CN105177469A - High-ferric-content amorphous magnetically soft alloy and preparing method thereof - Google Patents

High-ferric-content amorphous magnetically soft alloy and preparing method thereof Download PDF

Info

Publication number
CN105177469A
CN105177469A CN201510618780.0A CN201510618780A CN105177469A CN 105177469 A CN105177469 A CN 105177469A CN 201510618780 A CN201510618780 A CN 201510618780A CN 105177469 A CN105177469 A CN 105177469A
Authority
CN
China
Prior art keywords
alloy
equal
amorphous soft
amorphous
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.)
Pending
Application number
CN201510618780.0A
Other languages
Chinese (zh)
Inventor
韩烨
井上明久
朱胜利
崔振铎
杨贤金
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin University
Original Assignee
Tianjin University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tianjin University filed Critical Tianjin University
Priority to CN201510618780.0A priority Critical patent/CN105177469A/en
Publication of CN105177469A publication Critical patent/CN105177469A/en
Pending legal-status Critical Current

Links

Landscapes

  • Soft Magnetic Materials (AREA)

Abstract

The invention discloses a high-ferric-content ferric-based amorphous alloy and a preparing method thereof. The formula of the alloy is FemMnSiaBbPcCd. M shows at least one of Cr, Mo and Nb; and m, n, a, b, c and d represent atomic percents of the components respectively and meet the following conditions that m is larger than or equal to 83 and smaller than or equal to 87, n is larger than or equal to 0.5 and smaller than or equal to 2, a is larger than or equal to 1 and smaller than or equal to 5, b is larger than or equal to 5 and smaller than or equal to 10, c is larger than or equal to 1 and smaller than or equal to 5, d is larger than or equal to 0 and smaller than or equal to 3, and the sum of m, n, a, b, c and d is 100. The alloy has high saturation flux density, excellent soft magnetic performance, annealing bending tenacity and good corrosion resistance; and in addition, due to the high ferric-element content, cost is effectively reduced, and the alloy can be widely used for various iron core soft magnetic materials.

