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.

Ionic electroactive polymers have been developed as mechanical sensors or actuators, taking advantage of the electromechanical coupling of the materials. This research attempts to take advantage of the chemomechanical and chemoelectrical coupling by characterizing the transient response as the polymer undergoes an ion exchange, thus using the polymer for ionic sensing. Nafion™ is a biocompatible material, and an implantable polymeric ion sensor which has applications in the biomedical field for bone healing research. An ion sensor and a strain gauge could determine the effects of motion allowed at the fracture site, thus improving rehabilitation procedures for bone fractures. The charge sensitivity of the material and the capacitance of the material were analyzed to determine the transient response. Both measures indicate a change when immersed in ionic salt solutions. It is demonstrated that measuring the capacitance is the best indicator of an ion exchange. Relative to a flat response in deionized water (±2%), the capacitance of the polymer exhibits an exponential decay of ~25% of its peak when placed in a salt solution. A linear correlation between the time constant of the decay and the ionic size of the exchanging ion was developed that could reasonably predict a diffusing ion. Tests using an energy dispersive spectrometer (EDS) indicate that 90% of the exchange occurs in the first 20 minutes, shown by both capacitance decay and an atomic level scan. The diffusion rate time constant was found to within 0.3% of the capacitance time constant, confirming the ability of capacitance to measure ion exchange. / Master of Science

Les hydrogels de Polyacrylamide (PAAM) hydrolysés sont des matériaux électroactifs biocompatibles non biodégradables. Ils possèdent des propriétés très proches de celles du muscle naturel et leur mode opérationnel basé sur la diffusion d’ions est similaire à celui existant dans les tissus musculaires naturels. Compte tenu de ces caractéristiques, ces hydrogels sont de bons candidats pour la conception de nouveaux muscles artificiels. Le problème qui limite leur utilisation réside dans leur temps de réponse qui reste encore inférieur à celui du système de fibres musculaires naturelles. Leur fonction actuatrice est limitée par le phénomène de diffusion en raison de leur structure massique qui est à l’origine de cycles de fonctionnement relativement lents. Dans le but de développer un nouveau système artificiel mimant le comportement du muscle squelettique naturel cette étude se divise en deux grandes étapes. La première étape vise le développement d’une étude de la synthèse de l’hydrogel de PAAM et de son mode de fonctionnement. Dans cette étude les effets des paramètres gouvernant la polymérisation sur les propriétés des hydrogels sont évalués. Les propriétés électrochimiques et le mécanisme d’activation des actuateurs soumis à une excitation électrique sont étudiés et le mode de fonctionnement des actuateurs est caractérisé et expliqué. La seconde étape est la proposition et le développement d’une nouvelle architecture de muscle artificiel à base de PAAM. Cette architecture consiste en une structure fibreuse du gel encapsulée par une couche en gel conducteur jouant le rôle d’électrodes. La structure fibreuse permet au système d’exhiber une réponse rapide et la couche en gel améliore ses propriétés mécaniques. Comme un premier pas dans la réalisation du modèle nous avons mis en place un nouveau procédé basé sur la technique d’électrofilage qui permet la génération de fibres linéairement disposées. En utilisant ce processus nous avons réussi à fabriquer des microfibres de PAAM réticulées, électroactives montrant des réponses rapides. / Hydrolyzed Polyacrylamide (PAAM) hydrogels are electroactive, biocompatible and non-biodegradable materials. Their main attractive characteristic is their operative similarity with biological muscles and particularly their life-like movement. They suit better the artificial muscle fabrication despite their response time which stays low compared to natural human muscle due to their bulky structure and due to the kinetics of the size dependence of their volume change. In order to copy the natural skeletal muscle design into a new artificial muscle system this study is divided into two steps. The first step is the development of a comprehensive study of the hydrogel itself in order to obtain the elementary background needed for the design of actuating devices based on this material. The effect of polymerization parameter on the hydrogel properties is investigated. The electrochemical properties and actuation mechanisms of the hydrogel is studied, the bending of PAAM actuators induced by electric field is discussed and a mechanism for the bending phenomenon is proposed. The second step is the proposition of a new artificial muscle architecture based on PAAM hydrogel. The model consists on a fiber like elements of hydrolyzed PAAM, working in parallel, embedded in a thin conducting gel layer which plays the role of electrodes. The fiber-like elements enable the system to exhibit relatively rapid response and the gel layers enhance their mechanical properties. Aiming to realize the model we have put in place a new electrospinning setup which is a modified process for the production of micro to nanofibers via electrostatic fiber spinning of polymer solutions. The main advantage of this technology is to produce aligned electrospun fibers over large areas by simple and a low cost process making it possible to produce fiberbased devices efficiently and economically. Using this setup, we succeeded in the fabrication of electroactive crosslinked hydrogel microfibers that can achieve fast electroactive response

