CN113990597A - Strip, high initial permeability amorphous nanocrystalline alloy, magnetic core and open-ended transformer - Google Patents
Strip, high initial permeability amorphous nanocrystalline alloy, magnetic core and open-ended transformer Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
- H01F1/14766—Fe-Si based alloys
- H01F1/14775—Fe-Si based alloys in the form of sheets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F27/00—Details of transformers or inductances, in general
- H01F27/24—Magnetic cores
- H01F27/25—Magnetic cores made from strips or ribbons
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0206—Manufacturing of magnetic cores by mechanical means
- H01F41/0213—Manufacturing of magnetic circuits made from strip(s) or ribbon(s)
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Abstract
The application relates to the technical field of alloys, and particularly discloses a strip, a high initial permeability amorphous nanocrystalline alloy, a magnetic core and an open-ended transformer. The strip consists of the following elements in percentage by weight: si: 7% -10%, B: 1.5% -2.5%, Nb: 5.0% -6.0%, Cu: 1.0-1.5%, unavoidable impurities <0.1%, and the balance of Fe. The amorphous nanocrystalline alloy has the advantages of high initial permeability, high maximum permeability and low coercive force; the magnetic core in this application has high magnetic permeability, accords with market demand.
Description
Technical Field
The present application relates to the field of alloy technology, and more particularly, to ribbon, high initial permeability amorphous nanocrystalline alloys, magnetic cores, and open-ended transformers.
Background
The metal and alloy which are composed according to a certain element proportion can instantly solidify atoms in a molten state into a solid state at a cooling speed of 100 ten thousand ℃/s, and the atoms are fixed in short time arrangement, so that crystal grains and crystal boundaries of crystalline alloy do not exist in the metal and alloy, a long-range disordered structure can be formed, and the metal and alloy has a structure similar to a liquid state, but a solid state appearance object is commonly called amorphous alloy and is also called liquid metal. The amorphous alloy comprises an iron-based amorphous alloy, a nickel-based amorphous alloy and a cobalt-based amorphous alloy, wherein the iron-based amorphous alloy is low in price, excellent in performance and simple in process, so that the iron-based amorphous alloy is widely applied. At present, Fe-Si-B series and Fe-Si-B-Nb-Cu series alloys in the iron-based amorphous alloy have excellent soft magnetic performance through certain component optimization and process treatment.
The amorphous alloy can be remelted and sprayed to obtain a strip. The strip is an amorphous thin strip, and materials or products with excellent performance can be obtained by proper treatment. The base material in the strip prepared from the iron-based amorphous alloy is Fe. By adding a proper amount of non-metallic elements or metallic elements into the iron-based alloy, the performance of the material or product prepared from the strip can be obviously improved, so that the application range of the material or product is enlarged.
Firstly, the strip is subjected to proper crystallization annealing treatment, a part of nanoscale crystalline phase can be separated out from an amorphous matrix of the strip, and the nanoscale crystalline phase is dispersed and distributed on the amorphous matrix to obtain the amorphous nanocrystalline alloy. Wherein, when the Fe-based amorphous alloy containing Fe and Nb is annealed at a proper temperature or above, a 10-20nm nanocrystalline grain structure is formed, which is called as the Fe-based amorphous nanocrystalline alloy. The material has excellent comprehensive soft magnetic performance and wide application. The currently common FINMET material (Finemet material is an iron-based amorphous nanocrystalline alloy with the weight percentage of each element of 73.53% of Fe, 1% of Cu, 1% of Nb, 1% of Si, 13.5% of B and 9% of the balance of unavoidable impurities), the iron-based amorphous nanocrystalline alloy material adopts Fe, Cu, Nb, Si and B as raw materials, is widely applied, and has the initial magnetic permeability of mu i-150 k-180 k. Although the initial permeability of the FINMET material is high, its application is still limited by its initial permeability. Therefore, the development of amorphous nanocrystalline alloys with higher initial permeability is of great significance.
Secondly, the strip material is wound into an iron core, the iron core is subjected to a proper heat treatment process, and then is cured and shaped to obtain the magnetic core for the mutual inductor. The mutual inductor has more requirements on the magnetic core, and the measurement accuracy and the sensitive current of the magnetic core of the mutual inductor under a power grid need to be improved, wherein the more important thing is that the magnetic core has higher initial magnetic conductivity and magnetic conductivity, and the amorphous nanocrystalline material has natural advantages in the aspect. At present, the magnetic permeability range of domestic soft magnetic material magnetic cores is 10-15k, but the mutual inductor is continuously developed towards small size and high precision, so that the development of the magnetic core with higher magnetic permeability has important significance.
Disclosure of Invention
In order to improve the initial permeability of the iron-based amorphous nanocrystalline alloy and the permeability of the magnetic core, the application provides a strip, the high initial permeability amorphous nanocrystalline alloy, the magnetic core and an open-ended transformer.
In a first aspect, the present application provides a strip material, using the following technical solution:
a strip material, said strip material consisting of the following elements in weight percent: si: 7% -10%, B: 1.5% -2.5%, Nb: 5.0% -6.0%, Cu: 1.0-1.5%, unavoidable impurities <0.1%, and the balance of Fe.
