Fosfoniumjonvätskor har tidigare studerats som potentiella nya avancerade smörjmedel på grund av sina unika fysikaliska egenskaper och fördelar jämfört med både traditionella smörjmedel och andra typer av jonvätskor. Dessa studier har uppvisat lovande resultat med avseende på reducering av nötning och friktion såväl som kontroll av dessa parametrar med en pålagd elektrisk potential. En multitud av frågor återstår dock att besvara om strukturering av jonarter i den skyddande gränssnittfilmen som bildas och kopplingen mellan strukturella drag i de involverade jonarterna och den skyddande funktionen av gränsnittsfilmen. I denna avhandling studeras ett flertal mono och dikatjon fosfoniumjonvätskor med icke halogena bis(oxalato)borat anjoner såväl som en binär blandning av dessa av intresse som nya avancerade smörjmedel och som additiv med neutronreflektometri vid ett elektrifierat elektrodgränssnitt med syfte att studera strukturella egenskaper av den gränsnittsfilmen som bildas samt elektroresponsiviteten av denna film. Resultaten av detta uppvisar egenskaper om både struktureringen av jonarterna och deras elektroresponsivitet av intresse för den fortsatta utvecklingen av avancerade smörjmedelslösningar med fosfoniumjonvätskor. / Phosphonium ionic liquids(ILs) has previously been investigated as advanced novel lubricants because of their physical unique properties and advantages compared to traditional lubricants and other ILs. These studies have showed promising results in wear and friction reduction as well as the tribotronic control of those properties. A multitude of questions however remain about the interfacial structuring of these protective films and the connection between structural features in the ionic species to the protective function of the interfacial film.In this thesis multiple non-halogenated mono- and di-cationic phosphonium ionic liquids with bis(oxalato)borate anion as well as a binary mixture of interest for advanced neat lubricants or additives has been studied by neutron reflectometry at an electrified electrode interface to investigate interfacial properties and electroresponsiveness of the species. The results elucidate properties of the structuring of key to the further development of phosphonium ILs for use in advanced lubrication formulations.

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Addition of a small amount of polar solvent (i.e. modifier) which contains an ionic component (i.e. additive) to a CO2 mobile phase has shown major improvement in the elution of ionic analytes via packed column supercritical fluid chromatography (SFC). Firstly, we focused on the elution of sodium arylsulfonate analytes by using various ionic additives, such as lithium acetate, ammonium acetate, tetramethylammonium acetate, tetrabutylammonium acetate, and ammonium chloride. The analytes were successfully eluted with all additives with good peak shape under isocratic/isobaric/isothermal conditions. Three stationary phases with different degrees of deactivation were considered. They were conventional Cyanopropyl, Deltabond Cyanopropyl, and non-chemically bonded silica. The effect of additive concentration and additive functionality on retention was also investigated. Secondly, solid state NMR of the silica packing material before and after being flushed with supercritical CO2 modified by methanol containing the ionic additives was performed to gain some insight into the retention mechanism(s). A fraction of silanol protons were undetected after being treated with the mobile phase which suggested replacement by the cationic component of the additive. CaChe calculations were carried out on several of the additives in an attempt to explain why different ionic additives produce different effects on chromatographic retention. Modification of the stationary phase and ion pairing with the analyte are two possible retention mechanisms being considered. As ion-pair formation was considered to be one of the retention mechanisms, the use of sodium sulfonates as mobile phase additives to elute secondary and quaternary ammonium salts was then studied. Propranolol HCl, benzyltrimethylammonium chloride, and cetylpyridium chloride were chosen as the probe analytes. Sodium ethansulfonate, sodium 1-heptanesulfonate, and sodium 1-decanesulfonate were studied as mobile phase additives. The analytes were successfully eluted from Deltabond Cyano phase within 5 minutes, but were retained strongly without additive or with ammonium acetate as the additive. An Ethylpyridine column showed dramatic advantages on the elution of these ammonium analytes. No additive was required to elute these ionic compounds. Protonation of some fraction of the pyridine functional groups and the deactivation of active silanol sites were believed to be the major mechanisms responsible for this behavior. Lastly, we successfully eluted large peptides (up to 40 mers) containing a variety of acidic and basic residues in SFC. We used trifluoroacetic acid as additive in a CO2/methanol mobile phase to suppress deprotonation of peptide carboxylic acid groups and to protonate peptide amino groups. The Ethylpyridine column was used for the majority of this work. The relatively simple mobile phase was compatible with mass spectrometric (MS) detection. To our knowledge, this is the first report of the elution of peptides of this size with a simple, MS-compatible mobile phase. Fast analysis speed, the possibility of coupling multiple columns to achieve desired resolution, a normal-phase retention mechanism, and less use of organic solvents are the advantages of SFC approach for peptide separation. / Ph. D.

