High-corrosion-resistance iron-based nanocrystalline magnetically soft alloy and preparation method thereof
阅读说明：本技术 高耐蚀性的铁基纳米晶软磁合金及制备方法 (High-corrosion-resistance iron-based nanocrystalline magnetically soft alloy and preparation method thereof ) 是由 李福山 易怀杰 崔亚辉 李海龙 张锁 王坦 陈辰 魏然 于 2021-07-01 设计创作，主要内容包括：本发明公开了一种高耐蚀性的铁基纳米晶软磁合金及制备方法,旨在解决现有铁基纳米晶合金综合软磁性能不足、耐蚀性不高及使用寿命难以满足应用要求且制备工艺不易控制的技术问题。该铁基纳米晶软磁合金表达式为Fe-(a)Si-(b)B-(c)P-(d)Cu-(e)Cr-(f),其中,a为74～84,b为3.2～4.5,c为7.1～8.5,d为3.2～4.5,e为0.6～0.72,f为1～10,且a+b+c+d+e+f=100。该合金综合软磁性能优良、耐蚀性高,且成型性好,热处理工艺要求宽松,生产成本低。(The invention discloses aA high corrosion resistance iron-based nanocrystalline soft magnetic alloy and a preparation method thereof aim at solving the technical problems that the prior iron-based nanocrystalline alloy has insufficient comprehensive soft magnetic performance, low corrosion resistance, difficult service life meeting the application requirement and difficult control of the preparation process. The expression of the iron-based nanocrystalline magnetically soft alloy is Fe a Si b B c P d Cu e Cr f Wherein a is 74 to 84, b is 3.2 to 4.5, c is 7.1 to 8.5, d is 3.2 to 4.5, e is 0.6 to 0.72, f is 1 to 10, and a + b + c + d + e + f = 100. The alloy has the advantages of excellent comprehensive soft magnetic performance, high corrosion resistance, good formability, loose requirements on heat treatment process and low production cost.)
1. A high-corrosion-resistance Fe-base nano-crystal soft magnetic alloy with Fe expressionaSibBcPdCueCrfWherein a is 74-84, b is 3.2-4.5, c is 7.1-8.5, d is 3.2-4.5, e is 0.6-0.72, f is 1-10, and a + b + c + d + e + f = 100.
2. The high corrosion resistance Fe-based nanocrystalline magnetically soft alloy according to claim 1, wherein the alloy is expressed as Fe82.47Si3.96B7.92P3.96Cu0.69Cr1。
3. The high corrosion resistance Fe-based nanocrystalline magnetically soft alloy according to claim 1, wherein the alloy is expressed as Fe81.63Si3.92B7.84P3.92Cu0.69Cr2。
4. The high corrosion resistance Fe-based nanocrystalline magnetically soft alloy according to claim 1, wherein the alloy is expressed as Fe80.8Si3.88B7.76P3.88Cu0.68Cr3。
5. The high corrosion resistance Fe-based nanocrystalline magnetically soft alloy according to claim 1, wherein the alloy is expressed as Fe79.97Si3.84B7.68P3.84Cu0.67Cr4。
6. The high corrosion resistance Fe-based nanocrystalline magnetically soft alloy according to claim 1, wherein the alloy is expressed as Fe78.3Si3.76B7.52P3.76Cu0.66Cr6。
7. The high corrosion resistance Fe-based nanocrystalline magnetically soft alloy according to claim 1, wherein the alloy is expressed as Fe76.64Si3.68B7.36P3.68Cu0.64Cr8。
8. The high corrosion resistance Fe-based nanocrystalline magnetically soft alloy according to claim 1, wherein the alloy is expressed as Fe74.97Si3.6B7.2P3.6Cu0.63Cr10。
9. The method for preparing the high corrosion resistance iron-based nanocrystalline magnetically soft alloy according to claim 1, comprising the steps of:
1) preparing materials: batching according to the atomic percentage content of the alloy expression;
2) smelting a master alloy: arc melting the proportioned raw materials into a master alloy in an inert gas atmosphere under the pressure of 0.04-0.05 MPa, and repeatedly melting for 3-5 times to ensure that the components of the master alloy ingot are uniformly distributed;
3) strip preparation: under the high vacuum condition and under the protection of inert gas, remelting the master alloy ingot into an alloy solution, and spraying the alloy solution on a copper wheel rotating at a high speed to form an amorphous thin strip, wherein the surface linear velocity of the copper wheel is 35-45 m/s;
4) nano-crystallization annealing: putting the amorphous thin strip obtained in the previous step into a quartz tube, and vacuumizing to 3-4 multiplied by 10-1And Pa, and then annealing at the temperature of 410-530 ℃ for 3-10 min.
