WO2019119637A1 - 一种铁基非晶合金及其制备方法 - Google Patents

一种铁基非晶合金及其制备方法 Download PDF

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WO2019119637A1
WO2019119637A1 PCT/CN2018/076206 CN2018076206W WO2019119637A1 WO 2019119637 A1 WO2019119637 A1 WO 2019119637A1 CN 2018076206 W CN2018076206 W CN 2018076206W WO 2019119637 A1 WO2019119637 A1 WO 2019119637A1
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iron
amorphous alloy
based amorphous
alloy
rare earth
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French (fr)
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杨东
李庆华
庞靖
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Qingdao Yunlu Advanced Materials Technology Co Ltd
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Qingdao Yunlu Advanced Materials Technology Co Ltd
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Priority to KR1020197024549A priority Critical patent/KR102293540B1/ko
Priority to EP18891889.0A priority patent/EP3572548B1/en
Priority to US16/482,701 priority patent/US11970761B2/en
Priority to PL18891889T priority patent/PL3572548T3/pl
Publication of WO2019119637A1 publication Critical patent/WO2019119637A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/02—Amorphous alloys with iron as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/003—Making ferrous alloys making amorphous alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15308—Amorphous metallic alloys, e.g. glassy metals based on Fe/Ni
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15341—Preparation processes therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/02—Magnetic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15325—Amorphous metallic alloys, e.g. glassy metals containing rare earths

Definitions

  • the invention relates to the technical field of magnetic materials, in particular to an iron-based amorphous alloy and a preparation method thereof.
  • iron-based amorphous material As an excellent soft magnetic amorphous material, iron-based amorphous material has been favored by researchers all over the world since its production. It has high magnetic permeability, low coercive force, low loss and high saturation magnetic induction. Favored by the industry.
  • the improvement of saturation magnetic density can reduce the magnetic core
  • it will reduce the material cost of other aspects of the transformer, thereby reducing the overall cost of the transformer; on the other hand, the higher saturation magnetic density can realize the design of high-capacity transformer. Based on this, researchers continue to study the development of components in highly saturated amorphous materials.
  • the disclosure discloses an amorphous alloy composition of Fe a Si b B c C d in the patent CN100549205, wherein a is 76 to 83.5 atom%, b is 12 atom% or less, c is 8 to 18 atom%, and d is 0.01. Up to 3 at%, wherein the Fe-based amorphous alloy ribbon has a saturation magnetic flux density of 1.6 T or more after annealing, and a maximum of about 1.67 T.
  • the patent elaborates on the reasonable proportional control of C and Si and ensures that the C segregation layer has a peak in the range of 2-20 nm on the surface, and can prepare Fe-based amorphous alloy strip with low loss, reduced embrittlement and thermal instability.
  • the distribution of the C segregation layer on the surface of the strip is relatively demanding.
  • the unevenness of the depth and range of the segregation layer of the inner portion C of the strip can cause uneven stress release and partially cause fragile problems.
  • Japanese Laid-Open Patent Publication No. Hei 6-220592 discloses a composition of an amorphous alloy ribbon represented by Fe a Co b Si c B d M x ; the atomic percentage thereof is: 60 ⁇ a ⁇ 83, 3 ⁇ b ⁇ 20, 80 ⁇ a + b ⁇ 86, 1 ⁇ c ⁇ 10, 11 ⁇ d ⁇ 16, and M is at least one of Sn and Cu.
  • Co in this patent can effectively improve the saturation magnetic induction of amorphous materials; however, Co is a relatively expensive element, although the Co-containing iron-based amorphous alloy ribbon has a relatively high saturation magnetic density, but the cost is too high. The mass production of this alloy material is severely restricted, and its use is limited to those where higher quality is required.
  • the existence of the nuclear dot form induces the surface crystallization of the strip, which is not conducive to the antegrade production of the belt; and the high-quality P alloy smelting process is quite complicated, and industrial production is difficult.
  • the patent illustrates the possibility of P addition in high-saturation amorphous, but does not provide a reasonable explanation and explanation for industrial production.
  • Japanese Patent Publication No. S57-185957 also proposes a replacement method for B in a conventional amorphous alloy by replacing 1-10% of P with an atomic percentage.
  • the patent discloses that the improvement of P can improve the ability to form an amorphous state. Function, but the patent does not specifically mention the annealing process containing P amorphous.
  • the P-containing amorphous ribbon has weak oxidation resistance, requires very low oxygen content during annealing, and is annealed in a conventional unprotected atmosphere. It is extremely easy to oxidize; experimental studies show that under the unprotected atmosphere, the percentage of P atoms is more than 1%, and the annealing temperature is about 200 °C.
  • the surface of the strip after annealing can show a light blue oxidation color.
  • the higher the P content, the material The higher the annealing temperature, the more severe the oxidation, the normal annealing temperature is obviously higher than 200 °C, and the surface with severe oxidation will show a deep blue and purple surface morphology. Because the strip is oxidized, the core loss of the material is abnormally large. All in all, the severity of annealing severely limits the industrialization of such alloys.
  • the technical problem to be solved by the present invention is to provide an iron-based amorphous alloy.
  • the iron-based amorphous alloy provided by the present application has the characteristics of high saturation magnetic induction, excellent soft magnetic properties, and high process directivity.
  • the present application provides an iron-based amorphous alloy as shown in formula (I).
  • d is the concentration of RE in the iron-based amorphous alloy, 10 ppm ⁇ d ⁇ 30 ppm.
  • the iron-based amorphous alloy has a saturation magnetic induction of ⁇ 1.63T.
  • the atomic percentage of the Fe is 83.2 ⁇ a ⁇ 86.8.
  • the atomic percentage of the B is 12.2 ⁇ b ⁇ 14.5.
