Traditionally, water has been used as the diluent for ionomeric polymer transducers. The water mobilizes the counterions within the polymer and allows electromechanical transduction to occur. However, these water-swollen devices have limited stability when operated in a non-aqueous environment. In this work, ionic liquids are demonstrated as viable diluents for ionomeric polymer transducers based on Nafion membranes. Ionic liquids are molten salts that are highly thermally stable and have an immeasureably low vapor pressure. Therefore, the ionic liquid-swollen transducers exhibit enhanced stability in their performance when operated for long periods of time in air. Methods for swelling Nafion membranes with ionic liquids are presented. Also, techniques for plating the ionic liquid-swollen transducers with metal electrodes are discussed. The performance of the ionic liquid-swollen transducers is compared to that of water-swollen transducers and differences are observed. Apart from the superior stability of the ionic liquid-swollen devices, they are observed to not exhibit the characteristic back-relaxation that is often associated with water-swollen transducers and limits their low frequency response. In order to investigate the physics of transduction in the ionic liquid-swollen membranes, structured experiments are performed using two different ionic liquids: 1-ethyl-3-methylimidazolium trofluoromethanesulfonate (EMI-Tf), which is water miscible, and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMI-Im), which is hydrophobic. The other experimental parameters are the counterion of the Nafion membrane and the swelling level of ionic liquid. Small-angle X-ray scattering (SAXS) is used to characterize the morphology of the ionic liquid-swollen Nafion membranes. The SAXS testing reveals that the clustered morphology of the Nafion membrane is preserved by the EMI-Tf ionic liquid, which is compatible with the hydrophilic cluster phase. By contrast, the hydrophobic EMI-Im ionic liquid is found to disrupt the clustered morphology and lead to partial homogenization of the polymer. This has the effect of inhibiting the ionic conductivity. The SAXS testing also reveals that the mean intercluster spacing increases as the content of ionic liquid and size of the counterions increases. Based on assumptions regarding the swelling mechanism, this is thought to arise from an increase in the mean size of the clusters. Spectroscopic investigations were also performed using Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR). These studies show that the ionic liquid interacts with the Nafion polymer by displacing the counterions away from the sulfonate exchange sites. The cations of the ionic liquid then associate with the sulfonate sites and the counterions associate with the anions of the ionic liquid. Above a certain critical uptake of ionic liquid, this displacement is complete and additional ionic liquid does not associate with the ions of the polymer. The critical uptake is found to decrease with increasing size of the counterions. / Ph. D.

Ionomeric polymer transducers (IPTs) are an exciting new class of smart materials that can serve a dual purpose in engineering or biomedical applications as sensors or actuators. Most commonly they are used for mechanical actuation, as they have the ability to generate large bending strains and moderate stress under low applied voltages. Although the actuation capabilities of IPTs have been extensively studied, the sensing capabilities of these transducers have yet to be fully explored. The work presented herein aims to investigate the fundamental sensing characteristics of these transducers and apply the acquired knowledge toward the development of an electronic stethoscope for digital auscultation. The sensors were characterized both geometrically and electrically to determine their effectiveness in resolving a signal from sub 1 Hz to 2 kHz. Impedance spectroscopy was used to interrogate the sensing mechanism. Following the characterization of the transducer, a bio–acoustic sensor was designed and fabricated. The bio–acoustic sensor was placed over the carotid artery to resolve the arterial pressure waveform in situ and on the thorax to measure the S1 and S2 sounds generated by the heart. The temporal response and spectral content was compared with previously known data and a commercially available electronic stethoscope to prove the acquisition of cardiovascular sounds. / Master of Science

