阅读说明：本技术 一种高饱和磁化强度Fe-B-P-C-Cu-M系非晶纳米晶软磁合金及制备方法 (High-saturation-magnetization Fe-B-P-C-Cu-M amorphous nanocrystalline magnetically soft alloy and preparation method thereof ) 是由 惠希东 李育洛 吕旷 窦正旭 白瑞 于 2020-05-11 设计创作，主要内容包括：一种高饱和磁化强度Fe-B-P-C-Cu-M系非晶纳米晶软磁合金及制备方法。具有如下所示的通式：Fe<Sub>x</Sub>B<Sub>y</Sub>P<Sub>z</Sub>C<Sub>a</Sub>Cu<Sub>b</Sub>M<Sub>c</Sub>,式中x,y,x,a,b,c分别表示各对应组分Fe、B、P、C、Cu、M的原子百分比,并满足下列条件：80≤x≤85,4≤y≤10,2≤z≤10,3.5≤a≤7.5,0.7≤b≤1.5,0≤c≤2,其中x+y+z+a+b+c＝100,M为Nb,Zr,V,Hf,Mo等中的一种或多种。本发明所涉及的合金系中不含Si元素,以具有更小原子尺寸半径和更高非晶形成能力的C元素作为重要添加元素,开发了一系列具有高饱和磁化强度(B<Sub>s</Sub>)和低矫顽力(H<Sub>c</Sub>)的铁基非晶纳米晶软磁合金。本发明所开发的铁基非晶纳米晶合金可作为电机铁芯、互感器铁芯,同时,也可用于电力工业变压器铁芯、逆变焊机、新能源、无线充电、数码及自动化等领域。(A Fe-B-P-C-Cu-M series amorphous nanocrystalline magnetically soft alloy with high saturation magnetization and a preparation method thereof.Has the following general formula: fe x B y P z C a Cu b M c Wherein x, y, x, a, B and C respectively represent the atomic percentages of the corresponding components Fe, B, P, C, Cu and M, and the following conditions are satisfied: x is more than or equal to 80 and less than or equal to 85, y is more than or equal to 4 and less than or equal to 10, z is more than or equal to 2 and less than or equal to 10, a is more than or equal to 3.5 and less than or equal to 7.5, b is more than or equal to 0.7 and less than or equal to 1.5, and c is more than or equal to 0 and less than or equal to 2, wherein x + y + z + a + b + c is 100, and M is one or more of Nb, Zr. The alloy system related by the invention does not contain Si element, takes C element with smaller atomic size radius and higher amorphous forming ability as important additive element, develops a series of alloy systems with high saturation magnetization (B) s ) And low coercivity (H) c ) The iron-based amorphous nanocrystalline soft magnetic alloy. The iron-based amorphous nanocrystalline alloy developed by the invention can be used as a motor iron core and a mutual inductor iron core, and can also be used in the fields of transformer iron cores in the power industry, inverter welding machines, new energy, wireless charging, digital codes, automation and the like.)

1. High saturation magnetization Fe-B-P-C-Cu-M amorphous nanocrystalline magnetically soft alloyThe soft magnetic alloy is characterized in that the expression of the chemical composition of the soft magnetic alloy is Fe_xB_yP_zC_aCu_bM_cWherein x, y, x, a, B and C respectively represent the atomic percentages of the corresponding components Fe, B, P, C, Cu and M, and the following conditions are satisfied: x is more than or equal to 80 and less than or equal to 85, y is more than or equal to 4 and less than or equal to 10, z is more than or equal to 2 and less than or equal to 10, a is more than or equal to 3.5 and less than or equal to 7.5, b is more than or equal to 0.7 and less than or equal to 1.5, c is more than or equal to 0 and less than or equal to 2, x + y + z + a + b + c is 100, and M is one or more of Nb, Zr; has high amorphous forming ability and high saturation magnetic induction (B)_s) And low coercive force (H)_c)。

2. The Fe-B-P-C-Cu-M amorphous nanocrystalline soft magnetic alloy according to claim 1, characterized in that the soft magnetic alloy is a silicon-free low-phosphorus iron-based amorphous nanocrystalline soft magnetic alloy with high saturation magnetization, and the chemical composition expression of the soft magnetic alloy is Fe_xB_yP_zC_aCu_bWherein: x is 83.3, y is not less than 8 and not more than 9, z is not less than 3 and not more than 4, a is not less than 3.7 and not more than 4.2, B is not less than 0.7 and not more than 0.8, and x + y + z + a + B is 100, the alloy strip has excellent forming performance, is an amorphous strip in a quenched state, and has saturation magnetization (B) after annealing at 480 ℃ for 6min_s) Can reach 1.87T, coercive force (H)_c) As low as 10A/m.