10. The method for preparing the high corrosion resistance iron-based nanocrystalline magnetically soft alloy according to claim 9, comprising the steps of:
in the step 1), the raw materials are as follows: fe with the purity of 99.9wt%, Si with the purity of 99.999wt%, FeB with the B content of 19.35wt%, FeP with the P content of 24.98wt%, Cu with the purity of 99.99wt% and Cr with the purity of 99.9 wt%;
the step 3) specifically comprises the following steps: firstly, polishing off surface oxide skin of the master alloy obtained by smelting in the previous step, then crushing the master alloy into small pieces, and cleaning the small pieces by using alcohol; taking 8-12 g of the powder each time, putting the powder into a quartz tube with a round hole with the diameter of 0.6-0.8 mm at the bottom, then putting the powder into an induction coil in a vacuum cavity, fixing the induction coil at a position 0.8-1.2 mm above a copper wheel, and sequentially vacuumizing the induction coil to 5-6 multiplied by 10 by a mechanical pump and a diffusion pump-3Introducing high-purity argon gas of 0.04-0.05 MPa as protective gas after Pa, then opening a copper wheel and an induction heating power supply which are filled with cooling water, and adopting a high-frequency induction heating mode to enable the quartz tube to be in the atmosphere of the argon gasThe mother alloy is melted uniformly, and then the melted and uniform mother alloy liquid is sprayed onto a copper wheel rotating at a high speed under the condition that the pressure difference between the inside and the outside of a quartz tube is 0.03-0.04 MPa, so that the amorphous thin strip is prepared.
Technical Field
The invention relates to the technical field of nanocrystalline alloys, in particular to an iron-based nanocrystalline magnetically soft alloy with high corrosion resistance and a preparation method thereof.
Background
The soft magnetic material plays a role in energy coupling transmission and conversion in various devices, and with the development of miniaturization and light weight of modern electric and electronic equipment, the nanocrystalline soft magnetic alloy shows greater and greater advantages in the soft magnetic material due to the performance characteristics of higher saturation magnetic induction intensity, high magnetic conductivity, low high-frequency loss and the like.
The nanocrystalline magnetically soft alloy is prepared by preparing an amorphous strip by a single-roller copper wheel rapid quenching method and carrying out appropriate thermal treatment and nanocrystallization on the basis of an amorphous alloy precursor. Because exchange coupling action exists between the nanocrystalline phase and the residual amorphous phase, the grain size is smaller than the thickness of a domain wall, so that partial magnetocrystalline anisotropy can be balanced, the average magnetocrystalline anisotropy of the alloy is reduced, and excellent comprehensive soft magnetic performance is shown. However, the saturation induction density of the nanocrystalline alloy is relatively low compared to the conventional soft magnetic material silicon steel, and the saturation induction density of the FeSiBCuNb series nanocrystalline alloy manufactured by hitachi metal company, japan, under the brand name Finemet, is only 1.24T. The saturation magnetic induction intensity of FeSiBPCu series Nanomet alloy researched and developed by professor Akihiro Makino of northeast China university of Japan can reach up to 1.88T after nano crystallization annealing, but the nano crystallization process is difficult to control due to the lack of transition metal elements with large atomic radius in the components, and the requirement on the annealing process is very strict, so the nano crystallization alloy is difficult to be put into industrial production and application.
