WO2021143476A1

WO2021143476A1 - Cold deformed and adjusted nanocomposite permanent magnet conductive contact and manufacturing method therefor

Info

Publication number: WO2021143476A1
Application number: PCT/CN2020/138799
Authority: WO
Inventors: 张敬敏
Original assignee: 山东光韵智能科技有限公司
Priority date: 2020-01-14
Filing date: 2020-12-24
Publication date: 2021-07-22
Also published as: CN111987508A

Abstract

A cold deformed and adjusted nanocomposite permanent magnet conductive contact and a manufacturing method therefor, said permanent magnet conductive contact consisting of 3 parts: a fixing sleeve, a core body, and a coil, wherein said core body has as raw material, in parts by weight, 6-8 parts neodymium, 3.5-4.5 parts molybdenum, 100-110 parts ferroboron FeB22C0.05, and 5-7 parts yttrium, said materials are mixed and subject to multiple subsequent cold pressure deformation adjustments and annealing, and an alloy ultimately obtained serves as a core, and pure copper serves as a casing, thereby obtaining a composite core body, the composite core body being sleeved inside the fixing sleeve; the coil is formed by an aniline modified carbon fiber aluminum core composite wiring wrapped around a surface of the core body, said coil being wrapped around an inside surface of the fixing sleeve. The present invention has a high Curie temperature, good thermostability, and is corrosion resistant and anti-oxidant.

Description

Cold deformed tissue adjustment nano composite permanent magnetic conductive contact and manufacturing method thereof

Technical field

The invention relates to the technical field of electrical devices, in particular to a cold-deformed tissue adjustment nano-composite permanent magnetic conductive contact and a manufacturing method thereof.

Background technique

The energy product research of Nd-Fe-B single-phase permanent magnet material has reached a bottleneck, and its shortcomings such as low Curie temperature, thermal stability, corrosion resistance and oxidation resistance are still difficult to overcome. New generation The preparation of Sm2Fe17Nx single-phase permanent magnet materials is also due to the uncontrollability of composition, phase composition and distribution, so far no breakthrough has been made. Therefore, the development of composite materials has become the focus of researchers. Theoretical research shows that the dual-phase nanocomposite permanent magnetic material has the high saturation magnetization of the soft magnetic phase and the high coercive force of the hard magnetic phase, and the obvious remanence enhancement effect appears, and the theoretical magnetic energy product can reach 1MJ/m3. Years of experimental results have shown that although the remanence of the dual-phase nanocomposite permanent magnetic material has been significantly improved, the coercivity has dropped significantly. The trade-off relationship makes the squareness of the demagnetization curve poor, and the actual magnetic energy product is far lower than the theoretical value. Therefore, it is necessary to conduct in-depth research on the mechanism of intergranular exchange coupling of dual-phase nano-permanent magnetic materials, soft/hard magnetic grain size and volume fraction, coercive force mechanism and organization control methods.　　

technical problem

There is an urgent need in the market for a nano-composite permanent magnetic conductive contact with high Curie temperature, good thermal stability, corrosion resistance, and oxidation resistance.

Technical solutions

The invention aims to provide a method for manufacturing a nano composite permanent magnetic conductive contact with high Curie temperature, good thermal stability, corrosion resistance, and oxidation resistance.

In order to achieve the above objective, the present invention adopts the following technical solution: a method for manufacturing a cold-deformed structure adjustment nano-composite permanent magnetic conductive contact, including the following steps:

1) Raw material preparation

①Preparation of raw materials: prepare 6-8 parts of pure copper powder, 6-8 parts of neodymium metal, 3.5-4.5 parts of molybdenum, 100-110 parts of boron iron FeB22C0.05, 5-7 parts of yttrium according to weight parts, Fixed sleeve, sufficient carbon fiber aluminum core composite wire, sufficient aniline, 0.2-0.5 parts of ammonium persulfate initiator;

② Preparation of auxiliary materials: prepare a sufficient amount of a mixture of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1, a sufficient amount of 10% solute mass fraction of hydrochloric acid aqueous solution, and a sufficient amount of argon;

