Susceptibility to stress corrosion cracking of NiTi laser weldment in Hanks’ solution

In this study, the susceptibility to stress corrosion cracking (SCC) of laser-welded NiTi wires in Hanks’ solution at 37.5 °C was studied by the slow strain-rate test (SSRT) at open-circuit potential and at different applied anodic potentials. The weldment shows high susceptibility to SCC when the applied potential is near to the pitting potential of the heat-affected zone (HAZ). The pits formed in the HAZ become sites of crack initiation when stress is applied, and cracks propagate in an intergranular mode under the combined effect of corrosion and stress. In contrast, the base-metal is immune to SCC under similar conditions. The increase in susceptibility to SCC in the weldment could be attributed to the poor corrosion resistance in the coarse-grained HAZ.

Microabrasion-corrosion of cast CoCrMo alloy in simulated body fluids

Wear and corrosion of metal-on-metal hip replacements results in wear debris and metal-ion release in vivo, which may subsequently cause pain and hypersensitivity for patients. Retrieved metal-on-metal hip replacements have revealed that two-body sliding wear and three-body abrasive wear are the predominant wear mechanisms. However, there is a lack of understanding of the combined effects of wear/corrosion, especially the effect of abrasion-corrosion.

This study investigates the sliding-corrosion and abrasion-corrosion performance of a cast CoCrMo alloy in simulated hip joint environments using a microabrasion rig integrated with an electrochemical cell. Tests have been conducted in 0.9% NaCl, phosphate buffered saline solution, 25% and 50% bovine serum solutions with 0 or 1 g cm(-3) SiC at 37 degrees C. Experimental results reveal that under abrasion-corrosion test conditions, the presence of proteins increased the total specific wear rate. Conversely, electrochemical noise measurements indicated that the average anodic current levels were appreciably lower for the proteinaceous solutions when compared with the inorganic solutions. A severely deformed nanocrystalline layer was identified immediately below the worn surface for both proteinaceous and inorganic solutions. The layer is formed by a recrystallisation process and/or a strain-induced phase transformation that occurs during microabrasion-corrosion. (C) 2008 Elsevier Ltd. All rights reserved.

Micro- and Nano-scale Tribo-Corrosion of Cast CoCrMo

Previous studies have established that some of the wear damage seen on cast CoCrMo joint surface is caused by entrained third-body hard particles. In this study, wet-cell micro-indentation and nano-scratch tests have been carried out with the direct aim of simulating wear damage induced by single abrasive particles entrained between the surfaces of cast CoCrMo hip implants. In situ electrochemical current noise measurements were uniquely performed to detect and study the wear-induced corrosion as well as the repassivation kinetics under the micro-/nano-scale tribological process. A mathematical model has been explored for the CoCrMo repassivation kinetics after surface oxide film rupture. Greater insights into the nature of the CoCrMo micro-/nano-scale wear-corrosion mechanisms and deformation processes are determined, including the identification of slip band formation, matrix/carbide deformation, nanocrystalline structure formation and strain-induced phase transformation. The electrochemical current noise provides evidence of instantaneous transient corrosion activity at the wearing surface resulting from partial oxide rupturing and stripping, concurrent with the indent/scratch.

Abrasive size and concentration effects on the tribo-corrosion of cast CoCrMo alloy in simulated body fluids

Some retrieved CoCrMo hip implants have shown that abrasive wear is one of the possible wear mechanisms invoked within such joints. To date, little work has focused on the third body abrasion of CoCrMo and therefore there is a general lack of understanding of the effect of abrasive size and volume concentration on the tribo-corrosion performance of the CoCrMo alloys. The present work assessed the tribo-corrosion behaviour of cast CoCrMo (F-75) under various abrasion-corrosion conditions by using a modified microabrasion tester incorporating a three-electrode electrochemical cell. The effects of reduced abrasive size/hardness and volume concentration, as well as the role of proteins on the tribo-corrosion performance of the cast CoCrMo alloy were addressed. The correlation between electrochemical and mechanical processes for different abrasion-corrosion test conditions has been discussed in detail. Results show that the reduction in abrasive size and volume concentration can significantly affect the abrasion-corrosion wear mechanisms and the wear-induced corrosion response of the material. The finding of this study implies that the smaller/softer third body particles generated in vivo could also result in significant wear-induced corrosion and therefore potential metal ion release, which could be potentially detrimental to both the patient health and the life span of the implants. © 2009 Elsevier Ltd. All rights reserved.

