TC4合金表面Zr增效硅化物涂层的组织及高温摩擦磨损性能

doi:10.15541/jim20170006

摘要/Abstract

摘要：

采用扩散共渗的方法在TC4合金表面制备了Zr增效硅化物涂层, 研究了涂层在600℃时的摩擦磨损性能, 讨论了其磨损机制。结果表明: 所制备的涂层具有多层结构, 由(Ti, X)Si₂ (X代表Zr, Al和V)外层, TiSi中间层和Ti₅Si₄+Ti₅Si₃内层组成; 渗剂中添加Zr能够抑制涂层的生长速率, 有利于降低涂层的内应力, 改善其组织致密性。涂层的硬度明显高于TC4合金, 且由外向内呈梯度降低趋势。高温摩擦磨损试验结果表明, Zr增效硅化物涂层能够为TC4合金提供良好的高温磨损防护; 与GCr15对磨时, 涂层的表面只发生了轻微的磨损, 主要为GCr15在其磨损面的擦涂和一定程度的氧化磨损; 与Al₂O₃球对磨时, 磨损机制为犁削磨损、疲劳磨损、黏着磨损和氧化磨损。

关键词: TC4合金, 硅化物涂层, Zr增效, 组织结构, 高温磨损, 磨损机制

Abstract:

Zr modified silicide coatings were prepared on TC4 alloy by Si-Zr co-deposition, the wear behavior of the coatings were investigated at 600℃, and the wear mechanisms were discussed. The results show that the obtained coating has a multi-layer structure, consisting of a (Ti, X)Si₂ (X represents Zr, Al and V elements) outer layer, a TiSi middle layer and an inner layer composed of a mixture of Ti₅Si₄+Ti₅Si₃. Addition of Zr in the pack mixtures can reduce the residual stress in the coating by lowering the coating growth rate, leading to a more compact coating structure. The micro-hardness of the coating is obviously higher than that of TC4 alloy, which shows a decrease tendency from the coating surface to its substrate. The high temperature wear tests reveal that the Zr modified silicide coating can offer effective protection for TC4 alloy at high temperatures. When using GCr15 ball as the counterpart, very slight wear occurred on the worn surface of the coating, and the main wear manners should be the transfers of GCr15 to the coating surface besides a certain extent of oxidation wear. Sliding against Al₂O₃ ball, the main wear mechanisms of the coating are considered to be plough wear, fatigue wear, adhesive wear, and oxidation wear.

Key words: TC4 alloy, silicide coating, Zr modification, coating structure, high-temperature wear, wear mechanisms

中图分类号:

TQ174

李轩, 田进, 田伟, 谢文玲, 李秀兰. TC4合金表面Zr增效硅化物涂层的组织及高温摩擦磨损性能[J]. 无机材料学报, 2017, 32(10): 1102-1108.

LI Xuan, TIAN Jin, TIAN Wei, XIE Wen-Ling, LI Xiu-Lan. Structure and High-temperature Wear Behavior of Zr Modified Silicide Coatings Prepared on TC4 Alloy[J]. Journal of Inorganic Materials, 2017, 32(10): 1102-1108.

图/表 6

图1 经1100 ℃保温4 h在TC4合金表面制备的Zr增效硅化物涂层的(a)截面BSE形貌, (b)沿截面的EDS成分分布和(c) XRD分析结果

Fig. 1 Cross-sectional BSE image (a), element concentration profiles (b) and XRD patterns (c) conducted on the outer and inner layers of the Zr modified silicide coating prepared on TC4 alloy at 1100 ℃ for 4 h

表1 渗包中被渗元素氟化物在1000℃时的标准吉布斯形成自由能和平衡气相分压

Table 1 Standard Gibbs formation energies and vapor pressures of the co-deposited species in the pack at 1000℃

Species	Δ_fG/(kJ•mol^-1)	Vapor pressure /(1.013×10⁵Pa)
ZrF₄	-757.2	3.55×10^-5
ZrF₃	-701.0	9.77×10^-7
ZrF₂	-569.7	3.68×10^-4
ZrF	-81.2	1.58×10^-9
SiF₄	-716.5	1.11×10^-6
SiF₃	-624.8	3.29×10^-11
SiF₂	-631.5	6.46×10^-8
SiF	-309.6	5.83×10^-13

图2 Zr增效硅化物涂层沿截面的硬度分布

Fig. 2 Micro-hardness distribution profile of the Zr modified silicide coating along direction from its near surface to the substrate

图3 TC4合金和Zr增效硅化物涂层与GCr15球在600℃对磨时的摩擦系数和磨损失重

Fig. 3 Friction coefficients and mass losses of TC4 alloy and Zr modified silicide coating sliding against GCr15 balls at 600℃(a) Friction coefficient-time curves; (b) Mass losses of TC4 alloy, the coating and their GCr15 counterparts after sliding for 60 min

图4 TC4合金和Zr增效硅化物涂层与Al2O3球在600℃对磨时的摩擦系数和磨损失重

Fig. 4 Friction coefficients and mass losses of TC4 alloy and Zr modified silicide coating sliding against Al2O3 ball at 600℃(a) Friction coefficient-time curves; (b) Mass losses of TC4 alloy, the coating and their Al2O3 balls after sliding for 60 min

图5 Zr增效硅化物涂层分别与GCr15球(a, a1和a2)和Al2O3球(b, b1和b2)在600℃对磨60 min后磨损面的SEM照片

Fig. 5 Wear morphologies of the Zr modified silicide coating after sliding against GCr15 (a, a1 and a2) and Al2O3 (b, b1 and b2) balls at 600℃ for 60 min

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