High-performance magnetically soft alloy and preparation method thereof

Abstract

The invention relates to the field of magnetic materials, and discloses a high-performance magnetically soft alloy, and the composition of the magnetically soft alloy is Fe < 15.5 > Ni < 80-x-y > Mo < 4.5 > Ti < x > Si < y > A < z >, wherein A is one or more of Tm, B and Mn, and x is more than or equal to 0 and less than or equal to 20wt%; 0 < = y < = 20 wt%; 0 < = z < = 10 wt%, and x, y and z are not 0 at the same time. Compared with an original formula, the soft magnetic alloy has the advantages that the initial magnetic conductivity ui is improved by 129 times, and the maximum magnetic conductivity um is improved by 9 times.

Description

Technical Field

[0001] The invention relates to the field of magnetic materials, and in particular to a high-performance soft magnetic alloy and a preparation method thereof. Background Art

[0002] Soft magnetic material refers to a material whose magnetization occurs when the coercive force Hc is not greater than 1000A / m. The maximum magnetization intensity can be achieved with the smallest external magnetic field. Its magnetic performance characteristics are magnetic materials with low coercive force and high magnetic permeability.

[0003] Because of the magnetic properties of this soft magnetic material, it is widely used in special functional fields with magneto-electric conversion and is a widely used functional material. In particular, the development of the new economic situation has put forward higher requirements for soft magnetic material devices, requiring the devices to develop in the direction of miniaturization, light weight, energy saving, high frequency, and high temperature resistance.

[0004] The magnetic parameters of the traditional high permeability alloy 1J85, such as initial permeability, maximum permeability, saturation magnetization and coercive force, are 3×104~6×104, 12×104~22×104, 0.7~1.6Am-1, 0.6~0.63T. Especially for today's increasingly severe electromagnetic pollution, the current 1J85 (its iron content is 14%~16%, nickel content is 75%~81%, and molybdenum content is between 4.0%~5.2%) soft magnetic alloy can no longer meet the use requirements, and higher performance soft magnetic alloys are needed to achieve miniaturization, lightweight, energy saving and high frequency of device functions. Summary of the invention

[0005] The main purpose of the present invention is to solve the technical problem that the soft magnetic alloy in the prior art cannot meet the requirements of miniaturization, light weight, energy saving and high frequency. A high-performance soft magnetic alloy, the soft magnetic alloy is composed of:

[0006] Fe 15.5 Ni 80-x-y Mo 4.5 Ti x Si y A z

[0007] Wherein, A is one or more of the elements Tm, B, and Mn, 0≤x≤20wt%; 0≤y≤20wt%; 0≤z≤10wt%, and x, y, and z are not 0 at the same time.

[0008] The present invention also provides a method for preparing a high-performance soft magnetic alloy, comprising the following steps:

[0009] Prepare raw materials according to the composition of soft magnetic alloy and weigh them accurately in proportion;

[0010] Under the protection of inert gas, the raw materials are melted to prepare a columnar ingot;

[0011] Stress relief annealing the alloy in vacuum to obtain a stress relief ingot;

[0012] Rolling the stress-relieved ingot to obtain a rolled soft magnetic alloy;

[0013] The rolled soft magnetic alloy is subjected to hydrogen heat treatment to obtain a high-performance soft magnetic alloy.

[0014] As a preferred technical solution, the specific process of smelting is:

[0015] The equipment is a magnetic suspension melting furnace, vacuum degree ≤10 -3 Pa, inert gas protection;

[0016] The smelting steps are:

[0017] Charge: Place in layers from fusible to refractory; Ni and Fe at the bottom, Mo and Tm at the top;

[0018] Vacuuming: The melting chamber is evacuated to ≤10 -3 Pa, fill with Ar gas to 0.05MPa, repeat 3 times to remove residual oxygen;

[0019] Melting: Start the electromagnetic suspension system and heat to 1600-1650℃ through high-frequency induction to ensure that Tm is completely melted; keep the liquid state for 10-15 minutes after melting, and use electromagnetic stirring to ensure uniform composition;

[0020] Casting: Rapid water-cooled copper mold casting to obtain columnar crystal ingots.

