Tannic acid compound as a corrosion inhibitor: film-forming characteristics and corrosion resistance
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摘要: 單寧酸由于環保、價格低的特點在金屬保護方面應用廣泛，然而單一利用單寧酸作為緩蝕劑取得的效果有限，有研究表明鹽類與緩蝕劑復配可以改善緩蝕劑的緩蝕效果。在此基礎上進行單寧酸復配緩蝕劑的研究，采用兩種復配劑氯化鐵、鉬酸鈉分別與單寧酸（TA）緩蝕劑進行復配，研究其對碳鋼Q235的緩蝕效果。通過硫酸銅點滴實驗、浸泡實驗、電化學實驗對比氯化鐵、鉬酸鈉分別與單寧酸復配后在碳鋼表面的成膜特性及緩蝕效果。硫酸銅點滴液變色時間隨著單寧酸中氯化鐵和鉬酸鈉兩種化合物濃度的升高出現先增加后降低的趨勢；浸泡實驗可以看出在單寧酸中加入氯化鐵和鉬酸鈉后，碳鋼表面僅出現個別點蝕坑；根據電化學測試結果，對比加入氯化鐵前后單寧酸緩蝕劑對碳鋼的緩蝕效果，發現兩者的電荷轉移電阻由2698變為3711 Ω·cm2，腐蝕電流密度由2.734降為1.902 μA·cm?2。加入鉬酸鈉后，電荷轉移電阻和腐蝕電流密度存在明顯的增加與下降，電荷轉移電阻由2698變為5100 Ω·cm2，腐蝕電流密度由2.734降為0.714 μA·cm?2。在單寧酸中添加氯化鐵和鉬酸鈉都能改善單寧酸的緩蝕效果，其中單寧酸與鉬酸鈉復配的緩蝕效果更好。Abstract: Tannic acid (TA) is widely used to protect metals from corrosion because it is environmentally friendly and inexpensive. However, the single effect of TA used as corrosion inhibitor has been widely investigated and studies focusing on the corrosion inhibition effect have been limited. Some studies have proven that the addition of a compound corrosion inhibitor can considerably improve the corrosion inhibition efficiency of an inhibitor, and this method can be applied to TA. The corrosion inhibition effect of the combination of two compounds, FeCl3 and Na2MoO4, with TA was analyzed on carbon steel Q235. Copper sulfate drip test, soaking test, and electrochemical test were used to compare the film-forming characteristics and corrosion inhibition effect of the combination of FeCl3 and Na2MoO4 with TA on carbon steel surface. The discoloration time of copper sulfate droplets initially increases and subsequently decreases with the increase in the concentrations of FeCl3 and Na2MoO4 in TA. At the end of the soaking test, fewer pits are observed on the surface of carbon steel following the addition of FeCl3 and Na2MoO4 to the TA inhibitor. Based on the results of the electrochemical tests, the corrosion inhibition effects of the TA inhibitor on carbon steel before and after the addition of FeCl3 were compared. The results reveal that the charge transfer resistance of the two inhibitors increases from 2698 to 3711 Ω·cm2, and the corrosion current density decreases from 2.734 to 1.902 μA·cm?2. A clear increase and decrease in the charge transfer resistance and corrosion current density, respectively, are observed once Na2MoO4 is added. Further, the charge transfer resistance increases from 2698 to 5100 Ω·cm2, and the corrosion current density decreases from 2.734 to 0.714 μA·cm?2. The following conclusions can be drawn from these results: the addition of FeCl3 or Na2MoO4 to TA can both improve the corrosion inhibition effect of TA; the compound system of TA and Na2MoO4 exhibits a better corrosion inhibition effect compared with the compound system of TA and FeCl3.