Ionic polymer membranes are commonly used in fuel cell power generation, water electrolysis and desalinization, chlorine generation, and other niche applications. Since the early 1990s ionic polymer membranes have also shown promise as distributed electromechanical actuators and sensors. The cost of these materials is very high because of the expensive noble metals that are used as the electrodes in these applications, however. Currently, high cost of these devices has prevented them from experiencing widespread use. The goal of the current research project is to study new methods of plating metal electrodes onto ionic polymer membranes in order to reduce the cost of these materials and open the door for potential industrial, aerospace, and biomedical applications. At this time ionic polymer actuators are only made using gold or platinum as the electrode in a lengthy and labor-intensive process. The current research focuses on using less costly metals and revising the metal deposition process. Several new methods allowing for faster deposition of metals onto ionic polymer membranes are developed and evaluated including sputter-coating, electroless plating, and impregnation/reduction. Using these methods, metal electrodes have been plated onto ionic polymer membranes in processes resulting in a purely surface deposition and in processes resulting in interpenetration of the metal into the polymer. This work shows that electromechanical coupling is present with all of these processes, although results indicate that interpenetration of the electrode is important for good adhesion of the metal and good performance of the transducers. Also studied were different metals; X-ray photoelectron spectroscopy (XPS) testing shows that the use of non-noble metals as the electrodes results in oxidation of the metal and corresponding loss of performance in the actuator. Noble metals are found to not experience the oxidation problem. Further work shows that non-noble metals can be effectively employed as electrodes if alloyed with noble metals by using a co-reduction technique. Also studied is the use of protective coatings of noble metal to stabilize the non-noble metal electrodes. Using these approaches, a new plating method is developed and the stability of the electrodes made using this method is studied. These results indicate that samples made using this new process may be actauted continuously for over 150,000 cycles with very little degredation in their performance. Using this new plating method, ionic polymer membrane transducers can be made in less than five hours. Characterization of these new devices shows that they have a mass energy density of 4-20 mJ/kg in the cantilevered mode. This compares well with a baseline material, which is found to have a mass energy density of 3-12 mJ/kg. Composition and morphology of the electrodes made using the new method are investigated using scanning electron microscopy (SEM) and the density and tensile modulus are measured. The density of the new material is found to be approximately 2100 kg/m^3 as compared to about 3200 kg/m^3 for the baseline material. Also, the tensile elastic modulus of the new material is about 55 MPa, or roughly one fourth of the tensile modulus of the baseline material (about 190 MPa). These results indicate that the new materials contain much less noble metal in the electrodes than the baseline material. The sensitivity of these devices has also been quantified and compared to the baseline. Results indicate that the new materials have a sensitivity on the order of 0.1-0.3 uA/mm/s whereas similarly sized samples of the baseline material typically have sensitivities on the order of 0.2-0.8 uA/mm/s. The most important conclusion of this work is that ionic polymer membrane transducers can be made using much less noble metal in the electrode than previously believed without sacrificing the performance of these devices. / Master of Science

Yes / A series of novel nopyl-derived chiral phosphonium ionic liquids have been successfully synthesised and characterised. Analysis of each novel ionic liquid was conducted in order to confirm structure, purity and thermal stability.

Ionomeric polymers are a promising class of intelligent material which exhibit electromechanical coupling similar to that of piezoelectric bimorphs. Ionomeric polymers are much more compliant than piezoelectric ceramics or polymers and have been shown to produce actuation strain on the order of 2\% at operating voltages between 1 V and 3 V \citep{Akle2}. Their high compliance is advantageous in low force sensing configurations because ionic polymers have a very little impact on the dynamics of the measured system. Here we present a variational approach to the dynamic modeling of structures which incorporate ionic polymer materials. The modeling approach requires a priori knowledge of three empirically determined material properties: elastic modulus, dielectric permittivity, and effective strain coefficient. Previous work by Newbury and Leo has demonstrated that these three parameters are strongly frequency dependent in the range between less than 1 Hz to frequencies greater than 1 kHz. Combining the frequency-dependent material paramaters with the variational method produces a second-order matrix representation of the structure. The frequency dependence of the material parameters is incorporated using a complex-property approach similar to the techniques for modeling viscoelastic materials. Three structural models are developed to demonstrate this method. First a cantilever beam model is developed and the material properties of a typical polymer are experimentally determined. These properties are then used to simulate both actuation and sensing response of the transducer. The simulations compare very well to the experimental results. This validates the variational method for modeling ionic polymer structures. Next, a plate model is developed in cylindrical coordinates and simulations are performed using a variety of boundary conditions. Finally a plate model is developed in cartesian coordinates. Methods for applying non-homogenious boundary conditions are then developed and applied to the cartesian coordinate model. Simulations are then compared with experimental data. Again the simulations closely match the experiments validating the modeling method for plate models in 2 dimensions. / Master of Science

