Effect of temperature on passive film formation of UNS N08031 Cr-Ni alloy in phosphoric acid contaminated with different aggressive anions

tThe influence of temperature and the effect of aggressive anions on the electrochemical behaviour of UNSN08031 stainless steel in a contaminated phosphoric acid solution were evaluated. Stabilisation of thepassive film was studied by potentiodynamic polarisation curves, potentiostatic tests, electrochemicalimpedance spectroscopy (EIS) measurements, Mott Schottky analysis and X-ray photoelectron spec-troscopy (XPS). The stability of the passive film was found to decrease as temperature increases. The filmformed on the stainless steel surface was a n-type semiconductor and the XPS spectrum revealed thepresence of fluoride ions.Authors express their gratitude to the Ministry of Education of Spain (MHE2011-00202) for its financial support during the stay at University of Manchester, to MAEC of Spain (PCI Mediterraneo C/8196/07, C/018046/08, D/023608/09 and D/030177/10) and to the Generalitat Valenciana (GV/2011/093) for the financial support. The authors would also like to acknowledge the support of the School of Materials at the University of Manchester for providing analytical and technical support for the study.Escrivá Cerdán, C.; Blasco Tamarit, ME.; García García, DM.; García Antón, J.; Akid, R.; Walton, J. (2013). Effect of temperature on passive film formation of UNS N08031 Cr-Ni alloy in phosphoric acid contaminated with different aggressive anions. Electrochimica Acta. 111:552-561. https://doi.org/10.1016/j.electacta.2013.08.040S55256111

Passive and transpassive behaviour of Alloy 31 in a heavy brine LiBr solution

The passive and transpassive behaviour of Alloy 31, a highly alloyed austenitic stainless steel (UNS N08031), has been investigated in a LiBr heavy brine solution (400 g/l) at 25 °C using potentiostatic polarisation combined with electrochemical impedance spectroscopy and Mott-Schottky analysis. The passive film formed on Alloy 31 has been found to be p-type and/or n-type in electronic character, depending on the film formation potential. The thickness of the film formed at potentials within the passive region increases linearly with applied potential. The film formed at transpassive potentials is thinner and more conductive than the film formed within the passive region. These observations are consistent with the predictions of the Point Defect Model for passive and transpassive films on metals and alloys

Assessment of the roughness factor effect and the intrinsic catalytic activity for hydrogen evolution reaction on Ni-based electrodeposits

The hydrogen evolution reaction (HER) was studied in 30 wt.% KOH solution at temperatures ranging between 30 and 80 °C on three type of electrodes: (i) rough pure Ni electrodeposits, obtained by applying a large current density; (ii) smooth NiCo electrodeposits; (iii) smooth commercial Ni electrodes. By using steady-state polarization curves and electrochemical impedance spectroscopy (EIS) the surface roughness factor and the intrinsic activities of the catalytic layers were determined. These techniques also permitted us to determine the mechanism and kinetics of the HER on the investigated catalysts. Different AC models were tested and the appropriate one was selected. The overall experimental data indicated that the rough/porous Ni electrode yields the highest electrocatalytic activity in the HER. Nevertheless, when the effect of the surface roughness was taken into consideration, it was demonstrated that alloying Ni with Co results in an increased electrocatalytic activity in the HER when comparing to pure Ni. This is due to an improved intrinsic activity of the material, which was explained on the basis of the synergism among the catalytic properties of Ni (low hydrogen overpotential) and of Co (high hydrogen adsorption).Isaac Herraiz-Cardona is grateful to the Ministerio de Ciencia e Innovacion (Spain) for a postgraduate grant (Ref. AP2007-03737). This work was supported by Generalitat Valenciana (Project PROMETEO/2010/023)Herraiz Cardona, I.; Ortega Navarro, EM.; Garcia-Anton, J.; Pérez-Herranz, V. (2011). Assessment of the roughness factor effect and the intrinsic catalytic activity for hydrogen evolution reaction on Ni-based electrodeposits. International Journal of Hydrogen Energy. 36(16):9428-9438. https://doi.org/10.1016/j.ijhydene.2011.05.047S94289438361

