CN111748755A - A novel high saturation magnetic induction iron-based soft magnetic amorphous alloy and preparation method thereof - Google Patents

Abstract

The invention discloses a novel high saturation magnetic induction iron-based soft magnetic amorphous alloy and a preparation method thereof, and the alloy is Fe_aCo_bB_cC_dCu_eThe atomic percentage of a of Fe is more than or equal to 70 and less than or equal to 90, the atomic percentage of B of Co is more than or equal to 0 and less than or equal to 20, the atomic percentage of C of B is more than or equal to 1 and less than or equal to 20, the atomic percentage of d of C is more than or equal to 1 and less than or equal to 20, and the original content of CuThe sub-percentage content e is more than or equal to 0.1 and less than or equal to 2, and a + b + c + d + e is 100; the novel high-saturation-magnetic-induction iron-based soft magnetic amorphous alloy has good amorphous forming capability and thermal stability, and can still maintain complete amorphous characteristics after annealing for 10 minutes at the temperature of 20-380 ℃; the novel high saturation magnetic induction iron-based soft magnetic amorphous alloy has excellent soft magnetic performance, including high saturation magnetic induction intensity of 1.85T and low coercive force of 2.0A/m.

Description

A novel high saturation magnetic induction iron-based soft magnetic amorphous alloy and preparation method thereof

technical field

The invention relates to the technical field of soft magnetic alloy functional materials, in particular to a novel high saturation magnetic induction iron-based soft magnetic amorphous alloy and a preparation method.

Background technique

Energy shortage and environmental pollution have become major problems restricting human survival and development, and the development of green and low-carbon economy has become the focus of common concern around the world. As an important energy material, the research and development and application of soft magnetic materials have played a key role in promoting the development of the power industry. As one of the important green energy-saving materials, iron-based amorphous nanocrystalline soft magnetic alloys are expected to be used in high-frequency transformers, motors and other fields due to their high saturation magnetic induction, low-loss soft magnetic properties, and high effective magnetic permeability. Promote and apply to meet the development of modern electrical equipment in the direction of high frequency, high efficiency and energy saving. However, the existing high-performance soft magnetic alloys have limited amorphous forming ability, are easily oxidized during the preparation process, and the comprehensive soft magnetic properties still need to be improved, which have become research hotspots, goals and bottlenecks in the field of amorphous materials.

At present, in view of the problem that the high saturation magnetic induction of iron-based alloys is still not comparable to that of traditional silicon steel, researchers have carried out a series of products such as Fe _83.3-84.3 Si ₄ B ₈ P _3-4 Cu _0.7 , Fe ₈₅ B ₁₃ Ni ₂ , Fe _83.2 The exploration work on the magnetic properties of high Fe content amorphous/nano-gold alloys such as P ₈ B ₂ C ₆ Cu _0.8 , however, the increase of the Fe content of the main element causes the decrease of the content of the remaining amorphous forming elements, which is bound to lead to the amorphous alloy of the alloy. The reduction of the forming ability causes the deterioration of the overall properties of the alloy. The addition of nonferromagnetic metalloids can promote the amorphous formation ability of the alloy, but its magnetic properties are deteriorated due to the hybridization between metal-metalloids. Therefore, how to balance the relationship between the alloy's amorphous formation ability and magnetic properties, and to find a new iron-based soft magnetic alloy system with high saturation magnetic induction and good amorphous formation ability is one of the key problems to be solved urgently in the development of soft magnetic alloys. To this end, on the basis of the existing alloy system, researchers have optimized the preparation process, adjusted the alloy composition, and researched and developed new alloy systems to improve the soft magnetic properties of amorphous nanocrystals and reduce processing costs.

The existing methods can generally improve the soft magnetic properties of amorphous/nanocrystalline alloys to varying degrees through elemental alloying and preparation processes, but there are still shortcomings in general: (1) The heat treatment process is demanding on the process, and the preparation The target alloy cannot achieve high saturation magnetic induction, low coercivity and high permeability at the same time; (2) the composition of the alloy contains one or more of noble metal elements such as Nb, Ni, Cr, Mo, Y, etc., resulting in Alloys are expensive and contain volatile elements, making it difficult to precisely control the machining process.

