WO2019024285A1 - 一种铁基非晶合金 - Google Patents
一种铁基非晶合金 Download PDFInfo
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- WO2019024285A1 WO2019024285A1 PCT/CN2017/108475 CN2017108475W WO2019024285A1 WO 2019024285 A1 WO2019024285 A1 WO 2019024285A1 CN 2017108475 W CN2017108475 W CN 2017108475W WO 2019024285 A1 WO2019024285 A1 WO 2019024285A1
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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
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/04—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering with simultaneous application of supersonic waves, magnetic or electric fields
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
- C21D1/76—Adjusting the composition of the atmosphere
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F27/00—Details of transformers or inductances, in general
- H01F27/24—Magnetic cores
- H01F27/25—Magnetic cores made from strips or ribbons
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2201/00—Treatment for obtaining particular effects
- C21D2201/03—Amorphous or microcrystalline structure
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
- C22C2200/02—Amorphous
Definitions
- the invention relates to the technical field of iron-based amorphous alloys, in particular to an iron-based amorphous alloy.
- Iron-based amorphous ribbon is a new type of energy-saving material, which is generally prepared by rapid rapid solidification production process. Compared with conventional silicon steel transformers, iron-based amorphous strip for transformer cores, the magnetization process is quite easy, thus greatly reducing the load losses of the transformer, when used in oil-immersed transformers also reduces CO, SO, NO x, etc. The emission of harmful gases is called the “green material” of the 21st century.
- iron-based amorphous ribbons with a saturation magnetic induction of about 1.56T are generally used.
- silicon steel of 2.0T iron-based amorphous
- iron-based amorphous There is a disadvantage of an increase in volume when preparing a transformer.
- Hitachi, Inc. discloses a Fe-Si-BC alloy with a saturation magnetic induction strength of 1.64T in the Chinese patent publication CN1721563A, but the disclosed process conditions mention that it is controlled by blowing C gas during the preparation process. The process of distributing the content of C element on the surface of the strip, which will directly lead to the difficulty in controlling the production process conditions of the product, and the stability of industrial production cannot be guaranteed.
- Nippon Steel Corporation announced a Fe-Si-BPC alloy in the patent CN1356403A. Although its saturation magnetic induction strength reaches 1.75T, its amorphous Fe formation capacity is too high, resulting in its industrial production. Forming an amorphous state, the magnetic properties of the strip are poor.
- C element is added to this alloy system, although C
- C The addition can improve the amorphous forming ability of the alloy system, but in the industrialization process, the introduction of C element mainly through two ways, one is to use pig iron, the other is to use graphite, but these two raw materials are not suitable for amorphous ribbon
- the smelting process of the material too much impurity content of the pig iron will lead to the crystallization of the strip during the preparation process and affect the magnetic tenderness; the melting point of the graphite is too high, and if the graphite is used in the current smelting process, the smelting process must be optimized or increased. Industrial production is more difficult.
- the present invention starts from the optimization design of the alloy composition and the optimization of the heat treatment process, and uses the FeSiBP quaternary alloy system to invent an iron-based amorphous alloy strip suitable for industrial production with high saturation magnetic induction and low loss.
- the technical problem to be solved by the present invention is to provide an iron-based amorphous alloy having high saturation magnetic induction.
- the present application provides an iron-based amorphous alloy as shown in formula (I).
- the atomic percentage of the B is 11.0 ⁇ c ⁇ 13.0.
- the atomic percentage of the P is 1 ⁇ d ⁇ 3.
- the iron-based amorphous alloy 83.0 ⁇ a ⁇ 84.0, 3.0 ⁇ b ⁇ 6.0, 9.0 ⁇ c ⁇ 13.0, and 1 ⁇ d ⁇ 3.
- the iron-based amorphous alloy has a saturation magnetic induction of ⁇ 1.62T.
