Protecção activa de corrosão na liga AA2024 por revestimentos sol-gel com inibidores de corrosão

Doutoramento em Ciência e Engenharia de MateriaisA 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.The aerospace industry employs high strength aluminum alloys as a constructional material for aircrafts. Aluminum alloys possess advanced mechanical requirements, though suffer from corrosion. Therefore, corrosion protection is always used for aluminum alloys. Up to now the most effective corrosion protection systems include chromium (VI) as the main constituent of pretreatments and corrosion inhibitive pigments. However, the chromates are strongly carcinogenic and the present health regulations banned the use of Cr (VI) containing materials in industry. Consequently, there is a need for environmentally safe corrosion protection systems. The main objective of the present work is the development of active anticorrosion pre-treatments for 2024 aluminum alloy on the basis of hybrid sol-gel layers. The effective corrosion pre-treatment should confer adequate adhesion together with good barrier properties and active corrosion protection ability. The active corrosion protection can be achieved by introducing the corrosion inhibitors in the pre-treatment. Successful fulfilment of the main objective required accomplishing of different stages of the work. At first the localized corrosion of AA2024 was investigated in detail. The obtained results provide better understanding of the intimate aspects of the corrosion susceptibility of AA2024. Different prospective corrosion inhibitors were investigated using electrochemical and microstructural methods. At the second stage the development of hybrid sol-gel coatings was performed. Titania and zirconia based derivatives were combined with organofunctional silanes in order to provide the enhanced adhesion between the metal and the coating and to confer good barrier properties. Industrial tests show that the developed sol-gel coatings are compatible with common organic protection systems. The stability and life time of the sol-gel formulations were also optimized by changing the storage temperature and the amount of water during the synthesis. Sol-gel systems were doped with the selected corrosion inhibitors and studied from the point of view of passive and active corrosion protective properties at the third stage of the work. The results demonstrate the influence of the inhibitive additives on the corrosion performance of the sol-gel coatings. Some inhibitors can provide active corrosion protection in combination with the sol-gel coating, but some chemically interact with the sol-gel matrix resulting in failure of the protective properties of coatings. New approaches of inhibitor incorporation and delivery were used in the fourth stage of the work due to problems associated with the direct introduction of inhibitors in the sol-gels. A nanoporous titania-based pre-layer applied directly to the alloy was employed for storage and release of inhibitors. Nanocontainers of corrosion inhibitors based on silica and halloysite nanoclay with Layer-by- Layer assembled polyelectrolyte shells were used in the second approach. Amorphous cerium molybdate nanowires have been used as corrosion inhibitor nanoparticles in the third approach. During the sol-gel synthesis these nanocontainers were added to impart active corrosion protective properties of the sol-gel coatings. Using these approaches the negative effect of inhibitor on the sol-gel matrix stability was eliminated. The developed sol-gel pretreatments demonstrate important active corrosion protection and self-healing ability. The obtained results show high potential of the developed hybrid sol-gel pretreatment doped with corrosion inhibitors for the corrosion protection of AA2024.FCT; FSE - SFRH/BD/25469/200

Layered double hydroxides for corrosion-related applications: main developments from 20 years of research at CICECO

This work describes the main advances carried out in the field of corrosion protection using layered double hydroxides (LDH), both as additive/pigmentbased systems in organic coatings and as conversion films/pre-treatments. In the context of the research topic “Celebrating 20 years of CICECO”, the main works reported herein are based on SECOP’s group (CICECO) main advances over the years. More specifically, this review describes structure and properties of LDH, delving into the corrosion field with description of pioneering works, use of LDH as additives to organic coatings, conversion layers, application in reinforced concrete and corrosion detection, and environmental impact of these materials. Moreover, the use of computational tools for the design of LDH materials and understanding of ion-exchange reactions is also presented. The review ends with a critical analysis of the field and future perspectives on the use of LDH for corrosion protection. From the work carried out LDH seem very tenable, versatile, and advantageous for corrosion protection applications, although several obstacles will have to be overcome before their use become commonplace.publishe

The Role of Cu-Based Intermetallic on the Direct Growth of a ZnAl LDH Film on AA2024

The direct ZnAl layered double hydroxide growth on AA2024 is a fast-occurring reaction, yet is characterized by an inhomogeneous film thickness. It has been shown that at the periphery of Cu-rich intermetallic, the flakes tend to be larger and denser. A combination of in situ and ex situ measurements were used to monitor the changes in the layered double hydroxide film grown on the regions of intermetallics. Immediately after immersion, an activation of the intermetallic phases is observed due to the dealloying process with an almost immediate film growth. Dealloying is followed by trenching of the adjacent Al matrix leading to an excessive production of large and dense layered double hydroxide flakes at the periphery of the intermetallic. However, the scanning electron microscopy cross-section images revealed that the trenching process leads to defects in the area surrounding the intermetallic. This could weaken the corrosion resistance performance of the layered double hydroxide conversion coating and lead to adhesion failure of consecutive polymer coatings. Nevertheless, this work highlights a few advantages and drawbacks of the layered double hydroxide conversion coatings and pathways to its potential optimization and improvement