[0021] As a preferred technical solution, the parameters of the stress relief annealing are:

[0022] Temperature: 850-900℃; Time: 4-6 hours, furnace cooled to 300℃ and then air cooled; Vacuum degree: ≤10 -3 Pa.

[0023] As a preferred technical solution, the rolling process is as follows:

[0024] Pretreatment: The ingot surface is machined to be flat and the thickness is reduced to 80% of the original thickness;

[0025] Cold rolling process: rolling in multiple passes, with the reduction in each pass ≤ 20%;

[0026] Intermediate annealing: After each pass, anneal at 750℃ in a vacuum furnace for 30 minutes;

[0027] The total deformation is controlled at 60-90% depending on the target size.

[0028] As a preferred technical solution, the process of hydrogen heat treatment is:

[0029] The equipment is a tubular furnace, which is fed with high-purity hydrogen with a dew point of ≤-40°C;

[0030] The process parameters are as follows:

[0031] Heating: 5-10℃ / min to 1200℃, keep warm for 2-4 hours;

[0032] Cooling: Slowly cool in the furnace at 1-2℃ / min to 200℃, then air cool.

[0033] The present invention has the following beneficial effects:

[0034] In the present invention, the alloying treatment of the base alloy Fe-Ni-Mo alloy by adding the necessary elements Ti and Si and the additional elements Tm or B or Mn can make the solidification structure of the alloy after smelting finer, the alloy structure dense and uniform, the grains have a good energy balance effect in the cleaning process, and eliminate the internal stress of the alloy during the solidification process and the inhomogeneity of the grain size and phase structure. These phase structures belong to the phase, which is an important reason for the improvement of the magnetic performance parameters of the soft magnetic alloy.

[0035] The alloy prepared by the patent of the present invention, due to its good soft magnetic properties, can effectively improve the sensor to give better signals and achieve high sensitivity, high reliability and high reliability of sensing compared to traditional 1J85 alloy.

[0036] Compared with the original formula, the initial magnetic permeability ui of the soft magnetic alloy of the present invention is increased by 129 times, and the maximum magnetic permeability um is increased by 9 times. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 It is a schematic diagram of the preparation method of the patented alloy of the present invention;

[0038] Figure 2 Fe 15.5 Ni 80-x-y Mo 4.5 Ti x Si y A z Metallographic microscope image of the alloy, where:

[0039] (a)Fe 15.5 Ni 80 Mo 4.5 Alloy, x, y, z = 0;

[0040] (b)Fe 15.5 Ni 79 Mo 4.5Ti1 alloy, x = 1, y, z = 0;

[0041] (c)Fe 15.5 Ni 79 Mo 4.5 Si1 alloy, x, z = 0, y = 1;

[0042] (d)Fe 15.5 Ni 78 Mo 4.5 Ti1Si1 alloy, x, y = 1, z = 0;

[0043] (e)Fe 15.5 Ni 77.3 Mo 4.5 Ti1Tm 0.7 alloy, x = 1, y = 0, z = 0.7;

[0044] (f)Fe 15.5 Ni 77.3 Mo 4.5 Si1Tm 0.5 Alloy, x = 0, y = 1, z = 0.5;

[0045] (g)Fe 15.5 Ni 77.3 Mo 4.5 Ti1B 0.7 alloy, x = 1, y = 0, z = 0.7;

[0046] (h)Fe 15.5 Ni 77.3 Mo 4.5 Si1B 0.7 Alloy, x = 0, y = 1, z = 0.7;

[0047] (i)Fe 15.5 Ni 77.3 Mo 4.5 Ti1Si1Tm 0.7 Alloy, x = 1, y = 1, z = 0.7;

[0048] (j)Fe15.5Ni 77.3 Mo 4.5 Ti1Si1Mn 0.7 Alloy, x = 1, y = 1, z = 0.7;

