CN111218625A

CN111218625A - Soft magnetic Co-based bulk amorphous alloy with high saturation magnetic induction intensity and preparation method thereof

Info

Publication number: CN111218625A
Application number: CN202010100201.4A
Authority: CN
Inventors: 张伟; 李艳辉; 黄大玮
Original assignee: Dalian University of Technology
Current assignee: Dalian University of Technology
Priority date: 2020-02-18
Filing date: 2020-02-18
Publication date: 2020-06-02
Anticipated expiration: 2040-02-18
Also published as: CN111218625B

Abstract

The invention provides a soft magnetic Co-based bulk amorphous alloy with high saturation magnetic induction, which has the following composition formula: co_aFe_bNi_cB_dSi_eP_fC_gA, b, c, d, e, f and g respectively represent the atom percentage content of each constituent element, and satisfy: 35<a is not less than 65, b is not less than 10 and not more than 35, c is not less than 0 and not more than 5, b + c is not less than 10 and not more than 35, d is not less than 5 and not more than 20, e is not less than 5 and not more than 10, f is not less than 0 and not more than 5, g is not less than 3 and not more than g, d + e + f + g is not less than 20 and not more than 30, and a + b + c + d + e + f is 100. The invention solves the problem that the prior Co-based bulk amorphous alloy contains front transition group elements or rare earth elements, so that the alloy is difficult to have strong amorphous forming capability and high B content_sAnd high cost.

Description

Soft magnetic Co-based bulk amorphous alloy with high saturation magnetic induction intensity and preparation method thereof

Technical Field

The invention relates to the technical field of new materials, in particular to a material without front transitionGroup metals and rare earth elements, having high saturation magnetic induction (B)_s) And Curie temperature (T)_c) Low coercive force (H)_c) High-strength Co-based bulk amorphous alloy and a preparation method thereof.

Background

The amorphous alloy (also called metallic glass) has physical, chemical and mechanical properties superior to those of common crystalline metallic materials, such as high strength and hardness, high toughness, low elastic modulus, high resistivity, high corrosion resistance, superplastic processing formability in a supercooled liquid phase region and the like, due to the unique long-range disordered and short-range ordered atomic arrangement structure. The soft magnetic material also has excellent soft magnetic performance for Fe and Co base amorphous alloy. The amorphous alloy has wide application prospect in the fields of energy, environment, power electronics, precision machinery, biomedicine and the like.

Fe. The disordered structure of the Co-based amorphous alloy ensures that the Co-based amorphous alloy has very small magnetocrystalline anisotropy, and the nail rolling of a magnetic domain wall is weakened without structural defects such as crystal boundary, dislocation and the like, so that the Co-based amorphous alloy has excellent soft magnetic properties such as Hc, low iron loss, high magnetic conductivity and the like. In 1967, U.S. researchers Duwez et al [ J.Appl.Phys.38(1967):4096] first reported Fe-P-C system amorphous alloys with soft magnetic properties, and subsequently, a plurality of Fe, Co based soft magnetic amorphous alloy systems were successively developed. In the 70-80 s of the 20 th century, soft magnetic amorphous alloys were first industrialized by Allied Chemical company in the united states. In recent years, soft magnetic amorphous alloys have been gradually applied to the fields of transformers and motor cores, switching power supplies, magnetic sensors, magnetic shields and the like. Compared with Fe-based amorphous alloy, the Co-based amorphous alloy has higher magnetic permeability and nearly zero magnetostriction coefficient, and can keep higher magnetic permeability and low loss particularly under high-frequency conditions. The Co-based amorphous alloy also has excellent mechanical properties such as high strength and high wear resistance. Therefore, Co-based amorphous alloys are used in the fields of magnetic amplifiers, high-frequency transformers, inductors, magnetic sensors, magnetic head cores, and the like in high-frequency switching power supplies.

