This thesis describes an investigation of corrosion processes occurring under thin polymeric layers (3 -5 mum) and suggests ways by which the films suppress the onset of corrosion of the bulk metal in corrosive aqueous environments. Synthetic solutions have been developed which replicate pH and conductivity conditions, likely to be found in beverage cans and which have been used to conduct corrosion studies of commercial lacquer systems. Studies carried out highlight the following points: i) The degree and nature of the film cross-linking has a role in the anti-corrosive action of the films. ii) The quantity of iron released into the beverage is much lower than expected when the corrosivity of the solution and the relative thinness of the film are considered. Work carried out indicates a possible means by which the iron might be complexed by the phenolic cross-linker component of the film with evidence having been obtained showing the ease with which phenolic cross-linker/iron complexes can be formed. iv) Optical Emission Glow discharge spectrometry has provided evidence that iron corrosion products are trapped within the polymer matrix. The work has also highlighted a means of accurately determining the film thickness. v) Water permeation across the cured films was followed using infra-red spectroscopy. The amount of water at found to migrate across films of different cross-linking densities was observed to vary with phenolic cross-linker level present vi) Permeation of ions across cured films has been followed with the use of ion selective electrodes. The films have also been shown to be perm-selective towards the diffusion of sodium ions in preference to chloride ions, in aqueous sodium chloride solutions, thus exhibiting a duality in the nature of the coatings towards the constituents of corrosive environments. vi) Alternating Current Impedance spectroscopy, has been used to observe the electrolyte penetration and corrosion initiation processes, in situ. A knowledge of the electrochemical processes occurring for these water-based epoxy-acrylate films during electrolyte penetration, saturation of the film and development of corrosion underneath the film has been obtained.

Fan vibration has become a significant issue in telecommunications environments due to increased performance and heat of internal components requiring greater airflow and higher speed fans. This thesis investigates fan vibration problems in telecommunications equipment and develops solutions to the problem in a retrofit scenario. A target value for vibration levels was determined by measuring vibration levels in an alternate existing product that exhibited no wear issues over a span of several years. Two successful vibration isolator designs were developed and implemented. The retrofit solution required minimal changes to the legacy design and achieved a large vibration reduction. The ultimate solution required extensive changes to the legacy design and achieved significant vibration reductions, with vibration levels below the target value in most scenarios. Both designs are Patent Pending.

Filmes de polipirrol (PPy) foram eletropolimerizados potenciostáticamente sobre a liga de alumínio 1100, após ativação galvanostática, em presença de diferentes dopantes a fim de avaliar a sua utilização como revestimento protetor à corrosão. O método de síntese, o dopante e o tipo de ácido utilizado na eletropolimerização de polipirrol influenciam no desempenho do filme na proteção da liga. Os filmes de PPy sintetizados potenciostáticamente a 1,0 V, até carga de 1,0 C, em solução contendo pirrol (Py) 0,4 mol L-1, dodecilbenzenosulfonato de sódio (SDBS) 0,1 mol L-1 e ácido oxálico (H2C2O4) 0,1 mol L-1 apresentaram maior resistência de polarização. Os filmes de PPy sintetizados na mesma condição anterior e em presença das argilas montmorilonita sódica (MT-Na) ou montmorilonita modificada (MT-M), nas concentrações de 1 e 5% p/p, resultaram em material nanocompósito. Os filmes polipirrol/montmorilonita (PPy/MT) 1% em peso apresentaram melhor desempenho na proteção à corrosão da liga de alumínio Os valores de condutividade obtidos para os filmes de PPy e PPy/MT sintetizados pelo método eletroquímico utilizado são de 2-5 ordens maiores que os valores obtidos por síntese química. A partir de planejamento fatorial estatístico