Duplex stainless steels have a large number of industrial applications and may replace high cost materials, especially in chloride-containing environments like seawater in off-shore platforms due to their high mechanical properties and good corrosion resistance. The influence of the ferrite content on the performance of duplex stainless steels in these corrosive environments is not well known. For the present paper, new superduplex stainless steels with ferrite between 30 and 60% were developed and their microstructure and corrosion resistance were evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) tests in NaCl 3.5% (wt %) at 26°C and 78°C. The results obtained at 26°C showed that the pitting potential (E pitt ) is little affected by the ferrite content, but for the materials with higher ferrite it was possible to observe an increase in the repassivation potential with a decrease in the corrosion potential and passive currents due to the presence of more resistive passive films. Tests performed at 78°C indicated a high decrease in the E pitt for all the samples, independently of the ferrite percentage, although maintaining superiority in higher ferrite content. Alloys with a 55% ferrite phase content, i.e. less dependent of Ni element, present a superior performance of corrosion resistance.
Neste trabalho é feito um estudo do comportamento eletroquímico de eletrodos formados por pó de ligas de hidreto metálico do tipo AB 5 com formulações LaNi (5-x) Z x , onde Z é um elemento metálico que substitui parcialmente o Ni, que inclui Sn, Al, Mn e Pd. No caso do Mn, algumas estruturas do tipo AB 6 são também consideradas. A substituição de uma pequena fração do Ni pelo Al, Sn e Mn (x ≅ 0.3) promove um aumento da capacidade de armazenamento de hidrogênio (CAH), enquanto que o Pd leva à um decréscimo desta propriedade. Em geral todas as ligas apresentam alta CAH inicial, mas exibem baixa estabilidade. Foi observado que a diminuição da pressão de equilíbrio de hidrogênio em função do teor de Mn, nas ligas AB 5 , relaciona-se diretamente com o aumento do volume da cela cristalina unitária. Através de experimentos de impedância eletroquímica nota-se um aumento significativo da cinética de reação de hidretação/desidretação com o aumento do número de ciclos de carga/descarga do eletrodo, devido ao aumento da área ativa. Também foi observado que, no geral, as ligas que apresentam maior CAH são aquelas que possuem menor energia de ativação para a reação de oxidação de hidrogênio.This work reports studies on the electrochemical behavior of AB 5 -type hydrogen storage alloys, formed by LaNi (5-x) Z x , where Z is a metallic element partially replacing Ni, which included Sn, Al, Mn, and Pd. In the case of Mn, some AB 6 -type structures were also considered. Substitution of a small fraction of Ni by Al, Sn, and Mn (x ≅ 0.3) leads to an increase of the hydrogen storage capability (HSC), while for Pd there is a decrease of this property. Generally all alloys presenting larger initial HSC exhibit lower stability. A decrease of the hydrogen equilibrium pressure as a function of Mn content is observed for the AB 5 alloys and this is related to an increase of the crystalline unit cell volume. Electrochemical impedance measurements show a significant increase of the hydration/dehydration reaction kinetics due to a raise on the active area as a function of the charge/discharge cycle number. It is also seen that the alloys presenting larger HSC are those showing smaller activation energies for the hydrogen oxidation reaction.Keywords: hydrogen storage materials, electrode materials, energy storage materials, nickelmetal hydride battery IntroductionThe use of metal-hydride (MH) alloys as negative electrode material in rechargeable alkaline batteries has grown in recent years, because of its high energy density, high rate capability, and environmental acceptability. Ni-MH batteries have been developed and commercialized to meet a strong market demand as a power source with a high performance/cost ratio. 1,2 Currently, the anodes of most Ni-MH batteries are based on the AB 5 family of intermetallic compounds. To improve the electrode performance and lower costs of hydrogen storage alloys, AB 5 type alloys have been developed with substitution of pure earth elements in A side (La) by a mischmetal-based multicomponent and the parti...