The imidazole ring offers great potential for a variety of applications including gene delivery vectors, ionic liquids, electromechanical actuators, and novel monomers and polymers. The imidazole ring provides a unique building block for these applications due to its thermal stability, aromatic nature, ability to form ionic salts, and ease of functionalization. Free radical polymerization of 1-vinylimidazole (1-VIm) and free radical copolymerizations with methyl methacrylate (MMA) and n-butyl acrylate (nBA) afforded homopolymers and copolymers with tunable solution and thermal properties. Aqueous SEC provided reproducible and reliable molecular weights for poly(1-VIm) in the absence of polymer aggregates. Analysis of the thermal properties revealed ideal random copolymers with MMA and non-ideal copolymers with nBA. Small angle X-ray scattering determined that the spacing between ionic groups remained constant with increased nonionic comonomer incorporation while the spacing between adjacent polymer backbones increased. Functionalization of 1-VIm with varying length alkyl halides and polymerization prepared a series of imidazolium homopolymers. Anion exchange reactions controlled the thermal and solution properties, and the bromide counteranion quantitatively exchanged to tetrafluoroborate (BF4), trifluoromethanesulfonate (TfO), and bis(trifluoromethanesulfonyl)imide (Tf2N). Thermogravimetric analysis revealed that thermal stability increased with decreased alkyl substituent length and larger counteranion size, and differential scanning calorimetry determined that glass transition temperature (Tg) decreased with increased alkyl substituent length and larger counteranion size. Electrochemical impedance spectroscopy determined the ionic conductivities of the imidazolium homopolymers, and analysis using the Vogel-Fulcher-Tammann equation revealed that the activation energy of ion conduction increased as alkyl substituent length increased. Polymer morphology determined using X-ray scattering also influenced the ionic conductivity. As the alkyl substituent length increased, the spacing between adjacent polymer backbones increased, which decreased the ionic conductivity due to the ion-hopping mechanism of ion conduction. Unsuccessful attempts to control the radical polymerization of 1-VIm led to the investigation of 1-(4-vinylbenzyl)imidazole (VBIm), which is a styrenic-based monomer with excellent propagating radical stability. Triblock copolymers incorporating VBIm monomer into a soft random copolymer center block and reinforcing, hard segment outer blocks provided a template for tuning the properties of the ionomer membranes for electroactive devices. Analysis of the morphology and mechanical properties using small angle X-ray scattering and dynamic mechanical analysis determined microphase separation and optimal mechanical properties for electromechanical transducer fabrication. Testing electromechanical transducers revealed superior performance relative to the benchmark Nafion®. Optimization of triblock copolymer design criteria through varying the comonomer ratio of VBIm and nBA in the soft center block, quaternization reactions, and ionic liquid introduction influenced mechanical properties and ionic conductivity. Higher percentages of VBIm and quaternization of VBIm in the random central block increased Tg and ionic conductivity. IL selectively incorporated into the imidazole-containing phases with no leakage observed for ionic systems, reduced the center block Tg, and increased ionic conductivity. Controlling charge density along poly(1-VIm) through well-defined alkylation reactions with 1-bromobutane provided a potential vector for nonviral gene delivery and polyanion binding. Analysis of DNA and heparin binding using gel electrophoresis revealed a decrease in N/P ratio with increased alkylation percentage. Dynamic light scattering indicated an increase in zeta potential with increasing alkylation percentages, and relatively uniform polyplex sizes in aqueous media. The MTT assay developed cytotoxicity profiles with little toxicity prior to 83% alkylation. Finally, the luciferase expression assay revealed inefficient nucleic acid delivery to multiple cell types. Synthesis of poly(1-VIm) vectors with glutathione conjugates provided an avenue for simultaneous therapeutic gene and anti-oxidant delivery in vitro. Cytotoxicity assays of cells pretreated with glutathione-conjugated poly(1-VIm) prior to oxidative stress showed that higher glutathione conjugation levels improved cell viability. / Ph. D.