In view of the above-mentioned defects, the creator of the present invention finally obtained the present invention after a long period of research and practice.

SUMMARY OF THE INVENTION

In order to solve the above-mentioned technical defects, the technical solution adopted in the present invention is to provide a novel high saturation magnetic induction iron-based soft magnetic amorphous alloy, which is Fe _a Co _b B _c C _d Cu _e , and the atomic percentage content a of Fe is 70≤a≤90, the atomic percentage b of Co is 0≤b≤20, the atomic percentage c of B is 1≤c≤20, the atomic percentage d of C is 1≤d≤20, the atomic percentage of Cu is 1≤d≤20. The atomic percentage e is 0.1≤e≤2, and a+b+c+d+e=100.

Preferably, the atomic percentage a of Fe is 80≤a≤86, the atomic percentage b of Co is 0≤b≤12, the atomic percentage c of B is 7≤c≤10, and the atomic percentage of C is 7≤c≤10. The fractional content d is 3≤d≤10, and the atomic percentage content e of Cu is 0.5≤e≤1.

Preferably, a method for preparing the novel high saturation magnetic induction iron-based soft magnetic amorphous alloy, comprising the steps of:

S1, the raw materials Fe, Co, B, Cu and iron-carbon alloy are prepared according to the molecular formula Fe _a Co _b B _c C _d Cu _e ;

S2, the raw material is loaded into the crucible of the smelting furnace, and smelted in an inert gas atmosphere to obtain a mother alloy ingot;

S3, preparing continuous amorphous alloy strips from the mother alloy ingot by means of melt rapid quenching and stripping equipment;

S4, cut the amorphous strip into a 40mm-70mm strip and put it into a quartz tube matched with a tubular annealing furnace. The tubular annealing furnace is provided with an external magnetic field, and a high vacuum is drawn. After the temperature of the furnace meets the temperature of 20 °C to 380 °C, the quartz tube is pushed into the tube furnace for 1 to 20 minutes, and finally quenched and cooled or cooled to room temperature in the air to obtain the iron-based amorphous alloy after magnetic field treatment.

Preferably, in the step S1, the purity of each of the raw materials is greater than 99%, and the mass percentage of C in the iron-carbon alloy is 4.0% to 5.0%.

Preferably, in the step S2, induction melting is adopted, and the alloy raw material is put into the crucible, placed in the induction coil of the induction melting furnace, evacuated to less than 1.0 × 10 ^-2 Pa, and then filled with inert The gas to the gas pressure is -0.06MPa～-0.02MPa, after melting, the temperature is kept for 15 minutes to 30 minutes, and then cooled in the furnace cavity for 20 minutes to 30 minutes.

Preferably, in the step S3, the continuous amorphous alloy strip is in strip shape, the strip width is 1mm-1.6mm, the thickness is 18μm-35μm, and the density is 7.5kg/m ³ ～7.6kg/m ³ .

Preferably, in the step S4, the heat treatment is performed under the external magnetic field, including starting the application of the magnetic field during the heating process, starting the application of the magnetic field during the heat preservation process and starting the application of the magnetic field during the cooling process, and the magnetic field strength of the external magnetic field is 100Oe～1600Oe.

Compared with the prior art, the beneficial effects of the present invention are as follows: 1. The novel high-saturation magnetic induction iron-based soft magnetic amorphous alloy of the present invention has good amorphous forming ability and thermal stability. After annealing for 10 minutes, it still maintains complete amorphous characteristics; the new high saturation magnetic induction iron-based soft magnetic amorphous alloy has excellent soft magnetic properties, including high saturation magnetic induction intensity of 1.85T and low coercivity of 2.0A/m 2, the preparation method of the novel high-saturation magnetic induction iron-based soft magnetic amorphous alloy is heat treated under an external magnetic field, including starting to add a magnetic field during the heating process, starting to add a magnetic field during the heat preservation process, and starting to add a magnetic field during the cooling process. The soft magnetic properties of the alloy are significantly improved on the premise of deteriorating the saturation magnetic induction of the alloy; the preparation method of the new high-saturation magnetic iron-based soft magnetic amorphous alloy is simple and the composition design does not contain precious metals such as Nb, Zr, Mo, Y, etc. The easily oxidizable element greatly reduces the processing cost of raw materials, promotes industrial production, facilitates popularization and application, and has excellent application prospects.

