Phosphonium ionic liquids as lubricants for aluminium-steel

The performance of a series of novel room temperature ionic liquids (ILs) based on the trihexyl(tetradecyl)phosphoniumcation (P66614 +) and a number of novel anions have been studied in pin-on-disk tests using a 100Cr6 steel ball on AA2024 aluminium disks.

The anions coupled to the (P66614 +) cation include diphenyl phosphate (DPP-), dibutyl phosphate (DBP-), bis (2,4,4-trimethyl pentyl) phosphinate (M3PPh-) and bis(2-ethyl hexyl) phosphate (BEH-).

More traditional anions such as bis(trifluoromethanesulfonyl) amide (NTf2 -) and bromide (Br-) were also investigated. Experiments were conducted at various loads to assess the IL film forming abilities.

The results suggest that the structure of the anion is important in forming a surface film that reduces the friction and wear of the aluminium disk. At 30N five of the six ILs tested showed a 30-90% reduction in wear, as determined from wear scar depth measurements, compared to fully formulated diesel oil.

The IL lubricant with a diphenyl phosphate anion achieved the lowest wear coefficient, showing a better performance than a typical fluorine-containing IL anion, NTf2.

To further investigate wear mechanisms and surface interactions the wear scars were analysed using a scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS).

High performance liquid chromatography with two simultaneous on-line antioxidant assays : evaluation and comparison of espresso coffees

The antioxidant profiles of various espresso coffees were established using HPLC with UV-absorbance detection and two rapid, simultaneous, on-line chemical assays that enabled the relative reactivity of sample components to be screened. The assays were based on (i) the colour change associated with reduction of the 2,2´-diphenyl-1-picrylhydrazyl radical (DPPH•); and (ii) the emission of light (chemiluminescence) upon reaction with acidic potassium permanganate. Results from the two approaches were similar and reflected the complex array of antioxidant species present in the samples. However, some differences in selectivity were observed. Chromatograms generated with the chemiluminescence assay contained more peaks, which was ascribed to the greater sensitivity of the reagent towards minor, readily oxidisable sample components. The three coffee samples produced closely related profiles, signifying their fundamentally similar chemical compositions and origin. Nevertheless, the overall intensity and complexity of the samples in both UV absorption and antioxidant assay chromatograms were aligned with the manufacturers description of flavour intensity and character.

Control of biodegradation of a Mg alloy in simulated body fluid

Mg alloy AZ31 is an attractive candidate for coronary artery stents, as it possesses excellent biocompatibility in human body and good mechanical properties. However, AZ31 magnesium alloys generally have poor corrosion resistance in the body environment. This paper reports on the early stages of an investigation into the corrosion mechanism and the morphology of corrosion of AZ31 in simulated body fluid (SBF). The investigation will also consider ways of improving corrosion resistance of this alloy in SBF through the use of ionic liquids. The results to date have shown that AZ31 suffers severe localized pitting corrosion in SBF. The pits mainly develop adjacent to the Al-Mn intermetallic second phase in the α matrix. Energy Dispersive X-Ray Spectroscopy results revealed the presence of Mg, O, Ca, and P in the layer of corrosion product. Treatment of the AZ31 alloy prior to corrosion testing in SBF with the ionic liquid trimethyl (butyl) phosphonium diphenyl phosphate (P1444DPP) produced some increase in the corrosion resistance of the alloy.

New 'green' corrosion inhibitors based on rare earth compounds

A series of rare earth organic compounds pioneered by our group have been shown to provide a viable alternative to theuse of chromates as corrosion inhibitors for some steel and aluminium applications. For example we have shown thatthe lanthanum 4-hydroxy cinnamate offers excellent corrosion mitigation for mild steel in aqueous environments whilerare earth diphenyl phosphates offer the best protection in the case of aluminium alloys. In both cases the protectionappears to be related to the formation of a nanometre thick interphase occurring on the surface that reduces theelectrochemical processes leading to metal loss or pitting. Very recent work has indicated that we may even be able toaddress the challenging issue of stress corrosion cracking of high strength steels. Furthermore, filiform corrosion can besuppressed when selected rare earth inhibitor compounds are added as pigments to a polymer coating. There is little doubtfrom the work thus far that a synergy exists between the rare earth and organic inhibitor components in these novelcompounds. This paper reviews some of the published research conducted by the senior author and colleagues over the past10 years in this developing field of green corrosion inhibitors

Chromate replacement in coatings for corrosion protection of aerospace aluminium alloys

Mixed rare earth organophosphates have been investigated as potential corrosion inhibitors for AA2024-T3 with the aim of replacing chromate-based technologies. Cerium diphenyl phosphate (Ce(dpp) 3) and mischmetal diphenyl phosphate (Mm(dpp) 3) were added to epoxy coatings applied to AA2024-T3 panels and they were effective in reducing the amount and rate of filiform corrosion in high humidity conditions. Ce(dpp) 3 was the most effective and characterisation of the coating formulations showed approximately a factor of 5 reduction in both the number of corrosion filaments initiated as well as the length of these. Mm(dpp) 3 appeared to reduce the corrosion growth rate by a factor of 2 although it was the more effective inhibitor in solution studies. Spectroscopic characterisation of the coatings indicated that the cerium based inhibitor may disrupt network formation in the epoxy thus resulting in a coating that absorbed more water and allowed greater solubilisation of the corrosion inhibiting compound.

