CN109719264B - Antirust amorphous alloy and preparation method thereof - Google Patents
Antirust amorphous alloy and preparation method thereof Download PDFInfo
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Abstract
The invention provides an antirust amorphous alloy and a preparation method thereof, belonging to the technical field of magnetic material preparation. The antirust amorphous alloy consists of the following element components in percentage by mass: cr: 4.5-6.8%; si: 6.2-8.5%; b: 2.5-3.6%; mn: 1.2-2.5%; c: 0.5-1.2%; p: 0.5-1.2%; sn: 0.3-1%; the balance being Fe. According to the invention, by optimizing the components and the proportion of alloy elements, the amorphous alloy product with excellent antirust performance and excellent soft magnetic performance is obtained.
Description
Technical Field
The invention relates to the technical field of magnetic material preparation, in particular to an antirust amorphous alloy and a preparation method thereof.
Background
The amorphous alloy is a solid alloy with a long-range disordered structure, which is obtained by solidification of the alloy in a super-quenching way and in which atoms are not arranged and crystallized in order, and crystal grains and crystal boundaries of crystalline alloy do not exist. The amorphous alloy has a plurality of unique properties, and is gradually the key point of research and development in the material science community at home and abroad due to excellent properties and simple process.
Wherein the iron base is amorphousThe alloy is composed of about 80% of Fe and about 20% of metal elements such as Si and B, and has the characteristics of high saturation magnetic induction (1.54T), and better magnetic conductivity, exciting current and iron loss than silicon steel sheets. 2605SC amorphous alloy manufactured by Allied-Signal company of America is Fe81B13.5Si3.5C2Saturation induction 1.61T, coercive force 3.2A/m, magnetic permeability (0.002T)2500 and maximum magnetic permeability 300000.
Amorphous alloys are commonly used for magnetic heads, transformers, choke coils, high-efficiency motors, reactors and the like, and therefore, the amorphous alloys are often required to be prepared into thin sheets to be rolled and stacked into a plurality of layers for use, which puts higher requirements on the rust prevention and corrosion prevention performance of the amorphous alloys. The conventional rust-proof and corrosion-proof method is not suitable for multilayer rolled amorphous alloy. For example, CN201220718554.1 discloses a method for protecting an amorphous alloy magnetic core, in which an anti-corrosion coating is disposed on the entire surface of the amorphous alloy magnetic core, but the material inside the coil layer is not protected.
CN201010160307.X discloses a Zr-based amorphous alloy surface treatment method, a colorless transparent coating is coated on the surface of a Zr-based amorphous alloy, the colorless transparent coating comprises a component A and a component B, and the component A comprises water-based epoxy resin, zirconium hydrofluoride, nano silicon dioxide, microcrystalline wax, a defoaming agent, a leveling agent and water; the component B comprises a waterborne epoxy modified amine curing agent and an epoxy curing accelerator. And (3) placing the sample sprayed with the transparent coating in a constant-temperature oven for baking at the baking temperature of 150 ℃ for 30 min. The method is not applicable to the rolled amorphous alloy with the thickness of a single sheet of which is about 10-20 microns, and the coating can influence the magnetic property of the amorphous alloy; secondly, the thickness of the amorphous alloy is increased after the coating is added, and the total thickness after the rolling and the stacking is far larger than the thickness without the coating; thirdly, the coating needs high-temperature curing, and has certain negative effect on the properties of components such as magnetic heads made of amorphous alloy.
CN201410052193.5 discloses a chemical polishing process for bulk amorphous and nanocrystalline alloy surface, and the polished alloy has antirust and anticorrosive properties. However, the polishing process is complicated, including mechanical pretreatment, alkali washing to remove oil, hot water washing, dilute nitric acid, water washing, drying and the like, and the whole process can seriously damage various performance indexes of the flaky amorphous alloy. Therefore, an amorphous alloy having good rust-proof and corrosion-proof properties is required.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides an antirust amorphous alloy and a preparation method thereof. According to the invention, by optimizing the components and the proportion of alloy elements, the amorphous alloy product with excellent antirust performance and excellent soft magnetic performance is obtained.