This work showcases the utility of switchable materials. Included are a switchable room-temperature ionic liquid, a switchable solvent, a switchable heterogeneous catalyst system, and a switchable gel. First, the switchable ionic liquid 2-butyl-1,1,3,3-tetramethylguanidium methylcarbonate is fully investigated. Its use in a complete chemical process (including reaction, separation, reformation, and recycle) is demonstrated with several reactions. Furthermore, its potential use for bitumen separation and purification and SO2 capture/isolation are discussed, and preliminary data is presented. Next, piperylene sulfone (PS), a switchable solvent, is synthesized and fully characterized. Anionic nucleophilic substitution reactions were performed in PS, the products were isolated in high yields, and then the PS was reformed for reuse. Then, we designed an immobilized fluorous microphase system that uses F-MonoPhos to induce high enantioselectivities as a switchable heterogeneous catalyst system. Finally, stable reversible polyethyleimine-CO2 gels have been synthesized with 1-octanol. Our findings indicate that PEI-1200/octanol/CO2 gels have potential as a possible drug carrier matrix for transdermal delivery applications.

Novel solvents utilizing a reversible CO₂ induced property switch are presented. The synthetic procedure for designing the solvents is discussed, along with detailed characterizations on both solvent forms to serve as a tool for optimal solvent identification as well as future solvent design. A reflectance infrared spectroscopic technique is introduced to allow for the examination of CO₂ and solvent composition under high pressures and temperatures. The magnitude of solvent property changes afforded by this "switch" creates opportunities for sustainable processing; discussed are the application to coupling reactions and separations, and CO₂ capture. The switchable solvents are shown to serve as effective media for running reactions, with the switch providing facile recovery of products and catalysts for solvent recycling. Lastly, the switch itself is exploited to provide for the separation of CO₂ from low partial pressure feed streams, and structure-property relationships were successfully used to develop next generation materials with enhanced absorption capacities. The viscosity of the solvents, as a function of temperature and composition, is also presented.

This thesis involves the synthesis of two main classes of triaminocyclopropenium (tac) Ionic Liquids (ILs) (i) Amino Acid Ionic Liquids (AAILs) and (ii) reduced-symmetry cations. [C₃(NEt₂)₂(NRR’)]X (X = TFSA and MeSO₄) were prepared, whereby NHR is derived from amino acids. Optically pure AAILs, [E₄AminoAcid]X (X = TFSA and MeSO₄) were obtained as a mixture of the IL and its zwitterion. The ratios of these mixtures were determined by pH titration and microanalysis. The AAILs specific rotations and pKa values were determined. AAILs can be used for chiral discrimination and form diasterreomeric salts with the entioenriched sodium salt of Mosher’s acid. The AAILs were also successfully used as a solvent and/or catalyst in an aldol reaction and a Diels-Alder reaction. The low-molecular weight series, [C₃(NMe₂)₂(NRR’)]X and [C₃(NMe₂)₂(NR’2)]X was synthesized and characterized: protic ILs NRR’, where R = ethyl, propyl, allyl, butyl, - CH2CH2OCH₃ and pentyl, R’ = H and X = TFSA: and aprotic ILs NRR’, where R = Me, R’ = ethyl, allyl, propyl, butyl, -CH2CH2OCH₃ and hexyl and X = TFSA and DCA. ILs with C2v symmetry [C₃(NEt₂)₂(NH2)]X (X = TFSA and MeSO₄), [C₃(NEt₂)₂(NBu2)]I, [C₃(NEt₂)₂(NHex₂)]I and [C₃(NEt₂)₂(NHex₂)]OTf were also synthesized and characterized. The C₃h cations, [C₃(NMeR)₃]X (R = ethyl, allyl, -CH2CH2OCH₃ and phenyl, X = TFSA and DCA) were successfully prepared as well. The D₃h cation salts [C₃(NEt₂)₃]X (X = MeC6H4SO₃, OTf, I and F5C6O) and [C₃(NBu2)₃]X (X = B(CN)4 and FAP) were also prepared. The tac-based ILs [C₃(NEt₂)₃]+ and [C₃(NBu2)₃]+ were also complexed with metal halides - - 2- 2- forming salts with FeCl₄ , SnCl₃ , CuCl₄ and ZnCl₄ . Reaction of pentachlorocyclopropane (C₃Cl5H) with BuNH2 gave the open ring allylium product [H2C₃(NBuH)4]2+. This was characterized as Cl- and TFSA- salt. During the synthesis of [C₃(NMe₂)₃]Cl, the open ring cation [HC₃(NMe₂)4]+ was also isolated and was characterized as the TFSA- salt. XX Abstract The TGA, DSC, density, viscosity, conductivity, and molar conductivity properties for the ILs were measured where possible. The viscosity and conductivity data was fitted for the Arrhenius and Vogel-Fulcher Tamman equations. The entire tac-based ILs lie below the KCl ideal line in Walden plot. A fragility plot was obtained by fitting the viscosity data and all the tac-based ILs were fragile. The crystal structures of [C₃(NPhH)₃]TFSA, [C₃(NEt₂)₃]FeCl₄ and [HC₃(NMe₂)4]Cl.2CH₃Cl were determined.

