Concentration effects of formic acid on the corrosion behavior of 316L stainless steel from passivation to activation
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摘要: 為深入認識316L不銹鋼在甲酸溶液中的鈍化-活化轉變行為，在90 ℃、質量分數為0~30%的甲酸溶液中對316L不銹鋼進行全浸試驗和陽極極化曲線測試。研究了甲酸質量分數對316L不銹鋼腐蝕速率、腐蝕形貌、開路電位、初始鈍化電位、臨界電流密度、鈍化電流密度和鈍化膜破裂電位的影響規律，分析了H+ 和HCOO? 含量對活化區、過渡區和鈍化區陽極反應的影響機制。結果表明，316L不銹鋼在甲酸溶液中發生非均勻的全面腐蝕。當甲酸質量分數達到30%、腐蝕速率為1.2×10?3 mm·a?1時，316L不銹鋼就具有明顯的鈍化?活化轉變。隨著甲酸質量分數增加，316L不銹鋼的初始鈍化電位正移、臨界電流密度增大、鈍化電流密度增大、鈍化膜破裂電位負移。甲酸溶液中H+ 和HCOO? 含量的增加，會加速316L不銹鋼活性溶解，抑制鈍化膜生長，促進鈍化-活化轉變。Abstract: One of the most aggressive organic acids for stainless steel is formic acid. In particular, the corrosion of 316L stainless steel in aqueous formic acid solutions at high temperatures is directly related to its safe operation and production efficiency. To better understand the passivation-activation transition behavior of 316L stainless steel in aqueous formic acid solutions, an investigation was conducted at the formic acid mass fractions of 0.5%, 5%, 15%, and 30% at 90 ℃. Laboratory immersion tests with a period of 1200 hours were performed at each formic acid mass fraction to document the corrosion rates and the corrosion morphologies of 316L stainless steel, and electrochemical tests, including open circuit potentials and anodic polarization curves, were conducted in the presence of dissolved oxygen using conventionally divided glass cells with three electrodes. The influences of formic acid mass fraction on corrosion rate, corrosion morphology, open circuit potential, primary passivation potential, critical current density, passive current density, and passive film breakdown potential were analyzed. In addition, the effects of H+ and HCOO? ions on anodic reactions occurring in the active region, the active-passive transition region, and the passive region were discussed. Due to the stability of the passive state, the laboratory immersion tests showed that at the formic acid mass fractions of 0.5%, 5%, and 15%, 316L stainless steel suffered from slight corrosion, and thus no measurable weight losses could be acquired. However, in the 30% aqueous formic acid solution, the corrosion rate of 316L stainless steel reached 1.2 × 10?3 mm·a?1, which indicated that 316L stainless steel was in the active state and the passivation-activation transition had occurred. The corrosion of 316L stainless steel in aqueous formic acid solutions is characteristic of non-uniform generalized corrosion. According to the results of electrochemical tests, with an increasing mass fraction of formic acid, the open circuit potentials and the primary passivation potentials became nobler, the critical current densities and the passive current densities increased, and the passive film breakdown potentials shifted to negative values. It is suggested that the passivation-activation transition of 316L stainless steel in aqueous formic acid solutions may be due to the competitive adsorption between HCOO? and OH? ions. Therefore, formic acid mass fraction increased, anodic dissolution accelerated, the formation of passive film was delayed, and corrosion susceptibility increased. In short, the concentration of formic acid significantly influences the corrosion behavior of 316L stainless steel from passivation to activation.
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Key words:
- stainless steel /
- formic acid /
- corrosion /
- electrochemistry /
- passivation
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圖 1 316L不銹鋼在不同質量分數甲酸溶液中的腐蝕速率
Figure 1. Corrosion rates of 316L stainless steel in the formic acid solutions of different mass fractions
圖 2 316L不銹鋼在不同質量分數甲酸溶液中的表面微觀形貌(圖（b）、（d）、（f）、（h）分別為圖（a）、（c）、（e）、（g）虛線框區域的局部放大圖).（a, b）0.5%; （c, d）5%; （e, f）15%; （g, h）30%
Figure 2. Surface microstructure of 316L stainless steel in the formic acid solutions of different mass fractions (figures (b), (d), (f) and (h) are local enlarged images of the dashed box areas in figures (a), (c), (e) and (g) respectively): (a, b) 0.5%, (c, d) 5%, (e, f) 15%, (g, h) 30%
圖 3 不同質量分數甲酸溶液中316L不銹鋼的開路電位隨浸泡時間的演變
Figure 3. Evolution of open circuit potential with immersion time in the formic acid solutions of different mass fractions for 316L stainless steel
圖 4 316L不銹鋼在不同質量分數甲酸溶液中的陽極極化曲線
Figure 4. Anodic polarization curves of 316L stainless steel in the formic acid solutions of different mass fractions
圖 5 316L不銹鋼在不同質量分數甲酸溶液中的初始鈍化電位(a)、臨界電流密度(b)、鈍化電流密度(c)和鈍化膜破裂電位(d)
Figure 5. Primary passivation potential (a), critical current density (b), passive current density (c), and passive film breakdown potential (d) of 316L stainless steel in the formic acid solutions of different mass fractions
表 1 四種質量分數甲酸溶液的pH值和電導率
Table 1. pH values and conductivities of the formic acid solutions at four different mass fractions
Formic acid mass fractions/% pH Conductivity/(mS·cm?1) 0.5 2.4 0.0017 5 2.0 7.14 15 1.5 9.71 30 0.7 11.04 
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