Nickel (Ni) and electroless nickel (EN) coatings are used extensively in caustic soda (NaOH) service. The corrosion resistance of an EN coating is dependent upon phosphorus (P) content, but not in the trend expected. High-phosphorus EN (HPEN) coatings have poorer corrosion resistance in hot, concentrated sodium hydroxide (NaOH) than low-phosphorus (LPEN) and medium-phosphorus (MPEN) coatings, which have a corrosion resistance comparable to Ni. The purpose of this work was to quantify the effect of P in EN coatings on their corrosion resistance in 50% NaOH at room temperature (RT). Electrochemical techniques were used to investigate the corrosion processes. X-ray photoelectron spectroscopy (XPS) was used to characterize coating surfaces. Very low corrosion rates (≤ 2 μm/y) were measured for all coatings. It was proposed that the detrimental effect of P in EN coatings exposed to a concentrated NaOH environment was a result of the higher solubility of nickel phosphate (Ni3[PO4]2) relative to nickel hydroxide (Ni[OH]2) and nickel oxide (NiO). This mechanism predicted an inverse relationship between the thickness of the protective film on EN and its P content, which was consistent with experimental observations.

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