By adopting the technical scheme, the amorphous nanocrystalline alloy obtained after the strip material is subjected to heat treatment has high initial permeability, high maximum permeability and low coercive force, and the initial permeability range is 194.3-226.4 k; at present, the initial permeability range of soft magnetic materials existing in domestic manufacturers is 60-130k, and the initial permeability range of the FINMET materials is 80-150 k; the maximum magnetic permeability range of the amorphous nanocrystalline alloy is 795.6-886.5k, the maximum magnetic permeability range of the soft magnetic material of the existing domestic manufacturer is 150-350k, the maximum magnetic permeability range of the FINMET material is 150-450k, and compared with the existing soft magnetic material, the initial magnetic permeability and the maximum magnetic permeability of the amorphous nanocrystalline alloy are remarkably improved. The coercive force range of the amorphous nanocrystalline alloy in the application is 0.4699-0.6195A/M, while the coercive force range of the soft magnetic material and the FINMET material of domestic manufacturers at present is 0.8-1.5A/M, which shows that the coercive force of the amorphous nanocrystalline alloy in the application is obviously reduced. Therefore, the amorphous nanocrystalline alloy has more excellent performance and a wider application range, and meets the market demand.
In addition, the amorphous nanocrystalline alloy in the application has the Curie temperature range of 565-. The Curie temperature range of soft magnetic materials and FINMET materials of domestic manufacturers at present is 565-575 ℃, the saturation magnetic induction range is 1.1-1.24T, and the remanence range is 0.3-0.8T, which shows that the amorphous nanocrystalline alloy in the application not only obviously improves the initial permeability and the maximum permeability and obviously reduces the coercive force, but also ensures that the Curie temperature, the saturation magnetic induction and the remanence are equivalent to those of the current soft magnetic materials and FINMET materials, and shows that the amorphous nanocrystalline alloy in the application has more excellent comprehensive performance.
In addition, the magnetic core prepared by adopting the strip material obtained by the elements with the weight percentage content has excellent performance, high magnetic conductivity and initial magnetic conductivity, and the magnetic conductivity range is 20.63k-25.13 k; currently, the permeability of commercially available soft magnetic material cores is typically in the range of 10k-15 k. It can be seen through the contrast that strip in this application through adjusting its each element weight percentage content for the magnetic core's that the preparation obtained magnetic permeability obtains showing and promotes, more is applicable to the transformer that the required precision is higher, accords with market demand.
The applicant also thinks that in the application, by adding a proper amount of Si, an alpha-Fe (Si) phase dispersed and distributed on an amorphous matrix is obtained, and compared with the alpha-Fe as a nanocrystalline phase component, the nanocrystalline phase component alpha- (Fe, Si) has lower magnetic anisotropy, so that the initial permeability of the obtained amorphous nanocrystalline alloy and the permeability of the magnetic core are both obviously improved. By adjusting the content of the Nb element, the crystal grain growth of the amorphous nanocrystalline alloy can be effectively inhibited, so that the amorphous nanocrystalline alloy with the average crystal grain size of 12-15nm is obtained. Because the coercive force of the amorphous nanocrystalline alloy is in direct proportion to the average grain size and the initial permeability is in inverse proportion to the average grain size, the initial permeability of the amorphous nanocrystalline alloy is improved, the coercive force is reduced, and the permeability of the magnetic core is further improved. The content of the Cu element is adjusted to effectively promote the nucleation and precipitation of alpha- (Fe, Si). Meanwhile, in order to ensure that the saturation magnetic induction intensity of the amorphous nanocrystalline alloy is not reduced, the content of B element and Fe element is properly adjusted, so that the amorphous nanocrystalline alloy has high amorphous forming capability and higher saturation magnetic induction intensity; meanwhile, alpha- (Fe, Si) nucleation and precipitation in the iron core are promoted, so that the magnetic conductivity of the prepared magnetic core is remarkably improved.
In summary, in the application, by adjusting the weight percentage of each element in the strip, the elements cooperate with each other, the initial permeability and the maximum permeability of the amorphous nanocrystalline alloy are remarkably improved, and the coercive force of the amorphous nanocrystalline alloy is remarkably reduced. The amorphous nanocrystalline alloy has better performance, the application range is enlarged, and the market demand is met. Meanwhile, the magnetic permeability of the magnetic core is remarkably improved, so that the application range of the magnetic core is wider, and the magnetic core has important significance.
Optionally, the weight percentage of the element Cu in the strip is: 1.2 to 1.4 percent.
By adopting the technical scheme, the content of the Cu element is adjusted, so that the Cu element can effectively promote alpha- (Fe, Si) nucleation and precipitation, the initial permeability of the amorphous nanocrystalline alloy is further improved, the coercive force of the amorphous nanocrystalline alloy is reduced, and the permeability of the magnetic core is improved.
Optionally, the content of Nb in the strip is in weight percent: 5.3 to 5.7 percent.
By adopting the technical scheme, the content of the Nb element is adjusted, so that the Nb element can effectively inhibit the crystal grain growth of the amorphous nanocrystalline alloy, the average crystal grain size of the amorphous nanocrystalline alloy in the application is smaller, the initial permeability of the amorphous nanocrystalline alloy is further improved, the coercive force of the amorphous nanocrystalline alloy is further reduced, and the permeability and the initial permeability of the magnetic core are further improved.
Optionally, the weight percentage of the element Si in the strip is: 7.8% -8.1%, wherein the weight percentage of the element B in the strip material is as follows: 1.6 to 1.8 percent.
By adopting the technical scheme, the content of the Si element and the B element is adjusted, the saturation magnetic induction intensity of the amorphous nanocrystalline alloy in the application is not reduced, the amorphous forming capability of the amorphous nanocrystalline alloy is improved, the preparation of the amorphous nanocrystalline alloy and the magnetic core is facilitated, and the performances of the amorphous nanocrystalline alloy and the magnetic core are improved.