In addition, for the iron-based nanocrystalline alloy, the corrosion resistance is also very important for the practical application of the alloy in various environments, and the improvement of the corrosion resistance of the nanocrystalline alloy has important significance for ensuring the service life of the alloy in industrial application.
Disclosure of Invention
The invention aims to provide a high-corrosion-resistance iron-based nanocrystalline magnetically soft alloy and a preparation method thereof, and aims to solve the technical problems that the conventional iron-based nanocrystalline alloy is insufficient in comprehensive performance, difficult to meet application requirements in service life and strict in preparation process conditions.
In order to solve the technical problems, the invention adopts the following technical scheme:
designing a high corrosion resistance iron-based nanocrystalline magnetically soft alloy, wherein the expression of the alloy is FeaSibBcPdCueCrfWherein a is 74 to 84, b is 3.2 to 4.5, c is 7.1 to 8.5, d is 3.2 to 4.5, e is 0.6 to 0.72, f is 1 to 10, and a + b + c + d + e + f = 100.
Further, preferred iron-based nanocrystalline soft magnetic alloys include:
Fe82.47Si3.96B7.92P3.96Cu0.69Cr1、Fe81.63Si3.92B7.84P3.92Cu0.69Cr2、Fe80.8Si3.88B7.76P3.88Cu0.68Cr3、Fe79.97Si3.84B7.68P3.84Cu0.67Cr4、Fe78.3Si3.76B7.52P3.76Cu0.66Cr6、Fe76.64Si3.68B7.36P3.68Cu0.64Cr8、Fe74.97Si3.6B7.2P3.6Cu0.63Cr10and the like.
The preparation method of the iron-based nanocrystalline magnetically soft alloy with high corrosion resistance comprises the following steps:
1) preparing materials: batching according to the atomic percentage content of the alloy expression;
the raw materials used are: fe with the purity of 99.9wt%, Si with the purity of 99.999wt%, FeB with the B content of 19.35wt%, FeP with the P content of 24.98wt%, Cu with the purity of 99.99wt% and Cr with the purity of 99.9 wt%;
2) smelting a master alloy: arc melting the proportioned raw materials into a master alloy in an inert gas atmosphere under the pressure of 0.04-0.05 MPa, and repeatedly melting for 3-5 times to ensure that the components of the master alloy ingot are uniformly distributed;
3) strip preparation: under the high vacuum condition and under the protection of inert gas, remelting the master alloy ingot into an alloy solution, and spraying the alloy solution on a copper wheel rotating at a high speed to form an amorphous thin strip, wherein the surface linear velocity of the copper wheel is 35-45 m/s;
the method specifically comprises the following steps: firstly, polishing off surface oxide skin of the master alloy obtained by smelting in the previous step, then crushing the master alloy into small pieces, and cleaning the small pieces by using alcohol; taking 8-12 g of the powder each time, putting the powder into a quartz tube with a round hole with the diameter of 0.6-0.8 mm at the bottom, then putting the powder into an induction coil in a vacuum cavity, fixing the induction coil at a position 0.8-1.2 mm above a copper wheel, and sequentially vacuumizing the induction coil to 5-6 multiplied by 10 by a mechanical pump and a diffusion pump-3And introducing high-purity argon gas of 0.04-0.05 MPa as protective gas after Pa, then opening a copper wheel and an induction heating power supply which are filled with cooling water, melting the master alloy in the quartz tube uniformly by adopting a high-frequency induction heating mode under the protection of the argon gas, and then spraying the uniformly molten master alloy liquid onto the copper wheel rotating at a high speed under the condition that the pressure difference between the inside and the outside of the quartz tube is 0.03-0.04 MPa to prepare the amorphous thin strip.