Oxygen-dependence of metabolic rate in the muscles of craniates

We present evidence that oxygen consumption (V_O2 ) is oxygen partial pressure (P_O2) dependent in striated muscles and P_O2 -independent in the vasculature in representatives of three craniate taxa: two teleost fish, a hagfish and a rat. Blood vessel V_O2 displayed varying degrees of independence in a P_O2 range of 15–95 mmHg, while V_O2 by striated muscle tissue slices from all species related linearly to P_O2 between 0 and 125 mmHg, despite V_O2 rates varying greatly between species and muscle type. In salmon red muscle, lactate concentrations fell in slices incubated at a P_O2 of either 30 or 100 mmHg, suggesting aerobic rather than anaerobic metabolism. Consistent with this finding, potential energy, a proxy of ATP turnover, was P_O2 -dependent. Our data suggest that the reduction in V_O2 with falling P_O2 results in a decrease in ATP demand, suggesting that the hypoxic signal is sensed and cellular changes effected. Viability and diffusion limitation of the preparations were investigated using salmon cardiac and skeletal muscles. Following the initial P_O2 depletion, reoxygenation of the Ringer bathing salmon cardiac muscle resulted in V_O2^s that was unchanged from the first run. V_O2 increased in all muscles uncoupled with p-trifluoromethoxylphenyl-hydrazone (FCCP) and 2,4-dinitrophenol (DNP). Mitochondrial succinate dehydrogenase activity, quantified by reduction of 3-(4,5-dimethylthiazol)-2,5-diphenyl-2H-tetrazolium bromide (MTT) to formazan, was constant over the course of the experiment. These three findings indicate that the tissues remained viable over time and ruled out diffusion-limitation as a constraint on V_O2.

Oxygen consumption and blood flow distribution in perfused skeletal muscle of chinook salmon

An isolated, perfused salmon tail preparation showed oxyconformance at low oxygen delivery rates. Addition of pig red blood cells to the perfusing solution at a haematocrit of 5 or 10% allowed the tail tissues to oxyregulate. Below ca. 60 ml O₂ kg⁻¹ h⁻¹ of oxygen delivery (DO₂), VO₂ was delivery dependent. Above this value additional oxygen delivery did not increase VO₂ of resting muscle above ca. 35 ml O₂ kg⁻¹ h⁻¹. Following electrical stimulation, VO₂ increased to ca. 65 ml O₂ kg⁻¹ h⁻¹, with a critical DO₂ of ca. 150 ml O₂ kg⁻¹ h⁻¹. Dorsal aortic pressure fell to 69% of the pre-stimulation value after 5 min of stimulation and to 54% after 10 min. Microspheres were used to determine blood flow distribution (BFD) to red (RM) and white muscle (WM) within the perfused myotome. Mass specific BFD ratio at rest was found to be 4.03 ± 0.49 (RM:WM). After 5 min of electrical stimulation the ratio did not change. Perfusion with saline containing the tetrazolium salt 3-(4,5-Dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) revealed significantly more mitochondrial activity in RM. Formazan production from MTT was directly proportional to time of perfusion in both red and WM. The mitochondrial activity ratio (RM:WM) did not change over 90 min of perfusion.

On corrosion behaviour of magnesium alloy AZ31 in simulated body fluids and influence of ionic liquid pretreatments

This paper reports on the corrosion of Mg alloy AZ31 in simulated body fluid (SBF) using static immersion tests and electrochemical impedance spectroscopy. A preliminary study on the effect of flowing SBF on the corrosion behaviour of AZ31 has also been carried out. Low toxicity ionic liquids (ILs) trimethyl(butyl)phosphonium diphenyl phosphate P1444DPP and trihexyl(tetradecyl)-phosphonium bis-2,4,4trimethylpentyl-phosphinate [P66614][ i(C8) 2PO2] have been used to provide corrosion protection for AZ31 in SBF. Time dependent immersion tests indicate that under static conditions, AZ31 suffers severe localised corrosion in SBF, with pits developing predominantly beside the Al-Mn intermetallic phase in the α matrix. At longer immersion times, the corrosion product eventually precipitates and covers the entire specimen surface. When exposed to SBF under flowing conditions with a shear stress of 0·88 Pa, more uniform corrosion was observed. The optical profilometry results and electrochemical impedance spectroscopy analysis suggest that both P
1444DPP and [P66614][i(C8)2PO2] pretreatments can increase the corrosion resistance of AZ31 in SBF, in particular by decreasing the number of deeper pits found on the alloy surface. Cytotoxic test shows that the presence of the ILs P
1444DPP and [P66614][i(C8)2PO2] in cell culture media slightly inhibits the growth of human coronary artery endothelial cells in comparison with the good cell viability around the treated specimen. A pretreatment with IL is used in order to improve the corrosion resistance of this alloy in SBF. © 2012 Institute of Materials, Minerals and Mining.