Description of drawings

Fig. 1 is the XRD pattern of the amorphous strips prepared in step S3 of Examples 1, 2, 3 and Comparative Example;

Fig. 2 is the DSC curve diagram of the amorphous strips prepared in step S3 of Examples 1, 2, 3 and Comparative Example;

3 is a hysteresis loop diagram of the amorphous ribbons prepared in step S3 in Examples 1, 2, 3 and Comparative Example;

Fig. 4 is the XRD pattern diagram of the alloy strip after the magnetic heat treatment in step S5 of Example 2 and the comparative example;

Fig. 5 is the hysteresis loop diagram of the amorphous strip obtained in step S4 and step S5 respectively in Example 2 and the comparative example;

FIG. 6 is a graph showing the variation of saturation magnetic induction and coercive force with temperature of the amorphous strip obtained in step S4 and step S5 in Example 2 and Comparative Example, respectively.

Detailed ways

The above and other technical features and advantages of the present invention will be described in more detail below with reference to the accompanying drawings.

The novel high saturation magnetic induction iron-based soft magnetic amorphous alloy described in the present invention is Fe _a Co _b B _c C _d Cu _e , wherein a, b, c, d and e represent the atomic percentages of the corresponding components respectively , where 70≤a≤90, 0≤b≤20, 1≤c≤20, 1≤d≤20, 0.1≤e≤2, and a+b+c+d+e=100.

Among the elements constituting the new high saturation magnetic induction iron-based soft magnetic amorphous alloy, Fe is a ferromagnetic element, which can improve the saturation magnetic induction intensity of the alloy; Co is a ferromagnetic element, which can not only improve the amorphous forming ability of the alloy, but also Improve the saturation magnetic induction intensity of the alloy; B and C are amorphous forming elements, which can effectively improve the amorphous forming ability of the alloy and improve its soft magnetic properties; Cu is a nanocrystalline forming element, as α-Fe/(Fe, Co) nanocrystalline Heterogeneous nucleation point of the phase.

Generally, the atomic percentage content a of Fe is 70≤a≤90, preferably 80≤a≤86. The atomic percentage content b of Co is 0≤b≤20, preferably 0≤b≤12. The atomic percentage content c of B is 1≤c≤20, preferably 7≤c≤10. The atomic percentage content d of C is 1≤d≤20, preferably 3≤d≤10. The atomic percentage content e of Cu is 0.1≤e≤2, preferably 0.5≤e≤1.

To sum up, after optimization, the alloy has both good amorphous formation ability and thermal stability, and also has excellent comprehensive soft magnetic properties. ~14.1A/m.

The preparation method of the novel high saturation magnetic induction iron-based soft magnetic amorphous alloy according to the present invention comprises the following steps:

S1, prepare Fe, Co, B, Cu and Fe ₃ C according to the molecular formula Fe _a Co _b B _c C _d Cu _e , wherein a, b, c, d and e represent the atomic percentages of the corresponding components respectively , where 70≤a≤90, 0≤b≤20, 1≤c≤20, 1≤d≤20, 0.1≤e≤2, and a+b+c+d+e=100;

S2, the raw materials that are proportioned in step S1 are loaded into the crucible of the smelting furnace, and smelted in an inert gas atmosphere to obtain a master alloy ingot with uniform composition;

S3, adopt the VF-RQB20 type melt quick quenching and stripping equipment produced by Japan True Wall Technology Co., Ltd. An appropriate amount of the mother alloy ingot obtained in step S2 is put into a quartz tube, fixed in the induction coil, the upper and lower positions of the quartz tube are adjusted to control the distance between the nozzle and the roller surface and the air pressure difference, and an appropriate amount of protective gas (high-purity argon) is filled after the high vacuum of the cavity is drawn. gas), set the speed of the copper rod, the surface linear speed of the copper roll is 35m/s ~ 50m/s, turn on the heating current, wait for the solenoid to heat and melt the master alloy to an appropriate temperature, press the spray button, and use the inner and outer parts of the quartz tube and cavity. The pressure difference of the molten alloy is quickly sprayed to the surface of the high-speed rotating copper rod for rapid cooling, and the continuous amorphous alloy strip is prepared;

