CN1110324A - Method for making iron-base ultramicro-crystal alloy - Google Patents
Method for making iron-base ultramicro-crystal alloy Download PDFInfo
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- CN1110324A CN1110324A CN 94119420 CN94119420A CN1110324A CN 1110324 A CN1110324 A CN 1110324A CN 94119420 CN94119420 CN 94119420 CN 94119420 A CN94119420 A CN 94119420A CN 1110324 A CN1110324 A CN 1110324A
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Abstract
The present invention belongs to a method for making ferrous alloy, mainly applicable to manufacture of iron-base ultramicro-crystal alloy. Said manufacture method is as follows: the ferrous alloy is prepared into an amorphous quenched band material, and then said band material or various iron cores made of said band material are placed in a heat treatment furnace to implement microcrystallization treatment. Said microcrystallization treatment is implemented in atomosphere or in a certain oxidizing atmosphere. For homopolar transformer and inductor iron core, when making microcrystallization treatment, a transverse magnetic field must be applied along the bandwidth direction of ring-shaped sample. Said invention makes the microcrystallization treatment without protective atmosphere, and can obtain the good magnetic property, so that it is simple in installation, and can save energy soure and reduce cost.
Description
The invention belongs to the manufacture method of ferrous alloy.Mainly be applicable to the manufacturing of iron-base ultramicro-crystal alloy, be particularly useful for making iron-base ultramicro-crystal alloy components and parts iron core.
Iron-base ultramicro-crystal alloy is since 1988 come out, because it has the excellent comprehensive performance, extremely payes attention to.Ferrite, silicon steel, permalloy and the amorphous alloy of alternative former usefulness have been widely used at present in components and parts such as range transformer, reactance coil, inducer, inverter arc welding machine or the equipment with the iron core of ultramicro-crystal alloy made.
In the prior art, the manufacture method of iron-base ultramicro-crystal alloy is on the basis of non-crystaline amorphous metal, forms through the ultra micro crystallization and thermal treatment.Its concrete manufacture method is as follows: at first ferrous alloy is made the Fe-based amorphous attitude alloy strip steel rolled stock of quenching, the attitude alloy strip steel rolled stock of perhaps further this amorphous being quenched is scratched or lamination is made various iron cores through uncoiling, shearing, volume, then, with quench attitude alloy strip steel rolled stock or handle through micritization of amorphous, make iron-base ultramicro-crystal alloy band or iron core at last by the made various iron cores of this band.Find out that thus in the manufacture method of iron-base ultramicro-crystal alloy, most critical technology is the miniaturization treatment process.
Non-crystaline amorphous metal ultra micro crystallization is handled and is subjected to following several characteristic Temperature Influence:
(1) crystallization temperature T
x(℃);
(2) compound phase (crystallization phases) is separated out temperature T
x' (℃);
The Curie temperature T of the ultra micro crystalline phase of (3) separating out
c(℃).
Usually the ultra micro crystallization is handled at T
x-T
x' carry out in the temperature range, because be lower than T
xTemperature can not form ultracrystallite, is higher than T
x' during temperature, will separate out the compound phase, make the magnetic severe exacerbation.For this reason, general ultra micro crystallization treatment temp should be higher than crystallization temperature more than 30～80 ℃.
In the clear 64-79342 of Japanese Patent, clear 64-31922, flat 1-247556, flat 1-247557, flat 4-21746, flat 3-146615 etc., except having announced some iron-base ultramicro-crystal alloys, various iron-base ultramicro-crystal treatment processs are also provided.In the iron-base ultramicro-crystal treatment process of above-mentioned patent, its common characteristic is that these ultra micro crystallization processing are all carried out under protective atmosphere, as carrying out in hydrogen, nitrogen, helium, argon gas or in a vacuum.Therefore, every cover thermal treatment unit also must have airing system and source of the gas, perhaps the addition of vacuum system.So whole thermal treatment unit complex structure, investment is big; In addition, in heat treatment process, also want the restriction of protected atmosphere, be difficult to guarantee quality product.
