Alternating current electrohydrodynamics (ac-EHD) has been reported as a promising technique for enhancing sensor performance by the intimate mixing of the analyte solution at the electrode surface. The lateral fluid motion created by the ac-EHD phenomenon can be tuned by changing the frequency, voltage, and electrode geometry. To date, various studies have been conducted on the use of 2D electrodes based ac- EHD devices for sensor applications. However, the use of 3D electrodes may provide better fluid mixing as compared to the 2D electrodes due to the high surface area of the electrodes. To test this hypothesis, 2D and 3D microelectrodes with different sizes were designed and fabricated for ac-EHD studies using standard lithography and etching processes. Previous methods to achieve 3D microstructures and common issues faced during fabrication are also discussed. The lateral fluid motion created by the 2D and 3D electrodes after the application of different voltages and frequencies was analyzed by tracking the motion of fluorescent beads present in the mixing fluid. Fluorescence microscopy technique was used to capture videos of the movement of fluorescent beads in the fluid. The videos were analyzed using ImageJ to calculate the speed of fluorescent beads in the case of 2D and 3D electrodes. Furthermore, a different pattern of the fluid motion was observed in the case of 3D electrodes, which highlights the complex fluid movement in the case of 3D electrodes as compared to the 2D electrodes.

No description available.

The purpose of this research project was to determine the processing conditions necessary for preparing flexible carbon nanofiber electrodes by electrospinning and to explore various applications for those electrodes. It was found that by varying only the relative humidity while electrospinning a poly(acrylonitrile) precursor, fragile or flexible freestanding carbon nanofiber electrodes were prepared. The relative humidity during electrospinning controlled the fiber diameter, the bulk porosity of the material, and flexibility of the final carbon electrode. Higher porosity mats electrospun in a high relative humidity environment prevented fiber sintering, which if not minimized, resulted in non-flexible carbon electrodes. Both flexible and fragile electrodes were freestanding, binderless, and collectorless. Additionally, they required no further processing before use and were 100 wt.% active material. When cycled galvanostatically as a lithium ion battery anode, the flexible electrode exhibited a specific capacity of 379 mAH g-1 at the 100th cycle and capacity retention was 97.4% relative to the fifth cycle. When applied as an active material support electrode for lithium ion battery cathodes, the carbon support was successfully utilized with both micron and nano structured active material and cycled for 100 cycles with limited capacity loss. The same electrodes were also found to be a viable replacement for Pt electrode based actuators/artificial muscles. However, this application requires much further research to understand better the required processing and effects of the physical properties of the electrode on actuator performance. In addition to this, the flexible electrodes have a wide variety of other potential applications including, electrochemical storage and conversion devices, chemical sensing, and filtration. The focus of this work was electrochemical storage and conversion devices in the form of lithium ion battery anodes and cathodes as well as ionic polymer composite actuators. / PHD

Flexible electronics attract research and commercial interests in last 2 decades for its flexibility, low cost, light weight and etc. To develop and improve the electro-mechanical properties of flexible electrodes is the most critical and important step. In this work, we have performed nanomechanical and electro-mechanical characterization of materials for flexible electrode applications, including metallic nanowires (NWs), indium tin oxide (ITO)-based and carbon nanotube (CNT)-based electrodes. First, we designed and developed four different testing platforms for nanomechanical and electro-mechanical characterization purpose. For the nano/sub-micro size samples, the micro mechanical devices can be used for uni-axial and bi-axial loading tests. For the macro size samples, the micro tester will be used for in situ monotonic tensile test, while the fatigue tester can be used for in situ cyclic tensile or bending testing purpose. Secondly, we have investigated mechanical behaviors of single crystalline Ni nanowires and single crystalline Cu nanowires under uni-axial tensile loading inside a scanning electron microscope (SEM) chamber. We demonstrated both size and strain-rate dependence on yield stress of single-crystalline Ni NWs with varying diameters (from 100 nm to 300 nm), and themolecular dynamics (MD) simulation helped to confirm and understand the experimental phenomena. Also, two different fracture modes, namely ductile and brittle-like fractures, were found in the same batch of Cu nanowire samples. Finally, we studied the electro-mechanical behaviors of flexible electrodes in macro scale. We reported a coherent study integrating in situ electro-mechanical experiments and mechanics modeling to decipher the failure mechanics of ITO-based and CNT-based electrodes under tension. It is believed that our combined experimental and simulation results provide some further insights into the important yet complicated deformation mechanisms for nanoscale metals and fracture mechanism for flexible electrodes applications.