- the heat treatment process of the iron-based amorphous alloy is carried out under a H 2 atmosphere, the holding temperature is 300-360 ° C, the time is 60-120 min, and the magnetic field strength is 800-1400 A/m.
- the iron-based amorphous alloy has a coercive force of ⁇ 4 A/m, a core loss of ⁇ 0.18 W/kg, and an excitation power of ⁇ 0.22 VA/kg.
- the iron-based amorphous alloy has a width of 100 to 200 mm and a thickness of 23 to 28 ⁇ m.
- the application also provides the use of the iron-based amorphous alloy in the core of an electric distribution transformer.
- the high Fe content is an important guarantee for the high saturation magnetic induction of iron-based amorphous alloy strips; Si and B are amorphous forming elements and are necessary for forming amorphous; P is also an amorphous forming element, and P and Fe have a large negative heat of mixing, which is advantageous for improving the stability of the supercooled liquid region of the alloy system, but introduces impurities, and therefore, the present application adds the above elements. And controlling its content, so that the saturation magnetic induction strength of the iron-based amorphous alloy is higher.
- the present application eliminates the magnetic stress of the iron-based amorphous alloy by magnetic field heat treatment under a hydrogen atmosphere, reduces the coercive force, improves the magnetic permeability, and finally obtains an iron-based amorphous alloy excellent in magnetic properties.
- FIG. 2 is a view showing the surface oxidation of the belt after heat treatment in the examples and comparative examples of the present invention
- Figure 3 is a graph showing the relationship between magnetic properties and heat treatment temperature of an embodiment of the present invention and a comparative example
- 4 is a comparison diagram of loss curves in an embodiment of the present invention and a comparative example at 50 Hz.
- the present application obtains an iron-based amorphous alloy by selecting an appropriate element and controlling the content thereof.
- the iron-based amorphous alloy is specifically An iron-based amorphous alloy represented by the formula (I),
- the invention provides an iron-based amorphous alloy with low saturation FeSiBP quaternary system with high saturation magnetic induction intensity. Further, in the heat treatment process, the oxidation of the strip is improved and the strip is improved by using a hydrogen atmosphere. Magnetic properties.
- the Fe element is a ferromagnetic element, which is a main source of magnetic properties of the iron-based amorphous alloy ribbon, and the high Fe content is a strip having a high saturation magnetic induction value.
- the atomic percentage of Fe in the present application is 81.0 ⁇ a ⁇ 84.0.
- the atomic percentage of Fe is 81.5-83, and more specifically, the atomic percentage of Fe is 81.5. 82, 82.5, 83, 83.5 or 84.
- the Si and B elements are amorphous forming elements and are necessary conditions for the alloy system to form amorphous under industrial production conditions.
- the atomic percentage of Si element is 1.0-6.0. Too low will lead to a decrease in amorphous forming ability and affect the magnetic properties of the strip. Too high a deviation from the eutectic point will also reduce the amorphous forming ability; in a specific embodiment
- the content of Si is 2.0 to 6.0. Specifically, the content of Si is 2.0, 3.0, 4.0, 5.0 or 6.0.
- the range of the B element is 9.0 to 14.0. When it is less than 9, the amorphous forming ability of the alloy is low. When it is greater than 14, the alloying ability is deviated from the eutectic point. In a specific embodiment, the content of the B is 11.0. ⁇ 13.0.
- the P element is the same as the Si and B elements, and is an amorphous forming element, and P and Fe have a large negative mixed heat.
- the addition of P is beneficial to improve the stability of the supercooled liquid region of the alloy system and to function as an amorphous forming element.
- the addition of P element is mainly realized by ferrophosphorus. A large amount of addition will introduce a large amount of impurities into the molten steel, which will seriously reduce the quality of the molten steel. On the one hand, it will affect the success rate of the preparation of the strip, and the strip cannot form amorphous. On the other hand, it also affects the magnetic properties of the strip.
