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研究了Gd含量对(Fe73B22Nb5)100–xGdx (x = 0, 0.5, 1, 1.5, 2.0)合金非晶形成能力、热稳定性和磁学性能的影响规律, 并对比分析了非晶氧化机制. 通过添加Gd元素, 合金的原子尺寸差超过13%, 构型熵增大了30%, 提升了合金的非晶形成能力. 随着Gd含量的增大, 过冷液相区范围达到73 K, 热稳定性得到明显增强. Gd元素导致合金局部各向异性受到限制, 准位错偶极子型缺陷密度降低. 这有效减少了阻碍磁畴壁旋转的钉扎位点, 提高合金软磁性能. 此外, Gd元素使得非晶在氧化过程中对温度的变化更为敏感, 达到最大氧化速率的温度降低了15 K, 但是并未恶化其抗氧化性能. Gd原子受结合能影响向表层迁移, 形成的富Gd氧化物填充了表层缺陷, 占据了大量顶部空间, 合金表面附近的结构更加致密. 这种结构减少了氧原子通过微观组织界面进行扩散的通道, 有助于增强抗氧化性能.In this work, we use the rapid solidification technique to prepare five kinds of metallic glasses with different Gd content, and investigate in depth the influences of Gd content on the amorphous formation capability, thermal stability, and magnetic properties of (Fe73B22Nb5)100–xGdx (x = 0, 0.5, 1, 1.5, 2) alloys . By comparing the microstructural morphology and solute distribution of oxidation product before adding Gd and those after adding Gd, the amorphous oxidation mechanism is analyzed systematically. With the addition of Gd, the atomic size difference of the alloys exceeds 13%, and the configuration entropy increases from 7.27 kJ/(mol·K) to 9.44 kJ/(mol·K). The glass-forming capability of the alloy is significantly improved. The increase of Gd content can increase the glass transition temperature of the alloy to 864 K, and the supercooled liquid region can reach 73 K, significantly enhancing the thermal stability of the metallic glasses. The Gd limits the local anisotropy of the alloy and reduces the density of quasi-dislocation dipole defects. This can effectively reduce the pinning sites that hinder the rotation of magnetic domain walls, thereby improving the soft magnetic property. By comparing with the metallic glasses without Gd, only 2% (atomic percentage) Gd can reduce the coercivity by 8%. Moreover, Gd makes the metallic glasses more sensitive to temperature variation in the oxidation process, and the temperature of the maximum oxidation rate is reduced by 15K. However, their antioxidant performance does not deteriorate. The Gd atoms are influenced by binding energy and migrate to the surface, forming Gd-rich oxides. They fill surface defects and occupy a large part of top space, leading to the structure becoming more compact near the surface. This structure reduces the channels for oxygen atoms to diffuse through the microstructure interface, which helps to improve antioxidant capability. This work provides a new approach for designing high performance Fe-based metallic glasses.
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Keywords:
- rare earth element /
- metallic glass /
- rapid solidification /
- oxidation mechanism
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图 1 四元Fe-B-Nb-Gd非晶合金的相分析 (a) XRD图谱; (b) Gd2合金的TEM明场像及选区电子衍射花样
Fig. 1. Phase analysis of quaternary Fe-B-Nb-Gd amorphous alloys: (a) XRD patterns; (b) bright-field TEM image and SAED patterns of Gd2 alloy.
图 2 不同Gd含量非晶Fe-B-Nb-Gd合金的DSC曲线 (a) 玻璃转变和结晶曲线; (b) 熔化曲线
Fig. 2. DSC curves of Fe-B-Nb-Gd metallic glasses with different Gd contents: (a) Glass transition and crystallization curves; (b) melting curves.
图 3 非晶合金的微观结构及热力学参数 (a) 各组成原子基本参数; (b) 原子尺寸差; (c) 构型熵; (d) 混合焓
Fig. 3. Microstructure and thermodynamic parameters of metallic glasses: (a) Basic parameters of each constituent atom; (b) atomic size difference; (c) configuration entropy; (d) enthalpy of mixing.
图 4 四元Fe-B-Nb-Gd非晶合金的磁学性能 (a) 磁滞回线;(b) 剩磁; (c) 矫顽力; (d) 饱和磁化强度
Fig. 4. Magnetic properties of quaternary Fe-B-Nb-Gd metallic glasses: (a) Hysteresis loop; (b) remanence; (c) coercivity; (d) saturated magnetization.
图 5 非晶Fe-B-Nb-Gd合金氧化过程与温度的相关性 (a) 氧化增重曲线; (b) 氧化增重速率曲线
Fig. 5. Temperature dependence of oxidation process for Fe-B-Nb-Gd metallic glasses: (a) Mass gain curves; (b) mass gain rate curves.
图 6 非晶Fe-B-Nb-Gd合金氧化产物的微观形貌与溶质分布 (a) Gd0; (b) Gd2
Fig. 6. Microstructure morphology and solute distribution of oxidation products for Fe-B-Nb-Gd metallic glasses: (a) Gd0; (b) Gd2.
图 7 非晶Fe-B-Nb-Gd合金的氧化机制(a), (b) 合金原子扩散和氧化物结构模型; (c), (d) 氧元素扩散模型
Fig. 7. The oxidation mechanism of Fe-B-Nb-Gd metallic glasses: (a), (b) Atomic diffusion and oxide structure models; (c), (d) oxygen diffusion models.
表 1 (Fe73B22Nb5)100–xGdx (x = 0, 0.5, 1.0, 1.5, 2.0)非晶合金的热物性参数
Table 1. Thermophysical parameters of (Fe73B22Nb5)100–xGdx (x = 0, 0.5, 1.0, 1.5, 2.0) metallic glasses.
Alloy Tg / K Tx / K Tp / K TS / K TL / K ∆T / K Trg γ Gd0 811 855 862 1409 1529 44 0.576 0.365 Gd0.5 826 875 885 1364 1521 49 0.606 0.377 Gd1 838 897 908 1362 1528 59 0.615 0.384 Gd1.5 863 933 941 1359 1504 70 0.635 0.398 Gd2 864 937 943 1357 1494 73 0.637 0.400 
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