Description

Amorphous soft-magnetic alloy of a kind of high Fe content and preparation method thereof
Technical field
The present invention relates to magnetic functional material field, particularly a kind of amorphous soft-magnetic alloy and preparation method thereof of high Fe content.
Background technology
Fe-based amorphous/nano-crystal soft magnetic alloy is a kind of type material with special construction and high-performance, there is the advantages such as splendid soft magnetism (lower coercive force, higher magnetic permeability and lower core loss), mechanical property and erosion resistance, obtain extensive investigation and application.And its preparation technology is simple, energy-conserving and environment-protective, is described as 21 century novel green energy-saving material, the attention and the deep research that obtain height have the appearance of industrialization commodity.(Fe, the Co)-Si-B AMORPHOUS ALLOY RIBBONS adopting plane foundry engieering to prepare by American Association chemical company through license in such as 1975 [1], achieve the commercialization of Fe-based amorphous soft magnetic materials first.Product Metglass2605SA1 quenches state saturation induction density 1.56T, and after annealing, coercive force is about 20A/m, is widely used in soft magnetic amorphous iron core and other soft magnetic materials fields.
In order to improve the performance of magnetics and integrated further, people were devoted to develop the amorphous/nanocrystalline non-retentive alloy composition with high saturated magnetic induction in recent years.By improving the content of ferro element in alloying constituent, heavy alloyed saturation induction density can be put forward further, falling low-alloyed cost simultaneously.Such as, also have in prior art report Fe atomic percentage conc close to 82% some serial Fe-Si-B system, Fe-Si-B-C system and Fe-Si-B-P-C system non-crystaline amorphous metal [2 ~ 6], obtain superior magnetic property and other physicalies.
Recently, applicant has developed Fe-Si-B-P-(C) alloy system that iron level is 83-85at%, annealed state alloy saturation induction density is not less than 1.6T, wherein reach as high as 1.72T, this alloy system has superior soft magnetism simultaneously, coercive force is lower than 10A/m, and initial permeability can more than 10000.In addition, this alloy system still can keep bending toughness after annealing, and doubling is continuous [7].
Applicant attempts synthesizing the non-crystaline amorphous metal with more high saturated magnetic induction further.But the increase of iron level can reduce the amorphous formation ability of composition, the acquisition of single amorphous phase alloy is caused to there is the maximum value of iron level.According to the document reported at present, the maximum value that iron-non-metal alloy system obtains single amorphous phase iron level is 85at%.There is research to point out, add the amorphous formation ability that a small amount of transition element can strengthen alloy, therefore, expect in composition, to add a small amount of transition element to change the atom conformation of non-crystal structure, thus obtain the amorphous soft-magnetic alloy of iron level higher than 85at%.Meanwhile, adding of transition element contributes to putting forward heavy alloyed solidity to corrosion, makes it obtain more superior over-all properties.
[reference]
[1] United States Patent (USP) No. 3856513 publication;
[2] Japanese Kohyo 5-503962 publication;
[3] Japanese Unexamined Patent Publication 7-100597 publication;
[4] Japanese Unexamined Patent Application Publication 2001-508129 publication;
[5] United States Patent (USP) No. 4217135 publication;
[6] U.S. Patent Publication No. 2004/0140016 publication;
[7] Chinese patent No. 104745972 publication.
Summary of the invention
The present invention is in order to obtain the amorphous soft-magnetic alloy of more high saturated magnetic induction, improve iron content further on the basis of existing technology, and the atom conformation of the short range order feature that is improved by a small amount of transition element of interpolation, thus enhance amorphous formation ability and the solidity to corrosion of alloy, simultaneously by the Composition Design of science, alloy is made to possess excellent soft magnetism and annealing bending toughness, to obtain excellent over-all properties.
In order to solve the problems of the technologies described above, the amorphous soft-magnetic alloy of a kind of high Fe content that the present invention proposes, its composition has following expression Fe mm nsi ab bp cc d, wherein M represents at least one of Cr, Mo, Nb tri-kinds of elements, and m, n, a, b, c and d represent the atomic percent of each component respectively, and meet the following conditions 83≤m≤87,0.5≤n≤2,1≤a≤5,5≤b≤10,1≤c≤5,0≤d≤3, m+n+a+b+c+d=100.
The amorphous soft-magnetic alloy of high Fe content of the present invention is annealed at a certain temperature between Curie temperature and crystallization temperature, can not crystallize out phase; Keep bending toughness after annealing, doubling is continuous; Alloy saturation induction density (B after annealing s) be not less than 1.4T, coercive force (H c) not higher than 15A/m; Corrosion electric current density (I in 25 DEG C of NaCl aqueous solution corr) not higher than 10 -5a/cm 2; The corrosion electric current density ratio of annealed state alloy state of quenching at least reduces an order of magnitude.
The preparation method of the amorphous soft-magnetic alloy of above-mentioned high Fe content, comprises the following steps:
Step one, to prepare burden according to the alloying constituent expression formula of the amorphous soft-magnetic alloy of high Fe content described in claim 1;
Step 2, under the protection of rare gas element, the raw material adopting high-frequency induction smelting furnace step one to be configured is smelted into uniform alloy liquid and cools, and the vacuum tightness of melting is not higher than 9.5 × 10 -3pa;
Step 3, master alloy ingot obtained for step 2 to be dissolved again, under the protection of rare gas element, adopt single roller quench to prepare alloy strip sample.
Further: in step 2, master alloy ingot ultrasonic cleaning in alcohol of will make.
In step 3, processing parameter prepared by single roller quench is: spraying pressure is 0.02-0.04Mpa, and copper roller rotating speed linear resonance surface velocity is 20-50m/s, injection temperature 800-1200 DEG C.
It is silica tube that single roller quench prepares the container placing mother alloy in alloy strip sample, and described silica tube mouth of pipe 1200-2000 sand papering is 0.7-0.8mm to diameter.