  • the atomic percentage of the Si is 2.5 ⁇ c ⁇ 3.5.
  • the RE is selected from one or more of La, Ce, Nd and Yb, and the concentration of the RE is 15 ppm ⁇ d ⁇ 25 ppm.
  • the application also provides a method for preparing an iron-based amorphous alloy, comprising:
  • the raw material after the compounding is smelted, and the molten steel reaches the target temperature during the smelting process, and then the rare earth alloy is added;
  • the molten melt is subjected to a single roll quenching to obtain an iron-based amorphous alloy
  • the rare earth alloy is added in an amount such that the concentration of the rare earth element in the iron-based amorphous alloy is 10 ppm to 30 ppm;
  • the target temperature is from 1450 to 1500 °C.
  • the iron-based amorphous alloy is in a completely amorphous state, and has a critical state of at least 30 ⁇ m and a width of 100 to 300 mm.
  • the method further comprises:
  • the iron-based amorphous alloy after quenching in a single roll is subjected to heat treatment
  • the heat treatment temperature is 300 to 380 ° C, and the heat treatment time is 30 to 150 min.
  • the core loss of the iron-based amorphous alloy is less than 0.16 W/kg at 50 Hz, 1.30 T; the core loss of the iron-based amorphous alloy is less than 0.20 W at 50 Hz, 1.40 T. /kg.
  • the present application provides an iron-based amorphous alloy represented by the formula Fe a B b Si c RE d , which includes Fe, Si, B and RE, wherein Fe, Si and B are favorable for forming iron with high saturation magnetic induction strength
  • RE can effectively reduce dissolved oxygen in the alloy, thereby significantly reducing the formation of other high melting point slag, reducing the content of high melting point slag, effectively reducing the casting temperature of the amorphous ribbon, and avoiding temperature drop.
  • other high melting point slags accumulate at the mouth of the mouth and produce heterogeneous nucleation in the strip matrix. Therefore, the iron-based amorphous alloy provided by the present application has the advantages of high saturation magnetic induction, excellent soft magnetic properties, and high process directivity due to the addition and control of the contents of Fe, Si, B, and RE.
  • the present invention improves the molten steel by the addition of rare earth trace elements on the basis of suitable principal component design, and solves the high saturation magnetic induction intensity amorphous alloy.
  • the material of the material is straightforward, and an amorphous alloy strip with high saturation magnetic induction, excellent soft magnetic properties and high process directivity is obtained.
  • the embodiment of the present application discloses an iron-based amorphous alloy as shown in formula (I).
  • d is the concentration of RE in the iron-based amorphous alloy, 10 ppm ⁇ d ⁇ 30 ppm.
  • Fe as a soft magnetic element, is a guarantee element for high saturation magnetic induction values. If the content of Fe is too low, the saturation magnetic induction is low, that is, its atomic percentage a ⁇ 83%, and the saturation magnetic induction density is lower than 1.63T; if the content is too high, the amorphous forming ability of the iron-based amorphous alloy is insufficient, and the thermal stability is poor. .
  • the atomic percentage of Fe in the present application is 83.0 ⁇ a ⁇ 87.0; in some embodiments, the atomic percentage of Fe is 83.2 ⁇ a ⁇ 86.8; in some embodiments, the Fe The atomic percentage is 85 ⁇ a ⁇ 86.6; more specifically, the atomic percentage of Fe is 83.7, 84, 84.3, 84.8, 85, 85.2, 85.6, 86.0, 86.2, 86.6 or 86.8.
  • B is an amorphous forming element in an iron-based amorphous alloy, and the higher the B content in a certain range, the stronger the amorphous forming ability.
  • the maximum thickness of the amorphous material is used as a criterion for evaluating the amorphous forming ability, and the higher the B content, the thicker the amorphous limit band thickness. If the B content is too low, it becomes more difficult to stably form an amorphous material, and the content is too high, resulting in insufficient Fe content, and a higher saturation magnetic density cannot be obtained. Based on actual production conditions and the basic requirements of high saturated materials for high Fe content.
  • the atomic percentage of B in the present application is 11.0 ⁇ b ⁇ 15.0; in some embodiments, the atomic percentage of B is 11.5 ⁇ b ⁇ 14.8; in some embodiments, the B The atomic percentage is 12.2 ⁇ b ⁇ 14.5; more specifically, the atomic percentage of B is 12.3, 12.6, 12.8, 13.2, 13.5, 13.8, 14.0, 14.3 or 14.5.
  • the atomic percentage of the Si is 2 ⁇ c ⁇ 4, and the content thereof is too low, thereby reducing the formability of the iron-based amorphous alloy strip and the thermal stability of the amorphous alloy strip, and forming the amorphous strip thermodynamics Unstable; at the same time, the viscosity of the alloy is reduced, the molten steel becomes active, the fluidity of the molten steel becomes better, and the surface tension of the alloy is reduced, which makes it difficult to form a stable molten metal, which makes the belt antegrade property worse; the content is too high to obtain Fe.
  • the atomic percentage of Si is 2.5 ⁇ c ⁇ 3.8; in some embodiments, the atomic percentage of Si is 2.8 ⁇ c ⁇ 3.5; more specifically, The atomic percentage of Si is 2.9, 3.0, 3.2, 3.4 or 3.5.
  • the present application considers that by optimizing the quality of the molten steel, on the one hand, the reduction of the pouring temperature is lowered, the relative cooling capacity is improved, and on the other hand, the effect of the high melting point slag on the preparation of the amorphous ribbon may be caused by heterogeneous nucleation; and the rare earth element is in the iron base.
  • the addition of an amorphous alloy is just perfect for achieving the above effects.
  • the rare earth element has strong deoxidation effect, and has a remarkable effect on reducing the oxygen content of the steel water and reducing the high melting point slag.
