The aim of this paper was to determine the influence of machining parameters on the surface layer, and consequently on the electrochemical properties, of ASTM F138 austenitic stainless steels. Eight different surface conditions were generated in cylindrical samples by turning and polishing. The surface was characterized by surface roughness Ra and Rt, Vickers microhardness and microstructural characteristics. Cyclic voltammetric tests were performed to evaluate the potential of repassivation and pitting. The surfaces were analyzed by Scanning Electron Microscopy after the electrochemical tests were performed. The cutting parameters were identified to have a significant influence, and the feed rate was as influential as the depth of cut. The use of polishing alone is not sufficient to ensure that a surface has good surface integrity. Even with the polishing application, usually used to produce prostheses, a significant reduction in corrosion resistance occurs if care is not taken to minimize surface machining damage. Corrosion resistance is lower and pitting nucleation is higher in the samples with no polishing and with more severe machining parameters. The tests indicated that softer machining parameters can contribute to an increase in the life of implantable components, reducing the probability of localized corrosion, as well as improving the mechanical properties of prostheses.

RESUMO A laminação é um processo de conformação por deformação plástica amplamente utilizado na indústria para o processamento de ligas metálicas semi-acabadas, pois, além de dar a forma comercial desejada ao produto, proporciona o aumento das propriedades mecânicas em um processo contínuo e de grande produtividade. Desta forma, é importante que o acadêmico de engenharia compreenda como funcionam os equipamentos utilizados na laminação e quais são as variáveis que influenciam este processo. Dentro deste contexto, e pensando que habilidades obtidas através de experimentos que relacionem a teoria com a prática são fundamentais para a formação de um engenheiro, a proposta deste trabalho foi projetar e adaptar um laminador didático do tipo duo, para metais não ferrosos que, empregado no decorrer da graduação, promova maior proximidade dos alunos de engenharia com este processo industrial. A adaptação deste dispositivo se deu com base em um laminador de joias manual já existente, o qual foi acoplado a um motor elétrico que promovesse a potência necessária para o processo. O resultado deste trabalho foi a adaptação de um laminador que atendesse as expectativas de laminação, estando disponível para a elaboração de atividades que propulsionam o entendimento acadêmico sobre o tema. Em relação aos metais que foram laminados, diversas características do processo de laminação a frio e de seus produtos descritos pela literatura e pela indústria da transformação mecânica foram observadas durante a execução dos testes de funcionamento e dos ensaios, validando, desta forma, a adaptação do equipamento e o alcance de seu principal objetivo.

ABSTRACT Lamination is a plastic deformation forming process widely used in the industry for the processing of semi-finished metal alloys, as it not only gives the desired commercial shape to the product, but also provides increased mechanical properties in a continuous and high productivity process. In this way, it is important that the engineering academic understand how the equipment used in the lamination works and what are the variables that influence this process. In this context, and thinking that skills obtained through experiments that relate theory to practice are fundamental for the formation of an engineer, the purpose of this work was to design and adapt a didactic laminator of the duo type, for nonferrous metals that, employee during the graduation, promote greater proximity of engineering students with this industrial process. The adaptation of this device was based on an existing manual jewelry mill, which was coupled to an electric motor that promoted the power needed for the process. The result of this work was the adaptation of a rolling mill that met the lamination expectations, being available for the elaboration of activities that propel the academic understanding on the subject. In relation to the metals that were rolled, several characteristics of the cold rolling process and its products described in the literature and in the mechanical transformation industry were observed during the execution of the tests of operation and of the tests, thus validating the adaptation of the equipment and the achievement of its main objective.

ABSTRACT Titanium and its alloys are the most popular metals applied on end osseous implants manufacturing. Commercially pure titanium (Ti c.p.) has been successfully used as a biomaterial because of its mechanical and chemical properties, excellent corrosion resistance and biocompatibility. In order to improve and accelerate the osseointegration process after implantation, superficial treatments are performed aiming properties that stimulate the growth of the newly-formed bone. In this work, self organized titanium dioxide (TiO2) nanotubes were obtained by anodic oxidation on Ti c.p. (grade 2). Also, it has been shown that the process is industrially reproducible for this purpose. As parameters for the anodizing process, it was concluded that the optimal electrolyte was H3PO4 solution + 0.15% HF under potentiostatic mode for 30 minutes. Potentials of 1, 5, 10, 15 and 20 V were tested in order to verify the best conditions to obtain nanotubes. In this case, potential was set at 10V. The morphology of the samples was characterized by Scanning Electron Microscopy (SEM), Scanning Electron Microscopy with Field Emission (SEM-FEG) and Atomic Force Microscopy (AFM). The results showed the nanotubes formation throughout the titanium samples surface. In accordance to the obtained roughness, it was observed that the formed nanotubes film is thin, however, the literature indicates that the film thickness is not relevant on the performance of nanostructures as optimizers of the osseointegration process, unlike the nanotubes morphology and diameter. In the wettability analysis, the nanotubes behaved as hydrophilic. Therefore, it is possible to obtain TiO2 nanotubes for using in implants by a superficial treatment, allowing a better osseointegration quality.

