Anna Norlin

Investigation of interfacial capacitance of Pt, Ti and TiN coated electrodes by electrochemical impedance spectroscopy

Electrochemical processes at the electrode-electrolyte (body fluid) interface are of ultimate importance for stimulating/sensing electrode function. A high electrode surface area is desirable for safe stimulation through double-layer charging and discharging. Pt and Pt-Ir alloys have been the most common electrode materials. The use of TiN coating as the surface layer on the electrode has found increasing interest because of its metal-like conductivity, excellent mechanical and chemical properties, and the fact that it can be deposited with a high surface area. In this work, electrochemical impedance spectroscopy (EIS), which is a sensitive and non-destructive technique and widely used for characterization of electrical properties of electrode-electrolyte interfaces, was applied to investigate pure Pt and Ti, and TiN coated electrodes exposed to a phosphate-buffered-saline (PBS) solution. Platinized Pt and Ti were also studied for comparison. The capacitance value of the electrodes in PBS was obtained through quantitative analysis of the EIS spectra. The results reveal that the capacitance of the TiN coated electrodes with a rough surface is several hundreds times higher than that of a smooth Pt surface. Platinization of Ti can also increase the capacitance to the same extent as platina. EIS has been shown to be a powerful technique for characterization of stimulating/sensing electrodes.

Investigation of Electrochemical Behavior of Stimulation/Sensing Materials for Pacemaker Electrode Applications I. Pt, Ti, and TiN Coated Electrodes

The electrochemical behavior, interfacial properties, and stability of Pt, Ti, smooth and rough TiN electrodes for pacemaker applications were investigated in a phosphate-buffered saline solution, ...

Degradation of zinc in saline solutions, plasma, and whole blood

The initial degradation of zinc has been investigated through exposures to simulated and real body fluids of increasing complexity: phosphate buffered saline (PBS), Ringers saline solution, human plasma, and whole blood. Real body fluids were used to close the electrolyte gap between simulated and in vivo environment. Polarization of zinc in whole blood show a passive response not present in other electrolytes. The analysis shows a decrease in corrosion rate with time for plasma and whole blood and an increase for PBS and Ringers. During exposure to plasma and whole blood a bi-layered corrosion product with poor adherence was formed over a uniformly corroding surface. The corrosion products comprise a mixture of inorganic material and biomolecules. Samples degrading in PBS were prone to localized corrosion and formed thick porous corrosion products of primarily zinc phosphates while in Ringers solution a gel like layer of zinc carbonate was formed over an interface with shallow pits. The use of whole blood or plasma as electrolytes for short term in vitro evaluation of potential biodegradable metals may provide an improved understanding of the behavior in vivo, while Ringers solution is preferred over PBS for long term degradation studies of zinc.

Fabrication of Porous Nb2O5 by Plasma Electrolysis Anodization and Electrochemical Characterization of the Oxide

People suffering from certain types of arrhythmia may benefit from the implantation of a cardiac pacemaker. Pacemakers artificially stimulate the heart by applying short electrical pulses to the cardiac tissue to restore and maintain a steady heart rhythm. By adjusting the pulse delivery rate the heart is stimulated to beat at desired pace. The stimulation pulses are transferred from the pacemaker to the heart via an electrode, which is implanted into the cardiac tissue. Additionally, the electrode must also sense the cardiac response and transfer those signals back to the electronics in the pacemaker for processing. The communication between the electrode and the tissue takes place on the electrode/electrolyte (tissue) interface. This interface serves as the contact point where the electronic current in the electrode is converted to ionic currents capable to operate in the body. The stimulation/sensing signals are transferred across the interface via three electrochemical mechanisms: i) non-faradaic charging/discharging of the electrochemical double layer, ii) reversible and iii) irreversible faradaic reactions. It is necessary to study the contribution of each mechanism to the total charge transferred to evaluate the pacing/sensing performance of the pacemaker electrode. In this thesis, the electrochemical properties and performance of stimulation/sensing electrodes for pacemaker applications have been investigated by electrochemical impedance spectroscopy, cyclic voltammetry and transient electrochemical techniques. All measurements were performed in synthetic body fluid with buffer capacity. Complementary surface analysis was performed with scanning electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The results reveal different interfacial behaviour and stability for electrode materials such as Pt, TiN, porous carbon, conducting oxides (RuO2 and IrO2 and mixed oxides) and porous Nb2O5 oxide. The influence of the charge/discharge rate on the electrode characteristics also has been evaluated. Although the rough and porous electrodes provide a high interfacial capacitance, the maximum capacitance cannot be fully employed at high charge/discharge rates because only a small part of the effective surface area is accessible. The benefit of pseudo-capacitive material properties on charge delivery was observed. However, these materials suffer similar limitations at high charge/discharge rate and, hence, are only utilising the surface bound pseudo-capacitive sites. Porous Nb2O5 electrodes were investigated to study the performance of capacitor electrodes. These electrodes predominantly deliver the charge via reversible non-faradaic mechanisms and hence do not produce irreversible by-products. They can deliver very high potential pulses while maintaining high impedance and, thus, charge lost by faradaic currents are kept low. By producing Nb oxide by plasma electrolysis oxidation a porous surface structure is obtained which has the potential to provide a biocompatible interface for cell adherence and growth. This thesis covers a multidisciplinary area. In an attempt to connect diverse fields, such as electrophysiology, materials science and electrochemistry, the first chapters have been attributed to explaining fundamental aspects of the respective fields. This thesis also reviews the current opinion of pacing and sensing theory, with special focus on some areas where detailed explanation is needed for the fundamental nature of electrostimulation/sensing.

Investigation of Electrochemical Behavior of Stimulation/Sensing Materials for Pacemaker Electrode Applications II. Conducting Oxide Electrodes

bSt. Jude Medical AB, SE-175 84 Jarfalla, Sweden The electrochemical behavior, interfacial properties, and stability of RuO 2-, IrO2-, sRu1˛xMnxdO2- and sIr1˛xMnxdO2-coated electrodes for pacemaker applications were investigated in a phosphate buffered saline solution, by electrochemical impedance spectroscopy and cyclic voltammetry ~CV!. The psuedocapacitive properties of these conducting oxides and influence of coating roughness and porosity were examined, and accelerated aging of the electrode materials was simulated by fast sweep rate CV cycles between ˛3 to 1 V vs. Ag/AgCl. Changes in surface composition and structure due to the accelerated aging were investigated using X-ray photoelectron spectroscopy and scanning electron microscopy. The conducting oxides exhibit high interfacial capacitance. At high sweep rates, not all of total capacitance could be utilized due to voltage drop associated with resistance down the pores. Above a certain sweep rate, the charging/discharging mechanism changes from capacitive to resistive character. Showing the best performance among the investigated materials, the RuO2 exhibits capacitive characteristics at sweep rates up to 20 V/s and excellent stability under the accelerated aging. The IrO 2 coating was not stable during the cycling. The mixed oxides experience limitations at high sweep rates due to the ohmic effects and some degradation due to the accelerated aging.

Electrochemical Behavior of Stimulation∕Sensing Materials for Pacemaker Electrode Applications III. Nanoporous and Smooth Carbon Electrodes

The electrochemical behavior of nanoporous and smooth carbon electrodes was investigated in a phosphate-buffered saline solution. The interfacial properties were characterized by electrochemical im ...