foi determinado que filmes de PPy sintetizados eletroquimicamente a 1 V até 1,5C em solução de Py 0,2 mol L-1, H2C2O4 0,1 mol L-1 e tungstato de sódio (Na2WO4) 0,05 mol L-1 propiciam maior resistência à corrosão da liga em meio de cloreto, devido à ação dopante e inibidora do ânion tungstato. / Polypyrrole (PPy) was deposited potentiostatically on aluminum alloy Al- 1100 after galvanostatic activation pretreatment, in the presence of different dopants, in order to obtain a protective film against corrosion. It has been shown that the corrosion resistance of the PPy recovered Al-1100 is strongly dependent on the surface pretreatment, pyrrole (Py) concentration and electropolimerization process. The higher polarization resistance of the recovered Al-1100 alloy was obtained for PPy films synthesized potentiostatically at 1.00 V, in a 0.1 mol L-1 dodecylbenzene sulfonate (SDBS) and 0.1 mol L-1 oxalic acid (H2C2O4) solution containing 0.4 mol L-1 Py. When Polypyrrole films are synthesized in the same conditions as above in the presence of 1 and 5% w/w of either Na+- Montmorillonite (MT-Na), or modified-Montmorillonite (MT-M), a nonocomposite material is obtained. It was observed that Al110 recovered with films of PPy/MTM 1% gives the higher corrosion protection. Moreover, the conductivity values obtained for the electrochemically synthesized PPy/SDBS and PPy/MT films are 2 to 5 orders of magnitude higher than those obtained by the chemical synthesis. By employing statistical factorial design it has been evidenced that the film PPy/OXA/W synthesized at 1.0 V, 5.0 C in 0.2 mol L-1 pyrrole, 0.1 mol L-1 H2C2O4 and 0.05 mol L-1 Na2WO4 solution, presents the best performance against corrosion in chloride media. Under these conditions, the tungstate anion plays the role of both dopant and inhibitor agent.

The depletion of natural resources has long been a concern since the rapid increase in energy consumption in recent years. The gradual increase of pollution worldwide accompanied by energy generation process also started to post threats to the environment. With the evolution of technology and materials, power generation and energy storage with significant improved efficiency can be made possible, and further benefits the reduction of degree of pollution generated. In this research, synthesis, processing, characterization and application of nano materials towards energy generation and energy storage devices are studied. In chapter 2, superior corrosion resistance properties of HVOF thermal spray of TiC and TiB2 coatings on 304H stainless steel, 430, and P91 steels were reported. The coatings successfully served at a protection layer by limiting oxygen penetration, sulfur attack, and decreased the formation of pits and cracks on the substrates at 750°C for up to 800 hours. In chapter 3, continuous smooth TiC nanofibers were successfully synthesized by carbothermal reduction of electrospun titanium based nanofibers. XRD and HR-TEM analysis results indicated the synthesized nanofibers were composed of high purity TiC. Electric conductivity of a single fiber was in the 2.00×10^5 range. Symmetrical cyclic voltammetry curve further indicated good electrochemical properties of the fibers. In addition, the TiC nanofibers also exhibited excellent sintering properties over TiC or TiB2 nanoparticles. Studies on morphology and electrochemical properties of MnOx nanofiber and nanoparticles is reported in chapter 4. MnOx, MnOx/SnO2, and MnOx/CNT nanofibers synthesized using electrospinning method showed specific capacitance of 166.12 F/g, 182 F/g for, and 472 F/g at scan rate of 10mV/s. Analysis results also showed positive impact of conductivity and fiber morphology on the electrochemical properties of the fibers. morphology and electrochemical properties of the MnOx nanoparticles synthesized using solvents with different polarity with gelation pH of 8.5, 9.0 and 10.0 were also studied. Analysis results show the impact of particle sized and morphology on the electrochemical properties. Highest specific capacitance measured for the synthesized nanoparticles was 231.38F/g@10mV/s and 165.13F/g@10mV/s for methanol and mixture of methanol and propanol based MnOx respectively. Effect of solvent polarity of the manganese sol on MnOx formation and phase transformation temperature is also shown in the chapter.

