CN1110825C - High saturation magnetic flux density and low remanence magnetism double-ferrromagnetism phase soft-magnetic alloy - Google Patents
High saturation magnetic flux density and low remanence magnetism double-ferrromagnetism phase soft-magnetic alloy Download PDFInfo
- Publication number
- CN1110825C CN1110825C CN 99124006 CN99124006A CN1110825C CN 1110825 C CN1110825 C CN 1110825C CN 99124006 CN99124006 CN 99124006 CN 99124006 A CN99124006 A CN 99124006A CN 1110825 C CN1110825 C CN 1110825C
- Authority
- CN
- China
- Prior art keywords
- alloy
- phase
- flux density
- ferrromagnetism
- magnetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Soft Magnetic Materials (AREA)
Abstract
The present invention relates to a high saturation magnetic flux density and low residual magnetism double-ferrromagnetism phase soft-magnetic alloy. In a Fe-Co-Ni alloy system, chemical components nearby an alpha-gamma phase boundary line are selected, and a proper quantity of alloy element Nb and rare earth is added; a method of twice heat treatment is utilized after a vacuum smelting procedure and a casting shaping procedure are carried out to obtain the double-ferrromagnetism phase soft magnetic alloy which takes the alpha phase as the main crystal phase and contains a proper quantity of gamma phase. The soft magnetic alloy has the characteristics of high saturation magnetic flux density, low residual magnetism and higher initial permeability. The present invention is a novel high-performance soft magnetic alloy suitable for solenoid electromagnetic valve iron cores having high performance requirements, gyroscopes, micromachines, etc.
Description
Technical field:
The present invention relates to a kind of double-ferrromagnetism phase soft-magnetic alloy, have characteristics such as high saturation magnetic flux density and low remanent magnetism, it is a kind of novel magnetically soft alloy of electromagnetic solenoid iron core that is applicable to that performance requirement is very high, also can be applicable to aspects such as gyroscope and micromachine, belong to the industrial alloy technology of electrotechnical, electronic field.
Background technology:
The general requirement of soft magnetic material has high saturation magnetic flux density, high permeability and low characteristics such as coercive force, but, often other magnetic performances such as saturation magnetostriction, magnetic anisotropy and residual magnetic flux density etc. also there is special requirement at different application.Connect each other between these performances, and certain restricting relation is arranged.Investigate existing commercial magnetically soft alloy,, have very high saturation flux density Bs as Fe such as pure iron, electrical sheet and Fe-Co alloy, Fe-Al-Si base alloy, generally more than 1.5T, but initial permeability μ
iRelatively low, remanent magnetization Br is also than higher.As far back as the eighties, Chinese scholar is once with reference to former Soviet Union's Precise Alloy product, successfully developed some low remanent magnetism Br (＜0.1T) magnetically soft alloy, 1J34H as inventions such as Chen Guojun, 1J34KH (patent application publication number CN85100770A) etc., but its saturation flux density is lower than 1.5T, and these alloys generally pass through transverse magnetic field heat treatment, and its initial permeability is also very low.Recently, Liu has greatly all developed a kind of Fe-11～14wt%-5wt%M (M=Si, Mn, Ti etc.) magnetically soft alloy bar (patent announcement CN1170941), though this magnetically soft alloy has higher magnetic permeability and lower remanent magnetism (Br＜0.4T), Bs＜1.4T.In actual applications, the core material of electromagnetic solenoid needs a kind of high saturation magnetic flux density B that satisfies
s＞1.8T, low remanent magnetism B
r＜0.2T, and initial permeability μ
iPerformance soft magnetism crystal alloy such as＞2000, this is that existing magnetically soft alloy performance institute is unappeasable.
Summary of the invention:
The objective of the invention is to according to industrial actual needs, above-mentioned deficiency at prior art, develop a kind of new magnetically soft alloy that has high saturation magnetic flux density and low remanent magnetism and higher initial permeability simultaneously, with the As soon as possible Promising Policy requirement of actual application.
For realizing such purpose, the present invention has developed a kind of crystalline state magnetically soft alloy that contains two ferromagnetism phases, well near above-mentioned every performance index.
Generally speaking, the saturation magnetization of magnetically soft alloy is that chemical composition is also closely related with the phase composition and the phase structure of alloy simultaneously by the chemical composition decision of alloy; The remanent magnetization of alloy is the responsive amount of structure, and is relevant with aspects such as the institutional framework of material, stress states, generally controls the size of remanent magnetism by magnetic-field heat treatment or stress heat treatment for the untextured material of isotropism.Obtain the alloy of low remanent magnetism, mostly adopt transverse magnetic field heat treatment, yet this heat treatment mode is when reducing alloy remanent magnetism, the initial permeability of alloy is descended, and adopt this mode to be difficult to obtain very low remanent magnetism the bigger alloy of magnetostriction coefficient.