The structural characterization of the amorphous soft-magnetic alloy of arbitrary high Fe content that the present invention obtains and performance test:
(1) non-crystal structure characterizes.Be fixed on side by side in sample table by two segment bands, the structure of sample upwards, is detected in free surface with X-ray diffractometer (XRD).XRD diffraction peak should be single diffuse peaks.
(2) thermal parameters is measured.About 10-20mg band sample is shredded, real as flattening in alumina crucible, the heating curve of alloy is recorded by differential scanning calorimeter (DSC).DSC heating curve has an exothermic peak at least.(the first) starting temperature of exothermic peak is defined as crystallization temperature T x.T xthe starting temperature that on curve, minor endothermic peak is corresponding is before Curie temperature T c.
(3) magnetic parameter is measured.State of quenching alloy strip is at T cand T xbetween arbitrary temp annealing be no less than 10 minutes to eliminate unrelieved stress.The magnetic hysteresis loop of alloy is measured to obtain its saturation induction density with vibration magnetometer (VSM); The coercive force of alloy is measured with B-H instrument.Annealed state alloy saturation induction density (B s) be not less than 1.4T, coercive force (H c) not higher than 15A/m.As preferably, B sreach as high as 1.76T.
(4) mechanical property is measured.State of quenching alloy strip is at T cand T xbetween arbitrary temp annealing be no less than 10 minutes to eliminate unrelieved stress.By alloy strip 180 degree of doublings, can not two-section be fragmented into after the doubling of this series alloy, namely there is bending toughness.
(5) solidity to corrosion is measured.Using alloy strip as working electrode, Pt electrode is as to electrode, and saturated calomel electrode, as reference electrode, adopts three-electrode system to measure the electrochemical behavior of alloy.Test soln can be selected but be not limited to the 3.5mass%NaCl aqueous solution, 0.05mol/LHCl or H 2sO 4the aqueous solution etc.This series alloy in 25 DEG C of NaCl aqueous solution corrosion electric current density not higher than 10 -5a/cm 2.The corrosion electric current density ratio of annealed state alloy state of quenching at least reduces an order of magnitude.
Compared with prior art, the invention has the beneficial effects as follows:
According to the present invention, a kind of iron base amorphous magnetically-soft alloy of high Fe content can be provided.Even if this alloy still can keep quite high amorphous formation ability at iron atom percentage composition more than in the specified range of 85%.This alloy has higher saturation induction density and superior soft magnetic performance, and excellent mechanical property, machinability, solidity to corrosion and lower cost, and can be applicable to the Production Flow Chart of mass product.
Accompanying drawing explanation
Fig. 1 is the Fe that embodiment 1 prepares 84-xc xm 2b 8si 2p 4(M=Cr, Mo; X=0,1) the XRD diffractogram of AMORPHOUS ALLOY RIBBONS;
Fig. 2 is the Fe that embodiment 1 prepares 84-xc xm 2b 8si 2p 4(M=Cr, Mo; X=0,1) the DSC heating curve of AMORPHOUS ALLOY RIBBONS;
Fig. 3 is the Fe that embodiment 1 prepares 84mo 2b 8si 2p 4outward appearance after alloy strip annealing;
Fig. 4 is the Fe that embodiment 1 prepares 84-xc xm 2b 8si 2p 4(M=Cr, Mo; X=0,1) magnetic hysteresis loop of AMORPHOUS ALLOY RIBBONS;
Fig. 5 is the Fe that embodiment 1 prepares 84-xc xm 2b 8si 2p 4(M=Cr, Mo; X=0,1) polarization curve of AMORPHOUS ALLOY RIBBONS;
Fig. 6 is the Fe that embodiment 2 prepares 85mo 1b 8si 2p 4, Fe 86mo 1b 8si 1.5p 3.5and Fe 86.5mo 1b 8si 1.5p 3the XRD diffractogram of AMORPHOUS ALLOY RIBBONS;
Fig. 7 is the Fe that embodiment 2 prepares 85mo 1b 8si 2p 4, Fe 86mo 1b 8si 1.5p 3.5and Fe 86.5mo 1b 8si 1.5p 3the DSC heating curve of AMORPHOUS ALLOY RIBBONS;
Fig. 8 is the Fe that embodiment 2 prepares 86mo 1b 8si 1.5p 3.5sEM photo near AMORPHOUS ALLOY RIBBONS folding line;
Fig. 9 is the Fe that embodiment 2 prepares 85mo 1b 8si 2p 4, Fe 86mo 1b 8si 1.5p 3.5and Fe 86.5mo 1b 8si 1.5p 3the magnetic hysteresis loop of AMORPHOUS ALLOY RIBBONS;
Figure 10 is the Fe that embodiment 3 prepares 84-xb 8.5si 4.5p 3(Nb 0.67cr 0.33) xthe XRD diffractogram of (x=1,2,3) AMORPHOUS ALLOY RIBBONS;
Figure 11 is the Fe that embodiment 3 prepares 84-xb 8.5si 4.5p 3(Nb 0.67cr 0.33) xthe DSC heating curve of (x=1,2,3) AMORPHOUS ALLOY RIBBONS;
Figure 12 is the Fe that embodiment 3 prepares 84-xb 8.5si 4.5p 3nb 0.67cr 0.33magnetic hysteresis loop;
Figure 13 is the Fe that embodiment 4 prepares 84b 8si 2p 4nb 1mo 1and Fe 84b 8si 2p 4cr 1nb 0.5mo 0.5the X ray diffracting spectrum of AMORPHOUS ALLOY RIBBONS;
Figure 14 is the Fe that embodiment 4 prepares 84b 8si 2p 4cr 1nb 0.5mo 0.5the indentation hardness optical microscope image of alloy;
Figure 15 is the Fe that embodiment 4 prepares 84b 8si 2p 4nb 1mo 1and Fe 84b 8si 2p 4cr 1nb 0.5mo 0.5two kinds of alloys are quenched the polarization curve under state.
Embodiment
Be described in further detail technical solution of the present invention below in conjunction with the drawings and specific embodiments, described specific embodiment only explains the present invention, not in order to limit the present invention.
Embodiment 1, single roller quench is adopted to prepare Fe 84-xc xm 2b 8si 2p 4(M=Cr, Mo; X=0,1) AMORPHOUS ALLOY RIBBONS, comprise the steps:
(1) according to alloy expression formula, atomic percent is converted to mass percent to prepare burden, takes high-purity Fe, Cr, Mo, B, Si and the Fe of respective quality 3p and Fe-C alloy (eutectic composition, the mass percent about 0.77% of C) mixes stand-by;
(2) the target component raw material of weighing is placed in vacuum high-frequency induction melting furnace, vacuum is evacuated to 9.5 × 10 -3argon gas is filled with as protective atmosphere during Pa.Be heated to alloy dissolve completely and pour copper mold into evenly and be cooled to room temperature, obtain target master alloy ingot;
(3) after target master alloy ingot being broken into fritter, (preferably using alcohol) ultrasonic cleaning is for subsequent use.Clean fritter mother alloy is placed in the silica tube with suitable size openings, and in the present embodiment, the container of placement mother alloy used is silica tube, and described silica tube mouth of pipe 1200-2000 sand papering is 0.7-0.8mm to diameter.Again this silica tube is fixed in the ruhmkorff coil of melting fast cooling device.Vacuum is evacuated to 9.5 × 10 -3be filled with argon gas during Pa as protective atmosphere, be sprayed onto with the spraying pressure of 0.02MPa when temperature about 1000 DEG C after dissolving alloy and prepare alloy strip with chilling on the copper roller of linear resonance surface velocity 40m/s rotation.Be generally after band cooling and take out alloy strip sample after spray completes 10 minutes.Alloy strip thickness is 0.01 ~ 0.03mm.
