4.6 Article

Relation Between the Semiconducting Properties of a Passive Film and Reduction Reaction Rates

期刊

JOURNAL OF THE ELECTROCHEMICAL SOCIETY
卷 156, 期 4, 页码 C154-C159

出版社

ELECTROCHEMICAL SOC INC
DOI: 10.1149/1.3077576

关键词

capacitance; chromium; chromium alloys; electrochemical impedance spectroscopy; metallic thin films; molybdenum alloys; nickel alloys; reaction rate constants; reduction (chemical); semiconductor thin films

资金

  1. Science and Technology Program
  2. Office of Civilian Radioactive Waste Management (OCRWM)
  3. U. S. Department of Energy (DOE) [DE-FC28-04RW12252]

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The films forming on pure chromium and Alloy C22 in aqueous borate buffer were investigated with potential polarization scans, electrochemical impedance spectroscopy, and Mott-Schottky analysis. The capacitances of both films were frequency dependent, and a constant phase element (CPE) best described the frequency dispersion. Cathodic polarization scans were used to assess the accuracy of flatband potential values calculated from Mott-Schottky tests using different models to extract an effective capacitance from a CPE. It was found that using effective capacitances calculated with an expression developed by Brug [J. Electroanal. Chem., 176, 275 (1984)] led to flatband potentials that closely agreed with cathodic polarization scans. Both films were found to be n-type, and flatband potentials of -1.217 and -0.617 V vs standard hydrogen electrode were found for Cr and Alloy C22, respectively.

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