The electrochemical corrosion behavior of mild steel in apple, grape, mango, orange and the mixture of these juices was investigated in this study. Open circuit potential and weight loss analytical techniques were employed to establish the comparative corrosion rates of this material in the agro media over the interval of five days for a sixty-day immersion period at an ambient temperature. The chemical compositions of both mild steel and the agro media were determined to ascertain corrosion mechanism for the reaction. Polarization behavior of mild steel in the agro media were determined by Tafel extrapolation curves. The analysis showed that cathodic polarization curves were almost identical irrespective of the concentration of the various media while the anodic polarization curves exhibited varying active and passive corrosion behaviour due to passivating oxide films. The analysis of the results further showed that the corrosion rate of the metallic sample decreased with longer immersion periods which could be attributed to a gradual decline in acidity of these media as revealed by the pH results. Hence, the evolution of hydrogen gas and reduction of dissolved oxygen molecules from the reacting system were presumed to be major factors retarding corrosion of the solution involved. Similarly, the presence of suspended particles on the surface of the test steel sample could have also led to the impediment to corrosion rates from the surrounding atmosphere. Microscopic analysis of the corroded mild steel specimens revealed uniform and localized corrosion with Fe2O3 spotted as the main corrosion product. The result obtained from the electrochemical study showed that the corrosion rate of the mild steel sample was highest in the orange medium (1.53mm/yr), followed by grape medium (1.40mm/yr), mixture of these media (0.67mm/yr), mango medium (0.40mm/yr) while the metal corroded least in the apple medium (0.30mm/yr) over the duration of immersion. / Engineering : Chemical / M. Tech. (Chemical Engineering)

Made available in DSpace on 2014-06-11T19:32:11Z (GMT). No. of bitstreams: 0 Previous issue date: 2013-02-27Bitstream added on 2014-06-13T19:21:30Z : No. of bitstreams: 1 akita_ah_dr_araiq.pdf: 3382357 bytes, checksum: 102eae2f1a8724ee2dfd30920d6c2c8d (MD5) / Nesta tese foi desenvolvida uma metodologia para avaliar a ação corrosiva de biodiesel usando as técnicas de espectroscopia de impedância eletroquímica e análise do ruído eletroquímico com eletrodos de carbono vítreo, aço carbono SAE 1020, cobre puro, latão e zinco puro em meio de biodiesel (B100), produzido a partir de óleo de soja e metanol, sem utilização de eletrólito de suporte. Devido à baixa condutividade ou elevada resistência à passagem de corrente do biodiesel foi necessária a realização de uma série de testes com potenciostato antes da realização das medidas eletroquímicas. Adicionalmente, foram realizados estudos para determinação do intervalo de amplitude de potencial AC mais adequado para a realização de medidas de impedância utilizando células eletroquímicas desenvolvidas para o estudo em meio de biodiesel. Todos os resultados de impedância eletroquímica obedeceram às premissas de causalidade, linearidade e estabilidade. Foram feitas medidas de impedância eletroquímica durante 5 ou 9 dias utilizando biodiesel sem degradação e degradado em diferentes condições, respectivamente. De forma geral, o biodiesel degradado a 110 ºC apresentou maior corrosividade quando comparado ao biodiesel sem degradação e biodiesel degradado a 170 ºC. Essa observação também foi confirmada pelos estudos de microscopia e microanálise feitos nas superfícies dos materiais. Esse comportamento provavelmente se deve a evaporação de espécies agressivas em maior temperatura. Foram feitas medidas de ruído eletroquímico em meio de biodiesel, mas os resultados ainda são pouco conclusivos e até o presente momento não é do conhecimento do grupo a existência de relatos na literatura sobre este tipo de medida neste meio. A espectroscopia na região do infravermelho indicou a formação de óxidos em algumas... / In this thesis we have developed a methodology for the electrochemical study of glassy carbon, SAE 1020 carbon steel, pure copper, brass and pure zinc in biodiesel (B100) medium, produced from soy bean oil and methanol, without the intentional addition of supporting electrolyte, utilizing electrochemical impedance spectroscopy and electrochemical noise analysis. Due to the biodiesel low conductivity or high resistance to current flow, it was needed to perform a series of tests with potentiostat before conducting the electrochemical measurements. Additionally, it was carried out studies in order to determine AC potential amplitude range more adequate to perform the impedance measurements by using electrochemical cells developed for using in biodiesel medium. All electrochemical impedance results obeyed the assumptions of