There has been progress in the surface modification of low carbon steel in order to enhance its surface hardness. This study contributes to this by investigating the introduction of carbon nanotubes and amorphous carbon in the carburization of mild steel. In order to achieve the goal, carbon nanotubes were synthesized in a horizontal tubular reactor placed in a furnace also called the chemical vapor deposition process at a temperature of 700oC. Catalyst was produced from Iron nitrate Fe(NO3)3.9H2O and Cobalt nitrate Co(NO3)2.6H2O on CaCO3 support while acetylene C2H2 was used as the carbon source and nitrogen N2 was used as contaminant remover. The as-synthesized carbon nanotubes were purified using nitric acid HNO3 and characterized using scanning electron microscopy (SEM), thermo-gravimetric analysis (TGA) and fourier transform infrared spectroscopy (FTIR). It was found that as-synthesized carbon nanotubes had varying lengths with diameters between 42-52 nm from the SEM and the TGA showed the as-synthesized CNTs with a mass loss of 78% while purified CNTs had 85% with no damage done to the structures after using the one step acid treatment. The as-synthesized and purified carbon nanotubes were used in carburizing low carbon steel (AISI 1018) at two austenitic temperatures of 750oC and 800oC and varying periods of 10-50 minutes while amorphous carbon obtained by pulverizing coal was also used as comparison. The mild steel samples were carburized with carbon nanotubes and amorphous carbon in a laboratory muffle furnace with a defined number of boost and diffusion steps. The carburizing atmosphere consisted of heating up to the varying temperatures at a speed of 10oC/minute, heating under this condition at varying periods, performing a defined number of boost and diffusion processes at the varying temperatures and cooling to room temperatures under the same condition. The carburized surfaces were observed with the Olympus SC50 optical microscope and the hardness distribution of the carburized layer was inspected with a Vickers FM 700 micro-hardness tester. The as-synthesized and purified CNT samples showed higher hardness on the surface of the mild steel than the amorphous carbon. In the same vein, the change in the microstructures of vi the steel samples indicated that good and improved surface hardness was obtained in this work with the reinforcements but with purified CNT having the highest peak surface hardness value of 191.64 ± 4.16 GPa at 800oC, as-synthesized CNT with 177.88 ± 2.35 GPa and amorphous carbon with 160.702 ± 5.79 GPa which are higher compared to the values obtained at 750oC and that of the original substrate which had a surface hardness of 145.188 ± 2.66 GPa. The percentage hardness obtained for the reinforcement with the amorphous carbon, the CNT and the pCNT showed an increase of 5.47%, 10.04% and 15.77% respectively at 750oC when compared to that of the normal substrate carburized without reinforcements. Furthermore, at 800oC, the reinforcement with the amorphous carbon, the CNT and the pCNT show a percentage hardness increase of 7.04%, 14.68% and 22.05% when compared to that of the normal substrate carburized without reinforcements. Comparing the reinforcement potential of the amorphous carbon, the CNT and the pCNT at 750oC, the percentage hardness reveal that using pCNT displayed an increase of 10.89% over that of amorphous carbon and of 6.37% over that of CNT. In addition, the use of CNT as reinforcement at 750oC displayed a percentage hardness increase of 4.83% over that of the amorphous carbon carburized at the same temperature / Civil and Chemical Engineering / M. Tech. (Chemical Engineering)

Corrosion of metallic materials is a natural process, and our study shows that even in an alkaline environment severe corrosion may occur on a carbon steel surface. While corrosion cannot be stopped it can be retarded. Many of the traditional anti-corrosion approaches such as the chromate process are effective but hazardous to the environment and human health. Mefp-1, a protein derived from blue mussel byssus, is well known for its extraordinary adhesion and film forming properties. Moreover, it has been reported that Mefp-1 confers a certain corrosion protection for stainless steel. All these facts indicate that this protein may be developed into corrosion inhibitors with ‘green’, ‘effective’ and ‘smart’ properties. In this study, a range of surface-sensitive techniques have been used to investigate adsorption kinetics, film forming and film compaction mechanisms of Mefp-1. In situ atomic force microscopy (AFM) enables the protein adsorption on substrates to be visualized, whereas the ex situ AFM facilitates the characterization of micro- and nano-structures of the protein films. In situ Peak Force AFM can be used to determine nano-mechanical properties of the surface layers. The quartz crystal microbalance with dissipation monitoring (QCM-D) was used to reveal the build-up of the Mefp-1 film on substrates and measure the viscoelastic properties of the adsorbed film. Analytical techniques and