The object of the present invention is to provide a kind of manufacture method that does not need under protective atmosphere or vacuum condition, to carry out the iron-base ultramicro-crystal alloy that micritization handles.
At first select suitable ferrous alloy; subsequently it is prepared into the amorphous attitude band of quenching; the various iron cores of its amorphous being quenched the attitude band or being made by this band are under no any protective atmosphere; that is carry out the micritization processing under atmosphere or in the heat treatment furnace under certain oxidizing atmosphere, the temperature T of its processing is:
T
x≤T≤T
x+（20～40）℃
0.5～2 hour treatment time.
Because it is to carry out under atmosphere or certain oxidizing atmosphere that micritization of the present invention is handled, oxygen can promote the formation of crystallization phase, has promptly promoted crystallization process.Simultaneously, form layer oxide film on the strip surface, the thickness of oxide film is with 200～300
Be advisable, and the inner oxygen level of strip is lower, the thickness of oxide film is (1～3) with the ratio of strip thickness: be advisable (99～97).The internal stress and the domain wall anchoring effect that are caused by oxide film are very little to the strip Effect on Performance.Therefore, in the crystallization treating processes of amorphous thin ribbon or sample, guarantee that the oxygen overwhelming majority in strip or the sample concentrates in the upper layer, be in apart from surperficial 300A with interior be one of gordian technique of the present invention.
The present invention is for unipolarity transformer and inductance iron core, in order to obtain low Br value, thereby improves work magnetic strength △ B, so when micritization is handled, must apply transverse magnetic field along annular sample bandwidth direction, the size in magnetic field is 24KA/m～40KA/m.After the processing, the domain structure of iron core alloy band by the farmland, attitude labyrinth of quenching change into tape spool at 45～the parallel strip farmland at 90 ° of angles, when magnetization,, not only reduced iron loss based on the farmland rotation, also make iron core obtain the characteristic of low Br value.
The present invention has carried out following test: with Fe
73.5Cu
1Nb
3Si
13.5B
9The volume iron core that amorphous alloy ribbon is made is a sample, and the micritization treatment process that adopts micritization treatment process of the present invention and prior art to adopt is usually handled above-mentioned sample respectively, and its concrete treatment process sees Table 1.Handle the back and adopt Auger spectrometer measure sample oxygen level from outward appearance to inner essence, and measured the static state and the dynamic magnetic performance of sample, its result is shown in Fig. 1 and table 2.In addition,, measured the degree of crystallization of sample and grain-size respectively with handling variation of temperature also by X-ray diffraction and transmission electron microscope, as shown in table 3.
Fig. 1 is Fe
73.5Cu
1Nb
3Si
13.5B
9Alloy is handled the variation of back oxygen level with the strip degree of depth at different atmosphere, and among the figure, ordinate is oxygen level (at%), and abscissa is sputtering time (min), and its sputter intensity is 300
/ min.Curve A, B represent the sample surfaces oxygen level that adopts method of the present invention and adopt treatment process under the conventional hydrogen shield of prior art with the sputtering time change curve respectively, and curve C is the oxygen level that amorphous is quenched the aspect product.
Found out that by Fig. 1 through the sample that the inventive method is handled, its surface oxygen content is apparently higher than the handled sample of prior art, and oxygen level concentrates on surperficial one deck, zone of oxidation is less than 300
, have 200 approximately
Thick oxide film.Correlation curve B, C find out; even curve B is the gained result under hydrogen shield; surperficial and inner oxygen level all is higher than the curve C of representing the non-prosperous attitude of quenching; this explanation micritization passes to hydrogen shield when handling; not only can not reduce oxygen level in the non-crystalline state sample, oxygen between the sample belt can not be discharged fully, but in thermal treatment; sample is oxidation still, and oxygen contains reason still to be increased.In addition, as seen from Table 3, handle through 540 ℃ of temperature micritizations under the hydrogen shield of existing routine techniques, iron core has good soft magnetic performance, and this moment, the crystallite degree of crystallization of sample was 50～63%; And the present invention handles 500～510 ℃ of temperature crystallization under unprotect atmosphere, and iron core just has good soft magnetic performance, and the sample crystallite degree of crystallization of this moment is also 50～61%.As seen from Table 4, both crystal grain is≤close grain of 20nm.