causality, linearity and stability. Electrochemical impedance measurements were conducted during 5 or 9 days using biodiesel without degradation and with different degradation conditions, respectively. In general, the biodiesel degraded at 110 ºC showed higher corrosivity compared to both non-degraded and degraded at 170 ºC. This observation was also confirmed by microscopy and microanalysis studies performed on the materials surface. This behavior is probably due to aggressive species evaporation at higher temperatures. Electrochemical noise analyses were carried out in biodiesel medium, however the results are still inconclusive and as far as our knowledge go, there is no literature reports using this kind of measurement in this medium. Infrared spectroscopy indicated the oxides formation in certain surface regions of copper, brass and zinc in contact with biodiesel. Non-degraded and degraded at 170 ºC biodiesel samples were analyzed by gas chromatography-mass spectrometry and the... (Complete abstract click electronic access below)

Made available in DSpace on 2014-06-11T19:32:50Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-09-03Bitstream added on 2014-06-13T20:04:24Z : No. of bitstreams: 1 baldissera_sc_dr_guara_prot.pdf: 12828080 bytes, checksum: 92f580d63d12b1909ff670e7cccf4175 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Ligas de Co-Cr-Mo tem tido boa aceitação na Odontologia como materiais de prótese. Na cavidade bucal estes materiais estão submetidos a efeitos simultâneos de esforços mecânicos e interação química. Durante o processo de fabricação de prótes, dusão, vazamento e resfriamento, ocorrem alteraçõesna microestrutura que podem afetar as propriedades mecânicas e resistência à corrosão. O objetivo deste trabalho foi estudar o efeito da refundição por maçarico com resfriamento lento e por indução com resfriamento rápido em 4 ligas Co-Cr-Mo comerciais. Os parâmetros investigados foram a microestrutura após ataque eletroquímico, resistência química com imersão de amostras durante 12 meses em soro fisiológico a 37ºC e a resistência à corrosão através de medidas de parâmetros eletroquímicos utilizando as técnicas de medidas de potencial em circuito aberto, polarização potenciodinâmica, voltametria cíclica e impedância eletroquímica. Os resultados indiam que os processos de refundição provocam diminuição do caráter dendrítico, levando a uma estrutura heterogênea com aumento no teor de Cr e Mo na região interdendrítica. Todas as ligas liberam íons de cobalto, cromo e molibdênio em solução em proporções diferentes da composição química de liga, observando-se maior liberação para as ligas refundidas pelo método indução com resfriamento rápido. Todas as ligas apresentam uma extensa região de passividade e baixa densidade de corrente semelhante ao comportamento eletroquímico do metal cromo, indicando ser este o elemento responsável pela passivação das ligas. Análise de impedância indicam comoportamento típico de formação de filme passivador sendo interpretado em termos de uma dupla camada constituída de uma subcamada interna resistiva e uma subcamada externa porosa. / Co-Cr-Mo alloys have good acceptance as dental prosthesis material. In mouth cavity these materials are submitted to simultaneous effects of mechanical efforts and chemical interactions. Microstructure changes than can modiy the mechanical and chemical properties of prosthesis material can occur during the prosthesis fabrication process which involves recasting of its material. Recasting process Co-Cr-Mo alloy(induction (IND) or blowtorch (FLAME) the influence of upon corrosion behavior of four commercial Co-Cr-Mo dental alloys in simulated physiological serum has been investigated using chemical electrochemical techniques. The morphology of microstructure after electrochemical etching resistance on 12 months physiological serum at 37º C immersion and corrosion resistance were the parameters analyzed. Corrosion resistance was determined by electrochemical measurements technique as open circuit potential measurement, potentiodynamic polarizationo, cyclic voltammetryc and eletrochemical impedance measurement. Results show that Co-Cr-Mo alloy recasting by induction (IND) or by blowtorch (FLAME) produces a reduction on dendritic strucutres formation, obtaining a heterogeneous structure rich in Cr and Mo in interdendritic regions. All the four Co-Cr-Mo commercial alloys studied in this work release Co, Cr and Mo ions in physiological serum solution at different proportion. Alloys re-cast by induction procedure and quenched release more Co, Cr and Mo ions. These alloys present and extended region of passivity and lower current density, wich similar to Cr metal elctrochemical behavior, indicating that Cr is responsible for alloys passivation. Impedance analysis shows that the passive film formed is a double layred film with an inner resitive sub-layer and an external porous sub-layer.