  • the rare earth and the dissolved oxygen in the molten steel form a high melting point stable oxide, and the high melting point rare earth oxide formed by the rare earth addition is partially removed by a slagging process; and a small amount of residual rare earth oxide reacts with a part of the silica in the alloy to form a
  • the silicate-like substance exhibits an amorphous substance in its structure, which is consistent with the matrix structure of the strip, and its amorphous structure does not adversely affect the amorphous matrix formation.
  • the rare earth addition effectively reduces the dissolved oxygen in the alloy, thereby significantly reducing the formation of other high melting point materials; the reduction of the high melting point slag content can effectively reduce the pouring temperature of the amorphous ribbon, and also avoid the temperature lowering process.
  • Other high melting point slags accumulate at the mouth of the mouth and produce heterogeneous nucleation in the strip matrix. The above process significantly compensates for the lack of amorphous performance of a highly saturated amorphous component composed of only Fe, Si, and B elements.
  • the concentration of the rare earth element in the iron-based amorphous alloy in the present application is 10 ppm ⁇ d ⁇ 30 ppm; in some embodiments, the concentration of the rare earth element in the iron-based amorphous alloy is 15 ppm ⁇ d ⁇ 28 ppm; In some embodiments, the concentration of the rare earth element in the iron-based amorphous alloy is 18 ppm ⁇ d ⁇ 25 ppm; more specifically, the concentration of the rare earth element in the iron-based amorphous alloy is 19 ppm, 20 ppm, 22 ppm. , 24ppm or 25ppm.
  • the rare earth element described in the present application is a rare earth element well known to those skilled in the art, and the present application is not particularly limited; for example, the rare earth element is selected from one or more of La, Ce, Nd or Yb; In a specific embodiment, the rare earth element is selected from one or more of La and Ce.
  • the application also provides a method for preparing an iron-based amorphous alloy, comprising:
  • the raw material after the compounding is smelted, and the molten steel reaches the target temperature during the smelting process, and then the rare earth alloy is added;
  • the molten melt is subjected to a single roll quenching to obtain an iron-based amorphous alloy
  • the rare earth alloy is added in an amount such that the concentration of the rare earth element in the iron-based amorphous alloy is 10 ppm to 30 ppm;
  • Fe, Si, B and RE are specifically added by adding a certain amount of rare earth elements in the Fe, Si, B alloy steel water, and adding rare earth elements at a high temperature stage to ensure rapid melting of the rare earth elements.
  • the temperature of the molten steel is lowered, the alloy is calmed in a low temperature zone, the sedation time is not less than 40 min, and the formed oxidized slag is cleaned by using a special slag blasting agent; at the same time, a certain amount of molten steel is allowed after the rare earth deoxidation slag is slag Rare earth element solutes.
  • the rare earth element is added at a temperature of from 1450 to 1500 °C.
  • the molten melt After the molten melt is obtained, it is subjected to a single roll quenching to obtain an iron-based amorphous alloy ribbon.
  • the iron-based amorphous alloy strip prepared by the present application is in a completely amorphous state, and has a critical state of at least 30 ⁇ m and a width of 100 to 300 mm.
  • the heat treatment temperature is 300 to 380 ° C, and the heat treatment time is 30 to 150 min.
  • the experimental results show that the core loss of the iron-based amorphous alloy after heat treatment is less than 0.16 W/kg at 50 Hz and 1.30 T; the core loss of the iron-based amorphous alloy is less than 0.20 at 50 Hz and 1.40 T. W/kg.
  • the iron-based amorphous alloy provided by the present application can be used for a magnetic core material of a power transformer, an electrode, and an inverter.
  • molten steel of Fe85Si2.7B12.3 was prepared by using industrial raw materials such as iron, boron iron and silicon. Amorphous strips with a thickness of about 20 ⁇ m, 30 ⁇ m and 40 ⁇ m were prepared respectively.
  • the smelting temperature was 1450-1500 °C. Insulation for 5 ⁇ 10min, adding a certain amount of rare earth alloy La or Ce at this stage, high temperature can promote rapid melting of rare earth alloy; make rare earth alloy rapidly entrained in molten steel, avoid rare earth alloy floating on molten steel surface and react with oxygen in air; smelting At the end, cool down to 1400 ⁇ 1420 ° C calm, sedation time is not less than 40min.
  • the antegrade property of the alloy ribbon was evaluated by the adjustment of the rare earth addition amount and the matching of the pouring temperature.
  • the amorphous state of the amorphous material is evaluated by X-ray diffractometry to evaluate the amorphous forming ability of the material.
  • the content of the oxidized slag in the nozzle is measured by an energy spectrometer, and the gas element in the alloy is tested by an oxygen-nitrogen hydrogen analyzer. Content, the content of rare earth elements in the alloy was tested by direct reading spectrometer, and the evaluation data of the belt is shown in Table 1 below;
  • the rare earth-added alloy can effectively reduce Al, V, Ti, etc. in the molten steel, which may form a high melting point element, which is low in the pouring temperature and narrow in the nozzle gap. It is very easy to accumulate at the nozzle, which makes the spray belt go smoothly. The accumulation of slag causes the slag line to be generated during the belt making process, and the strip is severely produced, causing the spray belt to end prematurely.
  • the reaction of rare earth with oxygen reduces the free oxygen in the molten steel, and the reduction of the oxygen content can reduce the high melting point slag.
  • the amount of rare earth added is not as high as possible. As can be seen from Comparative Example 3, although the amount of RE added accounts for 0.03%, which is slightly increased compared with the amount added in the examples, the gas content in the alloy does not decrease, but increases, and the ratio is not added. Comparative Example 1 of the rare earth is even higher. According to the analysis, this is mainly due to the oxygen-nitrogen analyzer testing the content of total oxygen (combination state, elemental free state) of the alloy. The side also indicates that the rare earth addition amount of molten steel is too large, not only reacts with free oxygen in molten steel, but also with the surface of molten steel.