4) Nano meterAnd (3) crystallization annealing: putting the amorphous thin strip obtained in the previous step into a quartz tube, and vacuumizing to 3-4 multiplied by 10-1And Pa, and then annealing at the temperature of 410-530 ℃ for 3-10 min.
The main mechanism of the component assembly of the iron-based nanocrystalline magnetically soft alloy is as follows:
fe is a ferromagnetic element, high content of Fe is beneficial to improving the saturation magnetic induction intensity of the alloy, but the amorphous forming capability of the alloy is reduced if the content of Fe is too high, so that the content of Fe in the alloy is set at a reasonable level.
Si and B belong to metalloid elements and have larger atomic radius difference with Fe, and in the iron-based nanocrystalline magnetically soft alloy system, B can stabilize an amorphous matrix and prevent grains from growing, so that the amorphous forming capability is improved; si can reduce the magnetostriction coefficient and improve the Curie temperature and the thermal stability of the alloy; although the B element can enhance the amorphous forming capability of the alloy, the temperature gap between the primary crystallization peak and the secondary crystallization peak can be reduced, and the precipitation probability of the Fe-B phase is increased, so that the content of the B element is controlled to be less than 10 at%, and the saturation magnetic induction intensity of the alloy is reduced due to the excessively high content of Si.
The solubility of the P element in the alpha-Fe crystal grains is very low, the P element is excluded from the alpha-Fe crystal grains and is enriched in the residual amorphous matrix, which is beneficial to inhibiting the further growth of the crystal grains and ensuring that the alpha-Fe crystal grains in the matrix are finer and more uniformly distributed.
During annealing, Cu and Fe have strong phase separation tendency, and Cu clusters are formed in an enrichment way at the initial annealing stage and can be used as nucleation sites for the non-uniform nucleation of alpha-Fe grains, so that the nucleation density is obviously improved, and the grain refinement is facilitated.
The addition of Cr can reduce the saturation magnetic induction intensity of the alloy to a certain extent, but the addition of proper Cr in the alloy system can improve the corrosion resistance of the nanocrystalline alloy and is beneficial to the practical production and application of the alloy.
Compared with the prior art, the invention has the main beneficial technical effects that:
1. the iron-based nanocrystalline soft magnetic alloy contains a proper amount of Cu elements, Cr elements and the like which are beneficial to improving the comprehensive performance of the Fe-based nanocrystalline soft magnetic alloy, does not contain Co, Ni and other expensive metal elements, and is beneficial to reducing the production cost.
2. The reasonable addition of Cr element is favorable for controlling the size of nanocrystalline grains, and the corrosion resistance of the alloy is improved while good soft magnetic performance is obtained.
3. The alloy strip has good forming capability, simple preparation process and simple and controllable annealing process, can obtain uniform and fine nanocrystalline structure under loose annealing conditions, and is beneficial to realizing large-scale industrial production.
4. The iron-based amorphous soft magnetic alloy has excellent comprehensive performance and high B contentSHigh mueLower, lowerH cAnd better corrosion resistance.
Drawings
FIG. 1 is an XRD pattern of the iron-based nanocrystalline magnetically soft alloy of examples 1-7; in the figure, the abscissa is the scan angle and the ordinate is the intensity.
FIG. 2 is a VSM diagram of the iron-based nanocrystalline magnetically soft alloy of examples 1-7 and comparative example 1 under different applied magnetic fields; in the figure, the abscissa represents the magnetic field strength and the ordinate represents the magnetization.
FIG. 3 is a graph of permeability of the iron-based nanocrystalline magnetically soft alloys of examples 1-7 and comparative example 1 at different applied frequencies; in the figure, the abscissa is frequency and the ordinate is effective permeability.
FIG. 4 is a coercivity diagram of the iron-based nanocrystalline magnetically soft alloys of examples 1-7 and comparative example 1 under different applied magnetic fields; in the figure, the abscissa represents the magnetic field strength and the ordinate represents the magnetization.
