CN100368584C - Rare earth magnetostrictive material preparation method and the material - Google Patents
Rare earth magnetostrictive material preparation method and the material Download PDFInfo
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- CN100368584C CN100368584C CNB200410037611XA CN200410037611A CN100368584C CN 100368584 C CN100368584 C CN 100368584C CN B200410037611X A CNB200410037611X A CN B200410037611XA CN 200410037611 A CN200410037611 A CN 200410037611A CN 100368584 C CN100368584 C CN 100368584C
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Abstract
The present invention provides a new preparation technology for a rare earth magnetostrictive material. The technology utilizes a rapid setting crystallization technique to prepare rapid setting sheets of magnetostrictive alloy, and the rapid setting sheets are prepared into powder; a powder metallurgic method of cementing or sintering, etc. is adopted to prepare the high-performance rare earth magnetostrictive material. The main phase of the magnetostrictive alloy prepared by the rapid setting crystallization technique is columnar crystal, and the orientation of the columnar crystal of alloy can be effectively controlled. During the process of preparing the magnetostrictive material by the powder metallurgic method, the columnar crystal of alloy can be integrally preserved, and the high-performance magnetostrictive material can be prepared. The technique of the present invention can effectively reduce the preparation cost of the rare earth magnetostrictive material and improve the magnetostatictive performance of the material.
Description
Technical field
The present invention relates to a kind of manufacture method of field of magnetic material middle-weight rare earths magnetostriction materials, and use the rare earth giant magnetostrictive material of this method preparation.
Technical background
Rare earth giant magnetostrictive material (giant magnetostrictive materials, be called for short GMM) be the new and high technology functional materials, compare with traditional magnetostriction materials Ni, Co with piezoelectric ceramics (PZT), the GMM material has particular performances: the magnetostrictive strain that at room temperature has super large, dependent variable reaches 1500-2000ppm, be several times of piezoelectric ceramics, Ni, Co etc. tens times have high energy density (14000-25000J/m
3), effciency of energy transfer height, characteristics such as response speed is fast, reaches μ m level, and power output is big.Have a wide range of applications in fields such as active damping, precision optical machinery control, mechanical transmission mechanism, fuel oil injection system, IT technology.
The initial stage seventies, U.S. doctor clark at first found TbFe
2, DyFe
2At room temperature has very big magnetostriction coefficient Deng binary rare earth compounds.Subsequently, U.S.'s Ames Lab has been developed three rod iron rare earth compound, i.e. ReFe based on this
2Class alloy (R=Dy, Tb, Ho, Sm etc.).Its typical case is represented as Dy
xTb
1-xFe
2-y, it has lower anisotropy field, very big magnetostriction coefficient makes practical application become possibility, and for this reason the ternary alloy application patent, its patent is US3949351.U.S. RTREMA company based on this, making rare earth giant magnetostrictive material commercialization, its trade names in the eighties is TERFENOL-D, it represents composition Tb
0.3Dy
0.7Fe
1.93After the U.S., countries such as Japan, Britain, Sweden have successively carried out the research of this type of material and application, and have formed characteristics and advantage separately rapidly, have occupied one seat in the rare-earth magnetostrictive field.The research of rare-earth magnetostrictive device has become the emphasis and the focus of various countries' research.The rare earth giant magnetostrictive material that uses in the development magnetostrictive device nearly all is to prepare the rare earth magnetostriction rod material by directional solidification method.This preparation method is the production cost height not only, and the consistence of material is difficult to be guaranteed, and this bar fragility is big, in use is easy to generate eddy current, and the generation of eddy current has limited the range of frequency that this material is used.
Adopt powder metallurgic method can prepare bonding and sintering rare-earth magnetostriction materials, can improve the consistence, particularly bonding rare earth magnetostriction materials of material, can eliminate the fragility of material, the eddying effect of reduction material effectively owing to used organic binding agent.The method of traditional preparation process sintering and bonding rare earth magnetostriction materials is earlier raw material to be smelted into common alloy pig, adopts powder metallurgic method to prepare into rare earth giant magnetostrictive material.The shortcoming of this technology is the alloy pig that adopts conventional cast technology to obtain, and is difficult to obtain the desired texture orientation of rare earth giant magnetostrictive material, and therefore, performance is difficult to be improved, and is difficult to satisfy the requirement of use properties.Now in order to improve the performance of rare-earth magnetostrictive, rare earth magnetostriction rod material with directional freeze is a raw material, adopt powder metallurgic method to prepare bonding and sintering rare-earth magnetostriction materials, this technology can obtain desired texture orientation, can improve the performance of rare earth giant magnetostrictive material, but, make the cost of rare earth giant magnetostrictive material higher because raw material is the rare earth magnetostriction rod material of directional freeze, and its performance is limited by the rare earth magnetostriction rod material.Adopt rapid hardening to become the rare-earth magnetostrictive alloy rapid-hardening flake of crystal technique preparation, can obtain the required texture orientation of rare earth giant magnetostrictive material.Simultaneously, this processing method is simple, and the production efficiency height can reduce the cost of material effectively.And because technological process is controlled easily, the stability and the consistence of product are greatly enhanced.