The technical scheme of the invention is as follows:
the preparation method of the antirust amorphous alloy comprises the following element components in percentage by mass: cr: 4.5-6.8%; si: 6.2-8.5%; b: 2.5-3.6%; mn: 1.2-2.5%; c: 0.5-1.2%; p: 0.5-1.2%; sn: 0.3-1%; the balance being Fe; the rust-proof amorphous alloy comprises the following steps:
(1) adding the raw materials into a smelting furnace according to a ratio, preserving heat for 10-30 min at 1520-1560 ℃ after melting, adding a purifying agent, standing for many times and slagging to finally enable all components in the alloy mother liquor to be uniformly distributed, wherein the respective contents of Al, O and N are below 10 ppm;
(2) introducing alloy mother liquor in a smelting furnace into a tundish, sealing a water gap by using a stopper rod, and standing for 30-40 min to ensure that the temperature of the mother liquor is uniform;
(3) then the plug rod is lifted, the mother liquor enters a nozzle bag and is sprayed onto a cooling roller rotating at high speed through a nozzle, so that the alloy mother liquor is 10 degrees6～107Cooling and forming at the speed of 1400 ℃ to 1420 ℃ for spraying belt temperature;
(4) collecting the amorphous alloy strip by adopting an online automatic coiling mechanism to obtain an amorphous alloy strip coil product;
(5) winding the amorphous alloy strip coil product into an iron core with required specification, then placing the iron core into a magnetic field heat treatment furnace, and introducing 10-25 m of flow3The protective gas is subjected to heat preservation for 2-4 h at the temperature of 370-.
The purifying agent in the step (1) is composed of 50-55% of silicon dioxide, 35-40% of calcium oxide and 10-15% of iron scale.
The width of the nozzle seam in the step (3) is 80-200 microns; the distance between the nozzle and the cooling roller is 50-200 microns. And (4) the roughness Ra of the cooling roller in the step (3) is not more than 1 micron.
The beneficial technical effects of the invention are as follows:
elements contained in the components of the iron-based amorphous alloy and the stress condition inside the iron-based amorphous alloy structure are important factors influencing the antirust performance and the soft magnetic performance of the amorphous alloy. According to the invention, by redesigning alloy components, optimizing alloy element formula and adopting elements which are high in oxidation resistance and corrosion resistance and capable of improving amorphous forming capability, the amorphous alloy strip coil product which is high in saturation magnetic induction (magnetic flux is about 1.8T), low in coercive force (about 0.3A/m), low in iron loss (about 0.06W/kg) and has remarkable rust prevention and rust resistance is obtained. According to the invention, the obtained amorphous alloy strip coil product is further subjected to heat treatment, and the heat treatment conditions are optimized, so that the internal stress and residual stress existing in the amorphous alloy structure can be greatly reduced, and the corrosion resistance and the static magnetic property of the amorphous alloy product are further improved.
Detailed Description
The present invention will be described in detail with reference to examples and test examples.
Examples 1 to 4:
(1) adding the raw materials into a smelting furnace according to the mass ratio shown in Table 1, preserving the temperature for about 20min at about 1540 ℃ after melting, adding a purifying agent, standing for many times, and slagging to finally enable the components in the alloy mother liquor to be uniformly distributed, wherein the contents of Al, O and N are respectively below 10 ppm; the purifying agent consists of 55% of silicon dioxide, 35% of calcium oxide and 10% of iron scale;
(2) introducing alloy mother liquor in a smelting furnace into a tundish, sealing a water gap by using a stopper rod, and standing for about 30min to ensure that the temperature of the mother liquor is uniform;
(3) then the plug rod is lifted, the mother liquor enters a nozzle bag and is sprayed onto a cooling roller (a water-cooling copper roller) rotating at a high speed through a nozzle, so that the alloy mother liquor is 10 degrees6～107Cooling at a speed of about 1400 deg.C/sec, and molding under a pressure of about 1.2MPa, at a linear speed of 25m/s, at a spray temperature of about 1400 deg.C; the nozzle slot width was 100 microns; the distance between the front edge of the nozzle and the cooling roller right below the nozzle is 50 micrometers, and the distance between the rear edge of the nozzle and the cooling roller right below the nozzle is 150 micrometers; the roughness Ra of the cooling roller is 0.5 micron;
(4) collecting the amorphous alloy strip by adopting an online automatic coiling mechanism to obtain an amorphous alloy strip coil product;
(5) winding the amorphous alloy strip coil product into an iron core with required specification, then loading the iron core into a magnetic field heat treatment furnace, and introducing the iron core with the flow of 20m3H protective gas, and keeping the temperature at 380 ℃ for 3 h.
TABLE 1 (unit:%)
Example 5:
the heat treatment temperature and time in step (5) in the preparation method of example 1 were replaced with 370 ℃ and 4 hours, and the other steps were the same, and the raw material elements were the same in mass percentage as in example 1.
Example 6:
the heat treatment temperature and time in step (5) in the preparation method of example 1 were changed to 375 ℃ and 2 hours, and the other steps were the same, and the mass percentages of the raw material elements were the same as in example 1.
Comparative examples 1 to 6:
the preparation method is the same as that of examples 1-4, and the mass percentages of the raw material elements are shown in table 1.