Made available in DSpace on 2014-06-11T19:32:50Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-12-01Bitstream added on 2014-06-13T21:05:02Z : No. of bitstreams: 1 silva_jwj_dr_guara.pdf: 2585287 bytes, checksum: b0304efc039af53412ee1f7353c6f71a (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Um grande número de ligas metálicas é usado na Odontologia para fabricação de próteses fixas e removíveis. Na cavidade oral essas estruturas estão expostas a um meio quimicamente adverso, com a saliva sendo o agente mais corrosivo, devido à alta concentração de íons cloreto que são causadores de corrosão localizada. Além disso, soluções contendo íons fluoreto também são frequentemente utilizadas em agentes profiláticos nos tratamentos dentários para prevenir a formação de placas dentárias e o desenvolvimento de cáries. Neste sentido, considerou-se importante investigar o comportamento eletroquímico e a resistência à corrosão de ligas dentárias Ni-Cr-Mo em meio fluoretado tamponado, que simula a agressividade dos colutórios e dos cremes dentários. Para tanto, foram realizados ensaios eletroquímicos de corrosão, em uma solução tampão HF/NaF, de três ligas avaliadas comercialmente (N, W 99 e SB) que se diferenciam com respeito às mudanças nas suas composições químicas, em especial, nos teores de níquel e de cromo. Para maior compreensão da morfologia das ligas estudadas, foi realizada a análise metalográfica, utilizando-se microscopia óptica e microscopia eletrônica de varredura. Para avaliar o comportamento eletroquímico, foram aplicadas técnicas eletroquímicas tradicionalmente utilizadas nas pesquisas de corrosão, tais como: polarização potenciodinâmica (PDS), polarização cíclica (CP) e espectroscopia de impedância eletroquímica (EIS). De acordo com os resultados obtidos, verificou-se o melhor desempenho para a liga N e o pior para W99, apresentando SB um comportamento intermediário. / A great number of metal alloys is used in dentistry to manufacture fixed and removable prostheses. In oral cavity these structures are exposed to a chemically adverse environment, with saliva being the most corrosive agent, due to high chloride ions concentration, which are causing localized corrosion. Moreover, solutions containing fluoride ions are also commonly used in prophylactic agents in dental treatments to prevent dental plaque formation and caries expansion. Thus, it was considered important to investigate the electrochemical behavior and corrosion resistance of Ni-Cr-Mo dental alloys in buffered fluoride medium, which simulates aggressiveness of mouthwashes and dental creams. This being so, electrochemical corrosion tests were carried out in a buffer HF/NaF solution of three commercially evaluated alloys (N, W 99 and SB) which are different in relation to changes in chemical compositions, in particular, in nickel and chromium content. For a better understanding of the studied alloys morphology, it was performed metallographic analysis, by using optical microscopy and scanning electron microscopy. In order to evaluate the electrochemical behavior, it was applied electrochemical techniques traditionally used in corrosion research, such as: potentiodynamic polarization (PDS), cyclic polarization (CP) and electrochemical impedance spectroscopy (EIS). According to the obtained results, it was observed the best performance for N alloy and the worst for W 99, with SB presenting and intermediate behavior.