However, although the Co-based amorphous alloy has excellent soft magnetic properties and poor amorphous forming ability, it is currently mainly applied in a low dimensional shape such as a thin strip, a filament and a powder, which is usedNot only increases the preparation difficulty, but also limits the application range. Therefore, researchers have been working on improving the amorphous forming ability of Co-based alloys and developing bulk amorphous alloys. In 2000, Inoue et al (Mater. Trans., JIM,41(2000):1256, a Japanese researcher]The first report of Co-based Co₄₀Fe₂₂Nb₆Zr₂B₃₀Bulk amorphous alloy forming amorphous critical diameter (d)_c) Is 1.0mm, B_sAnd H_c0.41T and 1.2A/m respectively, and has higher effective permeability and lower magnetostriction coefficient. In 2003, Inoue et al [ Nature Mater.,2(2003):661]And further develop d_cIs 2mm of Co₄₃Fe₂₀Ta_5.5B_31.5Bulk amorphous alloy of B_sIs 0.49T, H_cIs 0.25A/m. Thereafter, researchers have developed soft magnetic Co-based bulk amorphous alloys in alloy systems such as (Co, Fe) -ETM-B (ETM means an early transition metal element), (Co, Fe) -ETM- (B, Si), (Co, Fe) -ETM-B-RE (RE means a rare earth element), and Co-ETM- (P, B) in succession. The components of the existing Co-based bulk amorphous alloy are analyzed, and the Co-based bulk amorphous alloy contains early transition group metals such as Nb, Ta and Mo, or rare earth elements such as Dy, Y and Gd. The addition of these early transition group or rare earth elements, although advantageous for improving the amorphous forming ability of the alloy, results in B of the alloy_sGreatly reduced. In addition, elements such as Nb, Ta, Dy, Gd and the like are rare metals, the price of raw materials is high, the elements are easy to oxidize in the preparation process, the requirement on preparation conditions is high, and the raw materials and the preparation cost of the Co-based bulk amorphous alloy are increased.

In summary, a novel soft magnetic Co-based bulk amorphous alloy with strong amorphous forming ability and no early transition metals or rare earth elements was developed to increase B content in the alloy_sAnd the raw material and preparation cost can be reduced, the application of the Co-based bulk amorphous alloy is further promoted, and the miniaturization and the light weight of power electronic equipment and components are realized.

Disclosure of Invention

Aiming at the problem that the prior Co-based bulk amorphous alloy contains an early transition group element or a rare earth element, the alloy is difficult to have strong amorphous forming capability and high B_sThe invention provides a high-B-content rare earth-containing catalyst which does not contain an early transition group element or a rare earth element_sAnd T_cLow H_cThe high-strength Co-based bulk amorphous alloy can be prepared into a bulk amorphous alloy bar with the diameter of 1-3 mm by a copper mold casting method in the air, and B is a high-strength Co-based bulk amorphous alloy bar_s0.95 to 1.24T, H_c0.5 to 4.6A/m, mu at 1kHz_eIs 16200-30600, T_c451-516 ℃, the compressive yield strength is 3.2-3.6 GPa, and the compressive plastic strain is 0.3-2.5%.

The technical means adopted by the invention are as follows:

the invention provides a soft magnetic Co-based bulk amorphous alloy with high saturation magnetic induction, which has the following composition formula: co_aFe_bNi_cB_dSi_eP_fC_gA, b, c, d, e, f and g respectively represent the atom percentage content of each constituent element, and satisfy: 35<a≤65，10≤b≤35，0≤c≤5，10≤b+c≤35，5≤d≤20，5≤e≤10，0≤f≤5，0≤g≤5，3≤f+g，20≤d+e+f+g≤30，a+b+c+d+e+f＝100。

Further, the compositional formula of the alloy is Co₄₀Fe₃₅B₁₅Si₇P₃Or Co₅₀Fe₂₅B₁₅Si₇P₃。

Further, the compositional formula of the alloy is Co₄₅Fe₃₀B₁₄Si₇P₂C₂。

Further, the alloy has a saturation magnetic induction of 0.95-1.24T, a coercive force of 0.5-4.6A/m, an effective magnetic permeability of 11700-18500 at 1kHz, a Curie temperature of 451-516 ℃, a compressive yield strength of 3.2-3.6 GPa, and a compressive plastic strain of 0.3-2.5%.

The invention also provides a preparation method of the soft magnetic Co-based bulk amorphous alloy with high saturation magnetic induction, which comprises the following steps:

the method comprises the following steps: ingredient Co_aFe_bNi_cB_dSi_eP_fC_g

Selecting Co, Fe, Ni, Si, B, C and FeP alloy raw materials with the purity higher than 99 percent, and weighing and proportioning the raw materials according to the alloy composition proportion;

step two: master alloy ingot melting

Putting the mixed raw materials weighed in the step one into a crucible of an induction melting furnace, and melting in an argon or nitrogen atmosphere to obtain a master alloy ingot with uniform components; if the alloy does not contain P element, smelting the alloy in a non-consumable electric arc furnace in the argon or nitrogen atmosphere to obtain a master alloy ingot;

step three: preparation of bulk amorphous alloy

Crushing the master alloy ingot, then putting the crushed master alloy ingot into a quartz tube, and preparing a block sample by a copper mold casting method, namely heating the master alloy ingot to a molten state by induction melting under the atmosphere of argon, nitrogen or atmosphere, and spraying an alloy melt into a copper mold by using high-pressure gas to prepare an amorphous alloy bar with the diameter of 1-3 mm.

