Undercooling Solidification Method for Preparing Amorphous OR Nanocrystalline Soft Magnetic Alloy with High Fe Content
20240312681 ยท 2024-09-19
Inventors
- CHEN WU (HANGZHOU, CN)
- Kebing Wang (Hangzhou, CN)
- Xinyang Zhang (Hangzhou, CN)
- MI YAN (HANGZHOU, CN)
- JIAYING JIN (HANGZHOU, CN)
Cpc classification
B22F9/008
PERFORMING OPERATIONS; TRANSPORTING
C22C38/004
CHEMISTRY; METALLURGY
C21D9/52
CHEMISTRY; METALLURGY
C22C38/002
CHEMISTRY; METALLURGY
C22C38/005
CHEMISTRY; METALLURGY
B22F2998/10
PERFORMING OPERATIONS; TRANSPORTING
H01F1/15333
ELECTRICITY
B22F2999/00
PERFORMING OPERATIONS; TRANSPORTING
B22F1/08
PERFORMING OPERATIONS; TRANSPORTING
C22C38/12
CHEMISTRY; METALLURGY
B22F1/142
PERFORMING OPERATIONS; TRANSPORTING
International classification
B22F1/08
PERFORMING OPERATIONS; TRANSPORTING
B22F1/142
PERFORMING OPERATIONS; TRANSPORTING
B22F9/08
PERFORMING OPERATIONS; TRANSPORTING
B22F9/00
PERFORMING OPERATIONS; TRANSPORTING
C21D9/52
CHEMISTRY; METALLURGY
C22C38/12
CHEMISTRY; METALLURGY
Abstract
The present invention provides an undercooling solidification method for preparing an amorphous or nanocrystalline soft magnetic alloy with high Fe content and the applicable amorphous or nanocrystalline alloy composition. The undercooling solidification is realized by glass purification combined with cyclical superheating or electromagnetic levitation melting. An undercooling solidification alloy is prepared into amorphous strips or powders through rapid quenching or atomization of melt, and can be prepared into a nanocrystalline alloy through heat treatment. The chemical formula of the applicable amorphous or nanocrystalline alloy is FeSiBM, wherein M is one or more of P, C, Nb, Mo, Zr, Hf, Mo, Y, Cu and Co. The amorphous or nanocrystalline alloy prepared by undercooling non-equilibrium solidification has the characteristics of high amorphous forming ability, high saturation magnetization and low coercive force.
Claims
1. An undercooling solidification method for preparing an amorphous or nanocrystalline soft magnetic alloy with high Fe content, wherein the alloy is undercooled and solidified by means of glass fluxing combined with cyclical superheating or electromagnetic levitation melting, reducing the additive amount of elements promoting amorphous formation in the Fe-based amorphous or nanocrystalline soft magnetic alloy, increasing the proportion of the Fe element and achieving the goals of enhancing saturation magnetization and reducing coercive force.
2. The undercooling solidification method for preparing an amorphous or nanocrystalline soft magnetic alloy with high Fe content according to claim 1, wherein the method of glass fluxing combined with cyclical superheating comprises the following steps: step 1: the chemical formula of the amorphous or nanocrystalline alloy is FeSiBM, wherein M is one or more of P, C, Nb, Mo, Zr, Hf, Mo, Y, Cu and Co; removing the surface oxidation layers of raw materials of the alloy, cleaning the raw materials, weighing the raw materials according to a certain mass ratio, vacuumizing the weighed raw materials in a vacuum induction melting furnace or vacuum arc melting furnace to at least 10.sup.?3 Pa, filling inert gas for protection, then melting the raw materials, and repeating melting for 4-6 times to obtain an alloy ingot; step 2: putting the alloy ingot into a crucible, and covering the upper and lower surfaces with a glass purifying agent with a certain mass ratio so that the glass purifying agent completely covers the alloy ingot; step 3: after vacuumizing to at least 10.sup.?2 Pa, filling inert gas for protection, heating the alloy to the molten state, then heating up to 1200-1500? C., preserving heat for 1-10 min, and turning off the heating electric power to make the alloy naturally cool; step 4: implementing a cycle process of heating-heat preservation-solidification for 3-6 times so that the alloy achieves the required degree of undercooling; step 5: quickly solidifying the undercooled and solidified alloy into strips or powders through rapid quenching or atomization of melt; step 6: for the obtained strips or powders, carrying out stress-relief annealing to obtain a Fe-based amorphous alloy or carrying out crystallization annealing to obtain a Fe-based nanocrystalline alloy.
3. The undercooling solidification method for preparing an amorphous or nanocrystalline soft magnetic alloy with high Fe content according to claim 2, wherein the inert gas is argon or nitrogen with the purity of not less than 99.9 vol %.
4. The undercooling solidification method for preparing an amorphous or nanocrystalline soft magnetic alloy with high Fe content according to claim 2, wherein the heat-resistance temperature of the crucible is not lower than 1400? C.