theoretical calculations were applied to gain insights into the formation and compaction processes such as oxidation and complexation of pre-formed Mefp-1 films. The electron probe micro analyzer (EPMA) and X-ray photoelectron spectroscopy (XPS) were utilized to obtain the chemical composition of the surface layer. Electrochemical impedance spectroscopy (EIS) measurements were performed to evaluate the corrosion inhibition efficiency of different forms of Mefp-1 on carbon steel substrates. The results demonstrate that Mefp-1 adsorbs on carbon steel surfaces across a broad pH interval, and it forms a continuous film covering the substrate providing a certain extent of corrosion protection. At a higher pH, the adsorption is faster and the formed film is more compact. At neutral pH, results on the iron substrate suggest an initially fast adsorption, with the molecules oriented preferentially parallel to the surface, followed by a structural change within the film leading to molecules extending towards solution. Both oxidation and complexation of the Mefp-1 can lead to the compaction of the protein films. Addition of Fe3+ induces a transition from an extended and soft protein layer to a denser and stiffer one by enhancing the formation of tri-Fe3+/catechol complexes in the surface film, leading to water removal and film compaction. Exposure to a NaIO4 solution results in the cross-linking of Mefp-1, which also results in a significant compaction of the pre-formed protein film. Mefp-1 is an effective corrosion inhibitor for carbon steel when added to an acidic solution, and the inhibition efficiency increases with time. As a film-forming corrosion inhibitor, the pre-formed Mefp-1 film provides a certain level of corrosion protection for short term applications, and the protection efficiency can be significantly enhanced by the film compaction processes. For the long term applications, a thin film composed of Mefp-1 and ceria nanoparticles was developed. The deposited Mefp-1/ceria composite film contains micro-sized aggregates of Mefp-1/Fe3+ complexes and CeO2 particles. The Mefp-1/ceria film may promote the further oxidation of ferrous oxides, and the corrosion resistance increases with time. Moreover, phosphate ions react with Fe ions released from the surface and form deposits preferentially at the surface defect sites. The deposits incorporate into the Mefp-1/ceria composite film and heal the surface defects, which result in a significantly improved corrosion inhibition effect for the Mefp-1/ceria composite film in both initial and prolonged exposure situations / <p>QC 20130610</p>

Analisaram-se os parâmetros tecnológicos mais significativos que influem na Usinagem por Eletroerosão (UEE). Foram desenvolvidos e comentados ensaios de usinagem de aço-carbono com eletrodos de cobre. Apresenta-se também um método de dimensionamento da ferramenta e da avaliação do tempo de usinagem, baseado nos dados obtidos. Foram confrontados os principais processos não-convencionais de usinagem, constatando-se que a UEE é um eficiente processo de fabricação. / The most important EDM technological parameters have been analyzed. Experiments on carbon-steel workpiece machined with copper tool-electrode have been developed and discussed. Based on the obtained data, this work suggests a method for designing the tool-electrode and evaluating the total machining time. Others usual non-traditional machining processes have been compared and it has been observed that EDM is an efficient manufacturing process.

O setor de açúcar e álcool etílico no Brasil tem experimentado um grande crescimento. Contribuem para isto as demandas crescentes do álcool etílico, um biocombustível, e do açúcar. A área industrial produtora de açúcar, um alimento, ainda convive com uma prática industrial ultrapassada, que vem a ser o uso do aço carbono, um material barato, mas com pequena resistência à corrosão. Os aços inoxidáveis são os materiais mais indicados para a substituição do aço carbono, entretanto, eles são considerados caros. Os evaporadores das usinas de açúcar são equipamentos importantes para a sua operação. Quando são usados tubos de aço carbono para a troca térmica, eles começam a ser substituídos a partir do segundo ano de operação devido à corrosão. Enquanto isso, os tubos em aços inoxidáveis podem durar décadas. O presente trabalho objetivou a avaliação do desempenho ambiental e financeiro de tubos para evaporadores construídos com aço carbono e, comparativamente, com os aços inoxidáveis 304, 444 e 439. Para alcançar estes objetivos foram utilizadas as metodologias de Avaliação do Ciclo de Vida (ACV) e de Custeio do Ciclo de Vida (CCV), respectivamente. Neste estudo de ACV foi adotada como função dos sistemas em estudo a massa de água evaporada. Na definição destes sistemas de produtos foram adotados os subsistemas de fabricação das bobinas de lâminas dos aços e fabricação, instalação e limpeza dos tubos. O consumo de gás natural, eletricidade e o transporte foram usados como subsistemas secundários. O período de avaliação destes sistemas foi de