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激光熔覆(CrFeNiAl)100–xMox高熵合金涂层的组织及耐磨耐蚀性能

赵小凤 崔洪芝 姜迪 宋晓杰

赵小凤, 崔洪芝, 姜迪, 等. 激光熔覆(CrFeNiAl)100–xMox高熵合金涂层的组织及耐磨耐蚀性能[J]. 复合材料学报, 2023, 40(11): 6311-6323. doi: 10.13801/j.cnki.fhclxb.20230222.008
引用本文: 赵小凤, 崔洪芝, 姜迪, 等. 激光熔覆(CrFeNiAl)100–xMox高熵合金涂层的组织及耐磨耐蚀性能[J]. 复合材料学报, 2023, 40(11): 6311-6323. doi: 10.13801/j.cnki.fhclxb.20230222.008
ZHAO Xiaofeng, CUI Hongzhi, JIANG Di, et al. Microstructure, wear and corrosion resistance of (CrFeNiAl)100–xMox high-entropy alloy coatings by laser cladding[J]. Acta Materiae Compositae Sinica, 2023, 40(11): 6311-6323. doi: 10.13801/j.cnki.fhclxb.20230222.008
Citation: ZHAO Xiaofeng, CUI Hongzhi, JIANG Di, et al. Microstructure, wear and corrosion resistance of (CrFeNiAl)100–xMox high-entropy alloy coatings by laser cladding[J]. Acta Materiae Compositae Sinica, 2023, 40(11): 6311-6323. doi: 10.13801/j.cnki.fhclxb.20230222.008

激光熔覆(CrFeNiAl)100–xMox高熵合金涂层的组织及耐磨耐蚀性能

doi: 10.13801/j.cnki.fhclxb.20230222.008
基金项目: 国家自然科学基金 (51971121);山东省重大科技创新工程项目(2019JZZY010303;2019JZZY010360)
详细信息
    通讯作者:

    崔洪芝,博士,教授,博士生导师,研究方向为高能束表面强化、增材制造、耐磨蚀抗热震材料等 E-mail: cuihongzhi@ouc.edu.cn

  • 中图分类号: TG174.4;TB331

Microstructure, wear and corrosion resistance of (CrFeNiAl)100–xMox high-entropy alloy coatings by laser cladding

Funds: National Natural Science Foundation of China (51971121); Major-Special Science and Technology Projects in Shandong Province (2019JZZY010303; 2019JZZY010360)
  • 摘要: 针对海洋环境下使用的材料易产生腐蚀和磨损失效,采用激光熔覆技术在304不锈钢(304 ss)表面制备(CrFeNiAl)100–xMox高熵合金涂层。分别对涂层的物相组成、显微组织、硬度、耐磨性和耐蚀性进行分析。结果表明:涂层由体心立方晶格(BCC)相+B2相双相组成,随着Mo含量的增加,B2相的含量逐渐增加,在枝晶内部析出纳米级别的B2相。涂层的硬度随着Mo含量的增加逐渐提高,硬度最高达到HV0.2 636.6 ,耐磨性也逐渐提高。在3.5wt%NaCl溶液中,腐蚀电流密度随着Mo含量的增加,先减小后增大,表明涂层的耐蚀性先提高后降低。浸泡腐蚀结果表明涂层在枝晶间区域发生选择性溶解。(CrFeNiAl)92Mo8涂层的腐蚀电流密度和钝化电流密度均小于304不锈钢,耐蚀性最好,并且具有较好的耐磨性。添加适当 Mo 元素,能提高(CrFeNiAl)100–xMox涂层的耐磨和耐蚀性。

     

  • 图  1  原始粉末的形貌

    Figure  1.  Morphologies of raw powders

    图  2  (CrFeNiAl)100–xMox涂层的XRD图谱(a) 和局部放大图(b)

    Figure  2.  XRD patterns (a) and local magnification patterns (b) of (CrFeNiAl)100–xMox coatings

    BCC—Body-centered cubic

    图  3  (CrFeNiAl)100−xMox涂层的截面宏观形貌:(a) Mo6;(b) Mo8;(c) Mo11;(d) Mo14

    Figure  3.  Macro morphologies of cross section of (CrFeNiAl)100−xMox coatings: (a) Mo6; (b) Mo8; (c) Mo11; (d) Mo14