The phase structure of alloy strip is characterized with X-ray diffractometer.Fig. 1 is the X ray diffracting spectrum of alloy strip, and each collection of illustrative plates only has a diffuse peaks, shows that this alloy is single amorphous phase.
The thermodynamical coordinate of alloy is characterized by differential scanning calorimeter.Fig. 2 is the DSC heating curve of alloy strip, and each curve all has two exothermic peaks, shows that crystallization process is two step reaction.Table 1 summarizes the crystallization temperature (T of each alloying constituent x) and Curie temperature (T c).
By alloy strip at respective T xanneal 10 minutes at-100K temperature.Fig. 3 is Fe 84mo 2b 8si 2p 4outward appearance after alloy strip annealing, after annealing, alloy strip still remains bending toughness, and doubling is continuous.
With vibration strong magnetic measurement amount alloy magnetic hysteresis loop and record B s, measure H with B-H instrument c.Fig. 4 is the magnetic hysteresis loop of four kinds of alloys of the present embodiment 1, shows typical soft magnetic materials feature.B sand H cin table 1.
Measure the polarization curve of alloy to evaluate its solidity to corrosion with three-electrode system, experiment condition is the 298K3.5mass%NaCl aqueous solution.Four kinds of alloys that Fig. 5 illustrates the present embodiment 1 are quenched the polarization curve under state, the corrosion potential (E of state of quenching and annealed state alloy corr) and corrosion electric current density (I corr) in table 2.
As can be seen from Table 2, the corrosion electric current density of annealed state alloy state of comparatively quenching declines to some extent.This is because the alloy atom conformation after annealing changes, reach the state that energy is lower.Thus improve the position of point excessively of anodic reaction, cause the raising of corrosion potential, accordingly, corrosion electric current density reduces, and the solidity to corrosion of alloy is enhanced.
Embodiment 2, single roller quench is adopted to prepare Fe 85mo 1b 8si 2p 4, Fe 86mo 1b 8si 1.5p 3.5and Fe 86.5mo 1b 8si 1.5p 3aMORPHOUS ALLOY RIBBONS, comprises the steps:
(1) according to alloy expression formula, atomic percent is converted to mass percent to prepare burden, takes high-purity Fe, Cr, Mo, B, Si and the Fe of respective quality 3the mixing of P alloy is stand-by;
(2) the target component raw material of weighing is placed in vacuum high-frequency induction melting furnace, vacuum is evacuated to 9.5 × 10 -3argon gas is filled with as protective atmosphere during Pa.Be heated to alloy dissolve completely and pour copper mold into evenly and be cooled to room temperature, obtain target master alloy ingot;
(3) for subsequent use with alcohol ultrasonic cleaning after target master alloy ingot being broken into fritter.Clean fritter mother alloy is placed in the silica tube with suitable size openings, and in the present embodiment, the container of placement mother alloy used is identical with embodiment 1, then is fixed on by this silica tube in the ruhmkorff coil of melting fast cooling device.Vacuum is evacuated to 9.5 × 10 -3be filled with argon gas during Pa as protective atmosphere, be sprayed onto with the spraying pressure of 0.02MPa when temperature about 1000 DEG C after dissolving alloy and prepare alloy strip with chilling on the copper roller of linear resonance surface velocity 40m/s rotation.Take out after band cooling.Alloy strip thickness is 0.01 ~ 0.03mm.
The phase structure of alloy strip is characterized with X-ray diffractometer.Fig. 6 is the X ray diffracting spectrum of alloy strip, and each collection of illustrative plates only has a diffuse peaks, shows that this alloy is single amorphous phase.As previously mentioned, the maximum value that iron-non-metal alloy system obtains single amorphous phase iron level is 85at%.And by adding a small amount of transition element and other non-metallic element content of rational proportion in the present invention, obtain the single amorphous phase of iron level higher than 85at%.Illustrate that the interpolation of transition element improves the amorphous formation ability of alloy.This is because transition element has the atomic radius larger than iron and in nonmetallic mixture heat, enhance three optimal conditions forming amorphous: (1) composition has more than three kinds elements; (2) different element has larger atomic radius difference; (3) there is negative mixture heat between element.
The thermodynamical coordinate of alloy is characterized by differential scanning calorimeter.Fig. 7 is the DSC heating curve of alloy strip, and each curve all has two exothermic peaks, shows that crystallization process is two step reactions.Table 1 summarizes the T of each alloying constituent xand T c.
By alloy strip at respective T xanneal 30 minutes at-100K temperature, after annealing, alloy strip still remains bending toughness, and doubling is continuous.Fig. 8 is Fe 86mo 1b 8si 1.5p 3.5sEM photo after alloy strip annealing near folding line, can see and distributed shear zone near folding line, shows that alloy owing to possessing bending toughness, shear deformation occurs in bending process.
With vibration strong magnetic measurement amount alloy magnetic hysteresis loop and record B s, measure H with B-H instrument c.Fig. 9 is the magnetic hysteresis loop of three kinds of alloys of the present embodiment 2, shows typical soft magnetic materials feature.B sand H cin table 1.
Embodiment 3, single roller quench is adopted to prepare Fe 84-xb 8.5si 4.5p 3(Nb 0.67cr 0.33) x(x=1,2,3) AMORPHOUS ALLOY RIBBONS, comprises the steps:
(1) according to alloy expression formula, atomic percent is converted to mass percent to prepare burden, takes high-purity Fe, Cr, Nb, B, Si and the Fe of respective quality 3the mixing of P alloy is stand-by;
(2) the target component raw material of weighing is placed in vacuum high-frequency induction melting furnace, vacuum is evacuated to 9.5 × 10 -3argon gas is filled with as protective atmosphere during Pa.Be heated to alloy dissolve completely and pour copper mold into evenly and be cooled to room temperature, obtain target master alloy ingot;