Compared with the prior art, the invention has the following advantages:

1. the Co-based bulk amorphous alloy provided by the invention only consists of ferromagnetic Co, Fe and Ni and non (similar) metal elements B, Si, P and C, and does not contain front transition metal and rare earth elements; the alloy has good amorphous forming capability, and can form a block amorphous alloy bar with dc of 1-3 mm.

2. The Co-based bulk amorphous alloy provided by the invention has excellent soft magnetic performance, and B_sThe maximum can reach 1.24T, T_cThe maximum temperature is 516 ℃, which is much higher than all Co-based bulk amorphous alloys reported in the prior publication, and simultaneously has low H_cAnd higher mu_eHigh B_sIs favorable for realizing the miniaturization and high T of the device_cThe application of the high-temperature-resistant coating to the high-temperature field can be expanded;

3. the Co-based bulk amorphous alloy provided by the invention has the yield strength of 3.2-3.6 GPa and certain compressive plastic deformation capacity;

4. the Co-based bulk amorphous alloy provided by the invention does not contain rare metals, can be prepared in air, and has low raw material and preparation cost.

The Co-based bulk amorphous alloy material provided by the invention has strong amorphous forming capability and high B_sAnd T_cLow H_cThe soft magnetic material has the advantages of high strength and the like, is low in raw material cost and simple in preparation process, and can be used as a high-performance soft magnetic material to be applied to electronic power equipment and components.

For the reasons mentioned above, the present invention can be widely applied to the field of new materials.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is a 2mm diameter Co₄₀Fe₃₅Si₇B₁₅P₃X-ray diffraction spectrum of the alloy copper die casting rod-shaped sample.

FIG. 2 is Co₄₀Fe₃₅Si₇B₁₅P₃Differential scanning calorimetry curve of amorphous alloy strip.

FIG. 3 is Co₄₀Fe₃₅Si₇B₁₅P₃Hysteresis loop of amorphous alloy.

FIG. 4 is a 1mm diameter Co₄₀Fe₃₅Si₇B₁₅P₃Compressive stress-strain curves of amorphous alloy rod-like samples.

Detailed Description

It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.

The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.

Further, saturation magnetic induction B of the alloy_s0.95-1.24T, coercive force H_c0.5-4.6A/m, effective magnetic permeability mu under 1kHz_e11700 to 18500, Curie temperature T_c451-516 ℃, the compressive yield strength is 3.2-3.6 GPa, and the compressive plastic strain is 0.3-2.5%.

the method comprises the following steps: ingredients

step two: master alloy ingot melting

step three: preparation of bulk amorphous alloy

The present invention will be described in further detail with reference to the accompanying drawings and examples.

Example 1: co₄₀Fe₃₅B₁₅Si₇P₃

The method comprises the following steps: ingredients

Selecting Co, Fe, B, Si and Fe with purity higher than 99%₃Weighing and proportioning the P alloy raw material according to the alloy composition proportion;

step two: preparation of master alloy ingot

Putting the mixed raw materials weighed in the step one into a graphite crucible arranged in a vacuum induction melting furnace, and melting in an argon or nitrogen atmosphere to obtain a master alloy ingot with uniform components;

step three: preparation of amorphous strips

Crushing the master alloy ingot, putting the crushed master alloy ingot into a quartz tube, and preparing a rapid quenching strip sample by adopting a single-roller strip throwing method. Heating a master alloy ingot to a molten state by induction melting in an argon or nitrogen atmosphere, and then spraying an alloy melt onto a copper roller rotating at a high speed by using high-pressure gas, wherein the linear speed of the copper roller is about 40m/s, the width of a prepared rapid quenching strip is about 1mm, and the thickness of the prepared rapid quenching strip is about 25 mu m;

step four: preparation of bulk amorphous

Crushing a master alloy ingot, then putting the crushed master alloy ingot into a quartz tube, and preparing a block sample by a copper mold casting method, namely heating the master alloy ingot to a molten state by induction melting under the atmosphere of argon or nitrogen, and then spraying an alloy melt into a copper mold by using high-pressure gas to prepare an amorphous alloy bar with the diameter of 2 mm;