2) Core preparation

①Under the protection of sufficient argon gas prepared in stage 1), step ②, the neodymium, molybdenum, ferroboron FeB22C0.05 and yttrium prepared in stage 1) are mixed and smelted by electroslag remelting, and then cooled to Make a primary alloy billet at room temperature;

②The primary alloy billet obtained in step ① is ball-milled into alloy powder of 500 mesh to 1000 mesh. The alloy powder is used as a raw material and smelted in a vacuum induction melting furnace integrated with electromagnetic stirring equipment. The melting process is: vacuum to 1× before heating. 10-2Pa-1×10-3Pa, count when the raw material starts to melt when the temperature is reached, turn on electromagnetic stirring at a stirring rate of 100rpm/min-250rpm/min, and keep it for 20min-23min, then stop heating and use nitrogen for rapid cooling, and then out of the furnace , Get a magnetic blank;

③ Apply pressure to the primary magnetic blank obtained in step ② in a direction that is straight to the magnetic induction direction of the coil required by the design, and perform room temperature cold compression molding at a deformation rate of 0.2mm-0.25mm each time, until the molding meets the molding size. The molded size is the final core design size with a unilateral increase of 0.3mm-0.5mm, and a rough magnetic blank is obtained after compression molding;

④The rough magnetic core obtained in step ③ is annealed at a temperature of 730℃-750℃ under a vacuum degree of 1×10-2Pa-1×10-3Pa, and then the cylindrical surface of the rough magnetic core obtained after annealing and two The end faces are mechanically polished to remove the thickness of 0.3mm-0.5mm to obtain a regular magnetic core;

⑤After the pure copper powder prepared in step 1) is heated to melting, it is sprayed uniformly on the regular magnetic core surface obtained in step ③ by supersonic flame spraying, and then mechanically polished to obtain the two end faces of the composite material to obtain the desired final product Magnetic core

3) Wire preparation

① Completely immerse the carbon fiber aluminum core composite wire prepared in step 1) in step ① into the mixed solution of concentrated sulfuric acid and concentrated nitric acid prepared in step ②, and use 200W-250W ultrasonic treatment for 3.5h-4h to obtain carboxylated passivated composite wire , And then rinse the composite wire with clean water;

② Immerse the carboxylated and passivated composite wire obtained in step ① into the hydrochloric acid aqueous solution prepared in step ②, immerse the hydrochloric acid aqueous solution in an ice bath at -5°C~-10°C, and turn it on at a rate of 120rpm/min-150rpm/min Stir, then put in the aniline prepared in step 1), and finally put the ammonium persulfate initiator prepared in step 1 into the reaction solution at a mass rate of 10%/min. Stir for 40min-50min, take out the reaction solution and remove it. Place it in a refrigerator at -5℃~-10℃ for 0.5 days to 1 day, filter out the solidified material, and rinse with ethanol and water until it is clean to obtain a modified composite wire;

4) Conductive contact molding

① Put the final magnetic core obtained in stage 2) as a movable structure in the fixed sleeve prepared in stage 1), and then cut off the head and tail ends of the modified composite wire obtained in stage 3) and wind it in the fixed sleeve The inner surface of the barrel ensures that the modified composite wire does not contact the surface of the final magnetic core, and a composite core structure is obtained. The composite core structure is the nano composite permanent magnetic conductive contact required for cold deformation organization adjustment.

A cold deformed structure adjustment nano composite permanent magnetic conductive contact. The permanent magnetic conductive contact is composed of three parts: a fixed sleeve, a core and a coil. The core is 6-8 parts by weight of neodymium, Molybdenum 3.5 parts-4.5 parts, boron iron FeB22C0.05 100 parts-110 parts, and yttrium 5-7 parts as raw materials. After mixing, it is subjected to multiple cold pressing deformation adjustments at a deformation rate of 0.2mm-0.25mm each time. The alloy finally obtained after annealing is the core, and the composite core is obtained by using pure copper as the shell. The composite core is set in a fixed sleeve; the coil is wound by the aniline modified carbon fiber aluminum core composite wire wound on the surface of the core. , The coil is wound on the inner surface of the fixed sleeve.