FIG. 5 is a polarization curve of examples 1 to 7 and comparative example 1; in the figure, the abscissa represents the potential and the ordinate represents the current density.
Detailed Description
The following examples are intended to illustrate the present invention in detail and should not be construed as limiting the scope of the present invention in any way.
The instruments and devices referred to in the following examples are conventional instruments and devices unless otherwise specified; the raw materials are conventional raw materials in the market if not specifically mentioned, and the preparation and detection methods are conventional if not specifically mentioned.
Example 1: high corrosion resistance iron-based nanocrystalline soft magnetic alloy Fe82.47Si3.96P7.92B3.96Cu0.69Cr1And labeled Y1.
The preparation method comprises the following steps:
1) preparing materials: fe with the purity of 99.9wt%, Si with the purity of 99.999wt%, FeB with the B content of 19.35wt%, FeP with the P content of 24.98wt%, Cu with the purity of 99.99wt% and Cr with the purity of 99.9wt% are adopted to be calculated and proportioned according to the atom percentage content in the alloy expression;
2) smelting a master alloy: placing the proportioned raw materials into a non-consumable vacuum electric arc furnace, and vacuumizing to 4 multiplied by 10-3Pa, filling argon protective gas with the pressure of 0.05 MPa; smelting the raw materials into a master alloy ingot through electric arc smelting, overturning the master alloy ingot after each smelting, and repeatedly smelting for 5 times to ensure that the components of the master alloy ingot are uniformly distributed.
3) Preparing a strip material: under the condition of discontinuous production, the master alloy ingot is remelted under the condition of high vacuum and under the protection of argon gas, and is sprayed on a copper wheel rotating at high speed to prepare an amorphous thin strip, and the surface linear velocity of the copper wheel is controlled to be 40 m/s.
4) Nano-crystallization annealing: putting the amorphous thin strip into a quartz tube, and vacuumizing to 3 multiplied by 10-1Pa, and then putting the ingot into a tubular furnace which is heated in advance for heat preservation and annealing, wherein the heat preservation temperature is 500 ℃, and the time is 6 min.
Example 2: high corrosion resistance iron-based nanocrystalline soft magnetic alloy Fe81.63Si3.92P7.84B3.92Cu0.69Cr2And labeled Y2.
The preparation method comprises the following steps:
1) preparing materials: fe with the purity of 99.9wt%, Si with the purity of 99.999wt%, FeB with the B content of 19.35wt%, FeP with the P content of 24.98wt%, Cu with the purity of 99.99wt% and Cr with the purity of 99.9wt% are adopted for proportioning according to the atom percentage content in the alloy expression;
2) smelting a master alloy: placing the proportioned raw materials into a non-consumable vacuum electric arc furnace, and vacuumizing to 4.5 multiplied by 10- 3Pa, filling argon protective gas with the pressure of 0.05 MPa; smelting the raw materials into a master alloy ingot by arc melting, overturning the master alloy ingot after each smelting, and repeatedly smelting for 5 times to ensure that the components of the master alloy ingot are uniform.
3) Preparing a strip material: under the condition of discontinuous production, the master alloy ingot is remelted under the condition of high vacuum and under the protection of argon gas, and is sprayed on a copper wheel rotating at high speed to prepare an amorphous thin strip, and the surface linear velocity of the copper wheel is 40 m/s.
4) Nano-crystallization annealing: putting the amorphous thin strip into a quartz tube, and vacuumizing to 3 multiplied by 10-1Pa, and then putting the ingot into a tubular furnace which is heated in advance for heat preservation and annealing, wherein the heat preservation temperature is 500 ℃, and the time is 6 min.
Example 3: iron-based nanocrystalline soft magnetic alloy Fe with corrosion resistance80.8Si3.88P7.76B3.88Cu0.68Cr3And labeled Y3.