Ionic electroactive polymer (IEAP) actuators are a class of electroactive polymer devices that exhibit electromechanical coupling through ion transport in the device. They consist of an ionomeric membrane coated with conductive network composites (CNCs) and conductive electrodes on both sides. A series of experiments on IEAP actuators with various types of CNCs has demonstrated the existence of a direct correlation between the performance of actuators and physical and structural properties of the CNCs. Nanostructure of CNC is especially important in hosting electrolyte and boosting ion mobility. This dissertation presents a series of systematic experiments and studies on IEAP actuators with two primary focuses: 1) CNC nanostructure, and 2) ionic interactions. A novel approach for fabrication of CNC thin-films enabled us to control physical and structural properties of the CNC thin-films. We, for the first time, facilitated use of layer-by-layer ionic self-assembly technique in fabrication of porous and conductive CNCs based on polymer and metal nanoparticles. Results were porous-conductive CNCs. We have studied the performance dependence of IEAP actuators on nano-composition and structure of CNCs by systematically varying the thickness, nanoparticle size and nanoparticle concentration of CNCs. We have also studied influence of the waveform frequency, free-ions and counterions of the ionomeric membrane on the performance and behavior of IEAP actuators. Using the LbL technique, we systematically changed the thickness of CNC layers consisting of gold nanoparticles (AuNPs) and poly(allylamine hydrochloride). It was observed that actuators consisting of thicker CNCs exhibit larger actuation curvature, which is evidently due to uptake of larger volume of electrolyte. Actuation response-time exhibited a direct correlation to the sheet-resistance of CNC, which was controlled by varying the AuNP concentration. It was observed that size and type of free-ions and counterion of ionomeric membrane are also influential on the actuation behavior or IEAP actuators and that the counterion of ionomeric membrane participates in the actuation process. / Ph. D.

Ionic polymer materials are a class of electroactive polymers that have been used in recent applications that take advantage of their large bending deflection. Although these materials have been around since the 1960s, it has only been in the last decade that their electromechanical coupling has been discovered. Because their life as a transducer has been relatively short, the underlying mechanisms for their mechanical motion have not yet been fully characterized. Modeling has been performed with ionic polymers, but there is no existing model, to date, that explains all the physical phenomena associated them. The work presented in this document will contribute to the characterization of these materials. To better understand the dehydration effect of ionic polymers operating in an open air environment, research was performed to help characterize this effect. Through the use of frequency response analysis, trends were established showing how the material's response characteristics varied with time, as the polymer dehydrated. These tests were also run at different humidity levels to assess the impact environmental conditions had on the response. It was shown that lower humidity levels cause the system parameters to shift at a higher rate. The two configurations tested were clamped-free and clamped-clamped, in an effort to bound the performance of the actuators for engineering applications. The clamped-clamped condition also facilitated applying tension to the polymers for evaluation of the dehydrating effects. Several comparisons to beam theory were made throughout the analysis, using it as a baseline condition illustrator. Though qualitative results were obtained with the polymers, there was much discrepancy in quantitative measures. This was to be expected though, because ionic polymers are composite actuators that exhibit nonlinear behavior, while uniform beams are linear. Environmental testing was not all that was done, however. Control techniques were applied to improve the closed-loop performance of the actuators. Using proportional-integral control, it was demonstrated that ionic polymers are capable of tracking reference inputs better than it was previously thought. This result will validate future experimentation with ionic polymers for micro-manipulation applications. The simplicity of integral control also eliminated the need for cumbersome model derivations and control system designs, reducing the time necessary to implement and test an actuator. Through the use of this control algorithm, the closed-loop bandwidth was also characterized for the cantilever and clamped-clamped polymers. / Master of Science

In this thesis, three different types of polymer-based gels are fabricated and characterized for passive and active applications. Silica aerogel is a 3D mesoporous solid material that can be used for thermal insulation or in the biomedical industry. In this thesis, silica aerogel is cross- linked with diisocyanate to improve its strength and flexibility, which greatly opens up the range of applications. Then, soft polymer gel with tissue equivalent characteristics is fabricated to mimic the spin-lattice (T1) and spin-spin (T2) relaxation times for the magnetic resonance imaging (MRI) phantom of a liver with lesions. This study demonstrates a relationship between the composition of a gelling agent, and T1 and T2 modifiers on its dielectric, mechanical and imaging properties. Finally, an ionic electroactive polymer (EAP) that can be actuated on an electric field is fabricated, and its swelling and bending behaviours on design parameters are closely examined.