Existing rare earth giant magnetostrictive material patent mainly concentrates on magnetostriction bar aspect, the patent US4378258 of the patent US4308474 of application in 1981 and nineteen eighty-three application, mainly concentrate on the theory and the composition Study of rare earth giant magnetostrictive material, preparation technology is a horizontal zone-melting technique.U.S. Pat 4609402 in 1986 has announced that the vertical area process of smelting prepares rare earth giant magnetostrictive material.U.S. Pat 4770704 in 1988 has announced that a kind of down draw process prepares rare earth giant magnetostrictive material.U.S. Pat 4818304 had been announced rare earth magnetostriction rod material thermomagnetic treatment technology in 1989.U.S. Pat 5114467 in 1992 has announced that a kind of using plasma melting technology prepares rare earth giant magnetostrictive material.Patent about bonding rare earth magnetostriction materials aspect mainly contains two, and the patent US005792284A of application in 1998 relates generally to and uses the tefemol-D bar to make the rare-earth magnetostrictive powder as raw material, then powder and binding agent mixing compression moulding.The patent US6312530B1 of calendar year 2001 application, announced a kind of novel process for preparing rare earth giant magnetostrictive material, main contents comprise, use quick quenching technique to prepare rare-earth magnetostrictive amorphous powder or amorphous thin ribbon, handle (Tb, Dy) Fe of formation crystal grain by crystallization less than 100nm
2Phase is made the bonding rare earth magnetostriction materials then.But this kind technology is difficult to prepare the required best texture orientation of rare earth giant magnetostrictive material.
Summary of the invention
The purpose of this invention is to provide a kind of production efficiency height, production cost low, can effectively improve the rare earth giant magnetostrictive material performance, and be fit to the method for preparing powder metallurgy of the rare earth giant magnetostrictive material of suitability for industrialized production.
Another object of the present invention provides the purposes of the prepared rare earth giant magnetostrictive material of this technology and this material thereof, and this material will be widely used in sensing, energy transformation and actuator field.
According to a first aspect of the invention, provide a kind of method for preparing rare earth giant magnetostrictive material, described method comprises the steps:
The step of preparation rare-earth magnetostrictive alloy rapid-hardening flake becomes crystal technique the alloy liquation to be prepared into the rare-earth magnetostrictive alloy rapid-hardening flake with specific texture by rapid hardening;
The step of preparation rare earth giant magnetostrictive material is made powder to described rare-earth magnetostrictive alloy rapid-hardening flake, by powder metallurgic method described powdered preparation is become high performance rare earth giant magnetostrictive material.
The step of described preparation rapid-hardening flake comprises: with pack into smelting pot in the rapid hardening Cheng Jinglu of alloy raw material, adopt a kind of or described alloy of several method melting of Medium frequency induction melting, high-frequency induction melting, arc melting, resistance wire heating, make described alloy melting, then the alloy liquation is made rare-earth magnetostrictive alloy rapid-hardening flake by quick solidification apparatus, this quick solidification apparatus can adopt the metal wheel or the salver of rotation.In the rapid-hardening flake crystallisation process by control teeming temperature, when cast alloy flow (teeming temperature of rare-earth magnetostrictive alloy solution is 900-1700 ℃, the amount of metal wheel that the rare-earth magnetostrictive alloy solution waters rotation is 0.001-50.0Kg/min) and the rotating speed of the metal wheel of controls revolution or salver control the crystallisation process of rapid-hardening flake, the water-cooled metal of rotation is taken turns or the rotating speed of salver is 0.1-50.0m/s.For example be 1m/s, 5m/s, 10m/s or 15m/s.
Described alloy raw material is selected from following raw material: metal or alloy raw materials such as rare earth, iron are pressed stoichiometric equation RE-Fe
(2+ δ-y)-M
yProportioning, here, RE represents one or more thuliums in 17 kinds of rare earth elements that comprise Sc, Y; M represents among Ni, Co, Mg, Ta, Nb, Zr, Hf, V, W, Mo, Si and the B one or more ,-0.2≤δ≤0.2,0≤y≤1.
The principal phase of described rapid-hardening flake is the column crystal along the cooling direction, the rich rare earth crystal boundary uniform distribution that hands down; The column crystal width is 0.01 μ m-10mm, and length is 0.01 μ m-10mm.