5. The undercooling solidification method for preparing an amorphous or nanocrystalline soft magnetic alloy with high Fe content according to claim 2, wherein the process for preparing the glass purifying agent comprises: weighing and placing powdered Na.sub.2B.sub.4O.sub.7 and B.sub.2O.sub.3 with the purity of not less than 98% in a high purity corundum crucible respectively, firing at 400-600? C. for 1-8 h, then melting and firing at 800-1000? C. for 2-16 h, and mixing the fired Na.sub.2B.sub.4O.sub.7 and B.sub.2O.sub.3 to obtain the purifying agent, wherein the mass ratio of Na.sub.2B.sub.4O.sub.7 to B.sub.2O.sub.3 is 1:1-20.
6. The undercooling solidification method for preparing an amorphous or nanocrystalline soft magnetic alloy with high Fe content according to claim 2, wherein the mass ratio of the glass purifying agent to the alloy ingot is 1:1-5.
7. The undercooling solidification method for preparing an amorphous or nanocrystalline soft magnetic alloy with high Fe content according to claim 1, wherein the method of electromagnetic levitation melting comprises the following steps: step 1: the chemical formula of the amorphous or nanocrystalline alloy is FeSiBM, wherein M is one or more of P, C, Nb, Mo, Zr, Hf, Mo, Y, Cu and Co; removing the surface oxidation layers of raw materials of the alloy, cleaning the raw materials, weighing the raw materials according to a certain mass ratio, vacuumizing the weighed raw materials in a vacuum induction melting furnace or vacuum arc melting furnace to at least 10.sup.?3 Pa, filling inert gas for protection, then melting the raw materials, and repeating melting for 4-6 times to obtain an alloy ingot; step 2: after vacuumizing to at least 10.sup.?3 Pa, filling inert gas for protection, placing the alloy ingot below a suspended coil, and stably suspending the parent alloy in the center of a heating coil by the Lorentz force formed by the interaction between the electromagnetic field and the induced current; step 3: heating the alloy by induction of the heating coil to the molten state, then heating up to 1200-1500? C., preserving heat for 1-10 min, and then turning off the heating electric power to make the alloy naturally cool; step 4: implementing a cycle process of heating-heat preservation-solidification for 3-6 times so that the alloy achieves the required degree of undercooling; step 5: solidifying the undercooled and solidified alloy into strips or powders through rapid quenching or atomization of melt; step 6: for the obtained strips or powders, carrying out stress-relief annealing to obtain a Fe-based amorphous alloy or carrying out crystallization annealing to obtain a Fe-based nanocrystalline alloy.
8. The undercooling solidification method for preparing an amorphous or nanocrystalline soft magnetic alloy with high Fe content according to claim 2, wherein the chemical formula of the amorphous or nanocrystalline soft magnetic alloy with high Fe content is FeSiBM, wherein M is one or more of P, C, Nb, Mo, Zr, Hf, Mo, Y, Cu and Co, the total atomic percent of alloy elements is 100%, and the content of each element is as follows: Fe is 80.0-89.0 at %, Si is 1.0-9.0 at %, B is 3.0-12.0 at %, P is 0-5.0 at %, C is 0-5.0 at %, Nb is 0-3.0 at %, Zr is 0-3.0 at %, Hf is 0-3.0 at %, Mo is 0-3.0 at %, Y is 0-5.0 at %, Cu is 0-2.0 at % and Co is 0-16.0 at %.
9. The undercooling solidification method for preparing an amorphous or nanocrystalline soft magnetic alloy with high Fe content according to claim 7, wherein the chemical formula of the amorphous or nanocrystalline soft magnetic alloy with high Fe content is FeSiBM, wherein M is one or more of P, C, Nb, Mo, Zr, Hf, Mo, Y, Cu and Co, the total atomic percent of alloy elements is 100%, and the content of each element is as follows: Fe is 80.0-89.0 at %, Si is 1.0-9.0 at %, B is 3.0-12.0 at %, P is 0-5.0 at %, C is 0-5.0 at %, Nb is 0-3.0 at %, Zr is 0-3.0 at %, Hf is 0-3.0 at %, Mo is 0-3.0 at %, Y is 0-5.0 at %, Cu is 0-2.0 at % and Co is 0-16.0 at %.
10. The undercooling solidification method for preparing an amorphous or nanocrystalline soft magnetic alloy with high Fe content according to claim 7, wherein the inert gas is argon or nitrogen with the purity of not less than 99.9 vol %.
11. The undercooling solidification method for preparing an amorphous or nanocrystalline soft magnetic alloy with high Fe content according to claim 7, wherein the amorphous alloy is annealed within a temperature range of 50-100? C. below the crystallization temperature, and the nanocrystalline alloy is annealed within a temperature range of 0-100? C. above the crystallization temperature.