(3) after target master alloy ingot being broken into fritter, ultrasonic cleaning is for subsequent use.Clean fritter mother alloy is placed in the silica tube with suitable size openings, and in the present embodiment, the container of placement mother alloy used is identical with embodiment 1, then is fixed on by this silica tube in the ruhmkorff coil of melting fast cooling device.Vacuum is evacuated to 9.5 × 10 -3be filled with argon gas during Pa as protective atmosphere, be sprayed onto with the spraying pressure of 0.02MPa when temperature about 1000 DEG C after dissolving alloy and prepare alloy strip with chilling on the copper roller of linear resonance surface velocity 40m/s rotation.Take out after band cooling.Alloy strip thickness is 0.01 ~ 0.03mm.
The phase structure of alloy strip is characterized with X-ray diffractometer.Figure 10 is the X ray diffracting spectrum of alloy strip, and each collection of illustrative plates only has a diffuse peaks, shows that this alloy is single amorphous phase.
The thermodynamical coordinate of alloy is characterized by differential scanning calorimeter.Figure 11 is the DSC heating curve of alloy strip, and each curve all has two exothermic peaks, shows that crystallization process is two step reactions.Table 1 summarizes the T of each alloying constituent xand T c.
By alloy strip at respective T xanneal 10 minutes at-100K temperature, after annealing, alloy strip still remains bending toughness, and doubling is continuous.As everyone knows, after the annealing of most of Fe-based amorphous alloy, all present bending fragility, as business-like Fe 78si 9b 13alloy doubling after 320 DEG C of annealing can be fractured into two-section.And still can keep bending toughness after the annealing of this series alloy, material is possessed good machinability.
With vibration strong magnetic measurement amount alloy magnetic hysteresis loop and record B s, measure H with B-H instrument c.Figure 12 is Fe in the present embodiment 3 83b 8.5si 4.5p 3nb 0.67cr 0.33the magnetic hysteresis loop of alloy, shows typical soft magnetic materials feature.The each alloy B of the present embodiment 3 sand H cin table 1.
With the addition of Cr and Nb two kinds of elements in the alloying constituent of the present embodiment 3 simultaneously, and the element kind phasor of business-like SENNTIX alloy interpolation.It is pointed out that in the present embodiment 3 addition passing through to improve iron content and decrease transition element, make alloy obtain higher B s.
Embodiment 4, single roller quench is adopted to prepare Fe 84b 8si 2p 4nb 1mo 1and Fe 84b 8si 2p 4cr 1nb 0.5mo 0.5aMORPHOUS ALLOY RIBBONS, comprises the steps:
(1) according to alloy expression formula, atomic percent is converted to mass percent to prepare burden, takes high-purity Fe, Cr, Nb, B, Si and the Fe of respective quality 3the mixing of P alloy is stand-by;
(2) the target component raw material of weighing is placed in vacuum high-frequency induction melting furnace, vacuum is evacuated to 9.5 × 10 -3argon gas is filled with as protective atmosphere during Pa.Be heated to alloy dissolve completely and pour copper mold into evenly and be cooled to room temperature, obtain target master alloy ingot;
(3) after target master alloy ingot being broken into fritter, ultrasonic cleaning is for subsequent use.Clean fritter mother alloy is placed in the silica tube with suitable size openings, and in the present embodiment, the container of placement mother alloy used is identical with embodiment 1, then is fixed on by this silica tube in the ruhmkorff coil of melting fast cooling device.Vacuum is evacuated to 9.5 × 10 -3be filled with argon gas during Pa as protective atmosphere, be sprayed onto with the spraying pressure of 0.02MPa when temperature about 1000 DEG C after dissolving alloy and prepare alloy strip with chilling on the copper roller of linear resonance surface velocity 40m/s rotation.Take out after band cooling.Alloy strip thickness is 0.01 ~ 0.03mm.
The phase structure of alloy strip is characterized with X-ray diffractometer.Figure 13 is the X ray diffracting spectrum of alloy strip, and each collection of illustrative plates only has a diffuse peaks, shows that this alloy is single amorphous phase.
The thermodynamical coordinate of alloy is characterized by differential scanning calorimeter.The T of two kinds of alloying constituents that DSC heating curve obtains included by table 1 xand T c.
By alloy strip at respective T xanneal 10 minutes at-100K temperature, after annealing, alloy strip still remains bending toughness, and doubling is continuous.Carry out hardness test with Vickers' hardness instrument, Figure 14 is Fe 84b 8si 2p 4cr 1nb 0.5mo 0.5the indentation hardness optical microscope image of alloy, can see and occur slip line around impression, shows that alloy possesses good toughness.The hardness of this alloy is 733HV, far above the hardness of traditional silicon steel.
With vibration strong magnetic measurement amount alloy magnetic hysteresis loop and record B s, measure H with B-H instrument c, the results are shown in Table 1.
Measure the polarization curve of alloy to evaluate its solidity to corrosion with three-electrode system, experiment condition is the 298K3.5mass%NaCl aqueous solution.Two kinds of alloys that Figure 15 illustrates the present embodiment 4 are quenched the polarization curve under state.
The Fe being better than not containing Cr containing Cr alloy corrosion resistance can be found out from experimental result 84b 8si 2p 4nb 1mo 1alloy.There is research to point out that Cr and Mo coexists and coexisting of Cr and Nb can effectively put forward heavy alloyed solidity to corrosion, and can find out that coexisting of Nb and Mo does not make alloy corrosion resistance significantly improve from the present embodiment 4.Can infer, the corrosion proof raising of Nb and Mo alloy is that the passivation effect by strengthening Cr realizes.
Table 1, the crystallization temperature (T of the alloying constituent of embodiment 1 to 4 x), Curie temperature (T c), annealing after saturation induction density (B s) and coercive force (H c)
Table 2, state of quenching and annealed state Fe 84-xc xm 2b 8si 2p 4(M=Cr, Mo; X=0,1) corrosion potential (E of non-crystaline amorphous metal corr) and corrosion electric current density (I corr)
Although invention has been described by reference to the accompanying drawings above, but the present invention is not limited to above-mentioned embodiment, above-mentioned embodiment is only schematic, instead of it is restrictive, those of ordinary skill in the art is under enlightenment of the present invention, when not departing from present inventive concept, a lot of distortion can also be made, such as: adopt corresponding method (casting in bronze method, water quenching etc.) to replace single roller quench to obtain the non-retentive alloy of other forms such as powder, block, sheet material; These all belong within protection of the present invention.