Traditional magnetically soft alloy is a monophase materials, should avoid the appearance of nonferromagnetic second phase, because this can cause some structure sensitive magnetic performances to worsen.Yet, if contain two kinds of ferromagnetism phases in the magnetically soft alloy, utilize the different alternate interaction of ferromagnetism of these two kinds of performances, but might improve the soft magnet performance of alloy.The most typical be Yoshizawa etc. by crystallizing amorphous alloy, form nano soft magnetic alloy with two kinds of ferromagnetic phases, have excellent soft magnet performance (U.S. Patent number US4881989).
Inspired by this, the present invention is object studied with the Fe-Co-Ni ternary alloy three-partalloy.The fifties Bozorth etc. studies show that two kinds of phase α of this alloy and γ all be ferromagnetism mutually, and think and to make alloy have very high saturation induction density (as Bs＞1.8T), should select the composition (Bozorth of high Co content and low Ni, Ferromagnetism, Van Nostrand (1951) pp.102-119).In recent years, in research such as the Omata Fe-Co-Ni alloy firm, select the alloying component of low Ni content, making alloy is principal crystalline phase with bcc structure α mutually, can obtain the very high magnetically soft alloy of saturation induction density, if alloy mainly exists mutually with fcc structure γ, its saturation magnetization then will reduce (U.S. Patent number US5091266).The present invention is in the Fe-Co-Ni alloy system, select near the chemical composition in α-γ phase boundary line, and add an amount of alloy element Nb and rare earth (as Ce), manage by heat treatment, obtaining with α is principal crystalline phase mutually, and contain the double-ferrromagnetism phase soft-magnetic alloy of an amount of γ phase, thereby obtain high saturation and magnetic intensity.Because these two kinds of ferromagnetism have different magnetics behaviors mutually, especially have different magnetostriction directions and different magnetocrystalline anisotropy energies, therefore, under their acting in conjunction, can obtain nearly zero saturation magnetostriction coefficient alloy, pass through transverse magnetic field heat treatment again, form the induced uniaxial anisotropy, reduce remanent magnetism Br value, can satisfy the requirement of above-mentioned soft magnet performance.
Concrete technical scheme of the present invention is as follows:
Adopt electrolysis Fe and technical pure metal Co, Ni, pure Nb of commodity and rare earth are raw material, and its purity is all greater than 99.0%.
The proportioning of these raw metals is Fe:30～50wt%, and the content of rare earth that Co:20～50wt%, Ni:10～25wt%, Nb:2～5wt%, total contents such as impurity C, S, P, Mn are no more than the 0.1wt%. interpolation is no more than 0.2wt%.
The processing step that the present invention adopts is as follows:
1. with above-mentioned raw materials vacuum metling, vacuum degree is greater than 10
-3The mmHg post.Casting is after forge, be rolled into all size shape.
2. in vacuum furnace, solution heat treatment under 1100～1150 ℃ of hydrogen atmospheres, 100 ℃/hour are chilled near 750 ℃, accelerate cooldown rate, with 250～300 ℃/hour cooling rates to room temperature.
3. carry out magnetic-field heat treatment again, in the coexistence region of alloy system, temperature is to be incubated 1～2 hour in 600～750 ℃ of scopes, makes alloy form two ferromagnetism phases.
4. carry out magnetic cooling under protective atmosphere, add transverse magnetic field 40～60KA/m, be cooled to 300 ℃ with 50～100 ℃, demagnetizing field is chilled to room temperature.
The alloy sample phase structure of making is analyzed with Rigaku D/max-RC type X-ray diffractometer.With the static magnetic performance of direct current magnetic characteristic measuring apparatus beta alloy,, draw saturation induction density Bs, remanent magnetism Br and the initial permeability μ of magnetic alloy by analyzing magnetization curve and the magnetic hysteresis loop that experiment records
iWith magnetics performance parameters such as coercivity H; Strain gauge method is measured the saturation magnetostriction coefficient lambda s of magnetically soft alloy.
The two ferromagnetism magnetically soft alloy phase structures and the magnetic performance that adopt above-mentioned technology to make are as follows:
Phase composition:
α phase ferrite is a principal crystalline phase, volume content 85～92%, and all the other are γ phase ferromagnetism SWShi body.The static-magnetic performance is:
Saturation induction density Bs＞1.8T;
Residual magnetic flux density Br is near 0.25T;
Initial permeability μ
i1600～2500
Saturation magnetostriction coefficient lambda s (* 10
-6)-20～5
Induce anisotropy coefficient Ku300～700J/m
3
The present invention can obtain double-ferrromagnetism phase soft-magnetic alloy under optimized process conditions, have performances such as the low remanent magnetism of high saturation magnetic flux density, can satisfy the practical application of high-performance electromagnetic solenoid iron core.This in addition novel magnetically soft alloy also can be applicable to aspects such as gyroscope and micromachine.
