Active corrosion protection of AA2024 by sol-gel coatings with corrosion inhibitors

A indústria aeronáutica utiliza ligas de alumínio de alta resistência para o fabrico dos elementos estruturais dos aviões. As ligas usadas possuem excelentes propriedades mecânicas mas apresentam simultaneamente uma grande tendência para a corrosão. Por esta razão essas ligas necessitam de protecção anticorrosiva eficaz para poderem ser utilizadas com segurança. Até à data, os sistemas anticorrosivos mais eficazes para ligas de alumínio contêm crómio hexavalente na sua composição, sejam pré-tratamentos, camadas de conversão ou pigmentos anticorrosivos. O reconhecimento dos efeitos carcinogénicos do crómio hexavalente levou ao aparecimento de legislação banindo o uso desta forma de crómio pela indústria. Esta decisão trouxe a necessidade de encontrar alternativas ambientalmente inócuas mas igualmente eficazes. O principal objectivo do presente trabalho é o desenvolvimento de prétratamentos anticorrosivos activos para a liga de alumínio 2024, baseados em revestimentos híbridos produzidos pelo método sol-gel. Estes revestimentos deverão possuir boa aderência ao substrato metálico, boas propriedades barreira e capacidade anticorrosiva activa. A protecção activa pode ser alcançada através da incorporação de inibidores anticorrosivos no prétratamento. O objectivo foi atingido através de uma sucessão de etapas. Primeiro investigou-se em detalhe a corrosão localizada (por picada) da liga de alumínio 2024. Os resultados obtidos permitiram uma melhor compreensão da susceptibilidade desta liga a processos de corrosão localizada. Estudaram-se também vários possíveis inibidores de corrosão usando técnicas electroquímicas e microestruturais. Numa segunda etapa desenvolveram-se revestimentos anticorrosivos híbridos orgânico-inorgânico baseados no método sol-gel. Compostos derivados de titania e zirconia foram combinados com siloxanos organofuncionais a fim de obter-se boa aderência entre o revestimento e o substrato metálico assim como boas propriedades barreira. Testes industriais mostraram que estes novos revestimentos são compatíveis com os esquemas de pintura convencionais actualmente em uso. A estabilidade e o prazo de validade das formulações foram optimizados modificando a temperatura de armazenamento e a quantidade de água usada durante a síntese. As formulações sol-gel foram dopadas com os inibidores seleccionados durante a primeira etapa e as propriedades anticorrosivas passivas e activas dos revestimentos obtidos foram estudadas numa terceira etapa do trabalho. Os resultados comprovam a influência dos inibidores nas propriedades anticorrosivas dos revestimentos sol-gel. Em alguns casos a acção activa dos inibidores combinou-se com a protecção passiva dada pelo revestimento mas noutros casos terá ocorrido interacção química entre o inibidor e a matriz de sol-gel, de onde resultou a perda de propriedades protectoras do sistema combinado. Atendendo aos problemas provocados pela adição directa dos inibidores na formulação sol-gel procurou-se, numa quarta etapa, formas alternativas de incorporação. Na primeira, produziu-se uma camada de titania nanoporosa na superfície da liga metálica que serviu de reservatório para os inibidores. O revestimento sol-gel foi aplicado por cima da camada nanoporosa. Os inibidores armazenados nos poros actuam quando o substrato fica exposto ao ambiente agressivo. Numa segunda, os inibidores foram armazenados em nano-reservatórios de sílica ou em nanoargilas (halloysite), os quais foram revestidos por polielectrólitos montados camada a camada. A terceira alternativa consistiu no uso de nano-fios de molibdato de cério amorfo como inibidores anticorrosivos nanoparticulados. Os nano-reservatórios foram incorporados durante a síntese do sol-gel. Qualquer das abordagens permitiu eliminar o efeito negativo do inibidor sobre a estabilidade da matriz do sol-gel. Os revestimentos sol-gel desenvolvidos neste trabalho apresentaram protecção anticorrosiva activa e capacidade de auto-reparação. Os resultados obtidos mostraram o elevado potencial destes revestimentos para a protecção anticorrosiva da liga de alumínio 2024.