  • the rare earth elements in the rare earth oxide slag and the alloy in the nozzle are obviously high. It also indicates that the addition of rare earth is excessive; due to the need to properly control the rhythm of the spray belt, the time required for the reaction of the rare earth oxide with the silica is limited, so the excess residual rare earth oxide is not completely formed by the reaction of silica. The substance is caused to accumulate at the nozzle as a new introduced high melting point slag.
  • the amount of rare earth added should be between 0.005 and 0.025%. Considering the difference in raw material materials, it can be evaluated that the rare earth content in the strip is 15 ppm to 30 ppm.
  • a highly saturated amorphous alloy especially a highly saturated amorphous ribbon of Fe, Si and B.
  • the rational design of amorphous forming elements and the rational matching of process parameters are particularly important. Taking 30 ⁇ 1 ⁇ m strip as the evaluation standard, the opening temperature is below 1420°C, and an appropriate amount of RE element can be added to obtain an amorphous strip with a thickness of about 30 ⁇ m. See Examples 4-9.
  • Comparing Comparative Example 6 with the composition of the composition of Example 7 is similar to the alloy, which reduces the temperature of the molten steel, and for the highly saturated amorphous component, a thicker amorphous ribbon can be obtained.
  • Comparing Comparative Examples 4 to 6 and Examples 4 to 5 the addition of an excessive amount of rare earth causes an increase in rare earth oxides in the strip, which induces crystallization as a nucleation site, which is disadvantageous for amorphous formation.
  • Comparative Examples 7 to 8 since the Fe element is too high, the amorphous forming element is obviously insufficient, and even under the process conditions of lowering the pouring temperature and rationally adding the rare earth alloy, it is impossible to form amorphous at a thickness of 20 ⁇ m.
  • Reasonable composition design and matching of process conditions for highly saturated amorphous components is the key to obtaining highly saturated amorphous ribbons.
  • the selected strips in Table 2 were tested to a completely amorphous strip at a thickness of 20 ⁇ 1 ⁇ m, and wound into a sample ring having an inner diameter of 50.5 mm and an outer diameter of 53.5 to 54 mm, and the sample loop was carried out using a box annealing furnace. Stress annealing, annealing is carried out in an argon-protected atmosphere, between 300 and 380 ° C, each interval is 10 ° C, and the holding time is 30 to 150 min.
  • the heat treatment process adds a magnetic field along the strip preparation direction with a magnetic field strength of 1200 A/m.