A critical review on the production and application of graphene and graphene-based materials in anti-corrosion coatings

Among the many potential applications of graphene and graphene-based materials, their use as protective films or as additives in coatings for corrosion protection has seen an increased level of interest in the last decade. Much of this interest is motivated by the need to implement additional functionalities, to enhance anti-corrosion performance and to ultimately extend the service life of metallic structures. Pristine graphene films, with their impermeable nature allied to flexibility and mechanical strength, appear as particularly attractive candidates for barrier films against corrosive agents, while graphene-based materials such as graphene oxide and reduced graphene oxide offer a wide range of opportunities for their dispersion in polymeric matrices for composite anti-corrosive coatings. Simultaneously, considerable progress in the development of scalable graphene and graphene-based materials production techniques has been made during the last several years. Currently, a broad range of graphene materials with different morphologies and properties is available, making the need for an adequate fit between the production method and the desired application even more evident. This review article aims to give the reader a general overview of the recent trends in both the production of graphene and graphene-based materials, and their implementation in different anti-corrosion solutions. Moreover, the present work provides a critical look on this subject, highlighting the areas in need of further exploration.publishe

Application of AFM-Based Techniques in Studies of Corrosion and Corrosion Inhibition of Metallic Alloys

In this review several scanning probe microscopy techniques are briefly discussed as valuable assets for corrosionists to study corrosion susceptibility and inhibition of metals and alloys at sub-micrometer resolution. At the beginning, the review provides the reader with background of atomic force microscopy (AFM) and related techniques such as scanning Kelvin probe force microscopy (SKPFM) and electrochemical AFM (EC-AFM). Afterwards, the review presents the current state of corrosion research and specific applications of the techniques in studying important metallic materials for the aircraft and automotive industries. Different corrosion mechanisms of metallic materials are addressed emphasizing the role of intermetallic inclusions, grain boundaries, and impurities as focal points for corrosion initiation and development. The presented information demonstrates the importance of localized studies using AFM-based techniques in understanding corrosion mechanisms of metallic materials and developing efficient means of corrosion prevention

As-cast and extruded MgZnCa systems for biodegradable implants: Characterization and corrosion behavior

The aim of the present study is to evaluate the effect of alloy processing and composition as well as the pH control and testing medium on the in vitro corrosion performance of MgZnCa systems for biodegradable implants. The grain size and secondary phases were analyzed by optical microscopy, scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. Scanning kelvin probe force microscopy (SKPFM) was used to analyze the Volta potential values of the second phases. The corrosion performance of the three alloys was evaluated by electrochemical and hydrogen evolution methods in α-MEM with and without organic species (i.e. complete and inorganic α-MEM). Two strategies were followed to evaluate the influence of the pH on the corrosion behavior: daily solution replacement and CO2 flow based pH control. For all the materials, the organic medium accelerates the corrosion process. Constant pH maintained by CO2 flow through the medium results in considerably higher corrosion rates for all alloys. The impact of pH is lesser on the as-cast alloys due to the barrier effect of the secondary phases, particularly pronounced in the Mg1Zn1Ca alloy which showed the lowest corrosion rate. The wrought Mg0.5Zn0.2Ca alloy that lacks the refined secondary phase network and exhibits high number of twins undergoes accelerated uniform corrosion under constant pH conditions

One-step synthesis and growth mechanism of nitrate intercalated ZnAl LDH conversion coatings on zinc

An approach for the synthesis of ZnAl-NO3 LDH conversion coatings on zinc in an aqueous acidic Al(NO3)3/NaNO3 solution is demonstrated for the first time. The growth mechanism has been investigated using time resolved structural, microstructural and analytical methods. A LDH growth model involving both electrochemical and chemical processes is suggested.publishe

Atomic layer deposition of nanometric alumina for corrosion protection of heterogeneous metallic surfaces: the case of aeronautical grade aluminium alloy 2024-T3

Nanometric layers of Al2O3 were applied by atomic layer deposition (ALD) on 2024-T3 aluminium alloy. The ALD layers suppressed the corrosion of the alloy as confirmed by Scanning Kelvin Probe Force Microscopy (SKPFM), polarization curves and Electrochemical Impedance Spectroscopy (EIS). The protection provided by the ALD layers weakened with the time of immersion and this was attributed to the incorporation of hydroxyl species in the film during the deposition at low temperature (100 ◦C) making them vulnerable to water.publishe