CN103647019B - The giant magnetostriction material of a kind of light rare earth modulation and preparation technology thereof - Google Patents

The giant magnetostriction material of a kind of light rare earth modulation and preparation technology thereof Download PDF

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CN103647019B
CN103647019B CN201310617774.4A CN201310617774A CN103647019B CN 103647019 B CN103647019 B CN 103647019B CN 201310617774 A CN201310617774 A CN 201310617774A CN 103647019 B CN103647019 B CN 103647019B
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rare earth
light rare
giant magnetostriction
giant
melting
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CN103647019A (en
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时阳光
胡成超
阚彩侠
施大宁
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Nanjing University of Aeronautics and Astronautics
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Abstract

The present invention provides a kind of trace to add light rare earth to conventional compensation system and by controlling the method that fusion process directly obtains columnar orientation crystalline substance giant magnetostriction material.The method utilizes big Spontaneous magnetostriction and the feature of low magnetocrystalline anisotropy of light rare earth Pr and Nd, existing compensation system is optimized, and in melting, add supercool program, directly obtain and there is the Rare-Earth Giant Magnetostrictive Materials that part<100>or<111>is orientated.The method is simple, time-consuming and energy consumption cost, provides a kind of approach for quickly preparing oriented crystal.

Description

The giant magnetostriction material of a kind of light rare earth modulation and preparation technology thereof
Technical field:
The present invention relates to giant magnetostriction material and the preparation technology thereof of a kind of light rare earth modulation, it belongs to metal material field.
Background technology:
Rare-Earth Giant Magnetostrictive Materials is the new function material of the exploitation eighties, is primarily referred to as RFe2(R=rare earth) rare earth Cubic AlN compound between metal.The efficient conversion that this kind of material is capable of between electromagnetic energy and mechanical energy.The U.S. The O.D.McMasters of the A.E.Clark in naval surface weapon research center etc. and USDOE's Ames Lab Cooperation, is compensated by magnetocrystalline anisotropy between rare earth, has obtained not only having big low field magnetostriction but also have low The Tb of magnetocrystalline anisotropy0.27Dy0.73Fe2Alloy.This invention be applied as Patent No. US3949351 and The United States Patent (USP) of US4308474.At the end of the eighties, the RTREMA company of famous American with this counterfeit dualization alloy is Basis makes rare earth giant magnetostrictive material commercialization, its product designation Terfenol-D.Traditional rare earth giant magnetostrictive driver material The preparation technology of material is grasped by the U.S., mostly such as Patent No. US4609402 of 1986, the Patent No. of 1988 US4770704, the United States Patent (USP) of Patent No. US4818304 of 1989 disclose respectively vertical area fusion method, The method that pulling method, magnetic-field annealing method etc. prepare rare earth giant magnetostrictive material.Within 2002, Japanese researchers utilizes microgravity bar <111>orientation TbDyFe alloy is obtained under part.China Patent Publication No. CN1232275A rare-earth-iron super magnetostriction material Material and manufacturing process provide a kind of prepare<110>and are oriented to main manufacturing process.China Patent Publication No. CN1435851A giant magnetostriction material and manufacturing process provide one<113>and are oriented to main giant magnetostriction material Manufacturing process.Although the magnetoelastic properties of the material that directional solidification method obtains is significantly improved, but preparation orientation Alloy, need first to obtain alloy mother metal and then regrow at crystal growing furnace and pilot process length, can not be interrupted, make The preparation cost obtaining material increases and the longest.