  • the silicon steel tester was used to test the strip loss after heat treatment. The test conditions were respectively measured at 1.30T and 1.40T loss values at 50Hz.
  • the performance was selected under the optimal heat treatment process.
  • the test results are shown in Table 3.
  • the Bs test was selected.
  • the saturation magnetic induction value of the annealed amorphous ribbon is tested using a vibrating sample magnetometer, see Table 3;
  • Comparative Example 4 was significantly larger than that of the examples, indicating that a large amount of residual rare earth oxide in the strip deteriorated the performance.
  • the rare earth oxide reacts with a part of the silica in the alloy, and the formed silicate material exhibits an amorphous substance in structure, which is consistent with the strip substrate mechanism and has an amorphous structure. It does not affect the performance; however, if there is more rare earth oxide due to excessive addition of rare earth, it will act as a heterogeneous nucleation point, even if it is amorphous during the preparation stage of the ribbon, it will be soft magnetic. The formation has an adverse effect.
  • the rare earth oxide acts as a strong pinning point, suppresses the removal of stress and the deflection of the magnetic domain in the magnetization direction, resulting in poor soft magnetic properties after annealing, and increased magnetic density and deterioration of performance. To be serious.

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Abstract

一种铁基非晶合金Fe aB bSi cRE d，a、b、c分别表示对应组分的原子百分含量；83.0≤a≤87.0，11.0＜b＜15.0，2.0≤c≤4.0，a+b+c＝100；d为RE在所述铁基非晶合金中的浓度，10ppm≤d≤30ppm。该铁基非晶合金的饱和磁感应强度不低于1.63T；可用于制作电源变压器、电机以及逆变器的磁芯材料。

Description

一种铁基非晶合金及其制备方法
本申请要求于2017年12月21日提交中国专利局、申请号为201711392745.7、发明名称为“一种铁基非晶合金及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及磁性材料技术领域，尤其涉及一种铁基非晶合金及其制备方法。
背景技术
铁基非晶作为一种优异的软磁非晶材料，自产生至今一直备受各国科研工作者青睐，其磁导率高、矫顽力低、损耗低以及饱和磁感应强度高的特性，一直备受业界青睐。但是近年来对于变压器小型化、低成本以及高容量的设计需求，迫切需要提高作为磁芯的非晶材料的饱和磁密度；这是由于：一方面，饱和磁密的提高，可以减小磁芯，同时还会降低变压器其他方面的材料成本，从而降低变压器综合成本；另一方面，更高饱和磁密可以实现高容量变压器设计。基于此，研究者在高饱和非晶材料在成分开发方面也在持续研究。
公开号为CN100549205专利中提到Fe aSi bB cC d的非晶合金成分，其中a为76至83.5原子％，b为12原子％或以下，c为8至18原子％，d为0.01至3原子％，其中所述Fe基非晶态合金带在退火后的饱和磁通密度为1.6T以上，最大约为1.67T。该专利中详细阐述了C与Si合理比例控制及保证C偏析层在表面2～20nm范围内有峰值，可以制备出低损耗、降低脆化、热不稳定性的Fe基非晶态合金带材；但是对C偏析层在带材表面的分布要求相对苛刻。如文中所述，对于带材内部部分区域C偏析层深度与范围的不均匀，都可以使得应力释放不均，部分产生易碎问题。应对上述问题需要通过合理的带宽控制吹送到结晶器上面的CO或CO 2气体，气流过大或者过小都会影响C偏析层产生的范围，工艺相对复杂，制备难度较大。
日本公开号为No.平6-220592公开了一种由Fe aCo bSi cB dM x表示的无定形合金薄带的组成；其原子百分量为：60≤a≤83，3≤b≤20，80≤a+b≤86，1≤c≤10，11≤d≤16，M是Sn、Cu中的至少一种。该专利中加入了Co，可以有效的提高非晶材料的饱和磁感应强度；然而Co是相对贵的元素，虽然含Co的铁基无 定形合金薄带具有相对高的饱和磁密，但成本过高严重制约着这种合金材料的批量生产，其使用仅限于在一些要求质量较高的用量较少的场合。
