Effect of ball milling time on microstructure and oxidation resistance of self-passivating W alloys
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摘要:
钨具有高熔点、高热导率、高密度、低膨胀系数、低物理溅射系数及低氚滞留等优异的物理化学性能，常用作高温工作的关键部件材料。但由于钨的抗高温氧化性能差，严重阻碍了它的实际应用。Si是一种具有自钝化功能的元素，本文将Si引入到W中，采用机械合金化法(MA)结合放电等离子体烧结技术(SPS)制备了具有自钝化功能的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，并探究了它们的抗高温氧化性能。合金均由W、W5Si3和SiOx组成。球磨时间短制得的合金中W5Si3相为连续相。在1000 ℃氧化10 h后，球磨时间短制得的合金氧化增重为37.4 mg，氧化层厚度为167.0 μm，比球磨时间长制得的合金具有更优异的抗氧化性能，这是由于其W5Si3相原位氧化成的WO3/SiO2复合氧化层为连续相，有效抑制了合金的内氧化。 1000 ℃氧化2 h的(a) 球磨4 h粉末制得的合金和(b) 球磨20 h粉末制得的合金截面的背散射SEM图像 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 contributes to the improvement of the microhardness of the alloys. After oxidized at 1000 ℃ for 10 h, the weight 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.-
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. BSE-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图像和断口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； (1) 表面；(2) 断口
Figure 4. Surface backscatter SEM images and fracture SEM images of the W-Si alloys: (a) Alloy made from the powder milled for 4 h; (b) Alloy made from the powder milled for 20 h; (1) Surface; (2) Fracture
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
Figure 5. Oxidation weight 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、10 h的XRD图谱：(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 6. XRD patterns of the W-Si alloys oxidized for 0 h, 2 h and 10 h, respectively: (a) Alloy made from the powder milled for 4 h; (b) Alloy made from the powder 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：(a) 球磨4 h粉末制得的合金；(b) 球磨20 h粉末制得的合金；(1) 氧化0 h的合金表面；(2) 氧化2 h的合金表面；(3) 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: (a) Alloy made from the powder milled for 4 h; (b) Alloy made from the powder milled for 20 h; (1) Surface oxidized for 0 h; (2) Surface oxidized for 2 h; (3) 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. BSE-SEM images of the cross-sections of the W-Si alloys oxidized at 1000℃ for 2 h: (a) Alloy made from the powder milled for 4 h; (b) Alloy made from the powder milled for 20 h
表 1 分别球磨4 h和20 h的W-Si粉末的W的晶粒尺寸和固溶度
Table 1. Grain size and solid solubility of W in the W-Si powders ball milled for 4 h and 20 h, respectively
Ball milling time Grain size/nm Solid solubility/at% 4 h 41.82 6.81 20 h 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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