In this thesis, three different types of polymer-based gels are fabricated and characterized for passive and active applications. Silica aerogel is a 3D mesoporous solid material that can be used for thermal insulation or in the biomedical industry. In this thesis, silica aerogel is cross- linked with diisocyanate to improve its strength and flexibility, which greatly opens up the range of applications. Then, soft polymer gel with tissue equivalent characteristics is fabricated to mimic the spin-lattice (T1) and spin-spin (T2) relaxation times for the magnetic resonance imaging (MRI) phantom of a liver with lesions. This study demonstrates a relationship between the composition of a gelling agent, and T1 and T2 modifiers on its dielectric, mechanical and imaging properties. Finally, an ionic electroactive polymer (EAP) that can be actuated on an electric field is fabricated, and its swelling and bending behaviours on design parameters are closely examined.

Electrical motors and/or hydraulics and pneumatics cylinders are commonly used methods of actuation in mechanical systems. Over the last two decades, due to arising market needs, novel self-independent mobile systems such as mobility assistive devices have emerged with the help of new advancements in technology. The actuation criteria for these devices differ greatly from typical mechanical systems, which has made the implementation of classical actuators difficult within modern assistive devices. Among the numerous challenges, limited energy storage capabilities by mobile systems have restricted their achievable operational time. Furthermore, new expectations for device weight and volume, as well as actuator structural compliance, have added to this quandary. Electroactive polymers, a category of smart materials, have emerged as a strong contender for the use in low-cost efficient actuators. They have demonstrated great potential in soft robotic and assistive device/prosthetic applications due to their actuation potential and similar mechanical behaviour to human skeletal muscles. Dielectric Elastomers, in particular, have shown very promising properties for these types of applications. Their structures have shown large achievable deformation, while remaining light-weight, mechanically efficient, and low-cost. This thesis aims to characterize, and model the behaviour of 3MTM VHB polyacrylic dielectric elastomer, in order to establish a foundation for its implementation in a proposed novel linear actuator concept. In this thesis, a comprehensive experimental evaluation is accomplished, which resulted in the better understanding of the elastomer’s biaxial mechanical and electro-mechanically coupled behaviours. Subsequently, a constitutive biaxial mechanical model was derived in order to provide a predictive design equation for future actuator development. This model proved effective in providing a predictive tool for the biaxial mechanical tensile response of the material. Finally, a simplified prototype was devised as a proof of concept. This first iteration applied experimental findings to validate the working principles behind the proposed actuator design. The results confirmed the proof of concept, through achieved reciprocal linear motion, and provided insight into the design considerations for prototype optimization and final actuator development.

Ionic polymer transducers (IPTs) are soft sensors and actuators which operate through a coupling of micro-scale chemical, electrical, and mechanical mechanisms. The use of ionic liquid as solvent for an IPT has been shown to dramatically increase transducer lifetime in free-air use, while also allowing for higher applied voltages without electrolysis. This work aims to further the understanding of the dominant mechanisms of IPT actuation and how these are affected when an ionic liquid is used as solvent. A micromechanical model of IPT actuation is developed following a previous approach given by Nemat-Nasser, and the dominant relationships in actuation are demonstrated through an analysis of electrostatic cluster interactions. The elastic modulus of Nafion as a function of ionic liquid uptake is measured using uniaxial tension tests and modeled in a micromechanical framework, showing an excellent fit to the data. Charge transport is modeled by considering both the cation and anion of the ionic liquid as mobile charge carriers, a phenomenon which is unique to ionic liquid IPTs as compared to their water-based counterparts. Numerical simulations are performed using the finite element method, and a modified theory of ion transport is discussed which can be extended to accurately describe electrochemical migration of ionic liquid ions at higher applied voltages. The results presented here demonstrate the dominant mechanisms of IPT actuation and identify those unique to ionic liquid IPTs, giving directions for future research and transducer development. / Master of Science

Electroactive polymers are a class of materials capable of reallocating their shape in response to an electric field while also having the ability to harvest electrical energy when the materials are mechanically deformed. Electroactive polymers can therefore be used as sensors, actuators, and energy harvesters. The parameters for manufacturing flexible electroactive polymers are complex and rate limiting due to number of steps, their necessity, and time intensity of each step. Successful additive manufacturing processes for electroactive polymers will allow for scalability and flexibility beyond current limitations, advancing the field, opening additional manufacturing possibilities, and increasing output. The goal for this research was to use additive manufacturing techniques to print conductive and dielectric substrates for building flexible circuits and sensors. Printing flexible conductive layers and substrates together allows for added creativity in design and application.