Applications of chromium vary widely (refractories, chemicals and metallurgical); however, the greatest benefit of chromium is its ability to improve the corrosion resistance, strength and hardness of steel. South Africa possesses approximately 75% of the viable global chromite reserves and, as a result, dominates the ferrochrome market with production in excess of 5 million mega tonnes per year - making it an industry of extreme importance to the South African economy Submerged arc ferroalloy production furnaces mainly use Soderberg electrodes - self–baking continuous electrodes that are produced in situ during furnace operation. Electrode breakings may affect a furnace in a number of ways depending on the nature and location of the break. Low furnace power input, abnormal charging and tapping conditions, as well as loss of production are among the more common negative implications associated with electrode breaks. The successful operation of Soderberg electrodes is dependent on two main factors: high quality electrode paste and effective electrode management procedures. This study focused on electrode paste quality. The raw materials utilised in the production of Soderberg electrode paste consists of calcined anthracite mixed with a tar pitch binder. In this study the focus was on the development of an experimental procedure to measure the dimensional changes of electrode paste raw materials as a function of temperature by means of thermomechanical analysis (TMA). Three uncalcined anthracite (Zululand chips, Zululand duff, and Tendele duff) and two tar pitch samples (low and high softening point pitches, i.e. LSP and HSP) were obtained from a local paste producer. Electrode graphite samples were also obtained from a local pre–baked electrode supplier. The experimental procedure for both the anthracite and tar pitches consisted of two phases: sample preparation and TMA measurements. During the sample preparation procedure for the tar pitches, the two tar pitches were heat treated in order to prevent softening in the TMA (preventing possibly damage the instrument), where after pellets were pressed for TMA measurement. The anthracite samples were calcined at 1200, 1300 and 1400°C in the anthracite sample preparation phase. TMA sample pellets of calcined and uncalcined anthracite were pressed using only water as a binder. TMA was performed on pellets produced from the heat–treated tar pitch samples, uncalcined and calcined anthracite samples, as well as core drilled pellets of the pre–baked electrode graphite. The dimensional changes of these pellets were measured, as a function of temperature, through three consecutive heating (room temperature to 1300°C) and cooling (1300°C to approximately 100°C) cycles under a N2 atmosphere. A significant shrinkage (> 12%) for both the LSP and HSP tar pitches occurred during the first TMA heating cycle. During the second and third heating cycles of the LSP and HSP tar pitches, dimensional changes were approximately 2%. This indicates that substantial structural reordering of the carbonaceous binder takes place during the first heating cycle. TMA results obtained for all three the calcined anthracite samples investigated indicated thermal dimensional changes of less than 1%. The anthracite samples calcined at the highest experimental calcination temperature (1400°C) prior to TMA analysis had the smallest dimensional changes. This confirmed that higher calcination temperatures result in a higher level of structural ordering and dimensional stability. Considering the combined calcined anthracite and tar pitches TMA results, the importance of the initial baking of a Soderberg electrode at temperatures exceeding the baking isotherm temperature (475°C) becomes apparent - the dimensional behaviour of the tar pitch binder and the calcined anthracite differ dramatically, making the newly–formed electrode very susceptible to breakage. Once structural reordering of the pitch had taken place, thermal dimensional behaviours of the materials are much more similar, significantly reducing the risk of thermal shock–induced electrode breakages. In contrast to the relatively small dimensional changes measured for the calcined anthracite samples, the shrinkages measured for the uncalcined samples during the first TMA heating/cooling cycle were substantial (6–8%). This indicates the importance of the anthracite calcination process, before the electrode paste is formulated. Improperly calcined anthracite present in electrode paste would result in additional dimensional shrinkage that would have to be accommodated in the baking of a new electrode section. Considering the large shrinkage of the tar pitch that already takes place, it is unlikely that a strong enough electrode would be formed if this occurs. From the results, it also became apparent that the anthracite with the highest fixed carbon and lowest ash contents exhibited the smallest shrinkage during in situ TMA calcination. High fixed carbon, low ash type anthracites are therefore less prone to dimensional instabilities in Soderberg electrodes, as a result of poor calcination. The dimensional changes observed in the calcined anthracites were very similar to those observed for the electrode graphite samples. The expansions/shrinkages observed in the graphite samples were mostly less than 0.5%, whereas the expansions/shrinkages observed in the various calcined anthracites were approximately 0.6 to 0.9%. The difference in the magnitude of the dimensional behaviour between the calcined anthracites and the graphite can be attributed to the fact that the graphite had already undergone maximum structural ordering (having been pre–baked at 3000°C). / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2012.

Applications of chromium vary widely (refractories, chemicals and metallurgical); however, the greatest benefit of chromium is its ability to improve the corrosion resistance, strength and hardness of steel. South Africa possesses approximately 75% of the viable global chromite reserves and, as a result, dominates the ferrochrome market with production in excess of 5 million mega tonnes per year - making it an industry of extreme importance to the South African economy Submerged arc ferroalloy production furnaces mainly use Soderberg electrodes - self–baking continuous electrodes that are produced in situ during furnace operation. Electrode breakings may affect a furnace in a number of ways depending on the nature and location of the break. Low furnace power input, abnormal charging and tapping conditions, as well as loss of production are among the more common negative implications associated with electrode breaks. The successful operation of Soderberg electrodes is dependent on two main factors: high quality electrode paste and effective electrode management procedures. This study focused on electrode paste quality. The raw materials utilised in the production of Soderberg electrode paste consists of calcined anthracite mixed with a tar pitch binder. In this study the focus was on the development of an experimental procedure to measure the dimensional changes of electrode paste raw materials as a function of temperature by means of thermomechanical analysis (TMA). Three uncalcined anthracite (Zululand chips, Zululand duff, and Tendele duff) and two tar pitch samples (low and high softening point pitches, i.e. LSP and HSP) were obtained from a local paste producer. Electrode graphite samples were also obtained from a local pre–baked electrode supplier. The experimental procedure for both the anthracite and tar pitches consisted of two phases: sample preparation and TMA measurements. During the sample preparation procedure for the tar pitches, the two tar pitches were heat treated in order to prevent softening in the TMA (preventing possibly damage the instrument), where after pellets were pressed for TMA measurement. The anthracite samples were calcined at 1200, 1300 and 1400°C in the anthracite sample preparation phase. TMA sample pellets of calcined and uncalcined anthracite were pressed using only water as a binder. TMA was performed on pellets produced from the heat–treated tar pitch samples, uncalcined and calcined anthracite samples, as well as core drilled pellets of the pre–baked electrode graphite. The dimensional changes of these pellets were measured, as a function of temperature, through three consecutive heating (room temperature to 1300°C) and cooling (1300°C to approximately 100°C) cycles under a N2 atmosphere. A significant shrinkage (> 12%) for both the LSP and HSP tar pitches occurred during the first TMA heating cycle. During the second and third heating cycles of the LSP and HSP tar pitches, dimensional changes were approximately 2%. This indicates that substantial structural reordering of the carbonaceous binder takes place during the first heating cycle. TMA results obtained for all three the calcined anthracite samples investigated indicated thermal dimensional changes of less than 1%. The anthracite samples calcined at the highest experimental calcination temperature (1400°C) prior to TMA analysis had the smallest dimensional changes. This confirmed that higher calcination temperatures result in a higher level of structural ordering and dimensional stability. Considering the combined calcined anthracite and tar pitches TMA results, the importance of the initial baking of a Soderberg electrode at temperatures exceeding the baking isotherm temperature (475°C) becomes apparent - the dimensional behaviour of the tar pitch binder and the calcined anthracite differ dramatically, making the newly–formed electrode very susceptible to breakage. Once structural reordering of the pitch had taken place, thermal dimensional behaviours of the materials are much more similar, significantly reducing the risk of thermal shock–induced electrode breakages. In contrast to the relatively small dimensional changes measured for the calcined anthracite samples, the shrinkages measured for the uncalcined samples during the first TMA heating/cooling cycle were substantial (6–8%). This indicates the importance of the anthracite calcination process, before the electrode paste is formulated. Improperly calcined anthracite present in electrode paste would result in additional dimensional shrinkage that would have to be accommodated in the baking of a new electrode section. Considering the large shrinkage of the tar pitch that already takes place, it is unlikely that a strong enough electrode would be formed if this occurs. From the results, it also became apparent that the anthracite with the highest fixed carbon and lowest ash contents exhibited the smallest shrinkage during in situ TMA calcination. High fixed carbon, low ash type anthracites are therefore less prone to dimensional instabilities in Soderberg electrodes, as a result of poor calcination. The dimensional changes observed in the calcined anthracites were very similar to those observed for the electrode graphite samples. The expansions/shrinkages observed in the graphite samples were mostly less than 0.5%, whereas the expansions/shrinkages observed in the various calcined anthracites were approximately 0.6 to 0.9%. The difference in the magnitude of the dimensional behaviour between the calcined anthracites and the graphite can be attributed to the fact that the graphite had already undergone maximum structural ordering (having been pre–baked at 3000°C). / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2012.

A transparent conductive electrode (TCE) is an important component in many of our modern optoelectronic devices like photovoltaics, light emitting diodes and touch screens. These devices require good current injection and spreading as well as a high transparency. In this thesis we explore the use of graphene as an alternative to the current widely used indium tin oxide (ITO) as TCE in gallium nitride (GaN) based light emitting diodes (LEDs). Monolayer crystalline graphene can be produced on copper foils using chemical vapor deposition (CVD), where metals (especially copper) has a catalysing effect on the formation of graphene. However, transfer of graphene from copper foils is not suitable for an industrial scale and it results in a poor contact with the target substrate. We investigate the possibility of directly integrating graphene on GaN-based LEDs by using plasma-enhanced chemical vapor deposition (PECVD). We try to obtain the optimal conditions under these catalyst-free circumstances and propose a recipe adapted for the setup that we used. We will also study ideas of using a metal (we tried copper and nickel) to assist the direct growth that could help to increase the fraction of sp2 carbon bonds and reduce the sheet resistance. The metals are evaporated onto our samples either before or after we grow a carbon film to either assist the growth or rearrange the carbon respectively. The focus was not on trying to optimize the conditions for one metal treatment but rather to briefly explore multiple methods to find a suitable path for further studies. The direct grown pristine carbon films shows indications from Raman measurements of being nanocrystalline graphene with a sheet resistance ranging from about 20-50 kΩ/sq having a transmittance of approximately 96 % at 550 nm. A transmittance at this level is closely related to the value of an ideal monolayer graphene, which indicates that our carbon films could be close to one atom in thickness while being visually homogeneous and complete in coverage. Due to the use of a temperature close to the melting point of copper we struggled to keep the assisting copper from evaporating too fast or staying homogeneous after the treatment. Nickel has a higher melting temperature, but it appears as if this metal might be diffusing into the GaN substrate which changes the properties of both the GaN and carbon film. Even though the metal treatments that we tested did not provide any noticeable improvements, there is need for further investigations to obtain suitable treatment conditions. We suggest that the treatments involving copper are a more promising path to pursue as nickel seem to cause unavoidable intermixing problems.

Zinc coated steels are widely used in the automotive industry, because of the improved protection against corrosion. Their use has consequences for the resistance welding process, which is the most widely used method of joining body panels. The zinc coating alloys with the copper electrode, resulting in increased electrode wear, and a reduction in electrode life. The welding current must be increased, because of the reduced contact resistance and thus heavier cables and power sources are required. A novel form of power source, the Medium Frequency Direct Current inverter, offers advantages over the traditional AC transformer. The higher operating frequency results in a lighter transformer, and a smaller welding current may be used, because the DC welding current generates heat at a constant rate, and is thus more effective than an AC power source. A potential advantage of this technology is that the increased frequency allows improved resolution in monitoring and control. Novel signal conditioning circuitry was developed, allowing significant improvement in the time resolution of the voltage and resistance signals. A series of welding trials was conducted, while monitoring the welding process. The correlation between weld quality and various process variables was assessed, and a control algorithm to compensate for electrode wear was proposed. This algorithm, based on a constant voltage principle, was implemented on a bespoke welding timer. A significant improvement in electrode life was obtained using this technique. The control algorithm was shown effective experimentally, but practical limitations do not permit testing under all possible conditions. A numerical model of the spot welding process, using Finite Difference technique, was developed. Following successful validation, the model was used to predict the performance of the control algorithm under various conditions of electrode wear. The results indicate that a constant voltage algorithm can compensate for an increase in electrode tip diameter, but that a change in contact resistance may result in unsatisfactory welds.

No description available.

Foram sintetizadas quatro naftaleno-diimidas (NDIs) funcionalizadas com grupos N-alquil-amino e N-alquil-hidroxi. Essas espécies foram caracterizadas pelos métodos espectrométricos convencionais. As propriedades eletroquímicas destas NDIs foram estudadas por voltametria cíclica em acetonitrila e N-metil-pirrolidona. Os voltamogramas obtidos mostram dois processos redox reversíveis com E1/2 ao redor de -970 mV e de -1400 mV (vs fc/Fc+). Estes resultados são consistentes com trabalhos previamente reportados. Algumas das NDIs exibiram grande afinidade por superfícies de carbono vítreo anodizado, adsorvendo irreversivelmente. Esta propriedade foi explorada na obtenção de eletrodos modificados. As propriedades eletroquímicas de eletrodos de carbono vítreo modificados por adsorção das NDIs foram investigadas por voltametria cíclica (VC) e cronoamperometria de degrau de potencial (CADP). Os voltamogramas são caracterizados pela presença de um único processo redox reversível, com E1/2 na faixa de -360 mV a -385 mV (vs Ag/AgCl). Os transientes de CADP forneceram estimativas para as constantes de velocidade k para as reações de transferência de elétrons na superfície dos eletrodos. Foram observados desvios em relação à cinética de primeira ordem, atribuídos ao caráter micro-heterogêneo da superfície. O modelo de Albery, que considera a dispersão dos valores de k, foi aplicado e comparado com dados obtidos por ajuste de funções exponenciais. Foram também preparados compósitos à base de NDIs e nanotubos de carbono de parede simples (NTCPS) sobre eletrodos de ouro. A resposta voltamétrica dos compósitos NDI/NTCPS é caracterizada pela presença de um processo redox reversível na faixa de -336 mV a -349 mV (vs Ag/AgCl). A cinética de transferência de elétrons nestes eletrodos modificados foi estudada por metodologia análoga à descrita anteriormente. Os resultados sugerem que os eletrodos estudados podem encontrar aplicação no desenvolvimento de sensores químicos, dispositivos eletroquímicos e em eletrocatálise. / Four naphthalene-diimides (NDIs) were synthesized functionalyzed with N- alkyl-amino and N-alkyl-hydroxi groups. These NDIs were characterized by conventional spectrometric methods. The electrochemical properties of NDIs were studied through cyclic voltametry in acetonitrile and N-metyl-pyrrolidone. Typical voltammograms present two reversible redox processes with E1/2 around -970 mV and -1400 mV (vs Fc/Fc+ ). These results are consistent with previous reported works. Some NDIs showed a strong affinity to anodized glassy carbon surfaces, with irreversible adsorption. This property was used to obtain new modified glassy carbon electrodes. The electrochemical properties of glassy carbon electrodes modified by adsorption of the NDIs were studied by cyclic voltammetry (CV) and potential step chronoamperometry (PSCA). The voltammograms are characterized by the presence of a single reversible redox process, with E1/2 around -360 mV to -385 mV (vs Ag/AgCl). The PSCA transients offered estimates for the k rate constants for the electron transfer reactions on the electrode surfaces. Deviations with respect to the first order kinetics were observed and considered due to the micro-heterogeneity of the surface. Albery´s model, wich takes into account the dispersion in k values, was applied and results compared with those obtained by exponential functions fitting. Composites based on NDIs and single walled carbon nanotubes (SWNT) were also prepared on gold electrodes. The voltammetric response from NDI/SWNT composites is characterized by the presence of reversible redox process in the range from -336 mV to -349 mV (vs Ag/AgCl). The kinetics of the electron transfers on those modified electrodes was studied using a methodology similar to the one previously described. The results suggest that these modified electrodes may find application in the development of chemical sensors, electrochemical devices and in electrocatalysis.