The preparation method comprises the following steps:
1) preparing materials: fe with the purity of 99.9wt%, Si with the purity of 99.999wt%, FeB with the B content of 19.35wt%, FeP with the P content of 24.98wt%, Cu with the purity of 99.99wt% and Cr with the purity of 99.9wt% are adopted for proportioning according to the atom percentage content in the alloy expression;
2) smelting a master alloy: placing the proportioned raw materials into a non-consumable vacuum electric arc furnace, and vacuumizing to 4.3 multiplied by 10- 3Pa, filling argon protective gas with the pressure of 0.043 MPa; smelting the raw materials into a master alloy ingot by electric arc smelting, overturning the master alloy ingot after each smelting, and repeatedly smelting for 5 times to ensure that the components of the master alloy ingot are uniform.
3) Preparing a strip material: under the condition of discontinuous production, the master alloy ingot is remelted under the condition of high vacuum and under the protection of argon gas, and is sprayed on a copper wheel rotating at high speed to prepare an amorphous thin strip, and the surface linear velocity of the copper wheel is 40 m/s.
4) Nano-crystallization annealing: putting the amorphous thin strip into a quartz tube, and vacuumizing to 3.3 multiplied by 10-1Pa, and then putting the ingot into a tubular furnace which is heated in advance for heat preservation and annealing, wherein the heat preservation temperature is 530 ℃ and the time is 6 min.
Example 4: iron-based nanocrystalline soft magnetic alloy Fe with corrosion resistance79.97Si3.84P7.68B3.84Cu0.67Cr4And labeled Y4.
The preparation method comprises the following steps:
1) preparing materials: fe with the purity of 99.9wt%, Si with the purity of 99.999wt%, FeB with the B content of 19.35wt%, FeP with the P content of 24.98wt%, Cu with the purity of 99.99wt% and Cr with the purity of 99.9wt% are adopted for proportioning according to the atom percentage content in the alloy expression;
2) smelting a master alloy: placing the proportioned raw materials into a non-consumable vacuum electric arc furnace, and vacuumizing to 4.2 multiplied by 10- 3Pa, filling argon protective gas with the pressure of 0.046 MPa; smelting the raw materials into a master alloy ingot by arc melting, overturning the master alloy ingot after each smelting, and repeatedly smelting for 5 times to ensure that the components of the master alloy ingot are uniform.
3) Preparing a strip material: under the condition of discontinuous production, the master alloy ingot is remelted under the condition of high vacuum and under the protection of argon gas, and is sprayed on a copper wheel rotating at high speed to prepare an amorphous thin strip, and the surface linear velocity of the copper wheel is 40 m/s.
4) Nano-crystallization annealing: putting the amorphous thin strip into a quartz tube, and vacuumizing to 3.4 multiplied by 10-1Pa, and then putting the ingot into a tubular furnace which is heated in advance for heat preservation and annealing, wherein the heat preservation temperature is 500 ℃, and the time is 6 min.
Example 5: iron-based nanocrystalline soft magnetic alloy Fe with corrosion resistance78.3Si3.76P7.52B3.76Cu0.66Cr6And labeled Y5.
The preparation method comprises the following steps:
1) preparing materials: fe with the purity of 99.9wt%, Si with the purity of 99.999wt%, FeB with the B content of 19.35wt%, FeP with the P content of 24.98wt%, Cu with the purity of 99.99wt% and Cr with the purity of 99.9wt% are adopted for proportioning according to the atom percentage content in the alloy expression;
2) smelting a master alloy: placing the proportioned raw materials into a non-consumable vacuum electric arc furnace, and vacuumizing to 4.5 multiplied by 10- 3Pa, filling argon protective gas with the pressure of 0.05 MPa; smelting the raw materials into a master alloy ingot by arc melting, overturning the master alloy ingot after each smelting, and repeatedly smelting for 5 times to ensure that the components of the master alloy ingot are uniform.
