CN110306130B

CN110306130B - Fe-Si-B-P-Cu-Nb amorphous nanocrystalline magnetically soft alloy with high iron content and preparation method thereof

Info

Publication number: CN110306130B
Application number: CN201910590589.8A
Authority: CN
Inventors: 惠希东; 窦正旭; 吕旷; 李育洛
Original assignee: Luoyang Zhonghe Amorphous Technology Co ltd; University of Science and Technology Beijing USTB
Current assignee: Luoyang Zhonghe Amorphous Technology Co ltd; University of Science and Technology Beijing USTB
Priority date: 2019-07-02
Filing date: 2019-07-02
Publication date: 2021-05-07
Anticipated expiration: 2039-07-02
Also published as: CN110306130A

Abstract

A Fe-Si-B-P-Cu-Nb series amorphous nanocrystalline alloy with high iron content and a preparation method thereof. Its chemical composition expression is Fe _a Si _b B _c P _d Cu _e Nb _f , where a, b, c, d, e, f represent the corresponding components of Fe, Si, B, P, Cu, and Nb, respectively. Atomic percentage, and meet the following conditions: 85.5≤a≤86.5, 1≤b≤2, 8≤c≤9.8, 2.6≤d≤4, 0≤e≤1, 0≤f≤0.55, a+b+c+ d+e+f=100. The alloy has low cost, and the existing single-roller spin quenching technology can be used to prepare quenched nanocrystalline and quenched amorphous soft magnetic thin ribbons. The addition of a small amount of Cu and Nb elements improves the amorphous forming ability and toughness of the alloy. , saturation magnetization and refinement of nanocrystalline grain size. Among them, the saturation magnetization of the quenched nanocrystalline thin ribbon in the alloy of the present invention reaches 1.82T. The saturation magnetization of the nanocrystalline thin ribbon after crystallization and annealing of the amorphous thin ribbon reaches 1.84T. The prepared amorphous nanocrystalline alloy is suitable for the fields of electric power industry transformer core, inverter welding machine, new energy, wireless charging, digital and automation, etc. as devices such as motors and transformers.

Description

Fe-Si-B-P-Cu-Nb amorphous nanocrystalline magnetically soft alloy with high iron content and preparation method thereof

Technical Field

The invention belongs to the field of amorphous nanocrystalline alloys, and particularly relates to a Fe-Si-B-P-Cu-Nb amorphous nanocrystalline alloy with high iron content and high saturation magnetization.

Background

The amorphous alloy refers to an alloy with long-range disorder and short-range order in the atomic arrangement in the internal structure. Under the condition of enough cooling speed, the viscosity of the alloy is rapidly increased, the time required by atoms or molecules to reach internal equilibrium is delayed by orders of magnitude, and the crystallization process is not in time, so that the disordered liquid structure is preserved to form the amorphous alloy. With the advent of Fe-based amorphous alloys in the end of the 60 s of the 20 th century, it was found that it has excellent ferromagnetism. The existing silicon steel sheet used as the transformer core has the defects of large loss and complex production process, and can not meet the requirement of energy conservation. The amorphous soft magnetic alloy has excellent performances such as high resistivity, low coercive force, low iron loss and the like, but the saturation magnetic induction intensity is low, so that the application range of the amorphous soft magnetic alloy is limited. Aiming at the defects of the amorphous soft magnetic alloy, the nanocrystalline soft magnetic alloy is further developed. The nanocrystalline soft magnetic alloy is a special structure in which fine nano particles are uniformly distributed on an amorphous matrix, and compared with a single amorphous phase, the double-phase structure improves the saturation magnetic induction intensity, reduces the internal stress and has good high-frequency soft magnetic performance. At present, amorphous and nanocrystalline soft magnetic alloys are widely applied to the fields of power, electronics, information transmission and conversion and the like as important energy-saving materials.