RESUMO O nióbio é um metal que forma óxido aderente e protetor em contato com o ar, possuindo a propriedade de se autoproteger. O método utilizado para acelerar o crescimento do óxido é conhecido como anodização, no qual o óxido formado pode ser do tipo barreira ou poroso. O óxido poroso é amplamente estudado e pode ser utilizado em células solares, sensores de gás, como biomaterial, entre outros. No entanto, óxidos porosos em nióbio têm sido obtidos com uso de F-, o que provoca intenso processo de dissolução do óxido. Com intuito de minimizar essa reação, eletrólitos contendo glicerina tem favorecido o processo de anodização formando superfícies porosas uniformes. Nesse sentido, o objetivo deste trabalho é obter estruturas nanoporosas em nióbio por anodização a partir de parâmetros conhecidos. A partir de (12,73 mA.cm-2, 100 V), tempos (5 e 30 minutos), concentração de HF (2,24%) e uso de cátodo de platina, já utilizados em estudo anterior, foi inicialmente testada a influência do cátodo de aço inoxidável em substituição à platina, visando promover uma futura transferência tecnológica. A partir disso, a fim de minimizar o processo de dissolução que ocorreu com o uso de HF (2,24%), apenas a HF (1%) foi testada. Finalmente, para obter uma estrutura de óxido mais uniforme, adicionou-se glicerina ao eletrólito de HF (1%). O uso do cátodo de aço inoxidável, apesar de influenciar os resultados dos transientes de anodização, devido a sua provável dissolução química, mostrou-se eficaz no processo. Amostras anodizadas com menores concentrações de HF e com adição de glicerina, como esperado, apresentaram menor dissolução durante a formação dos óxidos, originando estruturas nanoporosas, além de microcones.

ABSTRACT Niobium is a metal that forms adherent protective oxide in contact with the air, which has the property of self-protection. The method used to accelerate the growth of the oxide is known as anodizing, in which the oxide formed may be barrier or porous. Porous oxide is widely studied and can be used in solar cells, gas sensors, as biomaterial, among others. However, porous oxides in niobium have been obtained with the use of F-, which causes an intense dissolution process of the oxide. In order to minimize this reaction, electrolytes containing glycerine have favored the anodizing process forming uniform porous surfaces. In this sense, the objective of this study is to obtain nanoporous structures in niobium by anodization from known parameters. From (12.73 mA.cm-2, 100 V), times (5 and 30 minutes), HF concentration (2.24%) and platinum cathode use, already used in a previous study, was initially tested the influence of the cathode of stainless steel in substitution to the platinum, aiming to promote a future technological transference. From this, in order to minimize the dissolution process that occurred using HF (2.24%), only HF (1%) was tested. Finally, in order to obtain a more uniform oxide structure, glycerin was added to the HF electrolyte (1%). The use of the stainless steel cathode, although influencing the results of the anodizing transients, due to its probable chemical dissolution, proved effective in the process. Anodized samples with lower concentrations of HF and with addition of glycerine, as expected, presented lower oxide dissolution during oxide formation, originating nanoporous structures, besides microcones.

ABSTRACT In many places, charcoal production, using Australian Blackwood, is still a rudimentary process, generating huge environmental impact, due to the release of pyrolysis smoke into the atmosphere. Both the society and governmental agencies is pushing the factories to condense the smoke, generating byproduct known as pyroligneous liquor. Although it's largely used for agricultural purpose, as a fertilizer and phytosanitizer, its chemical composition presents hydrogen and oxygen rich compounds, making it a potential electrolyte in the surface treatment industry, especially for anodization. Organic alternatives are being used to replace these electrolytes to make the anodizing process cleaner. Then, for the first time, Australian Blackwood pyroligneous liquor was used as an anodizing electrolyte for titanium TICP-G2, to obtain oxides for protection and coloring of the metal. For such, suitable parameters to execute the process were determined (dilution, current density, temperature, agitation, pH, conductivity) and an analysis of the transient potential over time was made. The anodized surfaces were characterized using top view Scan Electronic Microscopy (SEM) and Grazing Incidence X-ray Diffraction (GIXRD). Based on the results presented, it can be concluded that the best parameters to anodize the titanium were obtained with 50% pyroligneous liquor diluted in water, obtaining colored surfaces and promoting the formation of oxide crystallites clusters mainly in longer process times (3600s).