3) Preparing a strip material: under the condition of discontinuous production, the master alloy ingot is remelted under the condition of high vacuum and under the protection of argon gas, and is sprayed on a copper wheel rotating at high speed to prepare an amorphous thin strip, and the surface linear velocity of the copper wheel is 40 m/s.
4) Nano-crystallization annealing: putting the amorphous thin strip into a quartz tube, and vacuumizing to 3.2 multiplied by 10-1Pa, and then putting the mixture into a tubular furnace which is heated in advance for heat preservation and annealing, wherein the heat preservation time is 6min at 530 ℃.
Example 6: iron-based nanocrystalline soft magnetic alloy Fe with corrosion resistance76.64Si3.68P7.36B3.68Cu0.64Cr8And labeled Y6.
The preparation method comprises the following steps:
1) preparing materials: fe with the purity of 99.9wt%, Si with the purity of 99.999wt%, FeB with the B content of 19.35wt%, FeP with the P content of 24.98wt%, Cu with the purity of 99.99wt% and Cr with the purity of 99.9wt% are adopted for proportioning according to the atom percentage content in the alloy expression;
2) smelting a master alloy: placing the proportioned raw materials into a non-consumable vacuum electric arc furnace, and vacuumizing to 4.5 multiplied by 10- 3Pa, filling argon protective gas of 0.05 MPa; smelting the raw materials into a master alloy ingot by arc melting, overturning the master alloy ingot after each smelting, and repeatedly smelting for 5 times to ensure that the components of the master alloy ingot are uniform.
3) Preparing a strip material: under the condition of discontinuous production, the master alloy ingot is remelted under the condition of high vacuum and under the protection of argon gas, and is sprayed on a copper wheel rotating at high speed to prepare an amorphous thin strip, and the surface linear velocity of the copper wheel is 40 m/s.
4) Nano-crystallization annealing: putting the amorphous thin strip into a quartz tube, and vacuumizing to 3 multiplied by 10-1Pa, and then putting the tube furnace heated in advance for heat preservation and annealing, wherein the heat preservation temperature is 410 ℃, and the time is 6 min.
Example 7: iron-based nanocrystalline soft magnetic alloy Fe with corrosion resistance74.97Si3.6P7.2B3.6Cu0.63Cr10And labeled Y7.
The preparation method comprises the following steps:
1) preparing materials: fe with the purity of 99.9wt%, Si with the purity of 99.999wt%, FeB with the B content of 19.35wt%, FeP with the P content of 24.98wt%, Cu with the purity of 99.99wt% and Cr with the purity of 99.9wt% are adopted for proportioning according to the atom percentage content in the alloy expression;
2) smelting a master alloy: the proportioned raw materials are put into a non-consumable vacuum electric arc furnace, and the degree of vacuum pumping is 4.6 multiplied by 10- 3Pa, filling argon protective gas with the pressure of 0.05 MPa; smelting the raw materials into a master alloy ingot by electric arc smelting, overturning the master alloy ingot after each smelting, and repeatedly smelting for 5 times to ensure that the components of the master alloy ingot are uniform.
3) Preparing a strip material: under the condition of discontinuous production, the master alloy ingot is remelted under the condition of high vacuum and under the protection of argon gas, and is sprayed on a copper wheel rotating at high speed to prepare an amorphous thin strip, and the surface linear velocity of the copper wheel is 40 m/s.
4) Nano-crystallization annealing: putting the amorphous thin strip into a quartz tube, and vacuumizing to 3.4 multiplied by 10-1Pa, and then putting the tube furnace heated in advance for heat preservation and annealing, wherein the heat preservation temperature is 410 ℃, and the time is 6 min.
Carrying out structure test on the iron-based nanocrystalline magnetically soft alloy ribbons obtained in the above examples 1-7 by using an X-ray diffractometer (XRD, Empyrean); adopting Cu palladium and K alpha rays, wherein the scanning range is 30-90 degrees; the XRD curve is shown in figure 1, diffraction peaks appear in the XRD pattern at diffraction angles of about 45 degrees, 65 degrees and 85 degrees, and correspond to alpha-Fe crystal grains with BCC structures, and the result shows that the iron-based nanocrystalline magnetically soft alloy is good in crystallization and has no precipitation of a second phase with deteriorated performance.
