Preparation and corrosion resistance of titanium-containing coating on AZ31B magnesium alloy
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摘要: 含钛氧化膜因具有自封孔现象而引起关注。采用四因素三水平正交实验，研究氟钛酸钾（K2TiF6）、植酸（H12Phy）和氟化钠（NaF）浓度以及终电压对氧化膜耐蚀性影响，使用扫描电子显微镜（SEM）、X射线能谱仪（EDS）、X射线衍射（XRD）和电化学方法表征涂层性能。结果表明：影响氧化膜耐蚀性的主次顺序是植酸浓度 > NaF浓度 > 终电压 > K2TiF6浓度；氧化膜主要由TiO2、MgF2、Mg2PO4F和Mg2TiO4组成；微弧氧化膜可明显提高镁合金的耐蚀性，但随着浸泡时间延长，膜层耐蚀性降低。Abstract: The titanium-containing oxide film has attracted attention due to the phenomenon of self-sealing pores. The influences of fluorotitanate (K2TiF6), phytic acid (H12Phy) and sodium fluoride(NaF) concentrations as well as final voltage on corrosion resistance of oxide film were investigated by an orthogonal experiment with four factors and three levels. The coating performances were characterized by using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and electrochemical methods. The results show that the sequence of processing factors on the corrosion resistance of oxide film is H12Phy concentration > NaF concentration > final voltage > K2TiF6 concentration. Anodic coatings are mainly composed of TiO2, MgF2, Mg2PO4F and Mg2TiO4. Micro-arc oxidation (MAO) coating can significantly improve the corrosion resistance of magnesium alloy. However, with the prolonging of immersion time, the coating corrosion resistance decreases.
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Key words:
- Mg alloy /
- MAO /
- K2TiF6 /
- corrosion resistance /
- orthogonal experiment
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图 1 9个工艺制备的氧化膜表面形貌
Figure 1. Surface morphologies of anodic coatings fabricated by nine processes （a）No.1；（b）No.2；（c）No.3；（d）No.4；（e）No.5；（f）No.6；（g）No.7；（h）No.8；（i）No.9
图 2 9个工艺制备的氧化膜截面形貌
Figure 2. Cross-sectional morphologies of anodic coatings fabricated by nine processes （a）No.1；（b）No.2；（c）No.3；（d）No.4；（e）No.5；（f）No.6；（g）No.7；（h）No.8；（i）No.9
图 3 AZ31B镁合金基体和4种工艺制备的氧化膜XRD结果
Figure 3. XRD patterns of substrate and anodic coatings developed on samples of No.2，No.3，No.5 and No.6
图 4 基体和9个工艺制备的氧化膜动电位极化曲线
Figure 4. Potentiodynamic polarization curves of substrate and MAO samples fabricated by nine processes
图 5 9个氧化膜P、F和Ti含量与icorr之间的相关性（a）和膜层孔隙率、截面厚度与icorr之间的相关性（b）
Figure 5. Correlation between P，F and Ti amounts in nine MAO treated samples with icorr （a）and correlation between porosity and coating thickness with icorr（b）
图 6 No.5样品在3.5% NaCl溶液中浸泡不同时间的EIS谱图 （a）Nyquist图；（b）Bode图
Figure 6. EIS spectra of No.5 specimen immersed in 3.5% NaCl solution for different times （a）Nyquist plots；（b）Bode plots of frequency vs |Z| and phase angle
图 7 等效电路图 （a）基体；（b）No.5样品浸泡6 h、12 h、24 h、48 h、72 h
Figure 7. Equivalent electrical circuit diagrams （a）substrate；（b）specimen No.5 immersed in 3.5% NaCl solution for 6 h, 12 h, 24 h, 48 h and 72 h
表 1 正交实验表和实验结果
Table 1. Orthogonal experimental array and experimental results