Stress corrosion cracking in Al-Zn-Mg-Cu aluminum alloys in saline environments

Copyright 2013 ASM International. This paper was published in Metallurgical and Materials Transactions A, 44A(3), 1230 - 1253, and is made available as an electronic reprint with the permission of ASM International. One print or electronic copy may be made for personal use only. Systematic or multiple reproduction, distribution to multiple locations via electronic or other means, duplications of any material in this paper for a fee or for commercial purposes, or modification of the content of this paper are prohibited.Stress corrosion cracking of Al-Zn-Mg-Cu (AA7xxx) aluminum alloys exposed to saline environments at temperatures ranging from 293 K to 353 K (20 °C to 80 °C) has been reviewed with particular attention to the influences of alloy composition and temper, and bulk and local environmental conditions. Stress corrosion crack (SCC) growth rates at room temperature for peak- and over-aged tempers in saline environments are minimized for Al-Zn-Mg-Cu alloys containing less than ~8 wt pct Zn when Zn/Mg ratios are ranging from 2 to 3, excess magnesium levels are less than 1 wt pct, and copper content is either less than ~0.2 wt pct or ranging from 1.3 to 2 wt pct. A minimum chloride ion concentration of ~0.01 M is required for crack growth rates to exceed those in distilled water, which insures that the local solution pH in crack-tip regions can be maintained at less than 4. Crack growth rates in saline solution without other additions gradually increase with bulk chloride ion concentrations up to around 0.6 M NaCl, whereas in solutions with sufficiently low dichromate (or chromate), inhibitor additions are insensitive to the bulk chloride concentration and are typically at least double those observed without the additions. DCB specimens, fatigue pre-cracked in air before immersion in a saline environment, show an initial period with no detectible crack growth, followed by crack growth at the distilled water rate, and then transition to a higher crack growth rate typical of region 2 crack growth in the saline environment. Time spent in each stage depends on the type of pre-crack (“pop-in” vs fatigue), applied stress intensity factor, alloy chemistry, bulk environment, and, if applied, the external polarization. Apparent activation energies (E a) for SCC growth in Al-Zn-Mg-Cu alloys exposed to 0.6 M NaCl over the temperatures ranging from 293 K to 353 K (20 °C to 80 °C) for under-, peak-, and over-aged low-copper-containing alloys (~0.8 wt pct), they are typically ranging from 20 to 40 kJ/mol for under- and peak-aged alloys, and based on limited data, around 85 kJ/mol for over-aged tempers. This means that crack propagation in saline environments is most likely to occur by a hydrogen-related process for low-copper-containing Al-Zn-Mg-Cu alloys in under-, peak- and over-aged tempers, and for high-copper alloys in under- and peak-aged tempers. For over-aged high-copper-containing alloys, cracking is most probably under anodic dissolution control. Future stress corrosion studies should focus on understanding the factors that control crack initiation, and insuring that the next generation of higher performance Al-Zn-Mg-Cu alloys has similar longer crack initiation times and crack propagation rates to those of the incumbent alloys in an over-aged condition where crack rates are less than 1 mm/month at a high stress intensity factor

Effect of temperature on the passive state of Alloy 31 in a LiBr solution: Passivation and Mott-Schottky analysis

The passive behaviour of Alloy 31, a highly‐alloyed austenitic stainless steel (UNS N08031), has been investigated in a LiBr heavy brine (700 g/l) at different temperatures using potentiostatic polarisation and Mott‐Schottky analysis. Cation vacancies have been found to be the dominant defect in the passive films formed on Alloy 31. An increase in temperature enhanced the generation of cation vacancies at the film/solution interface and raised the steady‐state passive current density. The density of defects within the passive film also increased significantly with temperature, making the film more conductive and less protective against localised attacks

Effect of alloying elements on the electronic properties of thin passive films formed on carbon steel, ferritic and austenitic stainless steels in a highly concentrated LiBr solution

The influence of alloying elements on the electrochemical and semiconducting properties of thin passive films formed on several steels (carbon steel, ferritic and austenitic stainless steels) has been studied in a highly concentrated lithium bromide (LiBr) solution at 25 °C, by means of potentiodynamic tests and Mott-Schottky analysis. The addition of Cr to carbon steel promoted the formation of a p-type semiconducting region in the passive film. A high Ni content modified the electronic behaviour of highly alloyed austenitic stainless steels. Mo did not modify the electronic structure of the passive films, but reduced the concentration of defects