RESUMO A elevada resistência à corrosão dos revestimentos decorativos de cromo hexavalente obtidos nos processos de galvanoplastia é bem conhecida pela sua grande utilização e alta eficiência. Esse revestimento tem sido amplamente utilizado na indústria moveleira e de calçados, obtido por eletrodeposição em peças de zamac. No entanto, o processo galvânico apresenta alto grau poluidor devido à quantidade de efluentes geradas e à toxicidade dos produtos químicos utilizados no processo. Sabe-se que o cromo hexavalente é um agente cancerígeno e os resíduos associados são perigosos e difíceis de serem tratados. Neste contexto, o desenvolvimento de novas tecnologias tem visado à obtenção de processos resistentes à corrosão, ambientalmente corretos e economicamente viáveis. A tecnologia alternativa que pode ir ao encontro desta necessidade é o PVD - physical vapor deposition, com o processo de sputtering. Neste sentido, este estudo tem como objetivo avaliar e comparar o desempenho de revestimentos de cromo aplicados por sputtering com verniz em relação ao desempenho do revestimento de cromo eletrodepositado. Para tanto, os revestimentos foram aplicados em zamac e foram caracterizados morfologicamente, eletroquimicamente e físico-quimicamente. Os resultados mostraram que os acabamentos de cromo depositados por sputtering apresentam características equivalentes quanto ao desempenho eletroquímico se comparados ao revestimento cromado no processo convencional, podendo ser uma alternativa de substituição com âmbito sustentável.

ABSTRACT The high corrosion resistance of decorative hexavalent chromium coating, obtained thru electroplating processes, is well known for its wide usage and elevated efficiency. This coating has been used all throughout furniture and shoe’s industries, obtained via electrodeposition in Zamac pieces. However, the galvanic process presents a high pollution degree, due to the amount of generated waste, and the toxicity of the chemicals used. It is well known the hexavalent chromium is a carcinogenic agent, and how its residues are dangerous and hard treat properly. Because of this, the development of new technologies is aiming towards ecofriendly, economically viable, with a high corrosion resistance. The alternate technology that might be heading in this direction is PVD (Physical Vapor Deposition), with the sputtering process. In this sense, this paper’s main objective is to evaluate and compare the development of varnished sputtering applied chromium coatings, in relation to the performance of electrodeposited chromium coatings. For such, they were applied in Zamac and morphologically, electrochemically, and physically-chemically characterized. The results showed that the sputtering deposited chromium coatings presented similar characteristics to the conventional coating method, so it might be a suitable and clean alternative in those regards.

Abstract Squeeze casting is the most industrially advantageous process for producing zamak 5 parts. However, this process generates porosity defects in parts, compromising their corrosion resistance. Therefore, this work aims to minimize defects and improve zamak 5 corrosive performance through the anodizing process. For this purpose, zamak 5 was anodized in 300 mol.m-3 oxalic acid and analyzed by ATR-FTIR, SEM, wettability and EIS techniques. The anodizing process promoted the formation of oxalate and oxide layers of Zn and Al, thereby reducing porosity defects. Although the anodized layer has fragile behavior, being porous and permeable, the immersion time of anodized zamak 5 in NaCl forms corrosion products in the alloy that exhibit better protection.

This study investigated a conversion coating based on hexafluorozirconic acid solution on cold-rolled (AISI 1006) steel sheets, in situ, at different pH values and immersion times. Electrochemical characterization was carried out by electrochemical impedance spectroscopy (EIS) with hexafluorozirconic acid bath as the electrolyte. Laser scanning confocal microscopy (LSCM) was used to evaluate the morphology of the coating in situ, i.e., during the coating formation. According to the results, the polarization resistance (Rp) of the conversion coating is affected by the immersion time and by the pH of the conversion bath. The electrochemical analyzes point out conversion baths at pH between 3.5 and 4.5 and immersion times from 600 to 900 s as optimal operating conditions, achieving an average polarization resistance of 713 ± 107 Ω cm2.

