Measurement of the tree root growth using electrical impedance spectroscopy

Abstract

Solid-state reference and ion-selective electrodes : towards portable potentiometric sensing

Potentiometric sensors are very attractive tools for chemical analysis because of their simplicity, low power consumption and low cost. They are extensively used in clinical diagnostics and in environmental monitoring. Modern applications of both fields require improvements in the conventional construction and in the performance of the potentiometric sensors, as the trends are towards portable, on-site diagnostics and autonomous sensing in remote locations. The aim of this PhD work was to improve some of the sensor properties that currently hamper the implementation of the potentiometric sensors in modern applications. The first part of the work was concentrated on the development of a solid-state reference electrode (RE) compatible with already existing solid-contact ion-selective electrodes (ISE), both of which are needed for all-solid-state potentiometric sensing systems. A poly(vinyl chloride) membrane doped with a moderately lipophilic salt, tetrabutylammonium-tetrabutylborate (TBA-TBB), was found to show a satisfactory stability of potential in sample solutions with different concentrations. Its response time was nevertheless slow, as it required several minutes to reach the equilibrium. The TBA-TBB membrane RE worked well together with solid-state ISEs in several different situations and on different substrates enabling a miniature design. Solid contacts (SC) that mediate the ion-to-electron transduction are crucial components of well-functioning potentiometric sensors. This transduction process converting the ionic conduction of an ion-selective membrane to the electronic conduction in the circuit was studied with the help of electrochemical impedance spectroscopy (EIS). The solid contacts studied were (i) the conducting polymer (CP) poly(3,4-ethylienedioxythiophene) (PEDOT) and (ii) a carbon cloth having a high surface area. The PEDOT films were doped with a large immobile anion poly(styrene sulfonate) (PSS-) or with a small mobile anion Cl-. As could be expected, the studied PEDOT solid-contact mediated the ion-toelectron transduction more efficiently than the bare glassy carbon substrate, onto which they were electropolymerized, while the impedance of the PEDOT films depended on the mobility of the doping ion and on the ions in the electrolyte. The carbon cloth was found to be an even more effective ion-to-electron transducer than the PEDOT films and it also proved to work as a combined electrical conductor and solid contact when covered with an ion-selective membrane or with a TBA-TBB-based reference membrane. The last part of the work was focused on improving the reproducibility and the potential stability of the SC-ISEs, a problem that culminates to the stability of the standard potential E°. It was proven that the E° of a SC-ISE with a conducting polymer as a solid contact could be adjusted by reducing or oxidizing the CP solid contact by applying current pulses or a potential to it, as the redox state of the CP solid-contact influences the overall potential of the ISE. The slope and thus the analytical performance of the SC-ISEs were retained despite the adjustment of the E°. The shortcircuiting of the SC-ISE with a conventional large-capacitance RE was found to be a feasible instrument-free method to control the E°. With this method, the driving force for the oxidation/reduction of the CP was the potential difference between the RE and the SC-ISE, and the position of the adjusted potential could be controlled by choosing a suitable concentration for the short-circuiting electrolyte. The piece-to-piece reproducibility of the adjusted potential was promising, and the day-today reproducibility for a specific sensor was excellent. The instrumentfree approach to control the E° is very attractive considering practical applications.

Responses of silver birch saplings to low soil temperature

Abstract

Modelling of potentiometric ion sensors

Potentiometric ion sensors are a very important subgroup of electrochemical sensors, very attractive for practical applications due to their small size, portability, low-energy consumption, relatively low cost and not changing the sample composition. They are investigated by the researchers from many fields of science. The continuous development of this field creates the necessity for a detailed description of sensor response and the electrochemical processes important in the practical applications of ion sensors. The aim of this thesis is to present the existing models available for the description of potentiometric ion sensors as well as their applicability and limitations. This includes the description of the diffusion potential occurring at the reference electrodes. The wide range of existing models, from most idealised phase boundary models to most general models, including migration, is discussed. This work concentrates on the advanced modelling of ion sensors, namely the Nernst-Planck-Poisson (NPP) model, which is the most general of the presented models, therefore the most widely applicable. It allows the modelling of the transport processes occurring in ion sensors and generating the potentiometric response. Details of the solution of the NPP model (including the numerical methods used) are shown. The comparisons between NPP and the more idealized models are presented. The applicability of the model to describe the formation of diffusion potential in reference electrode, the lower detection limit of both ion-exchanger and neutral carrier electrodes and the effect of the complexation in the membrane are discussed. The model was applied for the description of both types of electrodes, i.e. with the inner filling solution and solidcontact electrodes. The NPP model allows the electrochemical methods other than potentiometry to be described. Application of this model in Electrochemical Impedance Spectroscopy is discussed and a possible use in chrono-potentiometry is indicated. By combining the NPP model with evolutionary algorithms, namely Hierarchical Genetic Strategy (HGS), a novel method allowing the facilitation of the design of ion sensors was created. It is described in detail in this thesis and its possible applications in the field of ion sensors are indicated. Finally, some interesting effects occurring in the ion sensors (i.e. overshot response and influence of anionic sites) as well as the possible applications of NPP in biochemistry are described.