众所周知，铁磁性元素的增加是提高饱和磁感应强度的保障，由此而导致类金属的降低，将使其非晶形成能力降低以至不能形成完全非晶。鉴于此，公开号为CN1124362的专利提到将一定量的P元素添加到一定量的Fe、Si、B、C的合金中制备非晶合金，以提高合金非晶形成能力，它的组成以原子百分数计：82＜Fe≤90，2≤Si＜4，5＜B≤16，0.02≤C≤4，0.2≤P≤12，退火后BS值高达1.74T；同时，文中提到实施例的含P合金成分退火优势，P的加入可以有效提高非晶铁芯的退火窗口。而专利中并未提及P的有效加入方法以及对P合金原材料的要求。诚然，低品质的P合金成本很低，但是低品质P合金含有多种高熔点合金元素，比如V、Ti、Al，上述物质冶炼过程中形成高熔点氧化物，在带材中以异质形核点的形式存在，诱导带材表面晶化，不利于生产制带的顺行；而高品质的P合金冶炼工艺相当复杂，工业生产难度大。该专利从成分实验的基础上说明了P在高饱和非晶添加的可能性，但未对工业化生产做合理的说明和解释。
日本公开号为NO.S57-185957同样提出了一种用原子百分数为1-10％的P替代传统非晶合金中B的置换方式，专利中公开了P的提高可以提高形成无定形状态能力的作用，但专利中未具体提及含P非晶的退火工艺，含P非晶带材具有很弱的抗氧化性，对退火过程中氧气含量要求极低，在传统无保护的气氛中退火，极易氧化；实验研究表明无保护的气氛下，含P原子百分比1％以上，退火温度约200℃条件下，退火后的带面即可呈现出浅蓝色氧化色，P含量越高、材料退火温度越高，氧化愈严重，正常退火温度显然高于200℃，氧化严重的带面会呈现深蓝色、紫色的表面形貌。因为带材氧化，材料的铁芯损耗异常偏大。总而言之，退火的苛刻度严重制约该类合金工业化。
发明内容
本发明解决的技术问题在于提供一种铁基非晶合金，本申请提供的铁基非晶合金具有饱和磁感应强度高、软磁性能优良以及工艺顺行度高的特点。
有鉴于此，本申请提供了一种如式(Ⅰ)所示的铁基非晶合金，
Fe aB bSi cRE d      (Ⅰ)；
其中，a、b、c分别表示对应组分的原子百分含量；83.0≤a≤87.0，11.0＜b＜15.0，2.0≤c≤4.0，a+b+c＝100；
d为RE在所述铁基非晶合金中的浓度，10ppm≤d≤30ppm。
优选的，所述铁基非晶合金的饱和磁感应强度≥1.63T。
优选的，所述Fe的原子百分含量为83.2≤a≤86.8。
优选的，所述B的原子百分含量为12.2≤b≤14.5。
优选的，所述Si的原子百分含量为2.5≤c≤3.5。
优选的，所述RE选自La、Ce、Nd和Yb中的一种或多种，所述RE的浓度为15ppm≤d≤25ppm。
本申请还提供了一种铁基非晶合金的制备方法，包括：
按照式Fe aB bSi c的铁基非晶合金的原子百分比配料，将配料后的原料熔炼，在熔炼的过程中钢水达到目标温度后加入稀土合金；
将熔炼后的熔液进行单辊快淬，得到铁基非晶合金；
所述稀土合金的加入量以使稀土元素在所述铁基非晶合金中的浓度为10ppm～30ppm；
其中，83.0≤a≤87.0，11.0＜b＜15.0，2.0≤c≤4.0，a+b+c＝100。
优选的，所述目标温度为1450～1500℃。
优选的，所述铁基非晶合金为完全非晶状态，临界状态至少为30μm，宽度为100～300mm。
优选的，单辊快淬之后还包括：
将单辊快淬后的铁基非晶合金进行热处理；
所述热处理的温度为300～380℃，所述热处理的时间为30～150min。
优选的，在50Hz，1.30T条件下，所述铁基非晶合金的铁芯损耗小于0.16W/kg；在50Hz，1.40T条件下，所述铁基非晶合金的铁芯损耗小于0.20W/kg。
本申请提供了一种如式Fe aB bSi cRE d所示的铁基非晶合金，其包括Fe、Si、B与RE，其中Fe、Si和B有利于形成高饱和磁感应强度的铁基非晶合金，RE可有效降低合金中溶解氧，进而显著减少了其他高熔点渣的形成，高熔点渣含量的降低，可有效的降低非晶制带的浇注温度，同时也避免了温度降低过程中 其他高熔点渣的嘴缝处积聚及在带材基体中产生异质形核。因此，本申请提供的铁基非晶合金由于添加并控制Fe、Si、B和RE的含量，使铁基非晶合金具有饱和磁感应强度高、软磁性能优良以及工艺顺行度高的优点。
具体实施方式
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
针对现有技术铁基非晶合金制备过程中出现的问题，本发明在合适的主成分设计的基础上，通过稀土微量元素的添加，使钢水得到了净化，解决了高饱和磁感应强度非晶合金材料的制带顺行难题，从而获得了饱和磁感应强度高、软磁性能优异以及工艺顺行度高的非晶合金带材。具体的，本申请实施例公开了一种如式(Ⅰ)所示的铁基非晶合金，
Fe aB bSi cRE d      (Ⅰ)；
其中，a、b、c分别表示对应组分的原子百分含量；83.0≤a≤87.0，11.0＜b＜15.0，2.0≤c≤4.0，a+b+c＝100；
d为RE在所述铁基非晶合金中的浓度，10ppm≤d≤30ppm。
在本申请中，Fe作为软磁性元素，是高饱和磁感应强度值的保证元素。Fe元素含量过低，则饱和磁感应强度低，即其原子百分含量a＜83％，饱和磁感应密度低于1.63T；含量过高，铁基非晶合金的非晶形成能力不足，热稳定性差。本申请中Fe的原子百分含量为83.0≤a≤87.0；在某些具体实施例中，所述Fe的原子百分含量为83.2≤a≤86.8；在某些具体实施例中，所述Fe的原子百分含量为85≤a≤86.6；更具体的，所述Fe的原子百分含量为83.7、84、84.3、84.8、85、85.2、85.6、86.0、86.2、86.6或86.8。
B是铁基非晶合金中的非晶形成元素，一定范围内B含量越高非晶形成能力越强。以材料形成非晶的最大厚度作为评估非晶形成能力的判据，则B含量越高非晶极限带厚越厚。B含量过低，则使稳定形成无定形材料变得更加困难，而含量过高，导致Fe含量不足，无法获得更高的饱和磁密。基于实际的生产情况及高饱和材料对高Fe含量的基本要求。本申请中B的原子百分含量为11.0＜b＜15.0；在某些具体实施例中，所述B的原子百分含量为 11.5≤b≤14.8；在某些具体实施例中，所述B的原子百分含量为12.2≤b≤14.5；更具体的，所述B的原子百分含量为12.3、12.6、12.8、13.2、13.5、13.8、14.0、14.3或14.5。
所述Si的原子百分含量为2≤c≤4，其含量过低，则降低铁基非晶合金带材可成形性以及非晶合金带材的热稳定性，形成的非晶带材热力学不稳定；同时合金粘度降低，钢水变活跃，钢水流动性变好，致使合金表面张力减小，进而形成稳定的熔液变得困难，使得制带顺行性变差；含量过高无法获得Fe含量更高、Bs更高的非晶合金带材。在某些具体实施例中，所述Si的原子百分含量2.5≤c≤3.8；在某些具体实施例中，所述Si的原子百分含量2.8≤c≤3.5；更具体的，所述Si的原子百分含量为2.9、3.0、3.2、3.4或3.5。