Oxygen Reduction Reaction on Metal-Terminated MnCr2O4 Nano-octahedron Catalyzing MnS Dissolution in an Austenitic Stainless Steel

To understand pitting corrosion in stainless steel is very important, and a recent work showed that the MnS dissolution catalyzed by MnCr2O4{111} is a starting point of pit g. This demonstrates the need to understand the oxygen reduction reaction (ORR) on MnCr2O4{111}, which is the other half-reaction to complete pitting corrosion. In this study, the adsorption behaviors of all oxygen-containing species on MnCr2O4{111}, which has several possible terminations, are explored via density functional theory calculations. It is found that O-2 adsorbs on MnCr2O4{111) surfaces very strongly. Many possible reactions are investigated and the favored reaction mechanism of ORR is determined. The interactions between O-2 and H2O on the two metal-terminated MriCr(2)O(4){111} are found to be different according to the atomic configurations of the two surfaces. All the calculated results suggest that ORR can readily occur on the MnCr2O4{111} surfaces.

Identification of MnCr2O4 nano-octahedron in catalysing pitting corrosion of austenitic stainless steels

Pitting corrosion of stainless steels, one of the classical problems in materials science and electrochemistry, is generally believed to originate from the local dissolution in MnS inclusions, which are more or less ubiquitous in stainless steels. However, the initial location where MnS dissolution preferentially occurs is known to be unpredictable, which makes pitting corrosion a major concern. In this work we show, at an atomic scale, the initial site where MnS starts to dissolve in the presence of salt water. Using in situ ex-environment transmission electron microscopy (TEM), we found a number of nano-sized octahedral MnCr2O4 crystals (with a spinel structure and a space group of Fd (3) over barm) embedded in the MnS medium, generating local MnCr2O4/MnS nano-galvanic cells. The TEM experiments combined with first-principles calculations clarified that the nano-octahedron, enclosed by eight {1 1 1} facets with metal terminations, is "malignant", and this acts as the reactive site and catalyses the dissolution of MnS. This work not only uncovers the origin of MnS dissolution in stainless steels, but also presents an atomic-scale evolution in a material's failure which may occur in a wide range of engineering alloys and biomedical instruments serving in wet environments. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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.