Description of drawings and embodiment:
Fig. 1 is chemical composition and bcc, fcc alpha region and the boundary line of Fe-Co-Ni ternary alloy system, and the selected alloying component area schematic of the present invention.
Fig. 2 is typical alloy sample phase structure X-ray diffractometer analysis result.
Among the figure, typical alloy sample composition is (Fe
40Co
40Ni
20)
0.98Nb
0.02, be selected in Fig. 1 shadow region near the alloy α-γ phase boundary line.
Fig. 3 is the magnetic hysteresis loop of Fig. 2 sample test.
This pair of ferromagnetism magnetically soft alloy compared with 1J34 or the 1J34KH magnetically soft alloy of develop and application, All be the Fe-Co-Ni alloy system, and add a small amount of Nb, but different be that alloying component is selected, 1J34 is alloy The content of middle Ni is about 34wt.%, and its principal crystalline phase is fcc structure γ phase, so its saturation magnetization relatively Low, general Bs about 1.5T, although can obtain very low residual induction by transverse magnetic field heat treatment, at the beginning of it The beginning magnetic conductivity is below 1000, and is relatively low; And the alloy of this newly development to contain simultaneously two kinds of performances different The ferromagnetism phase, when obtaining low remanent magnetism, saturation magnetization and initial permeability are high than 1J34 all. Use this Plant double-ferrromagnetism phase soft-magnetic alloy and make the iron core of electromagnetic solenoid, can greatly improve the workability of magnetic valve Energy.
Further specify effect of the present invention below by specific embodiment.
Electrolysis Fe, Co, Ni and Nb raw metals such as (purity＞99.9%) is pressed table 1 proportioning, and the sample of two kinds of heterogeneities is respectively joined 5kg. melting in a vacuum, and vacuum degree is greater than 10
-3The mmHg post.Casting is after forge, and is cold rolling through hot rolling, and finish to gauge amount is down made the strip of 0.1mm about 80%, obtain the magnetically soft alloy sample of two kinds of heterogeneities.
The set of dispense ratio of two kinds of heterogeneity alloys of table 1.
Numbering Co (wt%) Ni (wt%) Fe (wt%) Nb (wt%)
1 43.1 15.7 39.2 2
2 39.2 19.6 39.2 2
Alloy thin band is turned to annulus φ 20/24 * 10 * 0.1mm after the electrophoresis coating respectively,, test its phase structure and magnetic performance through after the above-mentioned process system heat treatment.
The magnetic performance of table 2. different component alloy sample
Alloy B s Br Hc μ
iKu λ s
Numbering (T) is (A/M) (H=4mA/m) (J/m (T)
3) (x10
-6)
1 1.81 0.34 43 1624 320 -12
2 1.8 0.26 56 2185 680 3
The chemical composition of these two kinds of alloys is all in the zone that accompanying drawing 1 is indicated, promptly near the boundary line of two-phase section, alloy sample adopts identical manufacturing process and means of testing, the performance of alloy is slightly different, the sample performance of numbering 2 is superior to numbering 1, is in particular in remanent magnetism and initial permeability, and this is because the sample of numbering 2 contains an amount of γ phase, have only very a spot of γ phase and number 1 sample, to depart from the phase boundary line slightly far relevant with its composition for this.
Claims (3)
1, a kind of high saturation magnetic flux density and low remanence magnetism double-ferrromagnetism phase soft-magnetic alloy, it is characterized in that containing simultaneously two kinds of ferromagnetism phase α and γ, its chemical composition range is Fe:30～50wt%, Co:20～50wt%, Ni:10～25wt%, Nb:2～5wt%, impurity C, S, P, Mn total content are no more than 0.1wt%, and the content of rare earth of interpolation is no more than 0.2wt%.
2,, it is characterized in that being used to make the electromagnetic solenoid iron core as said high saturation magnetic flux density of claim 1 and low remanence magnetism double-ferrromagnetism phase soft-magnetic alloy.