In a second aspect, the present application provides an amorphous nanocrystalline alloy with high initial permeability, which adopts the following technical scheme: an amorphous nanocrystalline alloy with high initial permeability is prepared by the following operations:
preparing amorphous nanocrystalline alloy: annealing the strip, naturally cooling to 22 +/-3 ℃, and taking out to obtain amorphous nanocrystalline alloy;
the annealing treatment process comprises the following steps: the first stage, heating to 400-; the second stage, heating to 460-480 deg.C, and maintaining the temperature for 90-120 min; and the third stage, heating to 560-570 ℃, preserving the heat for 90-100min, and reducing the temperature to 240-300 ℃ within 20-60min to obtain the amorphous nanocrystalline alloy.
By adopting the technical scheme, the amorphous nanocrystalline alloy is simple and stable to prepare and can be produced in large batch, and the prepared amorphous nanocrystalline alloy has the advantages of high initial permeability and maximum permeability, low coercive force, excellent performance and wide application range.
Optionally, the strip has a thickness of 25-35 μm and a width of 5-8 mm.
By adopting the technical scheme, the initial permeability of the amorphous nano gold alloy obtained after the strip is subjected to heat treatment is higher.
Optionally, the average grain size of the amorphous nanocrystalline alloy is 12-15 nm.
By adopting the technical scheme, the amorphous nanocrystalline alloy has high initial permeability and low coercive force, and when the average grain size of the amorphous nanocrystalline alloy is larger than 15nm, the initial permeability is reduced and the coercive force is increased.
In a third aspect, the present application provides a magnetic core, which adopts the following technical scheme:
a magnetic core prepared by the operations of:
step S1: rolling the strip into an iron core;
step S2: annealing the iron core, specifically: the first stage, heating to 400-; the second stage, heating to 460-480 deg.C, and maintaining the temperature for 90-120 min; the third stage, heating to 560-570 ℃, preserving heat for 90-100min, and reducing the temperature to 240-300 ℃ within 20-60 min;
step S3: and (S2) cooling the iron core to 22 +/-3 ℃, putting the iron core into glue solution containing epoxy resin glue and a curing agent, and drying, curing, shaping and cutting to obtain the high-permeability open-ended transformer magnetic core.
Through adopting above-mentioned technical scheme for the preparation of magnetic core is simple, stable, and the magnetic conductivity of the magnetic core that the preparation obtained compares and obtains showing the improvement in magnetic core sold in the market, makes the magnetic core in this application more be applicable to the mutual-inductor that the required precision is higher, accords with market demand.
In a fourth aspect, the present application provides an open-ended transformer, which adopts the following technical scheme:
an iron core of the open-ended transformer adopts the magnetic core.
Through adopting above-mentioned technical scheme for compare in commercially available mutual-inductor, the precision of opening mutual-inductor in this application obtains further improvement, and the range of application is wider.
In summary, the present application has at least the following beneficial effects:
1. according to the strip, the weight percentage of each element in the strip is adjusted, so that the initial permeability and the maximum permeability of the amorphous nanocrystalline alloy prepared by annealing the strip are remarkably improved, the coercive force is remarkably reduced, the comprehensive performance of the amorphous nanocrystalline alloy is excellent, the application range of the amorphous nanocrystalline alloy is expanded, and the market demand is met;
2. by adopting reasonable crystallization annealing treatment, the inside of the amorphous strip is crystallized to a certain degree, so that the initial magnetic conductivity of the amorphous nanocrystalline is improved, the coercive force of the amorphous nanocrystalline is reduced, and meanwhile, the internal stress introduced in the preparation process of the amorphous nanocrystalline alloy is reduced, so that the coercive force of the amorphous nanocrystalline alloy is further reduced;
3. the magnetic core is prepared from the strip, so that compared with a commercially available magnetic core, the magnetic core has high magnetic conductivity and high initial magnetic conductivity, is more suitable for a mutual inductor with high precision requirement, and meets the market requirement.
Drawings
FIG. 1 shows the static hysteresis loop and the basic magnetization curve of examples I-14 in the present application;
FIG. 2 is a static hysteresis loop and a basic magnetization curve of the FINFET material of comparative example I-1.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples.
Raw materials
The epoxy glue is EP008 type and is CEMEDINE brand hardened for sensitivity.
Preparation example
Table 1 preparation examples 1-4 the weight percentage of each element in the strip (%)
| Element(s) | Preparation example 1 | Preparation example 2 | Preparation example 3 | Preparation example 4 |
| Si | 7 | 10 | 8 | 9 |
| B | 2.5 | 1.5 | 1.8 | 2.1 |
| Nb | 5.3 | 5 | 5.6 | 6 |
| Cu | 1.7 | 1 | 1.5 | 1.8 |
| Fe | 83.45 | 82.45 | 83.06 | 81.06 |
| Inevitable impurities | 0.05 | 0.05 | 0.04 | 0.04 |
Preparation example 1
A strip material having the elements in the weight percentages given in Table 1.
A method of making a strip comprising the steps of:
step Sa: uniformly mixing pure Fe (with the purity of 99.95%), pure Cu (with the purity of 99.99%), simple substance Si (with the purity of 99.6%), Fe-B alloy (with the mass fraction of 20%) and Fe-Nb alloy (with the mass fraction of Nb of 60%) according to a ratio, adding the mixture into a crucible of a vacuum induction smelting furnace, vacuumizing to below 1Pa, heating until the raw materials are completely melted, breaking vacuum, removing slag, repeating the processes of vacuumizing, breaking vacuum and removing slag for 5 times, and cooling to 23 ℃ to obtain an initial master alloy ingot;
and Sb: remelting the initial master alloy ingot in a vacuum induction melting furnace by 106The condensation rate was adjusted to 25 μm in thickness and 5mm in width by spray casting at a rate of condensation of DEG C/s.