结合上述成分设计方向可知，对于高饱和磁感应强度铁基非晶合金带材，为确保饱和磁感应强度不低于设计值，需保证铁磁性金属元素铁的含量，同时对于剩余类金属元素的含量需要合理设计，保证高饱和非晶的一定的非晶形成能力。而对于仅有Fe、Si、B元素组成的高饱和非晶带材的制备，仅有成分设计是远远不够的，需要在制带工艺及钢水质量合理优化，提高合金制带的工艺可成形性及性能的稳定性。本申请考虑通过优化钢水质量，一方面实现开浇温度降低，提高相对冷却能力，另一方面降低高熔点夹渣对制备非晶带材可能产生异质形核的影响；而稀土元素在铁基非晶合金中添加恰好可以完美的实现上述作用。
稀土元素具有强脱氧作用，对降低钢水氧含量进而减少高熔点夹渣具有显著效果。稀土与钢水中溶解氧形成高熔点稳定氧化物，通过打渣工艺将稀土添加形成的高熔点含稀土氧化物部分去除；同时少量残余的稀土氧化物与合金中部分二氧化硅发生反应，形成的硅酸盐类物质，其结构方面呈现非晶质物质，与带材基体结构一致，其非晶质的结构，对非晶基体非晶形成无不利影响。由此可见，稀土添加有效的降低合金中溶解氧，进而显著减少了其他高熔点物质形成；高熔点渣含量的降低，可以有效的降低非晶制带的浇注温度，同时也避免了温度降低过程其他高熔点渣的嘴缝处积聚及在带材基体中产生异质形核。上述工艺方法显著的弥补了仅有Fe、Si、B元素组成的高饱和非晶成分的非晶性能能力的不足。本申请中稀土元素在铁基非晶合金中的浓度为 10ppm≤d≤30ppm；在某些具体实施例中，所述稀土元素在铁基非晶合金中的浓度为15ppm≤d≤28ppm；在某些具体实施例中，所述稀土元素在铁基非晶合金中的浓度为18ppm≤d≤25ppm；更具体的，所述稀土元素在铁基非晶合金中的浓度为19ppm、20ppm、22ppm、24ppm或25ppm。本申请所述稀土元素为本领域技术人员熟知的稀土元素，对此本申请没有特别的限制；示例的，所述稀土元素选自La、Ce、Nd或Yb中的一种或多种；在具体实施例中，所述稀土元素选自La和Ce中的一种或多种。
本申请还提供了一种铁基非晶合金的制备方法，包括：
按照式Fe aB bSi c的铁基非晶合金的原子百分比配料，将配料后的原料熔炼，在熔炼的过程中钢水达到目标温度后加入稀土合金；
将熔炼后的熔液进行单辊快淬，得到铁基非晶合金；
所述稀土合金的加入量以使稀土元素在所述铁基非晶合金中的浓度为10ppm～30ppm；
其中，83.0≤a≤87.0，11.0＜b＜15.0，2.0≤c≤4.0，a+b+c＝100。
在本申请中，Fe、Si、B和RE的具体添加方式为：通过在Fe、Si、B合金钢水中添加一定量的稀土元素，在高温阶段加入稀土元素，确保稀土元素的快速熔入，合金熔入后降低钢水温度，使合金在低温区镇静，镇静时间不少于40min，将所形成的氧化渣使用特制打渣剂清理掉；同时，在稀土脱氧打渣后允许钢水中有一定含量的稀土元素溶解物。按照本发明，所述稀土元素加入的温度为1450～1500℃。
待得到熔炼后的熔液后则将其进行单辊快淬，以得到铁基非晶合金带材。
本申请制备的铁基非晶合金带材为完全非晶状态，其临界状态至少为30μm，宽度为100～300mm。
在实际应用时，需要将上述得到的铁基非晶合金带材进行热处理，所述热处理的温度为300～380℃，所述热处理的时间为30～150min。
实验结果表明，经过热处理后的铁基非晶合金在50Hz，1.30T条件下铁芯损耗小于0.16W/kg；在50Hz，1.40T条件下，所述铁基非晶合金的铁芯损耗小于0.20W/kg。本申请提供的铁基非晶合金可用于电源变压器、电极以及逆变器的磁芯材料。
为了进一步理解本发明，下面结合实施例对本发明提供的铁基非晶合金进行详细说明，本发明的保护范围不受以下实施例的限制。
实施例稀土添加效果评估
使用工业用原材料铁、硼铁、硅配制熔炼Fe85Si2.7B12.3的钢水约150kg，分别制备带厚约为20μm、30μm、40μm带宽为80mm的非晶带材；在冶炼温度为1450～1500℃保温5～10min，该阶段加入一定量的稀土合金La或Ce，高温可促使稀土合金快速熔化；使稀土合金快速卷入钢液中，避免稀土合金浮于钢液表面与空气中氧气反应；熔炼结束，降温至1400～1420℃镇静，镇静时长不少于40min。通过稀土添加量调整及开浇温度的匹配，评估合金制带的顺行性。
通过X射线衍射仪评估非晶材料不同带厚情况下的非晶度来评估材料的非晶形成能力，通过能谱仪测试喷嘴内氧化渣含量，通过氧氮氢分析仪测试合金内的气体元素含量，通过直读光谱仪测试合金中的稀土元素含量，制带评估数据见下表1；
表1不同冶炼制带工艺下合金及带材属性评估
Figure PCTCN2018076206-appb-000001
Figure PCTCN2018076206-appb-000002
与未添加稀土元素的比较例1相比，添加稀土的合金可以有效的降低钢水中的Al、V、Ti等可能形成高熔点的元素，上述元素在开浇温度较低及喷嘴缝隙较窄时，极容易在喷嘴处积聚，致使喷带顺行难度大，积聚渣使带材制带过程中产生渣线，严重的产生分条，致使喷带提前结束。稀土与氧反应降低钢水内游离氧，氧含量的降低可以使高熔点渣减少。通过与比较例1喷嘴处渣的测试结果对比，可以看出：实施例1～3稀土元素的添加可有效降低喷嘴处其他高熔点渣的积聚。另一方面，薄带中的高熔点渣还会作为异质形核点，诱导带材晶化；XRD测试结果，比较例1在1400℃开浇温度下仅带厚在20μm左右显示为非晶态，其他带厚带材均发生晶化。而实施例1～3因为稀土元素的强脱氧作用，在钢液中完成与钢水溶解氧的快速反应并有效清除，即便有少量稀土氧化物参与也不会影响制带，因为稀土氧化物与合金中部分二氧化硅发生反应，形成的硅酸盐类物质，该物质为非晶质结构，对于Fe基非晶基体形成方面无不利影响。
稀土添加量并非越多越好，由比较例3可见，虽然RE添加量占比0.03％，较实施例添加量略有增加，但是合金内的气体含量并没有降低，反而增加，且比未添加稀土的比较例1还要高。分析认为，这主要是由于氧氮分析仪测试合金全氧(化合态、单质游离态)含量所致，侧面也说明钢水稀土添加量过大，不仅与钢水中游离氧发生反应，还与钢水表面的氧发生反应，致使打渣过程完成后，钢水中的富余稀土将空气中的氧再次卷入钢水中，致使氧、氮虚高；同时，喷嘴内稀土氧化物渣及合金中稀土元素明显偏高，也说明稀土加入过量；由于需要合理控制喷带时间节奏，留给稀土氧化物与二氧化硅反应的时间有 限，所以过量残余的稀土氧化物未能完全被二氧化硅反应形成的硅酸盐类物质，致使其作为一种新的引入的高熔点渣积聚在喷嘴处。
