In Operando Analysis of Passive Film Growth on Ni-Cr and Ni-Cr-Mo Alloys in Chloride Solutions

Abstract

The instantaneous kinetics of oxide formation and growth, in competition with passive film dissolution and breakdown, were investigatedfor Ni-22 Cr and Ni-22 Cr-6 Mo (wt%) during single step passivation at +0.2 VSCE. Experiments were conducted in selected acidic and alkaline chloride-containing environments using simultaneous AC and DC electrochemistry; including on-line Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). In parallel experiments, in-situ neutron reflectometry (NR) and ex-situ X-ray photoelectron spectroscopy (XPS) were utilized to characterize the formation of surface oxide films as a function of time. The specific roles of pH and Mo during passivation and breakdown kinetics are highlighted, providing an insight into the fate of the elements which comprise the alloys, and their effects on passivation behavior. It was observed that early oxidation of both Ni and Cr-species occurred in acidic electrolyte. Preferential dissolution of Ni2+ at later times enabled gradual Cr3+ enrichment within the surface film. However, greater relative stability of NiO and Ni(OH)2 was observed in the alkaline condition. Upon alloying Ni-Cr with Mo, Cr3+ became increasingly enriched in the surface film during anodic polarization. Oxides were interpreted to consist of non-stoichiometric solid solutions formed via solute capture.

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Document Details

Document Type
Technical Report
Publication Date
May 16, 2019
Accession Number
AD1103705

Entities

People

  • Hung M. Ha
  • John R. Scully
  • Katie L. Cwalina
  • Nick Birbilis
  • Noemie Ott
  • Petra Reinke

Organizations

  • University of Virginia

Tags

Communities of Interest

  • Advanced Electronics

DTIC Thesaurus Topics

  • Alloys
  • Base Metal
  • Chemical Reactions
  • Chemical Stability
  • Chemistry
  • Current Density
  • Density Functional Theory
  • Detection
  • Detectors
  • Mass Spectrometry
  • Materials
  • Materials Science
  • Oxide Films
  • Solid Solutions
  • Spectra
  • Spectroscopy
  • Thin Films

Readers

  • Electrochemical Engineering/ Fuel Cell Technologies
  • Materials Science and Engineering.
  • Thin Film Deposition Science.

Technology Areas

  • Microelectronics
  • Microelectronics - Graphene