12. The undercooling solidification method for preparing an amorphous or nanocrystalline soft magnetic alloy with high Fe content according to claim 10, wherein the annealing is carried out in an inert gas atmosphere or in an environment with the vacuum degree of better than 10.sup.?1 Pa.
Description
DETAILED DESCRIPTION
[0033] Embodiments of the present invention are described in detail below. An amorphous or nanocrystalline soft magnetic alloy with high Fe content, which has high saturation magnetization, is obtained by adjusting the alloy composition and the degree of undercooling.
Embodiment 1
[0034] Preparing FeSiB amorphous alloy by undercooling solidification
[0035] A FeSiB system alloy is prepared, wherein in alloy 1, the Fe content is 83.0 at %, the Si content is 8.0 at %, and the B content is 9.0 at %; in alloy 2, the Fe content is 85.0 at %, the Si content is 7.0 at %, and the B content is 8.0 at %; and in alloy 3, the Fe content is 88.0 at %, the Si content is 3.0 at %, and the B content is 9.0 at %; [0036] Step 1: removing the surface oxidation layers of raw materials of the alloy, cleaning the raw materials, and weighing the raw materials according to a certain mass ratio. Vacuumizing the weighed raw materials in a vacuum arc melting furnace to 8?10.sup.?4 Pa, filling argon with the purity of 99.9 vol % for protection, then melting the raw materials, and repeating melting for 5 times to obtain an alloy ingot; [0037] Step 2: putting the alloy ingot into a crucible, and covering the upper and lower surfaces with a glass purifying agent formed by mixing Na.sub.2B.sub.4O.sub.7 and B.sub.2O.sub.3 at a mass ratio of 1:5 so that the glass purifying agent completely covers the alloy ingot; [0038] Step 3: after vacuumizing to 5?10.sup.?3 Pa, filling argon with the purity of 99.9 vol % for protection, heating the alloy to the molten state, then heating up to 1350? C., preserving heat for 2 min, and turning off the heating electric power to make the alloy naturally cool; [0039] Step 4: implementing a cycle process of heating-heat preservation-solidification for 4 times and 6 times respectively so that the alloy achieves the degrees of undercooling of about 190? C. and 260? C.; [0040] Step 5: solidifying the undercooled and solidified alloy into strips through rapid quenching of melt; [0041] Step 6: carrying out stress-relief annealing of the obtained strips at 300? C. to obtain a Fe-based amorphous alloy;
[0042] The saturation magnetization and coercive force of the alloy at different degrees of undercooling are shown in the table below:
TABLE-US-00001 TABLE 1 Saturation Magnetization and Coercive Force of FeSiB Amorphous Alloy at Different Degrees of Undercooling Saturation Coercive Magnetization Force Sample Number (T) (A/m) Alloy 1 (Not undercooled) 1.66 2.5 Alloy 1 (Undercooled at 190? C.) 1.66 1.5 Alloy 1 (Undercooled at 260? C.) 1.67 1.2 Alloy 2 (Not undercooled) 1.69 250.7 Alloy 2 (Undercooled at 190? C.) 1.71 3.7 Alloy 2 (Undercooled at 260? C.) 1.72 1.7 Alloy 3 (Not undercooled) 1.70 312.5 Alloy 3 (Undercooled at 190? C.) 1.72 15.4 Alloy 3 (Undercooled at 260? C.) 1.73 3.1
Embodiment 2
[0043] Preparing FeSiBPC amorphous alloy by undercooling solidification
[0044] A FeSiBPC system alloy is prepared, wherein in alloy 1, the Fe content is 84.0 at %, the Si content is 2.0 at %, the B content is 8.0 at %, the P content is 5.0 at %, and the C content is 1.0 at %; in alloy 2, the Fe content is 84.0 at %, the Si content is 2.0 at %, the B content is 8.0 at %, the P content is 1.0 at %, and the C content is 5.0 at %; and in alloy 3, the Fe content is 89.0 at %, the Si content is 2.0 at %, the B content is 8.0 at %, the P content is 0.5 at %, and the C content is 0.5 at %; [0045] Step 1: removing the surface oxidation layers of raw materials of the alloy, cleaning the raw materials, and weighing the raw materials according to a certain mass ratio. Vacuumizing the weighed raw materials in a vacuum arc melting furnace to 7?10.sup.?4 Pa, filling nitrogen with the purity of 99.9 vol % for protection, then melting the raw materials, and repeating melting for 6 times to obtain an alloy ingot; [0046] Step 2: putting the alloy ingot into a crucible, and covering the upper and lower surfaces with a glass purifying agent formed by mixing Na.sub.2B.sub.4O.sub.7 and B.sub.2O.sub.3 at a mass ratio of 1:4 so that the glass purifying agent completely covers the alloy ingot; [0047] Step 3: after vacuumizing to 4?10.sup.?3 Pa, filling nitrogen with the purity of 99.9 vol % for protection, heating the alloy to the molten state, then heating up to 1400? C., preserving heat for 3 min, and turning off the heating electric power to make the alloy naturally cool; [0048] Step 4: implementing a cycle process of heating-heat preservation-solidification for 4 times and 6 times respectively so that the alloy achieves the degrees of undercooling of about 160? C. and 255? C.; [0049] Step 5: solidifying the undercooled and solidified alloy into strips through rapid quenching of melt; [0050] Step 6: carrying out stress-relief annealing of the obtained strips at 300? C. to obtain a Fe-based amorphous alloy;