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Key words:
- tannic acid /
- low-carbon steel /
- compound /
- conversion film /
- corrosion resistance /
- electrochemistry
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圖 1 TA和TA轉化膜的傅里葉變換紅外光譜
Figure 1. Fourier transform infrared spectra of tannic acid (TA) and TA conversion film
圖 3 TA質量濃度和轉化時間對單寧酸轉化膜耐蝕性能的影響
Figure 3. Effect of TA mass concentration and conversion time on the corrosion resistance of TA conversion coatings
圖 4 單寧酸轉化膜表面形貌圖. (a) 光鏡圖；(b) 致密區掃描電鏡圖；(c)缺陷區掃描電鏡圖
Figure 4. Surface morphology of TA conversion film: (a) OM image; (b) SEM image of dense areas; (c) SEM image of defect area
圖 5 單寧酸中添加不同量FeCl3后轉化膜的電鏡形貌圖. (a) 0；(b) 0.01 g?L?1；(c) 0.03 g?L?1；(d) 0.05 g?L?1；(e) 0.07 g?L?1；(f) 0.1 g?L?1
Figure 5. SEM images of conversion films with different amounts of FeCl3 in TA: (a) 0; (b) 0.01 g?L?1; (c) 0.03 g?L?1; (d) 0.05 g?L?1; (e) 0.07 g?L?1; (f) 0.1 g?L?1
圖 6 單寧酸中添加不同量FeCl3后轉化膜的光鏡形貌圖. (a) 0；(b) 0.01 g?L?1；(c) 0.03 g?L?1；(d) 0.05 g?L?1；(e) 0.07 g?L?1；(f) 0.1 g?L?1
Figure 6. OM images of conversion films with different amounts of FeCl3 in TA: (a) 0; (b) 0.01 g?L?1; (c) 0.03 g?L?1; (d) 0.05 g?L?1; (e) 0.07 g?L?1; (f) 0.1 g?L?1
圖 7 硫酸銅變色時間隨氯化鐵質量濃度變化圖
Figure 7. Chromogenic time of copper sulfate changing with the concentration of FeCl3
圖 8 單寧酸中添加不同量Na2MoO4后轉化膜的掃描電鏡形貌圖. (a) 0；(b) 0.05 g?L?1；(c) 0.10 g?L?1；(d) 0.15 g?L?1；(e) 0.20 g?L?1；(f) 0.30 g?L?1
Figure 8. SEM images of conversion films with different amounts of Na2MoO4 in TA: (a) 0; (b) 0.05 g?L?1; (c) 0.10 g?L?1; (d) 0.15 g?L?1; (e) 0.20 g?L?1; (f) 0.30 g?L?1
圖 9 單寧酸中添加不同量Na2MoO4后轉化膜的光鏡形貌圖. (a) 0；(b) 0.05 g?L?1；(c) 0.10 g?L?1；(d) 0.15 g?L?1；(e) 0.20 g?L?1；(f) 0.30 g?L?1
Figure 9. OM images of conversion films with different amounts of Na2MoO4 in TA: (a) 0; (b) 0.05 g?L?1; (c) 0.10 g?L?1; (d) 0.15 g?L?1; (e) 0.20 g?L?1; (f) 0.30 g?L?1
圖 10 硫酸銅變色時間隨鉬酸鈉質量濃度變化圖
Figure 10. Chromogenic time of copper sulfate changing with the mass concentration of Na2MoO4
圖 11 不同單寧酸體系轉化膜的阻抗譜. (a) Nyquist；(b) 阻抗的膜值∣z∣；(c) 相位角
Figure 11. Electrochemical impedance parameters of TA conversion films in different systems: (a) Nyquist diagram; (b) Bode diagram; (c) phase angle diagram
圖 13 單寧酸體系轉化膜極化曲線
Figure 13. Polarization curves of TA conversion film in different systems
表 1 浸泡實驗對比圖表
Table 1. Comparison of soaking test
緩蝕劑 5 min 10 min 15 min 30 min 無 
TA 
TA/Fe3+ 
TA/${\rm{MoO}}_4^{2 - }$ 
下載: 導出CSV
表 2 電化學擬合參數
Table 2. Electrochemical fitting parameters
緩蝕劑 Rs/(Ω·cm2) Rct/(Ω·cm2) CPE Y/(10?5 S·sn·cm?2) n 無 30.1 1416 80.4 0.84 TA 18.3 2698 78.4 0.78 TA/Fe3+ 16.5 3711 34.5 0.75 ${\rm{TA}}/{\rm{MoO}}_4^{2 - }$ 13.2 5100 25.0 0.80
下載: 導出CSV
中文字幕在线观看表 3 極化曲線擬合數據
Table 3. Polarization curve fitting data
緩蝕劑 Ecorr/V Icorr/(μA·cm?2) βa βc Rp/(Ω·cm?2) 無 ?0.862 6.012 113.8 217.5 5396 TA ?0.831 2.734 121.2 137.0 10213 TA/Fe3+ ?0.859 1.902 144.3 104.9 13867 ${\rm{TA}}/{\rm{MoO}}_4^{2 - }$ ?0.783 0.714 167.3 49.0 23048
下載: 導出CSV
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