Preparation examples 2 to 4
A tape was distinguished from preparation example 1 in that the contents of the respective elements in percentage by weight were different and are shown in Table 1, and the rest was the same as preparation example 1.
Table 2 weight percentage of each element (%)
| Raw materials | Preparation example 5 | Preparation example 6 | Preparation example 7 | Preparation example 8 | Preparation example 9 | Preparation example 10 |
| Si | 8 | 8 | 8 | 8 | 8 | 8 |
| B | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 |
| Nb | 5.6 | 5.6 | 5.6 | 5.3 | 5.5 | 5.7 |
| Cu | 1.2 | 1.3 | 1.4 | 1.3 | 1.3 | 1.3 |
| Fe | 83.36 | 83.24 | 83.14 | 83.56 | 83.34 | 83.14 |
| Inevitable impurities | 0.04 | 0.06 | 0.06 | 0.04 | 0.06 | 0.06 |
Preparation examples 5 to 7
A strip which differs from the strip of preparation 3 in the weight percentages of the elements Cu, Fe, which are indicated in table 2.
Preparation examples 8 to 10
A strip which differs from the strip of preparation 6 in the weight percentages of Nb and Fe elements, which are indicated in table 2.
Table 3 weight percentage of each element (%) -based on amorphous nanocrystalline alloy in preparation examples 11 to 14
| Raw materials | Preparation example 11 | Preparation example 12 | Preparation example 13 | Preparation example 14 |
| Si | 7.8 | 8.1 | 8.1 | 8.1 |
| B | 1.8 | 1.8 | 1.6 | 1.7 |
| Nb | 5.6 | 5.6 | 5.6 | 5.6 |
| Cu | 1.3 | 1.3 | 1.3 | 1.3 |
| Fe | 83.44 | 83.14 | 83.35 | 83.25 |
| Inevitable impurities | 0.06 | 0.06 | 0.05 | 0.05 |
Preparation examples 11 to 12
A strip differing from the strip of preparation 6 in the weight percentages of the elements Si, Fe, as shown in Table 3.
Preparation examples 13 to 14
A strip which differs from the strip of preparation 12 in the weight percentages of elements B, Fe, which are indicated in table 3.
Examples of amorphous nanocrystalline alloys
Example I-1
The amorphous nanocrystalline alloy with high initial permeability is prepared by the following method:
the strip is added into a vacuum annealing furnace for crystallization annealing treatment, and the strip is prepared by the preparation example 1;
the annealing treatment process comprises the following steps: in the first stage, heating to 400 ℃, and keeping the temperature for 30 min; in the second stage, heating to 460 ℃, and preserving heat for 120 min; and in the third stage, heating to 560 ℃, preserving the heat for 100min, and reducing the temperature to 240 ℃ within 60min to obtain the amorphous nanocrystalline alloy.
Example I-2
The amorphous nanocrystalline alloy with high initial permeability is prepared by the following method:
adding the strip into a vacuum annealing furnace for crystallization annealing treatment, wherein the strip is prepared by the preparation example 2;
the annealing treatment process comprises the following steps: in the first stage, heating to 407 ℃, and keeping the temperature for 15 min; in the second stage, heating to 465 ℃ and preserving heat for 100 min; and in the third stage, heating to 562 ℃, preserving the heat for 92min, and reducing the temperature to 260 ℃ within 30min to obtain the amorphous nanocrystalline alloy.
Example I-3
The amorphous nanocrystalline alloy with high initial permeability is prepared by the following method:
adding the strip into a vacuum annealing furnace for crystallization annealing treatment, wherein the strip is prepared by the preparation example 3;
the annealing treatment process comprises the following steps: the crystallization annealing treatment process comprises the following steps: the first stage, heating to 415 ℃, and keeping the temperature for 20 min; in the second stage, heating to 470 ℃, and keeping the temperature for 115 min; and in the third stage, heating to 567 ℃, keeping the temperature for 96min, and reducing the temperature to 280 ℃ within 40min to obtain the amorphous nanocrystalline alloy.
Example I-4
The amorphous nanocrystalline alloy with high initial permeability is prepared by the following method:
adding the strip into a vacuum annealing furnace for crystallization annealing treatment, wherein the strip is prepared by the preparation example 4;
the annealing treatment process comprises the following steps: the crystallization annealing treatment process comprises the following steps: the first stage, heating to 420 ℃, and keeping the temperature for 10 min; in the second stage, heating to 480 ℃, and preserving heat for 90 min; and in the third stage, heating to 570 ℃, preserving the heat for 90min, and reducing the temperature to 300 ℃ within 20min to obtain the amorphous nanocrystalline alloy.
Examples I-5 to I-14
The high initial permeability amorphous nanocrystalline alloys of examples I-5 to I-14 differ from example I-3 in that the ribbons were prepared from preparation examples 5 to 14, respectively, and the rest was the same as example I-3.
Comparative example of amorphous nanocrystalline alloy
Comparative example I-1
Selecting a commercially available FINMET material, wherein the weight percentage of each element is as follows: fe: 73.53%, Cu: 1%, Nb: 1%, Si: 13.5%, B: 9% and the balance unavoidable impurities.
Comparative example I-2
The high initial permeability amorphous nanocrystalline alloy differs from example I-14 in that the ribbon has 7 weight percent Nb, 81.85 weight percent Fe, and the remainder is the same as example I-14.