[0051] The saturation magnetization and coercive force of the alloy at different degrees of undercooling are shown in the table below:
TABLE-US-00002 TABLE 2 Saturation Magnetization and Coercive Force of FeSiBPC Amorphous Alloy at Different Degrees of Undercooling Saturation Coercive Magnetization Force Sample Number (T) (A/m) Alloy 1 (Not undercooled) 1.66 313.6 Alloy 1 (Undercooled at 160? C.) 1.72 24.5 Alloy 1 (Undercooled at 255? C.) 1.73 2.5 Alloy 2 (Not undercooled) 1.67 348.5 Alloy 2 (Undercooled at 160? C.) 1.73 27.7 Alloy 2 (Undercooled at 255? C.) 1.74 3.5 Alloy 3 (Not undercooled) 1.72 423.8 Alloy 3 (Undercooled at 160? C.) 1.78 17.5 Alloy 3 (Undercooled at 255? C.) 1.80 4.3
Embodiment 3
[0052] Preparing FeSiBC amorphous alloy by undercooling solidification
[0053] A FeSiBC system alloy is prepared, wherein in alloy 1, the Fe content is 84.0 at %, the Si content is 2.0 at %, the B content is 8.0 at %, and the C content is 6.0 at %; in alloy 2, the Fe content is 85.0 at %, the Si content is 2.0 at %, the B content is 8.0 at %, and the C content is 5.0 at %; and in alloy 3, the Fe content is 89.0 at %, the Si content is 2.0 at %, the B content is 8.0 at %, and the C content is 1.0 at %; [0054] Step 1: removing the surface oxidation layers of raw materials of the alloy, cleaning the raw materials, and weighing the raw materials according to a certain mass ratio. Vacuumizing the weighed raw materials in a vacuum induction melting furnace or vacuum arc melting furnace to 8?10.sup.?4 Pa, filling inert gas for protection, then melting the raw materials, and repeating melting for 6 times to obtain an alloy ingot; [0055] Step 2: after vacuumizing to 4?10.sup.?3 Pa, filling nitrogen with the purity of 99.9 vol % for protection, placing the alloy ingot below a suspended coil, and stably suspending the parent alloy in the center of a heating coil by the Lorentz force formed by the interaction between the electromagnetic field and the induced current; [0056] Step 3: heating the alloy by induction of the heating coil to the molten state, then heating up to 1500? C., preserving heat for 5 min, and then turning off the heating electric power to make the alloy naturally cool; [0057] Step 4: implementing a cycle process of heating-heat preservation-solidification for 3 times and 5 times respectively so that the alloy achieves the degrees of undercooling of about 150? C. and 225? C.; [0058] Step 5: solidifying the undercooled and solidified alloy into strips through rapid quenching of melt; [0059] Step 6: carrying out stress-relief annealing of the obtained strips at 300? C. to obtain a Fe-based amorphous alloy;
[0060] The saturation magnetization and coercive force of the alloy at different degrees of undercooling are shown in the table below:
TABLE-US-00003 TABLE 3 Saturation Magnetization and Coercive Force of FeSiBC Amorphous Alloy at Different Degrees of Undercooling Saturation Coercive Magnetization Force Sample Number (T) (A/m) Alloy 1 (Not undercooled) 1.68 363.6 Alloy 1 (Undercooled at 150? C.) 1.70 27.5 Alloy 1 (Undercooled at 225? C.) 1.71 3.1 Alloy 2 (Not undercooled) 1.71 368.5 Alloy 2 (Undercooled at 150? C.) 1.73 29.7 Alloy 2 (Undercooled at 225? C.) 1.74 3.8 Alloy 3 (Not undercooled) 1.72 427.8 Alloy 3 (Undercooled at 150? C.) 1.77 19.8 Alloy 3 (Undercooled at 225? C.) 1.79 5.3
Embodiment 4
[0061] Preparing FeSiBCu nanocrystalline alloy by undercooling solidification