Fig. 1 is that composition is Tb
0.3Dy
0.7Fe
1.98The metallograph of rapid-hardening flake, magnification is 200 times.That white in the drawings strip partly is column crystal is principal phase (Tb, Dy) Fe
2, the dark-coloured part between the white strip is rich rare earth phase.
Described rapid-hardening flake can form different texture along the length direction of column crystal, comprise＜111,＜112,＜110 etc. direction.The chemical ingredients of described rapid-hardening flake be RE-Fe (
2+ δ-y)-M
y, here, RE represents one or more thuliums in 17 kinds of rare earth elements that comprise Sc, Y; M represents among Ni, Co, Mg, Ta, Nb, Zr, Hf, V, W, Mo, Si and the B one or more, 0≤y≤1 ,-0.2≤δ≤0.2.The mean thickness of described rapid-hardening flake is 0.01-10.0mm.
Before described rare-earth magnetostrictive alloy rapid-hardening flake is made powder, can carry out hydrogen treatment in flakes to rapid hardening, described hydrogen treatment is carried out in hydrogenation furnace, comprise and inhale hydrogen and these two steps of dehydrogenation, in inhaling the hydrogen step, its pressure remains between the 0.01-10MPa, and the temperature when inhaling hydrogen is 10-800 ℃, and inhaling the hydrogen time is 0.1-50h; When dehydrogenation, desorption temperature is in 100-1000 ℃, and dehydrogenation time is 0.01-50h; One of make then with the following method hydrotreated rapid-hardening flake is made powdered alloy: airflow milling method, ball milling method and mill method.Perhaps rapid-hardening flake is not carried out hydrogen treatment, directly use Mechanical Crushing that rapid-hardening flake is made powdered alloy.
In addition, powdered alloy is mixed with binding agent, the ratio of used binding agent is 0.1-70% (volume percent), the blended powder is made the cementing magnetostrictive blank through briquetting process, and described blank obtains the rare-earth bound magnetostriction materials or the blended powder is directly made the bonding rare earth magnetostriction materials with injection moulding method through solidification treatment.Described binding agent is a kind of of thermosetting adhesive (Resins, epoxy, resol etc.) and thermoplastic adhesive (nylon, polypropylene, polyethylene, polyvinyl chloride etc.).Perhaps, described powdered alloy is directly made the magnetostriction blank through briquetting process, and described blank obtains the sintering rare-earth magnetostriction materials through sintering process in sintering oven.Described sintering oven can be vacuum sintering furnace, and sintering temperature is 700-1600 ℃, and the time is 0.1-8h.
In addition, described forming method adopts no pressing under magnetic field or magnetic field orientating moulding.One of described forming method comprises the steps: pre-molding in the magnetic field orientating molding device, and institute's plus-pressure is 0.1-10MPa; Final molding in isostatic cool pressing obtains the cementing magnetostrictive blank then, and institute's plus-pressure is 5-100MPa.Described another forming method is once shaped in the magnetic field orientating molding device, and institute's plus-pressure is 0.1-100MPa.
According to a second aspect of the invention, provide a kind of use the above-mentioned prepared rare earth giant magnetostrictive material of method for preparing rare earth giant magnetostrictive material have axial orientation＜110,＜112 or＜111〉texture one or more.
Advantage of the present invention is: the existing rare earth magnetostriction rod material technological process of production is long, production cost is high, and the rare earth magnetostriction rod material fragility of being produced is big, and eddy-current loss is big, be difficult to use under high frequency, and the consistence of material property and stability is not high.And the bonding and the sintering rare-earth magnetostriction materials that adopt rapid hardening of the present invention to become crystal technique to produce, can improve the mechanical property of material, particularly the bonding rare earth magnetostriction materials have reduced the fragility of material, the eddy-current loss of lightening material effectively, making rare earth giant magnetostrictive material be applied to high frequency becomes possibility.The bonding rare earth magnetostriction materials can also be according to using needs to prepare the shaped piece of different shape complexity.Owing to adopt rapid hardening to become crystal technique can prepare to have＜110,＜112 or＜111〉the rare-earth magnetostrictive alloy rapid-hardening flake that is orientated reach and prepare rare earth giant magnetostrictive material by described powder metallurgic method, therefore, can improve performance and the consistence and the reliability of rare earth giant magnetostrictive material.Can also improve the production efficiency of rare earth giant magnetostrictive material significantly, reduce cost, be fit to suitability for industrialized production.
Description of drawings
Fig. 1 is composition Tb
0.3Dy
0.7Fe
1.98The metallograph of rapid-hardening flake.
Embodiment
Describe the present invention below in conjunction with embodiment, so that understand purpose of the present invention, characteristic and advantage better.Though the present invention is described in conjunction with this specific embodiment, is not intended that the invention be limited to described specific embodiment.On the contrary, the embodiment that substitutes, improves and be equal to the embodiment that can be included in the protection domain defined in the claim of the present invention carries out all belongs to protection scope of the present invention.