step five: characterization of alloy Structure

The structure of the rod-shaped sample was measured by an X-ray diffractometer (XRD), and the results are shown in FIG. 1. As can be seen from the figure, no sharp diffraction peak appears in the spectrum of the sample, which indicates that the sample is a completely amorphous structure;

step six: performance testing of alloy samples

The thermal properties of the alloys were evaluated by Differential Scanning Calorimeter (DSC), and the results are shown in FIG. 2. From this, the glass transition temperature T of the alloy is known_gAnd width of supercooled liquid phase region Δ T_x534 ℃ and 31 ℃ respectively. The magnetic properties of the samples were measured using a Vibrating Sample Magnetometer (VSM) and a direct current soft magnetic measuring instrument (B-H Loop Tracer), the hysteresis Loop of which is shown in FIG. 3. Measuring the saturation magnetic induction B of the sample_sAnd coercive force H_cAre respectively 1.24T and 4.6Am^-1. The effective permeability at 1kHz was 12700. The compressive stress-strain curve of a rod-shaped specimen having a diameter of 1mm and a length of 2mm was measured by a universal mechanical tester, and the result is shown in FIG. 4. The compressive yield strength was measured to be 3.5GPa, and the compressive strain at break was measured to be 2.5%. The details are listed in table 1.

Example 2: co₅₀Fe₂₅B₁₅Si₇P₃

The method comprises the following steps: selecting Co, Fe, Si, B and Fe with purity higher than 99%₃The raw materials such as the P alloy are weighed and proportioned according to the alloy composition proportion.

The second, third, fourth, fifth and sixth steps are the same as the example 1, and finally the amorphous bar with the diameter of 1.5mm is prepared. The performance data are shown in table 1.

Example 3: co₆₀Fe₁₅B₁₅Si₇P₃

The second, third, fourth, fifth and sixth steps are the same as the example 1, and finally the amorphous bar with the diameter of 1.0mm is prepared. The performance data are shown in table 1.

Example 4: co₆₅Fe₁₃B₁₂Si₅P₅

Example 5: co₄₁Fe₃₀B₂₀Si₅P₄

The second, third, fourth, fifth and sixth steps are the same as the example 1, and finally the amorphous bar with the diameter of 2.0mm is prepared. The performance data are shown in table 1.

Example 6: co₄₅Fe₃₅B₅Si₁₀P₅

Example 7: co₄₃Fe₃₁Ni₁B₁₅Si₇P₃

The method comprises the following steps: selecting Co, Fe, Ni, Si, B and Fe with purity higher than 99%₃The raw materials such as the P alloy are weighed and proportioned according to the alloy composition proportion.

The second, third, fourth, fifth and sixth steps are the same as the example 1, and finally the amorphous bar with the diameter of 3.0mm is prepared. The performance data are shown in table 1.

Example 8: co₅₀Fe₂₂Ni₃B₁₅Si₅P₅

Example 9: co₆₀Fe₁₀Ni₅B₁₃Si₇P₅

Example 10: co₄₀Fe₃₅B₁₃Si₇C₅

The method comprises the following steps: selecting Co, Fe, Si, B, C and other raw materials with the purity higher than 99 percent, and weighing and proportioning according to the alloy composition proportion.

Step two: and (3) putting the weighed mixed raw materials in the step one into a graphite crucible in a vacuum induction melting furnace or melting the mixed raw materials in a non-consumable electric arc furnace in an argon or nitrogen atmosphere to obtain a master alloy ingot with uniform components.

The third, fourth, fifth and sixth steps are the same as the example 1, and finally the amorphous bar with the diameter of 1.5mm is prepared. The performance data are shown in table 1.

Example 11: co₄₅Fe₃₀B₁₄Si₇P₂C₂

The method comprises the following steps: selecting Co, Fe, Si, B, C and Fe with purity higher than 99%₃The raw materials such as the P alloy are weighed and proportioned according to the alloy composition proportion.

Example 12: co₃₆Fe₃₄B₁₅Si₁₀P₄C₁

Comparative example 1: co₇₁Mo₉P₁₄B₆

Selected from the documents [ Intermetallics,71(2016):7-11.]. The performance indexes of the amorphous alloy are listed in table 1. Since the alloy contains Mo element at a concentration of up to 9 at% (atomic percentage), B is contained in the alloy_sOnly 0.24T, which is much lower than the alloys provided by the present invention. In addition, T of the alloy_cLower, only 44 ℃, and lower plastic deformability, only 0.1% compressive plastic strain.

