CN110670001A - Preparation method of silicon-rich P-containing iron-based amorphous nanocrystalline alloy and iron-based amorphous alloy nanocrystalline magnetic core - Google Patents
Preparation method of silicon-rich P-containing iron-based amorphous nanocrystalline alloy and iron-based amorphous alloy nanocrystalline magnetic core Download PDFInfo
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Abstract
The invention provides a compound shown as formula FexSiyBzCueNbmPnThe application also provides a preparation method of the iron-based amorphous nanocrystalline alloy; according to the application, by adding a proper amount of P element, the coercive force of the iron-based amorphous nanocrystalline alloy is effectively reduced, the effective magnetic permeability of 1-20 kHz is improved, and the iron-based amorphous nanocrystalline alloy is good in amorphous forming capability and excellent in thermal stability by being matched with other elements.
Description
Technical Field
The invention relates to the technical field of magnetic materials, in particular to a preparation method of an iron-based amorphous nanocrystalline alloy and an iron-based amorphous alloy nanocrystalline magnetic core.
Background
Soft magnetic materials and their associated components (inductors, transformers and motors) play a key role in energy conversion throughout the world. Conversion of electrical energy involves bidirectional energy flow between energy sources, storage and the grid, and is widely used in the field of power electronics. With the introduction of Wide Bandgap (WBG) semiconductors, power conversion, electronics, and motor controllers were enabled to operate at higher frequencies. This can further reduce the size requirements of components (inductors and capacitors) in power electronics and allow for higher efficiency and higher rotational speeds. At the same time, the market demands for the properties of soft magnetic materials are also increasing.
Since the 19 th century, metallurgists, material scientists and related personnel have been pushing out improved materials when pure iron is the only soft magnetic material available. The 1900 silicon steel invention is a matter of concern for soft magnetic materials. At present, silicon steel and pure iron which occupy nearly 80% of the market share of metal soft magnetic materials are still the leading positions of the global soft magnetic market and are the first choice materials of large transformers and motors. However, the low resistance of silicon steel and pure iron seriously affects the eddy current effect, and particularly, the magnetic core has more serious eddy current loss when the working frequency is increased, which causes serious energy and environmental problems, and is not in accordance with the development direction of power electronic technology to high frequency, large current, miniaturization, high efficiency and energy conservation in recent years. After decades of development and research, the amorphous/nanocrystalline soft magnetic alloy of the new generation soft magnetic material has higher saturation magnetization B due to the excellent soft magnetic propertySAnd magnetic permeability mu and low iron loss PCAnd a large number of researchers at home and abroad are attracted to carry out a large amount of scientific research, and some research results are successfully industrialized.
Because of its outstanding soft magnetic performance and relatively low cost, Fe-based amorphous/nanocrystalline soft magnetic alloy is gradually replacing silicon steel, permalloy, ferrite, etc. and is widely used in power electronic devices such as high-frequency electronic transformers, inductors, etc., and can improve transformer efficiency, reduce volume, reduce weight, reduce loss, so it is known as a novel green energy-saving material in the 21 st century, and is now widely used in the field of power electronics.
The newly developed heat-generating soft magnetic composite material is suitable for obtaining extremely high resistivity due to insulation coating design and can adapt to higher working frequency, but the conductivity of the composite material is not high. Aiming at the current soft magnetic material condition, the iron-based amorphous nanocrystalline soft magnetic alloy with high saturation magnetic induction intensity, high magnetic conductivity and low loss is further developed, and is the key for meeting the requirements of power electronics on the soft magnetic material.
Disclosure of Invention
The invention aims to provide the iron-based amorphous nanocrystalline alloy with good amorphous forming capability, excellent thermal stability and excellent soft magnetic performance.
In view of the above, the present application provides an iron-based amorphous nanocrystalline alloy represented by formula (i),
FexSiyBzCueNbmPn(Ⅰ)；
wherein x, y, z, e, m and n respectively represent the atom percentage content of the corresponding components; x is not less than 71.5 and not more than 73.5, y is not less than 12.5 and not more than 15.5, z is not less than 1.0 and not more than 7.0, e is not less than 0.5 and not more than 2.0, m is not less than 1.0 and not more than 3.0, and n is more than 0 and not more than 3; and x + y + z + e + m + n is 100.