7XXX aluminum alloys show high mechanical resistance and low weight, both required properties for aircraft industry. Anodizing is an electrolytical process typically used to improve the corrosion resistance of aluminum alloys, through which a thicker and porous oxide is formed. Boiling water is used as a common sealing method to the anodic layer; however, it implies energy expenditure. In this work, a two-step coating system was performed: anodizing in tartaric-sulphuric acid and a post-treatment with a Zr-based conversion coating, obtained at room temperature by immersion in hexafluorozirconic acid (H2ZrF6). To establish the best condition for coating formation on the aluminum oxide layer, different concentration and pH values of the H2ZrF6 solution were studied. Morphological and chemical analyses were performed respectively by SEM and EDS. The corrosion resistance evaluation was carried out by EIS in 0.5 M NaCl. Heterogeneity was observed in the obtained coatings. However, the samples treated with H2ZrF6 had a higher corrosion resistance than unsealed samples. The best concentration and pH range observed for the H2ZrF6 solution were 1 % and 3 to 3.5, respectively. Under these conditions, a greater corrosion resistance was evidenced in comparison to that obtained with boiling water sealing.

The silicon alkoxides-based coating is an alternative to control the release of cytotoxic ions through metal implants. This study evaluated the influence of the number of layers of a hybrid coating on the surface of austenitic stainless steel AISI 316L on the corrosion resistance. This coating was produced from the precursors of silicon alkoxides 3-(trimethoxysilyl)propyl methacrylate (MAP) and tetraethoxisylane (TEOS) obtained by sol-gel process, and easily applied by dip-coating. Results indicated that a single layer of coating in the substrate showed a better protection than two layers. This single layer developed by the combination of the precursors TEOS-MAP was enough to create a compact and uniform film with good adherence to AISI 316L and higher electrochemical development. A single layer of TEOS-MAP coating is more adequate as a protective coating for the AISI 361L than the sample subjected to two layers and the non-coated substrate, because this film ensures its integrity in an aggressive environment.

In this present study was evaluated the influence of heat treatment on the wear resistance of electroless high phosphorus nickel coating (9-10% P wt.). In addition, both untreated and treated Ni-P deposits were then compared to electroplated hard chromium coatings in terms of wear behaviour. Three different heat treatment conditions were performed at temperatures of 320ºC, 400ºC and 500ºC under different holding times. The selection of the heat treatment conditions was chosen considering the results obtained by a differential scanning calorimetry (DSC) analysis. The wear behaviour of the Ni-P samples was investigated through a non-lubricated "ball on plate" test carried out against an Al2O3 counter-face. After an analysis of the friction coefficient, microstructure of the worn surface, width and chemical composition of the wear track, was possible to conclude that the heat treatment affect positively the wear resistance of Ni-P coatings. Treatment conditions of 320ºC with 9 hours holding time and 400ºC with 1 hour holding time showed the best results due to a structural change from amorphous supersatured solid solution of phosphorus in nickel to a crystalline structure of nickel crystallites and nickel phosphides (Ni3P) occurred between 320ºC and 360ºC that was verified after x-ray diffraction analysis. Moreover, Ni-P heat treated coatings showed better results when compared to electroplated hard chromium deposits, hence acting as a natural alternative for chromed coatings.

This study proposes a new pretreatment method that uses alkoxide precursors with a plasticizing agent; the purpose of this study is to improve the electrochemical and mechanical properties of a galvanized steel surface. Galvanized steel was covered with a hybrid film obtained from a sol that consisted of two alkoxide precursors, 3 - (trimethoxysilylpropyl) methacrylate (TMSM) and tetraethoxysilane (TEOS), with nitrate cerium in a concentration of 0.01 M and a polyethylene glycol (PEG) plasticizer. The hybrid coatings were obtained by dip-coating method with various concentrations of plasticizer (0, 20, 40 and 60 g.L-1). The hybrid films were analyzed by scanning electron microscopy (SEM), profilometry, contact angle measurements, a tribometer with the type-setting ball on the plate and electrochemical tests. The addition of the plasticizer into the hybrid films improves the corrosion resistance behavior compared to the sample without the plasticizer. The addition of 20 g.L-1 of plasticizer showed the best performance in the electrochemical tests. The mechanical behavior results indicated that higher PEG concentrations resulted in films with enhanced durability.