3. The Si-free high-saturation-magnetization Fe-based amorphous nanocrystalline soft magnetic alloy according to claim 1, characterized in that the soft magnetic alloy is a Si-free high-phosphorus type high-saturation-magnetization amorphous nanocrystalline alloy with a chemical composition expression of Fe_xB_yP_zC_aCu_bWherein: x is 83, y is not less than 4.5 and not more than 5.5, z is not less than 7.5 and not more than 8.2, a is not less than 3.7 and not more than 4.2, B is not less than 0.9 and not more than 1.1, x + y + z + a + B is 100, the alloy has excellent forming performance of thin strip, is amorphous in quenching state, and has saturation magnetization (B) after annealing for 6min at 480 DEG C_s) Can reach 1.76T, and the coercive force is as low as 5.1A/m.

4. The Fe-B-P-C-Cu-M amorphous nanocrystalline magnetically soft alloy according to claim 1, wherein the chemical composition expression is Fe_xB_yP_zC_aCu_bM_cWherein M is one or more of Nb, Zr, V, Hf and Mo, x, y, x, a, B and C respectively represent the atomic percentage of each corresponding component Fe, B, P, C, Cu and M, x is more than or equal to 82.5 and less than or equal to 83.5, y is more than or equal to 4 and less than or equal to 9.5, z is more than or equal to 2 and less than or equal to 9, a is more than or equal to 3.5 and less than or equal to 6, B is more than or equal to 0.8 and less than or equal to 1.1, C is more than or equal to 0.4 and less than or equal to 0.8, and x + y + z + a +.

5. The Fe-B-P-C-Cu-M amorphous nanocrystalline magnetically soft alloy according to claim 1 or 4, wherein the chemical composition expression is Fe_xB_yP_zC_aCu_bM_cWherein: x is 83, y is not less than 8 and not more than 9, z is not less than 2.35 and not more than 2.55, a is not less than 3.7 and not more than 4.2, B is not less than 0.9 and not more than 1.1, and x + y + z + a + B + c is 100, the alloy ribbon has excellent forming performance, is in an amorphous state in a quenched state, and has saturation magnetization (B) after annealing for 6min at 480 DEG C_s) Can reach 1.89T and the coercive force is 17.07A/m.

6. A method for preparing the high saturation magnetization Fe-B-P-C-Cu-M amorphous nanocrystalline soft magnetic alloy according to claims 1-5, characterized by comprising the following steps:

1) preparing materials: fe with the purity of 99.98 wt%, B with the purity of 99.95 wt% or industrial FeB alloy (the impurity content is lower than 0.8 wt%), industrial FeP alloy with the P content of 27.1 wt% (the impurity content is lower than 1.6 wt%) or P with the purity of 99.95, Cu with the purity of 99.95 wt%, C with the purity of 99.95 wt% or industrial FeC alloy (the impurity content is lower than 1.0 wt%) and M (Nb, Zr, V, Hf, Mo) with the purity of 99.90% are adopted;

2) smelting mother alloy through setting the material inside non-consumable vacuum arc furnace and vacuum pumping to 5 × 10^-3Pa, smelting the alloy in an argon atmosphere with the purity of 99.99 percent, and repeatedly smelting each alloy ingot for at least more than 4 times;

3) the strip is prepared by vacuumizing a single-roller rotary quenching furnace to 5 × 10^-2Remelting a master alloy ingot under the protection of argon, and spraying the master alloy ingot on a copper roller rotating at a high speed; the linear speed of the copper roller is 40-50 m/s, and the pressure of a spraying belt is 20-30 kPa; the thickness of the prepared thin strip is 18-23 mu m, and the width of the thin strip is1～1.5mm；

4) Thin strip heat treatment: and heating the annealing furnace to the required crystallization temperature, then putting the quartz glass tube packaged with the thin strip into the furnace, preserving the heat for a certain period of time, and taking out for water quenching or air cooling.