Single ion model calculates and shows PrFe2Spontaneous magnetostriction coefficient lambda at absolute zero111Reach 5600ppm, than TbFe2111=4400ppm) and DyFe2111=4200ppm) there is higher theoretical magnetostriction value.And NdFe2 The magnetostriction coefficient of absolute zero is also reached 2000ppm, compares HoFe2111=1600ppm) big 25%. Additionally, the resource of light rare earth Pr, Nd is abundanter, than the low price of heavy rare earth.So many work are devoted to light The exploitation of rare earth giant magnetostrictive material, CN1096546 as open in Chinese patent, CN1125265, CN1232275, CN1435851 etc. all take partially substituted method to be added to by Pr in the counterfeit dualization alloy of TbDyFe base, it is intended that Obtain the new material of high Pr content high-magnetostriction.But the light rare earth of excess adds membership and causes the generation of the second phase, sternly Ghost image rings the magnetoelastic properties of material.We find in the development process of light rare earth giant magnetostriction material, appropriate Light rare earth Pr, Nd introduce the magnetocrystalline anisotropy that can effectively reduce TbDyFe base magnetic striction material.Additionally, I Can directly obtain partially oriented magnetostriction materials by controlling fusion process, so make keeping material excellent While Magnetostriction, the preparation cost of material is greatly reduced.
Summary of the invention:
The present invention provides the giant magnetostriction material and preparation technology thereof that a kind of light rare earth modulates.Light rare earth base is used to compensate system System trace substitutes traditional rare earth and compensates system and control fusion process and directly obtain columnar orientation crystalline substance giant magnetostriction material.
The present invention adopts the following technical scheme that the giant magnetostriction material that a kind of light rare earth is modulated, and described material is by the most former Son is than the alloy of composition: (RR ')1-x(LR0.9Tb0.1)x(Fe1-yMy)z, (RR ') represent such as Tb0.27Dy0.73、Tb0.14Ho0.86's Tradition magnetocrystalline anisotropy compensates system, LR represent light rare earth Pr or Nd, M represent such as Ni, Co, Mn VIIB, The one of group VIIIB element or composition, wherein 0≤x≤0.35,0≤y≤0.2,1.85≤z≤2.1.
The present invention also adopts the following technical scheme that the preparation technology of the giant magnetostriction material that a kind of light rare earth modulates, its bag Include following steps:
1). preparation of raw material: employing purity is one or several in rare earth Tb, Dy, Ho, Pr, Nd of 99.9% With one or several in the transition-metal Fe that purity is 99.9%, Co, Ni, Mn according to stoichiometric equation (RR’)1-x(LR0.9Tb0.1)x(Fe1-yMy)zAtomic ratio proportioning;
2). conventional vacuum arc melting: by step 1) metal simple-substance that obtains puts into the copper of vacuum arc melting furnace intracavity In crucible, use rare earth under, transition metal is at upper modes of emplacement;Close furnace chamber, take out in advance with mechanical pump and add molecular pump The continuous mode taken out, until vacuum arrives 10 in furnace chamber-5Below Pa, is filled with argon shield gas to subatmospheric 0.06-0.09MPa;Use conventional melting 4 times repeatedly, until alloying component is uniform;
3). rapid cooling melting: recirculated water shifts to frozen water pattern, i.e. using temperature is that the frozen water of 0 degree Celsius is as recirculated water; Electric arc melting alloy, to molten condition, the alloy material that high speed electromagnetic stirring is melted, maintains 10-20 second, closes rapidly Arc current, and maintain high speed electromagnetic to stir 5-10 second, treat that material is cooled to room temperature;
4). vacuum annealing: material is taken out and carries out the 1-15 days time of vacuum annealing at 300-1000 degree Celsius, annealing After obtain the columnar orientation crystalline substance giant magnetostriction material of well-crystallized.
Further, the giant magnetostriction material of described light rare earth modulation has substantial amounts of column crystal to be formed along cooling direction.
There is advantages that
(1) introduce light rare earth and modulate existing heavy rare earth anisotropy compensation system, be prepared for magnetocrystalline anisotropy lower Multielement rare earth giant magnetostriction material, and use supercool melting technique one step to obtain partially oriented alloy, and traditional The vertical area fusion method preparing monocrystalline or oriented crystal generally requires substantial amounts of power consumption and time;
(2) present invention the most easily implements, time-consuming and energy consumption cost, for efficiently preparing rare earth orientation magnetostriction Material provides a kind of new approach.
Accompanying drawing illustrates:
Fig. 1 is rare earth component (Tb, Dy, Nd) or (Tb, Dy, Pr) phasor (face of polynary giant magnetostriction material Color depth is shallow represents composition).
Fig. 2 is Tb0.253Dy0.657Nd0.09(Fe0.9Co0.1)1.93The section microstructure of column crystal.
Fig. 3 is Tb0.253Dy0.657Nd0.09(Fe0.9Co0.1)1.93Column crystal bulk and x-ray diffractogram of powder spectrum.
Fig. 4 is Tb0.219Dy0.511Pr0.27(Fe0.9Co0.1)1.93Column crystal bulk and x-ray diffractogram of powder spectrum.
Fig. 5 is the (Tb of No yield point0.27Dy0.73)1-x(Nd0.9Tb0.1)x(Fe0.9Co0.1)1.93The magnetostriction of alloy and magnetocrystalline Opposite sex constant K1The ratio of absolute value with composition transfer curve.