[0049] (k)Fe 15.5 Ni 76.8 Mo 4.5 Ti1Si1Mn 0.5 Tm 0.7 Alloy, x=1, y=1, z=1.2. DETAILED DESCRIPTION

[0050] For ease of understanding, the specific process of the embodiment of the present invention is described below. The preparation method of the high-performance soft magnetic alloy in the embodiment of the present invention is as follows:

[0051] Prepare raw materials according to the composition of soft magnetic alloy and weigh them accurately in proportion;

[0052] Under the protection of inert gas, the raw materials are melted to prepare a columnar ingot; the specific process of the melting is:

[0053] The equipment is a magnetic suspension melting furnace, vacuum degree ≤10 -3 Pa, inert gas protection;

[0054] The smelting steps are:

[0055] Charge: Place in layers from fusible to refractory; Ni and Fe at the bottom, Mo and Tm at the top;

[0056] Vacuuming: The melting chamber is evacuated to ≤10 -3 Pa, fill with Ar gas to 0.05MPa, repeat 3 times to remove residual oxygen;

[0057] Melting: Start the electromagnetic suspension system and heat to 1600-1650℃ through high-frequency induction to ensure that Tm is completely melted. Keep the liquid state for 10-15 minutes after melting, and stir with electromagnetic to ensure uniform composition;

[0058] Casting: Rapid water-cooled copper mold casting to obtain columnar crystal ingots.

[0059] The alloy is subjected to stress relief annealing in vacuum to obtain a stress relief ingot; the stress relief annealing parameters are:

[0060] Temperature: 850-900℃; Time: 4-6 hours, furnace cooled to 300℃ and then air cooled; Vacuum degree: ≤10 -3 Pa.

[0061] The stress-relieved ingot is rolled to obtain a rolled soft magnetic alloy; the rolling process is as follows:

[0062] Pretreatment: The ingot surface is machined to be flat and the thickness is reduced to 80% of the original thickness;

[0063] Cold rolling process: rolling in multiple passes, with the reduction in each pass ≤ 20%;

[0064] Intermediate annealing: After each pass, anneal at 750℃ in a vacuum furnace for 30 minutes;

[0065] The total deformation is controlled at 60-90% depending on the target size.

[0066] The rolled soft magnetic alloy is subjected to hydrogen heat treatment to obtain a high-performance soft magnetic alloy. The process of the hydrogen heat treatment is:

[0067] The equipment is a tubular furnace, which is fed with high-purity hydrogen with a dew point of ≤-40°C;

[0068] The process parameters are as follows:

[0069] Heating: 5-10℃ / min to 1200℃, keep warm for 2-4 hours;

[0070] Cooling: Slowly cool in the furnace at 1-2℃ / min to 200℃, then air cool.

[0071] The alloy of the present invention is prepared according to the above process.

[0072] The alloying treatment of the base alloy Fe-Ni-Mo alloy by adding the necessary elements Ti and Si and the additional elements Tm, B or Mn can make Fe 15.5 Ni 80-x-y Mo 4.5 Ti x Si y A z Alloy, after smelting, the solidification structure has fine grains, the alloy structure is dense and uniform, and the internal stress, grain size and phase structure inhomogeneity of the alloy during solidification are eliminated. The specific implementation effect can be seen in the metallographic microstructure of the alloy after solidification. Figure 2 .

[0073] from Figure 2 It can be seen that (a) is the cast microstructure morphology of the alloy when x, y, z = 0, and (bk) is the microstructure morphology of different Ti, Si, Tm, B, and Mn contents (x, y, z contents are different). It can be seen that the morphology in Figure (a) is mostly irregular and coarse, and the solidification structure is uncontrollable, so before the product is used, an annealing process must be added to control the product. The grain boundaries of the alloy in Figure (bk) become regular and polygonal. With the addition of Ti, Si, Tm, B, and Mn elements, the grain size of the alloy continues to increase, accompanied by the appearance of annealing twins. When the grain size increases, the number of grain boundaries decreases, and the movement of the magnetic domain wall becomes easier, which makes magnetization easier, and the magnetic induction becomes higher, so that the soft magnetic properties such as magnetic permeability increase.