The amorphous nanocrystalline soft magnetic thin ribbon currently under research and application is mainly divided into the following two types: (1) amorphous or nanocrystalline alloys with high saturation magnetization. Including FeSiB-based amorphous alloys and nanome-type (fesibpuc) nanocrystalline alloys. The saturation magnetic induction of the FeSiB amorphous alloy is higher and is about 1.4-1.65T, and the typical alloy component is Fe₇₈Si₉B₁₃The Bs is only 1.56T, and although the Bs is not as good as that of silicon steel (1.8-2.03T), other magnetic properties such as coercive force, iron loss and the like are obviously superior to those of the silicon steel. The method is applied to the fields of transformers and the like at present. The nanome type nanocrystalline alloy emerging in recent years has high Bs (generally about 1.8T) which is accompanied by high Fe content and is far higher than the FeSiB amorphous alloy, but the ribbon preparation process is extremely complex, the crystallization annealing process is very harsh, and the requirement of the prior art of industrial production cannot be met, so that the nanome type nanocrystalline alloy can not be industrially applied so far. (2) Nanocrystalline alloys of high magnetic permeability. The mainstream of the current commercial nanocrystalline alloy is also Finemet alloy, the alloy is FeCuNbSiB, the magnetic conductivity of the alloy reaches more than 100000,but its saturation magnetization is low (B)_s1.25T), which limits its application to power electronics small devices and power transformers.

Disclosure of Invention

The invention relates to a Fe-B-Si-P-Cu-Nb amorphous nanocrystalline soft magnetic alloy with high iron content and high saturation magnetization. The alloy has low cost, good amorphous forming ability and high saturation magnetization, and can be widely used in the fields of electric power, electron and information transmission and conversion.

The present invention differs from the previously reported research work and invention applications in alloy design in that:

A. the content of Fe in the amorphous nanocrystalline alloy ranges from 85.5 to 86.5 percent (atomic percentage), and the high saturation magnetization of the nanocrystalline is ensured by the extremely high content of magnetic elements.

B. The addition of proper amounts of metalloid elements Si, B and P ensures the amorphous forming ability of the alloy, and the Fe-B binary system has the highest amorphous forming ability. Therefore, in the case of such a high Fe content, it is still necessary to ensure the highest B content in the metalloid, which is in the range of 8 to 9.8 atomic percent. In addition, the addition of proper amounts of P and Si further improves the amorphous forming capability of the alloy. In particular, since C faces the problem of composition control and the problem of strip brittleness in industrial applications, the present alloy system does not contain C element (except for unavoidable C in the master alloy raw material).

C. The addition of the transition metal Nb plays an important role in the toughness of Fe-based amorphous and nanocrystalline strips and the control of nanocrystalline grain size, but the addition of excessive Nb can reduce the saturation magnetization of nanocrystals, so that a small amount of Nb is added into the alloy.

An Fe-Si-B-P-Cu-Nb amorphous nanocrystalline alloy with high Fe content is characterized in that the alloy has saturation magnetization. The chemical composition expression of the alloy is Fe_aSi_bB_cP_dCu_eNb_fWherein a, B, c, d, e and f respectively represent the atomic percent of each corresponding component Fe, Si, B, P, Cu and Nb, and satisfy the following conditions: a is more than or equal to 85.5 and less than or equal to 86.5, b is more than or equal to 1 and less than or equal to 2, c is more than or equal to 8 and less than or equal to 9.8, d is more than or equal to 2.6 and less than or equal to 4,0≤e≤1,0≤f≤0.55，a+b+c+d+e+f＝100。

further, when f is 0, the chemical composition expression is Fe_aSi_bB_cP_dCu_eThe components are characterized in that: a is 86, b is more than or equal to 1 and less than or equal to 2, c is more than or equal to 8 and less than or equal to 9.8, d is more than or equal to 2.6 and less than or equal to 4, e is more than or equal to 0.3 and less than or equal to 1, and a + b + c + d + e is 100.