- the P element in the present application has a range of 0.05 to 3, on the one hand controlling the introduction of impurities, and on the other hand, improving the amorphous forming ability of the entire alloy system; in some embodiments, the P content is 1 ⁇ 3, more specifically, the content of P is 1.0, 2.0 or 3.0.
- the iron-based amorphous alloy of the present application inevitably contains an impurity element.
- An iron-based amorphous alloy having the above component content has better magnetic properties.
- the preparation method of the iron-based amorphous alloy described in the present application is prepared in a manner well known to those skilled in the art, and the specific scheme is not specifically described herein; however, in the heat treatment stage, the heat treatment process conditions of the present application are: protective atmosphere H 2
- the holding temperature is 320-380 ° C
- the holding time is 60-120 min
- the magnetic field strength is 800-1400 A/m.
- the heat treatment process is also a key factor.
- the annealing process can eliminate the stress of the amorphous magnetic material, reduce the coercive force, improve the magnetic permeability, and obtain excellent Magnetic properties.
- the heat treatment is carried out under the atmosphere conditions of the conventional strip, the surface of the strip is oxidized and the magnetic properties are deteriorated. Therefore, the magnetic field heat treatment is performed under the pure hydrogen atmosphere of the present invention, as shown in Fig. 1. According to a large number of experimental results, the iron-based amorphous alloy strip subjected to the above heat treatment process has no oxidation and excellent magnetic properties.
- the heat treatment process mainly includes three parameters in addition to the atmospheric conditions: the holding temperature, the holding time, and the magnetic field strength.
- the holding temperature must be lower than the crystallization temperature. Once higher than the crystallization temperature, the amorphous ribbon will crystallize and the magnetic properties will deteriorate sharply.
- the crystallization temperature of the alloy of the present invention is less than 500 ° C, lower than the crystal. Under the premise of the temperature, the suitable temperature range of the insulation is the guarantee of the excellent magnetic properties of the amorphous ribbon. According to the effect data of the embodiment of the present invention, the relationship between the core loss, the excitation power and the holding temperature of the strip is related to the insulation.
- the holding temperature is less than 300 ° C or more than 360 ° C, performance deterioration occurs, and acceptable magnetic properties can be obtained between 300 and 360 ° C.
- the principle is similar to the holding temperature, and there is a suitable time interval, and the holding time is too short or too long to achieve the optimal performance of the present invention.
- the appropriate magnetic field strength is the necessary guarantee for the magnetization of the material;
- the main reason for the magnetic field annealing of the amorphous material is that the fixed direction, fixed-strength magnetic field causes the magnetic domain of the material to deflect toward the magnetic field, reducing the magnetic anisotropy of the material, optimizing Soft magnetic performance; for the present invention, when the magnetic field strength is less than 800 A/m, the magnetization process of the material is incomplete and the best effect cannot be achieved. When the magnetic field strength is >1400 A/m, the material is completely magnetized and the magnetic properties are not caused by The optimization of the magnetic field strength increases the difficulty and cost of the heat treatment process.
- the iron-based amorphous alloy provided by the present application has a core loss P ⁇ 0.1800 W/kg after heat treatment, an excitation power Pe ⁇ 0.2200 VA/kg, and a coercive force Hc ⁇ 4 A/m.
- Coercivity is an important indicator for evaluating the properties of soft magnetic materials. The smaller the coercivity, the better the soft magnetic properties.
- the parameters for evaluating their magnetic properties mainly include two parameters: core loss and excitation power. The smaller these two parameters, the better the performance of the subsequent core and transformer.
- the iron-based amorphous alloy ribbon provided by the present invention will be described below with reference to the embodiments.
- the material is described in detail, and the scope of protection of the present invention is not limited by the following examples.