trinta anos. A partir dos resultados desta ACV, concluiu-se que os tubos em aço carbono apresentaram maior impacto ambiental que os tubos em aço inoxidável 304, 444 e 439, pois emitiram mais que 4,2 vezes a quantidade de dióxido de carbono; 2,8 vezes a de óxidos de nitrogênio; 3,1 vezes a de materiais particulados, 13 vezes a de materiais suspensos e 4,5 vezes a de resíduos totais. Os tubos em aço carbono consumiram também mais que 11 vezes o total de recursos naturais utilizados (carvão; lignita; calcita; dolomita; óleo; gás natural e minérios de ferro, cromo, níquel, molibdênio e manganês); 1,8 vezes a de água e 5 vezes a de energia. Com relação à emissão de óxidos de enxofre, os tubos em aço carbono emitiram quantidades semelhantes às emitidas pelos tubos em aços 444 e 439 e a metade que os tubos em aço 304. Na elaboração do CCV foram utilizados os componentes de custo compra, transporte, instalação, substituição e limpeza dos tubos e a venda das sucatas. Na avaliação financeira, todos os custos que aconteceram no período de trinta anos foram trazidos ao valor presente. A partir dos resultados obtidos concluiu-se que os aços inoxidáveis 439 e 444 apresentaram-se como opções de investimento mais interessantes que os tubos fabricados em aço carbono, já que apresentaram custos trazidos ao valor presente menores, na proporção de 0,76 para os tubos em aço 439; 0,79 para os tubos em aço 444 com 1,20 mm de espessura e 0,93 para tubos em aço 444 com 1,50 mm de espessura. Os tubos em aço 304 com 1,20 mm de espessura apresentaram desempenho financeiro semelhante aos tubos em aço carbono; enquanto que os tubos em aço 304 com 1,50 mm apresentaram custos ao valor presente 1,19 vezes maior. Os resultados obtidos indicam também que as metodologias ACV e CCV devem ser usadas em conjunto, pois mostram que produtos mais seguros ambientalmente podem vir a ser opções de investimentos também mais interessantes. / The sugar and ethanol sectors in Brazil have tried a great growth. The increasing demands for ethanol, a biocombustible, and for the sugar contributes for this situation. The producing industrial area of sugar, a foodstuff, still adopts the use of carbon steel pipes, a cheap product, of low corrosion resistance. The stainless steels are the materials more indicated for the substitution of carbon steel, however they are considered expensive. In sugar cane plants, the evaporators, are important equipments to operation. Carbon steel pipes are the main product used for the thermal exchange, and these pipes start to be replaced after the second year of operation. Meanwhile, stainless steel pipes can last for decades. This work evaluates the enviromental and financial performance of evaporators pipes constructed with carbon steel and with 304, 444 and 439 stainless steel. To reach these objectives the methodologies of Life Cycle Assessment (LCA) and the Life Cycle Costing (LCC) were applied, respectively. The water mass evaporated was adopted as function of the systems in LCA study. In the definition of these product systems were adopted the manufacturing of steel and the manufacturing, installation and cleanness of the pipes. Natural gas, electricity and transport had been considered. The evaluation time was thirty years. From the LCA results, there were concluded that the steel carbon pipes presented more enviromental impact performance than 304, 444 and 439 stainless steel pipes, because they emitted more than 4.2 times of carbon dioxide; 2.8 times nitrogen oxides; 3.1 times of particulated materials; 13 times of suspended materials and 4.5 times of total residues. The carbon steel pipes also consumed more than 11 times the sum of all natural resources used (coal, lignite, iron ground, chromium, nickel, molybdenum, manganese; calcite, dolomite; oil and natural gas); 1.8 times more of water and 5 times more of energy. Regards to sulphur oxides emission, the carbon steel pipes emitted the same amount of sulphur oxides as 444 and 439 stainless steel pipes and they emitted half than of 304 stainless steel pipe. In the life cycle costing (LCC) elaboration were applied the cost components: purchase, transportation, installation, substitution, cleanness and the scraps sale. In the financial evaluation, all the costs that have incurred in the period of thirty years have been brought to the present value. As results concluded that 439 and 444 stainless steels presented the best investment options, due to this they have presented less costs brought to the present value, in the ratio of 0.76 for the 439 steel pipe; 0.79 for 444 the steel pipe with 1.20 mm of thickness and 0.93 for 444 steel pipe with 1.50 mm of thickness. The 304 stainless steel pipes with 1.20 mm of thickness presented similar financial performance compared to carbon steel pipes; whereas the 304 steel pipes 1.50 mm of thickness presented costs to 1.19 times higher of the present value. The results also indicate that LCA and LCC methodologies must be used together; therefore, they show that safer enviromental products can become the more interesting investment options.