Corrosion Health Monitoring System for Steel Ship Structures

Corrosion represents one of the largest through life cost component of ships. Ship owners and operators recognize that combating corrosion significantly impacts the vessels’ reliability, availability and through life costs. Primary objective of this paper is to review various inspections, monitoring systems and life cycle management with respect to corrosion control of ships and to develop the concept of “Corrosion Health” (CH) which would quantify the extent of corrosion at any point of ships’ operational life. A system approach in which the ship structure is considered as a corrosion system and divided into several corrosion zones, with distinct characteristics, is presented. Various corrosion assessment criteria for assessment of corrosion condition are listed. A CH rating system for representation of complex corrosion condition with a numeric number along with recommendations for repair/maintenance action is also discussed

Corrosion by sulfate reducing bacteria that utilize nitrate

16S rRNA gene sequencing was used to identify a sulfate-reducing bacterium (SRB) from a Danish North Sea oilfield water injection system. This species was cultivated, purified and subsequently identified as being >97% similar to Desulfovibrio gracilis. Like some other Desulfovibrio species this SRB, strain OP102, could reduce nitrate as an electron acceptor and produce ammonia in the absence of sulfate. In addition, in the presence of sulfate, when nitrate was dosed at 100 mg/l it was again reduced by the bacterium, with some ammonium production. Therefore, this mechanism could be important in oilfield systems where nitrate is applied to prevent sulfide generation by SRB which leads to reservoir souring. In static tests the influence of this Desulfovibrio on corrosion was assessed using carbon steel coupons, in the presence of sulfate and in the presence of sulfate with 100 mg/l nitrate. Corrosion rates were less than 1.5 mpy when coupons were incubated in the same water, with sulfate and with nitrate. Furthermore, the occurrence of pitting corrosion was fairly low under all circumstances.

Caesalpinia decapetala extracts as inhibitors of lipid oxidation in beef patties

In this study we investigated the effects of Caesalpinia decapetala (CD) extracts on lipid oxidation in ground beef patties. Plant extracts and butylated hydroxytoluene (BHT) were individually added to patties at both 0.1% and 0.5% (w/w) concentrations. We assessed the antioxidant efficacy of CD by the ferric reducing antioxidant power (FRAP) assay and evaluated their potential as natural antioxidants for meat preservation by thiobarbituric acid reactive substance (TBARS) values, hexanal content, fatty acid composition and color parameters. These were tested periodically during 11 days of refrigerated storage. TBARS levels were significantly lower (p ≤ 0.05) in the samples containing plant extracts or BHT than in the non-treated control. In addition, the beef patties formulated with the selected plant extracts showed significantly (p ≤ 0.05) better color stability than those without antioxidants. These results indicate that edible plant extracts are promising sources of natural antioxidants and can potentially be used as functional preservatives in meat products.

The corrosion of austenitic 304 stainless steel in biodiesel

Fuel distribution uses 304 stainless steel containers for the storage of biofuels, however there are few reports in the literature about the corrosive aspects this. steel in biodiesel. The objective of this research is to study the corrosive behavior of 304 austenitic stainless steel in the presence of biodiesel, unwashed and washed, with aqueous solutions of citric, oxalic, acetic and ascorbic acids 0,01 mol L(-1), and compare with results obtained for the copper (ASTM D130). The employedtechniques were: atomic absorption spectrometry (AAS) and optical microscopy (OM). The results of EA A showed a low rate of corrosion for the stainless steel, the alloys elements studied were Cr, Ni and Fe, the highest rate was observed for the chrome, 1.78 ppm / day in biodiesel with or without washing. The OM of the 304 steel, when compared with that of copper has a low corrosion rate in the 304 steel/biodiesel system. Not with standing, this demonstrates that not only the 304 steel, but also the copper corrodes in biodiesel

Ultrafine grained ferrite formed by interrupted hot torsion deformation of plain carbon steel

A plain carbon steel was deformed using a hot torsion deformation simulator. A schedule known to produce strain-induced ferrite was used with the strain interrupted for increasing intervals of time to determine the effect of an isothermal hold on the final microstructure. Microscopy and electron back-scattered diffraction (EBSD) were used to analyse the changes that occurred in the partially transformed microstructure during the hold and the subsequent applied strain. The strain-induced ferrite coarsened during the hold and this coarsened ferrite was refined during the second deformation. These results were compared to those obtained for a different plain carbon steel deformed in single pass rolling close to the Ar3 temperature.