Preferably, the atomic percentage of Fe is 72-73.5, and the atomic percentage of Si is 13-15.5.
Preferably, the atomic percentage of B is 4-6, the atomic percentage of P is 0.5-2, the atomic percentage of Cu is 0.5-1.2, and the atomic percentage of Nb is 1.5-3.0.
Preferably, in the iron-based amorphous nanocrystalline alloy, n + z is 7.
Preferably, in the iron-based amorphous nanocrystalline alloy, n + y is 15.5.
Preferably, in the iron-based amorphous nanocrystalline alloy, n + x is 73.5.
Preferably, the iron-based amorphous nanocrystalline alloy is Fe73.5Si15.5B6Cu1Nb3P1、Fe73.5Si15.5B5Cu1Nb3P2、Fe73.5Si15.5B4Cu1Nb3P3、Fe73.5Si14.5B7Cu1Nb3P1、Fe73.5Si13.5B6Cu1Nb3P2、Fe73.5Si12.5B5Cu1Nb3P3、Fe73Si15.5B7Cu1Nb3P0.5、Fe72.5Si15.5B6Cu1Nb3P1、Fe72Si15.5B5Cu1Nb3P1.5Or Fe71.5Si15.5B4Cu1Nb3P2。
The application also provides a preparation method of the iron-based amorphous nanocrystalline magnetic core, which comprises the following steps:
the iron-based amorphous alloy nanocrystalline alloy according to claim 1 is prepared by blending and then smelting to obtain an iron-based amorphous nanocrystalline master alloy;
carrying out copper roller rapid quenching on the iron-based amorphous nanocrystalline master alloy to obtain an iron-based amorphous alloy thin strip;
and carrying out heat treatment on the iron-based amorphous alloy thin strip to obtain the iron-based amorphous nanocrystalline magnetic core.
Preferably, in the copper roller rapid quenching, the linear speed of the copper roller is 50 m/s-55 m/s.
Preferably, the initial temperature of the heat treatment is 200 ℃, the primary heating rate is 10 ℃/min, the heat preservation temperature of the first stage is 460-510 ℃, and the heat preservation time is 15 min; the secondary heating rate is 1 ℃/min, the heat preservation temperature of the second stage is 500-520 ℃, and the heat preservation time is 60 min; cooling to 300 ℃ with the furnace and air cooling.
The application provides an iron-based amorphous nanocrystalline alloy having the formula FexSiyBzCueNbmPnAccording to the iron-based amorphous nanocrystalline alloy, a proper amount of P element is added, so that the coercive force of the iron-based amorphous nanocrystalline alloy is effectively reduced, the effective magnetic conductivity of 1-20 kHz is improved, and the iron-based amorphous nanocrystalline alloy is good in amorphous forming capability and excellent in thermal stability by being matched with other elements; further, by heat treatment, the iron-based amorphous nanocrystalline alloyalpha-Fe nano magnetic particles with the nano particles of about 15nm also enable the iron-based amorphous nanocrystalline alloy to have excellent soft magnetic performance.
Drawings
FIG. 1 is a schematic view of the process flow of the Fe-based amorphous nanocrystalline alloy of the present invention;
FIG. 2 is an XRD spectrum of a first set of example series alloy strips in a quenched state;
FIG. 3 is an XRD spectrum of a second set of example series alloy strips in a quenched state;
FIG. 4 is an XRD spectrum of a third series of example series alloy strips in a quenched state.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Aiming at the requirements of the iron-based amorphous nanocrystalline alloy in the prior art, the magnetic performance is improved through the design and alloying of alloy components, so that the magnetic performance of the iron-based amorphous nanocrystalline alloy under high frequency is expected to be improved. Specifically, the embodiment of the invention discloses an iron-based amorphous nanocrystalline alloy as shown in a formula (I),
FexSiyBzCueNbmPn(Ⅰ)；
wherein x, y, z, e, m and n respectively represent the atom percentage content of the corresponding components; x is not less than 71.5 and not more than 73.5, y is not less than 12.5 and not more than 15.5, z is not less than 1.0 and not more than 7.0, e is not less than 0.5 and not more than 2.0, m is not less than 1.0 and not more than 3.0, and n is more than 0 and not more than 3; and x + y + z + e + m + n is 100.