7. The method of claim 6, wherein the raw material is one or more of Fe with a purity of 99.98 wt%, B with a purity of 99.95 wt%, industrial FeB alloy with a content of 18.38 wt% (impurity content less than 0.8 wt%), industrial FeP alloy with a P content of 27.1 wt% (impurity content less than 1.6 wt%), Cu with a purity of 99.95 wt%, C or industrial FeC alloy with a purity of 99.95 wt%, and Nb, Zr, V, Hf, Mo with a purity of 99.95 wt%.

8. The method for preparing Fe-B-P-C-Cu-M amorphous nanocrystalline magnetically soft alloy according to claim 6, wherein the key steps of alloy smelting are as follows: putting the volatile FeP alloy and the easy-to-splash pure boron at the bottom of a copper crucible, then putting pure carbon with relatively light mass, then putting pure iron, and finally putting one or more elements of Nb, Zr, V, Hf and Mo with relatively high melting point and relatively high atomic mass at the top for smelting; in order to ensure that the components of the master alloy ingot are uniform, the electric arc furnace is smelted for more than 4 times.

9. The method for preparing Fe-B-P-C-Cu-M amorphous nanocrystalline magnetically soft alloy according to claim 6, wherein the temperature of the heat treatment is 470-490 ℃; the heat treatment time is 5-10 min.

Technical Field

The invention belongs to the technical field of soft magnetic functional materials, relates to a silicon-free high saturation magnetization iron-based amorphous nanocrystalline soft magnetic alloy and a preparation method thereof, and particularly relates to a silicon-free iron-based amorphous nanocrystalline soft magnetic alloy with high carbon content and high amorphous forming capability and a preparation method thereof.

Background

Under the double pressure of energy shortages and environmental problems. It is important to improve the conversion efficiency of the equipment and reduce the loss of the equipment. In the electronic and power industry, the trend is to miniaturize, lighten and increase the efficiency of electric components, so higher requirements are put on the soft magnetic functional materials used in the electric components. Yoshizawa et al, Japan, first reported a Fe-Si-B-Cu-Nb alloy system in 1988. Through research and development for more than 20 years, the iron-based amorphous/nanocrystalline alloy has been mainly developed into three major systems, namely Finemet (Fe)_73.5Si_13.5B₉Cu₁Nb₃) The alloy may be selected from the group consisting of a series of alloys, Nanoperm (Fe-M-B, M ═ Zr, Hf, Nb, etc.) series alloys, and hipperm (Fe-Co-M-B, M ═ Zr, Hf, Nb, etc.) series alloys. A large amount of Hf, Zr, Nb and other elements are added into the Nanoperm and HIPPERM alloys, so that the production cost and the preparation process difficulty of the alloys are increased, the alloys are difficult to win in market competition, and the industrial production is not achieved. At present, only Finemet (Fe)_73.5Si_13.5B₉Cu₁Nb₃) The nanocrystalline magnetically soft alloy is industrially produced and applied. High initial permeability, low coercivity and loss are the greatest advantages of Finemet alloys, but their relatively low saturation induction (B)_s1.24T) limits its further use in electrical components. Therefore, the magnetic induction density (B) with high saturation is developed_s) The iron-based amorphous nanocrystalline soft magnetic alloy has great significance for promoting the development of electrical components towards miniaturization, light weight and high efficiency. NANOMETE (Fe-Si-B-P-Cu) nanocrystalline magnetically soft alloys were developed by Makino et al, Japan, 2009, whose saturation induction (B)_s) The development of amorphous nanocrystalline soft magnetic alloy materials is greatly promoted up to more than 1.80T, but as the alloy system has the iron content of up to 83 at.%, the alloy has atom clusters of about 3nm in a quenching state, and the thickness of an amorphous strip is only about 18 mu m, which indicates that the alloy has low amorphous forming capability. Therefore, the magnetic material is developed to have high saturation magnetic induction (B)_s) And iron-based amorphous soft magnetic alloys with high amorphous forming ability are particularly important.

