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

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

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

Conventional glass ionomer cements (GICs), which continue to gain acceptance as superbly biocompatible dental materials, were first released in the early 1970s as a result of research into combining the advantages of silicate cements and polyalkenate cements. The chemistry of GICs is based upon the aqueous reaction between an ion-leachable fluoride glass and polyacid which yields the final cross-linked insoluble ionomer (ionic polymer). The significant advantages of GICs include direct adhesion to tooth structures, fluoride release, minimal dimensional change on curing, significant ease of use and superb biocompatibility, to the extent that affected proximal tooth structures may be retained, remineralised , and strengthened against further caries. GICs have, however, been unfavourably compared with other restorative materials in their mechanical properties and setting characteristics, in particular their relative weakness, the time limitations for the acid-base reaction to proceed to acceptable maturity, and the susceptibility of the immature cement to water sorption or desiccation.

This thesis deals with developing a thermodynamically consistent model to simulate the electromechanical response of ionic polymer-metal composites based on Euler-Bernoulli beam theory. Constitutive assumptions are made for the Helmholtz free energy and the rate of dissipation. The governing equations involving small deformations are formulated using the conservation laws, the power theorem, and the maximum rate of dissipation hypothesis. The model is extended to solve large deformation cantilever beams involving pure bending which could be used in the characterization of the material parameters. A linear finite element solution along with a staggered time stepping algorithm is provided to numerically solve the governing equations of the small deformations problem under generalized electromechanical loading and boundary conditions. The results are in qualitative and quantitative agreement with the experiments performed on both Nafion and Flemion based Ionic Polymer-Metal Composite strips.

Conventional glass ionomer cements (GICs), which continue to gain acceptance as superbly biocompatible dental materials, were first released in the early 1970s as a result of research into combining the advantages of silicate cements and polyalkenate cements. The chemistry of GICs is based upon the aqueous reaction between an ion-leachable fluoride glass and polyacid which yields the final cross-linked insoluble ionomer (ionic polymer). The significant advantages of GICs include direct adhesion to tooth structures, fluoride release, minimal dimensional change on curing, significant ease of use and superb biocompatibility, to the extent that affected proximal tooth structures may be retained, remineralised , and strengthened against further caries. GICs have, however, been unfavourably compared with other restorative materials in their mechanical properties and setting characteristics, in particular their relative weakness, the time limitations for the acid-base reaction to proceed to acceptable maturity, and the susceptibility of the immature cement to water sorption or desiccation.

The synthesis method for PEG/alkyl-based imidazolium/pyridinium ionic liquids was studied. Four steps were used to fabricate the membranes: polymerization, chloromethylation, linkage of the polymers with the pendent groups and membrane cast. Permeabilities and CO2/N2 selectivity of two membranes were examined and each showed remarkable CO2/N2 selectivity. CO2 permeability of the [PSM-MIM][Cl] membrane is better than that of the [PSM-MEIM][Cl] membrane, which is due to the steric hindrance of the methoxyethyl group. The syntheses of PEG/alkyl-based imidazolium/pyridinium ionic liquids (IL) were studied. PEG-based ILs were demonstrated to have better H2S solubilities than the alkyl-based ILs. H2S solubilities of the imidazolium ILs and pyridinium ILs were compared. The anion effects on H2S solubilities have been investigated, while the temperature effects on H2S solubilities will need to be studied in the near future.

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

Ionomeric polymer transducers exhibit electromechanical coupling capabilities. The transport of charge due to electric stimulus is the primary mechanism of actuation for a class of polymeric active materials known as ionomeric polymer transducers (IPTs). The research presented in this dissertation focuses on modeling the cation transport and cation steady state distribution due to the actuation of an IPT. Ion transport in the IPT depends on the morphology of the hydrated Nafion membrane and the morphology of the metal electrodes. Recent experimental findings show that adding conducting powders at the polymer-conductor interface increases the displacement output. However, it is difficult for a traditional continuum model based on transport theory to include morphology in the model. In this dissertation, a two-dimensional Monte Carlo simulation of ion hopping has been developed to describe ion transport in materials that have fixed and mobile charge similar to the structure of the ionic polymer transducer. In the simulation, cations can hop around in a square lattice. A step voltage is applied between the electrodes of the IPT, causing the thermally-activated hopping between multiwell energy structures. By sampling the ion transition time interval as a random variable, the system evolution is obtained. Conducting powder spheres have been incorporated into the Monte Carlo simulation. Simulation results demonstrate that conducting powders increase the ion conductivity. Successful implementation of parallel computation makes it possible for the simulation to include more powder spheres to find out the saturation percentage of conducting powders for the ion conductivity. To compare simulation results with experimental data, a multiscale model has been developed to increase the scale of Monte Carlo simulation. Both transient responses and steady state responses show good agreement with experimental measurements. / Ph. D.

This thesis presents work done to improve the switching speed and contrast performance of electrochromic devices. Layer-by-Layer (LbL) assembly was used to deposit thin electrochromic films of materials ranging from organic, inorganic, conducting polymers, etc. The focus was on developing new materials with high contrast and long lifecycles. A detailed switching-speed study of solid-state EC devices of already-developed (PEDOT (Poly(3,4-ethylenedioxythiophene)), polyviologen, inorganic) materials and some new materials (Prodot-Sultone) was performed. Work was done to achieve the optimum thickness and number of bilayers in LbL films resulting in high-contrast and fast switching. Device sizes were varied for comparison of the performance of the lab-made prototype device with the commercially available "small pixel" size displays. Symmetrical EC devices were fabricated and tested whenever conducting polymers are used as an EC material. This symmetrical configuration utilizes conducting polymers as an electroactive layer on each of two ITO-coated substrates; potential is applied to the two layers of similar conducting polymers and the device changes color from one redox state to another. This method, along with LbL film assembly, are the main factors in the improvement of switching speed results over already-published work in the literature. PEDOT results show that EC devices fabricated by LbL assembly with a switching speed of less than 30 ms make EC flat-panel displays possible by adjusting film thickness, device size, and type of material. The high contrast value (84%) for RuP suggests that its LbL films can be used for low-power consumption displays where contrast, not fastest switching, is the prime importance. In addition to the electrochromic work, this thesis also includes a section on the application of LbL assembly in fabricating electromechanical bending actuators. For bending actuators based on ionic polymer metal composites (IPMCs), a new class of conductive composite network (CNC) electrode was investigated, based on LbL self-assembled multilayers of conductive gold (Au) nanoparticles. The CNC of an electromechanical actuator fabricated with 100 bilayers of polyallylamine hydrochloride (PAH)/Au NPs exhibits high strain value of 6.8% with an actuation speed of 0.18 seconds for a 26 µm thick IPMC with 0.4 µm thick LbL CNCs under 4 volts. / Ph. D.