3, the manufacture method of a kind of high saturation magnetic flux density as claimed in claim 1 and low remanence magnetism double-ferrromagnetism phase soft-magnetic alloy is characterized in that the processing step that adopts is as follows:
(1), with the rare earths material vacuum metling of Fe, Co, Ni, Nb and interpolation, vacuum degree is greater than 10
-3The mmHg post, casting is after forge, be rolled into all size shape;
(2), in vacuum furnace, solution heat treatment under 1100～1150 ℃ of hydrogen atmospheres, 100 ℃/hour are chilled near 750 ℃, accelerate cooldown rate, with 250～300 ℃/hour cooling rates to room temperature;
(3), again carry out magnetic-field heat treatment, in the coexistence region of alloy system, temperature is to be incubated 1～2 hour in 600～750 ℃ of scopes, makes alloy form two ferromagnetism phases;
(4), under protective atmosphere, carry out magnetic cooling, add transverse magnetic field 40～60KA/m, be cooled to 300 ℃ with 50～100 ℃, demagnetizing field is chilled to room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99124006 CN1110825C (en) | 1999-11-12 | 1999-11-12 | High saturation magnetic flux density and low remanence magnetism double-ferrromagnetism phase soft-magnetic alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99124006 CN1110825C (en) | 1999-11-12 | 1999-11-12 | High saturation magnetic flux density and low remanence magnetism double-ferrromagnetism phase soft-magnetic alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1254171A CN1254171A (en) | 2000-05-24 |
| CN1110825C true CN1110825C (en) | 2003-06-04 |
Family
ID=5283104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99124006 Expired - Fee Related CN1110825C (en) | 1999-11-12 | 1999-11-12 | High saturation magnetic flux density and low remanence magnetism double-ferrromagnetism phase soft-magnetic alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1110825C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1306528C (en) * | 2004-01-14 | 2007-03-21 | 施立新 | Uneasily-sintered magnetic powder |
| KR101963069B1 (en) * | 2015-02-09 | 2019-03-27 | 제이에프이 스틸 가부시키가이샤 | Raw material powder for soft magnetic powder, and soft magnetic powder for dust core |
| CN108565984A (en) * | 2018-05-03 | 2018-09-21 | 上海交通大学 | A kind of wireless electric energy transmission device |
| CN110257721B (en) * | 2019-07-01 | 2021-02-02 | 济南大学 | Fe-based soft magnetic alloy with low Fe content and preparation method and application thereof |
| CN110699573B (en) * | 2019-11-14 | 2020-08-11 | 北京理工大学 | NiMn-doped CoFe-based polycrystalline soft magnetic alloy and preparation method thereof |
-
1999
- 1999-11-12 CN CN 99124006 patent/CN1110825C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1254171A (en) | 2000-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102543347B (en) | A kind of Fe-based nanocrystalline magnetically soft alloy and preparation method thereof | |
| Luborsky | Amorphous metallic alloys | |
| CN104087833B (en) | Fe-based nanocrystalline magnetically soft alloy that high frequency performance is excellent and preparation method thereof | |
| CN105088107B (en) | Fe-based amorphous alloy with high saturated magnetic induction and strong amorphous formation ability | |
| Couderchon et al. | Some aspects of magnetic properties of Ni-Fe and Co-Fe alloys | |
| CN102867608A (en) | FeNi-based amorphous soft magnetic alloy and preparation method of soft magnetic alloy | |
| CN106498310A (en) | Cobalt base amorphous magnetically soft alloy material of a kind of low-coercivity low-loss and preparation method thereof | |
| CN110387500A (en) | A kind of high magnetic strength high frequency Fe-based nanocrystalline magnetically soft alloy and preparation method thereof | |
| Coey et al. | Influence of hydrogen on the magnetic properties of iron‐rich metallic glasses | |
| CN114807758A (en) | Low-coercivity iron-based nanocrystalline alloy and preparation method thereof | |
| CN1110825C (en) | High saturation magnetic flux density and low remanence magnetism double-ferrromagnetism phase soft-magnetic alloy | |
| Fujimori et al. | Magnetic and thermal expansion properties in hydrided Fe–Zr amorphous alloys | |
| CN105655079B (en) | A kind of Fe-based nanocrystalline magnetically soft alloy material and preparation method thereof | |
| CN109207871A (en) | A kind of amorphous-nano-crystalline magnetically soft alloy and preparation method thereof | |
| Fujimori et al. | Huge magnetostriction of amorphous bulk (Sm, Tb) Fe2-B with low exciting fields | |
| Fukamichi et al. | Magnetic properties and density of Fe-Ce amorphous alloys | |
| Fuerst et al. | Effect of manganese substitution in erbium‐iron‐manganese‐boron: Spin reorientation, moment compensation, and structure | |
| CA1172472A (en) | Isotropic and nearly isotropic permanent magnet alloys | |
| Goldman | The influence of atomic order on magnetic properties | |
| CN110468353A (en) | A kind of high saturated magnetic induction Fe-based amorphous alloy and preparation method | |
| Adams | Recent developments in soft magnetic alloys | |
| CN110257721A (en) | A kind of Fe base magnetically soft alloy of lower Fe content and its preparation method and application | |
| KR100710613B1 (en) | Fe-BASED NANO CRYSTALLINE ALLOY AND METHOD FOR MANUFACTURING THE SAME | |
| Meaden | The general physical properties of manganese metal | |
| Nakamura | Recent developments in magnetism and magnetic materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1065679 Country of ref document: HK |
|
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |