Aluminized steel Type 2 (AST2), often used for culvert pipes, is subject to corrosion which is the most important durability limitation factor. It was desired to determine if the outer aluminized layer will retain passivity and if protective galvanic action will develop. Thus, corrosion of unblemished and blemished AST2 surfaces was investigated in simulated natural waters. Experiments with unblemished specimens showed passive corrosion rates (~0.06 µm/yr) in scale-forming, 0.01 M Cl- solutions but sustained corrosion in other less protective media (with rates 3~10 µm/yr). Corrosion was manifested macroscopically by discoloration and few macro pits, but it likely proceeded also microscopically at the Fe-rich inclusion space scale. For blemished specimens, the aluminized coating galvanically protected to some extent the steel in all solutions. However, in 0.01 M Cl- solutions, protection was delayed until after some steel corrosion had occurred. In some solutions, complete consumption of the outer aluminized coating around exposed steel was noted. Elsewhere, coating appearance was similar to that of the unblemished condition. Nominal durability projections made for 16-gage AST2 ranged from >100 yr for unblemished AST2 to ~10 yr for the blemished condition. The present findings were used as a first step in proposing refinements of presently used durability guidelines of AST2 culvert pipe. Cyclic cathodic polarization tests to examine O2 and H2 reduction at the Fe-rich inclusions showed significant hysteresis, more pronounced with decreasing scan rate. The effect was tentatively associated to the amount of Fe+2 being deposited during the downward scan, a hypothesis supported by results from a physical model. A static polarization model was formulated for the blemished configuration. Results matched experimental trends and permitted evaluating the effect of solution conductivity s beyond the experimental range. Exposed steel corrosion rates at the steel were increasingly large for decreasing s. For the lowest s, corrosion rates at the exposed steel center were distinctly larger than at the edge, consistent with experiments. An impedance behavior model was also formulated. Results showed frequency dependent current distribution and predicted relatively small artifacts that were and not evident experimentally, but should be considered when exploring other system conditions.

Thin film coatings are used to improve the properties of components and products in such diverse areas as tool coatings, wear resistant biological coatings, miniature integrated electronics, micro-mechanical systems and coatings for optical devices. This thesis focuses on understanding the development of intrinsic stress and microstructure in coatings of the technologically important materials of aluminium nitride (AlN) and titanium vanadium nitride (TiVN) deposited by filtered cathodic arc deposition. Thin films of AlN are fabricated under a variety of substrate bias regimes and at different deposition rates. Constant substrate bias was found to have a significant effect on the stress and microstructure of AlN thin films. At low bias voltages, films form with low stress and no preferred orientation. At a bias voltage of -200 V, the films exhibited the highest compressive stress and contained crystals preferentially oriented with their c axis in the plane of the film. At the highest bias of -350 V, the film forms with low stress yet continue to contain crystallites with their c axis constrained to lie in the plane of the film. These microstructure changes with bias are explained in terms of an energy minimisation model. The application of a pulsed high voltage bias to a substrate was found to have a strong effect on the reduction of intrinsic stress within AlN thin films. A model has been formulated that predicts the stress in terms of the applied voltage and pulsing rate, in terms of treated volumes known as thermal spikes. The greater the bias voltage and the higher the pulse rate, the greater the reduction in intrinsic stress. At high pulsing and bias rates, a strong preference for the c axis to align perpendicular to the substrate is seen. This observation is explained by dynamical effects of the incident ions on the growing film, encouraging channelling and preferential sputtering. For the first time, the effect of the rate of growth on AlN films deposited with high voltage pulsed bias was investigated and found to significantly change the stress and microstructure. The formation of films with highly tensile stress, highly compressive stress and nano-composites of AlN films containing Al clusters were seen. These observations are explained in terms of four distinct growth regions. At low rates, surface diffusion and shadowing causes highly porous structures with tensile stress; increased rates produced Al rich films of low stress; increasing the growth rate further led to a dense AlN film under compressive stress and the highest rates produce dense, low stress, AlN due to increased levels of thermal annealing. Finally this thesis analyses the feasibility of forming ternary alloys of high quality TiVN thin films using a dual cathode filtered cathodic arc. The synthesised films show exceptional hardness (greater than either titanium nitride or vanadium nitride), excellent mixing of the three elements and interesting optical properties. An optimum concentration of 23% V content was found to give the highest stress and hardness.

Steel corrosion in reinforced concrete is a major concern to transportation agencies nationwide because of the expenses incurred for repair and ultimate shortening of bridge life. Cathodic protection (CP), as a remedy, has been applied to reinforced bridges in the US since 1974. However, application of this technique is largely empirical, lacking fundamental understanding. In order to optimize the performance of a CP system, it is important to monitor the rebar potential with respect to a reliable reference electrode. Moreover, because of potential variation in the concrete, reference cell placement is fundamental to ensure effective protection. The work plan was divided into two parts: laboratory scale experimentation and computer simulation. In the experimentation section, the response of graphite probes was compared to that of an Orion silver-silver chloride electrode. Graphite probes behaved as well as the standard electrode. Furthermore, the home-made graphite probes behaved the same as the commercial ones. This will allow much greater experimental latitude since the home-made probes are much more economical than the commercial ones. A finite difference code was developed to assess the performance of cathodic protection. The potential distribution in a two dimensional geometry of a concrete block with a sprayed zinc anode at one boundary and an iron cathode at the other side was calculated under cathodic protection. The equations were solved by means of a Gauss-Seidel iterative method with the help of an overrelaxation factor. An interval halving method was used to solve for nonlinear boundary condition at the iron. The effects of concrete pore saturation, concrete cover, and applied potential were studied to determine the degree of protection and proper placement of the reference electrode in concrete. Furthermore, a sensitivity analysis was performed versus input parameters: concrete conductivity, oxygen mass transfer coefficient, and oxygen reduction polarization parameters. The results of the simulation showed that the center of the rebar is less protected than the other locations. Therefore, the reference electrode should be located as close to the center as possible. / Graduation date: 1995

This research explores the thermal stability of ZrCrAlN material system. For this purpose fourteen different compositions of ZrCrAlN coatings were deposited onto tungsten carbide substrates by using reactive cathodic arc evaporation. These compositions were further annealed at 800oC, 900oC, 1000oC and 1100oC temperatures. EDS was employed to specify the compositions. The crystal structure of the coatings were analysed by XRD, and the hardness of these coatings was determined by Nanoindentation. The experimental findings reported a significant age hardening of Zr0.16Cr0.12Al0.72N and a delayed h-AlN formation in Zr0.07Cr0.40Al0.52N. ZrCrAlN was thus proved to be thermally stable. / Multifilms,A4:2 Growth and characterization of Multicomponent Nitrides by Magnetron Sputtering and Arc evaporation

The polarization performance of two types of commercial galvanic point anodes for protection of reinforced steel around patch repairs was investigated. Experiments included measurement of the polarization history of the anode under constant current impressed by galvanostatic circuits and in reinforced concrete slabs. The tests revealed, for both types of anodes, a potential-current function (PF) indicating relatively little anodic polarization from an open circuit potential at low current levels, followed by an abrupt increase in potential as the current approached an apparent terminal value. Aging of the anodes was manifested by a continually decreasing current output in the concrete tests, and by increasingly more positive potentials in the galvanostatic tests. Those changes reflected an evolution of the PF generally toward more positive open circuit potentials and, more importantly, to the onset of elevated polarized potentials at increasingly lower current levels. There was considerable variability among the performance of replicate units of a given anode type. Modest to poor steel polarization levels were achieved in the test yard slabs. Modeling of a generic patch configuration was implemented with a one-dimensional approximation. The model calculated the throwing distance that could be achieved by a given number of anodes per unit perimeter of the patch, concrete thickness, concrete resistivity, amount of steel and amount of polarization needed for cathodic prevention. The model projections and aging information suggest that anode performance in likely application scenarios may seriously degrade after only a few years of operation, even if a relatively optimistic 100 mV corrosion prevention criterion were assumed. Less conservative criteria have been proposed in the literature but are yet to be substantiated. Other investigations suggest a significantly more conservative corrosion prevention may apply instead. The latter case would question the ability of the point anodes to provide adequate corrosion prevention.

The filtered cathodic vacuum arc (FCVA) technique is a well established deposition method for wear resistant mechanical coatings. More recently, this method has attracted attention for growing ZnO based transparent conducting films. However, the potential of FCVA deposition to prepare ZnO layers for electronic devices is largely unexplored. This thesis addresses the use of FCVA deposition for the fabrication of active ZnO based electronic devices. The structural, electrical and optical characteristics of unintentionally doped ZnO films grown on different sapphire substrates were systematically investigated. The potential of FCVA to grow both polar and non-polar ZnO films was demonstrated. The resulting films showed considerable promise for device applications with properties including high transparency(> 90%), moderate intrinsic carrier concentrations (10¹⁷ - 10¹⁹ cm⁻³), electron mobilities up to 110 cm⁻²/Vs, low surface roughness (< 5 nm) and well-structured photoluminescence. Post-growth annealing in oxygen at temperatures up to 800 C produced significant improvements in the electronic and optical properties of these films, due to the formation of larger grains with lower inter-grain potential barriers. Silver oxide (AgOᵪ ) and iridium oxide (IrOᵪ) Schottky diodes fabricated on annealed FCVA ZnO films showed ideality factors as low as 1.20, barrier heights up to 0.85 eV and high sensitivity to ultraviolet light (up to ̴ 10⁻⁵ at -2 V). Transparent and opaque MESFETs fabricated on these films showed well defined field effect characteristics, channel mobilities up to 70 cm⁻²/Vs and insensitivity to 1 mW/cm⁻² visible light. These devices were further subjected to extensive bias and temperature stress tests. MESFET stability appeared to be strongly dependent on Schottky gate type, bias conditions and ZnO film morphology. Positive bias stress of AgOᵪ gated devices resulted in irreversible damage, that is thought to be due to Ag electromigration across the gate interface. Mapping of the surface potential of the ZnO channel material with Kelvin probe force microscopy suggested a strong relationship between the defect density at grain boundaries and both channel mobility and current stability. Interval growth techniques were found to reduce the density of defects at grain boundaries and produced MESFETs with higher current stability. IrOᵪ gated devices showed superior bias stability and temperature resilience from 25 C-195 C.