Made available in DSpace on 2014-12-17T15:41:43Z (GMT). No. of bitstreams: 1 ThiagoRR.pdf: 1895833 bytes, checksum: 59d0cd6d03df2b5c8165e3ae0bf39a80 (MD5) Previous issue date: 2008-04-25 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / An interesting development in surfactants science and technology is their application as corrosion inhibitors, since they act as protective films over anodic and cathodic surfaces. This work aims to investigate the efficiency of saponified coconut oil (SCO) as corrosion inhibitor and of microemulsified system (SCO + butanol + kerosene oil + distilled water), in saline medium, using an adapted instrumented cell, via techniques involving linear polarization resistance (LPR) and mass loss coupons (MLC). For this, curves of efficiency versus SCO concentration (ranging between 0 and 75 ppm) have been constructed. According to the obtained results, the following efficiency levels were reached with OCS: 98% at a 75 ppm concentration via the LPR method and 95% at 75 ppm via the MLC method. The microemulsified system, for a concentration of 15 ppm of SCO, obtained maximum inhibition of 97% (LPR) and 93% (MLC). These data indicate that it is possible to optimize the use of SCO in similar applications. Previous works have demonstrated that maximal efficiencies below 90% are attained, typically 65% as free molecules and 77% in microemulsified medium, via the LPR method in a different type of cell. Therefore, it can be concluded that the adapted instrumented cell (in those used methods) showed to be an important tool in this kind of study and the SCO was shown effective in the inhibition of the metal / Tensoativos v?m sendo alvo de interesse como inibidores de corros?o, pois funcionam como pel?culas protetoras sobre ?reas an?dicas e cat?dicas. Este trabalho teve como objetivo avaliar a efici?ncia de inibi??o ? corros?o do tensoativo ?leo de coco saponificado (OCS) e do sistema icroemulsionado (OCS + butanol + querosene + ?gua destilada), em meio salino, utilizando-se uma c?lula instrumentada adaptada. A efic?cia do OCS foi avaliada utilizando-se os m?todos de resist?ncia de polariza??o linear (LPR) e cupons de perda de massa (CPM), tendo sido constru?das curvas de efici?ncia versus concentra??o de OCS (variando de 0 a 75 ppm). De acordo com os resultados obtidos, verificou-se que este tensoativo apresenta a seguinte ordem de efici?ncia de inibi??o ? corros?o: para uma concentra??o de 75 ppm, 98% pelo m?todo LPR e 95% pelo m?todo CPM. O sistema microemulsionado, para uma concentra??o de 15 ppm de OCS, obteve inibi??o m?xima de 97% (LPR) e 93% (CPM). Atrav?s deste trabalho foi poss?vel otimizar o uso do tensoativo OCS, que em trabalhos anteriores mostrou efic?cia m?xima inferior a 90% (63% na sua forma livre e 77% na sua forma microemulsionada, pelo m?todo LPR, em um outro tipo de c?lula). Conclusivamente, pode-se dizer que a c?lula instrumentada adaptada (nos m?todos utilizados) provou ser uma ferramenta importante neste tipo de estudo e o OCS mostrou-se efetivo na inibi??o do metal

Made available in DSpace on 2014-12-17T15:41:59Z (GMT). No. of bitstreams: 1 CatiaGFTR.pdf: 919760 bytes, checksum: a600b348289df4c6fa4bb6a54fb4e084 (MD5) Previous issue date: 2007-08-17 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Corrosion inhibition efficiency of saponified coconut oil (SCO) and sodium dodecilbenzene sulfonate (DBS) surfactants in AISI 1020 carbon steel was evaluated by electrochemical methods. These surfactants were also evaluated as microemulsion systems (SCO-ME and DBS-ME), of O/W type (water-rich microemulsion), in a Winsor IV region. They were obtained according to the following composition: 15% SCO, 15% butanol (30% Co-surfactant/Surfactant C/T), 10% organic phase (FO, kerosene) and 60% aqueous phase (FA). These systems were also used to solubilize the following nitrogenated substances: Diphenylcarbazide (DC), 2,4-dinitro-phenyl-thiosemicarbazide (TSC) and the mesoionic type compound 1,3,4-triazolium-2-thiolate (MI), that were investigated with the purpose of evaluating their anticorrosive effects. Comparative studies of carbon steel corrosion inhibition efficiencies of free DBS and DBS-ME, in brine and acidic media (0.5%), showed that DBS presents better inhibition results in acidic media (free DBS, 89% and DBS-ME, 93%). However, the values obtained for DBS in salted solution (72% free DBS and 77% DBS-ME) were similar to the ones observed for the SCO surfactant in brine (63% free SCO and 74% SCO-ME). Analysis of corrosion inhibition of the nitrogenated substances that were solubilized in the SCO-ME microemulsion