S4, the amorphous strip obtained in step S3 is cut into a strip of 40mm-70mm, and then loaded into a quartz tube matched with the tubular annealing furnace, and a high vacuum is drawn, and when the temperature of the tube furnace and the vacuum degree of the quartz tube are satisfied After the required temperature is 20 ℃ ~ 380 ℃ and the required high vacuum degree, the quartz tube is pushed into the tube furnace for 1 minute to 20 minutes, and finally quenched and cooled or cooled to room temperature in the air to obtain the iron-based non-ferrous alloy with structural relaxation. crystal alloy.

S5, cut the amorphous strip obtained in step S3 into a strip of 40mm-70mm, put it into a quartz tube matched with the tubular annealing furnace (the furnace body has a special magnetic field control function), and pump a high vacuum, when the tube After the temperature of the furnace and the vacuum degree of the quartz tube meet the required temperature of 20℃～380℃ and the required high vacuum degree, the quartz tube is pushed into the tube furnace for 1 minute to 20 minutes, and finally quenched and cooled or cooled in air to At room temperature, an iron-based amorphous alloy after magnetic field treatment is obtained.

In the step S1, preferably, the purity of each raw material is greater than 99%, C is added in the form of iron-carbon alloy, and the mass percentage of C in the iron-carbon alloy is 4.0%-5.0%.

In the step S2, induction melting is adopted, the alloy raw material is put into the crucible, placed in the induction coil of the induction melting furnace, evacuated to less than 1.0 × 10 ^-2 Pa, and then filled with an inert gas to a pressure of -0.06MPa～-0.02MPa (relative pressure), keep warm for 15 minutes to 30 minutes after melting, and then cool in the furnace cavity for 20 minutes to 30 minutes.

In the step S3, the amorphous alloy is in strip shape, the strip width is 1mm-1.6mm, the thickness is 18μm-35μm, and the density is 7.5kg/m ³ -7.6kg/m ³ .

In the step S5, heat treatment is performed under an externally applied magnetic field, including starting to apply a magnetic field during the heating process, starting to apply a magnetic field during the heat preservation process, and starting to apply a magnetic field during the cooling process.

To sum up, based on the long-term scientific research practice in the technical field of amorphous soft magnetic alloys, the inventors have obtained through a lot of repeated experiments that the addition of Co element can effectively inhibit the precipitation of α-Fe crystal grains and significantly improve the amorphous formation of alloys. Ability and thermal stability, iron-based amorphous alloys whose structure is still amorphous can be prepared through a specific annealing process.

The new high-saturation magnetic induction iron-based soft magnetic amorphous alloy has good amorphous forming ability and thermal stability, and can still maintain complete amorphous characteristics when annealed in the temperature range of 20 ° C to 380 ° C for 10 minutes; the new high saturation The magnetic induction iron-based soft magnetic amorphous alloy has excellent soft magnetic properties, including a high saturation magnetic induction intensity of 1.85T and a low coercive force of 2.0A/m.

The preparation method of the novel high-saturation magnetic induction iron-based soft magnetic amorphous alloy is heat treated under an external magnetic field. Under the premise of magnetic induction, the soft magnetic properties of the alloy are significantly improved; the preparation method of the new high-saturation magnetic induction iron-based soft magnetic amorphous alloy is simple, and the composition design does not contain precious metals such as Nb, Zr, Mo, Y and other oxidizable elements. , which greatly reduces the processing cost of raw materials, promotes industrial production, facilitates popularization and application, and has excellent application prospects.