The method for preparing rare earth giant magnetostrictive material of the present invention comprises the steps:
(1) adopts rapid hardening to become crystal technique, prepare and possess the rare-earth magnetostrictive rapid-hardening flake that institute's texture that requires is orientated.Tb with preparation rare-earth magnetostrictive rapid-hardening flake, Dy, raw materials such as Fe are packed in the rapid hardening Cheng Jinglu, alloy melting adopts the Medium frequency induction melting, the high-frequency induction melting, arc melting, resistance wire adds one or more that pine for, in preparation rapid-hardening flake process, the rotating speed of rotating metallic wheel or salver is controlled at 0.1-50m/s, pass through teeming temperature, the flow of alloy during cast, the rotating speed of metal wheel or salver is controlled the crystallisation process of rapid-hardening flake, by control to the rapid-hardening flake crystallisation process, realization is to the control of rapid-hardening flake crystallization texture, prepare to have＜110,＜112 〉,＜111〉the rare-earth magnetostrictive alloy rapid-hardening flake of texture.
(2) rare-earth magnetostrictive alloy rapid-hardening flake is carried out hydrogen treatment.Hydrogen treatment is carried out in the hydrogenation furnace of special use, comprises hydrogen and these two processes of dehydrogenation of inhaling.In inhaling the hydrogen process, inhaling the hydrogen temperature is 10-800 ℃, and hydrogen pressure is controlled between the 0.01-10MPa.Adopt the source of the gas housing (to declare patent, the patent No.: ZL02157925.3) to quick-fried jar of air feed of hydrogen.By the hydrogen flow in the adjustable integration gold plaque of the manual throttle valve on the source of the gas housing raw material suction hydrogen process.In inhaling the hydrogen process, the pressure that hydrogen is quick-fried jar can keep stable, the hydrogen of the mass flowmeter record raw material on the source of the gas housing.Inhale and carry out dehydrogenation after hydrogen is finished, desorption temperature is at 100-1000 ℃, and dehydrogenation time is 0.01-50h.
(3) hydrotreated rapid-hardening flake pulverizing is obtained the rare-earth magnetostrictive powder.The powder process mode can adopt a kind of of ball milling, mill or airflow milling.
(4) rare-earth magnetostrictive alloy rapid-hardening flake is directly obtained the rare-earth magnetostrictive powder by mechanical disintegration powder process without the hydrogen fragmentation.Machinery powder process comprises mill, ball milling, airflow milling etc.
(5) step (3) or (4) rare-earth magnetostrictive powder and a certain proportion of binding agent are mixed, the powder that mixes is made blank through moulding process.Blank obtains the bonding rare earth magnetostriction materials through solidification treatment.
(6) step (3) or (4) rare-earth magnetostrictive powder and a certain proportion of binding agent are mixed, the powder that mixes is obtained the rare earth giant magnetostrictive material finished product through injection molding technique.
(7) the rare-earth magnetostrictive powder of step (3) or (4) preparation is made blank by compression moulding technology.Blank obtains the sintering rare-earth magnetostriction materials through sintering process in sintering oven.
In above-mentioned steps (5) or (6), the ratio of used binding agent is 0.1-70% (volume percent).
Used moulding process has two kinds in above-mentioned steps (5), (6) or (7): no pressing under magnetic field and magnetic field orientating moulding.
Curing process in the above-mentioned steps (5) is: 50-600 ℃ * 0.05-10h.
In the above-mentioned steps (7), sintering process is carried out in vacuum sintering furnace, and sintering process is: 700-1600 ℃ * 0.1-8h.
The composition of the rare-earth magnetostrictive alloy rapid-hardening flake that the present invention is prepared is RE-Fe
(2+ δ-y)-M
y, here, RE represents one or more thuliums in 17 kinds of rare earth elements that comprise Sc, Y; M represents among Ni, Co, Mg, Ta, Nb, Zr, Hf, V, W, Mo, Si and the B one or more, 0≤y≤1 ,-0.2≤δ≤0.2.
The rare-earth magnetostrictive alloy rapid-hardening flake of the present invention preparation is a columnar crystal structure, adopt the prepared rare earth giant magnetostrictive material of powder metallurgic method have axial orientation＜110,＜112,＜in 111〉texture one or more.