Cathodic processes occurring in the solutions containing Cu(II) tartaric complexes have been investigated. The equations accounting for the material balance have been constructed and used for the estimation of distribution of complexes and ligands in the bulk of solution. It was established that dominating particles in acidic media (pH < 3) are: Cu2+ and tartaric complex CuL, tartaric acid LH2 and its anion LH-. Potentials of non-polarized copper electrodes were found to be reversible and to follow Nernst equation. According to the analysis performed, surface oxide Cu2O is not able to form in acidic (pH < 3) media. Cathodic voltammograms obtained for the solutions of different acidity exhibit two characteristic current peaks arising from Cu(II) reduction and hydrogen evaluation. An analysis of voltammetric extrema shows that both processes are irreversible. Based on the regularities of the mass transport of chemically interacting substances, surface distribution of components has been simulated. These date were used for the transformation of experimental voltammograms into normalized Tafel plots. According to their analysis, the rate-controlling step of Cu(II) reduction is the transfer of the first electron onto Cu2+ aqua-complex. The values of kinetic parameters were found to be as follows: the cathodic charge transfer coefficient is equal to 0.33 and the exchange current density is equal to 50 mA cm-2. An analysis of the second current peak leads to the conclusion... [to full text]

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Thesis (PhD) - Swinburne University of Technology, School of Engineering and Science, 2008. / A thesis submitted for the degree of Doctor of Philosophy, School of Engineering and Science, Swinburne University of Technology, 2008. Typescript. Includes bibliographical references (p. 189-204).

A ortodontia pressupõe o uso de artefatos. Os bráquetes são ligados por fios ortodônticos, denominado arcos, para que possam ser movimentados juntamente com os dentes por sistemas de molas e ancoragens de vários materiais unidos por diferentes processos. Isto propicia uma pilha galvânica e liberação de níquel pelo aparelho. Atualmente existem materiais livres de níquel, porém os aços inoxidáveis possuem menor custo e maior facilidade de uso. A alergia ao níquel contido no aço inoxidável do aparelho causa desconforto e, em alguns casos, a interrupção do tratamento. Tal alergia provém dos íons de níquel liberados pelo aço inoxidável e transportados pela saliva até os tecidos do paciente. Este trabalho teve por objetivo aplicar a técnica dos anodos de sacrifício utilizada para a proteção catódica de estruturas metálicas expostas a meios salinos. Esta técnica foi aplicada na proteção do aço inoxidável e suas combinações com outros metais usados em tratamentos ortodônticos. Foram efetuadas várias combinações de anodos de sacrifício e eletrólitos em duas etapas de testes, com arranjos compostos por uma banda soldada com solda prata a um meio arco pré-contornado mais cinco bráquetes presos nele por um fio de amarril. Na primeira etapa foram avaliados quatro anodos de sacrifício amarrados aos arranjos e soluções aquosas com três salinidades obtendo-se em torno de cinquenta por cento de redução na liberação de níquel. A segunda etapa foi melhor sucedida e, a quantidade de níquel liberada, ficou abaixo do limite de detecção do equipamento de absorção atômica eletroquímica que foi utilizado neste trabalho. Nessa segunda etapa foram utilizados anodos de zinco e magnésio para a proteção e soro fisiológico com e sem fluoreto de sódio. O contato elétrico dos anodos de sacrifício com o aço inoxidável foi melhorado e, possivelmente, causou a menor liberação de níquel nesta etapa. Isto valida o método de proteção catódica na diminuição da liberação de níquel pelos aparelhos ortodônticos de aço inoxidável. / Orthodontics involves the use of artifacts. The orthodontic brackets are connected by wires, called arches, so that they can be moved together with the teeth by springs and anchoring systems of different materials together by different processes. This possibly creates a galvanic cell, and release of nickel by the device. Currently there are nickel-free materials. However stainless steels have lower value and ease of use. Allergy to nickel contained in the stainless steel unit causes discomfort and in some cases to discontinuation of treatment. This allergy comes from nickel ions released by stainless steel through the patient's saliva. This study aimed to apply the technique of sacrificial anodes used for cathodic protection of steel structures exposed to saline. This technique was applied to the stainless steel protection and their combinations with other metals used in orthodontic treatments. Various combinations of sacrificial anodes and electrolytes were made. Two stages of tests were carried out and arrangements consist of a welded band with silver solder in the middle pre-skirted five brackets bow stuck in it with amarril wire. In the first stage were evaluated four anodes sacrifice tied to the arrangements and aqueous solutions with various salinities yielding around fifty percent reduction in nickel release. The second step was more successful and the amount of nickel released, was below the detection limit of electrochemical atomic absorption device used in this work. In the second stage we used zinc and magnesium anodes for the protection and saline with and without sodium fluoride. The electrical contact of sacrificial anodes with stainless steel has been improved and possibly caused the lower nickel release at this stage. This validates the method of cathodic protection in the reduction of the release of nickel stainless steel orthodontic appliances.