Example 1

In this embodiment, the novel high-saturation magnetic induction iron-based soft magnetic amorphous alloy has a molecular formula composition satisfying: Fe _79.2 Co ₄ B ₁₀ C ₆ Cu _0.8 , and its preparation method is as follows:

S1, the raw materials such as _Fe , Co, B, C and _Cu with a purity of more _than 99% are _batched according to the alloy composition and the atomic percentage content of each composition _. In the form of adding, the mass percentage of C in the iron-carbon alloy is 4.05%;

S2, the raw materials that are proportioned in the step S1 are loaded into the ceramic crucible of the induction melting furnace, and the high-frequency induction melting obtains an alloy ingot with uniform composition;

S3, adopt the VF-RQB20 type melt quick quenching and stripping equipment produced by Japan True Wall Technology Co., Ltd. An appropriate amount of the master alloy obtained in the step S2 is loaded into a quartz tube, fixed in the induction coil, the upper and lower positions of the quartz tube are adjusted to control the distance between the nozzle and the roller surface and the air pressure difference, and an appropriate amount of protective gas (high-purity) is filled after the high vacuum of the cavity is drawn. Argon), set the speed of the copper rod, the surface line speed of the copper roll is 45m/s, turn on the heating current, wait for the solenoid to heat and melt the master alloy to an appropriate temperature, press the spray button, and use the air pressure difference between the quartz tube and the cavity The molten alloy liquid is rapidly sprayed onto the surface of the high-speed rotating copper rod for rapid cooling to prepare continuous amorphous alloy strips;

S4, the amorphous strip obtained in the step S3 is cut into a 60mm long strip and loaded into the quartz tube matched with the tubular annealing furnace, and a high vacuum is drawn, when the temperature of the tubular furnace and the vacuum degree of the quartz tube are all satisfied After the required temperature is 20℃～380℃ and the required high vacuum degree, the quartz tube is pushed into the tube furnace for 10 minutes, and finally quenched and cooled to room temperature to obtain the iron-based amorphous alloy with structural relaxation.

S5, the amorphous strip obtained in the step S3 is cut into a strip of 60mm and then loaded into the quartz tube matched with the tubular annealing furnace (the furnace body has a special magnetic field control function), high vacuum is drawn, when the tube is After the temperature of the furnace and the vacuum degree of the quartz tube meet the required temperature of 20 ℃ ~ 380 ℃ and the required high vacuum degree, the quartz tube is pushed into the tube furnace for 10 minutes, and finally quenched and cooled to room temperature to obtain the magnetic field treatment. Iron-based amorphous alloys.

In the step S2, induction melting is adopted, the alloy raw material is put into the crucible, placed in the induction coil of the induction melting furnace, evacuated to less than 1.0 × 10 ^-2 Pa, and then filled with an inert gas to a pressure of -0.06MPa (relative pressure), hold for 15 minutes after melting, and then cool in the furnace cavity for 25 minutes.

In the step S3, the amorphous alloy is in strip shape, the strip width is 1.1 mm˜1.3 mm, and the thickness is 25 μm˜30 μm.

Example 2

In this embodiment, the novel high-saturation magnetic induction iron-based soft magnetic amorphous alloy has a molecular formula composition satisfying: Fe _77.2 Co ₆ B ₁₀ C ₆ Cu _0.8 , and its preparation method is as follows:

S1, the raw materials such as _Fe , _Co , B, C and _Cu with a _purity greater _than 99% are prepared according to the alloy composition and the atomic percentage content of each composition. In the form of adding, the mass percentage of C in the iron-carbon alloy is 4.05%;

S2, the raw materials that are proportioned in the step S1 are loaded into the ceramic crucible of the induction melting furnace, and the high-frequency induction melting obtains an alloy ingot with uniform composition;

S3, adopt the VF-RQB20 type melt quick quenching and stripping equipment produced by Japan True Wall Technology Co., Ltd. An appropriate amount of the master alloy obtained in the step S2 is loaded into a quartz tube, fixed in the induction coil, the upper and lower positions of the quartz tube are adjusted to control the distance between the nozzle and the roller surface and the air pressure difference, and an appropriate amount of protective gas (high-purity) is filled after the high vacuum of the cavity is drawn. Argon), set the speed of the copper rod, the surface line speed of the copper roll is 45m/s, turn on the heating current, wait for the solenoid to heat and melt the master alloy to an appropriate temperature, press the spray button, and use the air pressure difference between the quartz tube and the cavity The molten alloy liquid is rapidly sprayed onto the surface of the high-speed rotating copper rod for rapid cooling to prepare continuous amorphous alloy strips;

S4, the amorphous strip obtained in the step S3 is cut into a 60mm long strip and loaded into the quartz tube matched with the tubular annealing furnace, and a high vacuum is drawn, when the temperature of the tubular furnace and the vacuum degree of the quartz tube are all satisfied After the required temperature is 20℃～380℃ and the required high vacuum degree, the quartz tube is pushed into the tube furnace for 10 minutes, and finally quenched and cooled to room temperature to obtain the iron-based amorphous alloy with structural relaxation.