[0062] A FeSiBCu system alloy is prepared, wherein in alloy 1, the Fe content is 80.5 at %, the Si content is 7.0 at %, the B content is 12.0 at %, and the Cu content is 0.5 at %; in alloy 2, the Fe content is 85.0 at %, the Si content is 2.5 at %, the B content is 12.0 at %, and the Cu content is 0.5 at %; and in alloy 3, the Fe content is 85.0 at %, the Si content is 1.2 at %, the B content is 12.0 at %, and the Cu content is 1.8 at %; [0063] Step 1: removing the surface oxidation layers of raw materials of the alloy, cleaning the raw materials, and weighing the raw materials according to a certain mass ratio. Vacuumizing the weighed raw materials in a vacuum induction melting furnace to 9?10.sup.?4 Pa, filling argon with the purity of 99.9 vol % for protection, then melting the raw materials, and repeating melting for 4 times to obtain an alloy ingot; [0064] Step 2: putting the alloy ingot into a crucible, and covering the upper and lower surfaces with a glass purifying agent formed by mixing Na.sub.2B.sub.4O.sub.7 and B.sub.2O.sub.3 at a mass ratio of 1:20 so that the glass purifying agent completely covers the alloy ingot; [0065] Step 3: after vacuumizing to 5?10.sup.?3 Pa, filling argon with the purity of 99.9 vol % for protection, heating the alloy to the molten state, then heating up to 1320? C., preserving heat for 5 min, and turning off the heating electric power to make the alloy naturally cool; [0066] Step 4: implementing a cycle process of heating-heat preservation-solidification for 3 times and 4 times respectively so that the alloy achieves the degrees of undercooling of about 205? C. and 255? C.; [0067] Step 5: solidifying the undercooled and solidified alloy into strips through rapid quenching of melt; [0068] Step 6: carrying out crystallization annealing of the obtained strips at 450? C. to obtain a Fe-based nanocrystalline alloy;
[0069] The saturation magnetization and coercive force of the alloy at different degrees of undercooling are shown in the table below:
TABLE-US-00004 TABLE 4 Saturation Magnetization and Coercive Force of FeSiBCu Nanocrystalline Alloy at Different Degrees of Undercooling Saturation Coercive Magnetization Force Sample Number (T) (A/m) Alloy 1 (Not undercooled) 1.55 30.6 Alloy 1 (Undercooled at 205? C.) 1.59 7.8 Alloy 1 (Undercooled at 255? C.) 1.60 5.6 Alloy 2 (Not undercooled) 1.65 320.7 Alloy 2 (Undercooled at 205? C.) 1.72 6.5 Alloy 2 (Undercooled at 255? C.) 1.75 4.5 Alloy 3 (Not undercooled) 1.66 512.5 Alloy 3 (Undercooled at 205? C.) 1.75 13.4 Alloy 3 (Undercooled at 255? C.) 1.77 1.7
Embodiment 5
[0070] Preparing FeSiBNbCu nanocrystalline alloy by undercooling solidification
[0071] A FeSiBNbCu system alloy is prepared, wherein in alloy 1, the Fe content is 80.0 at %, the Si content is 7.0 at %, the B content is 9.0 at %, the Nb content is 3.0 at %, and the Cu content is 1.0 at %; in alloy 2, the Fe content is 82.0 at %, the Si content is 6.0 at %, the B content is 9.0 at %, the Nb content is 2.0 at %, and the Cu content is 1.0 at %; and in alloy 3, the Fe content is 85.0 at %, the Si content is 4.5 at %, the B content is 9.0 at %, the Nb content is 0.5 at %, and the Cu content is 1.0 at %; [0072] Step 1: removing the surface oxidation layers of raw materials of the alloy, cleaning the raw materials, and weighing the raw materials according to a certain mass ratio. Vacuumizing the weighed raw materials in a vacuum arc melting furnace to 8?10.sup.?4 Pa, filling argon with the purity of 99.9 vol % for protection, then melting the raw materials, and repeating melting for 6 times to obtain an alloy ingot; [0073] Step 2: putting the alloy ingot into a crucible, and covering the upper and lower surfaces with a glass purifying agent formed by mixing Na.sub.2B.sub.4O.sub.7 and B.sub.2O.sub.3 at a mass ratio of 1:10 so that the glass purifying agent completely covers the alloy ingot; [0074] Step 3: after vacuumizing to 8?10.sup.?3 Pa, filling nitrogen with the purity of 99.9 vol % for protection, heating the alloy to the molten state, then heating up to 1380? C., preserving heat for 1 min, and turning off the heating electric power to make the alloy naturally cool; [0075] Step 4: implementing a cycle process of heating-heat preservation-solidification for 5 times and 6 times respectively so that the alloy achieves the degrees of undercooling of about 190? C. and 225? C.; [0076] Step 5: solidifying the undercooled and solidified alloy into strips through rapid quenching of melt; [0077] Step 6: carrying out crystallization annealing of the obtained strips at 550? C. to obtain a Fe-based nanocrystalline alloy;
[0078] The saturation magnetization and coercive force of the alloy at different degrees of undercooling are shown in the table below:
TABLE-US-00005 TABLE 5 Saturation Magnetization and Coercive Force of FeSiBNbCu Nanocrystalline Alloy at Different Degrees of Undercooling Saturation Coercive Magnetization Force Sample Number (T) (A/m) Alloy 1 (Not undercooled) 1.60 33.7 Alloy 1 (Undercooled at 190? C.) 1.62 4.6 Alloy 1 (Undercooled at 225? C.) 1.63 2.6 Alloy 2 (Not undercooled) 1.62 248.6 Alloy 2 (Undercooled at 190? C.) 1.66 4.8 Alloy 2 (Undercooled at 225? C.) 1.67 3.5 Alloy 3 (Not undercooled) 1.65 355.2 Alloy 3 (Undercooled at 190? C.) 1.71 5.1 Alloy 3 (Undercooled at 225? C.) 1.73 4.2
Embodiment 6
[0079] Preparing FeSiBMoCu nanocrystalline alloy by undercooling solidification
[0080] A FeSiBMoCu system alloy is prepared, wherein in alloy 1, the Fe content is 80.0 at %, the Si content is 7.0 at %, the B content is 9.0 at %, the Mo content is 3.0 at %, and the Cu content is 1.0 at %; in alloy 2, the Fe content is 82.0 at %, the Si content is 6.0 at %, the B content is 9.0 at %, the Mo content is 2.0 at %, and the Cu content is 1.0 at %; and in alloy 3, the Fe content is 83.3 at %, the Si content is 5.0 at %, the B content is 9.0 at %, the Mo content is 0.7 at %, and the Cu content is 1.0 at %; [0081] Step 1: removing the surface oxidation layers of raw materials of the alloy, cleaning the raw materials, and weighing the raw materials according to a certain mass ratio. Vacuumizing the weighed raw materials in a vacuum induction melting furnace to 8?10?4 Pa, filling argon with the purity of 99.9 vol % for protection, then melting the raw materials, and repeating melting for 4 times to obtain an alloy ingot; [0082] Step 2: putting the alloy ingot into a crucible, and covering the upper and lower surfaces with a glass purifying agent formed by mixing Na.sub.2B.sub.4O.sub.7 and B.sub.2O.sub.3 at a mass ratio of 1:1 so that the glass purifying agent completely covers the alloy ingot; [0083] Step 3: after vacuumizing to 1?10.sup.?2 Pa, filling argon with the purity of 99.9 vol % for protection, heating the alloy to the molten state, then heating up to 1370? C., preserving heat for 6 min, and turning off the heating electric power to make the alloy naturally cool; [0084] Step 4: implementing a cycle process of heating-heat preservation-solidification for 3 times and 5 times respectively so that the alloy achieves the degrees of undercooling of about 175? C. and 255? C.; [0085] Step 5: solidifying the undercooled and solidified alloy into strips through rapid quenching of melt; [0086] Step 6: carrying out crystallization annealing of the obtained strips at 500? C. to obtain a Fe-based nanocrystalline alloy;
[0087] The saturation magnetization and coercive force of the alloy at different degrees of undercooling are shown in the table below:
TABLE-US-00006 TABLE 6 Saturation Magnetization and Coercive Force of FeSiBMoCu Nanocrystalline Alloy at Different Degrees of Undercooling Saturation Coercive Magnetization Force Sample Number (T) (A/m) Alloy 1 (Not undercooled) 1.56 35.8 Alloy 1 (Undercooled at 175? C.) 1.57 4.7 Alloy 1 (Undercooled at 255? C.) 1.58 2.6 Alloy 2 (Not undercooled) 1.65 261.7 Alloy 2 (Undercooled at 175? C.) 1.68 5.1 Alloy 2 (Undercooled at 255? C.) 1.69 3.8 Alloy 3 (Not undercooled) 1.71 325.7 Alloy 3 (Undercooled at 175? C.) 1.75 12.3 Alloy 3 (Undercooled at 255? C.) 1.76 6.8
Embodiment 7
[0088] Preparing FeCoSiBCCu nanocrystalline alloy by undercooling solidification
[0089] A FeCoSiBCCu system alloy is prepared, wherein in alloy 1, the Fe content is 80.0 at %, the Co content is 5.0 at %, the Si content is 1.5 at %, the B content is 9.0 at %, the C content is 3.0 at %, and the Cu content is 1.5 at %; in alloy 2, the Fe content is 75.0 at %, the Co content is 10.0 at %, the Si content is 1.5 at %, the B content is 9.0 at %, the C content is 3.0 at %, and the Cu content is 1.5 at %; and in alloy 3, the Fe content is 70.0 at %, the Co content is 15.0 at %, the Si content is 1.5 at %, the B content is 9.0 at %, the C content is 3.0 at %, and the Cu content is 1.5 at %; [0090] Step 1: removing the surface oxidation layers of raw materials of the alloy, cleaning the raw materials, and weighing the raw materials according to a certain mass ratio. Vacuumizing the weighed raw materials in a vacuum arc melting furnace to 8?10.sup.?4 Pa, filling argon with the purity of 99.9 vol % for protection, then melting the raw materials, and repeating melting for 5 times to obtain an alloy ingot; [0091] Step 2: putting the alloy ingot into a crucible, and covering the upper and lower surfaces with a glass purifying agent formed by mixing Na.sub.2B.sub.4O.sub.7 and B.sub.2O.sub.3 at a mass ratio of 1:3 so that the glass purifying agent completely covers the alloy ingot; [0092] Step 3: after vacuumizing