Find out that by above the micritization that the present invention is carried out is handled under unprotect atmosphere,,, thereby obtain good magnetic performance (referring to table 2) with regard to the micritization degree and the grain-size of may command alloy as long as select the proper heat treatment temperature and time.
Compared with prior art, the most significant advantage of the present invention is exactly can carry out micritization under no any protective atmosphere and lower temperature to handle, and can obtain excellent soft magnetic performance; like this; not only make the micritization Equipment for Heating Processing simple, also saved the energy simultaneously, reduced cost.
Adopting chemical ingredients (at%) is Fe
73.5Cu
1Nb
3Si
13.5B
9The fast quenching amorphous alloy band be raw material, bandwidth 20mm, tape thickness 25 μ m; be wound into the garden annular core of φ 25 * 40 * 20mm; adopt respectively then under the unprotect atmosphere of the present invention with under the Comparative Examples hydrogen shield and carry out the micritization processing, temperature range is 480～580 ℃, soaking time 1 hour.Coercivity H, iron loss P and dynamic magnetic conductance (f=100KHZ B have been measured then respectively
m=0.1T) with handling the variation of temperature situation, its result is as shown in table 4.
As seen from Table 4, the present invention carries out micritization with Comparative Examples at 540 ℃ at 500 ℃, and to handle the magnetic properties of gained close, and optimum treatment temperature promptly of the present invention is 500 ℃, and Comparative Examples then is 540 ℃, than low 40 ℃ of Comparative Examples thermal treatment temp.
The amorphous thin ribbon alloying constituent of the sample that adopts, bandwidth, tape thickness and volume core dimensions and micritization treatment temp are all identical with embodiment 1 with the time.The present invention still handles under atmosphere, and Comparative Examples is still handled under hydrogen shield, and different is that the both adopts helix tube type electric furnace heat treated, and applies the transverse magnetic field of 32KA/m in whole heat treatment process along garden annular core width.Handle the static magnetic of back, with the ac permeability μ of three voltage method measure sample with the ballistic method measure sample
1And core loss value (frequency f=20KHZ, magnetic strength B
m=0.5T), measuring result is listed among Fig. 2 and Fig. 3.Fig. 2 is Fe
73.5Cu
1Nb
3Si
13.5B
9H
cAnd B
rWith the graph of a relation of the micritization treatment temp that adds transverse magnetic field under the different atmosphere, abscissa is the micritization treatment temp among the figure, and ordinate is H
cAnd B
r; Fig. 3 is Fe
73.5Cu
1Nb
3Si
13.5B
9The μ of alloy
1With the graph of a relation of the micritization treatment temp that adds transverse magnetic field under P and the different atmosphere, abscissa is the micritization treatment temp among the figure, and ordinate is P and μ
1Curve 1 is the micritization result of carrying out under atmosphere in Fig. 2 and Fig. 3, and curve 2 is the micritization result under hydrogen shield.
Can be found out by Fig. 2 and Fig. 3: after applying the transverse magnetic field processing, optimum treatmenting temperature of the present invention is 520 ℃, and Comparative Examples is 540 ℃; The remanent magnetism and the coercive force of gained are close; Ac permeability μ
1Also close with core loss value P.4 sets of curves Changing Patterns among the figure are quite consistent to be along 20 ℃ of temperature axis displacements.Though this illustrates that both heat-treating atmospheres are different with temperature, finally can make alloy obtain identical weave construction, has good soft magnetic performance equally.
Adopting chemical ingredients (at%) is Fe
73.5Cu
1Nb
3Si
13.5B
9The amorphous alloy ribbon sample, be wound into φ 50 * 80 * 20mm garden annular core, in tube type resistance furnace, carry out micritization and handle.The present invention's insulation 1 hour under atmosphere and under 490 ℃ of temperature, Comparative Examples under hydrogen shield when 510 ℃ of temperature insulation 1 temperature.After the processing, measure its iron loss P and magnetic permeability μ with three voltage methods
1, survey its crystallization phase composition and crystallization rate with the X-ray diffraction, transmission electron microscope calculates grain-size.Its result lists in the table 5.