system by the linear polarization method in brine (0.5% NaCl) showed that such compounds are very efficient an corrosion inhibitors [DC-ME-SCO (92%), TSC-ME-SCO (93%) and MI-ME-SCO (94%)] / A efici?ncia de inibi??o ? corros?o em a?o AISI 1020 dos tensoativos ?leo de coco saponificado (OCS) e dodecilbenzeno sulfonato de s?dio (DBS), foi avaliada por m?todos eletroqu?micos. Estes tensoativos foram tamb?m avaliados em sistemas microemulsionados (OCS-ME e DBS-ME), do tipo O/A (microemuls?o rica em ?gua) com regi?o de trabalho Winsor IV, e foram obtidos na seguinte composi??o: 15% de OCS, 15% de butanol (30% de Cotensoativo/tensoativo - C/T), 10% de fase org?nica (FO, querosene) e 60% de fase aquosa (FA), tendo sido utilizados, ainda, para a solubiliza??o das subst?ncias nitrogenadas difenilcarbazida (DC), 2,4-dinitro-fenil-tiossemicarbazida (TSC) e do heterociclo do tipo mesoi?nico 1,3,4-triaz?lio-2-tiolato (MI), que foram disponibilizadas para avalia??o dos seus efeitos anticorrosivos. Os estudos comparativos das efici?ncias dos tensoativos DBS livre e DBS-ME na inibi??o da corros?o de a?o carbono, em meios salino e ?cido (0,5%), mostraram que o DBS apresenta melhores resultados de inibi??o em meio ?cido (DBS livre, 89% e DBS-ME, 93%). No entanto, os valores obtidos para o DBS em meio salino (72% DBS livre e 77% DBS-ME) foram semelhantes aos valores observados para o tensoativo OCS em meio salino (63% OCS livre e 74% OCS-ME). A an?lise de inibi??o ? corros?o das subst?ncias nitrogenadas solubilizadas no sistema microemulsionado OCS-ME, pelo m?todo de curvas de polariza??o linear em meio salino (NaCl 0,5%) mostrou que tais compostos s?o muito eficazes na inibi??o ? corros?o [DC-ME-OCS (92%), TSC-ME-OCS (93%) e MI-ME-OCS (94%)]

O problema de corrosão é frequente para ligas ferrosas, notadamente o aço carbono. Para evitar os danos causados pela corrosão, uma série de processos é utilizada como o uso de ligas mais resistentes, filmes de pré-tratamento e a aplicação posterior de tintas ou vernizes, aplicação de banhos eletrolíticos para eletrodeposição de metais e outros. Os últimos desenvolvimentos tecnológicos relacionados à nanotecnologia trazem alternativas que consiste na aplicação de uma camada muito fina baseada em silanos como pré-tratamento de aço carbono para posterior pintura a fim de aumentar a aderência desta ao substrato pintado. Este pré-tratamento surge como alternativa ao uso de materiais nocivos ao meio ambiente e à saúde, como são o processo de fosfatização e os compostos de cromo hexavalente aplicados como eventuais passivantes após a fosfatização. Questões ambientais, de segurança e de custos têm sido consideradas, atualmente, no que diz respeito à utilização desses processos. Por esta razão, aumentaram as pesquisas de outros métodos de proteção contra a corrosão para aço carbono. O uso de silanos tem demostrado ser uma alternativa promissora como pré-tratamento por serem promotores de aderência e conferirem melhor resistência contra a corrosão em diferentes aplicações. A aplicação de pré-tratamentos com filmes híbridos, isto é, com características de filmes orgânicos como flexibilidade e características de filmes inorgânicos ou cerâmicos como elevada dureza e resistência a altas temperaturas, tem sido estudada com relativo sucesso. O presente trabalho apresenta o uso de revestimentos híbridos tetraetilortosilicato/metacriloxipropiltrimetoxisilano/metacrilato de metila, TEOS/MPTS/MMA, como pré-tratamento para aço-carbono com a finalidade de retardar ou diminuir o processo da corrosão e o emprego de quinonas como agente anti-gelificante da solução precursora do híbrido, aumentando sua vida de prateleira. A avaliação da resistência à corrosão dos filmes obtidos foi feita por técnicas eletroquímicas como espectroscopia de impedância eletroquímica (EIE), medida da resistência de polarização linear (Rp) e levantamento de curvas de polarização. Também foi realizado o estudo com quinonas para retardar o envelhecimento das soluções de híbrido e aumentar o tempo de vida em prateleira. Alguns fatores estudados foram: tempo de polimerização, uso de quinonas como agente anti-gelificante (nesse estudo foi feito um projeto fatorial de experimentos) e tempo de vida de prateleira da solução de híbrido. As variáveis resposta, do projeto de experimentos, para avaliação do filme de híbrido obtido foram: medidas de EIE, de Rp, levantamento de curvas de polarização, espessura de camada e medida de viscosidade das soluções com o tempo de envelhecimento. Os resultados obtidos foram: o melhor tempo de polimerização foi de 30 minutos e foi para esse tempo