In chlorine-containing environments such as oceans and oil fields, Cl- has a strong penetrating and destructive effect on passivation film, resulting in local dissolution of stainless steel passivation, increased pitting sensitivity and pitting corrosion, threatening the operation safety of equipment and pipelines. In different concentrations and pH values of S2- containing environments, the degree of corrosion and corrosion products of stainless steel will also be different. S2- preferentially adsorbs on the active site of stainless steel and induces pitting corrosion, resulting in passivation film destruction and sulfur corrosion products. The sulfur conversion film has good conductivity, catalysis and corrosion protection ability. In order to improve the pitting resistance of stainless steel in chlorine-containing environment, the work aims to use hydrothermal method to prepare sulfur conversion film on the surface of stainless steel, inspired by the fact that the corrosion product film can effectively reduce the pitting sensitivity of stainless steel.
The base material used in the experiment was 316L austenitic stainless steel sheet. The sample was polished step by step with sandpaper, rinsed with deionized water and ethanol, and dried by cold air. A working area of 10 mm×10 mm was reserved on the surface of the sample, and the electrochemical corrosion resistance was tested in artificial seawater solution at 25 ℃. Different concentrations of sodium sulfide solution were configured, and the pH of sodium sulfide solution was adjusted to 5 by 20% mass fraction of sulfuric acid solution. The polished stainless steel sample was put into the hydrothermal kettle. The sulfur conversion film was prepared on 316L stainless steel surface by changing the concentration of S2- (600, 800, 1 000, 1 200, 1 400 mg/L), reaction temperature (50, 60, 70, 80, 90 ℃) and reaction time (50, 60, 70, 80, 90 h).
By screening the preparation conditions of the sulfur conversion film, the corrosion resistance of the sulfur-containing conversion film prepared by soaking in the solution of 1 000 mg/L sulfur ion at 70 ℃ for 48 h was the best at 25 ℃ artificial seawater solution. Compared with untreated samples, the self-corrosion potential of vulcanized stainless steel increased from -0.18 V to 0.08 V, the pitting potential increased from 0.41 V to 1.10 V, the Tafel slope decreased, the critical point corrosion temperature increased significantly, and the corrosion tendency decreased. However, the self-corrosion current density of the vulcanized sample increased, and the chemical reaction existed in the sulfur conversion film, and the metal sulfide was oxidized to form metal oxide. In the EIS impedance, the arc radius and charge transfer resistance of the vulcanized samples decreased, and the phase angle decreased in the low frequency region in advance, indicating that the density of the sulfur conversion film was low. The sulfur conversion film was observed by SEM as tetrahedral particles attached to the surface of stainless steel, and the particle distribution was not continuous, which confirmed the speculation of impedance reduction in electrochemical testing. The main components of the sulfur conversion film were FeS2, FeS, Fe2S3, FeO and a small amount of Cr, Ni vulcanization and oxides. Through immersion experiment, it was found that the corrosion rate of vulcanized samples was reduced, and the sulfur conversion film was oxidized into a metal oxide film and stainless steel passivation film, which improved the uniform corrosion resistance of the stainless steel interface.
A sulfur conversion film with high pitting resistance has been prepared on the surface of 316L stainless steel by hydrothermal method. The sulfur conversion film is a discontinuous particle attached to the active site of stainless steel, which reduces the pitting sensitivity of stainless steel. In addition, the sulfur conversion film will react with O2 to gradually form iron oxide, which also increases the uniform corrosion resistance of the stainless steel surface.
Key words
sulfur conversion film /
316L stainless steel /
corrosion resistance /
chlorine-containing solution
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Funding
National Key Research and Development Program (2023YFB4005100); Qingdao Laoshan National Laboratory Project (LSKJ202205700)
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