Beneficial effect

The present invention has the following advantages: (1) Compared with the prior art focusing on studying the ratio of magnetic alloy elements, the present invention is more focused on adjusting the structure, size and proportional relationship of the effective phase in the alloy. Therefore, it has been studied for many times. And combined with the actual production, the cold deformation structure adjustment process of the special magnetic core is researched. The goal is to obtain the optimal grain size and total soft magnetic phase of 5nm-15nm soft magnetic phase grains and 25nm-35nm hard magnetic phase grains. Volume: The total volume of the hard magnetic phase is close to the optimal coupling structure of 1:1, which has never been paid attention to in the prior art. In fact, the present invention obtains the optimal performance of the magnet's coercive force Hcj=7.2kOe; maximum magnetic energy product (BH) max=17.8MGOe (the coercive force is increased by about 12%-15%, and the maximum magnetic energy Product increase by 30%-50%). (2) The hard magnetic properties of the special magnetic core of the present invention are derived from the fine and uniformly distributed soft magnetic phase α-Fe, Fe3B, while the hard magnetic phase comes from the Nd2Fe14B phase, and there is strong exchange coupling between the soft magnetic phase and the hard magnetic phase. effect. (3) The present invention adopts special heat treatment parameters obtained through a lot of basic research and long-term production practice for the special magnetic core. During the research, we found that if the heat treatment temperature is higher than that of the present invention, the magnetic phase crystal will be caused. The grains grow rapidly, and the too coarse grains will weaken the ferromagnetic exchange coupling effect between the magnetic phases, and the lower heat treatment temperature compared to the present invention cannot obtain sufficient magnetic functional phases. (4) The present invention actually obtains the contact of the surface layer of pure copper and the integral permanent magnet, which has high magnetic induction and a good conductor. The permanent magnet is used as the core and the pure copper is the shell, which not only obtains excellent magnetic properties, It avoids the stress-sensitive defects of nano-permanent magnetic materials, and at the same time, the surface layer is toughened and impact resistant, and the surface contact area is large. (5) The present invention refers to the finger contact instead of the bridge contact, so there is no metal fatigue problem, only impact damage and wear need to be considered. However, the present invention is not in the conventional technology, and the surface of the hard core is added The relatively soft permanent magnetic pure copper not only ensures that the magnetic core will not be deformed due to insufficient core strength, but also protects the impacted surface from damage. It also builds a relatively flexible buffer between the two hard bodies. The contact surface is improved, so the invention has strong anti-fatigue ability. (6) All the materials used in the present invention are resistant to high temperature. Since there is no curing material that is not resistant to high temperature such as soldering or resin, the non-flammable carbon fiber and the non-corrosive aluminum core are passivated and protected against aniline adhesion. The insulation treatment between the core and the core, and at the same time, due to the aniline, it also obtains the self-hydrophobic performance of the coil, which expands the scope of application and reduces the difficulty of surface protection. Therefore, the present invention has the characteristics of high Curie temperature, good thermal stability, corrosion resistance and oxidation resistance.

Embodiments of the present invention

Example 1:

A cold-deformed structure adjustment nano-composite permanent magnetic conductive contact. The permanent magnetic conductive contact is composed of three parts: a fixed sleeve, a core and a coil. The core is 7g neodymium, 4.2g molybdenum, and molybdenum in parts by weight. Ferro-boron FeB22C0.05 107g and yttrium 5.8g are mixed as raw materials, and then subjected to cold pressing deformation adjustment and annealing at a deformation rate of 0.2mm-0.25mm each time. The alloy is finally obtained as the core and pure copper as the shell. The core body, the composite core body is set in a fixed sleeve; the coil is made of aniline modified carbon fiber aluminum core composite wire wound on the surface of the core body, and the coil is wound on the inner surface of the fixed sleeve; the permanent magnet is conductive The manufacturing method of the contact includes the following steps:

1) Raw material preparation

①Preparation of raw materials: prepare 7g pure copper powder, 7g neodymium metal, 4.2g molybdenum, ferroboron FeB22C0.05 107g, yttrium 5.8g, fixed sleeve, sufficient carbon fiber aluminum core composite wire, sufficient aniline, persulfuric acid in parts by weight Ammonium initiator 0.2g-0.5g;

2) Core preparation

3) Wire preparation

4) Conductive contact molding

① Put the final magnetic core obtained in stage 2) as a movable structure in the fixed sleeve prepared in stage 1), and then cut off the head and tail ends of the modified composite wire obtained in stage 3) and wind it in the fixed sleeve The inner surface of the barrel ensures that the modified composite wire does not contact the surface of the final magnetic core, and a composite core structure is obtained. The composite core structure is the required cold deformed structure adjustment nano composite permanent magnetic conductive contact.