Experiment No. K2TiF6 concentration/（g·L–1） H12Phy concentration/（g·L–1） NaF concentration/（g·L–1） Final
voltage/Vicorr/
（10–8A·cm–2）No.1 5.00 8.00 6.00 300 7.50 No.2 5.00 12.00 9.00 350 4.81 No.3 5.00 16.00 12.00 400 17.00 No.4 10.00 8.00 9.00 400 2.31 No.5 10.00 12.00 12.00 300 1.51 No.6 10.00 16.00 6.00 350 47.30 No.7 15.00 8.00 12.00 350 6.54 No.8 15.00 12.00 6.00 400 5.35 No.9 15.00 16.00 9.00 300 12.40 K1 29.31 16.35 60.15 91.41 K2 51.12 11.67 19.52 58.65 K3 24.29 76.70 25.05 24.66 Difference 26.83 65.03 40.63 37.24 R 4 1 2 3 
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表 2 9个工艺制备的氧化膜化学成分（原子分数/%）
Table 2. Chemical compositions of anodic coatings fabricated by nine processes（atom fraction/%）
Sample C O F Mg P Ti No.1 8.51 ± 0.22 11.91 ± 1.50 55.00 ± 2.95 20.84 ± 0.16 2.17 ± 0.03 1.57 ± 0.08 No.2 9.35 ± 0.55 28.86 ± 1.16 34.13 ± 3.33 19.62 ± 0.07 5.32 ± 0.01 2.71 ± 0.01 No.3 6.12 ± 0.49 19.80 ± 2.78 47.89 ± 2.86 19.44 ± 0.10 2.71 ± 0.03 4.04 ± 0.21 No.4 6.09 ± 1.63 21.41 ± 1.30 45.6 ± 0.91 20.18 ± 0.71 2.78 ± 0.01 3.90 ± 0.03 No.5 7.81 ± 0.97 21.24 ± 0.75 43.95 ± 2.09 19.80 ± 0.35 3.52 ± 0.10 3.28 ± 0.01 No.6 7.52 ± 0.11 23.57 ± 1.90 41.96 ± 1.76 18.45 ± 0.21 4.17 ± 0.07 4.33 ± 0.19 No.7 6.35 ± 1.0 18.04 ± 1.14 47.78 ± 0.04 20.76 ± 0.32 2.44 ± 0.03 4.14 ± 0.02 No.8 8.43 ± 0.42 21.52 ± 3.07 42.11 ± 2.37 20.44 ± 0.04 4.63 ± 0.15 1.74 ± 0.01 No.9 6.80 ± 0.19 9.87 ± 1.30 57.19 ± 0.81 22.43 ± 0.34 1.89 ± 0.04 1.82 ± 0.05
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表 3 9个工艺制备的氧化膜电化学参数
Table 3. Electrochemical parameters of anodic coatings fabricated by nine processes
Experiment No. βa/mV βc/mV icorr/（A·cm–2） Ecorr /V Rp/Ω Substrate 75.7 155.8 1.23 × 10–5 –1.55 1.80 × 106 No.1 220.2 277.2 7.50 × 10–8 –1.46 7.11 × 108 No.2 63.0 204.4 4.81 × 10–8 –1.44 4.35 × 108 No.3 51.5 222.3 1.70 × 10–7 –1.40 1.07 × 108 No.4 104.5 370.9 2.31 × 10–8 –1.43 1.53 × 109 No.5 105.3 193.6 1.51 × 10–8 –1.52 1.96 × 109 No.6 92.5 230.1 4.70 × 10–7 –1.44 6.10 × 107 No.7 117.3 222.1 6.54 × 10–8 –1.46 5.10 × 108 No.8 169.2 177.7 5.35 × 10–8 –1.42 7.04 × 108 No.9 66.4 267.6 1.24 × 10–7 –1.48 1.87 × 108
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表 4 基体和No.5样品拟合电化学阻抗谱曲线得到的电化学参数
Table 4. Electrochemical data obtained by equivalent circuit fitting of EIS curves of substrate and specimen No.5
Immersed time RS/
（Ω·cm2）CPE1/
（Ω–1·sn·cm–2）n1 R1/
（Ω·cm2）CPE2/
（Ω–1·sn·cm–2）n2 R2/
（Ω·cm2）RL/
（Ω·cm2）L/
（H·cm–2）Substrate-0 h 52.91 9.17 × 10–6 0.9412 2.05 × 103 3.66 × 10–3 0.4507 – 405.8 1.11 × 104 6 h 28.47 3.89 × 10–4 0.6054 2.55 × 104 5.96 × 10–7 0.9231 3.85 × 104 – – 12 h 14.88 1.35 × 10–6 0.9495 2.11 × 104 8.97 × 10–5 0.6277 1.31 × 104 – – 24 h 11.87 2.14 × 10–4 0.64 9.14 × 104 2.59 × 10–6 0.9495 1.69 × 104 – – 48 h 9.791 4.23 × 10–4 0.6624 6.10 × 104 5.22 × 10–6 0.9477 1.28 × 104 – – 72 h 76.5 4.49 × 10–4 0.5065 9.02 × 104 5.00 × 10–6 0.9711 1.21 × 104 – –
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