Claims (7)

1. an amorphous soft-magnetic alloy for high Fe content, is characterized in that, this alloying constituent has following expression Fe mm nsi ab bp cc d, wherein M represents at least one of Cr, Mo, Nb tri-kinds of elements, and m, n, a, b, c and d represent the atomic percent of each component respectively, and meet the following conditions 83≤m≤87,0.5≤n≤2,1≤a≤5,5≤b≤10,1≤c≤5,0≤d≤3, m+n+a+b+c+d=100.
2. the amorphous soft-magnetic alloy of high Fe content according to claim 1, is characterized in that, anneal between Curie temperature and crystallization temperature at a certain temperature, can not crystallize out phase; Keep bending toughness after annealing, doubling is continuous; Alloy saturation induction density (B after annealing s) be not less than 1.4T, coercive force (H c) not higher than 15A/m; Corrosion electric current density (I in 25 DEG C of NaCl aqueous solution corr) not higher than 10 -5a/cm 2; The corrosion electric current density ratio of annealed state alloy state of quenching at least reduces an order of magnitude.
3. the preparation method of the amorphous soft-magnetic alloy of high Fe content according to claim 2, is characterized in that, comprise the following steps:
Step one, to prepare burden according to the alloying constituent expression formula of the amorphous soft-magnetic alloy of high Fe content described in claim 1;
Step 2, under the protection of rare gas element, the raw material adopting high-frequency induction smelting furnace step one to be configured is smelted into uniform alloy liquid and cools, and the vacuum tightness of melting is not higher than 9.5 × 10 -3pa;
Step 3, master alloy ingot obtained for step 2 to be dissolved again, under the protection of rare gas element, adopt single roller quench to prepare alloy strip sample.
4. the preparation method of the amorphous soft-magnetic alloy of high Fe content according to claim 3, is characterized in that, in step 2, by master alloy ingot ultrasonic cleaning in alcohol of making.
5. the preparation method of the amorphous soft-magnetic alloy of high Fe content according to claim 3, it is characterized in that, in step 3, processing parameter prepared by single roller quench is: spraying pressure is 0.02-0.04Mpa, copper roller rotating speed linear resonance surface velocity is 20-50m/s, injection temperature 800-1200 DEG C.
6. the preparation method of the amorphous soft-magnetic alloy of high Fe content according to claim 8, it is characterized in that, in step 3, it is silica tube that single roller quench prepares the container placing mother alloy in alloy strip sample, and described silica tube mouth of pipe 1200-2000 sand papering is 0.7-0.8mm to diameter.
7. the preparation method of the amorphous soft-magnetic alloy of high Fe content according to claim 8, is characterized in that, in step 3, when single roller quench prepares alloy strip sample, take out alloy strip sample after spray completes 10 minutes.
CN201510618780.0A 2015-09-25 2015-09-25 High-ferric-content amorphous magnetically soft alloy and preparing method thereof Pending CN105177469A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510618780.0A CN105177469A (en) 2015-09-25 2015-09-25 High-ferric-content amorphous magnetically soft alloy and preparing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510618780.0A CN105177469A (en) 2015-09-25 2015-09-25 High-ferric-content amorphous magnetically soft alloy and preparing method thereof