[0074] Table 1. Fe 15.5 Ni 80-x-y Mo 4.5 Ti x Si y A z Comparison of Magnetic Properties of Alloy Examples

[0075]

[0076] Comparison of Examples 1 and 2 in Table 1 shows that for Fe 15.5 Ni 80-x-y Mo 4.5 Ti x Si y A z Soft magnetic alloy, when x, y, z = 0, Fe 15.5 Ni 80 Mo 4.5 The alloy is the original formula of 1J85, and its initial magnetic permeability ui, maximum magnetic permeability um, magnetic induction intensity Bs, and coercive force Hc are 6213, 27570, 0.76T, and 4.11A / m respectively; when Ti is added to the matrix formula, the formula Fe 15.5 Ni 80-x-y Mo 4.5 Ti x Si y (Tm / B / Mn) z In the time when x=1, y, z=0, the alloy composition is Fe 15.5 Ni 79 Mo 4.5 The initial magnetic permeability ui, maximum magnetic permeability um, magnetic induction intensity Bs and coercive force Hc of the Ti1 alloy are 76850, 117100, 0.90T and 4.11A / m, respectively; among them, compared with the original formula embodiment 1 of 1j85, the initial magnetic permeability ui and the maximum magnetic permeability um are increased by 123 times, and the maximum magnetic permeability um is increased by 4 times.

[0077] Similarly, by comparing Example 1 with Example 3, it can be found that in the formula

[0078] Fe 15.5 Ni 80-x-y Mo 4.5 Ti x Si y (Tm / B / Mn) z When x, z = 0, y = 1, the alloy composition is Fe 15.5 Ni 79 Mo 4.5 Si1, the initial magnetic permeability ui, maximum magnetic permeability um, magnetic induction intensity Bs, and coercive force Hc of the alloy are 80420, 158451, 0.9366T, and 0.57A / m, respectively; among which the initial magnetic permeability ui and the maximum magnetic permeability um are increased by 129 times and 5 times compared with the original formula embodiment 1 of 1j85. The reason for the increase of its soft magnetic properties is: Figure 2It can be seen that the alloy containing Ti and Si elements has a continuously increasing grain size, accompanied by the appearance of annealing twins. When the grain size increases, the number of grain boundaries decreases, and the movement of the magnetic domain wall becomes easier, which makes magnetization easier, and the magnetic induction becomes higher, so that the soft magnetic properties such as magnetic permeability increase.

[0079] Table 2. Fe 15.5 Ni 80-x-y Mo 4.5 Ti x Si y A z Comparison of Magnetic Properties of Alloy Examples

[0080]

[0081] From Table 2, we can see that in Fe 15.5 Ni 80-x-y Mo 4.5 Ti x Si y (Tm / B / Mn) z In the soft magnetic alloy formula, when x, y, z = 0; x = 1, y, z = 0; x, z = 0, y = 1; x, y = 1, z = 0; x = 1, y = 0, z = 0.7; x = 0, y = 1, z = 0.5; x = 1, y = 0, z = 0.7; x = 0, y = 1, z = 0.7; x = 1, y = 1, z = 0.7; x = 1, y = 1, z = 0.7; x = 1, y = 1, z = 0.7; x = 1, y = 1, z = 1.2, the alloy formula Fe 15.5 Ni 80 Mo 4.5 ;Fe 15.5 Ni 79 Mo 4.5 Ti1;Fe 15.5 Ni 79 Mo 4.5 Si1;Fe 15.5 Ni 78 Mo 4.5 Ti1Si1;Fe 15.5 Ni 77.3 Mo 4.5 Ti1Tm 0.7 ;Fe 15.5 Ni 77.3 Mo 4.5 Si1Tm 0.5 ;Fe 15.5 Ni 77.3 Mo 4.5 Ti1B 0.7 ;Fe 15.5 Ni 77.3 Mo 4.5 Si1B 0.7; Fe 15.5 Ni 77.3 Mo 4.5 Ti1Si1Tm 0.7 ; Fe 15.5 Ni 77.3 Mo 4.5 Ti1Si1Mn 0.7 ; Fe 15.5 Ni 76.8 Mo 4.5 Ti1Si1Mn 0.5 Tm 0.7 The initial permeability μi, maximum permeability μm, magnetic induction intensity Bs, and coercive force Hc of 15.5 Ni 80-x-y Mo 4.5 Ti x Si y (Tm / B / Mn) z alloy (where 0 < x ≤ 20 wt%; 0 < y ≤ 20 wt%; 0 < z ≤ 10 wt%) are greatly improved in magnetic properties. The grain size of the alloy is uniform during solidification, and the crystallinity is good, effectively improving the soft magnetic properties of the material. Among them, the highest initial relative permeability reaches 48090, the maximum relative permeability reaches 407584, and the saturation magnetic induction intensity reaches 0.8 T, which is much higher than that of the original matrix alloy of 1J85.