In the iron-based amorphous nanocrystalline alloy, Fe is a ferromagnetic material and provides magnetism for the iron-based amorphous nanocrystalline alloy; the atomic percentage of Fe is 71.5-73.5; in a specific embodiment, the atomic percentage of Fe is 72-73.5.
Si and B are amorphous forming elements, wherein the content of Si has a large influence on the magnetic permeability of the iron-based amorphous nanocrystalline alloy. The atomic percentage of the Si is 12.5-15.5, and in a specific embodiment, the atomic percentage of the Si is 13-15.5. The atomic percentage of B is 1.0-7.0, and in a specific embodiment, the atomic percentage of B is 4-6.
Cu and Nb are taken as nanocrystal forming elements, and nanocrystalline particles with controllable sizes can be obtained in the annealing process. The atomic percentage of Cu is 0.5-2.0; in a specific embodiment, the atomic percentage of Cu is 0.5-1.2. The atomic percentage of Nb is 1.0-3.0, and in a specific embodiment, the atomic percentage of Nb is 1.5-3.0.
P can promote the amorphous forming ability, reduce the coercive force and improve the magnetic conductivity of the frequency band of 1kHz-20 kHz. The atomic percentage of the P is more than 0 and less than or equal to 3; in a specific embodiment, the atomic percentage of P is 0.5-2. Too much P content deteriorates the toughness of the quenched alloy strip and weakens the thermal stability of the alloy strip.
In a specific embodiment, said n + z is 7; the n + y is 15.5; and n + x is 73.5.
In a specific embodiment, the iron-based amorphous nanocrystalline alloy is Fe73.5Si15.5B6Cu1Nb3P1、Fe73.5Si15.5B5Cu1Nb3P2、Fe73.5Si15.5B4Cu1Nb3P3、Fe73.5Si14.5B7Cu1Nb3P1、Fe73.5Si13.5B6Cu1Nb3P2、Fe73.5Si12.5B5Cu1Nb3P3、Fe73Si15.5B7Cu1Nb3P0.5、Fe72.5Si15.5B6Cu1Nb3P1、Fe72Si15.5B5Cu1Nb3P1.5Or Fe71.5Si15.5B4Cu1Nb3P2。
The application also provides a preparation method of the iron-based amorphous nanocrystalline magnetic core, which comprises the following steps:
the method comprises the following steps of (1) mixing the components of the iron-based amorphous alloy nanocrystalline alloy and then smelting to obtain an iron-based amorphous nanocrystalline master alloy;
carrying out copper roller rapid quenching on the iron-based amorphous nanocrystalline master alloy to obtain an iron-based amorphous alloy thin strip;
and carrying out heat treatment on the iron-based amorphous alloy thin strip to obtain the iron-based amorphous nanocrystalline magnetic core.
In the preparation process of the iron-based amorphous alloy, the iron-based amorphous nanocrystalline alloy is prepared by firstly mixing the components of the iron-based amorphous nanocrystalline alloy and then smelting to obtain the iron-based amorphous nanocrystalline master alloy; in order to ensure the quality of the master alloy, vacuum pumping is carried out before smelting, and the vacuum degree is 1 multiplied by 10-3Within Pa; then high-purity argon is introduced, which can be used as protective gas, arc striking and heat source. During the smelting process, titanium ingots can be smelted in advance to absorb residual oxygen in the smelting furnace, and then smelting is started. The operation related to the specific smelting is not particularly limited in this application and is a technique known to those skilled in the art.
Carrying out copper roller rapid quenching on the iron-based amorphous nanocrystalline master alloy to obtain an iron-based amorphous alloy thin strip; in the process, the linear speed of the copper roller is 50-55 m/s.
According to the invention, the iron-based amorphous alloy thin strip is subjected to heat treatment to obtain the iron-based amorphous nanocrystalline magnetic core. In the application, the initial temperature of the heat treatment is 200 ℃, the primary heating rate is 10 ℃/min, the first-stage heat preservation temperature is 460-510 ℃, and the heat preservation time is 15 min; the secondary heating rate is 1 ℃/min, the heat preservation temperature of the second stage is 500-520 ℃, and the heat preservation time is 60 min; cooling to 300 ℃ with the furnace and air cooling. The heat treatment is carried out according to the above system, alpha-Fe is uniformly nucleated and grows into nanocrystalline particles in the crystallization annealing process, and the nanocrystalline particles are uniformly distributed in the amorphous alloy matrix to form an amorphous/nanocrystalline two-phase composite structure, so that excellent soft magnetic performance is obtained.