Ionic polymer-metal composites (IPMCs) are widely studied for their potential as electromechanical sensors and actuators. Bending of the IMPC depends on internal ion motion under an electric potential, and the addition of an ionic liquid and ionic self-assembled multilayer (ISAM) conductive network composite (CNC) strongly enhances bending and improves lifetime. Ion conducting polyelectrolytes poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) and Nafion® were incorporated into an ISAM CNC film with poly(allylamine hydrochloride) (PAH) and anionic gold nanoparticles actuators to further improve bending. CNC films were optimized for bending through pH adjustments in PAH and adding NaCl to the PAMPS and Nafion® solutions. PAMPS-containing actuators showed larger and faster bending than those containing Nafion® in the CNC. The IPMC actuator was also evaluated for its potential as a humidity sensor based on its relative humidity (RH) dependent steady-state current. The detection range is at least 10-80%RH, with 5%RH increment differentiation and likely better resolution. Effects of CNC presence and thickness were studied, in conjunction with ionic liquid at a range of RH values. A thin CNC (pH 4 PAH) produced the greatest current differentiation between RH values. The current's response speed to a large RH decrease was approximately 4 times faster than that of a fast commercial digital hygrometer. Additionally, the presence of a CNC and ionic liquid improved the current response time. These results indicate that an IPMC based humidity sensor using a CNC and ionic liquid is very promising and merits further study. / Master of Science

An ionic polymer actuator consists of a thin Nafion-117 sheet plated with gold or platinum on both sides. An ionic polymer actuator undergoes large deformation in the presence of low applied voltage across its thickness and exhibits low impedance. They can also be used as large displacement sensors by bending them to induce stresses and generate a voltage response. They operate best in a humid environment. Ionic polymer actuators have been used for various practical applications such as bio-mimetic robotic propulsion, flexible low mass robotic arms, propellors for swimming robotic structures, linear and platform type robotic actuators and active catheter systems. One of the disadvantages of ionic polymer actuators is that their settling time to a unit step voltage is on the order of 5-20 seconds in a cantilever configuration. The slow time constant of an ionic polymer limits the actuation bandwidth. The characteristics of ionic polymer actuators, low force and large displacement (as compared to other actuator technologies such as PZT or PVDF), cannot be used in applications requiring a faster response time for a given actuation signal. Due to this limitation, many applications will not be able to make use of the large displacement effectively because of the limited bandwidth of the actuator. Another disadvantage of using an ionic polymer actuator is that the stiffness of the actuator is a function of the hydration of the polymer. Difficulties in controlling the hydration, which changes with respect to time, results in inconsistencies in the mechanical response exhibited by the polymers during continual usage. Several physical models of ionic polymer actuators have been proposed. The physical phenomenon responsible for the bending is not completely understood and no clear set of principles have been able to explain the motion of the polymers completely. Physical phenomena like ionic motion, back diffusion of water and electrostatic force have been used to explain these models. This research demonstrates the use of feedback control to overcome the limitation of slow settling time. First, an empirical model of the ionic polymers developed by Kanno was modified by studying the step response of these actuators. The empirical model is used to design a feedback compensator by state space modeling techniques. Since the ionic polymer actuator has a slow settling time in the open-loop, the design objectives are to minimize the settling time and constrain the control voltage to be less than a prescribed value. The controller is designed using Linear Quadratic Regulator (LQR) techniques which reduced the number of design parameters to one variable. Simulations are performed which show settling times of 0.03 seconds for closed-loop feedback control are possible as compared to the open-loop settling time of 16-18 seconds. The maximum control voltage varied from 1.2 Volts to 3.5 Volts depending on the LQR design parameter. The controller is implemented and results obtained are consistent with the simulations. Closed-loop settling time is observed to be 4-8 seconds and the ratio of the peak response to the steady-state response is reduced by an order of magnitude. Discrepancies between the experiment and the simulations are attributed to the inconsistencies in the resonant frequency of the actuator. Experiments demonstrate that changes in the surface hydration of the polymer result in 20\% variations in the actuator resonance. Variations in the actuator resonance require a more conservative compensator design, thus limiting the performance of the feedback control system. / Master of Science