Embodiment
The raw material that with purity is 99.5%Tb, 99.5%Dy and 99.5%Fe is by metering-type Tb
0.3Dy
0.7Fe
1.96(atomic ratio) proportioning, total proportional quantity are 20kg.The raw material 20kg that proportioning is good packs in the smelting pot of rapid hardening Cheng Jinglu, adopt Frequency Induction Heating, make alloy melting, and be heated to 1500 ℃, form the alloy liquation, make the alloy liquation get rid of into rare-earth magnetostrictive alloy rapid-hardening flake by the water-cooled copper wheel of rotation, the rotating speed of the water-cooled copper wheel of rotation is 1.5m/s, and the flow during cast is 3kg/min.The thickness of the rare-earth magnetostrictive alloy rapid-hardening flake of its preparation is 0.2-0.25mm.Rare-earth magnetostrictive alloy rapid-hardening flake is carried out hydrogen treatment, and (density of hydrogen is 99.99%) whole suction hydrogen process continues 2h, and the pressure when inhaling hydrogen is 0.3MPa.Certain embodiments is carried out at 400 ℃, and the time is 3h.Use airflow milling technology to make powdered alloy hydrotreated rare-earth magnetostrictive alloy slice, mix with the Resins, epoxy of 10% (volume ratio), pre-molding in the magnetic field orientating molding device, institute's plus-pressure is 5MPa; Final molding in isostatic cool pressing obtains the cementing magnetostrictive blank then, and institute's plus-pressure is 30MPa.Be cured processing putting into vacuum drying oven through the magnetostriction blank of isostatic cool pressing, the temperature of solidification treatment is 150 ℃, and the time is 1h.Finally obtain the bonding rare earth magnetostriction materials, the performance of this material is under 10MPa precompression and 1KOe magnetic field, λ
//=1125ppm; d
33=(d λ/dH)
m=1.80ppm/Oe; Electromechanical coupling factor K
33=0.55.This material can be used for making the underwater acoustic transducer of sonar system.
Embodiment 2
The raw material that with purity is 99.9%Tb, 99.9%Dy, 99.9%Ho and 99.95%Fe is by metering-type Tb
0.25Dy
0.70Ho
0.05Fe
1.95(atomic ratio) proportioning, total proportional quantity are 10kg.The raw material 10kg that proportioning is good packs in the smelting pot of rapid hardening Cheng Jinglu, adopt electric-arc heating, make alloy melting, and be heated to 1345 ℃, form the alloy liquation, make the alloy liquation get rid of into rare-earth magnetostrictive alloy rapid-hardening flake by the water-cooled copper wheel of rotation, the rotating speed of the water-cooled copper wheel of rotation is 5m/s, and the flow during cast is 15kg/min.The thickness of the rapid-hardening flake of its preparation is 0.1-0.15mm.Rapid-hardening flake is carried out hydrogen treatment (density of hydrogen is 99.99%), and whole suction hydrogen process continues 1h, and the pressure when inhaling hydrogen is 0.2MPa.Certain embodiments is carried out at 500 ℃, and the time is 2h.Use ball-milling technology to make powdered alloy hydrotreated rapid-hardening flake, mix with the Resins, epoxy of 20% (volume ratio), pre-molding in the magnetic field orientating molding device, institute's plus-pressure is 5MPa; Final molding in isostatic cool pressing obtains the cementing magnetostrictive blank then, and institute's plus-pressure is 20MPa.Be cured processing putting into vacuum drying oven through the magnetostriction blank of isostatic cool pressing, the temperature of solidification treatment is 170 ℃, and the time is 2h.Finally obtain the bonding rare earth magnetostriction materials, the performance of this material is under 10MPa precompression and 1KOe magnetic field, λ
//=1250ppm; d
33=(d λ/dH)
m=1.96ppm/Oe; Electromechanical coupling factor K
33=0.65.Use this material and can be used for making fuel oil injection system.
Embodiment 3
The raw material that with purity is 99.9%Tb, 99.9%Dy and 99.9%Fe is by metering-type Tb
0.25Dy
0.75Fe
1.95(atomic ratio) proportioning, total proportional quantity are 10kg.The raw material 10kg that proportioning is good packs in the crucible of rapid hardening Cheng Jinglu, the heating of employing resistance wire, make alloy melting, and be heated to 1500 ℃ and form the alloy liquations, make the alloy liquation get rid of into the rare-earth magnetostrictive alloy slice by the water-cooled molybdenum wheel of rotation, the rotating speed of the water-cooled molybdenum wheel of rotation is 7.5m/s, and the flow during cast is 25kg/min.The thickness of the rare-earth magnetostrictive alloy rapid-hardening flake of its preparation is 0.05-0.10mm.Rapid-hardening flake is carried out hydrogen treatment, and whole suction hydrogen process continues 1.5h, and the pressure when inhaling hydrogen is 0.3MPa.Certain embodiments is carried out at 550 ℃, and the time is 1.5h.Use airflow milling technology to make powdered alloy hydrotreated rapid-hardening flake, pre-molding in the magnetic field orientating molding device, institute's plus-pressure is 5MPa; Final molding in isostatic cool pressing obtains the magnetostriction blank then, and institute's plus-pressure is 20MPa.Carry out sintering putting into vacuum sintering furnace through the magnetostriction blank of isostatic cool pressing, sintering temperature is 1100 ℃, and the time is 1h.Finally obtain the sintering rare-earth magnetostriction materials, the performance of material is under 10MPa precompression and 1KOe magnetic field, λ
//=1300ppm; d
33=(d λ/dH)
m=2.1ppm/Oe; Electromechanical coupling factor K
33=0.55.