Modelling of faults in low-voltage cables

Power line modelling has become an interesting research area in recent years as a result of advances in the power line distribution network system. Extensive knowledge about the power line cable characteristics can be implemented in a software algorithm in a modern broadband power-line communication modem. In this study, a novel approach for modelling power line cables (AMCMK) based on the broadband impedance spectroscopy (BIS) and transmission line matrix (TLM) techniques is recommended in characterizing a healthy cable and the various faults associated with low-voltage cables for both open and short circuit situation. Models for different cable conditions are developed and tuned, which include six models for both healthy and faulty cables situations. The models are on the basis of impedance response analysis of the cable. The resulting spectra from the simulations are also cross-correlated to determine the degree of similarities between the healthy cable spectra and their respective faulty spectra.

Applicability of Power-Line Communications to Data Transfer of On-line Condition Monitoring of Electrical Drives

The research of power-line communications has been concentrated on home automation, broadband indoor communications and broadband data transfer in a low voltage distribution network between home andtransformer station. There has not been carried out much research work that is focused on the high frequency characteristics of industrial low voltage distribution networks. The industrial low voltage distribution network may be utilised as a communication channel to data transfer required by the on-line condition monitoring of electric motors. The advantage of using power-line data transfer is that it does not require the installing of new cables. In the first part of this work, the characteristics of industrial low voltage distribution network components and the pilot distribution network are measured and modelled with respect topower-line communications frequencies up to 30 MHz. The distributed inductances, capacitances and attenuation of MCMK type low voltage power cables are measured in the frequency band 100 kHz - 30 MHz and an attenuation formula for the cables is formed based on the measurements. The input impedances of electric motors (15-250 kW) are measured using several signal couplings and measurement based input impedance model for electric motor with a slotted stator is formed. The model is designed for the frequency band 10 kHz - 30 MHz. Next, the effect of DC (direct current) voltage link inverter on power line data transfer is briefly analysed. Finally, a pilot distribution network is formed and signal attenuation in communication channels in the pilot environment is measured. The results are compared with the simulations that are carried out utilising the developed models and measured parameters for cables and motors. In the second part of this work, a narrowband power-line data transfer system is developed for the data transfer ofon-line condition monitoring of electric motors. It is developed using standardintegrated circuits. The system is tested in the pilot environment and the applicability of the system for the data transfer required by the on-line condition monitoring of electric motors is analysed.

Electrical characteristics of eddy current position sensor

In the thesis the principle of work of eddy current position sensors and the main cautions that must be taken into account while sensor design process are explained. A way of automated eddy current position sensor electrical characteristics measurement is suggested. A prototype of the eddy current position sensor and its electrical characteristics are investigated. The results obtained by means of the automated measuring system are explained.

Electrical Equivalent Circuit for Dry Bacteriorhodopsin Sensor

Bacteriorhodopsin (BR) is a photosensitive protein which functions as a light-driven proton pump. Due to its photoactivity, BR could be used in photosensing and information processing which has inspired researchers to study the photoelectric response and the appropriate measurement instrumentation for BR. In this thesis, the measurement instrumentation connected to a dry BR sensor was confirmed to affect the photovoltage response measured by using voltage amplifiers. Changing of the input impedance of the measurement instrumentation was shown to alter a part of the measured photovoltage response. The photocurrent measurements using transimpedance amplifier and the presented electrical equivalent circuit were used to show that the photocurrent measurements have no significant effect on the photoelectric response. The photocurrent was shown to be a derivate of the photovoltage response measured from the dry BR sensor when it was compared to the response measured with a voltage amplifier. This confirmed that another part of the photovoltage response was not affected by the measurement instrumentation. The time-variant behavior of the dry BR sensor was confirmed in both the photocurrent and the photovoltage measurements. This was caused by the fact that the capacitance of the dry BR sensor changes with the excitation light intensity.