Ionic liquids (ILs) are liquid organic salts at room temperature which are composed of only ions (cations and anions). Ionic liquids are regarded as “novel solvents” and have been gaining attention as alternatives to volatile molecular organic solvents. Ionic liquids have outstanding properties, such as negligible vapor pressure (no or limited evaporation or volatilization), low melting point, thermal stability, and ionic conductivity. They can be used in efficient and clean energy production and storage. The synthesis of the low-cost and performance-effective ionic liquids using inexpensive raw materials is presented and characterized. Characterization was done using Thermogravimetric Analysis (TGA), Fourier Transform Infrared Spectroscopy (FTIR), and Scanning Differential Thermometry (DSC-TGA). Cost effective ionic liquids were synthesized and characterized and then compared to commercially available ionic liquids. Results for newly synthesized ionic liquids suggest that these cost effective ionic liquids were electroconductive and thermally stable when compared to the raw materials used for synthesis of ionic liquids. The thermal stability of these ionic liquids was less, however, when compared to the regular higher cost ionic liquids. FTIR characterization also provided secondary evidence on expected functional groups of newly synthesized ionic liquids. Viscosity of the syntehsized ionic liquids was higher when comapred to the commercially avaialable ionic liquids.

Efficient heat management in energy intensive applications such as server and data centers has become a national concern due to the magnitude of the energy consumed. In that matter, the absorption refrigeration system is an attractive solution because the abundant waste heat available in the data centers can be recycled to run the heat pump, which will bring about significant cooling cost savings. The use of absorption refrigeration has been limited due to the drawbacks related to the working fluids in commercially available equipment. Recently, ionic liquids (ILs) have been suggested as the absorbent in absorption heat pumps due to their tunable properties, negligible volatility and high thermal stability. The non-random-two-liquid-model was initially used to analyze the feasibility of the new IL based working fluid. Hydrofluorocarbons (HFCs) were paired with IL absorbents due to their good properties as refrigerants. The cooling-to-total-energy (CE) efficiency had a local maximum with respect to desorber temperature due to the solubility limit at lower temperatures and large heating requirements at higher temperatures. The waste heat recycling coefficient of performance (COP) continually increased with respect to desorber temperature and among the HFCs studied in this work, R134 gave the highest COP value, which is up to 40 times higher than that of typical vapor compression systems and 60 times higher than NH3/H2O and H2O/LiBr absorption refrigeration systems. A Redlich-Kwong equation of state (RK-EOS) was employed for accurate computation of mixture properties over a wide range of operating conditions. Analysis using the RK-EOS model showed that the CE trend in refrigerants followed the trend of solubility in the [bmim][PF6] IL. However, the trend in COP was different from that of CE as the operating pressure ranges became an important factor. Required pumping work of the working fluids has also been analyzed using a two phase pressure drop equation and the results show that the impact of viscous IL flow is insignificant compared to the total pumping work. The HFCs studied in this work have very similar structures. However, the extent of solubility and system efficiency in the same IL, [bmim][PF6], made a large difference. Most surprisingly, even when the refrigerant had the same chemical formula, the change in fluorine position in tetrafluoroethane showed significantly different system performance. The symmetrical tetrafluoroethane had superior CE and COP over the asymmetrical tetrafluoroethane most likely due to the higher probability to form hydrogen bonding with the absorbent. The computational results for various HFC/IL pairs show that in selecting the working fluid pairs, the refrigerant should have high overall solubility in the IL and a large gradient of solubility with respect to temperature. Also, refrigerants with small pressure ranges are preferred. In addition to the simulation study, a bench-top absorption refrigeration system was built and operated using IL based working fluids for the first time. The effect of cooling was observed by operating the test system. The experimental results were congruent with the predictions from the modeling work. In conclusion, an absorption refrigeration system based on the IL chemical compressor has been shown to be a promising solution in applications which need efficient cooling and generate abundant waste heat.