- the invention is compounded according to the alloy composition of Fe a Si b B c P d M f , and the metal raw material is remelted by using an intermediate frequency smelting furnace, the melting temperature is 1300-1500 ° C, the time is 80-120 min; after smelting, After the smelted melt is heated and kept warm, a single roll is used for rapid quenching, and an iron-based amorphous broadband having a width of 142 mm and a thickness of 23 to 28 ⁇ m is obtained, and the temperature of the temperature rise is 1350 to 1470 ° C, and the heat retention time is It is 20 to 50 minutes.
- Table 1 lists the alloy composition of the present invention and the comparative examples, the saturation magnetic induction, the excitation power and the core loss data under the condition of 1.35 T/50 Hz; Examples 1 to 10 are examples of the invention, and Comparative Examples 11 to 15 For the comparative example.
- the heat treatment range in Table 1 means that the stability of the magnetic properties of the respective examples in this temperature range and time range, that is, the fluctuation of Pe and P is within the range of the optimum performance value ⁇ 0.01.
- the alloy composition according to the embodiment of the present invention can obtain a good saturation magnetic induction intensity, and the value is not less than 1.62 T, which exceeds the conventional iron-based amorphous material which is conventionally used in power transformers with a saturation magnetic induction of 1.56 T ( Comparative Example 13).
- the improvement of the saturation magnetic induction strength can further optimize the design of the transformer core, reduce the volume of the transformer, and reduce the cost; it can also be seen that the alloy composition according to the embodiment of the present invention can produce a completely amorphous strip, which is in accordance with the implementation of the present invention.
- the alloy composition of the example has good magnetic properties.
- the excitation power of the iron core after heat treatment is ⁇ 0.2200VA/kg