Filmes de polipirrol (PPy) foram eletropolimerizados potenciostáticamente sobre a liga de alumínio 1100, após ativação galvanostática, em presença de diferentes dopantes a fim de avaliar a sua utilização como revestimento protetor à corrosão. O método de síntese, o dopante e o tipo de ácido utilizado na eletropolimerização de polipirrol influenciam no desempenho do filme na proteção da liga. Os filmes de PPy sintetizados potenciostáticamente a 1,0 V, até carga de 1,0 C, em solução contendo pirrol (Py) 0,4 mol L-1, dodecilbenzenosulfonato de sódio (SDBS) 0,1 mol L-1 e ácido oxálico (H2C2O4) 0,1 mol L-1 apresentaram maior resistência de polarização. Os filmes de PPy sintetizados na mesma condição anterior e em presença das argilas montmorilonita sódica (MT-Na) ou montmorilonita modificada (MT-M), nas concentrações de 1 e 5% p/p, resultaram em material nanocompósito. Os filmes polipirrol/montmorilonita (PPy/MT) 1% em peso apresentaram melhor desempenho na proteção à corrosão da liga de alumínio Os valores de condutividade obtidos para os filmes de PPy e PPy/MT sintetizados pelo método eletroquímico utilizado são de 2-5 ordens maiores que os valores obtidos por síntese química. A partir de planejamento fatorial estatístico foi determinado que filmes de PPy sintetizados eletroquimicamente a 1 V até 1,5C em solução de Py 0,2 mol L-1, H2C2O4 0,1 mol L-1 e tungstato de sódio (Na2WO4) 0,05 mol L-1 propiciam maior resistência à corrosão da liga em meio de cloreto, devido à ação dopante e inibidora do ânion tungstato. / Polypyrrole (PPy) was deposited potentiostatically on aluminum alloy Al- 1100 after galvanostatic activation pretreatment, in the presence of different dopants, in order to obtain a protective film against corrosion. It has been shown that the corrosion resistance of the PPy recovered Al-1100 is strongly dependent on the surface pretreatment, pyrrole (Py) concentration and electropolimerization process. The higher polarization resistance of the recovered Al-1100 alloy was obtained for PPy films synthesized potentiostatically at 1.00 V, in a 0.1 mol L-1 dodecylbenzene sulfonate (SDBS) and 0.1 mol L-1 oxalic acid (H2C2O4) solution containing 0.4 mol L-1 Py. When Polypyrrole films are synthesized in the same conditions as above in the presence of 1 and 5% w/w of either Na+- Montmorillonite (MT-Na), or modified-Montmorillonite (MT-M), a nonocomposite material is obtained. It was observed that Al110 recovered with films of PPy/MTM 1% gives the higher corrosion protection. Moreover, the conductivity values obtained for the electrochemically synthesized PPy/SDBS and PPy/MT films are 2 to 5 orders of magnitude higher than those obtained by the chemical synthesis. By employing statistical factorial design it has been evidenced that the film PPy/OXA/W synthesized at 1.0 V, 5.0 C in 0.2 mol L-1 pyrrole, 0.1 mol L-1 H2C2O4 and 0.05 mol L-1 Na2WO4 solution, presents the best performance against corrosion in chloride media. Under these conditions, the tungstate anion plays the role of both dopant and inhibitor agent.

Master of Science / Department of Civil Engineering / Stacey E. Kulesza / Thousands of metallic drainage structures have been installed by the Kansas Department of Transportation (KDOT) to facilitate proper drainage of highway systems across the state. Several studies were conducted over the past 30 years by KDOT to determine the durability of different corrugated metal pipe (CMP) materials and estimate their performance against the deterioration that occurs due to the electrochemical process of corrosion. These past studies have influenced KDOT policy regarding pipe material, but a method to quickly determine the rate of deterioration, and accurately predict a service life, is still not well defined. With the last comprehensive study performed in 1990 by KDOT, there is now a need to perform a field evaluation to determine the performance of CMPs in Kansas. This research conducted a survey of observed CMP conditions for 80 sites across KDOT districts one and four using a quantitative observational rating system. The goal of the survey was to determine the performance of CMPs in the field. The findings of this study indicate that a 1975 change in KDOT pipe policy has increased the rapid deterioration of CMPs. An additional study was conducted to determine if accurate service life predictions could be made based on chemical and biological characteristics of soil taken near the CMP invert. A method to test the leachate water exposed to the soil sample was created. Laboratory results of four field samples indicated that the rate at which the invert deteriorated corresponded to the total amount of chloride anion mobilized in the leachate over a 72-hour period, along with the standard deviation of pH measured throughout the test. This contradicts most field corrosion tests that only measure field pH and resistivity. The developed method of measuring soil sample leachate may provide a more accurate estimate of the performance of CMP in the sample location.