    图  4  (CrFeNiAl)100−xMox 涂层中部的微观组织形貌:(a) Mo6;(b) Mo8;(c) Mo11;(d) Mo14

    Figure  4.  Topography of microstructure in the middle of (CrFeNiAl)100−xMox coatings: (a) Mo6; (b) Mo8; (c) Mo11; (d) Mo14

    图  5  Mo14的TEM图像:(a) 明场相TEM 图像; ((b), (c))晶粒内部的局部放大图;(d) 两个物相的高分辨透射电子显微镜(HRTEM)图像和选区电子衍射(SEAD)图像;(e) 相界面的反快速傅里叶变换(IFFT)图

    Z—Zone axis; FCC—Faced-centered cubic; d—Interplanar spacing

    Figure  5.  TEM images of Mo14: (a) Bright-field TEM image; ((b), (c)) Local magnified image of grain interior; (d) High-resolution transmission electron microscopy (HRTEM) image and selected area electron diffraction (SEAD) pattern of two phases; (e) Inverse fast fourier transform (IFFT) image of the interface of the phases

    图  6  Mo14枝晶内部的TEM高角环状暗场像(TEM-HAADF)图谱(a)和Cr (b)、Fe (c)、Ni (d)、Al (e)、Mo (f)的TEM-EDS图谱

    Figure  6.  TEM high-angle annular dark-field (TEM-HAADF) image (a) and TEM-EDS mappings of Cr (b), Fe (c), Ni (d), Al (e), Mo (f) in dendrite of Mo14

    图  7  (CrFeNiAl)100–xMox涂层的显微硬度

    Figure  7.  Microhardness of (CrFeNiAl)100–xMox coatings

    图  8  (CrFeNiAl)100–xMox涂层的摩擦系数

    Figure  8.  Coefficient of (CrFeNiAl)100–xMox coatings

    图  9  (CrFeNiAl)100–xMox涂层的磨痕截面轮廓(a)和磨损体积(b)

    Figure  9.  Wear sectional profiles (a) and wear volume losses (b) of (CrFeNiAl)100–xMox coatings

    图  10  (CrFeNiAl)100–xMox涂层磨损表面的SEM图像和三维形貌:((a1)~(a3)) Mo6;((b1)~(b3)) Mo8;((c1)~(c3)) Mo11;((d1)~(d3)) Mo14

    Figure  10.  SEM images and three-dimensional morphologies of the worn surfaces of (CrFeNiAl)100–xMox coatings: ((a1)-(a3)) Mo6; ((b1)-(b3)) Mo8; ((c1)-(c3)) Mo11; ((d1)-(d3)) Mo14

    图  11  (CrFeNiAl)100–xMox涂层和304 ss的动电位极化曲线

    Figure  11.  Potentiodynamic polarization curves of (CrFeNiAl)100–xMox coatings and 304 ss

    图  12  (CrFeNiAl)100–xMox涂层和304 ss的Nyquist (a)和 Bode图(b)

    Z—Impedance; ZImage—Imaginary part of impedance; ZRel—Real part of impedance

    Figure  12.  Nyquist plots (a) and Bode plots (b) of (CrFeNiAl)100–xMox coatings and 304 ss

    图  13  (CrFeNiAl)100–xMox涂层和304 ss的等效电路图

    Rs—Solution resistance; Rf—Outer layer resistance; Rct—Inner layer resistance; Qf—Capacitance of the outer layer; Qct—Capacitance of the inner layer

    Figure  13.  Equivalent circuits of (CrFeNiAl)100–xMox coatings and 304 ss

    图  14  (CrFeNiAl)100–xMox涂层在1 mol/L HCl 溶液浸泡120 h的腐蚀形貌的SEM图像和三维形貌:((a1), (a2)) Mo6;((b1), (b2)) Mo8;((c1), (c2)) Mo11;((d1), (d2)) Mo14

    Figure  14.  SEM images and three-dimensional morphologies of (CrFeNiAl)100–xMox coatings after immersion in 1 mol/L HCl for 120 h: ((a1), (a2)) Mo6; ((b1), (b2)) Mo8; ((c1), (c2)) Mo11; ((d1), (d2)) Mo14