Comparative example I-3
The high initial permeability amorphous nanocrystalline alloy differs from example I-14 in that the ribbon has 4 weight percent Nb, 84.85 weight percent Fe, and the remainder is the same as example I-14.
Comparative example I-4
The amorphous nanocrystalline alloy with high initial permeability differs from example I-14 in that the strip has 11.5 wt% of elemental Si and 79.85 wt% of elemental Fe, the remainder being the same as in example I-14.
Comparative examples I to 5
The high initial permeability amorphous nanocrystalline alloy differs from example I-14 in that the strip has an elemental Si content of 6 wt% and an Fe content of 85.35 wt%, the remainder being the same as in example I-14.
Comparative examples I to 6
The high initial permeability amorphous nanocrystalline alloy differs from example I-14 in that the strip has 4 weight percent elemental B, 80.95 weight percent Fe, and the remainder is the same as example I-14.
Comparative examples I to 7
The high initial permeability amorphous nanocrystalline alloy differs from example I-14 in that the strip has an element B content of 1% by weight and an Fe content of 83.95% by weight, all other things being equal to example I-14.
Performance test of amorphous nanocrystalline alloy
The amorphous nanocrystalline alloys in examples I-1 to I-14 and comparative examples I-1 to I-7 in the application are subjected to static hysteresis loop and basic magnetization curve by a soft magnetic direct current tester, and the following performance detection results are obtained through the static hysteresis loop and the basic magnetization curve; the curie temperatures of the amorphous nanocrystalline alloys in examples I-1 to I-14 and comparative examples I-1 to I-7 were measured using VSM (vibrating sample magnetometer); meanwhile, the grain size of the amorphous nanocrystalline alloy was measured by a transmission electron microscope, and the measurement results are shown in table 4.
TABLE 4 Performance test results for amorphous nanocrystalline alloys
As can be seen from Table 4, the high initial permeability amorphous nanocrystalline alloy of the present application has high initial permeability, with an initial permeability range of 194.3k-226.4 k; has higher Curie temperature, wherein the Curie temperature range is 565-; the magnetic induction saturation flux density is higher and ranges from 1.019T to 1.122T; has lower remanence, and the remanence range is 0.6112-0.7467T; the coercivity is low, and the coercivity range is 0.4699-0.6195A/M; has high maximum magnetic permeability, and the maximum magnetic permeability is in the range of 795.6k-886.5 k. Compared with the existing iron-based amorphous nanocrystalline alloy, the initial magnetic permeability of the alloy is remarkably improved, the coercive force is remarkably reduced, the performance is excellent, the market demand is met, and the development of the amorphous nanocrystalline alloy in China is promoted.
As can be seen from example I-3 and examples I-5 to I-7 in Table 4, when the contents of Cu and Fe in the amorphous nanocrystalline alloy were changed, the saturation induction density of the amorphous nanocrystalline alloy increased as the content of Cu was decreased and the corresponding content of Fe was increased, but the initial permeability thereof appeared to be decreased or increased. When the Cu content is 1.3%, the initial permeability is highest. This is because the micro-scale segregation of the Cu element in the amorphous nanocrystalline alloy can promote the precipitation of α -Fe (si) nucleation, however, as the Cu content increases, the Fe content decreases, thereby decreasing the saturation magnetic induction of the amorphous nanocrystalline alloy. Therefore, the addition of a proper amount of Cu can promote the precipitation of alpha-Fe (Si) nucleation, thereby being beneficial to the formation of amorphous nanocrystalline, improving the initial magnetic permeability and simultaneously ensuring that the saturation magnetic induction intensity is not reduced. However, the excessive addition of Cu can cause the nucleation and precipitation of alpha-Fe (Si) to be too fast, so that the magnetic induction intensity of the amorphous nanocrystalline alloy is reduced, the initial magnetic permeability of the amorphous nanocrystalline alloy is reduced, and the coercive force is improved.
It can be seen from the examples I-6 and I-8 to I-10 in Table 4 that the initial permeability of the amorphous nano-alloy is maximized when the Nb content is 5.6% by weight, and the initial permeability of the amorphous nano-alloy is decreased, the coercive force is increased, and the saturation magnetic induction is increased when the Nb content in the amorphous nano-alloy is decreased; and when the content of Nb is increased, the saturation magnetic induction intensity is reduced, the initial magnetic conductivity is slightly reduced, and the coercive force is equivalent. The solubility of Nb in the alpha-Fe phase in the amorphous nanocrystalline alloy is extremely low and the diffusion is slow, so that the addition of a proper amount of Nb can inhibit the growth of crystal grains of the amorphous nanocrystalline alloy, and the amorphous nanocrystalline alloy with smaller crystal grain size can be easily obtained. In combination with comparative example I-2 and comparative example I-3, when Nb is added too much, the Fe content is decreased, so that the saturation magnetic induction of the amorphous nanocrystalline alloy is decreased, and at the same time, the initial permeability of the amorphous nanocrystalline alloy is decreased. When the Nb is added too little, the amorphous nanocrystalline alloy with the average grain size of less than 20nm is difficult to obtain, so that the obtained amorphous nanocrystalline alloy has low initial permeability and maximum permeability and high coercive force.