Ionic liquid pretreatment as a means to control the corrosion behavior of magnesium alloys in simulated body fluid

Recently, the use of magnesium alloys as metallic implant materials for biodegradable coronary artery stents has been steadily growing in interest. However, AZ31 magnesium alloys present poor corrosion resistance in the body environment. This work reports on the use of a treatment with low-toxicity IL Trimethyl (butyl) phosphonium diphenyl phosphate P₁₄₄₄DPP, which provides corrosion protection for magnesium alloy AZ31 in simulated body fluid (SBF). Before IL treatment, surface was cleaned by HNO₃ and H₃PO₄ acid pickling solution. The effect of ionic liquid treatment on the corrosion performance of magnesium alloys AZ31in simulated body fluid has been investigated by electrochemical tests and the observation of surface morphology. The results show that this IL treatment succeeded in increasing the corrosion resistance of AZ31 when exposed to SBF.

Recent developments in corrosion inhibitors based on rare earth metal compounds

Rare earth organic compounds can provide an environmentally safe and non-toxic alternative to chromates as corrosion inhibitors for some steel and aluminium applications. For steel lanthanum 4-hydroxy cinnamate offers corrosion protection and reduces the susceptibility to hydrogen embrittlement. Recent work has also indicated that it inhibits the corrosion of steel in environments containing high levels of carbon dioxide. For aluminium alloys, cerium diphenyl phosphate provides excellent corrosion inhibition in chloride environments, and reduces susceptibly to stress corrosion cracking. Furthermore, for both steel and aluminium alloys filiform corrosion can be suppressed when rare earth inhibitor compounds are added as pigments to polymer coatings. The levels of inhibition observed are thought to be due to synergistic effects between the rare earth and organic parts of these novel compounds, and are related to the various species that may be present in the complex chemical conditions that develop in solution close to a metal surface. This paper reviews some of the published research conducted by the group at Deakin University over recent years.

The corrosion inhibition of aluminium alloy 7075-T651 with cerium and Mischmetal di phenyl phosphate

Previous studies have shown that cerium diphenyl phosphate (Cedpp) 3 is a very effective inhibitor of corrosion of aluminium alloys in chloride solutions. This paper describes the results of further studies using electrochemical and constant immersion corrosion tests to compare the effectiveness of Ce(dpp) 3 and Mischmetal diphenyl phosphate Mm(dpp) 3 as inhibitors of corrosion pitting on AA7075-T651 aluminium alloy. The results shows that both Ce(dpp) 3 and Mm(dpp) 3 are excellent inhibitors of pitting corrosion of this alloy in very aggressive environments of continuously aerated 0.1M and 1.0M sodium chloride (NaCl) solutions. Polarisation tests indicate that these compounds act as a cathodic inhibitors by reducing the rate of the oxygen reduction reaction, which results in a decreased corrosion current density and a separation of the corrosion potential from the pitting potential. This inhibition is thought to be due to the formation of a surface film consisting of rare earth metal oxide, aluminium oxide and a cerium-aluminium organo-phosphate complex. Surface analysis data from scanning electron microscopy and X-ray Energy Dispersive Spectroscopy show the complex nature of this protective film. This work further develops our understanding about the mechanisms through which these complex films form, and how inhibition occurs in the presence of these compounds.

Recent developments in corrosion inhibitors based on rare earth metal compounds

Rare earth organic compounds can provide an environmentally safe and non-toxic alternative to chromates as corrosion inhibitors for some steel and aluminium applications. For steel lanthanum 4-hydroxy cinnamate offers corrosion protection and reduces the susceptibility to hydrogen embrittlement. Recent work has also indicated that it inhibits the corrosion of steel in environments containing high levels of carbon dioxide. For aluminium alloys, cerium diphenyl phosphate provides excellent corrosion inhibition in chloride environments, and reduces susceptibly to stress corrosion cracking. Furthermore, for both steel and aluminium alloys filiform corrosion can be suppressed when rare earth inhibitor compounds are added as pigments to polymer coatings. The levels of inhibition observed are thought to be due to synergistic effects between the rare earth and organic parts of these novel compounds, and are related to the various species that may be present in the complex chemical conditions that develop in solution close to a metal surface. This paper reviews some of the published research conducted by the group at Deakin University over recent years.©2014 Institute of Materials, Minerals and Mining.

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.