Comparative example 1: iron-based nanocrystalline magnetically soft alloy Fe83.3Si4P8B4Cu0.7And labeled Y0. The preparation method comprises the following steps:
1) preparing materials: fe with the purity of 99.9wt%, Si with the purity of 99.999wt%, FeB with the B content of 19.35wt%, FeP with the P content of 24.98wt% and Cu with the purity of 99.99wt% are adopted to be mixed according to the atom percentage content in the alloy expression;
2) smelting a master alloy: placing the proportioned raw materials into a non-consumable vacuum electric arc furnace, and vacuumizing to 4.5 multiplied by 10- 3Pa, filling argon protective gas with the pressure of 0.05 MPa; smelting the raw materials into a master alloy ingot by arc melting, overturning the master alloy ingot after each smelting, and repeatedly smelting for 5 times to ensure that the components of the master alloy ingot are uniform.
3) Preparing a strip material: under the condition of discontinuous production, the master alloy ingot is remelted under the condition of high vacuum and under the protection of argon gas, and is sprayed on a copper wheel rotating at high speed to prepare an amorphous thin strip, and the surface linear velocity of the copper wheel is 40 m/s.
4) Nano-crystallization annealing: putting the amorphous thin strip into a quartz tube, and vacuumizing to 3 multiplied by 10-1Pa, and then putting the ingot into a tubular furnace which is heated in advance for heat preservation and annealing, wherein the heat preservation temperature is 500 ℃, and the time is 6 min.
The saturation magnetic induction of each of the samples of examples 1 to 7 and comparative example 1 was measured with a vibrating sample magnetometer (VSM, Lake Shore 7410); the coercive force of each sample of examples 1-7 and comparative example 1 is measured by a direct current hysteresis loop measuring instrument (RIKEN BHS-40); the effective permeability of each of the samples of examples 1 to 7 and comparative example 1 was measured by an impedance analyzer (KEYSIGHT E4990A) under an applied excitation magnetic field of different frequencies. The results are shown in Table 1.
TABLE 1 coercive force of each sampleH cIs effectiveMagnetic permeability mueSaturation magnetic induction BsPerformance parameter of
。
Taking Y0-Y7 strips for corrosion performance test: by electrochemical test, the sample was immersed in 3.5wt% NaCl solution for 30min, and after the open circuit potential was stabilized, a polarization curve was obtained, as shown in FIG. 5.
By comprehensively comparing fig. 2 to fig. 4 and table 1, it can be seen that, compared to comparative example 1, under the conventional annealing condition, although the saturation magnetic induction of the alloy in examples 1 to 7 is reduced, the magnetic permeability of the alloy in examples 1 to 4 is improved, the coercive force is reduced, and the comprehensive soft magnetic performance is superior to that of comparative example 1.
Comparing with FIG. 5, the corrosion potential of the alloys of examples 1-7 was gradually increased and the corrosion current density was gradually decreased, resulting in better corrosion resistance, compared to comparative example 1. Although the soft magnetic properties (magnetic permeability and coercive force) of the alloys in the examples 5 to 7 are inferior to those of the alloys in the examples 1 to 4 and the comparative example 1, the polarization curve of the alloy has an obvious passivation region, the corrosion potential is greatly increased, the corrosion current density is greatly reduced, and the corrosion resistance is greatly improved.
While the invention has been described in detail with reference to the drawings and examples, it will be understood by those skilled in the art that various changes in the specific parameters of the embodiments described above may be made or equivalents of related steps, methods and materials may be substituted without departing from the spirit of the invention to form multiple embodiments, which are common variations of the invention and will not be described in detail herein.