Submitted in fulfillment of the academic requirements for the Masters Degree in Technology: Chemistry, Durban University of Technology, 2008. / The thermodynamic properties of binary liquid mixtures involving ionic liquids (ILs) with alcohols were determined. ILs are an important class of solvents since they are being investigated as environmentally benign solvents, because of their negligible vapour pressure, and as potential replacement solvents for volatile organic compounds (VOCs) currently used in industries. Alcohols were chosen for this study because they have hydrogen bonding and their interaction with ILs will help in understanding the intermolecular interactions. Also, their thermodynamic properties are used for the development of specific chemical processes. The excess molar volumes of binary mixtures of {1-ethyl-3-methylimidazolium ethylsulfate + methanol or 1-propanol or 2-propanol}, {trioctylmethylammonium bis (trifluoromethyl-sulfonyl) imide + methanol or ethanol or 1-propanol}, {1-buty-3-methylimidazolium methylsulfate + methanol or ethanol or 1-propanol} were calculated from experimental density values, at T = (298.15, 303.15 and 313.15) K. The Redlich-Kister smoothing polynomial was fitted to the excess molar volume data. The partial molar volumes of the binary mixtures {1-ethyl-3-methylimidazolium ethylsulfate + methanol or 1-propanol or 2-propanol}, {trioctylmethylammonium bis (trifluoromethyl-sulfonyl) imide + methanol or ethanol or 1-propanol}, {1-buty-3-methylimidazolium methylsulfate + methanol or ethanol or 1-propanol} were calculated from the Redlich-Kister coefficients, at T = (298.15, 303.15 and 313.15) K. This information was used to better understand the intermolecular interactions with each solvent at infinite dilution. iii The isentropic compressibility of {trioctylmethylammonium bis (trifluoromethyl-sulfonyl) imide + methanol or ethanol or 1-propanol}, were calculated from the speed of sound data at T = 298.15 K. / National Research Fundation ; Durban University of Technology

Dissertation submitted in fulfilment of the requirements for the Masters Degree in Technology: Chemistry, Durban University of Technology, 2009. / The activity coefficients at infinite dilution ( γ13 ) were calculated for alkanes, alkenes, cycloalkanes, alkynes, ketones, alcohols and aromatic compounds from gas liquid chromatography (glc) measurements at three temperatures (303.15 and 313.15 and 323.15) K. The γ13 values were calculated from the retention data for two ionic liquids (ILs) with the same cation but different anions. The ionic liquids: [methyltrioctylammonium bis(trifluoromethylsulfonyl)imide and methyltrioctylammonium thiosalicylate] were used as the stationary phase. The γ13 data for methyltrioctylammonium thiosalicylate were higher than for methyltrioctylammonium bis(trifluoromethylsulfonyl)imide. For each temperature and each ionic liquid, γ13 values were determined for two columns and the average γ13 values were used for the calculation of the partial molar excess enthalpies at infinite dilution, H E 1 Δ , using the Gibbs-Helmholtz equation. Graphs of In γ13 vs 1/T were plotted to determine H E 1 Δ at T = 303.15 K. The selectivity, S12 , value for the hexane/benzene separation was calculated from the ratio of the avarage γ13 values to determine the suitability of the ILs as an entrainer for extractive distillation in the separation of aromatic and aliphatic compounds.The S12 values were also compared to the literature values for other ionic liquids. It was found that the longer chain alkyl group attached to the cation or anion gave lower S12 values. Both ILs have S12 values greater than one and in theory can be used as an entrainer for the hexane/ benzene separation. The capacities at infinite dilutions, k1 , were also calculated from the inverse of the avarage γ13 values for each IL at each temperature. / National Research Fund; Postgraduate Development and Support Directorate.