The amorphous nano soft magnetic alloy developed at present contains more or less certain silicon elements, and aims to improve the amorphous forming capability of the alloy, refine crystal grains and reduce the coercive force (H)_c) At the same time, in the crystallization process, the silicon element is dissolved in the α -Fe lattice to reduce the exchange coupling effect between the ferromagnetic elements, which is not favorable for realizing high saturation magnetization (B)_s). The patent specification with application publication No. CN 106756643A provides a Fe-Si-B-P-Cu-C alloy system with high saturation magnetization, in the examples of which Fe_84.2Si₂B₉P₄Cu_0.5C_0.3Alloy, amorphous strip of 34 μm thickness prepared at 50m/s, having a saturation strength after annealing heat treatment at 450 ℃ (B)_s) Can reach 1.81T and the coercive force is 17A/m. This indicates that the addition of a trace amount of C element has a great effect on the improvement of the amorphous forming ability of the alloy, but the alloyThe coercive force is relatively high, and the self loss of the soft magnetic material in the use process is increased. Japanese patent application publication No. JP2013-185162A discloses a high saturation magnetization (B)_s) Fe-Si-B-P-Cu-alloy system of (1), Fe provided in example 6_85.1B₅P₉Cu_0.9Saturation magnetization of alloy (B)_s) Up to 1.75T, but the present alloy has a relatively low amorphous forming ability. Therefore, innovative and subversive component design ideas are needed to develop the iron-based amorphous nanocrystalline soft magnetic alloy with high iron content and high amorphous forming capability.

The atomic radius of the iron element is 117pm, the atomic radius of the carbon element is 77pm, the relative atomic radius difference is 15.2%, the possibility of topological disordered atomic arrangement of the amorphous alloy is increased by mixing the iron element and the carbon element, meanwhile, the iron element and the carbon element have 50kJ/mol, the bonding force is strong, the complexity of interaction between amorphous alloy atoms is increased by the content of the carbon element, and the amorphous forming capability, the saturation magnetization and the coercive force are all obviously influenced. Based on the analysis, the applicant invents an iron-based amorphous nanocrystalline soft magnetic alloy without silicon, high carbon and high saturation magnetization and a preparation method thereof.

Disclosure of Invention

Aiming at the problems of low amorphous forming capability of a Fe-Si-B-P-Cu alloy system and high coercive force of the Fe-Si-B-P-C-Cu alloy system, the invention provides a Fe-B-P-C-Cu-M system iron-based amorphous nanocrystalline soft magnetic alloy with no silicon, high carbon and high saturation magnetization, and invents an amorphous ribbon quenching process and a heat treatment process suitable for the alloy components. The alloy system has the advantages of simple production process, low cost, mature process, controllable product quality, suitability for large-scale production and the like, and can be widely applied to the fields of power, electronics, information transmission and conversion and the like.

A high saturation magnetization Fe-B-P-C-Cu-M amorphous nanocrystalline magnetically soft alloy is characterized in that the expression of the chemical composition of the magnetically soft alloy is Fe_xB_yP_zC_aCu_bM_cWherein x, y, x, a, B and c respectively represent the corresponding components Fe, B, P,C. Cu and M, and the following conditions are satisfied: x is more than or equal to 80 and less than or equal to 85, y is more than or equal to 4 and less than or equal to 10, z is more than or equal to 2 and less than or equal to 10, a is more than or equal to 3.5 and less than or equal to 7.5, b is more than or equal to 0.7 and less than or equal to 1.5, c is more than or equal to 0 and less than or equal to 2, x + y + z + a + b + c is 100, and M is one or more of Nb, Zr, V; has high amorphous forming ability and high saturation magnetic induction (B)_s) And low coercive force (H)_c)。

Furthermore, the soft magnetic alloy is a silicon-free low-phosphorus iron-based amorphous nanocrystalline soft magnetic alloy with high saturation magnetization, and the chemical composition expression of the soft magnetic alloy is Fe_xB_yP_zC_aCu_bWherein: x is 83.3, y is not less than 8 and not more than 9, z is not less than 3 and not more than 4, a is not less than 3.7 and not more than 4.2, B is not less than 0.7 and not more than 0.8, and x + y + z + a + B is 100, the alloy strip has excellent forming performance, is an amorphous strip in a quenched state, and has saturation magnetization (B) after annealing at 480 ℃ for 6min_s) Can reach 1.87T, coercive force (H)_c) As low as 10A/m.