Comparative example 7:
the heat treatment temperature and time in step (5) in the preparation method of example 1 were replaced with 400 ℃ and 2 hours, and the other steps were the same, and the raw material elements were the same in mass percentage as in example 1.
Comparative example 8:
the heat treatment temperature and time in step (5) in the preparation method of example 1 were changed to 360 ℃ and 4 hours, and the other steps were the same, and the raw material elements were the same in mass percentage as in example 1.
Test example 1: soft magnetic Performance test
The soft magnetic properties and magnetic property test data of the amorphous alloys prepared in the examples and comparative examples were tested as specified in GB/T19346.1 are shown in Table 2.
TABLE 2
As can be seen from the data in Table 2, Si can improve the amorphization ability, and within a certain range, the higher the Si content, the better the magnetic properties of the product. The content of B is stable and is kept within a range in which an amorphous precursor is easily formed. The increase of P can improve the amorphous forming ability, and the product magnetism can be kept better under the condition of complementing the dosage of Si; however, considering the content of Fe, the decrease of Fe content causes the decrease of magnetic properties. In addition, the magnetic performance of the amorphous alloy product after magnetic field heat treatment is better within a certain temperature range.
Test example 2: test of rust inhibitive Property
The amorphous alloy strips prepared in examples and comparative examples were flattened, 10 samples each having a length of 10cm were cut out at random positions, without any protective treatment, placed in a ventilated environment at a temperature of 40 ℃ and a humidity of 80%, and examined for rusting on the surfaces of the samples after a certain period of time, the areas of the rusted spots of 10 samples belonging to the same strip were added and divided by the total area of 10 samples to obtain the percentage of the rusted area of the strips prepared in each of examples and comparative examples, and the results are shown in table 3.
Table 3 (unit:%)
| 5 days | 10 days | 20 days | 30 days | 60 days | 90 days | |
| Example 1 | 0 | 0.2 | 1.4 | 4.8 | 9.5 | 19.6 |
| Example 2 | 0 | 0.2 | 1.3 | 4.6 | 9.2 | 19.1 |
| Example 3 | 0 | 0.1 | 1.1 | 4.2 | 8.5 | 18.6 |
| Example 4 | 0 | 0 | 0.9 | 3.9 | 7.7 | 18.2 |
| Example 5 | 0 | 0.2 | 1.4 | 5.0 | 9.8 | 20.1 |
| Example 6 | 0 | 0.2 | 1.4 | 4.9 | 9.6 | 19.7 |
| Comparative example 1 | 0.1 | 1.7 | 5.6 | 11.3 | 24.3 | 39.2 |
| Comparative example 2 | 0.1 | 2 | 5.8 | 11.8 | 25.1 | 39.6 |
| Comparative example 3 | 0 | 1.5 | 4.9 | 11 | 23.8 | 38.9 |
| Comparative example 4 | 0 | 0.9 | 3.5 | 9.7 | 21 | 35.2 |
| Comparative example 5 | 0 | 1.2 | 4.2 | 9.9 | 22.2 | 36.8 |
| Comparative example 6 | 0 | 1.3 | 4.5 | 10.6 | 23.1 | 37.4 |
| Comparative example 7 | 0 | 0.4 | 1.8 | 5.6 | 11.1 | 21.8 |
| Comparative example 8 | 0 | 0.6 | 2.1 | 6.2 | 15.4 | 25.3 |
As can be seen from the data in Table 3, Cr, Mn and C play an important role in improving the anti-rust performance of the amorphous alloy, wherein the role of Cr is more critical, and when the content of Cr is too low, the amorphous alloy is easy to rust even if the content of Mn and C is high; when the content of Cr is high, the contents of Mn and C need to be controlled within a narrow range, and too high or too low may deteriorate the rust inhibitive performance of the product. In addition, the temperature for carrying out heat treatment on the amorphous alloy strip coil product needs to be controlled within a certain range, and the antirust performance of the product is reduced when the temperature is too high or too low.
