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Fe-based amorphous alloys are widely used in electronic devices such as high-frequency transformers and choke cores due to their low coercivity, low loss, and high saturation magnetic induction intensity. However, these alloys have a relatively low crystallization temperature and are prone to oxidation, which limits their applications in high-temperature environments. The addition of copper and niobium elements can suppress the growth of crystal nuclei and improve thermal stability. However, the influences on the alloy's high-temperature oxidation resistance and structural evolution are still unclear. In this work, static air oxidation is used to investigate the microstructure evolution of Fe73.5Si13.5B9Cu1Nb3 amorphous alloy after high-temperature oxidation and its influence on magnetic properties. Besides, long-time oxidation, say, 3000 hours or longer at 500 ℃, is generally hard to perform in the laboratory. Thus, the Van’t Hoff’s rule is used to evaluate outcomes under the condition of the long-time and relatively low-temperature oxidation through using rapid high-temperature oxidation. Based on Van’t Hoff’s rule, the oxidation at 650°C for 5 min will show similar or more severe oxidation effects on the microstructure of Fe73.5Si13.5B9Cu1Nb3 alloy after oxidation at 500 ℃ for 2730 h. The microstructure evolution reveals that silicon and niobium in this alloy will quickly diffuse toward the sample surface during oxidation at 650 ℃, and these two elements will form a dense layer to impede oxygen diffusion. Meanwhile, an α-Fe(Si) phase mainly composed of iron elements will be generated in the alloy, with its grain size slowly increasing in the oxidation process. Thermodynamic analysis indicates that the segregation of silicon and niobium can preserve the thermodynamic stability of the alloy system during oxidation and suppress the formation of intermetallic compounds during crystallization. The magnetic hysteresis loop results show that the coercivity of Fe73.5Si13.5B9Cu1Nb3 alloy after 5-min oxidation at 650°C will stay at approximately 0.3 Oe, suggesting that the Fe73.5Si13.5B9Cu1Nb3 alloy may be a candidate for operating at 500 ℃ for more than 2700 h. Subsequently, its coercivity gradually increases to 61 Oe as the oxidation time rises to 0.5 h, while its saturation magnetic induction intensity remains unchanged (~140 emu/g).
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Keywords:
- Fe-based amorphous alloys /
- high-temperature oxidation /
- crystallization mechanism /
- magnetic properties
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图 1 淬态Fe73.5Si13.5B9Cu1Nb3非晶薄带的TEM图像 (a) 明场像和 (b) 高角环形暗场像, 插图为选区电子衍射花样(SAED)
Figure 1. TEM images of as-quenched Fe73.5Si13.5B9Cu1Nb3 amorphous ribbon: (a) Bright-field image and (b) high-angel annular dark-field image, the inset corresponds to the selected area electron diffraction pattern.
图 2 淬态和经650 ℃氧化后Fe73.5Si13.5B9Cu1Nb3合金的DSC曲线
Figure 2. DSC curves of as-quenched Fe73.5Si13.5B9Cu1Nb3 amorphous ribbon and Fe73.5Si13.5B9Cu1Nb3 alloys after oxidation at 650 ℃.
图 6 经过650 ℃氧化后Fe73.5Si13.5B9Cu1Nb3非晶条带断面的二次电子显微图像 (a)—(c) 氧化1 min后未形成氧化层; (d)—(f) 氧化1 min后已形成氧化层; (g)—(i) 氧化3 min后的典型断面
Figure 6. SEM images of the fracture surface of Fe73.5Si13.5B9Cu1Nb3 amorphous ribbons after oxidation at 650℃: (a)–(c) 1 min, showing no obvious oxide layer, (d)—(f) 1 min, exhibiting oxide layer, and (g)–(i) 3 min.
图 7 经过650 ℃氧化后Fe73.5Si13.5B9Cu1Nb3合金断面的特征区域显微结构和能谱分析结果 (a) 氧化1 min; (b) 氧化3 min
Figure 7. The SEM images and EDS maps from the typical fracture surface of Fe73.5Si13.5B9Cu1Nb3 alloy after oxidation at 650 ℃ for (a) 1 min and (b) 3 min.
图 3 淬态和经过650 ℃氧化的Fe73.5Si13.5B9Cu1Nb3合金的XRD曲线
Figure 3. X-ray diffraction patterns of as-quenched Fe73.5Si13.5B9Cu1Nb3 amorphous ribbon and FeSiBCuNb alloys after oxidation at 650 ℃ for different times.
图 4 经过650 ℃氧化3 min后Fe73.5Si13.5B9Cu1Nb3非晶条带内部纳米晶的TEM表征 (a) 明场像; (b) 暗场像; (c) 选区电子衍射花样; (d) 晶粒尺寸分布图
Figure 4. The TEM characterization of newly formed nanograins in the amorphous ribbon after oxidation at 650℃ for 3 min: (a) Bright-field image; (b) dark-field image; (c) selected area electron diffraction pattern; (d) grain size distribution.
图 5 经过650 ℃氧化3 min后Fe73.5Si13.5B9Cu1Nb3条带内部的高角环形暗场像及其对应的Fe, Si, Nb和Cu元素的分布图
Figure 5. High-angel annular dark-field image combined elemental distribution maps of Fe, Si, Nb, and Cu among the Fe73.5Si13.5B9Cu1Nb3 ribbon after oxidation at 650 ℃ for 3 min.
图 8 经过650 ℃氧化后Fe73.5Si13.5B9Cu1Nb3非晶条带粉末、铁硅粉末和铁硅铝粉末 (a)—(c) VSM曲线, 其中(b), (c)为VSM曲线局部放大图, (d)饱和磁感应强度和矫顽力对比
Figure 8. (a)–(c) VSM curves, (d) M and Hc of Fe73.5Si13.5B9Cu1Nb3 amorphous powders after oxidation at 650 ℃ for different times, compared by FeWCr and FeSi9Al5 powders.
表 1 650 ℃高温氧化不同时间后非晶条带析出纳米晶晶粒尺寸计算结果
Table 1. The calculated grain size of newly formed nanograins in Fe73.5Si13.5B9Cu1Nb3 amorphous ribbons after oxidation at 650℃ for different times.
Sample No. Oxidation time
at 650 ℃/minFWHM
/(°)2θ
/(°)Dhkl
/nm650-1 1 0.960 44.7696 9.35 650-3 3 0.647 45.1310 13.89 650-5 5 0.564 45.1976 15.94 650-30 30 0.464 45.1826 19.37 650-60 60 0.415 45.1820 21.66 
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