Introduction: The mechanical properties and corrosion resistance of a material are dependent on its microstructure and can be modifi ed by phase transformation. When a phase transformation occurs in a material it usually forms at least one new phase, with physical-chemical characteristics that differ from the original phase. Moreover, most phase transformations do not occur instantly. This paper presents an evaluation of the phase transformation of martensitic stainless steels ASTM 420A and ASTM 440C when submitted to different thermal processes. Methods: Dilatometry tests were performed with several continuous heating and cooling rates in order to obtain the profi les of the continuous heating transformation (CHT) and continuous cooling transformation (CCT) diagrams for these two types of steel. Also, the temperature ranges for the formation of the different phases (ferrite and carbides; ferrite; austenite and carbides; non-homogeneous and homogeneous austenite phases) were identifi ed. Rockwell hardness (HRC) tests were performed on all thermally treated steels. Anodic and cathodic potential dynamic polarization measurements were carried out through immersion in enzymatic detergent as an electrolyte for different samples submitted to the thermal processes in order to select the best routes for the heat treatment and to recommend steels for the manufacture of surgical tools. Results: The martensitic transformation temperature tends to increase with increasing temperature for the initiation of cooling. The 440C steel had a higher hardness value than the 420A steel at the austenitizing temperature of 1100 °C. Above the austenitizing temperature of 1100 °C, the material does not form martensite at the cooling rate used, which explains the sharp decline in the hardness values. Conclusion: The study reported herein achieved its proposed objectives, successfully investigating the issues and indicating solutions to the industrial problems addressed, which are frequently encountered in the manufacture of surgical instruments.
The formation of grains and their growth based on the elimination of other grains, before thermal cycles are imposed, are essential for the correct conformation of a material and to control the microstructure, texture and orientation relationships between phases. However, when the boundary of a polycrystalline grain intersects the outer surface and the material is exposed to temperatures higher than half of its fusion temperature, a crack or groove appears. This research aims to apply a method to evaluate the energy of the grain boundary (GB) and also to compare the energy values of the faces of the GB, and to investigate commercially-pure grade 2 titanium in relation to the action of forces on the grain boundary of the free surface. The thermal attack under vacuum technique was used to reveal, at high temperatures, the titanium microstructure, which is preserved under a very thin oxide layer even when the sample is brought to room temperature. Thus, at room temperature, it was possible to analyze the Ti surface viewed at high temperature. The thermal cracks or grooves appearing due to the selective vaporization of atoms at the GB were measured geometrically using atomic force microscopy. The energy relationship of the GB was determined from the microstructural appearance at high temperatures and applying the equation g gb = 2·g s ·senj to the thermal crack formed between two grains.The results were compared experimentally with others reported in the literature. With the method applied in this study it was possible to evaluate the energy of the GB and it was verified that this energy was anisotropic for the material under study.Keywords Titanium, Grain boundary energy, Atomic force microscopy, Thermal attack under vacuum. Medida de energia de contorno de grão do titânio comercialmente purograu 2 -em alta temperaturaResumo A formação e o crescimento de grãos a partir de outros existentes, perante ciclos térmicos impostos, são fundamentais para a conformação adequada do material, para controlar a microestrutura, textura e relações de orientação entre as fases. Com o princípio da formação de uma fenda térmica á partir da exposição do material a temperaturas maiores que a metade de sua temperatura de fusão, esta pesquisa visa a comprovação de um método para avaliar a energia de contorno de grão (CG), comparar os valores da energia das faces do CG e investigar a ação das forças na superfície livre dos CGs do titânio comercialmente puro grau 2. A técnica de ataque térmico sob vácuo foi empregada para revelar, em altas temperaturas, a microestrutura do titânio, esta técnica permite a manutenção da estrutura "congelada" sob uma camada de óxido de pequena espessura mesmo quando a amostra é trazida à temperatura ambiente. Com este método foi possível analisar a superfície do Ti em temperatura ambiente, como se estivesse sendo visualizada em altas temperaturas. As trincas ou fendas térmicas provenientes da vaporização seletiva de átomos no CG foram medidas geometricamente utilizando Microscopia de Força Atômica. A energia d...
Walther Hermann Nernst received the Nobel Prize in Chemistry in 1920 for the formulation of the third law of thermodynamics, thus celebrating a century in this 2020 year. His work helped the establishment of modern physical chemistry, since he researched into fields, such as thermodynamics and electrochemistry, in which the Nernst equation is included. This paper reports on several experiments that used a Daniell galvanic cell working in different electrolyte concentrations for comparing results with the theoretical values calculated by the Nernst equation. The concentration and activity coefficients values employed for zinc sulfate and copper electrolytes showed activity can replaces concentrations in thermodynamic functions, and the results are entirely consistent with experimental data. The experimental electromotive force from standard Daniell cell, for ZnSO4 and CuSO4, with unitary activity and in different concentrations at room temperature is in agreement with those from theoretical calculations. Cu2+ ion concentrations and temperature were simultaneously varied; however, the cell potential cannot be included in calculations of Nernst equation for different temperatures than 25 °C because the standard potential value was set at 25 °C. The cell potential decreases drastically when the Cu2+ concentration was reduced and the temperature was above 80 oC.
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