[0082] As described above, the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high performance soft magnetic alloy, characterized in that: The components of the high performance soft magnetic alloy are: Want 15.5 In 80-x-y Know 4.5 Of x To y A z Wherein, A is one or more of the elements Tm, B, and Mn, 0≤x≤20wt%; 0≤y≤20wt%; 0≤z≤10wt%, and x, y, and z are not 0 at the same time.

2. The method for preparing a high-performance soft magnetic alloy according to claim 1, characterized in that: The following steps are involved: Prepare raw materials according to the composition of soft magnetic alloy and weigh them accurately in proportion; Under the protection of inert gas, the raw materials are melted to prepare a columnar ingot; Stress relief annealing the alloy in vacuum to obtain a stress relief ingot; Rolling the stress-relieved ingot to obtain a rolled soft magnetic alloy; The rolled soft magnetic alloy is subjected to hydrogen heat treatment to obtain a high-performance soft magnetic alloy.

3. The method for preparing a high-performance soft magnetic alloy according to claim 2, characterized in that: The specific process of the smelting is: The equipment is a magnetic suspension melting furnace, with a vacuum degree of ≤10-3Pa and inert gas protection; The smelting steps are: Charge: Place in layers from fusible to refractory; Ni and Fe at the bottom, Mo and Tm at the top; Vacuuming: evacuate the melting chamber to ≤10-3Pa, fill it with Ar gas to 0.05MPa, repeat 3 times to remove residual oxygen; Melting: Start the electromagnetic suspension system and heat to 1600-1650℃ through high-frequency induction to ensure that Tm is completely melted. Keep the liquid state for 10-15 minutes after melting, and stir with electromagnetic to ensure uniform composition; Casting: Rapid water-cooled copper mold casting to obtain columnar crystal ingots.

4. The method for preparing a high performance soft magnetic alloy according to claim 2, characterized in that: The parameters of the stress relief annealing are: Temperature: 850-900℃; Time: 4-6 hours, furnace cooled to 300℃ and then air cooled; Vacuum degree: ≤10-3Pa.

5. The method for preparing a high performance soft magnetic alloy according to claim 2, characterized in that: The rolling process is as follows: Pretreatment: The ingot surface is machined to be flat and the thickness is reduced to 80% of the original thickness; Cold rolling process: rolling in multiple passes, with the reduction in each pass ≤ 20%; Intermediate annealing: After each pass, anneal at 750℃ in a vacuum furnace for 30 minutes; The total deformation is controlled at 60-90% depending on the target size.

6. The method for preparing a high performance soft magnetic alloy according to claim 2, characterized in that: The process of the hydrogen heat treatment is: The equipment is a tubular furnace, which is fed with high-purity hydrogen with a dew point of ≤-40°C; The process parameters are as follows: Heating: 5-10℃ / min to 1200℃, keep warm for 2-4 hours; Cooling: Slowly cool in the furnace at 1-2℃ / min to 200℃, then air cool.

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