Further, when e is 0, the chemical composition expression thereof is Fe_aSi_bB_cP_dNb_fThe components are characterized in that: 85.75-86.5 of a, 1.05-1.8 of b, 8.9 of c, 3 of d, 0.55 of f and 100 of a + b + c + d + f, the alloy has excellent amorphous forming capability, and the saturation magnetization of a quenched amorphous ribbon after nano crystallization reaches 1.84T.

Further, the chemical composition expression of the alloy is Fe_aSi_bB_cP_dCu_eNb_fThe alloy has excellent amorphous forming ability, and the saturation magnetization of the quenched amorphous strip after nano crystallization reaches 1.69T.

The preparation method of the amorphous nanocrystalline alloy is characterized by comprising the following steps:

1) preparing materials: preparing Fe with the purity of 99.98 wt%, Si with the purity of 99.5 wt%, industrial FeB alloy with the B content of 18.38 wt% (impurity content is lower than 0.8 wt%), industrial FeP alloy with the P content of 27.1 wt% (impurity content is lower than 1.6 wt%), Cu with the purity of 99.5 wt% and Nb with the purity of 99.7 wt% according to the atom percentage;

2) smelting a master alloy: placing the prepared raw materials in a non-consumable vacuum electric arc furnace, vacuumizing to 5 x 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 5 times;

3) preparation of the strip: vacuumizing the single-roller rotary quenching furnace to 2 x 10^-2Pa, weighing the master alloy ingot under the protection of argonMelting and spraying the molten alloy on a copper roller rotating at high speed; the linear speed of the copper roller is 30-40 m/s, and the pressure of a spraying belt is 20-30 kPa; the thickness of the prepared thin strip is 23-30 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.

The invention has the beneficial effects that: provides a nanocrystalline alloy with high saturation magnetization and a preparation method thereof,

the invented soft magnetic alloy has the following characteristics:

(1) the nanocrystalline soft magnetic alloy has a high saturation magnetization. Chemical composition expression is Fe₈₆Si_1.3B_8.9P_3.5Cu_0.3And Fe₈₆Si_1.8B_8.9P₃Cu_0.3The saturation magnetization of the quenched nanocrystalline thin band reaches 1.79T and 1.82T. Chemical composition expression is Fe_86.25Si_1.3B_8.9P₃Nb_0.55The saturation magnetization of the amorphous ribbon after annealing for 6min at 470 ℃ reaches 1.84T. Chemical composition expression is Fe_85.75Si_1.8B_8.9P₃Cu_0.3Nb_0.25The saturation magnetization of the amorphous ribbon after annealing at 430 ℃ for 10min reaches 1.69T.

(2) The maximum content of Nb is 0.55 percent (atomic percent), the maximum content of Cu is 1 percent (atomic percent), and the alloy does not contain C elements with more difficult component control. The cost of the alloy is reduced, and the feasibility of alloy smelting and the accuracy of components are ensured.

(3) The amorphous forming ability of the alloy can be improved by properly adding Nb, which creates conditions for further industrialization. Chemical composition expression is Fe_86.5Si_1.05B_8.9P₃Nb_0.55And Fe_85.75Si_1.8B_8.9P₃Cu_0.3Nb_0.25Alloy XRD of (a) showed both amorphous states.

Drawings

FIG. 1 is an atomic percent Fe of the present invention₈₆Si_1.3B_8.9P_3.5Cu_0.3、Fe₈₆Si_1.3B_9.2P_3.2Cu_0.3、 Fe₈₆Si_1.3B_9.5P_2.9Cu_0.3、Fe₈₆Si_1.3B_9.8P_2.6Cu_0.3、Fe₈₆Si_1.8B_8.9P₃Cu_0.3XRD profile of the nanocrystalline thin band of (a);

FIG. 2 is an atomic percent Fe of the present invention_85.75Si_1.8B_8.9P₃Nb_0.55、Fe_86.25Si_1.3B_8.9P₃Nb_0.55、 Fe_86.5Si_1.05B_8.9P₃Nb_0.55XRD curve of the amorphous thin strip of (3);