Claims (4)
1. The preparation method of the antirust amorphous alloy is characterized in that the antirust amorphous alloy consists of the following element components in percentage by mass: cr: 4.5-6.8%; si: 6.2-8.5%; b: 2.5-3.6%; mn: 1.2-2.5%; c: 0.5-1.2%; p: 0.5-1.2%; sn: 0.3-1%; the balance being Fe; the rust-proof amorphous alloy comprises the following steps:
(1) adding the raw materials into a smelting furnace according to a ratio, preserving heat for 10-30 min at 1520-1560 ℃ after melting, adding a purifying agent, standing for many times and slagging to finally enable all components in the alloy mother liquor to be uniformly distributed, wherein the respective contents of Al, O and N are below 10 ppm;
(2) introducing alloy mother liquor in a smelting furnace into a tundish, sealing a water gap by using a stopper rod, and standing for 30-40 min to ensure that the temperature of the mother liquor is uniform;
(3) then the plug rod is lifted, the mother liquor enters a nozzle bag and is sprayed onto a cooling roller rotating at high speed through a nozzle, so that the alloy mother liquor is 10 degrees6～107Cooling and forming at the speed of 1400 ℃ to 1420 ℃ for spraying belt temperature;
(4) collecting the amorphous alloy strip by adopting an online automatic coiling mechanism to obtain an amorphous alloy strip coil product;
(5) winding the amorphous alloy strip coil product into an iron core with required specification, then placing the iron core into a magnetic field heat treatment furnace, and introducing 10-25 m of flow3The protective gas is subjected to heat preservation for 2-4 h at the temperature of 370-.
2. The preparation method according to claim 1, wherein the purifying agent in the step (1) is composed of 50-55% of silicon dioxide, 35-40% of calcium oxide and 10-15% of scale.
3. The method according to claim 1, wherein the nozzle slit width in the step (3) is 80 to 200 μm; the distance between the nozzle and the cooling roller is 50-200 microns.
4. The production method according to claim 1, characterized in that the roughness Ra of the cooling roll in the step (3) is not more than 1 μm.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031865A (en) * | 1987-09-05 | 1989-03-22 | 冶金工业部钢铁研究总院 | Amorphous alloy powder |
| CN1403615A (en) * | 2002-08-16 | 2003-03-19 | 安泰科技股份有限公司 | Iron-base bulk amorphous soft-magnetic alloy material |
| CN1730714A (en) * | 2005-09-07 | 2006-02-08 | 北京科技大学 | Highly corrosion-proof abrasion-proof iron matrix amorphous nanocrystalline coating and its preparation method |
| CN101840764A (en) * | 2010-01-25 | 2010-09-22 | 安泰科技股份有限公司 | Low-cost high-saturation magnetic induction intensity iron-based amorphous soft magnetism alloy |
| CN105047348A (en) * | 2015-08-03 | 2015-11-11 | 江苏奥玛德新材料科技有限公司 | Current transformer iron core of amorphous and nano-crystalline magnetically soft alloy and preparation method thereof |
| CN105143491A (en) * | 2013-01-25 | 2015-12-09 | 蒂森克虏伯钢铁欧洲股份公司 | Methods for creating a flat steel product with an amorphous, partially amorphous or finely crystalline structure and flat steel product of such a type |
| CN105825991A (en) * | 2016-03-23 | 2016-08-03 | 山东大学（威海） | Iron-based soft-magnet amorphous alloy with less components, low cost and high saturation magnetic induction intensity and manufacturing process thereof |
-
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- 2019-02-26 CN CN201910141929.9A patent/CN109719264B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031865A (en) * | 1987-09-05 | 1989-03-22 | 冶金工业部钢铁研究总院 | Amorphous alloy powder |
| CN1403615A (en) * | 2002-08-16 | 2003-03-19 | 安泰科技股份有限公司 | Iron-base bulk amorphous soft-magnetic alloy material |
| CN1730714A (en) * | 2005-09-07 | 2006-02-08 | 北京科技大学 | Highly corrosion-proof abrasion-proof iron matrix amorphous nanocrystalline coating and its preparation method |
| CN101840764A (en) * | 2010-01-25 | 2010-09-22 | 安泰科技股份有限公司 | Low-cost high-saturation magnetic induction intensity iron-based amorphous soft magnetism alloy |
| CN105143491A (en) * | 2013-01-25 | 2015-12-09 | 蒂森克虏伯钢铁欧洲股份公司 | Methods for creating a flat steel product with an amorphous, partially amorphous or finely crystalline structure and flat steel product of such a type |
| CN105047348A (en) * | 2015-08-03 | 2015-11-11 | 江苏奥玛德新材料科技有限公司 | Current transformer iron core of amorphous and nano-crystalline magnetically soft alloy and preparation method thereof |
| CN105825991A (en) * | 2016-03-23 | 2016-08-03 | 山东大学（威海） | Iron-based soft-magnet amorphous alloy with less components, low cost and high saturation magnetic induction intensity and manufacturing process thereof |
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Denomination of invention: Antirust amorphous alloy and its preparation method Effective date of registration: 20221223 Granted publication date: 20201002 Pledgee: Fuyang Erlijing Sub branch of China Construction Bank Corp. Pledgor: ANHUI ZHICI NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2022980028904 |