    表  1  (CrFeNiAl)100–xMox 涂层的化学成分(at%)

    Table  1.   Chemical composition of (CrFeNiAl)100–xMox coatings (at%)

    SampleCrFeNiAlMo
    Mo623.5023.5023.5023.50 6.00
    Mo823.0023.0023.0023.00 8.00
    Mo1122.2522.2522.2522.2511.00
    Mo1421.5021.5021.5021.5014.00
    下载: 导出CSV

    表  2  元素之间的混合焓$\Delta {H}_{{\rm{AB}}}^{\mathrm{m}\mathrm{i}\mathrm{x}}$ (kJ·mol−1)[30]

    Table  2.   Mixing enthalpy $\Delta {H}_{{\rm{AB}}}^{\mathrm{m}\mathrm{i}\mathrm{x}}$ of the elements (kJ·mol−1)[30]

    ElementCrFeNiMoAl
    Cr−1−7 0−10
    Fe−2−2−11
    Ni−7−22
    Mo −5
    Notes: $\Delta {H}_{{\rm{AB}}}^{\mathrm{m}\mathrm{i}\mathrm{x} }$−Mixing enthalpy, which is approximately equal to the value heat of mixing between A and B[30]; The more negative $\Delta {H}_{{\rm{AB}}}^{\mathrm{m}\mathrm{i}\mathrm{x} }$ is, the easier for A and B to form compounds[28].
    下载: 导出CSV

    表  3  (CrFeNiAl)100–xMox涂层和304不锈钢(304 ss)的腐蚀电位(Ecorr)、腐蚀电流密度(Icorr)和钝化电流密度(Ip)

    Table  3.   Corrosion potential (Ecorr), corrosion current density (Icorr) and passivation current density (Ip) of (CrFeNiAl)100–xMox coatings and 304 stainless steel (304 ss)

    SampleEcorr/mVIcorr/(μA·cm–2)Ip/(μA·cm–2)
    304 ss–326.900.532.32
    Mo6–221.600.651.18
    Mo8–184.400.400.91
    Mo11–179.200.421.31
    Mo14–200.900.650.95
    下载: 导出CSV

    表  4  (CrFeNiAl)100–xMox涂层和304 ss的等效电路的拟合参数

    Table  4.   Fitting parameters of the equivalent circuit model of (CrFeNiAl)100–xMox coatings and 304 ss

    SampleRs
    /(Ω·cm2)
    Rf
    /(103 Ω·cm2)
    Rct
    /(103 Ω·cm2)
    Y1
    /(μF·cm−2)
    n1Y2
    /(μF·cm−2)
    n2χ2
    304 ss 7.4 6.4 82.6 100.5 0.87 199.7 0.94 2.0×10−3
    Mo6 3.6 2.6 127.5 57.6 0.75 551.4 0.91 7.6×10−4
    Mo8 2.0 2.6 366.3 53.6 0.64 678.9 0.86 6.2×10−4
    Mo11 1.8 2.2 360.1 64.3 0.84 106.5 0.85 4.8×10−4
    Mo14 1.6 7.4 268.5 21.3 0.59 67.3 0.86 8.0×10−4
    Notes: Rs—Solution resistance; Rf—Outer layer resistance; Rct—Inner layer resistance; Y1—Capacitance of the outer layer; Y2—Capacitance of the inner layer; n1—CPEf index; n2—CPEct index; χ2—Good fitting quality; CPEf—Constant phase element of the outer layer; CPEct—Constant phase element of the inner layer.
    下载: 导出CSV
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    TAO Jichuang, LU Yiping. Effect of Mo content on microstructure, mechanical properties and corrosion resistance of Al0.1CoCrCu0.5FeNiMox high-entropy alloys[J]. Material Reports,2020,34(4):18096-18099(in Chinese).
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出版历程
  • 收稿日期:  2022-12-05
  • 修回日期:  2023-01-13
  • 录用日期:  2023-02-08
  • 网络出版日期:  2023-02-23
  • 刊出日期:  2023-11-01

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