FIG. 3 is an atomic percent Fe of the present invention_85.75Si_1.8B_8.9P₃Cu_0.3Nb_0.25XRD curve of the amorphous thin strip of (3);

FIG. 4 is an atomic percent Fe of the present invention_85.75Si_1.8B_8.9P₃Cu_0.3Nb_0.25、Fe_85.5Si_1.8B_8.9P₃Cu_0.3Nb_0.5DSC curve of the amorphous thin band of (a);

FIG. 5 is an atomic percent Fe of the present invention₈₆Si_1.3B_8.9P_3.5Cu_0.3、Fe₈₆Si_1.3B_9.2P_3.2Cu_0.3、 Fe₈₆Si_1.3B_9.5P_2.9Cu_0.3、Fe₈₆Si_1.3B_9.8P_2.6Cu_0.3、Fe₈₆Si_1.8B_8.9P₃Cu_0.3The VSM curve of the nanocrystalline thin strip of (a);

FIG. 6 is an atomic percent Fe of the present invention_85.75Si_1.8B_8.9P₃Nb_0.55、Fe_86.25Si_1.3B_8.9P₃Nb_0.55、 Fe_86.5Si_1.05B_8.9P₃Nb_0.55470 ℃ of amorphous ribbonAnnealing the VSM curve after 6 min;

FIG. 7 is an atomic percent Fe of the present invention_85.75Si_1.8B_8.9P₃Cu_0.3Nb_0.25The amorphous ribbon of (2) was annealed at 430 ℃ for 10min to obtain a VSM curve.

Detailed Description

Table 1 shows some examples of the alloys of the present invention, and the preparation, characterization and properties of the alloys of the examples of Table 1 are described in detail below.

(1) Preparing materials: the 14 alloys of table 1 were each dosed in the atomic percent content described above using high precision electron analysis with Fe of 99.98 wt% purity, Si of 99.5 wt%, a commercial FeB alloy with a B content of 18.38 wt% (impurity content less than 0.8 wt%), a commercial FeP alloy with a P content of 27.1 wt% (impurity content less than 1.6 wt%), Cu of 99.5 wt% purity, and Nb balance of 99.7 wt%.

(2) Smelting a master alloy: the prepared raw materials are put into a copper crucible of a non-consumable vacuum arc furnace, FeB alloy and FeP alloy which are easy to splash or volatilize are placed at the bottom of the copper crucible, and then block Fe is paved above the copper crucible. Closing the oven door, and evacuating to 5 × 10 with mechanical pump and molecular pump^-3Below Pa, filling a proper amount of argon with the purity of 99.99 percent. Before the alloy is smelted, a Ti ingot is smelted to absorb the residual oxygen in the furnace, and then the alloy raw material is smelted. In order to ensure that the components of the master alloy ingot are uniform, the alloy ingot is turned over by a material turning shovel to be smelted again after each smelting, and each alloy ingot is smelted repeatedly at least for more than 5 times.

(3) Preparation of the strip: vacuumizing the single-roller rotary quenching furnace to 2 x 10^-2And Pa, remelting the master alloy ingot under the protection of argon, and spraying the remelted master alloy ingot onto a copper roller rotating at a high speed to prepare an amorphous strip. The process conditions for preparing the 14 alloy thin strips are as follows: the linear speed of the copper roller is set to be 30-40 m/s, the pressure of the spraying belt is 20-30 kPa, the thickness of the prepared thin belt is 23-30 mu m, and the width 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.

(5) Benefit toAnd (4) detecting the structure of the sample by using an X-ray diffractometer to obtain an XRD curve of the thin strip. Determination of the crystallization temperature T of thin bands by means of differential scanning calorimetry (NETZSCH STA type) at a heating rate of 20K/min_xPhase transition and melting point, and obtaining the DSC curve of the thin strip. The VSM curve of the thin strip was measured by a PPMS apparatus (manufactured by Quantum Design, USA), and the saturation magnetization of the thin strip was analyzed.