成分设计中提到，仅有Fe、Si、B三种元素的高饱和非晶成分，因为非晶形成元素降低，其非晶形成能力相对不足，通过降低钢水开浇温度，降低钢水过热度，提高相对冷却能力，弥补非晶形成能力不足的缺陷，实施例3与比较例2可以看出：降低钢水温度，带材极限非晶带厚显著增加。综上，稀土适量添加降低其他高熔点渣含量，改善了钢水质量，为低温制带创造了可能条件。
综上稀土添加量应在0.005～0.025％为宜，考虑到原材料材质的差异，可以评估带材内稀土含量以15ppm～30ppm为宜。
实施例
1)合金成分对非晶形成能力的评估
获取高饱和的非晶合金，特别是Fe、Si、B三元素的高饱和非晶带材，非晶形成元素的合理设计与工艺参数的合理性匹配显得尤为重要。以30±1μm带材作为评估标准，开浇温度在1420℃以下，适量添加RE元素，均可获得30μm左右带厚的非晶带材，见实施例4～9。
表2高饱和非晶成分非晶形成能力评估表
Figure PCTCN2018076206-appb-000003
对比对比例6与实施例7成分相近成分合金可见，降低钢水温度，对于高饱和非晶成分而言，可以获的带厚更厚的非晶带材。对比对比例4～6与实施例4～5可见，过量的稀土添加导致带材内稀土氧化物增加，作为形核点会诱导晶化，不利于非晶形成。而对比例7～8因为Fe元素过高，非晶形成元素明显不足，即便是开浇温度降低以及合理添加稀土合金的工艺条件下，也未能在20μm带厚下形成非晶。对于高饱和非晶成分合理的成分设计及工艺条件的匹配是获取高饱和非晶带材的关键。
2)非晶合金带材的饱和磁感应强度与磁性能
将表2中的选取带厚为20±1μm区间测试为完全非晶的带材，卷绕成内径为50.5mm，外径为53.5～54mm的样环，使用箱式退火炉将样环进行去应力退火，退火选择在氩气保护的气氛中进行，由300～380℃之间，每个间隔为10℃，保温时间30～150min。热处理过程加沿着带材制备方向的磁场，磁场强度为1200A/m。使用硅钢测试仪测试热处理后带材损耗，测试条件在50Hz分别测1.30T与1.40T损耗值；性能选取最佳热处理工艺条件下的最优性能值，测试结果如表3所示；Bs测试选用具有最佳退火性能的非晶带材，使用振动样品磁强计测试退火的非晶带材的饱和磁感应强度值，见表3；
表3非晶材料软磁性能数据表
Figure PCTCN2018076206-appb-000004
Figure PCTCN2018076206-appb-000005
由实施例4～8可以看出，铁基非晶合金材料随着Fe含量的增加其饱和磁感应强度值明显增加，上述实施例不低于1.63T，比较相近成分的实施例4与比较例4可以发现：稀土氧化物过量添加及带材内大量残余，虽然对非晶形成有不利影响，但对其已经形成非晶的饱和磁感应强度值几无影响。
但是，比较例4的损耗值较实施例明显偏大，说明带材内大量残余的稀土氧化物对性能造成恶化影响。本申请上述已经记载：稀土氧化物与合金中部分二氧化硅发生反应，形成的硅酸盐类物质，其结构方面呈现非晶质物质，与带材基体机构相一致，其非晶质的结构，不会对性能产生影响；但是，若有因为稀土添加过量而产生更多富余的稀土氧化物则会作为异质形核点，即便在薄带制备阶段已形成非晶，也会对软磁形成产生不利影响。因此，在去应力退火过程中，稀土氧化物作为强有力的钉扎点，抑制应力的去除及磁畴的沿磁化方向的偏转，导致退火后软磁性能差，并且磁密增加，性能恶化更为严重。
综上，合理的成分设计基础上，匹配合理的工艺要求是制备高饱和非晶材料的一个有效途径。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (11)

  1. 一种如式(Ⅰ)所示的铁基非晶合金，
    Fe aB bSi cRE d    (Ⅰ)；
    其中，a、b、c分别表示对应组分的原子百分含量；83.0≤a≤87.0，11.0＜b＜15.0，2.0≤c≤4.0，a+b+c＝100；
    d为RE在所述铁基非晶合金中的浓度，10ppm≤d≤30ppm。
  2. 根据权利要求1所述的铁基非晶合金，其特征在于，所述铁基非晶合金的饱和磁感应强度≥1.63T。
  3. 根据权利要求1所述的铁基非晶合金，其特征在于，所述Fe的原子百分含量为83.2≤a≤86.8。
  4. 根据权利要求1所述的铁基非晶合金，其特征在于，所述B的原子百分含量为12.2≤b≤14.5。
  5. 根据权利要求1所述的铁基非晶合金，其特征在于，所述Si的原子百分含量为2.5≤c≤3.5。
  6. 根据权利要求1所述的铁基非晶合金，其特征在于，所述RE选自La、Ce、Nd和Yb中的一种或多种，所述RE的浓度为15ppm≤d≤25ppm。
  7. 一种铁基非晶合金的制备方法，包括：
    按照式Fe aB bSi c的铁基非晶合金的原子百分比配料，将配料后的原料熔炼，在熔炼的过程中钢水达到目标温度后加入稀土合金；
    将熔炼后的熔液进行单辊快淬，得到铁基非晶合金；
    所述稀土合金的加入量以使稀土元素在所述铁基非晶合金中的浓度为10ppm～30ppm；
    其中，83.0≤a≤87.0，11.0＜b＜15.0，2.0≤c≤4.0，a+b+c＝100。
  8. 根据权利要求7所述的制备方法，其特征在于，所述目标温度为1450～1500℃。
  9. 根据权利要求7所述的制备方法，其特征在于，所述铁基非晶合金为完全非晶状态，临界状态至少为30μm，宽度为100～300mm。
  10. 根据权利要求7所述的制备方法，其特征在于，单辊快淬之后还包括：
    将单辊快淬后的铁基非晶合金进行热处理；
    所述热处理的温度为300～380℃，所述热处理的时间为30～150min。
  11. 根据权利要求10所述的制备方法，其特征在于，在50Hz，1.30T条件下，所述铁基非晶合金的铁芯损耗小于0.16W/kg；在50Hz，1.40T条件下，所述铁基非晶合金的铁芯损耗小于0.20W/kg。
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CN108018504A (zh) 2018-05-11
EP3572548B1 (en) 2021-01-06
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