Comparative example 2: co₄₀Fe₂₂Nb₆Zr₂B₃₀

Selected from the group of documents [ Itoi T, et al, mater. trans.,9(2000):1256]. The performance indexes of the amorphous alloy are listed in table 1. The alloy contains 6 at.% Nb and 2 at.% Zr element, B_sOnly 0.41T, which is much lower than the alloys provided by the present invention.

Comparative example 3: co₄₀Fe₂₂Ta_5.5B_31.5

Selected from the literature [ Inoue A, et al, Nature Mater.,2(2003):661]. The performance indexes of the amorphous alloy are listed in table 1. The alloy has a high mu_eBut containing 5.5 at.% of Ta element, B_sOnly 0.49T, which is much lower than the alloys provided by the present invention. In addition, the alloy has no obvious yield phenomenon and plastic deformation at room temperature.

Comparative example 4: co₄₁Fe₂₈Mo₄Y₅B₂₂

Selected from the literature [ Man Q, et al, J.Alloys Compd.,504S (2010): S132]. The performance indexes of the amorphous alloy are listed in table 1. The alloy contains 4 at.% Mo and 5 at.% Y element, B_sOnly 0.80T, much lower than the alloys provided by the present invention.

Comparative example 5: co₄₀Fe₂₂Nb₆Dy₂B₃₀

Selected from Chinese patent publication No. CN102373388A]. The performance indexes of the amorphous alloy are listed in table 1. The alloy contains 6 at.% of Nb and 2 at.% of Dy element, B_sOnly 0.42T, much lower than the alloys provided by the present invention.

Comparative example 6: [ (Co)_0.6Fe_0.4)_0.75B_0.2Si_0.05]₉₆Nb₄

Selected from the literature [ Shen B, et al, J.Appl.Phys.100(2006):013515]. The performance indexes of the amorphous alloy are listed in table 1. The alloy contains 4 at.% Nb, B thereof_s0.97T, which is the highest value in the Co-based bulk amorphous alloy which is published and reported, but is lower than the alloy provided by the invention. In addition, the alloy has no significant yield and plastic deformability.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

TABLE 1 thermal Properties, glass-forming ability, magnetic Properties and mechanical Properties of Co-based bulk amorphous alloys of examples and comparative examplesEnergy parameter, wherein T_gIs the glass transition temperature,. DELTA.T_xIn the supercooled liquid phase region, d_cIs the critical dimension of the amorphous alloy sample, B_sTo saturate the magnetic induction, H_cIs coercive force, mu_e(1kHz) as effective permeability, σ_c,yFor compressive yield strength,. epsilon_c,pIs a compressive plastic strain

Claims

1. A soft magnetic Co-based bulk amorphous alloy with high saturation induction, characterized in that: the alloy has the composition formula: co_aFe_bNi_cB_dSi_eP_fC_gA, b, c, d, e, f and g respectively represent the atom percentage content of each constituent element, and satisfy: 35<a≤65，10≤b≤35，0≤c≤5，10≤b+c≤35，5≤d≤20，5≤e≤10，0≤f≤5，0≤g≤5，3≤f+g，20≤d+e+f+g≤30，a+b+c+d+e+f＝100。

2. A soft magnetic Co-based bulk amorphous alloy with high saturation induction according to claim 1, characterized in that: the alloy has the composition formula of Co₄₀Fe₃₅B₁₅Si₇P₃Or Co₅₀Fe₂₅B₁₅Si₇P₃。

3. A soft magnetic Co-based bulk amorphous alloy with high saturation induction according to claim 1, characterized in that: the alloy has the composition formula of Co₄₅Fe₃₀B₁₄Si₇P₂C₂。

4. A soft magnetic Co-based bulk amorphous alloy with high saturation induction according to claim 1 or 2, characterized in that: the alloy has the saturation magnetic induction of 0.95-1.24T, the coercive force of 0.5-4.6A/m, the effective magnetic conductivity of 11700-18500 at 1kHz, the Curie temperature of 451-516 ℃, the compressive yield strength of 3.2-3.6 GPa and the compressive plastic strain of 0.3-2.5%.

5. A method for producing a soft magnetic Co-based bulk amorphous alloy with high saturation induction according to claim 1, comprising the steps of:

the method comprises the following steps: ingredient Co_aFe_bNi_cB_dSi_eP_fC_g

step two: master alloy ingot melting

step three: preparation of bulk amorphous alloy