- the core loss is ⁇ 0.1800W/g
- the conventional amorphous material (pair) Compared to the ratio 13
- Figure 3 illustrates that the alloy of the present invention has stable magnetic properties over a wide temperature range of at least 20 ° C, i.e., the fluctuation of Pe and P is within ⁇ 0.01; compared to conventional 1.56 T amorphous ribbon
- the optimum heat treatment temperature is at least 20 ° C, which can reduce the temperature control requirements of the heat treatment equipment, increase the service life of the heat treatment equipment, and indirectly reduce the cost of the heat treatment process.
- Figure 4 illustrates that the alloy of the present invention has a better performance advantage in comparison with conventional iron-based amorphous materials under higher working magnetic density conditions; that is, a core prepared from an iron-based amorphous material prepared from the alloy composition of the present invention. And the transformer can be operated under higher working magnetic density conditions.
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Abstract
一种铁基非晶合金Fe aSi bB cP d ,其中,a、b、c与d分别表示对应组分的原子百分含量;81.0≤a≤84.0,1.0≤b≤6.0,9.0≤c≤14.0,0.05≤d≤3,a+b+c+d=100。通过调整铁基非晶合金的组分与含量,使得到的铁基非晶合金具有较高的饱和磁感应强度。
Description
本申请要求于2017年07月31日提交中国专利局、申请号为201710637409.8、发明名称为“一种铁基非晶合金”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。
本发明涉及铁基非晶合金技术领域,尤其涉及一种铁基非晶合金。
铁基非晶带材是一种新型节能材料,一般采用快速急冷凝固生产工艺制备。与传统硅钢变压器相比,铁基非晶带材用于变压器铁芯,磁化过程相当容易,从而大幅度降低变压器的空载损耗,若用于油浸变压器还可减少CO、SO、NOx等有害气体的排放,被称为21世纪的“绿色材料”。
目前,国内外在非晶变压器的制备过程中,普遍使用的均为饱和磁感应强度为1.56T左右的铁基非晶带材,与硅钢接近2.0T的饱和磁感应强度相比,铁基非晶在制备变压器时存在着体积增大的缺点。为了增强铁基非晶材料在变压器行业的竞争力,需开发饱和磁感应强度大于1.6T的铁基非晶材料。
对于具有高饱和磁感应强度的非晶材料研发,已经开展了很多年。最具有代表性的是美国Allied-Signal公司开发的一款牌号为Metglas2605Co的合金,这种合金的饱和磁感应强度达到1.8T,但其合金中包含18%的Co元素使其成本过高无法在工业生产中应用。
日立公司在公开号为CN1721563A的中国专利中公开了一种Fe-Si-B-C合金,其饱和磁感应强度在1.64T,但其公开的工艺条件中提到了在制备过程中通过吹含C气体而控制带材表面C元素含量分布的工艺,这将直接导致其产品生产工艺条件难以控制,工业生产稳定性无法保证。新日本制铁公司在专利CN1356403A中公布了一种Fe-Si-B-P-C的合金,虽然其饱和磁感应强度达到1.75T,但由于其Fe含量过高非晶形成能力较差导致在其工业化生产中无法形成非晶态,带材磁性能较差。