Embodiment 4
The raw material that with purity is 99.5%Tb, 99.0%Dy, 99.5%Mn and 99.5%Fe is by metering-type Tb
0.3Dy
0.7Fe
1.85Mn
0.15(atomic ratio) proportioning, total proportional quantity are 15kg.The raw material 15kg that proportioning is good packs in the smelting pot of rapid hardening Cheng Jinglu, adopt high-frequency induction heating, make alloy melting and be heated to 1250 ℃, form the alloy liquation, make the alloy liquation get rid of into rare-earth magnetostrictive alloy rapid-hardening flake by the water-cooled molybdenum wheel of rotation, the rotating speed of the water-cooled molybdenum wheel of rotation is 3.5m/s, and the flow during cast is 8kg/min.The thickness of the rare-earth magnetostrictive alloy rapid-hardening flake of its preparation is 0.15-0.20mm.Use ball-milling technology to make powdered alloy the rare-earth magnetostrictive alloy slice, pre-molding in the magnetic field orientating molding device, institute's plus-pressure is 5MPa; Final molding in isostatic cool pressing obtains the magnetostriction blank then, and institute's plus-pressure is 30MPa.Carry out sintering putting into vacuum sintering furnace through the magnetostriction blank of isostatic cool pressing, the temperature of sintering processes is 1050 ℃, and the time is 1.5h, finally obtains the sintering rare-earth magnetostriction materials, and the performance of this material is under 10MPa precompression and 1KOe magnetic field, λ
//=1150ppm; d
33=(d λ/dH)
m=1.90ppm/Oe; Electromechanical coupling factor K
33=0.50.
Embodiment 5
The raw material that with purity is 99.5%Tb, 99.5%Dy and 99.5%Fe is by metering-type Tb
0.3Dy
0.7Fe
1.99(atomic ratio) proportioning, total proportional quantity are 15kg.The raw material 15kg that proportioning is good packs in the smelting pot of rapid hardening Cheng Jinglu, adopt Frequency Induction Heating, make alloy melting and be heated to 1250 ℃, form the alloy liquation, make the alloy liquation get rid of into rare-earth magnetostrictive alloy rapid-hardening flake by the water-cooled molybdenum wheel of rotation, the rotating speed of the water-cooled molybdenum wheel of rotation is 5m/s, and the flow during cast is 13kg/min.The thickness of the rare-earth magnetostrictive alloy rapid-hardening flake of its preparation is 0.05-0.10mm.Use mill technology to make powdered alloy the rare-earth magnetostrictive alloy slice, adopt one time the magnetic field orientating moulding process, obtain the magnetostriction blank, institute's plus-pressure is 30MPa.The magnetostriction blank is put into vacuum sintering furnace carry out sintering, the temperature of sintering processes is 1050 ℃, and the time is 1.5h, finally obtains the sintering rare-earth magnetostriction materials, and the performance of this material is under 10MPa precompression and 1KOe magnetic field, λ
//=1100ppm; d
33=(d λ/dH)
m=2ppm/Oe; Electromechanical coupling factor K
33=0.55.
Embodiment 6
The raw material that with purity is 99.5%Tb, 99.5%Dy and 99.5%Fe is by metering-type Tb
0.25Dy
0.75Fe
1.95(atomic ratio) proportioning, total proportional quantity are 10kg.The raw material 10kg that proportioning is good packs in the smelting pot of rapid hardening Cheng Jinglu, adopt electric-arc heating, make alloy melting, and be heated to 1345 ℃, form the alloy liquation, make the alloy liquation get rid of into the rare-earth magnetostrictive alloy slice by the water-cooled copper wheel of rotation, the rotating speed of the water-cooled copper wheel of rotation is 4m/s, and the flow during cast is 12kg/min.The thickness of the rare-earth magnetostrictive alloy rapid-hardening flake of its preparation is 0.1-0.15mm.Rapid-hardening flake is carried out hydrogen treatment (density of hydrogen is 99.99%), and whole suction hydrogen process continues 1h, and the pressure when inhaling hydrogen is 0.2MPa.Certain embodiments is carried out at 500 ℃, and the time is 2h.Use ball-milling technology to make powdered alloy hydrotreated rapid-hardening flake, mix with the nylon of 20% (volume ratio), adopt injection molding technique in magnetic field, finally obtain the bonding rare earth magnetostriction materials, the performance of this material is under 10MPa precompression and 3KOe magnetic field, λ
//=1400ppm; d
33=(d λ/dH)
m=2ppm/Oe; Electromechanical coupling factor K
33=0.65.