Diamond microelectrodes for corrosion studies

Este trabalho teve como objetivos a produção, caracterização e aplicação de microelétrodos (MEs) de diamante como sensores amperométricos e potenciométricos em sistemas de corrosão nos quais a agressividade do meio e a presença de produtos de corrosão, constituem obstáculos que podem diminuir o desempenho, ou inviabilizar a utilização, de outros tipos de sensores. Os microeléctrodos são baseados em filmes finos de diamante dopado com boro (BDD – Boron Doped Diamond) depositados sobre fios de tungsténio afiados, através do método de deposição química a partir da fase vapor, assistida por filamento quente (HFCVD – Hot Filament Chemical Vapor Deposition). A otimização das diversas etapas de fabricação dos MEs deu origem ao desenvolvimento de um novo sistema de afiamento eletroquímico para obtenção destes fios e a várias opções para a obtenção dos filmes de diamante condutor e seu isolamento com resinas para exposição apenas da ponta cilíndrica. A qualidade cristalina dos filmes de diamante foi avaliada por espectroscopia de Raman. Esta informação foi complementada com uma caracterização microestrutural dos filmes de diamante por microscopia eletrónica de varrimento (SEM), em que se fez a identificação da tipologia dos cristais como pertencendo às gamas de diamante nanocristalino ou microcristalino. Os filmes de BDD foram utilizados na sua forma não modificada, com terminações em hidrogénio e também com modificação da superfície através de tratamentos de plasma RF de CF4 e O2 indutores de terminações C-F no primeiro caso e de grupos C=O, C-O-C e C-OH no segundo, tal como determinado por XPS. A caracterização eletroquímica dos MEs não modificados revelou uma resposta voltamétrica com elevada razão sinal/ruído e baixa corrente capacitiva, numa gama de polarização quasi-ideal com extensão de 3 V a 4 V, dependente dos parâmetros de crescimento e pós-tratamentos de superfície. Estudou-se a reversibilidade de algumas reações heterogéneas com os pares redox Fe(CN)6 3-/4- e FcOH0/+ e verificou-se que a constante cinética, k0, é mais elevada em elétrodos com terminações em hidrogénio, nos quais não se procedeu a qualquer modificação da superfície. Estes MEs não modificados foram também testados na deteção de Zn2+ onde se observou, por voltametria cíclica, que a detecção da redução deste ião é linear numa escala log-log na gama de 10-5-10-2 M em 5 mM NaCl. Realizaram-se também estudos em sistemas de corrosão modelares, em que os microeléctrodos foram usados como sensores amperométricos para mapear a distribuição de oxigénio e Zn2+ sobre um par galvânico Zn-Fe, com recurso a um sistema SVET (Scanning Vibrating Electrode Technique). Foi possível detetar, com resolução lateral de 100 μm, um decréscimo da concentração de O2 junto a ambos os metais e produção de catiões de zinco no ânodo. Contudo verificou-se uma significativa deposição de zinco metálico na superfície dos ME utilizados. Os MEs com superfície modificada por plasma de CF4 foram testados como sensores de oxigénio dissolvido. A calibração dos microeléctrodos foi efetuada simultaneamente por voltametria cíclica e medição óptica através de um sensor de oxigénio comercial. Determinou-se uma sensibilidade de ~0.1422 nA/μM, com um limite de deteção de 0.63 μM. Os MEs modificados com CF4 foram também testados como sensores amperométricos com os quais se observou sensibilidade ao oxigénio dissolvido em solução, tendo sido igualmente utilizados durante a corrosão galvânica de pares Zn-Fe. Em alguns casos foi conseguida sensibilidade ao ião Zn2+ sem que o efeito da contaminação superficial com zinco metálico se fizesse sentir. Os microeléctrodos tratados em plasma de CF4 permitem uma boa deteção da distribuição de oxigénio, exibindo uma resposta mais rápida que os não tratados além de maior estabilidade de medição e durabilidade. Nos MEs em que a superfície foi modificada com plasma de O2 foi possível detetar, por cronopotenciometria a corrente nula, uma sensibilidade ao pH de ~51 mV/pH numa gama de pH 2 a pH 12. Este comportamento foi associado à contribuição determinante de grupos C-O e C=O, observados por XPS com uma razão O/C de 0,16. Estes MEs foram igualmente testados durante a corrosão galvânica do par Zn-Fe onde foi possível mapear a distribuição de pH associada ao desenvolvimento de regiões alcalinas causadas pela redução do oxigénio, acima da região catódica, e de regiões ácidas decorrentes da dissolução anódica do ânodo de zinco. Com o par galvânico imerso em 50 mM NaCl registou-se uma variação de pH aproximadamente entre 4,8 acima do ânodo de zinco a 9,3 sobre o cátodo de ferro. A utilização pioneira destes MEs como sensores de pH é uma alternativa promissora aos elétrodos baseados em membranas seletivas.

The initial oxidation of transition metal surfaces

Due to their numerous novel technological applications ranging from the example of exhaust catalysts in the automotive industry to the catalytic production of hydro- gen, surface reactions on transition metal substrates have become to be one of the most essential subjects within the surface science community. Although numerous applications exist, there are many details in the different processes that, after many decades of research, remain unknown. There are perhaps as many applications for the corrosion resistant materials such as stainless steels. A thorough knowledge of the details of the simplest reactions occuring on the surfaces, such as oxidation, play a key role in the design of better catalysts, or corrosion resistant materials in the future. This thesis examines the oxidation of metal surfaces from a computational point of view mostly concentrating on copper as a model material. Oxidation is studied from the initial oxidation to the oxygen precovered surface. Important parameters for the initial sticking and dissociation are obtained. The saturation layer is thoroughly studied and the calculated results arecompared with available experimental results. On the saturated surface, some open questions still remain. The present calculations demonstrate, that the saturated part of the surface is excluded from being chemically reactive towards the oxygen molecules. The results suggest, that the reason for the chemical activity of the saturated surface is due to a strain effect occuring between the saturated areas of the surface.