中国科学院宁波材料研究所在公开号为CN101840764A的中国专利中公布了一种Fe-Si-B-P-C合金,但其专利中使用的均为实验室原材料制备非晶带材,在其工业化过程中有以下问题:在此合金体系中添加了C元素,虽然C
的添加能提高合金体系的非晶形成能力,但在工业化过程中,C元素的引入主要通过两个途径,一是使用生铁,二是使用石墨,但这两种原材料均不适用于非晶带材的冶炼过程;生铁杂质含量过高过多引入会导致带材在制备过程中晶化进而影响磁性嫩;石墨熔点过高,在目前的冶炼过程中若使用石墨必须优化或增加冶炼流程,使工业化生产难度增大。
从以上问题出发,本发明从合金成分优化设计、热处理工艺优化方面入手,采用FeSiBP四元合金体系发明了具有高饱和磁感应强度、低损耗的适用于工业生产的铁基非晶合金带材。
发明内容
本发明解决的技术问题在于提供一种具有高饱和磁感应强度的铁基非晶合金。
有鉴于此,本申请提供了一种如式(Ⅰ)所示的铁基非晶合金,
FeaSibBcPd(Ⅰ);
其中,a、b、c与d分别表示对应组分的原子百分含量;81.0≤a≤84.0,1.0≤b≤6.0,9.0≤c≤14.0,0.05≤d≤3,a+b+c+d=100。
优选的,所述B的原子百分含量为11.0≤c≤13.0。
优选的,所述P的原子百分含量为1≤d≤3。
优选的,所述铁基非晶合金中,83.0≤a≤84.0,3.0≤b≤6.0,9.0≤c≤13.0,1≤d≤3。
优选的,所述铁基非晶合金中,81.5≤a≤82.5,b=3.0,12.5≤c≤14.0,1≤d≤3。
优选的,所述铁基非晶合金的饱和磁感应强度≥1.62T。
优选的,所述铁基非晶合金的热处理工艺在H2气氛下进行,保温温度为300~360℃,时间为60~120min,磁场强度为800~1400A/m。
优选的,经过热处理后,所述铁基非晶合金的矫顽力≤4A/m,铁芯损耗≤0.18W/kg,激磁功率≤0.22VA/kg。
优选的,经过热处理后,所述铁基非晶合金的宽度为100~200mm,厚度为23~28μm。
本申请还提供了所述的铁基非晶合金在电力配电变压器铁芯中的应用。
本申请提供了一种铁基非晶合金,其具有如式FeaSibBcPd的铁基非晶合金,其中,a、b、c与d分别表示对应组分的原子百分含量;81.0≤a≤84.0,1.0≤b≤6.0,
9.0≤c≤14.0,0.05≤d≤3,a+b+c+d=100;本申请提供的铁基非晶合金中Fe元素为铁磁性元素,为铁基非晶合金磁性的主要来源,高的Fe含量是铁基非晶合金带材具有高饱和磁感应强度的重要保证;Si和B是非晶形成元素,是形成非晶的必要条件;P同样也为非晶形成元素,且P和Fe具有较大的负的混合热,其有利于提高合金***过冷液相区的稳定性,但会引入杂质,因此,本申请通过添加上述元素并控制其含量,使铁基非晶合金的饱和磁感应强度较高。进一步的,本申请通过在氢气气氛下进行磁场热处理,消除了铁基非晶合金的磁性应力,降低了矫顽力,提高了磁导率,最终获得了磁性能优良的铁基非晶合金。
图1为本发明实施例与对比例制备态的XRD图谱;
图2为本发明实施例与对比例的热处理后的带面氧化情况;
图3为本发明实施例与对比例的磁性能与热处理温度的关系图;
图4为本发明实施例与对比例的50Hz条件下的损耗曲线对比图。
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。
为了得到具有高饱和磁感应强度的铁基非晶合金,本申请通过选择适当的元素并控制其含量得到了一种铁基非晶合金,具体的,所述铁基非晶合金具体为一种如式(Ⅰ)所示的铁基非晶合金,
FeaSibBcPd(Ⅰ);
其中,a、b、c与d分别表示对应组分的原子百分含量;81.0≤a≤84.0,1.0≤b≤6.0,9.0≤c≤14.0,0.05≤d≤3,a+b+c+d=100。
本发明提供了一种具有高饱和磁感应强度的、低损耗的FeSiBP四元体系的铁基非晶合金,进一步的,在热处理过程中通过使用氢气气氛,改善带材氧化情况以及提高了带材的磁性能。
具体的,在上述铁基非晶合金中,所述Fe元素为铁磁性元素,为铁基非晶合金带材磁性的主要来源,高的Fe含量是带材具有高饱和磁感应强度值的
重要保障;但过高的Fe元素会导致合金的非晶形成能力下降,使工业生产难以实现。本申请中Fe的原子百分含量为81.0≤a≤84.0,在具体实施例中,所述Fe的原子百分含量为81.5~83,更具体的,所述Fe的原子百分含量为81.5、82、82.5、83、83.5或84。