Fluidized bed CrN coating formation on prenitrocarburized plain carbon steel

CrN coatings were formed on plain carbon steel by prenitrocarburizing, followed by thermoreactive deposition and diffusion (TRD) in a fluidized bed furnace at 570 °C. During TRD, Cr was transferred from Cr powder in the fluidized bed to the nitrocarburized substrates by gas-phase reactions initiated by reaction of HCl gas with the Cr. The microstructural processes occurring in the white layer, caused by N diffusion toward the surface during this stage were studied. This study compares TRD atmospheres employing inert gas and HCl or inert gas, H2, and HCl. Surface characterization was performed by scanning electron microscopy (SEM), x-ray diffraction (XRD), and glow-discharge optical-emission spectroscopy (GDOES).

The static, dynamic and metadynamic recrystallisation of a medium carbon steel

Grain refinement during and after hot isothermal deformation of a medium carbon steel has been investigated. The average austenite grain size decreased with an increase in strain for the hot deformed and recrystallised material, with refinement extending beyond the strain for the peak stress. A window of strain that corresponds to transition from classical static to metadynamic recrystallisation was observed in respect to the recrystallised material. Within this post-dynamic transition window the strain at which strain independent softening occurs was different for different volume fractions of the recrystallised material. This led to a new terminology corresponding to initiation of strain independent softening. For the alloy of this study, strain independent softening for the start of post-deformation recrystallisation occurred near the strain to the peak stress. The strain corresponding to complete metadynamic recrystallisation, which was defined as when all levels of recrystallisation were strain independent, was much greater than the strain for the peak stress.

The production of ultrafine ferrite in low-carbon steel by strain-Induced transformation

An investigation into the production of ultrafine (1 µm) equiaxed ferrite (UFF) grains in low-carbon steel was made using laboratory rolling, compression dilatometry, and hot torsion techniques. It was found that the hot rolling of thin strip, with a combination of high shear strain and high undercooling, provided the conditions most suitable for the formation of this type of microstructure. Although high strains could be applied in compression and torsion experiments, large volume fractions of UFF were not observed in those samples, possibly due to the lower level of undercooling achieved. It is thought that ferrite refinement was due to a strain-induced transformation process, and that ferrite grains nucleated on parallel and linear deformation bands that traversed austenite grains. These bands formed during the deformation process, and the undercooling provided by the contact between the strip and the work rolls was sufficient to drive the transformation to homogeneous UFF grains.

Dynamic softening of ferrite during large strain warm deformation of a plain-carbon steel

The evolution of dynamic ferrite softening in a plain-carbon steel was investigated by torsion tests during warm deformation at 810 °C, in the two-phase (ferrite + austenite) region, and strain rate of 0.1 s−1 with different strains up to 50. The warm flow behaviour and ferrite microstructural parameters, such as grain size, misorientation angle across ferrite/ferrite boundaries, and the fraction of high-angle and low-angle grain/subgrain boundaries were quantified using electron back scatter diffraction. The results show that with increasing strain up to not, vert, similar2, the ferrite grain size and fraction of high-angle boundaries rapidly decrease and the fraction of low-angle boundaries increases. However, these parameters remain approximately unchanged with increasing strain from not, vert, similar2 to 50. The dynamic softening mechanism observed during large strain ferritic deformation is explained by dynamic recovery and continuous dynamic recrystallization.

Characterization on ferrite microstructure evolution during large strain warm torsion testing of plain low carbon steel

Ferrite grain/subgrain structures evolution during the extended dynamic softening of a plain low carbon steel was investigated throughout the large strain warm deformation by hot torsion. Microstructural analysis with electron back-scattering diffraction (EBSD) scanning electron microscope (FEG/SEM) was carried out on the ferrite microstructural parameters. The results showed that the warm flow stress–strain curves are similar to those affected only by dynamic softening and an extended warm flow softening is seen during large strain deformation up to 30. Furthermore, with an increase in strain up to ~ vert, similar1 the grain size of ferrite, misorientation angle and fraction of high-angle boundaries gradually decrease and fraction of low-angle boundaries increases. With a further increase in the strain beyond ~, vert, similar2, these parameters remain approximately unchanged. No evidence of discontinuous dynamic recrystallisation involving nucleation and growth of new grains was found within ferrite. Therefore, the dynamic softening mechanism observed during large strain ferritic deformation is explained by continuous dynamic recrystallization (CDRX).

In-situ observations of Widmanstätten ferrite formation in a low carbon steel

An in situ laser-scanning confocal microscopy study has been undertaken into Widmanstätten ferrite formation in an Fe–C alloy, in combination with electron backscattered diffraction. It has been found for the first time that the sympathetic nucleation of Widmanstätten ferrite on grain boundary allotriomorphs can exhibit a step wise change in orientation and growth direction until the most favourable growth conditions are achieved.