TABLE 1 basic parameters and magnetic Properties of iron-based amorphous nanocrystalline thin ribbons with high iron content

In the table, a represents an amorphous body, and NC represents a nanocrystal.

Claims

1. a high Fe content Fe-Si-BP-Cu-Nb amorphous nanocrystalline alloy, it is characterized in that this alloy has saturation magnetization; The chemical composition expression of alloy is Fe _a Si _b B _c P _d Cu _e Nb _f , where a, b, c, d, e, f represent the atomic percentage of each corresponding component Fe, Si, B, P, Cu, Nb, respectively, and satisfy the following conditions: 85.5≤a≤86.5, 1≤b ≤2,8≤c≤9.8,2.6≤d≤4,0≤e≤1,0≤f≤0.55, a+b+c+d+e+f=100;

The preparation method of the amorphous nanocrystalline alloy comprises the following steps:

1) Ingredients: Fe with a purity of 99.98wt%, Si with a purity of 99.5wt%, an industrial FeB alloy with a B content of 18.38wt%, an industrial FeP alloy with a P content of 27.1wt%, and Cu with a purity of 99.5wt% and Nb with a purity of 99.7wt%, according to the atomic percentage content;

2) Master alloy smelting: place the prepared raw materials in a non-consumable vacuum arc furnace, evacuate to 5×10 ^-3 Pa, and then smelt the alloy in an argon atmosphere with a purity of 99.99%. Repeat smelting more than 5 times;

3) Preparation of strip: vacuumize the single-roll rotary quenching furnace to 2×10 ^-2 Pa, remelt the master alloy ingot under argon protection, and spray it on the high-speed rotating copper roll; the line speed of the copper roll is 30～ 40m/s, the pressure of the spray belt is 20-30kPa; the thickness of the thin strip prepared is 23-30μm, and the width is 1-1.5mm;

4) Thin strip heat treatment: the annealing furnace is heated up to the required crystallization temperature, and then the quartz glass tube encapsulated with the thin strip is put into the furnace, and after holding for a certain period of time, it is taken out and quenched by water.

2. a kind of high Fe content Fe _a Si _b B _c P _d Cu _e Nb _f amorphous nanocrystalline alloy according to claim 1, is characterized in that when f=0, its chemical composition expression is Fe _a Si _b B _c P _d Cu _e , and its composition characteristics are: a=86, 1≤b≤2, 8≤c≤9.8, 2.6≤d≤4, 0.3≤e≤1, a+b+c+d+e =100, the alloy strip has excellent forming properties, the quenched state is nanocrystalline thin strip, and its saturation magnetization in the quenched state reaches 1.82T.

3. a kind of high Fe content Fe _a Si _b B _c P _d Cu _e Nb _f amorphous nanocrystalline alloy according to claim 1 is characterized in that when e=0, its chemical composition expression is Fe _a Si _b B _c P _d Nb _f , and its compositional characteristics are: 85.75≤a≤86.5, 1.05≤b≤1.8, c=8.9, d=3, f=0.55, a+b+c+d+f=100, the The alloy has excellent amorphous forming ability, and the saturation magnetization of the quenched amorphous thin ribbon after nano-crystallization reaches 1.84T.

4. a kind of high Fe content Fe _a Si _b B _c P _d Cu _e Nb _f amorphous nanocrystalline alloy according to claim 1, it is characterized in that the chemical composition expression of alloy is Fe _a Si _b B _c P _d Cu _e Nb _f , the atomic percentage of each component in the formula satisfies the following conditions: 85.5≤a≤85.75, b=1.8, c=8.9, d=3, e=0.3, 0.25≤f≤0.5, a+b+c+d +e+f=100, the alloy has excellent amorphous forming ability, and the saturation magnetization of the quenched amorphous ribbon after nano-crystallization reaches 1.69T.