As can be seen from example I-6 and examples I-11 to I-12 in Table 4, when the Si content in the amorphous nanocrystalline alloy is decreased, the initial permeability of the amorphous nanocrystalline alloy is decreased and the coercive force is increased. Because the nanocrystalline phase component in the amorphous nanocrystalline alloy is alpha-Fe (Si), compared with the alpha-Fe phase, the alpha- (Fe, Si) has lower magnetic anisotropy, so the addition of a proper amount of Si leads the initial magnetic permeability of the amorphous nanocrystalline alloy to be increased, and the coercive force to be reduced. And by combining the comparative example I-4 and the comparative example I-5, the saturation magnetic induction intensity of the amorphous nanocrystalline alloy is reduced along with the excessive addition of Si, the amorphous forming capability of the amorphous nanocrystalline alloy is reduced, and when the addition of Si is too small, the initial magnetic conductivity of the amorphous nanocrystalline alloy is reduced, the coercive force is increased, and the performance of the amorphous nanocrystalline alloy is reduced.
As can be seen from examples I-12 and I-13 to I-14 in Table 4, when the content of B in the amorphous nano-gold alloy is decreased, the Fe content thereof is increased, so that the saturation induction of the amorphous nano-crystalline alloy is increased. When the content of B added is excessively low, the amorphous forming ability of the alloy is reduced, and the initial permeability of the amorphous nanocrystalline alloy is lowered. Therefore, the addition of a proper amount of B can improve the amorphous forming capability of the amorphous nanocrystalline alloy, and the initial magnetic permeability and the coercive force of the amorphous nanocrystalline alloy are improved and reduced. And then, the excessive B is added by combining the comparative example I-6 and the comparative example I-7, so that the saturation magnetic induction intensity of the obtained amorphous nanocrystalline alloy is reduced, the initial magnetic conductivity and the maximum magnetic conductivity are reduced, and the coercive force is increased.
Comparing comparative example I-1 and example I-14 with the combination of FIG. 1, FIG. 2 and Table 4, the initial permeability of the amorphous nanocrystalline alloy obtained in comparative example I-1 is only 94.22k, and the coercive force is 1.096A/M; the initial permeability of the amorphous nanocrystalline alloy in example I-14 of the present application was 226.4k, the coercivity was 0.4699a/M, and the initial permeability of the amorphous nanocrystalline alloy in the present application (example I-14) was significantly higher than that of the amorphous nanocrystalline alloy in comparative example I-1. The weight percentage of each element of the amorphous nanocrystalline alloy in the comparative example I-1 is the element proportion of the iron-based amorphous nanocrystalline alloy which is commonly used at home and abroad at present. Through a large amount of experimental researches of the applicant, the content of each element in the amorphous nanocrystalline alloy is adjusted, so that the initial permeability and the maximum permeability of the amorphous nanocrystalline alloy are remarkably improved, the coercive force is remarkably reduced, meanwhile, the Curie temperature of the amorphous nanocrystalline alloy is kept at 576 ℃, and the saturation magnetic induction intensity of the amorphous nanocrystalline alloy is equivalent to that of the amorphous nanocrystalline alloy obtained in the comparative example I-1, so that the amorphous nanocrystalline alloy in the application is more suitable for transformers with higher precision requirements, the application range of the amorphous nanocrystalline alloy is enlarged, and the market requirements are met.
Embodiments of the magnetic core
Example II-1
A magnetic core prepared by the method of:
step S1: coiling a strip material into an iron core, wherein the strip material is prepared from preparation example 1;
step S2: annealing the iron core;
the annealing treatment process comprises the following steps: in the first stage, heating to 400 ℃, and keeping the temperature for 30 min; in the second stage, heating to 460 ℃, and preserving heat for 120 min; the third stage, heating to 560 ℃, preserving heat for 100min, and reducing the temperature to 240 ℃ within 60 min;
step S3: and (5) after the iron core is cooled to 23 ℃ in the step S2, putting the iron core into glue solution containing epoxy resin glue and curing agent vinyl triamine in a mass ratio of 1:1.2 for 25min, ensuring that the glue solution fully permeates into the middle of the strip material and the strip material, putting the iron core into an oven, drying, curing and shaping, and putting the shaped iron core into a cutter for cutting treatment to obtain the high-permeability open-ended transformer magnetic core.
Example II-2
A magnetic core prepared by the method of:
step S1: coiling a strip material into an iron core, wherein the strip material is prepared from preparation example 2;
step S2: annealing the iron core;
the annealing treatment process comprises the following steps: in the first stage, heating to 407 ℃, and keeping the temperature for 15 min; in the second stage, heating to 465 ℃ and preserving heat for 100 min; in the third stage, heating to 562 ℃, preserving heat for 92min, and reducing the temperature to 260 ℃ within 30 min; step S3: and (5) after the iron core is cooled to 22 ℃ in the step S2, putting the iron core into glue solution containing epoxy resin glue and curing agent vinyl triamine in a mass ratio of 1:1.2 for 25min, ensuring that the glue solution fully permeates into the middle of the strip material and the strip material, putting the iron core into an oven, drying, curing and shaping, and putting the shaped iron core into a cutter for cutting treatment to obtain the high-permeability open-ended transformer magnetic core.
Example II to 3
A magnetic core prepared by the method of:
step S1: coiling a strip material into an iron core, wherein the strip material is prepared from preparation example 3;
step S2: annealing the iron core;
the annealing treatment process comprises the following steps: the first stage, heating to 415 ℃, and keeping the temperature for 20 min; in the second stage, heating to 470 ℃, and keeping the temperature for 115 min; in the third stage, heating to 567 ℃, keeping the temperature for 96min, and reducing the temperature to 280 ℃ within 40 min;
step S3: and (5) after the iron core is cooled to 25 ℃ in the step S2, putting the iron core into glue solution containing epoxy resin glue and curing agent vinyl triamine in a mass ratio of 1:1.2 for 25min, ensuring that the glue solution fully permeates into the middle of the strip material and the strip material, putting the iron core into an oven, drying, curing and shaping, and putting the shaped iron core into a cutter for cutting treatment to obtain the high-permeability open-ended transformer magnetic core.