The invention improves the magnetic property of the strip of the iron-based amorphous nanocrystalline alloy by adding a proper P element, analyzes the annealed structure of the alloy strip in each group of examples by XRD, and only detects alpha-Fe (Si) nano magnetic particles with the nano particles of about 15nm, which is also the reason for obtaining excellent soft magnetic property of the alloy strip.
For further understanding of the present invention, the following examples are given to illustrate the iron-based amorphous nanocrystalline alloy and the preparation method thereof in detail, and the scope of the present invention is not limited by the following examples.
Examples
(1) Melting of master alloys
The alloy designed by the invention has the chemical general formula of FexSiyBzCueNbmPn(#), wherein x is not less than 71.5 and not more than 73.5, y is not less than 12.5 and not more than 15.5, z is not less than 1.0 and not more than 7.0, e is not less than 0.5 and not more than 2.0, m is not less than 1.0 and not more than 3, n is more than 0 and not more than 3, x + y + z + e + m + n is 100, and letters x, y, z, e, m and n in the component general formula in the invention are all expressed in atomic percentage content unless otherwise specified.
The industrial raw materials required by the master alloy are elementary substance elements Fe, Cu, Nb, Mo and Si, FeB and FeP alloy, and the purity of the raw materials is shown in Table 1;
TABLE 1 raw material and purity table thereof
The raw materials are weighed according to the formula, and then smelted by using a WK-II A type non-consumable vacuum arc melting furnace. In order to ensure the quality of the master alloy, the furnace body is vacuumized before smelting, so that the vacuum degree reaches 1 multiplied by 10-3Pa, then introducing high-purity argon (purity 99.99%), wherein the argon also serves as an arc striking and heat source besides serving as protection. When each batch of samples are smelted, a smelting pot is reserved for containing titanium ingots, the titanium ingots are smelted firstly during smelting so as to absorb residual oxygen in the smelting furnace, then experimental samples are smelted, and each sample needs to be overturned for repeated smelting for 4 times so as to ensure the uniformity of alloy components, reduce the segregation of elements and obtain high-quality master alloy.
(2) Method for preparing amorphous alloy thin strip by copper roller rapid quenching method
The amorphous alloy strip is prepared by using an NMS-II type induction type solution quick quenching strip throwing machine, wherein before strip throwing, a copper roller is rotated at a linear speed of less than 15m/s, an oxide layer on the surface of the copper roller is slightly ground by using sand paper of more than 2000 meshes, and then dirt on the surface is wiped by using gauze dipped with acetone, so that the surface of the copper roller is clean and has no oxide layer, and the cooling effect is ensured.
Grinding the melted mother alloy by using a grinding wheel machine to remove an oxide layer on the surface layer, crushing the mother alloy into an alloy block with the diameter of about 5-8 mm, putting the alloy block into a quartz tube, fixing the quartz tube right above a copper roller, wherein the caliber of the quartz tube hole is 0.4-0.6 mm, and the height from the orifice to the surface of the copper roller is controlled at 0.25 mm; after the test tube is installed, the furnace door is closed, and the furnace body is vacuumized to be lower than 6 multiplied by 10-3And Pa, closing the vacuumizing valve, filling high-purity argon into the furnace chamber to serve as protective gas, filling air into the air pressure chamber connected with the test tube, and adjusting the air pressure of the air pressure chamber to be greater than the air pressure of the furnace chamber by 0.03-0.04 MPa. Heating the master alloy by using a medium-frequency induction coil, after the alloy is melted, when observing that the color of the melt is suddenly changed from orange to yellow, pressing a switch for switching on a pressure cavity, and spraying the melt onto a rapidly rotating copper roller with the linear speed of 50-55 m/s by using pressure difference to prepare an alloy strip with the thickness of about 25mm and the width of about 1.2 mm;
(3) x-ray diffraction analysis (XRD) and Differential Scanning Calorimetry (DSC) analysis
Verifying whether the prepared alloy thin strip is in a complete amorphous structure or not by adopting an X-ray diffraction analysis (XRD) method, wherein in order to ensure that the alloy strip is in the complete amorphous structure, the XRD spectrums of all quenched alloy samples are from the free surface (the other side relative to the surface of the copper roller) of the alloy strip; the relevant test conditions and parameters were: wavelength of X-rays
