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铁基非晶合金具有高的饱和磁感应强度及低的矫顽力和损耗, 是高频变压器和扼流圈铁芯等器件的理想材料. 然而, 该类合金晶化温度低并容易氧化, 其在高温环境中的应用受到限制. 铜和铌的添加可抑制晶核长大、提高热稳定性, 但对合金的高温抗氧化性能及结构演化的影响尚不明确. 本文利用静态空气氧化实验研究了Fe73.5Si13.5B9Cu1Nb3非晶合金高温氧化后微纳尺度结构的演变及其对合金性能的影响. 微纳结构演化揭示硅和铌在650 ℃氧化过程中快速扩散至氧化区域并形成致密氧化层, 进而阻碍氧元素向合金内部扩散; 合金内部则形成以铁元素为主的α-Fe(Si)相, 其晶粒尺寸随着氧化时间而缓慢长大. 热动力学行为表明氧化过程中硅和铌的偏析能提高合金体系热力学稳定性, 抑制晶化过程中形成多种金属间化合物. 磁滞回线结果表明, 经650 ℃氧化后, 合金的饱和磁感应强度保持不变; 同时, 氧化时间为5 min时, 矫顽力约为0.3 Oe, 氧化时间延长至0.5 h后, 矫顽力逐渐增大至61 Oe.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)
Fig. 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
Fig. 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
Fig. 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
Fig. 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
Fig. 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
Fig. 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
Fig. 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
Fig. 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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[1] Lang R Q, Chen H Y, Zhang J R, Li H P, Guo D F, Kou J Y, Zhao J, Fang Y K, Wang X Q, Qi X W, Wang Y D, Ren Y, Wang H Z 2024 Adv. Sci. 11 2402162
Google Scholar
[2] Panda A K, Mohanta O, Mitra A, Jiles D C, Lo C C H, Melikhov Y 2007 J. Magn. Magn. Mater. 316 e886
Google Scholar
[3] 董哲, 陈国钧, 彭伟锋, 高温应用软磁材料 2005 金属功能材料 12 35
Google Scholar
Dong Z, Chen G J, Peng W F 2005 Met. Funct. Mater. 12 35
Google Scholar
[4] 熊政伟, 杨江, 王雨, 杨陆, 管弦, 曹林洪, 王进, 高志鹏 2022 物理学报 71 157502
Google Scholar
Xiong Z W, Yang J, Wang Y, Yang L, Guan X, Cao L H, Wang J, Gao Z P 2022 Acta Phys. Sin. 71 157502
Google Scholar
[5] Silveyra J M, Ferrara E, Huber D L, Monson T C 2018 Science 362 80
Google Scholar
[6] Zhang R, Zhou C, Chen K Y, Cao K Y, Zhang Y, Tian F H, Murtaza A, Yang S, Song X P 2021 Scr. Mater. 203 114043
Google Scholar
[7] Santhosh Kumar R, Rashmi, Sundara Rajan J 2022 IEEE International Conference on Nanoelectronics, Nanophotonics, Nanomaterials, Nanobioscience & Nanotechnology (5NANO) Kottayam, India, April 28–29, 2022 p1
[8] Knipling K E, Daniil M, Willard M A 2009 Appl. Phys. Lett. 95 2
[9] Luo Z G, Fan X A, Zhang Y L, Yang Z J, Wang J, Wu Z Y, Liu X, Li G Q, Li Y W 2021 J. Alloy. Compd. 862 158595
Google Scholar
[10] Du T, Varaprasad B S D C S, Guo Z, Gellman A J, Zhu J G, Laughlin D E 2021 J. Magn. Magn. Mater. 539 168347
Google Scholar
[11] Wu L C, Li Y H, He A N, Zhu Z W, Zhang H F, Zhang W 2023 Intermetallics 163 108040
Google Scholar
[12] Yu R H, Basu S, Ren L, Zhang Y, Parvizi-Majidi A, Unruh K M, Xiao J Q 2000 IEEE Tran. Magn. 36 3388
Google Scholar
[13] Corodeanu S, Hlenschi C, Chiriac H, Óvári T A, Lupu N 2023 IEEE International Magnetic Conference Sendai, Japan, May 15–19, 2023
