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.

The effect of pH on wool fiber diameter and fabric dimensions

Wool fabrics are often treated under conditions of varying pH in dyeing and finishing processes. It is known that in air the dimensions of wool fabrics change with the amount of fiber swelling at different regain. In this work, it has been shown that a similar relationship between fiber swelling and fabric dimensions existed in water at different pH values. The diameters of Merino and Corriedale wool fibers in water at different pH values were measured with an OFDA 2000 fiber diameter analyzer, fitted with a specially constructed accessory liquid cell. The results showed that the mean diameters of swollen wool fibers in water varied with pH. Minimum swelling was obtained in the range pH 5-7. It was found that the dimensions of wool fabric in water were dependent on the pH. The changes in fiber diameter in water could be attributed to changes in ionic interactions between charged acid and basic groups in wool protein with variations in pH.

Self-healing dendrimers based on ionic or hydrogen-bonding supramolecular interactions

This PhD project dealt with the development and characterisation of a number of metallo and hydrogen-bonded supramolecular dendrimers for applications in the area of self-healing materials

Microscopic interactions in nanocomposite electrolytes

Nanocomposite electrolytes of a fully amorphous trifunctional polyether (3PEG) and poly- (methylene ethylene oxide) (PMEO) have been complexed with two lithium salts and nanoparticulate (~20 nm) fillers of TiO2 and Al2O3. Addition of the fillers to the polymer salt complexes shows a significant change in the conformational modes of both polymers, especially the D-LAM region between 200 and 400 cm-1, indicating a reduced segmental flexibility of the chain. These changes are more pronounced with the use of TiO2 than Al2O3. Incorporation of the nanoparticulate fillers to the electrolytes fails to influence the degree of ion association, suggesting that the number of charge carriers available for conduction in both polymers using both LiClO4 and LiCF3SO3 is not the source of any conductivity increase. Addition of the fillers, which was seen to increase the conductivity in PEO-based systems, generally lowers the conductivity in the present PMEO systems, while the addition of TiO2 has little or no effect except in the cases of 3PEG 1.5 and 1.25 mol/kg LiClO4. In this case, 10 wt % TiO2 provides a conductivity increase of half an order of magnitude at approximately 60 °C. We also report for the first time a Raman spectroscopy investigation into the PEO-based nanocomposite electrolytes. The present results are discussed in terms of the electrostatic interactions involving dielectric properties of the fillers, of special interest being the interactions between the polymer and the fillers and between the ionic species and the fillers, when the effect of crystallization can be ignored.

NMR determination of ionic structure in plasticized polyether-urethane polymer electrolytes

Solid polymer electrolytes based on amorphous polyether-urethane networks combined with lithium or sodium salts and a low molecular weight cosolvent (plasticizer) have been investigated in our laboratories for several years. Conductivity enhancements of up to two orders of magnitude can be obtained whilst still retaining solid elastomeric properties. In order to understand the effects of the plasticizers and their mechanism of conductivity enhancement, multinuclear NMR has been employed to investigate ionic structure in polymer electrolyte systems containing NaCF₃SO₃, LiCF₃SO₃ and LiClO₃ salts.

With increasing dimethyl formamide (DMF) and propylene carbonate (PC) concentration the increasing cation chemical shift with fixed salt concentration indicates a decreasing anion-cation association consistent with an increased number of charge carriers. ¹³C chemical shift data for the same systems suggests that whilst DMF also decreases cation-polymer interactions, PC does the opposite, presumably by shielding cation-anion interactions. Temperature dependent ⁷Li spin-lattice relaxation times indicate the expected increase in ionic mobility upon plasticization with a shift of the T₁ minimum to lower temperatures. The magnitude of T₁ at the minimum increases upon addition of DMF whereas there is a slight decrease when PC is added. This also supports the suggestion that the DMF preferentially solvates the cation whereas the action of PC is limited to coulomb screening, hence freeing the anion.

An nmr investigation of ionic structure and mobility in plasticized solid polymer electrolytes

²³Na and ¹⁹F nuclear magnetic resonance spectroscopy is used to investigate the effect of plasticizer addition on ionic structure and mobility in a urethane crosslinked polyether solid polymer electrolyte. The incorporation of dimethyl formamide and propylene carbonate plasticizers in a sodium triflate/polyether system results in an upfield chemical shift for the ²³Na resonance consistent with decreased anion-cation association and increased cation-plasticizer interactions. The ¹⁹F resonances appears less susceptible to changes in chemical environment with only minor chemical shift changes recorded. Spin lattice relaxation measurements for the ¹⁹F nucleus are also reported. Two minima are observed in the relaxation measurements consistent with both an inter and intramolecular relaxation mechanism.