de polimerização que se fez o estudo de uso das diferentes quinonas (hidroquinona e p-benzoquinona), tendo sido a p-benzoquinona o melhor anti-gelificante. Verificou-se que a espessura de camada do filme híbrido aumenta com o tempo de vida de prateleira da solução precursora do híbrido e com o tempo de permanência na solução do híbrido, o que leva o filme a funcionar como uma barreira mais eficiente contra a corrosão. A viscosidade foi determinada para cada uma das soluções de híbrido, tanto para aquelas que não foram usadas para a deposição de filmes e para aquelas que foram usadas para a deposição de filmes, com e sem quinonas. Observou-se que a viscosidade da solução de híbrido sem ser usada para deposição de filmes se manteve praticamente constante, mas a viscosidade da solução de híbrido que serviu para as deposições do filme híbrido no substrato aumentou com o tempo de prateleira, devido provavelmente à presença de íons metálicos do substrato liberados na solução de híbrido que podem catalisar as reações de polimerização dos silanos e do monômero MMA gerando moléculas de maior peso molecular. / The corrosion problem is common for ferrous alloys, especially carbon steel. To avoid corrosion damage a series of processes are used such as the use of resistant alloys, films of pre-treatment and the subsequent application of paints or varnishes, the application of electrolytic baths for the electrodeposition of metals and others. The latest technological developments related to nanotechnology bring an alternative process consisting in appling a very thin layer based on silanes as pretreatment for subsequent painting carbon steel in order to increase the adhesion of this to the painted substrate. This pretreatment is an alternative to the use of hazardous materials to the environment and health, as are the process of phosphating and hexavalent chromium compounds applied as eventual passivating substances after phosphating. Environmental, safety and costs concerns have been considered today in the use of these processes. Therefore, increased research for other methods of protection against corrosion of carbon steel has been developed. The use of polysilane films has been demonstrated to be a promising alternative as pre-treatment mainly because they have been employed as adhesion promoters what confers better corrosion resistance in different applications. This paper presents the use of hybrid coatings tetraethilorthosilicate /methacryloxypropyltrimethoxysilane/methylmethacrylate, TEOS/MPTS/MMA, as pre-treatment for carbon steel in order to delay or reduce the corrosion process and the use of quinones as anti-gelling agents of the hybrid precursor solution increasing its shelf life. The evaluation of the corrosion resistance of the films was made by electrochemical techniques such as electrochemical impedance spectroscopy (EIS), measurement of linear polarization resistance (Rp) and polarization curves. The use of quinones to slow the aging of hybrid solutions and increase their shelf-life time was also studied. A factorial design of experiments was performed for these purposes. The variables studied were: polymerization time, residence time of the substrate in the hybrid solution, use of quinones as anti-gelling agent and shelf life of the hybrid solution. The response variables for the design of experiments for evaluation of the hybrid films obtained were: EIS and Rp measurements, polarization curves, layer thickness and kinematic viscosity measurement of the solutions with aging time. The results obtained for best polymerization time was 30 minutes and for this polymerization time the study of use of different quinones (hydroquinone and p-benzoquinone) was made and p-benzoquinone was found to be the best anti-gelling agent. It was found that the thickness of the film layer increases with longer shelf life of the hybrid solution, which leads to more effective barrier films against corrosion. The viscosity was measured for each hybrid solution: for those that were not used for the deposition of films and for those that were used for the deposition of films, with or without quinones. It has been noted that the viscosity of the hybrid solution not used for the deposition of films was kept nearly constant but the viscosity increased with the shelf life for the hybrid solution that served for the hybrid film deposition on the metallic substrate, due to the influence of the metallic ions from the substrate released in the hybrid solution that can catalyze polimerization reactions of silanes and MMA monomer generating molecules of high molecular weight.