Filtering by a graphite monochromator, wherein the tube voltage is 40kV, the tube current is 30mA, the test range is 20-90 degrees, the step length is 0.02 degrees, and the scanning speed is 8 degrees/min;in the application, the amorphous alloy strip can be determined by XRD spectrum, and if the characteristic spectrum of the amorphous alloy strip presents wide diffraction peaks (also called 'steamed bun peaks'), the strip can be judged to be in a completely amorphous structure;
performing thermal analysis on the alloy strip by using a Differential Scanning Calorimetry (DSC) method to examine the crystallization behavior and the thermal stability of the alloy strip, wherein an SDT Q600 type differential scanning calorimeter produced by TA Instrument company in the United states is used as equipment, and a DSC curve of the amorphous strip is measured in a DSC-TGA mode;
the strip was cut into small pieces having an area of less than 1mm by 1mm before testing, weighed about 20mg and placed on a sample table in an alumina crucible at N2Heating the sample by raising the temperature under the protection of the atmosphere, wherein the heating rate is 20 ℃/min, and the heating range is 300-800 ℃; by analyzing DSC curve of the sample, the phase change of each sample in the heating process can be obtained, and the thermal characteristic temperature parameter value, such as Curie temperature TcGlass transition temperature TgAnd the crystallization starting temperature T of the alloy stripxAnd crystallization peak temperature Tp(ii) a According to the characteristic temperature value of the DSC curve of the alloy strip, the thermal stability of the alloy strip can be reflected, a reference is provided for determining the heat treatment process of the amorphous strip, and the approximate annealing temperature range is determined.
(4) Preparation and heat treatment of annular magnetic core
Coiling the quenched alloy strip into an annular magnetic core with the specification of Dxd XH being 16 × 12 × 1.2mm, and controlling the magnetic core to have consistent lamination coefficient by weighing weight and inner and outer diameters; then carrying out heat treatment crystallization annealing treatment on the annular magnetic core, wherein the heat treatment equipment is a programmable control single vacuum tube high-temperature sintering furnace produced by Nobady materials science and technology company Limited, and the model of the furnace is NBD-O1200-60 IT; during heat treatment, a magnetic core sample is placed in a tube furnace for crystallization annealing treatment, and alpha-Fe (Si) nanocrystalline phase is precipitated; in the heat treatment process, the furnace temperature is 200 ℃, the primary heating speed is 10 ℃/min, the heat preservation temperature of the first stage is 460-510 ℃, and the heat preservation time is 15 min; the secondary heating rate is 1 ℃/min, and the heating is carried out to the second stage heat preservation temperature Ta(preferably 520 ℃) and keeping the temperature for 60min, and then opening a furnace cover to cool to 300 ℃ along with the furnace to dischargeFurnace air cooling, in order to prevent the oxidation of the magnetic core of the alloy strip, N is introduced into the magnetic core in the annealing process2And (4) protecting.
(5) Magnetic Property test and results
The static magnetic hysteresis loop of the alloy strip magnetic core sample is measured by MATS-2010SD soft magnetic direct current equipment produced by the science and technology of the United nations of Hunan province, and the intrinsic coercive force Hc of the magnetic core is obtained.
Measuring the saturation magnetization intensity Ms of the alloy strip in an annealed state by using a Vibration Sample Magnetometer (VSM) developed by Beijing Objective photoelectric technology company; the device obtains the curve relation of the sample magnetic moment changing along with the external magnetic field based on the principle of electromagnetic induction, and the range of the test magnetic field is as follows: -12500 to 12500 Oe; before testing, the equipment was calibrated with prepared Ni markers, then the magnetic sample to be tested was crushed, weighed to about 0.032g, wrapped tightly with tinfoil, and placed in a copper mold for measurement.
Measuring the single-pound inductance of the magnetic core sample in the range of 1kHz to 200kHz by using a precision magnetic element analyzer model 1J3260B from Wayne Kerr Electronics, UK; the test conditions were: the voltage is 50mV, the frequency of a switching power supply is 1kHz, and the diameter of the enameled copper wire is 0.50 mm; and then converted into effective permeability by a formula.