Furthermore, the soft magnetic alloy is a silicon-free high-phosphorus type amorphous nanocrystalline alloy with high saturation magnetization, and the chemical composition expression of the soft magnetic alloy is Fe_xB_yP_zC_aCu_bWherein: x is 83, y is not less than 4.5 and not more than 5.5, z is not less than 7.5 and not more than 8.2, a is not less than 3.7 and not more than 4.2, B is not less than 0.9 and not more than 1.1, x + y + z + a + B is 100, the alloy has excellent forming performance of thin strip, is amorphous in quenching state, and has saturation magnetization (B) after annealing for 6min at 480 DEG C_s) Can reach 1.76T, and the coercive force is as low as 5.1A/m.

Furthermore, the chemical composition expression of the soft magnetic alloy is Fe_xB_yP_zC_aCu_bM_cWherein M is one or more of Nb, Zr, V, Hf and Mo, x, y, x, a, B and C respectively represent the atomic percentage of each corresponding component Fe, B, P, C, Cu and M, x is more than or equal to 82.5 and less than or equal to 83.5, y is more than or equal to 4 and less than or equal to 9.5, z is more than or equal to 2 and less than or equal to 9, a is more than or equal to 3.5 and less than or equal to 6, B is more than or equal to 0.8 and less than or equal to 1.1, C is more than or equal to 0.4 and less than or equal to 0.8, and x + y + z + a +.

Furthermore, the chemical composition expression of the soft magnetic alloy is Fe_xB_yP_zC_aCu_bM_cWherein: x is 83, y is more than or equal to 8 and less than or equal to 9, z is more than or equal to 2.35 and less than or equal to 2.55, a is more than or equal to 3.7 and less than or equal to 4.2, b is more than or equal to 0.9 and less than or equal to 1.1, and x + y + z + a + b + c is 100Is amorphous, and has saturation magnetization (B) after annealing at 480 deg.C for 6min_s) Can reach 1.89T and the coercive force is 17.07A/m.

The preparation method of the Fe-B-P-C-Cu-M amorphous nanocrystalline soft magnetic alloy with high saturation magnetization is characterized by comprising the following steps of:

1) preparing materials: pure Fe, pure B or industrial FeB alloy, industrial FeP alloy or pure P, pure Cu, pure C or industrial FeC alloy and pure metal M are adopted;

2) smelting mother alloy through setting the material inside non-consumable vacuum arc furnace and vacuum pumping to 5 × 10^-3Pa, smelting the alloy in an argon atmosphere with the purity of 99.99 percent, and repeatedly smelting each alloy ingot for at least more than 4 times;

3) the strip is prepared by vacuumizing a single-roller rotary quenching furnace to 5 × 10^-2Remelting a master alloy ingot under the protection of argon, and spraying the master alloy ingot on a copper roller rotating at a high speed; the linear speed of the copper roller is 40-50 m/s, and the pressure of a spraying belt is 20-30 kPa; the thickness of the prepared thin strip is 18-23 mu m, and the width of the thin strip is 1-1.5 mm;

4) thin strip heat treatment: and heating the annealing furnace to the required crystallization temperature, then putting the quartz glass tube packaged with the thin strip into the furnace, preserving the heat for a certain period of time, and taking out for water quenching or air cooling.

Preferably, the raw material is one or more metal elements selected from the group consisting of Fe with a purity of 99.98 wt%, B with a purity of 99.95 wt%, or industrial FeB alloy with a content of 18.38 wt% (impurity content less than 0.8 wt%), industrial FeP alloy with a P content of 27.1 wt% (impurity content less than 1.6 wt%), Cu with a purity of 99.95 wt%, C with a purity of 99.95 wt%, or industrial FeC alloy, and Nb, Zr, V, Hf, Mo, etc., with a purity of 99.95 wt%.

Preferably, the key steps of alloy smelting are as follows: putting the volatile FeP alloy and the easy-to-splash pure boron at the bottom of a copper crucible, then putting pure carbon with relatively light mass, then putting pure iron, and finally putting one or more elements of Nb, Zr, V, Hf and Mo with relatively high melting point and relatively high atomic mass at the top for smelting; in order to ensure that the components of the master alloy ingot are uniform, the electric arc furnace is smelted for more than 4 times.