Publications (1)

Publication Number Publication Date
CN105177469A true CN105177469A (en) 2015-12-23

Family

ID=54899886

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510618780.0A Pending CN105177469A (en) 2015-09-25 2015-09-25 High-ferric-content amorphous magnetically soft alloy and preparing method thereof

Country Status (1)

Country Link
CN (1) CN105177469A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107103976A (en) * 2016-02-22 2017-08-29 天津大学 A kind of iron cobalt-based toughness nano-crystal soft magnetic alloy and preparation method thereof
CN107799258A (en) * 2016-09-07 2018-03-13 天津大学 Cobalt base amorphous magnetically soft alloy material of iron of high saturated magnetic induction and preparation method thereof
CN108130493A (en) * 2016-12-01 2018-06-08 天津大学 High saturated magnetic induction, low-coercivity, high magnetic permeability iron cobalt base amorphous alloy material and preparation method thereof
CN109554635A (en) * 2018-12-05 2019-04-02 浙江农林大学暨阳学院 A kind of porous amorphous soft magnet composite wave-suction material and preparation method thereof
CN109778083A (en) * 2019-02-02 2019-05-21 清华大学 High saturated magnetic induction Fe-based amorphous alloy and preparation method thereof
CN111279001A (en) * 2017-08-25 2020-06-12 萨尔布吕肯大学 Sulfur-containing alloys for forming metallic glasses
CN115029647A (en) * 2021-03-05 2022-09-09 南京理工大学 Iron-based amorphous alloy lead with abnormal heat release phenomenon

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101800109A (en) * 2009-12-09 2010-08-11 青岛云路新能源科技有限公司 Iron-based amorphous alloy with high soft magnet performance and low cost and manufacturing method thereof
US20110272065A1 (en) * 2009-01-20 2011-11-10 Hitachi Metals, Ltd. Soft magnetic alloy ribbon and its production method, and magnetic device having soft magnetic alloy ribbon
CN104073749A (en) * 2014-06-18 2014-10-01 安泰科技股份有限公司 Iron-based amorphous magnetically soft alloy with uniform element distribution and preparation method thereof
CN104745972A (en) * 2013-12-27 2015-07-01 井上明久 High magnetic flux density soft magnetic amorphous alloy with high ductility and high workability