The magnetic performance of the magnetic core manufactured according to this embodiment is: the coercive force Hcj=7.2kOe; the optimized performance of the maximum magnetic energy product (BH) max=17.8MGOe (the coercive force is increased by about 12%-15%, the maximum magnetic energy Product increase by 30%-50%). (The same below)

Example 2:

The whole is consistent with Example 1, the difference lies in:

Raw materials: pure copper powder 8g, metal neodymium 6g, molybdenum 3.5g, boron iron FeB22C0.05 100g, yttrium 5g, ammonium persulfate initiator 0.2g;

Example 3:

The whole is consistent with Example 1, the difference lies in:

Raw materials: pure copper powder 6g, metal neodymium 8g, molybdenum 4.5g, boron iron FeB22C0.05 110g, yttrium 7g, ammonium persulfate initiator 0.5g;

Industrial applicability

(1) The present invention uses special heat treatment parameters obtained through a lot of basic research and long-term production practice for the special magnetic core. In the research, we found that if the heat treatment temperature is higher than that of the present invention, it will cause magnetic phase crystallization. The grains grow rapidly, and the too coarse grains will weaken the ferromagnetic exchange coupling effect between the magnetic phases, and the lower heat treatment temperature compared to the present invention cannot obtain sufficient magnetic functional phases. (2) The present invention actually obtains the contact of pure copper on the surface and integral permanent magnet, which has both high magnetic induction and good conductor. The permanent magnet is used as the core and the pure copper is the shell, which not only obtains excellent magnetic properties, It avoids the stress-sensitive defects of nano-permanent magnetic materials, and at the same time, the surface layer is toughened and impact resistant, and the surface contact area is large. (3) The present invention refers to the finger contact instead of the bridge contact, so there is no metal fatigue problem, only impact damage and wear need to be considered. However, the present invention is not in the conventional technology, and the surface of the hard core is added The relatively soft permanent magnetic pure copper not only ensures that the magnetic core will not be deformed due to insufficient core strength, but also protects the impacted surface from damage. It also builds a relatively flexible buffer between the two hard bodies. The contact surface is improved, so the invention has strong anti-fatigue ability. (4) All the materials used in the present invention are resistant to high temperature. Since there is no curing material that is not resistant to high temperature such as soldering or resin, the non-flammable carbon fiber and the non-corrosive aluminum core are passivated and protected against aniline adhesion. The insulation treatment between the core and the core, and at the same time, due to the aniline, it also obtains the self-hydrophobic performance of the coil, which expands the scope of application and reduces the difficulty of surface protection. Therefore, the present invention has the characteristics of high Curie temperature, good thermal stability, corrosion resistance and oxidation resistance.

Sequence Listing Free Content

The foregoing description of the disclosed embodiments is only to enable those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown in this document, but should conform to the widest scope consistent with the principles and novel features disclosed in this document.

Claims

A method for manufacturing a cold-deformed tissue-adjusting nano-composite permanent magnetic conductive contact is characterized in that it comprises the following steps:

1) Raw material preparation

①Preparation of raw materials: prepare 6-8 parts of pure copper powder, 6-8 parts of neodymium metal, 3.5-4.5 parts of molybdenum, 100-110 parts of boron iron FeB22C0.05, 5-7 parts of yttrium according to weight parts, Fixed sleeve, sufficient carbon fiber aluminum core composite wire, sufficient aniline, 0.2-0.5 parts of ammonium persulfate initiator;

② Preparation of auxiliary materials: prepare a sufficient amount of a mixture of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1, a sufficient amount of 10% solute mass fraction of hydrochloric acid aqueous solution, and a sufficient amount of argon;