Embodiment 4
With chemical ingredients (at) is Fe
73.5Cu
1Nb
3Si
13.5B
9The amorphous ribbon of alloy is a sample, and is wound into the mutual inductor iron core of φ 20 * 30 * 15mm, carries out crystallization then and handle in large-scale bell furnace under atmosphere, and treatment temp is 510 ℃, soaking time half an hour, 5 batches of these transformer iron core samples of co-processing.The magnetic property of measure sample in batches then, its result lists in the table 6.
Claims (3)
1, a kind of manufacture method of iron-base ultramicro-crystal alloy at first is prepared into ferrous alloy the amorphous attitude band of quenching, and the attitude band or carry out micritization by the various iron cores that this band is made in heat treatment furnace and handle then this amorphous quenched is characterized in that:
(1) micritization is handled under atmosphere or under certain oxidizing atmosphere and is carried out;
(2) micritization treatment temp T (℃) be:
T
X≤T≤
X+(20～40)
T in the formula
XFor crystallization temperature (℃);
(3) the micritization treatment time is 0.5～2 hour.
2, method according to claim 1 is characterized in that for unipolarity transformer and inductance iron core, when micritization is handled, must apply transverse magnetic field along annular sample bandwidth direction.
3, method according to claim 2, the intensity that it is characterized in that transverse magnetic field is 24～40KA/m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94119420A CN1036664C (en) | 1994-12-22 | 1994-12-22 | Method for making iron-base ultramicro-crystal alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94119420A CN1036664C (en) | 1994-12-22 | 1994-12-22 | Method for making iron-base ultramicro-crystal alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1110324A true CN1110324A (en) | 1995-10-18 |
| CN1036664C CN1036664C (en) | 1997-12-10 |
Family
ID=5039221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94119420A Expired - Fee Related CN1036664C (en) | 1994-12-22 | 1994-12-22 | Method for making iron-base ultramicro-crystal alloy |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055315C (en) * | 1997-07-08 | 2000-08-09 | 冶金工业部钢铁研究总院 | Heat treatment method for iron-base ultramicaolith iron core |
| CN101445896B (en) * | 2008-12-29 | 2010-09-29 | 安泰科技股份有限公司 | Fast quenching amorphous alloy ribbon and preparation method thereof |
| CN102360664A (en) * | 2011-06-22 | 2012-02-22 | 上海常春新材料科技有限公司 | Magnetically soft block material with low eddy current loss and preparation method thereof |
| CN106158344A (en) * | 2016-08-30 | 2016-11-23 | 贵州鑫湄纳米科技有限公司 | A kind of ZCT magnetic core Annealing Crystallization technique |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5225006A (en) * | 1988-05-17 | 1993-07-06 | Kabushiki Kaisha Toshiba | Fe-based soft magnetic alloy |
-
1994
- 1994-12-22 CN CN94119420A patent/CN1036664C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055315C (en) * | 1997-07-08 | 2000-08-09 | 冶金工业部钢铁研究总院 | Heat treatment method for iron-base ultramicaolith iron core |
| CN101445896B (en) * | 2008-12-29 | 2010-09-29 | 安泰科技股份有限公司 | Fast quenching amorphous alloy ribbon and preparation method thereof |
| CN102360664A (en) * | 2011-06-22 | 2012-02-22 | 上海常春新材料科技有限公司 | Magnetically soft block material with low eddy current loss and preparation method thereof |
| CN106158344A (en) * | 2016-08-30 | 2016-11-23 | 贵州鑫湄纳米科技有限公司 | A kind of ZCT magnetic core Annealing Crystallization technique |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1036664C (en) | 1997-12-10 |
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Free format text: CORRECT: PATENTEE; FROM: GENERAL RESEARCH INST. OF IRON AND STEEL, MINISTRY OF METALLURGICAL INDUSTRY TO: ANTAI SCIENCE AND TECHNOLOGY CO., LTD. |
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