Synthesis and physical property characterisation of phosphonium ionic liquids based on P(O)2(OR)2− and P(O)2(R)2− anions with potential application for corrosion mitigation of magnesium alloys

Phosphonium cation based ionic liquids (ILs) have become of interest due to their unique chemical and electrochemical stability as well as their promising tribological properties. At the same time, interest has also grown in the use of phosphate and phosphinate based ionic liquids for corrosion protection of reactive metals. In this work we describe the synthesis and characterization of six novel ionic liquids based on the tetraalkylphosponium cation coupled with organophosphate and organophosphinate anions and their sulfur analogues. The conductivity and viscosity of these ILs has been measured and discussed in terms of the nature of the interactions, effect of anion basicity and the extent of ionic character. The reaction of the IL with a ZE41 magnesium aerospace alloy surface is also demonstrated.

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).

Transition in wear performance for ionic liquid lubricants under increasing load

The effect of ionic liquid (IL) lubrication for aluminium/steel systems is highly dependant on the applied load and the IL structure. This study illustrates that a change in anion of an IL lubricant results in different physicochemical properties that will alter its performance at a given load. As the load is increased there is a shift in lubricant performance and mechanism of the IL. Up to a load of 30 N the lowest wear coefficient was achieved by a phosphonium diphenylphosphate IL, whilst above 30 N a phosphonium bis(trifluoromethanesulfonyl)amide IL was able to form a more tenacious tribolayer that resulted in the lowest wear.

Halogen-free chelated orthoborate ionic liquids and organic ionic plastic crystals

Five halogen-free orthoborate salts comprised of three different cations (cholinium, pyrrolidinium and imidazolium) and two orthoborate anions, bis(mandelato)borate and bis(salicylato)borate, were synthesised and characterised by DSC, X-ray diffraction and NMR. DSC measurements revealed that glass transition points of these orthoborate salts are in the temperature range from −18 to −2 °C. In addition, it was found that [EMPy][BScB] and [EMIm][BScB] salts have solid–solid phase transitions below their melting points, i.e. they exhibit typical features of plastic crystals. Salts of the bis(salicylato)borate anion [BScB]− have higher melting points compared with corresponding salts of the bis(mandelato)borate anion [BMB]−. Single crystal X-ray diffraction crystallography (for [Chol][BScB] crystals) and solid-state multinuclear (13C, 11B and 15N) NMR spectroscopy were employed for the structural characterisation of [Chol][BScB], [EMPy][BScB] and [EMIm][BScB], which are solids at room temperature: a strong interaction between [BScB]− anions and [Chol]+ cations was identified as (i) hydrogen bonding between OH of [Chol]+ and carbonyl groups of [BScB]− and (ii) as the inductive C–Hπ interaction. In the other salt, [EMIm][BScB], anions exhibit ππ stacking in combination with C–Hπ interactions with [EMIm]+ cations. These interactions were not identified in [EMPy][BScB] probably because of the lack of aromaticity in cations of the latter system. Our data on the formation of a lanthanum complex with bis(salicylato)borate in the liquid mixture of La3+(aq) with [Chol][BScB] suggest that this class of novel ILs can be potentially used in the extraction processes of metal ions of rare earth elements.

A review of ionic liquid lubricants

Due to ever increasing demands on lubricants, such as increased service intervals, reduced volumes and reduced emissions, there is a need to develop new lubricants and improved wear additives. Ionic liquids (ILs) are room temperature molten salts that have recently been shown to offer many advantages in this area. The application of ILs as lubricants in a diverse range of systems has found that these materials can show remarkable protection against wear and significantly reduce friction in the neat state. Recently, some researchers have shown that a small family of ILs can also be incorporated into non-polar base oils, replacing traditional anti-wear additives, with excellent performance of the neat IL being maintained. ILs consist of large asymmetrical ions that may readily adsorb onto a metal surface and produce a thin, protective film under boundary lubrication conditions. Under extreme pressure conditions, certain IL compounds can also react to form a protective tribofilm, in particular when fluorine, phosphorus or boron atoms are present in the constituent ions.

Water-soluble complexes of an acrylamide copolymer and ionic liquids for inhibiting shale hydration

Here, we report water-soluble complexes of an acrylamide copolymer and ionic liquids for inhibiting shale hydration. The copolymer, denoted as PAAT, was synthesised via copolymerisation of acrylamide (AM), acrylic acid (AA) and N,N-diallyl-4-methylbenzenesulfonamide (TCDAP), and the ionic liquids used were 3-methyl imidazoliumcation-based tetrafluoroborates. X-ray diffraction showed that compared with commonly used KCl, the water-soluble complex of PAAT with 2 wt% ionic liquid 1-methyl-3-H-imidazolium tetrafluoroborate (HmimBF4) could remarkably reduce the d-spacing of sodium montmorillonite in water from 19.24 to 13.16 Å and effectively inhibit clay swelling. It was also found that the PAAT-HmimBF4 complex with 2 wt% HmimBF4 could retain 75% of the shale indentation hardness and increase the anti-swelling ratio to 85%. 13C NMR revealed that there existed interactions between PAAT and HmimBF4. Moreover, the thermal stability of the PAAT-HmimBF4 complex is superior to PAAT, suggesting that this water-soluble complex can be used to inhibit clay and shale hydration in high-temperature oil and gas wells.