AZ31B镁合金表面含钛涂层的制备及耐蚀性

师晓亭 朱园园 李国强 张淑芳 赵融芳 张祎家 张荣发

师晓亭, 朱园园, 李国强, 张淑芳, 赵融芳, 张祎家, 张荣发. AZ31B镁合金表面含钛涂层的制备及耐蚀性[J]. 航空材料学报, 2019, 39(1): 17-25. doi: 10.11868/j.issn.1005-5053.2018.001019
引用本文: 师晓亭, 朱园园, 李国强, 张淑芳, 赵融芳, 张祎家, 张荣发. AZ31B镁合金表面含钛涂层的制备及耐蚀性[J]. 航空材料学报, 2019, 39(1): 17-25. doi: 10.11868/j.issn.1005-5053.2018.001019
Xiaoting SHI, Yuanyuan ZHU, Guoqiang LI, Shufang ZHANG, Rongfang ZHAO, Yijia ZHANG, Rongfa ZHANG. Preparation and corrosion resistance of titanium-containing coating on AZ31B magnesium alloy[J]. Journal of Aeronautical Materials, 2019, 39(1): 17-25. doi: 10.11868/j.issn.1005-5053.2018.001019
Citation: Xiaoting SHI, Yuanyuan ZHU, Guoqiang LI, Shufang ZHANG, Rongfang ZHAO, Yijia ZHANG, Rongfa ZHANG. Preparation and corrosion resistance of titanium-containing coating on AZ31B magnesium alloy[J]. Journal of Aeronautical Materials, 2019, 39(1): 17-25. doi: 10.11868/j.issn.1005-5053.2018.001019

AZ31B镁合金表面含钛涂层的制备及耐蚀性

doi: 10.11868/j.issn.1005-5053.2018.001019
基金项目: 国家自然科学基金项目(51361011,51861007)
详细信息
    通讯作者:

    张荣发(1965—),男,博士,教授,主要从事金属材料表面改性的研究,(E-mail)rfzhang-10@163.com

  • 中图分类号: TG174

Preparation and corrosion resistance of titanium-containing coating on AZ31B magnesium alloy

  • 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。

     

  • 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/V
    icorr/
    (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
    下载: 导出CSV

    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
    下载: 导出CSV

    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
    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
    下载: 导出CSV

    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
    下载: 导出CSV
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出版历程
  • 收稿日期:  2018-09-11
  • 修回日期:  2018-12-11
  • 网络出版日期:  2019-01-21
  • 刊出日期:  2019-02-01

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