Considerando-se a preocupação crescente com a toxicidade dos efluentes, pela presença de metais e a ocorrência de novos poluentes orgânicos, esse estudo aplicou o Processo Oxidativo Avançado (POA) de fotoeletrooxidação (FEO) como polimento para o efluente após o processo convencional de tratamento de efluentes da indústria metalomecânica, que, muitas vezes, não remove, satisfatoriamente, metais e aditivos orgânicos. A FEO associou, à degradação de aditivos orgânicos, a remoção do níquel. Foram avaliados efluentes sintéticos com composição similar a efluentes do processo de eletrodeposição de níquel contendo aditivos. Empregando o ânodo de Ti revestido com 70%TiO2/30%RuO2 sob incidência de radiação UV de uma lâmpada de vapor de mercúrio de 250 W e um cátodo de aço inox, 2,5 L de efluente foram tratados em um reator de 1,6 L, com vazão de recirculação de 1 L.min-1. Aplicando diferentes densidades de corrente, observou-se redução da DQO de até 83% e remoção de Ni acima de 90%. Os ensaios de citotoxicidade indicaram que a FEO não gerou intermediários mais tóxicos, pois não ocorreu aumento do efeito tóxico na comparação das soluções antes e após a FEO.

Considering the growing concern about effluent toxicity, generated by the presence of metals and the occurrence of new organic pollutants, this study applied an advanced oxidation process (AOP), denominated the photo-electro-oxidation (PEO), for polishing after the effluent passed through the conventional wastewater treatment from the metal finishing industry that often does not satisfactorily remove metals and organic additives. PEO associated organic additive degradation with nickel removal. A synthetic wastewater, whose composition is similar to a nickel bath containing additives, was evaluated. Employing a Ti anode coated with 70%TiO2/30%RuO2 under an incidence of UV radiation from a mercury vapor lamp of 250 W and a stainless steel cathode, 2.5 L of wastewater were treated in a 1.6 L reactor, at a flow rate of 1L.min-1. Applying different current densities, there was a reduction of up to 83% COD and removal of Ni above 90%. The cytotoxicity assays indicated that PEO did not generate more toxic intermediates because there was no increase in the toxic effect when the solutions were compared before and after PEO.

A descarga de efluentes contendo metais pesados e cianeto pelas indústrias de galvanoplastia é uma das maiores fontes de poluição dos recursos hídricos. O emprego da técnica de eletrodiálise para o tratamento de um efluente sintético contendo aproximadamente 0,0089 mol L-1 de cádmio e 0,081 mol L-1 de cianeto foi estudado utilizando uma célula de eletrodiálise de cinco compartimentos. Os resultados demonstram que a remoção de cádmio e cianeto depende da densidade de corrente aplicada e é limitada pela precipitação de cádmio sobre a membrana catiônica.

The discharge of galvanic industry wastewaters containing heavy metals and cyanide is one of the largest sources of water pollution. The use of the electrodialysis technique for the treatment of a synthetic wastewater containing approximately 0.0089 mol L-1 cadmium and 0.081 mol L-1 cyanide was studied using a five-compartment electrodialysis cell. The results demonstrate that the removal of cadmium and cyanide depends on the applied current density and it is limited by the precipitation of cadmium on the cation-exchange membrane in the diluate central cell compartment.

Neste trabalho estudou-se o tratamento, por eletrodiálise, de um efluente alcalino, oriundo de um processo de galvanoplastia, contendo íons de Zn, Ni, Cu, Fe e Al, bem como de Na e CN-. O estudo foi feito tanto em células de bancada quanto em uma planta piloto, utilizando-se membranas íon-seletivas Nafion e Selemion. Os resultados mostraram que os íons metálicos apresentam, em sua maioria, caráter aniônico devido à formação de complexos de coordenação. Cada tipo de íon metálico apresentou uma diferente taxa de extração da solução tratada, dependendo do controle do processo ser potenciostático ou galvanostático. Para Zn, Ni e Cu houve maior extração sob controle galvanostático. Já para o Al foi verificado uma maior remoção do efluente quando o controle era potenciostático. Observou-se um comportamento anômalo para os íons ferro, os quais não são removidos do mesmo modo que os demais íons metálicos. O rendimento da extração foi máximo em tempos de ensaio relativamente baixos (2-3 h).

Metal finishing wastewater containing ions of Zn, Ni, Cu, Fe and Al, as well as of Na and CN- in alkaline pH was treated by electrodialysis. The treatment was conducted in a laboratory cell and in a pilot plant unity. The experiments were carried out using Nafion and Selemion membranes. Results showed most of the metallic ions to have an anionic nature, due to the formation of coordination complexes. Each metallic ion showed a different rate of extraction from the treated solution, depending on the galvanostatic or potentiostatic operation mode. Zn, Ni and Cu have shown higher extraction under galvanostatic control. For Al, higher extraction was observed when the experiment was conducted in a potentiostatic mode. Fe ions exhibited an unexpected behavior, not being removed in the same way as the other ions. The best extraction results were obtained within 2-3 h of treatment.