Though this specification sheets has only been narrated several specific embodiment of the present invention, should be appreciated that the present invention can be implemented by many other particular forms, and do not break away from design of the present invention and protection domain.Cited example is just in order to illustrate the present invention, do not have restrictedly, and the present invention is not limited to the details that goes out given herein, can improve in the scope of claim of the present invention and in the four corner that equates.
Claims (20)
1. method for preparing rare earth giant magnetostrictive material, it is characterized in that: the step of preparation rare-earth magnetostrictive alloy rapid-hardening flake, become crystal technique with the melting of corresponding raw material process by rapid hardening, cooling is prepared into rare-earth magnetostrictive alloy rapid-hardening flake fast, this rare-earth magnetostrictive alloy rapid-hardening flake has＜and 111 〉,＜112 〉,＜110〉one or more in the texture, the mean thickness of rapid-hardening flake is 0.01-10.0mm, the principal phase of rapid-hardening flake is the column crystal along the cooling direction, the rich rare earth crystal boundary uniform distribution that hands down, the column crystal width is 0.01 μ m-10mm, length is 0.01 μ m-10mm, and the chemical ingredients of rapid-hardening flake is RE-Fe
(2+ δ-y)-M
y, here, RE represents one or more in 17 kinds of rare earth elements that comprise Sc, Y; M represents among Ni, Co, Mg, Ta, Nb, Zr, Hf, V, W, Mo, Mn, Si and the B one or more ,-0.2≤δ≤0.2,0≤y≤1;
Use powder metallurgic method to prepare the step of rare earth giant magnetostrictive material, described rare-earth magnetostrictive alloy rapid-hardening flake is made powder, then described powdered preparation is become high performance rare earth giant magnetostrictive material;
The rapid hardening that wherein prepares rare-earth magnetostrictive alloy rapid-hardening flake becomes crystal technique to comprise the steps:
A) preparation process of rare-earth magnetostrictive alloy rapid-hardening flake is carried out at the state of vacuum or protection of inert gas;
B) one or more method heating rare-earth magnetostrictive raw materials wherein with Medium frequency induction melting, high-frequency induction melting, arc melting, resistance wire heating melting form the alloy liquation;
C) make rare-earth magnetostrictive alloy liquation by rotation water-cooled or gas cooling metal wheel or salver fast cooling obtain rare-earth magnetostrictive alloy rapid-hardening flake.
2. according to the method for claim 1, it is characterized in that described rare-earth magnetostrictive alloy rapid-hardening flake makes powder and comprise and use hydrogen treatment or do not use hydrotreated method.
3. according to the method for claim 1, it is characterized in that the step of described preparation rare earth giant magnetostrictive material comprises:
The rare-earth magnetostrictive powdered alloy is mixed with binding agent, the blended powder is made the cementing magnetostrictive blank through briquetting process, described blank obtains the bonding rare earth magnetostriction materials through solidification treatment.
4. according to the method for claim 1, it is characterized in that the step of described preparation rare earth giant magnetostrictive material comprises:
The rare-earth magnetostrictive powdered alloy is mixed with binding agent, the blended powder is made the bonding rare earth magnetostriction materials through injection moulding method.
5. according to the method for claim 1, it is characterized in that the step of described preparation rare earth giant magnetostrictive material comprises:
The rare-earth magnetostrictive powdered alloy is made the magnetostriction blank through compression moulding, and described blank obtains rare earth giant magnetostrictive material through sintering process in sintering oven.
6. according to the method for claim 1, it is characterized in that: the metal wheel of rotation or the rotating speed of salver are 0.1-50.0m/s, and rare-earth magnetostrictive alloy liquation waters the metal wheel of rotation or the amount of salver is 0.001-50.0Kg/min.
7. according to the method for claim 1, it is characterized in that: the metal wheel of rotation or salver material are a kind of or its alloy in copper, molybdenum, titanium, tantalum, tungsten, the zirconium.
8. according to the method for claim 1, it is characterized in that: the main chemical compositions of rapid-hardening flake is Tb
xDy
1-xFe
1.8-2.0, 0≤x≤1.
9. according to the method for claim 2, it is characterized in that described rare-earth magnetostrictive alloy rapid-hardening flake makes the powder step and comprise: rare-earth magnetostrictive alloy rapid-hardening flake is carried out hydrogen treatment, one of make then with the following method the rare-earth magnetostrictive alloy rapid-hardening flake after the hydrogen treatment is made powder: airflow milling method, ball milling method and mill method.