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110272065A1 (en) * 2009-01-20 2011-11-10 Hitachi Metals, Ltd. Soft magnetic alloy ribbon and its production method, and magnetic device having soft magnetic alloy ribbon
CN101800109A (en) * 2009-12-09 2010-08-11 青岛云路新能源科技有限公司 Iron-based amorphous alloy with high soft magnet performance and low cost and manufacturing method thereof
CN104745972A (en) * 2013-12-27 2015-07-01 井上明久 High magnetic flux density soft magnetic amorphous alloy with high ductility and high workability
CN104073749A (en) * 2014-06-18 2014-10-01 安泰科技股份有限公司 Iron-based amorphous magnetically soft alloy with uniform element distribution and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
胡壮麒等: "《亚稳金属材料》", 31 December 2006, 科学出版社 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107103976A (en) * 2016-02-22 2017-08-29 天津大学 A kind of iron cobalt-based toughness nano-crystal soft magnetic alloy and preparation method thereof
CN107799258A (en) * 2016-09-07 2018-03-13 天津大学 Cobalt base amorphous magnetically soft alloy material of iron of high saturated magnetic induction and preparation method thereof
CN108130493A (en) * 2016-12-01 2018-06-08 天津大学 High saturated magnetic induction, low-coercivity, high magnetic permeability iron cobalt base amorphous alloy material and preparation method thereof
CN111279001A (en) * 2017-08-25 2020-06-12 萨尔布吕肯大学 Sulfur-containing alloys for forming metallic glasses
US11384417B2 (en) 2017-08-25 2022-07-12 Universität des Saarlandes Sulfurous metallic glass forming alloy
CN109554635A (en) * 2018-12-05 2019-04-02 浙江农林大学暨阳学院 A kind of porous amorphous soft magnet composite wave-suction material and preparation method thereof
CN109778083A (en) * 2019-02-02 2019-05-21 清华大学 High saturated magnetic induction Fe-based amorphous alloy and preparation method thereof
CN109778083B (en) * 2019-02-02 2021-09-10 清华大学 High-saturation magnetic induction intensity iron-based amorphous alloy and preparation method thereof
CN115029647A (en) * 2021-03-05 2022-09-09 南京理工大学 Iron-based amorphous alloy lead with abnormal heat release phenomenon
CN115029647B (en) * 2021-03-05 2023-08-22 南京理工大学 Iron-based amorphous alloy lead wire with abnormal heat release phenomenon

Similar Documents

Publication Publication Date Title
CN105177469A (en) High-ferric-content amorphous magnetically soft alloy and preparing method thereof
CN102543347B (en) A kind of Fe-based nanocrystalline magnetically soft alloy and preparation method thereof
CN108461246B (en) A kind of iron base amorphous magnetically-soft alloy and preparation method thereof
CN110387500B (en) High-magnetic-induction high-frequency iron-based nanocrystalline magnetically soft alloy and preparation method thereof
CN109930080B (en) Copper-free nanocrystalline magnetically soft alloy and preparation method thereof
CN106373690A (en) Nanocrystal magnetically soft alloy with high processing property and high saturation magnetic induction strength, and preparation method therefor
CN109930085B (en) High-temperature-resistant corrosion-resistant high-entropy amorphous soft magnetic alloy and preparation method thereof
CN110541116B (en) Crystallization-controllable iron-based nanocrystalline magnetically soft alloy
CN106917042A (en) A kind of high frequency high magnetic flux density Fe-based nanocrystalline magnetically soft alloy and preparation method thereof
CN110306130A (en) A kind of high Fe content Fe-Si-B-P-Cu-Nb amorphous and nanocrystalline soft magnetic alloy and preparation method
CN103290342B (en) Fe base noncrystal alloy and preparation method thereof
CN103915231B (en) Iron-based amorphous-nanometer crystalline state magnetically soft alloy with high saturation magnetic induction density and application thereof
CN104264080B (en) Preparation process for improving forming ability of Fe-base amorphous alloys
CN102049515B (en) Iron-silicon-aluminum soft magnetic powder and manufacturing method thereof
CN108130493A (en) High saturated magnetic induction, low-coercivity, high magnetic permeability iron cobalt base amorphous alloy material and preparation method thereof
CN109112434A (en) A kind of new iron-based amorphous and nanocrystalline soft magnetic alloy and preparation method thereof
CN101787499B (en) Iron-based nano-crystalline thin ribbon and manufacturing method thereof
CN101503784B (en) High magnetostriction iron based amorphous alloy and preparation thereof
CN102936685A (en) Fe-based magnetically soft alloy with high-saturation magnetic flux density and preparation method of alloy
CN109295401A (en) A kind of new iron-based amorphous and nanocrystalline soft magnetic alloy and preparation method thereof
CN107799258A (en) Cobalt base amorphous magnetically soft alloy material of iron of high saturated magnetic induction and preparation method thereof
CN108597715B (en) A kind of multicomponent iron base amorphous magnetically-soft alloy
CN109754975A (en) Nanometer crystal alloy and preparation method thereof with excellent toughness
CN107267887B (en) Iron-based soft magnetic amorphous steel and its application
Tan et al. Magnetic properties of Fe–Co–Nd–Y–B magnet prepared by suction casting

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20151223

WD01 Invention patent application deemed withdrawn after publication