Ni-Cr based super-alloys have exceptional corrosion resistance, which is further improved with Mo alloying. The correlation between passive layer performance and composition was studied to gain a deeper mechanistic understanding of the role of Mo by comparing the behavior of Ni-22Cr to Ni-22Cr-6Mo (wt%) alloys. The passive layers were formed using galvanostatic holds to create fast and slow growth conditions using high and low current densities. A potentiostatic hold was added to initiate exposure aging. The passive film was characterized using electrochemical impedance spectroscopy (EIS), linear sweep voltammetry (LSV), atomic emission spectro-electrochemistry (AESEC), and X-ray photoelectron spectroscopy (XPS). Combined electrochemical and XPS characterization offered insight in cation concentrations and stratification, bonding states (oxide, hydroxide), and their modulation as a function of electrochemical conditions and performance. Most importantly: (i) Mo addition enhanced Cr(III) bound in oxide, (ii) fast growth conditions resulted in less corrosion resistant films, and (iii) exposure aging increased Cr-enrichment and reduced stratification of Mo-cations. The correlation between passive film performance and Cr, Ni, and Mo oxidation states, bonding, oxide-hydroxide contributions, and stratification is discussed. Generally accepted correlations, such as Cr-cation concentration and performance of the passive layer, have to be reexamined in order to account for the complex chemical make-up of the passive layer.
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Dealloying Behavior of NiCo and NiCoCu Thin Films
Porous metals and alloys, such as those fabricated via electrochemical dealloying, are of interest for a variety of energy applications, ranging from their potential for enhanced catalytic behavior to their use as high surface area supports for pseudocapacitor materials. Here, the electrochemical dealloying process was explored for electrodeposited binary NiCo and ternary NiCoCu thin films. For each of the four different metal ratios, films were dealloyed using linear sweep voltammetry to various potentials in order to gain insight into the evolution of the film over the course of the linear sweep. Electrochemical capacitance, scanning electron microscopy, and energy dispersive X-ray spectroscopy were used to examine the structure and composition of each sample before and after linear sweep voltammetry was performed. For NiCo films, dealloying resulted in almost no change in composition but did result in an increased capacitance, with greater increases occurring at higher linear sweep potentials, indicating the removal of material from the films. Dealloying also resulted in the appearance of large pores on the surface of the high nickel percentage NiCo films, while low nickel percentage NiCo films had little observable change in morphology. For NiCoCu films, Cu was almost completely removed at linear sweep potentials greater than 0.5 V versus Ag/AgCl. The linear sweep removed large Cu-rich dendrites from the films, while also causing increases in measured capacitance.
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- Award ID(s):
- 1104725
- PAR ID:
- 10025971
- Date Published:
- Journal Name:
- International Journal of Electrochemistry
- Volume:
- 2016
- ISSN:
- 2090-3529
- Page Range / eLocation ID:
- 1 to 10
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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