatility (almost zero/ low vapor ), thermal stability and low corrosiveness, which make them interesting for applications such as catalysts and as entrainers. In this work, experimental data for the vapor pressure of pure ethanol and water in the pressure range of 20 to 101 kPa were obtained as well as for vapor-liquid equilibrium (VLE) of the system ethanol + water at atmospheric pressure; and equilibrium data of ethanol + water + 2-HDEAA (2- hydroxydiethanolamine acetate) at strategic points in the diagram. The device used for these experiments was the Fischer ebulliometer, together with density measurements to determine phase compositions. The experimental data were consistent with literature data and presented thermodynamic consistency, thus the methodology was properly validated. The results were favorable, with the increase of ethanol concentration in the vapor phase, but the increase was not shown to be pronounced. The predictive model COSMO-SAC (COnductor-like Screening MOdels Segment Activity Coefficient) proposed by Lin & Sandler (2002) was studied for calculations to predict vapor-liquid equilibrium of systems ethanol + water + ionic liquids at atmospheric pressure. This is an alternative for predicting phase equilibrium, especially for substances of recent interest, such as ionic liquids. This is so because no experimental data nor any parameters of functional groups (as in the UNIFAC method) are needed

BIOMOLECULES EXTRACTED BY ATPS: PRACTICAL EXAMPLES

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)