S5, the amorphous strip obtained in the step S3 is cut into a strip of 60mm and then loaded into the quartz tube matched with the tubular annealing furnace (the furnace body has a special magnetic field control function), high vacuum is drawn, when the tube is After the temperature of the furnace and the vacuum degree of the quartz tube meet the required temperature of 20 ℃ ~ 380 ℃ and the required high vacuum degree, the quartz tube is pushed into the tube furnace for 10 minutes, and finally quenched and cooled to room temperature to obtain the magnetic field treatment. Iron-based amorphous alloys.

In the step S2, induction melting is adopted, the alloy raw material is put into the crucible, placed in the induction coil of the induction melting furnace, evacuated to less than 1.0 × 10 ^-2 Pa, and then filled with an inert gas to a pressure of -0.06MPa (relative pressure), hold for 15 minutes after melting, and then cool in the furnace cavity for 25 minutes.

In the step S3, the amorphous alloy is in strip shape, the strip width is 1.1 mm˜1.2 mm, and the thickness is 25 μm˜30 μm.

In the step S5, heat treatment is performed under an external magnetic field (the magnetic field is applied at the beginning of the heat preservation process), and the magnetic field strength of the external magnetic field is 1000 Oe.

Example 3

In this embodiment, the novel high-saturation magnetic induction iron-based soft magnetic amorphous alloy has a molecular formula composition that satisfies: Fe _73.2 Co ₁₀ B ₁₀ C ₆ Cu _0.8 , and its preparation method is as follows:

S1, the raw materials such as _Fe , Co, B, C and _Cu with a purity greater _{than 99} % are _batched according to the alloy composition and the atomic percentage content of each composition. In the form of adding, the mass percentage of C in the iron-carbon alloy is 4.05%;

S2, the raw materials that are proportioned in the step S1 are loaded into the ceramic crucible of the induction melting furnace, and the high-frequency induction melting obtains an alloy ingot with uniform composition;

S3, adopt the VF-RQB20 type melt quick quenching and stripping equipment produced by Japan True Wall Technology Co., Ltd. An appropriate amount of the master alloy obtained in the step S2 is loaded into a quartz tube, fixed in the induction coil, the upper and lower positions of the quartz tube are adjusted to control the distance between the nozzle and the roller surface and the air pressure difference, and an appropriate amount of protective gas (high-purity) is filled after the high vacuum of the cavity is drawn. Argon), set the speed of the copper rod, the surface line speed of the copper roll is 45m/s, turn on the heating current, wait for the solenoid to heat and melt the master alloy to an appropriate temperature, press the spray button, and use the air pressure difference between the quartz tube and the cavity The molten alloy liquid is rapidly sprayed onto the surface of the high-speed rotating copper rod for rapid cooling to prepare continuous amorphous alloy strips;

S4, the amorphous strip obtained in the step S3 is cut into a 60mm long strip and loaded into the quartz tube matched with the tubular annealing furnace, and a high vacuum is drawn, when the temperature of the tubular furnace and the vacuum degree of the quartz tube are all satisfied After the required temperature is 20℃～380℃ and the required high vacuum degree, the quartz tube is pushed into the tube furnace for 10 minutes, and finally quenched and cooled to room temperature to obtain the iron-based amorphous alloy with structural relaxation.

S5, the amorphous strip obtained in the step S3 is cut into a strip of 60mm and then loaded into the quartz tube matched with the tubular annealing furnace (the furnace body has a special magnetic field control function), high vacuum is drawn, when the tube is After the temperature of the furnace and the vacuum degree of the quartz tube meet the required temperature of 20 ℃ ~ 380 ℃ and the required high vacuum degree, the quartz tube is pushed into the tube furnace for 10 minutes, and finally quenched and cooled to room temperature to obtain the magnetic field treatment. Iron-based amorphous alloys.

In the step S2, induction melting is adopted, the alloy raw material is put into the crucible, placed in the induction coil of the induction melting furnace, evacuated to less than 1.0 × 10 ^-2 Pa, and then filled with an inert gas to a pressure of -0.06MPa (relative pressure), hold for 15 minutes after melting, and then cool in the furnace cavity for 25 minutes.

In the step S3, the amorphous alloy is in a strip shape, the strip width is 1.1 mm-1.4 mm, and the thickness is 24 μm-31 μm.

In the step S5, heat treatment is performed under an external magnetic field (the magnetic field is applied at the beginning of the heat preservation process), and the magnetic field strength of the external magnetic field is 1000 Oe.

Comparative ratio:

The raw materials such as Fe, B, C and Cu with a purity of more than 99% are batched according to the alloy composition and the atomic percentage content of each composition. The molecular formula is Fe _83.2 B ₁₀ C ₆ Cu _0.8 . The mass percentage of C in the carbon alloy is 4.05%.

The preparation method is exactly the same as the preparation method described in Examples 1, 2 and 3.

The testing methods for the alloy structure, thermal properties and magnetic properties are exactly the same as those described in the examples.

As shown in Figure 1, Figure 1 is the XRD pattern of the amorphous strips prepared in step S3 in Examples 1, 2, 3 and the comparative example. The XRD was measured by a D8Advance polycrystalline X-ray diffractometer, and the examples were compared In contrast, the XRD pattern of the sample before and after adding Co in the figure shows a diffuse diffuse scattering peak, and no obvious crystallization diffraction peak appears, which is a typical amorphous structure. The difference is that the average thickness of the alloy strips increases slightly after adding Co element, indicating that the addition of Co can effectively improve the amorphous forming ability of the alloy.

As shown in Figure 2, Figure 2 is the DSC curve diagram of the amorphous strips prepared in step S3 in Examples 1, 2, 3 and the comparative example, wherein the DSC curve is measured by a NETZSCHDSC404C differential scanning calorimeter, and the measured The heating rate was 40 K/min. Example Compared with the comparative example, the first initial crystallization peak temperature T _x1 of the Co-added amorphous strip moves to the low temperature region, while the second initial crystallization peak temperature T _x2 moves to the high temperature region, indicating that the heat of the remaining amorphous phase is increased. Improved stability.

As shown in FIG. 3, FIG. 3 is a hysteresis loop diagram of the amorphous ribbons prepared in step S3 in Examples 1, 2, 3 and Comparative Example, wherein the hysteresis loop adopts a vibrating sample magnetometer ( VSM, Lakeshore7410) measurement, used to test the saturation magnetic induction of alloys. Comparing the example with the comparative example, it can be seen that the saturation magnetic induction of the quenched alloy added with Co is significantly improved, reaching 1.77 T, and its coercivity is similar to that of the comparative example, which is maintained at about 13.0 A/m.

As shown in Figure 4, Figure 4 shows the XRD patterns of the alloy strips of Example 2 and Comparative Example after the magnetic heat treatment in step S5. The Example is compared with the Comparative Example, and the sample in the figure is annealed under an external magnetic field at 360 °C for 10 minutes. , still showed a diffuse diffuse scattering peak, no obvious crystallization diffraction peak appeared, indicating that the alloy did not crystallize under this condition.

As shown in FIG. 5 , FIG. 5 is a hysteresis loop diagram of the amorphous strips obtained in Step S4 and Step S5 respectively in Example 2 and Comparative Example. It can be seen that before and after adding Co, the hysteresis loops of the alloy after annealing at 360 °C for 10 minutes before and after applying a magnetic field are almost the same, indicating that the magnetic field heat treatment has little effect on the saturation magnetic induction of the alloy. But compared with the comparative example, the saturation magnetic induction of the Co-added alloy is significantly improved.