[14] Zhou J, Li X S, Hou X B, Ke H B, Fan X D, Luan J H, Peng H L, Zeng Q S, Lou H B, Wang J G, Liu C T, Shen B L, Sun B A, Wang W H, Bai H Y 2023 Adv. Mater. 35 2304490
[15] Ma Y, Wang Q, Zhou X Y, Hao J M, Gault B, Zhang Q Y, Dong C, Nieh T G 2021 Adv. Mater. 33 2006723
Google Scholar
[16] Shi R M, Wang Z, Han Y M 2019 AIP Adv. 9 055222
Google Scholar
[17] Fu P X, Shi J L, Shi R C, Zhang Y Y, Qi J T, Yang Y Z 2023 Mater. Today Commun. 36 106685
Google Scholar
[18] Wu Y, Dai Z K, Liu R R, Zhou H T 2024 J. Alloy. Compd. 981 173713
Google Scholar
[19] Zhang Y K, Zhu J, Li S, Wang J, Ren Z M 2022 J. Mater. Sci. Technol. 102 66
Google Scholar
[20] Kowalczyk M, Ferenc J, Liang X B, Kulik T 2006 J. Magn. Magn. Mater. 304 e651
Google Scholar
[21] Han L L, Maccari F, Soldatov I, Peter N J, Souza Filho I R, Schafer R, Gutfleisch O, Li Z M, Raabe D 2023 Nat. Commun. 14 8176
Google Scholar
[22] Wang Y F, Xu J, Liu Y J, Liu Z W 2022 Mater. Charact. 187 111830
Google Scholar
[23] Silveyra J M, Illeková E 2014 J. Alloy. Compd. 610 180
Google Scholar
[24] Shivaee H A, Golikand A N, Hosseini H R M, Asgari M 2010 J. Mater. Sci. 45 546
Google Scholar
[25] García J A, Pierna A R, Elbaile L, Crespo R D, Vara G, Marzo F F, Tejedor M 2006 J. Non-Cryst. Solids 352 5118
Google Scholar
[26] Zhu Z H, Yin L, Hu Q, Song H 2014 Rare Metal Mat. Eng. 43 1037
Google Scholar
[27] Blázquez J S, Conde C F, Conde A, Roth S, Güth A 2006 J. Magn. Magn. Mater. 304 627
Google Scholar
[28] May J E, Oliveira M F, Kuri S E 2003 Mater. Sci. Eng. A 361 179
Google Scholar
[29] Stuart F A F C, 1912 Huygens Institute-Royal Netherlands Academy of Arts and Sciences (KNAW) Amsterdam, Netherlands, March 30, 1912 p1159
[30] 余秀冬, 刘海顺, 薛琳, 张响, 杨卫明 2024 物理学报 73 98801
Google Scholar
Yu X D, Liu H S, Xue L, Zhang X, Yang W M 2024 Acta Phys. Sin. 73 98801
Google Scholar
[31] Liu H S, Du Y W, Miao X X, Han K, Shen X P, Bu W K 2008 Rare Metals 27 545
Google Scholar
[32] Wang Y F, Xu J, Liu Y J, Liu Z W 2022 Mater. Charact. 187 111830
Google Scholar
[33] Luo T, Liu H L, Huang C M, Yue G, Hou F T, Yang Y Z 2023 J Mater. Sci. - Mater. Electron. 34 2167
Google Scholar
[34] Jonghee H, Seoyeon K, Sungwoo S, Jan S, Haein C Y 2020 Metals 10 1297
Google Scholar
[35] 郭琦, 邓志旺, 朱乾科, 陈峰华, 胡勇, 张克维 2020 铸造技术 41 1005
Guo Q, Deng Z W, Zhu Q K, Chen F H, Hu Y, Zhang K W 2020 Foundry Technology 41 1005
[36] 张哲峰, 屈瑞涛, 刘增乾 2016 金属学报 52 1171
Google Scholar
Zhang Z F, Qu R T, Liu Z Q 2016 Acta Metall. Sin. 52 1171
Google Scholar
[37] Lu L, Du P C, Jiang T X, Zhou T C, Wen Q B, Wang Y L, Zeng Y, Xiong X 2025 J. Eur. Ceram. Soc. 45 116885
Google Scholar
[38] Sun Y, Li J W, Xie L, He A N, Dong Y Q, Liu Y X, Wang C J, Zhang K W 2021 J. Non-Cryst. Solids 566 120839
Google Scholar
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