Anthony Somers

Novel halogen-free chelated orthoborate–phosphonium ionic liquids: synthesis and tribophysical properties

We report on the synthesis, characterisation, and physical and tribological properties of halogen-free ionic liquids based on various chelated orthoborate anions with different phosphonium cations, both without halogen atoms in their structure. Important physical properties of the ILs including glass transition temperatures, density, viscosity and ionic conductivity were measured and are reported here. All of these new halogen-free orthoborate ionic liquids (hf-BILs) are hydrophobic and hydrolytically stable liquids at room temperature. As lubricants, these hf-BILs exhibit considerably better antiwear and friction reducing properties under boundary lubrication conditions for steel-aluminium contacts as compared with fully formulated (15W-50 grade) engine oil. Being halogen free these hf-BILs offer a more environmentally benign alternative to ILs being currently developed for lubricant applications.

Ionic Liquids as Antiwear Additives in Base Oils: Influence of Structure on Miscibility and Antiwear Performance for Steel on Aluminum

The use of ionic liquids as additives to base oil for the lubrication of steel on aluminum was investigated. The miscibility and wear performance of various phosphonium, imidazolium, and pyrrolidinium ionic liquids in a range of polar and nonpolar base oils was determined. The structure and ion pairing of the ionic liquids was found to be important in determining their miscibility in the base oils. In wear tests, some of the miscible base oil/IL blends reduced the aluminum wear depth when compared to that found with the base oil alone. The nonpolar base oil/IL blends were able to withstand higher wear-test loads than the polar base oil/IL blends. At 10 N, as little as 0.01 mol/kg of IL, or 0.7-0.9 wt %, in the nonpolar base oils was enough to drastically reduce the wear depth on the aluminum. XPS analysis of the wear surfaces suggested that the adsorbing of the IL to the surface, where it can form low-shear layers and also react to form tribofilms, is important in reducing friction and wear. The largest reductions in wear at the highest load tested were found for a mineral oil/P6,6,6,14 (i)(C8)2PO2 blend.

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 (NTf(2)) anion containing ILs. However, in the case of the FAP and NTf(2) based systems, a cation dependence was observed, with relatively poor wear resistance obtained in the case of an imidazolium FAP and two pyrrolidinium NTf(2) 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.

Quantifying rubber degradation using NMR

Ageing can lead to the degradation of the tensile properties of natural rubber. The ageing process causes changes in the polymer segmental motion as well as the chemical structure, both of which can be monitored using nuclear magnetic resonance (NMR) spectroscopy. This work demonstrates that NMR can quantify rubber degradation due to ageing, and also that relatively simple NMR equipment can be used. This simpler equipment can be made portable and so could give a simple and fast indication of the condition of rubber in service. The 1H NMR transverse relaxation time, T2, and the 13C NMR spectrum using cross polarization and magic angle spinning (CP MAS) for samples taken at various levels of a degraded natural rubber liner were compared. These experiments showed that, as the level of degradation increased, the 1H NMR transverse relaxation time decreased. The 13C spectra showed considerable peak broadening, indicative of decreased mobility with increased level of degradation as well as the presence of degradation products. Further investigations using lower powered NMR equipment to measure the 1H NMR transverse relaxation times of two different series of natural rubbers were also performed. This work has shown that this simpler method is also sensitive to structural and mechanical property changes in the rubber. This method of monitoring rubber degradation could lead to the non-destructive use of NMR to determine the condition of a part in service.

Ionic Liquid Adsorption and Nanotribology at the Silica-Oil Interface : Hundred-Fold Dilution in Oil Lubricates as Effectively as the Pure Ionic Liquid

The remarkable physical properties of ionic liquids (ILs) make them potentially excellent lubricants. One of the challenges for using ILs as lubricants is their high cost. In this article, atomic force microscopy (AFM) nanotribology measurements reveal that a 1 mol % solution of IL dissolved in an oil lubricates the silica surface as effectively as the pure IL. The adsorption isotherm shows that the IL surface excess need only be approximately half of the saturation value to prevent surface contact and effectively lubricate the sliding surfaces. Using ILs in this way makes them viable for large-scale applications.