Electrochemical studies on Metal phthalocyanines

The primary aim of these investigations was to probe the elecnuchemical and material science aspects of some selected metal phthalocyanines(MPcs).Metal phthalocyanines are characterised by a unique planar molecular structure. As a single class of compounds they have been the subject of ever increasing number of physicochemical and technological investigations. During the last two decades the literature on these compounds was flooded by an outpour of original publications and patents. Almost every branch of materials science has benefited by their application-swface coating, printing, electrophotography, photoelectrochemistry, electronics and medicine to name a few.The present study was confined to the electrical and electrochemical properties of cobalt, nickel, zinc. iron and copper phthalocyanines. The use of soluble Pes as corrosion inhibitor for aluminium was also investigated.In the introductory section of the thesis, the work done so far on MPcs is reviewed. In this review emphasis is given to their general methods of synthesis and the physicochemical properties.In phthalocyanine chemistry one of the formidable tasks is the isolation of singular species. In the second chapter the methods of synthesis and purification are presented with necessary experimental details.The studies on plasma modified films of CoPe, FePc, ZnPc. NiPc and CuPc are also presented.Modification of electron transfer process by such films for reversible redox systems is taken as the criterion to establish enhanced electrocatalytic activity.Metal phthalocyanines are p- type semiconductors and the conductivity is enhanced by doping with iodine. The effect of doping on the activation energy of the conduction process is evaluated by measuring the temperature dependent variation of conductivity. Effect of thennal treatment on iodine doped CoPc is investigated by DSC,magnetic susceptibility, IR, ESR and electronic spectra. The elecnucatalytic activity of such doped materials was probed by cyclic voltammetry.The electron transfer mediation characteristics of MPc films depend on the film thickness. The influence of reducing the effective thickness of the MPc film by dispersing it into a conductive polymeric matrix was investigated. Tetrasulphonated cobalt phthalocyanine (CoTSP) was electrostatically immobilised into polyaniline and poly(o-toluidine) under varied conditions.The studies on corrosion inhibition of aluminium by CoTSP and CuTSP and By virtue of their anionic character they are soluble in water and are strongly adsorbed on aluminium. Hence they can act as corrosion inhibitors. CoTSP is also known to catalyze the reduction of dioxygen.This reaction can accelerate the anodic dissolution of metal as a complementary reaction. The influence of these conflicting properties of CoTSP on the corrosion of aluminium was studied and compared with those of CuTSP.In the course of these investigations a number of gadgets like cell for measuring the electrical conductivity of solids under non-isothermal conditions, low power rf oscillator and a rotating disc electrode were fabricated.

Corrosion behavior of pure titanium in artificial saliva solution

The biocompatibility of commercially pure (cp) titanium stems from its chemical stability within an organism, due to a fine film of impermeable titanium oxide covering the metal surface, which guarantees its resistance to corrosion. Despite its biocompatible characteristic, this material does not promote the formation of a hydroxyapatite layer, therefore, many research groups have sought to alter the material`s surface, introducing modifications that might influence corrosion resistance. The electrochemical behavior of cp Ti, with hydroxyapatite coating and without hydroxyapatite coating, commonly used in implant materials, was investigated using an artificial saliva solution at 25 degrees C and pH=7.4. In the conditions of the study it was observed that the hydroxyapatite layer influences the properties of corrosion resistance. This study of the behavior of cp Ti with and without hydroxyapatite coating, in naturally aerated artificial saliva solution at 25 degrees C, was based on open circuit potential measurements and potentiodynamic polarization curves. At approximately 1x10(-6) A/cm(2) the potential for cp Ti with and without hydroxyapatite coating begins to increase at a faster rate, but at -74mV (SCE) for coated cp Ti and at 180mV (SCE) for uncoated cp Ti the increase in potential begins to slow. This behavior, characterized by a partial stabilization of current density, indicates that in those potential ranges a protective passive film is formed.

