Effect of ball milling time on microstructure and oxidation resistance of self-passivating W alloys
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摘要: 自钝化W合金具有优异的抗高温氧化性能，可望用于高温环境中的关键部件。为了揭示合金的组织结构与高温抗氧化性能之间关系，采用机械合金化法结合放电等离子体烧结技术制备了自钝化W-Si合金，研究了不同机械合金化时间对合金显微组织结构的影响，并探究了合金的抗高温氧化性能。结果表明：合金由W、W5Si3和SiOx组成，当球磨时间由4 h增加到20 h，合金中SiOx的含量由16.2%增加到23.6%，而W5Si3的含量由57.8%降低到43.6%，且W和W5Si3的晶粒尺寸均减小，晶粒的细化有助于合金显微硬度的提高。在1000 ℃氧化10 h后，球磨4 h制得的合金增重为37.4 mg，而球磨20 h制得的合金增重达到了141.6 mg，它们的氧化层厚度分别约为167.0 μm和415.7 μm。球磨时间短制得的合金具有更优异的抗氧化性能，这是由于其W5Si3为连续相。W5Si3原位氧化形成的WO3/SiO2复合氧化物亦为连续相，形成了保护性氧化层，对合金的内氧化起到了有效的抑制作用。Abstract: Self-passivating W alloys exhibit excellent high temperature oxidation resistance and are expected to be used in key components in high temperature environments. In order to reveal the relationship between the microstructure and high temperature oxidation resistance of the alloy, a self-passivating W-Si alloy was prepared by mechanical alloying method combined with spark plasma sintering. The effect of different mechanical alloying time on the microstructure of the alloy was studied. And the high temperature oxidation resistance of the alloys was investigated. The results show that the alloys are composed of W, W5Si3 and SiOx phases. When the ball milling time increases from 4 h to 20 h, the content of SiOx in the alloys increases from 16.2% to 23.6%, while the content of W5Si3 decreases from 57.8% to 43.6%, and the grain sizes of W and W5Si3 are both reduced. The grain refinement contri-butes to the improvement of the microhardness of the alloys. After oxidized at 1000 ℃ for 10 h, the mass gain of the alloy prepared by ball milling for 4 h is 37.4 mg, while that of the alloy prepared by ball milling for 20 h reaches 141.6 mg, and their oxide layer thicknesses are about 167.0 μm and 415.7 μm, respectively. The alloy prepared with short ball milling time has better oxidation resistance, because the W5Si3 in this alloy is a continuous phase. The WO3/SiO2 composite oxide formed by in situ oxidation of W5Si3 is also a continuous phase, forming a protective oxide layer and effectively inhibiting the internal oxidation of the alloy.
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Key words:
- self-passivating /
- W-Si alloy /
- mechanical alloying /
- spark plasma sintering /
- oxidation resistance
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图 1 球磨不同时间的W-Si粉末的背散射SEM图像：(a) 4 h；(b) 20 h
Figure 1. Backscatter SEM images of W-Si powders ball milled for different time: (a) 4 h; (b) 20 h
图 2 球磨4 h和20 h后的W-Si粉末的XRD图谱
Figure 2. XRD patterns of W-Si powders after ball milling for 4 h and 20 h
图 3 球磨4 h和20 h的W-Si粉末制得的合金的XRD图谱
Figure 3. XRD patterns of the alloys made from the W-Si powders milled for 4 h and 20 h
图 4 W-Si合金表面的背散射SEM图像 ((a1), (b1)) 和断口SEM图像 ((a2), (b2))：(a) 4 h；(b) 20 h
A, B, C—Three different phases
Figure 4. Surface backscatter SEM images ((a1), (b1)) and fracture SEM images ((a2), (b2)) of the W-Si alloys: (a) 4 h；(b) 20 h
图 5 球磨4 h和20 h的W-Si粉末制得的合金的氧化增重图
Δm—Quality difference before and after oxidation
Figure 5. Oxidation mass gain of the alloys made from the W-Si powders milled for 4 h and 20 h
图 6 W-Si合金分别氧化0 h、2 h和10 h的XRD图谱：(a) 球磨4 h；(b) 球磨20 h
Figure 6. XRD patterns of the W-Si alloys oxidized for 0 h, 2 h and 10 h, respectively: (a) Milled for 4 h; (b) Milled for 20 h
图 7 W-Si合金在1000℃氧化不同时间的氧化层的SEM图像：((a1)~(a3)) 球磨4 h粉末制得的合金氧化0 h、2 h的合金表面和氧化2 h的氧化层侧表面；((b1)~(b3)) 球磨20 h粉末制得的合金氧化0 h、2 h的合金表面和氧化2 h的氧化层侧表面
Figure 7. SEM images of the oxide layer of the W-Si alloys oxidized for different time: ((a1)-(a3)) Alloy made from the powder milled for 4 h with surface oxidized for 0 h, 2 h and side surface oxidized for 2 h; ((b1)-(b3)) Alloy made from the powder milled for 20 h with surface oxidized for 0 h, 2 h and side surface oxidized for 2 h
图 8 1000℃氧化2 h的W-Si合金截面的背散射SEM图像：(a) 球磨4 h粉末制得的合金；(b) 球磨20 h粉末制得的合金
Figure 8. Backscatter SEM images of the cross-sections of the W-Si alloys oxidized at 1000℃ for 2 h: (a) Milled for 4 h; (b) Milled for 20 h
表 1 粉末中W的晶粒尺寸和Si在W中的固溶度
Table 1. Grain size of W and solid solubility of Si in W for the powders
Ball milling time/h Grain size/nm Solid solubility/at% 4 41.82 6.81 20 18.91 6.86 
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表 2 不同球磨时间制得的W-Si合金中各个相的面积含量
Table 2. Area content of each phases in the W-Si alloys prepared by different ball milling time
W-Si alloy SiOx/% W5Si3/% W/% Alloy made from the
powder milled for 4 h16.2 57.8 26.0 Alloy made from the
powder milled for 20 h23.6 43.6 32.8
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