2) Core preparation

①Under the protection of sufficient argon gas prepared in stage 1), step ②, the neodymium, molybdenum, ferroboron FeB22C0.05 and yttrium prepared in stage 1) are mixed and smelted by electroslag remelting, and then cooled to Make a primary alloy billet at room temperature;

②The primary alloy billet obtained in step ① is ball-milled into alloy powder of 500 mesh to 1000 mesh. The alloy powder is used as a raw material and smelted in a vacuum induction melting furnace integrated with electromagnetic stirring equipment. The melting process is: vacuum to 1× before heating. 10-2Pa-1×10-3Pa, count when the raw material starts to melt when the temperature is reached, turn on electromagnetic stirring at a stirring rate of 100rpm/min-250rpm/min, and keep it for 20min-23min, then stop heating and use nitrogen for rapid cooling, and then out of the furnace , Get a magnetic blank;

③ Apply pressure to the primary magnetic blank obtained in step ② in a direction that is straight to the magnetic induction direction of the coil required by the design, and perform room temperature cold compression molding at a deformation rate of 0.2mm-0.25mm each time, until the molding meets the molding size. The molded size is the final core design size with a unilateral increase of 0.3mm-0.5mm, and a rough magnetic blank is obtained after compression molding;

④The rough magnetic core obtained in step ③ is annealed at a temperature of 730℃-750℃ under a vacuum degree of 1×10-2Pa-1×10-3Pa, and then the cylindrical surface of the rough magnetic core obtained after annealing and two The end faces are mechanically polished to remove the thickness of 0.3mm-0.5mm to obtain a regular magnetic core;

⑤After the pure copper powder prepared in step 1) is heated to melting, it is sprayed uniformly on the regular magnetic core surface obtained in step ③ by supersonic flame spraying, and then mechanically polished to obtain the two end faces of the composite material to obtain the desired final product Magnetic core

3) Wire preparation

① Completely immerse the carbon fiber aluminum core composite wire prepared in step 1) in step ① into the mixed solution of concentrated sulfuric acid and concentrated nitric acid prepared in step ②, and use 200W-250W ultrasonic treatment for 3.5h-4h to obtain carboxylated passivated composite wire , And then rinse the composite wire with clean water;

② Immerse the carboxylated and passivated composite wire obtained in step ① into the hydrochloric acid aqueous solution prepared in step ②, immerse the hydrochloric acid aqueous solution in an ice bath at -5°C~-10°C, and turn it on at a rate of 120rpm/min-150rpm/min Stir, then put in the aniline prepared in step 1), and finally put the ammonium persulfate initiator prepared in step 1 into the reaction solution at a mass rate of 10%/min. Stir for 40min-50min, take out the reaction solution and remove it. Place it in a refrigerator at -5℃~-10℃ for 0.5 days to 1 day, filter out the solidified material, and rinse with ethanol and water until it is clean to obtain a modified composite wire;

4) Conductive contact molding

① Put the final magnetic core obtained in stage 2) as a movable structure in the fixed sleeve prepared in stage 1), and then cut off the head and tail ends of the modified composite wire obtained in stage 3) and wind it in the fixed sleeve The inner surface of the barrel ensures that the modified composite wire does not contact the surface of the final magnetic core, and a composite core structure is obtained. The composite core structure is the required cold deformed structure adjustment nano composite permanent magnetic conductive contact.
A cold-deformed structure adjustment nano composite permanent magnetic conductive contact, which is characterized in that: the permanent magnetic conductive contact is composed of three parts: a fixed sleeve, a core and a coil, wherein the core is 6 parts by weight of neodymium -8 parts, molybdenum 3.5 parts -4.5 parts, boron iron FeB22C0.05 100 parts-110 parts and 5-7 parts of yttrium as raw materials are mixed and then subjected to cold pressing deformation adjustment and annealing at a deformation rate of 0.2mm-0.25mm each time. The alloy is finally obtained as the core and pure copper as the shell. The composite core is sleeved in a fixed sleeve; the coil is wound by an aniline modified carbon fiber aluminum core composite wire wound on the surface of the core, and the coil is wound on the inner surface of the fixed sleeve.

To