As shown in FIG. 6 , FIG. 6 is a graph showing the variation of saturation magnetic induction and coercive force with temperature of the amorphous ribbon obtained in step S4 and step S5 respectively in Example 2 and Comparative Example. It can be seen that the saturation magnetic induction of the Co-added alloy has no obvious change before and after the application of the magnetic field, and it increases with the increase of the annealing temperature. The alloy has obvious changes before and after applying a magnetic field. After annealing at 360 °C for 10 minutes, the coercivity decreases from 3.9 A/m without a magnetic field to 2.2 A/m, indicating that the magnetic field heat treatment can significantly improve the soft magnetic properties of the alloy. Compared with the comparative example, the magnetic properties of the Co-added alloy are significantly improved.

The above descriptions are only preferred embodiments of the present invention, which are merely illustrative rather than limiting for the present invention. Those skilled in the art understand that many changes, modifications and even equivalents can be made within the spirit and scope defined by the claims of the present invention, but all fall within the protection scope of the present invention.

Claims (7)

1. A novel high saturation magnetic induction iron-based soft magnetic amorphous alloy is characterized by being Fe_aCo_bB_cC_dCu_eThe atomic percentage of a of Fe is more than or equal to 70 and less than or equal to 90, the atomic percentage of B of Co is more than or equal to 0 and less than or equal to 20, the atomic percentage of C of B is more than or equal to 1 and less than or equal to 20, the atomic percentage of d of C is more than or equal to 1 and less than or equal to 20, the atomic percentage of e of Cu is more than or equal to 0.1 and less than or equal to 2, and a + B + C + d + e ═ e100。

2. The new high saturation induction Fe-based soft magnetic amorphous alloy according to claim 1, characterized in that the atomic percentage a of Fe is 80 ≤ a ≤ 86, the atomic percentage B of Co is 0 ≤ B ≤ 12, the atomic percentage C of B is 7 ≤ C ≤ 10, the atomic percentage d of C is 3 ≤ d ≤ 10, and the atomic percentage e of Cu is 0.5 ≤ e ≤ 1.

3. A method for preparing a novel iron-based soft magnetic amorphous alloy with high saturation induction as claimed in claim 1 or 2, characterized by comprising the steps of:

s1, mixing Fe, Co, B, Cu and Fe-C alloy according to the formula_aCo_bB_cC_dCu_eBlending;

s2, putting the raw materials into a crucible of a smelting furnace, and smelting in an inert gas atmosphere to obtain a master alloy ingot;

s3, preparing the master alloy ingot into a continuous amorphous alloy strip through melt rapid quenching strip throwing equipment;

s4, cutting the amorphous strips into strips with the length of 40-70 mm, then placing the strips into a quartz tube matched with a tube annealing furnace, arranging an external magnetic field in the tube annealing furnace, vacuumizing, pushing the quartz tube into the tube furnace to keep the temperature for 1-20 minutes after the temperature of the tube furnace meets the temperature of 20-380 ℃, and finally quenching and cooling or cooling in air to room temperature to obtain the iron-based amorphous alloy after magnetic field treatment.

4. The preparation method according to claim 3, wherein in the step S1, the purity of each raw material is greater than 99%, and the mass percentage of C in the iron-carbon alloy is 4.0-5.0%.

5. The method of claim 3, wherein in step S2, the alloy raw material is placed in a crucible by induction melting, placed in an induction coil of an induction melting furnace, and vacuumized to below 1.0 × 10^-2pa, thenFilling inert gas until the air pressure is-0.06 MPa to-0.02 MPa, preserving the heat for 15 minutes to 30 minutes after melting, and then placing the mixture in a furnace cavity for cooling for 20 minutes to 30 minutes.

6. The method according to claim 3, wherein in the step S3, the continuous amorphous alloy ribbon is in a ribbon shape, the ribbon width is 1mm to 1.6mm, the thickness is 18 μm to 35 μm, and the density is 7.5kg/m³～7.6kg/m³。

7. The method according to claim 3, wherein in step S4, the heat treatment is performed in the presence of the external magnetic field, and the heat treatment includes starting the heating process, and starting the heating process, wherein the magnetic field intensity of the external magnetic field is 100Oe to 1600 Oe.

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