Made available in DSpace on 2014-12-17T14:06:57Z (GMT). No. of bitstreams: 1 RomuloRMS.pdf: 3055902 bytes, checksum: 75eaf485a85529179129dd468ccfc772 (MD5) Previous issue date: 2007-12-18 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / &#65279;The ionic plasma nitriding is one of the most important plasma assisted treatment technique for surface modification, but it presents some inherent problems mainly in nitriding pieces with complex geometries. In the last four years has appeared a plasma nitriding technique, named ASPN (Active Screen Plasma Nitriding) in which the samples and the workload are surrounded by a metal screen on which the cathodic potential is applied. This new technique makes possible to obtain a perfect uniform nitrided layer apart from the shape of the samples. The present work is based on the development of a new nitriding plasma technique named CCPN (Cathodic Cage Plasma Nitriding) Patent PI 0603213-3 derived from ASPN, but utilizes the hollow cathode effect to increase the nitriding process efficiency. That technique has shown great improvement on the treatment of several types of steels under different process conditions, producing thicker and harder layers when compared with both, ASPN and ionic plasma nitriding, besides eliminating problems associated with the later technique. The best obtained results are due to the hollow cathode effect on the cage holes. Moreover, characteristic problems of ionic plasma nitriding are eliminated due to the fact that the luminescent discharge acts on the cage wall instead of on the samples surface, which remains under a floating potential. In this work the enhancement of the cathodic cage nitriding layers proprieties, under several conditions for some types of steels was investigated, besides the mechanism for nitrides deposition on glass substrate, concluding that the CCPN is both a diffusion and a deposition process at the same time / &#65279;A nitreta??o i?nica ? um dos processos de revestimento superficial dos mais importantes, mas apresenta alguns problemas inerentes, principalmente, na nitreta??o de pe?as com geometria complexa. Nos ?ltimos quatro anos surgiu uma nova t?cnica de nitreta??o a plasma, denominada de ASPN (Active Screen Plasma Nitriding), na qual as amostras s?o envolvidas por uma tela polarizada catodicamente e com ela ? poss?vel obter uma camada nitretada, perfeitamente uniforme, independente da forma da amostra. O nosso trabalho baseia-se no desenvolvimento, no ?mbito do LabPlasma, de uma nova t?cnica de nitreta??o em plasma, denominada nitreta??o em gaiola cat?dica (NGC) dep?sito de patente PI 0603213-3 derivada da ASPN, mas que utiliza o efeito de c?todo oco para aumentar a efici?ncia do processo de nitreta??o. Esta t?cnica apresentou bastante efic?cia na nitreta??o de v?rios tipos de a?os, nas mais variadas condi??es de tratamento, proporcionando a obten??o de camadas mais espessas e de maior dureza, quando comparada com a ASPN e com a nitreta??o i?nica convencional, al?m de eliminar problemas de irregularidades associados ? t?cnica convencional. Sua maior efici?ncia deve-se ? utiliza??o do efeito de c?todo oco estabelecido nas paredes dos furos da gaiola, enquanto que a elimina??o dos problemas inerentes ? t?cnica convencional, deve-se ao fato do plasma atuar na gaiola e n?o nas amostras, as quais permanecem em potencial flutuante. Neste trabalho, foram avaliadas as condi??es de otimiza??o da nitreta??o, realizada com esta t?cnica, para diferentes tipos de a?os, al?m de investigarmos os mecanismos que atuam, quando da deposi??o de nitretos em substratos de vidro, observando que a NGC ? um processo misto de difus?o e deposi??o

Made available in DSpace on 2014-12-17T14:07:04Z (GMT). No. of bitstreams: 1 GineideCA_DISSERT.pdf: 4064193 bytes, checksum: e2de6f4f6fcb019525ce377c5625f694 (MD5) Previous issue date: 2012-10-26 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / In the search for products that act as corrosion inhibitors and do not cause environmental, impact the use of plant extracts as corrosion inhibitors is becoming a promising alternative. In this work the efficiency of polar extracts (ethanol extracts) obtained from the plants Anacardium occidentale Linn (AO) and Phyllantus amarus Schum. & Thonn (PA) as corrosion inhibitors were evaluated in different concentrations. For that AO and PA extracts were solubilized in the microemulsion systems (SME) containing saponified coconut oil as surfactant (SME -OCS and SME-OCS-1) in saline (NaCl 3,5 %) solution, which was also used as electrolyte. Both SME-OCS and SME-OCS-1 were characterized by surface tension and viscosity methods showing a Newtonian fluid behavior. The SME-OCS and SME-OCS-1 systems satisfactorily solubilized the polar extracts AO and PA with measurements carried out by ultraviolet spectroscopy. The measurements of corrosion inhibition efficiencies were performed by the electrochemical linear polarization resistance (LPR) technique as well as weight loss, on the surface of AISI 1020 carbon steel. The maximum corrosion inhibition efficiencies were determined by extrapolation of Tafel plots, showing the following values: 95,6 % for the system SME-OCS-AO, 98,9 % for the system SME-OCS-AO-1 and 93,4 % for the system SME-OCS-PA / Na busca por