Examples II to 4
A magnetic core prepared by the method of:
step S1: coiling a strip material into an iron core, wherein the strip material is prepared from preparation example 4;
step S2: annealing the iron core;
the annealing treatment process comprises the following steps: the first stage, heating to 420 ℃, and keeping the temperature for 10 min; in the second stage, heating to 480 ℃, and preserving heat for 90 min; the third stage, heating to 570 ℃, preserving heat for 90min, and reducing the temperature to 300 ℃ within 20 min; step S3: and (5) after the iron core is cooled to 22 ℃ in the step S2, putting the iron core into glue solution containing epoxy resin glue and curing agent vinyl triamine in a mass ratio of 1:1.2 for 25min, ensuring that the glue solution fully permeates into the middle of the strip material and the strip material, putting the iron core into an oven, drying, curing and shaping, and putting the shaped iron core into a cutter for cutting treatment to obtain the high-permeability open-ended transformer magnetic core.
Examples II to 5
Magnetic core, which differs from example II-3 in that the tape was prepared from preparation example 6.
Examples II to 6
Magnetic core, which differs from example II-3 in that the tape was prepared from preparation example 8.
Examples II to 7
Magnetic core, which differs from example II-3 in that the tape was prepared from preparation example 12.
Examples II to 8
Magnetic core, which differs from example II-3 in that the tape was prepared from preparation 14.
Comparative example of magnetic core
Comparative example II-1
Magnetic core, which differs from example II-8 in that the strip has an element Nb content of 7% by weight and an Fe content of 81.85% by weight, the rest being identical to example II-8.
Comparative example II-2
Magnetic core, which differs from example II-8 in that the tape has an element Nb content of 4% by weight and an Fe content of 84.85% by weight, the remainder being identical to example II-8.
Comparative example II-3
A magnetic core, which differs from example II-8 in that the tape had an elemental Si content of 11.5% by weight and an Fe content of 79.85% by weight, the remainder being the same as in example II-8.
Comparative examples II to 4
Magnetic core, which differs from example II-8 in that the tape had an elemental Si content of 6% by weight and an Fe content of 85.35% by weight, the remainder being the same as in example II-8.
Comparative examples II to 5
Magnetic core, which differs from example II-8 in that the tape had an element B content of 4% by weight and an Fe content of 80.95% by weight, the rest being identical to example II-8.
Comparative examples II to 6
Magnetic core, which differs from example II-8 in that the tape had an element B content of 1% by weight and an Fe content of 83.95% by weight, the rest being the same as in example II-8.
Comparative example II-1
A commercially available amorphous nanocrystalline alloy magnetic core is adopted, and the weight percentage of each element is as follows: fe: 73.53%, Cu: 1%, Nb: 1%, Si: 13.5%, B: 9% and the balance unavoidable impurities.
Performance test of magnetic core
The magnetic cores prepared in examples II-1 to II-8 and comparative examples II-1 to II-6 and the magnetic permeability of the magnetic core of comparative example II-1 were measured using a model number ZX-2736 voltammetry chart; at the same time, soft magnetic direct current testers were used to test the initial permeability of the magnetic cores prepared in examples II-1 to II-8 and comparative examples II-1 to II-6, and the test results are shown in Table 5.
TABLE 5 results of testing the properties of magnetic cores
As can be seen from table 5, the magnetic core of the present application has a high magnetic permeability and has a high initial magnetic permeability. The magnetic core has a magnetic permeability in the range of 20.63k to 25.13k and an initial magnetic permeability in the range of 194.6k to 226.1 k. At present, the magnetic permeability range of the domestic commercially available soft magnetic material magnetic core is 10k-15k, and compared with the existing magnetic core, in the application, the magnetic permeability of the prepared magnetic core is remarkably improved by adjusting the weight percentage content of each element in the strip material, the application range of the magnetic core is improved, and the market demand is met.
As can be seen from examples II-8, comparative examples 11-1, and comparative examples II-2 in Table 5, the magnetic permeability of the core is significantly reduced when the weight percent of the element Nb in the ribbon is outside of 5.0% to 6.0%. When the weight percentage of the element Nb is 5.6%, the magnetic core prepared has the highest magnetic conductivity and more excellent performance.
As can be seen from examples II-8, comparative examples 11-3, and comparative examples II-4 in Table 5, the magnetic permeability of the core is significantly reduced when the weight percentage of elemental Si in the ribbon is outside of 7% to 10%; and as can be seen from examples II-8, comparative examples 11-5, and comparative examples II-6 in table 5, the magnetic permeability of the core is significantly reduced when the weight percentage of element B in the ribbon is outside of 1.5% to 2.5%. The addition of the element Si and the element B in a proper amount is beneficial to improving the amorphous forming capability of the amorphous nanocrystalline, thereby being beneficial to improving the magnetic permeability of the magnetic core.
As can be seen from the example II-8 and the comparative example II-1 in table 5, the magnetic core in the example II-8 of the present application has a magnetic permeability of 25.13k, and compared with the commercially available amorphous nanocrystalline magnetic core, the magnetic core in the present application is prepared by using the strip material having a high initial magnetic permeability after the heat treatment, so that the magnetic core in the present application has a significantly improved magnetic permeability, and is suitable for an inductor having a higher precision requirement, and meets the market demand.