to 8?10.sup.?3 Pa, filling nitrogen with the purity of 99.9 vol % for protection, heating the alloy to the molten state, then heating up to 1350? C., preserving heat for 8 min, and turning off the heating electric power to make the alloy naturally cool; [0093] Step 4: implementing a cycle process of heating-heat preservation-solidification for 3 times and 6 times respectively so that the alloy achieves the degrees of undercooling of about 150? C. and 265? C.; [0094] Step 5: solidifying the undercooled and solidified alloy into strips through rapid quenching of melt; [0095] Step 6: carrying out crystallization annealing of the obtained strips at 400? C. to obtain a Fe-based nanocrystalline alloy;
[0096] The saturation magnetization and coercive force of the alloy at different degrees of undercooling are shown in the table below:
TABLE-US-00007 TABLE 7 Saturation Magnetization and Coercive Force of FeCoSiBCCu Nanocrystalline Alloy at Different Degrees of Undercooling Saturation Coercive Magnetization Force Sample Number (T) (A/m) Alloy 1 (Not undercooled) 1.68 285.6 Alloy 1 (Undercooled at 150? C.) 1.78 6.5 Alloy 1 (Undercooled at 265? C.) 1.79 3.8 Alloy 2 (Not undercooled) 1.70 302.5 Alloy 2 (Undercooled at 150? C.) 1.80 7.1 Alloy 2 (Undercooled at 265? C.) 1.81 5.9 Alloy 3 (Not undercooled) 1.71 328.3 Alloy 3 (Undercooled at 150? C.) 1.81 7.8 Alloy 3 (Undercooled at 265? C.) 1.83 6.4
Embodiment 8
[0097] Preparing FeSiBZrHfCu nanocrystalline alloy by undercooling solidification
[0098] A FeSiBZrHfCu system alloy is prepared, wherein in alloy 1, the Fe content is 80.0 at %, the Si content is 6 at %, the B content is 9.0 at %, the Zr content is 3.0 at %, the Hf content is 1.0 at %, and the Cu content is 1.0 at %; in alloy 2, the Fe content is 80.0 at %, the Si content is 6.0 at %, the B content is 9.0 at %, the Zr content is 1.0 at %, the Hf content is 3.0 at %, and the Cu content is 1.0 at %; and in alloy 3, the Fe content is 87.0 at %, the Si content is 2.0 at %, the B content is 9.0 at %, the Zr content is 0.5 at %, the Hf content is 0.5 at %, and the Cu content is 1.0 at %; [0099] Step 1: removing the surface oxidation layers of raw materials of the alloy, cleaning the raw materials, and weighing the raw materials according to a certain mass ratio. Vacuumizing the weighed raw materials in a vacuum induction melting furnace or vacuum arc melting furnace to 8?10.sup.?4 Pa, filling inert gas for protection, then melting the raw materials, and repeating melting for 6 times to obtain an alloy ingot; [0100] Step 2: after vacuumizing to 4?10.sup.?3 Pa, filling nitrogen with the purity of 99.9 vol % for protection, placing the alloy ingot below a suspended coil, and stably suspending the parent alloy in the center of a heating coil by the Lorentz force formed by the interaction between the electromagnetic field and the induced current; [0101] Step 3: heating the alloy by induction of the heating coil to the molten state, then heating up to 1400? C., preserving heat for 10 min, and then turning off the heating electric power to make the alloy naturally cool; [0102] Step 4: implementing a cycle process of heating-heat preservation-solidification for 4 times and 6 times respectively so that the alloy achieves the degrees of undercooling of about 210? C. and 270? C.; [0103] Step 5: solidifying the undercooled and solidified alloy into strips through rapid quenching of melt; [0104] Step 6: carrying out crystallization annealing of the obtained strips at 550? C. to obtain a Fe-based nanocrystalline alloy;
[0105] The saturation magnetization and coercive force of the alloy at different degrees of undercooling are shown in the table below:
TABLE-US-00008 TABLE 8 Saturation Magnetization and Coercive Force of FeSiBZrHfCu Nanocrystalline Alloy at Different Degrees of Undercooling Saturation Coercive Magnetization Force Sample Number (T) (A/m) Alloy 1 (Not undercooled) 1.55 15.8 Alloy 1 (Undercooled at 210? C.) 1.57 3.2 Alloy 1 (Undercooled at 270? C.) 1.58 1.5 Alloy 2 (Not undercooled) 1.56 223.7 Alloy 2 (Undercooled at 210? C.) 1.57 4.6 Alloy 2 (Undercooled at 270? C.) 1.59 2.1 Alloy 3 (Not undercooled) 1.70 286.5 Alloy 3 (Undercooled at 210? C.) 1.72 12.3 Alloy 3 (Undercooled at 270? C.) 1.73 3.5
Embodiment 9
[0106] Preparing FeSiBYCu nanocrystalline alloy by undercooling solidification