Si和B元素为非晶形成元素,是合金***在工业生产条件下能形成非晶的必要条件。Si元素的原子百分含量为1.0~6.0,过低会导致非晶形成能力下降,且影响带材的磁性能,过高会偏离共晶点同样会降低非晶形成能力;在具体实施例中,Si的含量为2.0~6.0,具体的,所述Si的含量为2.0、3.0、4.0、5.0或6.0。B元素的范围为9.0~14.0,小于9时,合金非晶形成能力偏低,大于14时,偏离共晶点,合金非晶形成能力降低;在具体实施例中,所述B的含量为11.0~13.0。
P元素与Si、B元素一样,同为非晶形成元素,且P和Fe有较大的负的混合热。P的添加有利于提高合金***的过冷液相区的稳定性,起非晶形成元素的作用。但在实际工业生产过程中,P元素的添加主要通过磷铁实现,大量添加会在钢水中引入大量杂质,使钢水质量严重下降,一方面影响带材的制备成功率,带材无法形成非晶,另一方面也会影响带材的磁性能,大量夹杂固化在带材中,会在带材内部形成内部缺陷及质点,热处理过程中对磁畴有钉轧作用,从而使带材的磁性能恶化;当P含量的添加小于0.05时,P元素在整个合金***中是以微量元素的形式存在,无法起到提高合金***过冷液相区的作用,也无法改善铁基非晶带材的磁性能。因此,本申请中P元素的范围为0.05~3,一方面控制杂质的引入,另一方面能提高整个合金***的非晶形成能力;在某些具体实施例中,所述P的含量为1~3,更具体的,所述P的含量为1.0、2.0或3.0。本申请铁基非晶合金中不可避免的含有杂质元素。
在某些具体实施例中,所述铁基非晶合金各组分的含量为:83.0≤a≤84.0,3.0≤b≤6.0,9.0≤c≤13.0,1≤d≤3;在某些具体实施例中,所述铁基非晶合金各组分的含量为:81.5≤a≤82.5,b=3.0,12.5≤c≤14.0,1≤d≤3。具有上述组分含量的铁基非晶合金具有更好的磁性能。
本申请所述铁基非晶合金的制备方法按照本领域技术人员熟知的方式制备得到,具体流程此处不进行特别的赘述;但是在热处理阶段,本申请的热处
理工艺条件为:保护气氛H2,保温温度为320~380℃,保温时间为60~120min,磁场强度为800~1400A/m。
非晶、纳米晶软磁材料磁性能的影响因素除自身合金成分外,热处理工艺也是一个关键因素,通过退火处理可以消除非晶磁性材料的应力,降低矫顽力,提高磁导率,获得优良的磁性能。对于本发明而言,若采用常规带材的气氛条件进行热处理,会导致带材表面氧化,进而磁性恶化,故本发明纯氢气气氛下进行磁场热处理,见附图1对比。根据大量的实验结果得出,经过上述热处理工艺的铁基非晶合金带材带面无氧化,磁性能优良。对于铁基非晶带材而言,其热处理工艺除了气氛条件外还主要包含三个参数:保温温度、保温时间、磁场强度。首先对于保温温度必须低于晶化温度,一旦高于晶化温度,非晶带材会发生晶化,磁性能急剧恶化,本发明所述合金的晶化温度均小于500℃,在低于晶化温度的前提下,合适的保温温度区间是非晶带材获得优良磁性能的保障,根据本发明实施例的效果数据可知,带材的铁芯损耗、激磁功率与保温温度的关系是随着保温温度的提高,此两项参数有先降低后增大的趋势。因此对于本发明而言,当保温温度小于300℃或大于360℃时,都会出现性能恶化的现象,在300~360℃之间能获得合格的磁性能。其次,对于保温时间,其原理与保温温度相似,有一合适的时间区间,保温时间过短或过长,均不能使本发明达到最优的性能。最后,合适的磁场强度是材料磁化的必要保证;对非晶材料进行磁场退火的主要原因是固定方向、固定强度的磁场促使材料的磁畴偏转向磁场方向,降低材料的磁各向异性,优化软磁性能;对于本发明而言,当磁场强度小于800A/m时,材料磁化过程不完全,无法达到最佳的效果,当磁场强度>1400A/m时,材料磁化完全,磁性能不会因磁场强度的增大而优化,反而会增加热处理过程的难度及成本。
因此,本申请提供的铁基非晶合金经过热处理后铁芯损耗P≤0.1800W/kg,激磁功率Pe≤0.2200VA/kg,矫顽力Hc≤4A/m。矫顽力为评价软磁材料性能的一项重要指标,矫顽力越小,软磁性能越好。对于应用于配电变压器行业的非晶带材而言,评价其磁性能的参数主要包含两个参数:铁芯损耗、激磁功率。此两项参数越小,对后续铁芯及变压器的性能越好。
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带
材进行详细说明,本发明的保护范围不受以下实施例的限制。
实施例
本发明按FeaSibBcPdMf的合金组成进行配料,使用中频冶炼炉将金属原材料重熔,所述熔炼的温度为1300~1500℃,时间为80~120min;在熔炼之后,将熔炼后的熔液升温保温后采用单辊快淬,而得到了宽度为142mm,厚度为23~28μm的铁基非晶宽带,所述升温的温度为1350~1470℃,所述保温的时间为20~50min。表1中列举了本发明例与对比例的合金成分、饱和磁感应强度、1.35T/50Hz条件下的激磁功率及铁芯损耗数据;其中实施例1~10为本发明例,对比例11~15为对比例。