Preferably, the temperature of the heat treatment is 470-490 ℃; the heat treatment time is 5-10 min.

Compared with the prior iron-based amorphous nanocrystalline alloy, the alloy of the invention mainly has the following advantages:

(1) the Fe-B-P-C-Cu-M alloy system does not contain Si element, so that the improvement of the mass percentage content of the magnetic element Fe can be effectively ensured, and the saturation magnetization of the alloy is further improved;

(2) the Fe-B-P-C-Cu-M alloy system contains relatively high C element, and can obviously improve the amorphous forming capability of the alloy and reduce the melting point of the alloy, so that the melting temperature can be reduced during alloy melting, the energy is saved, the cost is reduced, and the industrial application is facilitated.

(3) The Fe-B-P-C-Cu-M alloy system contains relatively high C element, and can obviously improve the amorphous forming capability of the alloy, so that the critical thickness of an amorphous alloy strip can be increased, the lamination coefficient of an iron core can be increased when the amorphous alloy strip is wound into the iron core, and the loss reduction of the iron core is improved.

(4) In the Fe-B-P-C-Cu-M alloy system, the addition of Nb, Zr, V, Hf and Mo elements not only can refine the grain size of the alloy and improve the stability of Fe-B compounds, but also can further improve the amorphous forming capability of the alloy by proper addition.

In conclusion, the Fe-B-P-C-Cu-M alloy disclosed by the invention improves the saturation magnetic flux density and the amorphous forming capability of the alloy, reduces the loss of an iron core and the production cost of the alloy, is beneficial to large-scale marketization production and market competition, and meets the requirements of the development of the existing electronic power devices towards miniaturization, high efficiency, light weight and greenness to the greatest extent.

Drawings

FIG. 1 shows example 1 (Fe) of the present invention_83.3B₉P₃C₄Cu_0.7) Example 2 (Fe)_82.9B₉P₃C₄Cu_1.1) Example 3 (Fe)₈₃B₉P_2.4C₄Cu₁V_0.6) Example 4 (Fe)₈₃B₄P₈C₄Cu₁) And comparative example 1 (Fe)_83.3Si₄B₉P₃Cu_0.7) As-cast XRD profile of the alloy;

FIG. 2 shows example 1 (Fe) of the present invention_83.3B₉P₃C₄Cu_0.7) Example 2 (Fe)_82.9B₉P₃C₄Cu_1.1) Example 3 (Fe)₈₃B₉P_2.4C₄Cu₁V_0.6) Example 4 (Fe)₈₃C₄B₄P₈Cu₁) And comparative example 1 (Fe)_83.3Si₄B₉P₃Cu_0.7) A DSC curve of the alloy;

FIG. 3 shows example 1 (Fe) of the present invention_83.3B₉P₃C₄Cu_0.7) Example 2 (Fe)_82.9B₉P₃C₄Cu_1.1) Example 3 (Fe)₈₃B₉P_2.4C₄Cu₁V_0.6) Example 4 (Fe)₈₃C₄B₄P₈Cu₁) And comparative example 1 (Fe)_83.3Si₄B₉P₃Cu_0.7) Coercive force (H) of the alloy after annealing at 350-480 ℃_c) A curve;

FIG. 4 shows example 1 (Fe) of the present invention_83.3B₉P₃C₄Cu_0.7) Example 2 (Fe)_82.9B₉P₃C₄Cu_1.1) Example 3 (Fe)₈₃B₉P_2.4C₄Cu₁V_0.6) Example 4 (Fe)₈₃C₄B₄P₈Cu₁) And comparative example 1 (Fe)_83.3Si₄B₉P₃Cu_0.7) Saturation induction (B) of alloy after annealing at 350-480 ℃_s) Curve line.

Detailed Description

In order to further illustrate the present invention, the following examples are further provided to illustrate the preparation method of an iron-based amorphous nanocrystalline alloy. It should be understood that these examples are presented in the light of the technical solution of the present invention, and the detailed embodiments and specific procedures are given only for further illustrating the features and advantages of the present invention, not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.