10. according to the method for claim 2, it is characterized in that described hydrogen treatment carries out in hydrogenation furnace, comprise and inhale hydrogen and these two steps of dehydrogenation, in inhaling the hydrogen step, hydrogen pressure remains between the 0.01Mpa-10MPa, and inhaling the hydrogen temperature is 10-800 ℃, and the time is 0.01-50h; In dehydrogenation step, desorption temperature is between 100-1000 ℃, and dehydrogenation time is 0.01-50h.
11. method according to claim 2, it is characterized in that described rare-earth magnetostrictive alloy rapid-hardening flake makes the powder step and comprise: rare-earth magnetostrictive alloy rapid-hardening flake is not carried out hydrogen treatment, directly use Mechanical Crushing that rare-earth magnetostrictive alloy rapid-hardening flake is made powder, Mechanical Crushing refers to ball milling or mill or airflow milling.
12. the method according to claim 3 is characterized in that: solidification value is 50～600 ℃, and be 0.05～10h set time.
13. according to the method for claim 3 or 4, the ratio of used binding agent is 0.1-70% (volume percent), described binding agent is thermosetting adhesive or thermoplastic adhesive.
14. according to the method for claim 5, it is characterized in that described sintering process carries out in vacuum sintering furnace, sintering temperature is 700-1600 ℃, the time is 0.1-8h.
15., it is characterized in that described forming method adopts one of no pressing under magnetic field or magnetic field orientating moulding according to the method for claim 3 or 5.
16. according to claim 15 method, it is characterized in that described forming method comprises the steps: pre-molding in the magnetic field orientating molding device, institute's plus-pressure is 0.1MPa-10MPa; Final molding in isostatic cool pressing then, institute's plus-pressure is 5-100MPa.
17. according to claim 15 method, it is characterized in that described forming method comprises the steps: once shaped in magnetic field, institute's plus-pressure is 0.1-100MPa.
18. according to claim 15 method, it is characterized in that described forming method comprises the steps: not have under the magnetic field, pre-molding in molding device, institute's plus-pressure is 0.1MPa-10MPa; Final molding in isostatic cool pressing then, institute's plus-pressure is 5-100MPa.
19. according to claim 15 method, it is characterized in that described forming method comprises the steps: not have the magnetic field once shaped, institute's plus-pressure is 0.1-100MPa.
20. according to the method for claim 1, it is characterized in that described rare earth giant magnetostrictive material have＜110,＜112 and＜in 111〉texture one or more.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1743479B (en) * | 2005-10-17 | 2010-10-06 | 有研稀土新材料股份有限公司 | Method for preparing rare-earth super magnetostrictive material using main-auxiliary alloy powder metallurgy |
| EP2390377B1 (en) * | 2009-01-23 | 2017-09-27 | Alps Electric Co., Ltd. | Iron-based soft magnetic alloy and dust core comprising the iron-based soft magnetic alloy |
| CN103451734A (en) * | 2012-05-29 | 2013-12-18 | 太仓子午电气有限公司 | Preparation method of monocrystal giant magnetostrictive material |
| CN103862052B (en) * | 2012-12-17 | 2017-10-31 | 北京中科三环高技术股份有限公司 | A kind of manufacturing process of isotropism neodymium iron boron magnetic body |
| CN104575478B (en) * | 2013-10-11 | 2018-03-20 | 有研稀土新材料股份有限公司 | A kind of driving element and the Re Super Magnetostrictive Transducer comprising the driving element |
| CN104550944B (en) * | 2013-10-11 | 2017-05-03 | 有研稀土新材料股份有限公司 | Preparation method of composite rare earth magnetostriction material |
| EP3124930B1 (en) * | 2014-03-28 | 2021-04-21 | Hitachi Metals, Ltd. | Soft magnetic component for torque sensor, and torque sensor using same |
| CN106636846A (en) * | 2016-12-15 | 2017-05-10 | 南京理工大学 | MnCoSi-based alloy with lowered metamagnetic phase change critical field |
| CN108220739A (en) * | 2016-12-22 | 2018-06-29 | 北京有色金属研究总院 | A kind of Y-Fe bases rare earth hydrogen storage material and preparation method thereof |
| CN109811163A (en) * | 2017-11-20 | 2019-05-28 | 有研稀土新材料股份有限公司 | A kind of preparation method of sintering rare-earth giant magnetostrictive material |
| CN111326303A (en) * | 2020-03-04 | 2020-06-23 | 南京大学 | Method for manufacturing rare earth alloy spherical single crystal magnetic powder and <111> oriented rare earth giant magnetostrictive material |
| CN112575237B (en) * | 2020-12-09 | 2021-11-02 | 南京航空航天大学 | Co-Ni-Mn-Si-Tb giant magnetostrictive material and preparation method thereof |
| CN115770877A (en) * | 2022-12-15 | 2023-03-10 | 洛阳科威钨钼有限公司 | Preparation method of amorphous strip cooling roller |
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