Structural and electrochemical characteristics of Mg((55-x))Ti(x)Ni((45-y))Pt(y) metal hydride electrodes

In recent years, Mg-Ni-based metastable alloys have been attracting attention due to their large hydrogen sorption capacities, low weight, low cost, and high availability. Despite the large discharge capacity and high activity of these alloys, the accelerated degradation of the discharge capacity after only few cycles of charge and discharge is the main shortcoming against their commercial use in batteries. The addition of alloying elements showed to be an effective way of improving the electrode performance of Mg-Ni-based alloys. In the present work, the effect of Ti and Pt alloying elements on the structure and electrode performance of a binary Mg-Ni alloy was investigated. The XRD and HRTEM revealed that all the investigated alloy compositions had multi-phase nanostructures, with crystallite size in the range of 6 nm. Moreover, the investigated alloying elements demonstrated remarkable improvements of both maximum discharge capacity and cycling life. Simultaneous addition of Ti and Pd demonstrated a synergetic effect on the electrochemical properties of the alloy electrodes. Among the investigated alloys, the best electrochemical performance was obtained for the Mg(51)Ti(4)Ni(43)Pt(2) composition (in at.%), which achieved 448 mAh g(-1) of maximum discharge capacity and retained almost 66% of this capacity after 10 cycles. In contrast, the binary Mg(55)Ni(45) alloy achieved only 248 mAh g(-1) and retained 11% of this capacity after 10 cycles. (C) 2010 Elsevier By. All rights reserved.

Exploring corrosion protection of Mg via ionic liquid pretreatment

We present the development of a 10–100 nanometer thick surface film upon pure Mg on exposure to an ionic liquid (IL) based on the bis(trifluoromethanesulfonyl)amide (TFSA) anion. This film formation is the result of the oxidative reactivity of the metal in the IL, with the subsequent effect of ultimately protecting the underlying metal from corrosion in aqueous chloride containing solution. Film formation was studied in the IL using an electrochemical droplet cell. It was seen that this film is adherent and subsequently facilitates appreciable protection against corrosion as judged by subsequent electrochemical testing in the form of potentiodynamic polarization and impedance spectroscopy, along with direct observation. The physical film morphology was studied by electron microscopy and focused ion beam.

The corrosion inhibition mechanism of new rare earth cinnamate compounds — electrochemical studies

A combination of linear polarisation resistance (LPR) and cyclic potentiodynamic polarisation (CPP) measurements demonstrated that the lanthanum-4 hydroxy cinnamate compound could inhibit both the cathodic and anodic corrosion reactions on mild steel surfaces exposed to 0.01 M NaCl solutions. However, the dominating response was shown to vary with inhibitor concentration. At the concentrations for which the highest level of protection was achieved, both REM-4 hydroxy cinnamate (REM being lanthanum and mischmetal) displayed a strong anodic behaviour for mild steel and their inhibition performance, including their resistance against localised attack, improved with time.

Electrochemical impedance spectroscopy (EIS) measurements and modelling were carried out so as to propose a simple electrical model and correlate the extracted parameters to the inhibition mechanism put forward for REM-cinnamate based compounds. The results supported the high corrosion inhibition performance of the compounds as well as the build-up of a protective film with time. Based on a two-layer model the results suggested that the upper layer of the inhibitor film seemed to offer less resistance to the diffusion of electrochemically active species than the highly resistive inner layer at the film/metal interface.

The nature of the surface film on steel treated with cerium and lanthanum cinnamate based corrosion inhibitors

The corrosion inhibition mechanisms of new cerium and lanthanum cinnamate based compounds have been investigated through the surface characterisation of the steel exposed to NaCl solution of neutral pH. Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy was used to identify the nature of the deposits on the metal surface and demonstrated that after accelerated tests the corrosion product commonly observed on steel (i.e. lepidocrocite, γ-FeOOH) is absent. The cinnamate species were clearly present on the steel surface upon exposure to NaCl solution for short periods and appeared to coordinate through the iron. At longer times the Rare Earth Metal (REM) oxyhydroxide species are proposed to form as identified through the bands in the 1400–1500 cm⁻¹ region. These latter bands have been previously assigned to carbonate species adsorbed onto REM oxyhydroxide surfaces. The protection mechanism appears to involve the adsorption of the REM–cinnamate complex followed by the hydrolysis of the REM to form a barrier oxide on the steel surface.