Microstructure, wear and corrosion resistance of (CrFeNiAl)100–xMox high-entropy alloy coatings by laser cladding
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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。Abstract: For the corrosion and wear failure of materials used in the marine environment, the (CrFeNiAl)100–xMox high-entropy alloy coatings were prepared on 304 stainless steel (304 ss) by laser cladding. The phase composition, microstructure, hardness, wear resistance and corrosion resistance of the coatings were analyzed. The results show that the coatings are composed of body-centered cubic (BCC)+B2 phases. With the increase of Mo, the content of B2 phase gradually increases, and nano scale B2 phase precipitates in the dendrite. The hardness of the coating increases with the increase of Mo content, the highest hardness reaches HV0.2 636.6, and the wear resistance increases gradually. The corrosion current density firstly decreases and then increases with the increase of Mo, indicating that the corrosion resistance of the coating firstly increases and then decreases in 3.5wt%NaCl solution. The results of immersion corrosion show that the coatings are selectively dissolved in the interdendritic region. The corrosion current density and passivation current density of (CrFeNiAl)92Mo8 coating are lower than 304 ss, and the corrosion resistance is the best with good wear resistance. Adding appropriate Mo element can improve the wear resistance and corrosion resistance of (CrFeNiAl)100–xMox coatings.
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Key words:
- laser cladding /
- high-entropy alloy coatings /
- hardness /
- wear resistance /
- corrosion resistance
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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 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%)
Sample Cr Fe Ni Al Mo Mo6 23.50 23.50 23.50 23.50 6.00 Mo8 23.00 23.00 23.00 23.00 8.00 Mo11 22.25 22.25 22.25 22.25 11.00 Mo14 21.50 21.50 21.50 21.50 14.00 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]
Element Cr Fe Ni Mo Al 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]. 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)
Sample Ecorr/mV Icorr/(μA·cm–2) Ip/(μA·cm–2) 304 ss –326.90 0.53 2.32 Mo6 –221.60 0.65 1.18 Mo8 –184.40 0.40 0.91 Mo11 –179.20 0.42 1.31 Mo14 –200.90 0.65 0.95 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
Sample Rs
/(Ω·cm2)Rf
/(103 Ω·cm2)Rct
/(103 Ω·cm2)Y1
/(μF·cm−2)n1 Y2
/(μF·cm−2)n2 χ2 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. -
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