Application example
Application example 1
An open-ended transformer comprises a primary winding, a secondary winding, an iron core, a framework, a shell and a connecting terminal which are insulated from each other, wherein the iron core is prepared from the magnetic core prepared in embodiment II-4. The internal structure and the processing and mounting process of the open-ended transformer are mature technologies, and are not described in detail herein.
Application example 2
An open-ended transformer, which is different from application example 1 in that the magnetic core prepared in examples II to 8 was used as the iron core, and the rest was the same as application example 1.
Comparative application
An open-ended transformer which is different from application example 2 in that a magnetic core obtained in comparative example II-1 was used as an iron core, and the rest was the same as application example 2.
Performance testing of open transformers
The current transformer calibration device in shenyang zhongchuan was used in application examples 1 and 2, and the specific difference and the angular difference were measured under the conditions of 1% current point, 5% current point, 20% current point, 100% current point, 120% current point, Imax, and 1.2Imax, and the measurement results are shown in table 6.
TABLE 6 detection results of open-ended transformers
As can be seen from table 6, with the open-ended transformers in the present application, the angular difference and the specific difference at 5% current point, 20% current point, 100% current point, and 120% current point are significantly lower than the specific difference and the angular difference of the 0.1-class (highest precision) current transformer in the GB20840 edition of national standard. In application example 1, the specific difference of the open-ended transformer at a 5% current point is 0.064%, and the angular difference is 8.4'; in application example 2, the specific difference of the open-end transformer at a 5% current point is 0.012%, and the angular difference is 3.9'; the open-ended transformer of the comparative example was used with a specific difference of 0.455% at 5% current point and an angular difference of 15.5'. In addition, in application example 1, the specific difference of the open-ended transformer at a 120% current point is 0.019%, and the angular difference is 6.0'; in application example 2, the specific difference of the open-ended transformer at a 120% current point is 0.002%, and the angular difference is 2.8'; the open-ended transformer of the comparative example was used with a specific difference of 0.104% at 120% current point and an angular difference of 5.7'. By comparison, the opening transformer in application example 2 has the smallest angular difference and the smallest specific difference, the highest precision and the better performance.
In addition, the magnetic core prepared in example II-4 in application example 1 had a magnetic permeability of 20.63 k; the magnetic cores prepared in examples II to 8 in application example 2 had a permeability of 25.13 k; application comparative example a magnetic core obtained in comparative example II-1 (commercially available) and having a magnetic permeability of 14.10k was used, and it can be seen from comparison that as the magnetic permeability of the magnetic core increased, the angular difference and the specific difference of the open-ended transformer decreased, thereby making the accuracy thereof higher. Therefore, the magnetic core prepared by the strip material in the application has high magnetic permeability, and the angular difference and the specific difference of the open-end transformer prepared by the magnetic core in the application are obviously lower than those of the open-end transformer prepared by the commercially available magnetic core under the same conditions, and are obviously lower than those of a 0.1-grade (highest precision) current transformer in the GB20840 edition national standard. Therefore, the precision of the open-end transformer in the application is remarkably improved, and the market demand is met.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (9)
1. A strip material, characterized in that the strip material consists of the following elements in weight percent: si: 7% -10%, B: 1.5% -2.5%, Nb: 5.0% -6.0%, Cu: 1.0-1.5%, unavoidable impurities <0.1%, and the balance of Fe.
2. A strip according to claim 1, wherein the strip comprises the following elements in weight percent: 1.2 to 1.4 percent.
3. A strip according to claim 1, wherein the Nb content in the strip is, in weight percent: 5.3 to 5.7 percent.
4. A strip according to claim 1, wherein the strip comprises the following elements in percentage by weight: 7.8% -8.1%, wherein the weight percentage of the element B in the strip material is as follows: 1.6 to 1.8 percent.
5. An amorphous nanocrystalline alloy with high initial permeability is characterized by being prepared by the following operations:
preparing amorphous nanocrystalline alloy: annealing the strip of any one of claims 1 to 4, naturally cooling to 22 ± 3 ℃, and taking out to obtain an amorphous nanocrystalline alloy;
the annealing treatment process comprises the following steps: the first stage, heating to 400-; the second stage, heating to 460-480 ℃, and preserving heat for 90-120 min; and the third stage, heating to 560 ℃ and 570 ℃, preserving the heat for 90-100min, and reducing the temperature to 240 ℃ and 300 ℃ within 20-60min to obtain the amorphous nanocrystalline alloy.
6. The amorphous nanocrystalline alloy of claim 5, wherein the strip has a thickness of 25-35 μm and a width of 5-8 mm.
7. The amorphous nanocrystalline alloy of claim 5, wherein the average grain size of the amorphous nanocrystalline alloy is 12-15 nm.
8. A magnetic core, prepared by:
step S1: rolling the strip of any of claims 1 to 4 into a core;
step S2: annealing the iron core, specifically: the first stage, heating to 400-; the second stage, heating to 460-480 ℃, and preserving heat for 90-120 min; the third stage, heating to 560 ℃ and 570 ℃, preserving the heat for 90-100min, and reducing the temperature to 240 ℃ and 300 ℃ within 20-60 min;
step S2: and (S2) cooling the iron core to 22 +/-3 ℃, putting the iron core into glue solution containing epoxy resin glue and a curing agent, and drying, curing, shaping and cutting to obtain the high-permeability open-ended transformer magnetic core.
9. An open transformer, characterized in that the iron core of the open transformer is the magnetic core of claim 8.
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