表1实施例与对比例的组分与性能数据表
备注:a:表1中磁性能为各发明例在最佳的保温温度及保温时间点热处理得到的磁性能。
b:表1中热处理范围指的是各实施例在此温度范围及时间范围处理可得到稳定的磁性能,即Pe与P的波动在最佳性能值±0.01范围内。
由表1可知,符合本发明实施例的合金成分均能获得较好的饱和磁感应强度,数值不小于1.62T,超过目前电力变压器常规使用的饱和磁感应强度为1.56T的常规铁基非晶材料(对比例13)。饱和磁感应强度的提高可进一步优化变压器铁芯的设计,降低变压器的体积,减少成本;还可以看出,符合本发明实施例的合金成分均能制备出完全非晶的带材,符合本发明实施例的合金成分具有较好的磁性能,在50Hz,1.35T的条件下,热处理后的铁芯的激磁功率≤0.2200VA/kg、铁芯损耗≤0.1800W/g,与常规非晶材料(对比例13)相比,达到了使用要求。
结合表1及附图1(从实施例1~10与对比例11)可以看出,过量添加P的合金成分会导致带材出现晶化的现象,主要是由于工业制备的磷铁杂质含量过高,当P元素添加>3时,会引入过量的杂质,使本发明在实际工业生产中无法制备出完全非晶的带材。从实施例1~10与对比例12可以看出,当Fe含量过高时,合金的非晶形成能力较差,带材会出现晶化的现象。
结合表1及附图2(从实施例1~10与比较例13、比较例14、15对比,附图2中左图为氢气气氛处理的铁基非晶合金,右图为氩气气氛处理的铁基非晶合金)可以看出,本发明例只有使用氢气气氛才能在热处理后不出现氧化情况,
比较例14、15使用纯氩气处理,表面出现氧化(发蓝)情况,且磁性能恶化相当严重。
附图3说明了本发明合金在较宽的温度范围内,至少20℃,均有稳定的磁性能,即Pe与P的波动在±0.01范围内;与常规1.56T的非晶带材相比,其最佳热处理温度偏低至少20℃,可以降低对热处理设备的温控要求,增加热处理设备的使用寿命,间接降低热处理过程的成本。
附图4说明本发明合金与常规铁基非晶对比,在较高的工作磁密条件下有较好的性能优势;也就是说,由本发明合金成分制备的铁基非晶材料制备的铁芯及变压器可在更高的工作磁密条件下运行。
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 (10)
- 一种如式(Ⅰ)所示的铁基非晶合金,FeaSibBcPd(Ⅰ);其中,a、b、c与d分别表示对应组分的原子百分含量;81.0≤a≤84.0,1.0≤b≤6.0,9.0≤c≤14.0,0.05≤d≤3,a+b+c+d=100。
- 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11.0≤c≤13.0。
- 根据权利要求1所述的铁基非晶合金,其特征在于,所述P的原子百分含量为1≤d≤3。
- 根据权利要求1所述的铁基非晶合金,其特征在于,所述铁基非晶合金中,83.0≤a≤84.0,3.0≤b≤6.0,9.0≤c≤13.0,1≤d≤3。
- 根据权利要求1所述的铁基非晶合金,其特征在于,所述铁基非晶合金中,81.5≤a≤82.5,b=3.0,12.5≤c≤14.0,1≤d≤3。
- 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≥1.62T。
- 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热处理工艺在H2气氛下进行,保温温度为300~360℃,时间为60~120min,磁场强度为800~1400A/m。
- 根据权利要求7所述的铁基非晶合金,其特征在于,经过热处理后,所述铁基非晶合金的矫顽力≤4A/m,铁芯损耗≤0.18W/kg,激磁功率≤0.22VA/kg。
- 根据权利要求7所述的铁基非晶合金,其特征在于,经过热处理后,所述铁基非晶合金的宽度为100~200mm,厚度为23~28μm。
- 权利要求1~9任一项所述的铁基非晶合金在电力配电变压器铁芯中的应用。
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EP3584350A1 (en) | 2019-12-25 |
CN107236911A (zh) | 2017-10-10 |
KR20190094209A (ko) | 2019-08-12 |
US20190368018A1 (en) | 2019-12-05 |
EP3584350A4 (en) | 2020-03-18 |
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