After the preparation and testing method (shown in fig. 1) of the fe-based amorphous nanocrystalline alloy is described above, the following steps are performed for the fe-based amorphous nanocrystalline alloy with specific components:
A) first group of embodiments
On the premise of satisfying the formula (#) and the condition thereof, n + z is 7, and the variation range of n is more than or equal to 0 and less than or equal to 6, the alloy is weighed and matched according to the component proportion, the series of alloys are smelted according to the method of the step (1) to obtain the master alloy for the melt spinning, then the amorphous alloy ribbon is prepared according to the method of the step (2), the XRD spectrum of the alloy ribbon sample is shown in figure 2, as can be seen from figure 2, the alloy ribbon begins to crystallize from n being more than or equal to 4, and the XRD diffraction spectrum of all the alloy ribbon samples only appears a broadened diffuse scattering peak near 2 theta of about 45 degrees within the range of 0 being more than or equal to 3, so that the alloy sample is in a complete amorphous structure. DSC curves of all samples were determined by DSC analysisThe lines all have two obvious exothermic peaks corresponding to the precipitation of alpha-Fe (Si) and Fe- (B, P) compounds, and the first-stage initial crystallization temperature mark of the alloy strip is Tx1(i.e., alpha-Fe (Si) initial precipitation temperature point), and the second-stage initial crystallization temperature is denoted as Tx2(i.e. the temperature point of the initial precipitation point of the Fe- (B, P) compound), and the difference between the two-stage initial crystallization temperatures is marked as delta Tx(definition: Δ T)x＝Tx2-Tx1). And (4) carrying out heat treatment and magnetic property test on the alloy strip in the completely amorphous state according to the steps (3) and (4). A comparison of the thermal characteristic temperature and magnetic properties of the alloy strip of this set of examples is summarized in Table 2.
TABLE 2 data table of characteristic temperature and annealed magnetic properties of alloy strip of the first group of examples
Table 2, structure of the quenched alloy strip: a represents a completely amorphous structure; b represents an amorphous + partially crystalline state. X indicates that the item of data is not given.
B) Second group of embodiments
On the premise of satisfying the (#) formula and the conditions thereof, n + y is 15.5, and the variation range of n is more than or equal to 1 and less than or equal to 4, the alloy is weighed and matched according to the component proportion, the series of alloys are smelted according to the method of the step (1) to obtain a master alloy for melt spinning, then an amorphous alloy ribbon is prepared according to the method of the step (2), the XRD spectrum of the alloy ribbon sample is shown in figure 3, the XRD diffraction spectrum of all the alloy ribbon samples only has a broadened diffuse scattering peak near 2 theta of about 45 degrees, and the alloy sample is indicated to be in a complete amorphous structure. DSC analysis shows that two obvious exothermic peaks appear on DSC curves of all samples, and the two obvious exothermic peaks respectively correspond to the precipitation of alpha-Fe (Si) and Fe- (B, P) compounds. And (4) carrying out heat treatment and magnetic property test on the alloy strip in the completely amorphous state according to the steps (3) and (4). A comparison of the thermal characteristic temperature and magnetic properties of the alloy strip of this set of examples is summarized in Table 3.
TABLE 3 data table of characteristic temperature and annealed magnetic properties of alloy strip of the second group of examples
Table 3, structure of the quenched alloy strip: a represents a completely amorphous structure.
C) Third group of embodiments
On the premise of satisfying the (#) formula and the conditions thereof, making n + x equal to 73.5, and making n have a variation range of 0.5-2.0, weighing and matching the alloy according to the component proportion, smelting the series of alloys according to the method of the step (1) to obtain a master alloy for strip throwing, then preparing an amorphous alloy thin strip according to the method of the step (2), wherein the XRD spectrum of the alloy strip sample is shown in figure 4, and the XRD diffraction spectrum of all the alloy strip samples only has a broadened diffuse scattering peak near 2 theta of about 45 degrees, which indicates that the alloy sample is a complete amorphous structure. DSC analysis shows that two obvious exothermic peaks appear on DSC curves of all samples, and the two obvious exothermic peaks respectively correspond to the precipitation of alpha-Fe (Si) and Fe- (B, P) compounds. And (4) carrying out heat treatment and magnetic property test on the alloy strip in the completely amorphous state according to the steps (3) and (4). A comparison of the thermal characteristic temperature and magnetic properties of the alloy strip of this set of examples is summarized in Table 4.
