INNOVATIVE APPLICATIONS OF IONIC LIQUIDS AS “GREEN” ENGINEERING LIQUIDS

Over the past decade, ionic liquids (ILs) have become one of the fastest growing “green” media for chemists and engineers due to their superb physicochemical properties. The applications of these remarkable salts in reactions and extraction processes have been extensively investigated and reviewed. This review, however, highlights recent advances of ILs as versatile “green” engineering liquids in a variety of industrial applications including heat transfer fluids, azeotrope-breaking liquids, lubricants, electrolytes, liquid crystals, supported IL membranes, plasticizers, and more. This review is not intended to be comprehensive, but rather to discuss the potentials of ILs for diverse industrial applications.     

Control of local friction of metal/ceramic contacts in aqueous solutions with an electrochemical method

Ball-on-plate sliding friction experiments were designed and performed to show the possibility of local friction control by electrochemical methods. By partitioning a metal plate into charged and uncharged zones, the friction coefficient in these zones can be differential when an external voltage is applied during rubbing. It is also possible to achieve differential friction at different locations of contact by arranging the position of the auxiliary electrode on which the range of electrochemical effects on friction depends. The morphological differences in the worn surfaces between the different zones are given, together with a discussion on the principles of the electrochemical control of friction.     

Direct observation of the interface during sliding tribo-corrosion

A new test apparatus has been developed to allow the sliding interface between the inert and “active” surfaces during tribo-corrosion to be viewed directly. This apparatus allows the nominal contact area to be viewed and will, it is hoped, eventually allow the real contact area and the role of wear debris to be clearly revealed. Initial experiments reciprocating glass plates against AISI 316 balls in 0.1 M Na₂SO₄ have shown that the corrosion current does not linearly depend on the wear scar area and that the electrochemical contribution to the total material loss increases with increasing sliding distance.     

Electrochemical degradation of bisphenol A on different anodes

Laboratory experiments were carried out on the kinetics, pathways and mechanisms of electrochemical (EC) degradation of bisphenol A (BPA) on four types of anodes, Ti/boron-doped diamond (BDD), Ti/Sb-SnO₂, Ti/RuO₂ and Pt. There were considerable differences among the anodes in their effectiveness and performance of BPA electrolysis. BPA was readily destructed at the Ti/Sb-SnO₂ and Ti/BDD anodes, the Pt anode had a moderate ability to remove BPA, and the Ti/RuO₂ anode was incapable of effectively oxidising BPA. The intermediate products of EC degradation of BPA were detected and quantified by high-performance liquid chromatography (HPLC), and a general BPA degradation pathway was proposed based on the analytical results. It was suggested that OH radicals produced by water electrolysis attacked BPA to form hydroxylated BPA derivatives that were then transformed into one-ring aromatic compounds. These compounds underwent ring breakage, which led to the formation of aliphatic acids that were eventually mineralised by electrolysis to CO₂. Compared to the Pt and Ti/RuO₂ anodes, the Ti/Sb-SnO₂ and Ti/BDD anodes were found to have higher oxygen evolution potentials and higher anodic potentials for BPA electrolysis under the same current condition. However, the stability and durability of the Ti/Sb-SnO₂ anode still needs to be greatly improved for actual application. In comparison, with its high durability and good reactivity for organic oxidation, the Ti/BDD anode appears to be the more promising one for the effective EC treatment of BPA and similar endocrine disrupting chemical (EDC) pollutants.     

Electroluminescent zinc sulphide devices produced by sol-gel processing

Zinc sulphide thin film electroluminescent devices doped with Mn or Tb have been produced on p-type Si substrates using a process in which doped zinc oxide films are deposited by a sol-gel drain coating method from a solution of zinc acetate containing a manganese or terbium dopant. The films are then converted to ZnS by heating them in an atmosphere containing hydrogen sulphide which replaces the oxygyn with sulphur. The composition, crystalline structure and optical properties of films have shown that complete conversion from the oxide to the sulphide takes place. The luminescent characteristics of the devices so produced have been measured as a function of the doping concentrations, film thickness, insulator thickness and driving voltage and frequency. It has been found that yellow or green luminescence can be obtained using Mn or Tb doping respectively.     

Cover Picture: UV‐Light‐Induced Swelling and Visible‐Light‐Induced Shrinking of a TiO2‐Containing Redox Gel (Adv. Mater. 9/2007)

Polyacrylate gels containing Ag⁺ and TiO₂ nanoparticles are shown to swell under UV light and shrink under visible light in water. In work reported by Tetsu Tatsuma and co‐workers on p. 1249, the TiO₂ absorbs UV light and reduces the Ag⁺, whereas the deposited Ag absorbs visible light and dissolves itself. These redox reactions change the interactions between the polymer chains and eventually the volume of the gel, as shown on the cover.     

Electrochemical investigation and characterization of thin-film porosity

In thin-film applications it is necessary to control film properties such as homogeneity and porosity to obtain high-quality coatings. Electrochemistry can be a very helpful tool since it can provide information about processes taking place at the interface between substrate and coating. Different thin carbon-based coatings were deposited via physical vapour deposition methods and vapour phase polymerization on pure iron substrates: fullerene films, which were modified by an ion bombardment and thin films of poly(p-xylylene), which is a very good insulating polymer. The film porosity and stability of the film/substrate system against aqueous corrosion were investigated and compared using cyclic voltammetry. The dependence of porosity and film stability on various deposition process parameters such as film thickness and plasma conditions was measured via the dissolution current density and the open circuit potential shift of the substrate material. It could be shown that the two measurements, current density I_crit. and open circuit potential E_ocp. can provide useful complementary information about film porosity that can lead to a better understanding of the coatings properties and the deposition process as well.     

In-situ X-ray diffraction study of the initial dealloying of Cu3Au(001) and Cu0.83Pd0.17(001)

Dealloying and selective dissolution are serious corrosion processes, but also employed in technology. We studied the surface structure of Cu_0.83Pd_0.17(001) and Cu₃Au(001) during electrochemical selective Cu dissolution below the critical potential in-situ in 0.1 M H₂SO₄ (pH = 1) electrolyte. In both cases we observe the formation of an epitaxial layer of nano-scale islands of the noble component of the original alloy (Au or Pd). These islands form a metallic passivation layer suppressing massive dissolution of Cu. The Au islands developed {111} facets. By re-deposition of Cu ions from the electrolyte solution onto Pd islands, an epitaxial Cu layer is formed.     

Optical rotation and electron spin resonance of an electro-optically active polythiophene

A chiroptical polythiophene, is synthesized by electrolytic polymerization in a cholesteric liquid crystal electrolyte solution. The polymer displays a fingerprint texture similar to that of the cholesteric electrolyte solution. Upon electrochemical doping, the polymer displays optical rotation at wavelengths corresponding to the doping band observable in the absorption spectra. The formation of polarons on the main-chain is confirmed by electron spin resonance measurements. The results demonstrate the intermolecular chirality of polarons in this π-conjugated polymer, indicating continuum delocalized polarons are in a three-dimensional helical environment.