produtos que combatam a corros?o e ao mesmo tempo n?o agridam o meio ambiente, a utiliza??o de extratos vegetais como inibidores de corros?o v?m se tornando uma alternativa promissora. Neste trabalho a efici?ncia de inibi??o ? corros?o foi avaliada em diferentes concentra??es de extratos polares (etan?licos) obtidos das plantas Anacardium occidentale Linn (AO) e Phyllantus amarus Schum. & Thonn (PA). Para tanto, os extratos AO e PA foram solubilizados no sistema microemulsionado (SME) contendo o tensoativo ?leo de coco saponificado (SME-OCS e SME-OCS-1) em solu??o salina (NaCl 3,5 %), que tamb?m foi utilizada como eletr?lito. Estes sistemas microemulsionados foram caracterizados por m?todos que avaliam a tens?o superficial e viscosidade, tendo sido evidenciado que se comportam como fluidos Newtonianos. As medidas de efici?ncia de inibi??o ? corros?o foram realizadas atrav?s da t?cnica eletroqu?mica de resist?ncia ? polariza??o linear (LPR) e perda de massa, na superf?cie de a?o carbono AISI 1020. A corrente aplicada ao eletrodo foi controlada pelo equipamento Potenciostato/Galvanostato possibilitando a medi??o da diferen?a de potencial el?trico entre o eletrodo de trabalho e o de refer?ncia. Os sistemas SME-OCS e SME-OCS-1 solubilizaram os extratos etan?licos AO e PA, com quantifica??es realizadas por espectroscopia na regi?o do ultravioleta. As efici?ncias m?ximas de inibi??o ? corros?o foram determinadas atrav?s da extrapola??o das curvas de Tafel, tendo apresentado os seguintes valores: 95,6 % para o sistema SME-OCS-AO, 98,9 % para o sistema SMEOCS- 1-AO e 93,4 % para o sistema SME-OCS-PA

There has been progress in the surface modification of low carbon steel in order to enhance its surface hardness. This study contributes to this by investigating the introduction of carbon nanotubes and amorphous carbon in the carburization of mild steel. In order to achieve the goal, carbon nanotubes were synthesized in a horizontal tubular reactor placed in a furnace also called the chemical vapor deposition process at a temperature of 700oC. Catalyst was produced from Iron nitrate Fe(NO3)3.9H2O and Cobalt nitrate Co(NO3)2.6H2O on CaCO3 support while acetylene C2H2 was used as the carbon source and nitrogen N2 was used as contaminant remover. The as-synthesized carbon nanotubes were purified using nitric acid HNO3 and characterized using scanning electron microscopy (SEM), thermo-gravimetric analysis (TGA) and fourier transform infrared spectroscopy (FTIR). It was found that as-synthesized carbon nanotubes had varying lengths with diameters between 42-52 nm from the SEM and the TGA showed the as-synthesized CNTs with a mass loss of 78% while purified CNTs had 85% with no damage done to the structures after using the one step acid treatment. The as-synthesized and purified carbon nanotubes were used in carburizing low carbon steel (AISI 1018) at two austenitic temperatures of 750oC and 800oC and varying periods of 10-50 minutes while amorphous carbon obtained by pulverizing coal was also used as comparison. The mild steel samples were carburized with carbon nanotubes and amorphous carbon in a laboratory muffle furnace with a defined number of boost and diffusion steps. The carburizing atmosphere consisted of heating up to the varying temperatures at a speed of 10oC/minute, heating under this condition at varying periods, performing a defined number of boost and diffusion processes at the varying temperatures and cooling to room temperatures under the same condition. The carburized surfaces were observed with the Olympus SC50 optical microscope and the hardness distribution of the carburized layer was inspected with a Vickers FM 700 micro-hardness tester. The as-synthesized and purified CNT samples showed higher hardness on the surface of the mild steel than the amorphous carbon. In the same vein, the change in the microstructures of vi the steel samples indicated that good and improved surface hardness was obtained in this work with the reinforcements but with purified CNT having the highest peak surface hardness value of 191.64 ± 4.16 GPa at 800oC, as-synthesized CNT with 177.88 ± 2.35 GPa and amorphous carbon with 160.702 ± 5.79 GPa which are higher compared to the values obtained at 750oC and that of the original substrate which had a surface hardness of 145.188 ± 2.66 GPa. The percentage hardness obtained for the reinforcement with the amorphous carbon, the CNT and the pCNT showed an increase of 5.47%, 10.04% and 15.77% respectively at 750oC when compared to that of the normal substrate carburized without reinforcements. Furthermore, at 800oC, the reinforcement with the amorphous carbon, the CNT and the pCNT show a percentage hardness increase of 7.04%, 14.68% and 22.05% when compared to that of the normal substrate carburized without reinforcements. Comparing the reinforcement potential of the amorphous carbon, the CNT and the pCNT at 750oC, the percentage hardness reveal that using pCNT displayed an increase of 10.89% over that of amorphous carbon and of 6.37% over that of CNT. In addition, the use of CNT as reinforcement at 750oC displayed a percentage hardness increase of 4.83% over that of the amorphous carbon carburized at the same temperature / Civil and Chemical Engineering / M. Tech. (Chemical Engineering)