TABLE 4 third set of data sheets of characteristic temperature and annealed magnetic properties of example alloy strip
Table 4, structure of the quenched alloy strip: a represents a completely amorphous structure.
According to the three groups of embodiments, the coercive force of the iron-based amorphous nanocrystalline alloy strip can be effectively reduced and the effective magnetic permeability of 1kHz to 20kHz can be improved by adding a proper P element; fe as in the first set of examples73.5Si15.5B6Cu1Nb3P1After annealing of the alloy strip coreThe coercive force is 1.2A/m, and the effective magnetic conductivity under 1kHz is 120 k; fe in the third group of examples72.5Si15.5B6Cu1Nb3P1The alloy strip magnetic core has the coercive force of 0.6A/m after annealing and the effective magnetic permeability of 87k at 1 kHz.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. An iron-based amorphous nanocrystalline alloy as shown in formula (I),
FexSiyBzCueNbmPn(Ⅰ)；
wherein x, y, z, e, m and n respectively represent the atom percentage content of the corresponding components; x is not less than 71.5 and not more than 73.5, y is not less than 12.5 and not more than 15.5, z is not less than 1.0 and not more than 7.0, e is not less than 0.5 and not more than 2.0, m is not less than 1.0 and not more than 3.0, and n is more than 0 and not more than 3; and x + y + z + e + m + n is 100.
2. The Fe-based amorphous nanocrystalline alloy according to claim 1, wherein the atomic percentage of Fe is 72-73.5, and the atomic percentage of Si is 13-15.5.
3. The Fe-based amorphous nanocrystalline alloy according to claim 1, wherein the atomic percent of B is 4 to 6, the atomic percent of P is 0.5 to 2, the atomic percent of Cu is 0.5 to 1.2, and the atomic percent of Nb is 1.5 to 3.0.
4. The fe-based amorphous nanocrystalline alloy according to claim 1, wherein n + z is 7.
5. The fe-based amorphous nanocrystalline alloy according to claim 1, wherein n + y is 15.5.
6. The fe-based amorphous nanocrystalline alloy according to claim 1, characterized in that n + x in the fe-based amorphous nanocrystalline alloy is 73.5.
7. The Fe-based amorphous nanocrystalline alloy of claim 1, wherein said Fe-based amorphous nanocrystalline alloy is Fe73.5Si15.5B6Cu1Nb3P1、Fe73.5Si15.5B5Cu1Nb3P2、Fe73.5Si15.5B4Cu1Nb3P3、Fe73.5Si14.5B7Cu1Nb3P1、Fe73.5Si13.5B6Cu1Nb3P2、Fe73.5Si12.5B5Cu1Nb3P3、Fe73Si15.5B7Cu1Nb3P0.5、Fe72.5Si15.5B6Cu1Nb3P1、Fe72Si15.5B5Cu1Nb3P1.5Or Fe71.5Si15.5B4Cu1Nb3P2。
8. A preparation method of an iron-based amorphous nanocrystalline magnetic core comprises the following steps:
the iron-based amorphous alloy nanocrystalline alloy according to claim 1 is prepared by blending and then smelting to obtain an iron-based amorphous nanocrystalline master alloy;
carrying out copper roller rapid quenching on the iron-based amorphous nanocrystalline master alloy to obtain an iron-based amorphous alloy thin strip;
and carrying out heat treatment on the iron-based amorphous alloy thin strip to obtain the iron-based amorphous nanocrystalline magnetic core.
9. The preparation method of claim 8, wherein in the copper roller rapid quenching, the linear speed of the copper roller is 50-55 m/s.
10. The preparation method according to claim 8, wherein the initial temperature of the heat treatment is 200 ℃, the primary heating rate is 10 ℃/min, the first-stage heat preservation temperature is 460-510 ℃, and the heat preservation time is 15 min; the secondary heating rate is 1 ℃/min, the heat preservation temperature of the second stage is 500-520 ℃, and the heat preservation time is 60 min; cooling to 300 ℃ with the furnace and air cooling.
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