[0107] A FeSiBYCu system alloy is prepared, wherein in alloy 1, the Fe content is 81.0 at %, the Si content is 4.0 at %, the B content is 9.0 at %, the Y content is 5.0 at %, and the Cu content is 1.0 at %; in alloy 2, the Fe content is 84.0 at %, the Si content is 4.0 at %, the B content is 9.0 at %, the Y content is 2.0 at %, and the Cu content is 1.0 at %; and in alloy 3, the Fe content is 87.0 at %, the Si content is 2.0 at %, the B content is 9.0 at %, the Y content is 1.0 at %, and the Cu content is 1.0 at %; [0108] Step 1: removing the surface oxidation layers of raw materials of the alloy, cleaning the raw materials, and weighing the raw materials according to a certain mass ratio. Vacuumizing the weighed raw materials in a vacuum arc melting furnace to 8?10.sup.?4 Pa, filling inert gas for protection, then melting the raw materials, and repeating melting for 4 times to obtain an alloy ingot; [0109] Step 2: after vacuumizing to 5?10.sup.?3 Pa, filling argon with the purity of 99.9 vol % for protection, placing the alloy ingot below a suspended coil, and stably suspending the parent alloy in the center of a heating coil by the Lorentz force formed by the interaction between the electromagnetic field and the induced current; [0110] Step 3: heating the alloy by induction of the heating coil to the molten state, then heating up to 1500? C., preserving heat for 3 min, and then turning off the heating electric power to make the alloy naturally cool; [0111] Step 4: implementing a cycle process of heating-heat preservation-solidification for 3 times and 6 times respectively so that the alloy achieves the degrees of undercooling of about 180? C. and 255? C.; [0112] Step 5: solidifying the undercooled and solidified alloy into strips through rapid quenching of melt; [0113] Step 6: carrying out crystallization annealing of the obtained strips at 500? C. to obtain a Fe-based nanocrystalline alloy;
[0114] The saturation magnetization and coercive force of the alloy at different degrees of undercooling are shown in the table below:
TABLE-US-00009 TABLE 9 Saturation Magnetization and Coercive Force of FeSiBYCu Nanocrystalline Alloy at Different Degrees of Undercooling Saturation Coercive Magnetization Force Sample Number (T) (A/m) Alloy 1 (Not undercooled) 1.60 23.6 Alloy 1 (Undercooled at 180? C.) 1.65 16.5 Alloy 1 (Undercooled at 255? C.) 1.66 4.7 Alloy 2 (Not undercooled) 1.65 125.3 Alloy 2 (Undercooled at 180? C.) 1.70 18.6 Alloy 2 (Undercooled at 255? C.) 1.71 8.6 Alloy 3 (Not undercooled) 1.72 205.3 Alloy 3 (Undercooled at 180? C.) 1.75 20.2 Alloy 3 (Undercooled at 255? C.) 1.77 9.5
[0115] In conclusion, the present invention has the technical effects of improving the amorphous forming ability of Fe-based alloys through glass purification combined with cyclical superheating or electromagnetic levitation melting and achieving the goals of reducing the content of elements promoting amorphous formation and increasing the content of ferromagnetic elements, so as to obtain the amorphous or nanocrystalline soft magnetic alloy with large saturation magnetization and low coercive force. The principle of achieving the technical effects is as follows: during the process of glass purification combined with cyclical superheating, glass fluxing can adsorb heterogeneous nucleation points in fused alloys, and the cold and hot cycle process of superheating and heating up-heat preservation-cooling also can lead to thermal decomposition of heterogeneous nucleation points at high temperatures and cause substance exchange in the process of heat convection between the interior and the surface, effectively reducing the heterogeneous nucleation points in the alloy. During the process of electromagnetic levitation melting, the alloy can be effectively prevented from introducing impurities in the melting process through containerless melting, and the heterogeneous nucleation points in the alloy are thermally decomposed through superheating at high temperature. Both of the above methods can reduce or avoid the crystallization phenomenon and improve the amorphous forming ability. On one hand, the reduction of heterogeneous nucleation points can optimize the microstructure of the alloy, weaken the destructive effect on magnetic exchange coupling and increase the saturation magnetization of the alloy. On the other hand, the improvement of the amorphous forming ability of the alloy is conducive to the formation of a more disordered amorphous structure, which effectively eliminates the magnetocrystalline anisotropy and reduces or avoids the blocking effect of the heterogeneous nucleation points on magnetic inversion, so as to obtain low coercive force.