Surface-scribed transparency-based microplates

Transparency sheets, which are normally associated with use on overhead projectors, offer lowered costs and high amenability for optical diagnostics in microplate instrumentation. An alternative microplate design in which circles are scribed on the surface of the transparency to create the boundaries to hold the drop in place is investigated here. The 3D profile of the scribed regions obtained optically showed strong likelihood of affecting three-phase contact line interactions. During dispensation, the contact angle (≈95°) was larger than the drop advancing state (≈80°) due to a period of nonadhesion, where the contact angle later reduced to the drop advancing state followed by increase in the liquid area coverage on the substrate. It was established that 50 μL was needed to fill the well fully, and the maximum volume retainable before breaching was 190 μL. While the tilt angle needed for displacement reduced significantly from 50 to 95 μL, this was markedly better than nonscribed surfaces, where tilt angles always had to be kept to within 30°. It was found that there was greater ability to fill the well with smaller volumes with dispensation at the center. This was attributed to the growing contact line not meeting the scribed edge in parallel if liquid was dispensed closer to it, wherein pinning reduction in some directions permitted liquid travel along the scribed edge to undergo contact angle hysteresis. Fluorescence measurements conducted showed no performance compromise when using scribed transparency microplates over standard microplates.

In-Situ-Activated N-Doped Mesoporous Carbon from a Protic Salt and Its Performance in Supercapacitors

Protic salts have been recently recognized to be an excellent carbon source to obtain highly ordered N-doped carbon without the need of tedious and time-consuming preparation steps that are usually involved in traditional polymer-based precursors. Herein, we report a direct co-pyrolysis of an easily synthesized protic salt (benzimidazolium triflate) with calcium and sodium citrate at 850 °C to obtain N-doped mesoporous carbons from a single calcination procedure. It was found that sodium citrate plays a role in the final carbon porosity and acts as an in situ activator. This results in a large surface area as high as 1738 m2/g with a homogeneous pore size distribution and a moderate nitrogen doping level of 3.1%. X-ray photoelectron spectroscopy (XPS) measurements revealed that graphitic and pyridinic groups are the main nitrogen species present in the material, and their content depends on the amount of sodium citrate used during pyrolysis. Transmission electron microscopy (TEM) investigation showed that sodium citrate assists the formation of graphitic domains and many carbon nanosheets were observed. When applied as supercapacitor electrodes, a specific capacitance of 111 F/g in organic electrolyte was obtained and an excellent capacitance retention of 85.9% was observed at a current density of 10 A/g. At an operating voltage of 3.0 V, the device provided a maximum energy density of 35 W h/kg and a maximum power density of 12 kW/kg.

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).

Evaporative micro-particle self assembly influenced by capillary evacuation.

As evaporation does not incur energy introduction, the droplet coffee-stain patterning approach is attractive for biochemical tests conducted in the field or in third world environments. A practical strategy uses chemically functionalized microbeads for the coffee stain deposition process. From an application perspective, it will be necessary to minimize the coffee stain deposition time, as evaporation, depending on the volume of the droplet, can be a slow process. The introduction of a porous media will generate a capillary flow (or wicking) that removes any remnant liquid in the droplet, thus permitting it to be done inexpensively and in the field. Using optical profilometry, we were able to establish that polystyrene microspheres developed more copious and defined single ring coffee depositions than silica of the same size and concentration in a suspension. In analyzing the droplet capillary evacuation process with a porous media, we found the liquid bridge formed during the later stages to rupture and leave behind some liquid material for a second stage evaporation process. This was responsible for a two ring structure that was more visible with silica microspheres. A high degree of hysteresis of the contact angle was found to develop at the contact line in which values below 5° could be achieved. Dynamic observations showed the copious and dense packing of polystyrene particles to be more resistant to ring break up from the evacuation flow. Nevertheless, erosion of the back array portions of the ring was evident notwithstanding either type of microsphere used.

Addition of low concentrations of an ionic liquid to a base oil reduces friction over multiple length scales: a combined nano- and macrotribology investigation

The efficacy of ionic liquids (ILs) as lubricant additives to a model base oil has been probed at the nanoscale and macroscale as a function of IL concentration using the same materials. Silica surfaces lubricated with mixtures of the IL trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate and hexadecane are probed using atomic force microscopy (AFM) (nanoscale) and ball-on-disc tribometer (macroscale). At both length scales the pure IL is a much more effective lubricant than hexadecane. At the nanoscale, 2.0 mol% IL (and above) in hexadecane lubricates the silica as well as the pure IL due to the formation of a robust IL boundary layer that separates the sliding surfaces. At the macroscale the lubrication is highly load dependent; at low loads all the mixtures lubricate as effectively as the pure IL, whereas at higher loads rather high concentrations are required to provide IL like lubrication. Wear is also pronounced at high loads, for all cases except the pure IL, and a tribofilm is formed. Together, the nano- and macroscales results reveal that the IL is an effective lubricant additive - it reduces friction - in both the boundary regime at the nanoscale and mixed regime at the macroscale.