Fig. 6 is Tb0.253Dy0.657Nd0.09(Fe0.9Co0.1)1.93The magnetostriction contrast of column crystal and No yield point alloy.
Detailed description of the invention:
Refer to shown in Fig. 1 to Fig. 6, the present invention compensates system trace by light rare earth base and substitutes traditional rare earth compensation system And directly obtain columnar orientation crystalline substance giant magnetostriction material by controlling fusion process.
It is embodied as being to compensate system Pr by two class light rare earth bases0.9Tb0.1Fe1.9And Nd0.9Tb0.1Fe1.9Trace add, Make Tb0.27Dy0.73Anisotropy compensates the magnetocrystalline anisotropy of system and reduces and add supercool program one step and taken To material, wherein transition metal moieties uses the Co replacement Fe of 10% to be optimized.
In order to obtain above-mentioned columnar orientation crystalline substance giant magnetostriction material, the present invention uses following process, and it includes as follows Step:
1). preparation of raw material: rare earth Tb, Dy, Pr, the Nd and the purity that use purity to be 99.9% are the transition of 99.9% Metal Fe and Co is according to (Tb0.27Dy0.73)1-x(Nd0.9Tb0.1)x(Fe0.9Co0.1)1.93With (Tb0.27Dy0.73)1-x(Pr0.9Tb0.1)x(Fe0.9Co0.1)1.93(atomic ratio) proportioning.Fig. 1 is polynary giant magnetostriction material Rare earth component (Tb, Dy, Nd) phasor (shade represents composition);
2). conventional vacuum arc melting: by step 1) metal simple-substance that obtains puts into the copper of vacuum arc melting furnace intracavity In crucible, use rare earth under, transition metal is at upper modes of emplacement;Close furnace chamber, take out in advance with mechanical pump and add molecular pump The continuous mode taken out, until vacuum arrives 10 in furnace chamber-5Below Pa, is filled with argon shield gas to subatmospheric about 0.06-0.09MPa;Use conventional melting 4 times repeatedly, until alloying component is uniform;
3). rapid cooling melting: recirculated water shifts to frozen water pattern, i.e. using temperature is that the frozen water of 0 degree Celsius is as recirculated water; Electric arc melting alloy, to molten condition, the alloy material that high speed electromagnetic stirring is melted, maintains 10-20 second, closes rapidly Arc current, and maintain high speed electromagnetic to stir 5-10 second, treat that material is cooled to room temperature;
4). vacuum annealing: material is taken out and carries out the 1-15 days time of vacuum annealing, specifically at 300-1000 degree Celsius Annealing temperature and time-dependent, in the composition of alloy, obtain the columnar orientation crystalline substance giant magnetostriction material of well-crystallized after annealing.
Wherein step 3) recirculated water uses temperature to be the frozen water of 0 degree Celsius.After the alloy 10-20 second that electromagnetic agitation is melted To close rapidly arc current, and maintain high speed electromagnetic to stir 5-10 second.
The texture of synthetic material is with composition mutually: by the profile of material, it can be seen that have substantial amounts of post along cooling direction Shape crystalline substance is formed.By the XRD (X-ray diffraction) of column crystal bulk and powder it may be seen that<110>or<111> The diffraction maximum in direction has had significant enhancing, this show supercool under the conditions of material along<110>or<111>direction be orientated.
In order to preferably illustrate the process of above-mentioned columnar orientation crystalline substance giant magnetostriction material, concrete below by two Embodiment is described in detail.
Embodiment 1
Being Tb, Dy, Nd of 99.9% by purity, Fe, Co simple substance of 99.9% according to stoichiometric equation is (Tb0.27Dy0.73)1-x(Nd0.9Tb0.1)x(Fe0.9Co0.1)1.93(atomic ratio) proportioning, x span is 0≤x≤0.20.Fig. 1 Rare earth component (Tb, Dy, Nd) phasor (shade represents composition) for polynary giant magnetostriction material.Will preparation Good raw material loads in the copper crucible of electric arc melting, and copper crucible, initially with conventional water circulating cooling, uses electric arc melting to add The mode melt back of electromagnetic agitation 4 times, obtains composition uniform alloy mother metal.Recirculated water is shifted to frozen water pattern, i.e. Using temperature is that the frozen water of 0 degree Celsius is as recirculated water;Electric arc melting alloy is to molten condition, and high speed electromagnetic stirring is melted Alloy material, maintain 10 seconds, close rapidly arc current, and maintain high speed electromagnetic to stir 5 seconds, allow alloy Cooling rapidly.Until room temperature is down to by alloy, loads material into vacuum annealing furnace and carry out vacuum annealing 5 days.Fig. 2 is x=0.1 I.e. materials chemistry formula is Tb0.253Dy0.657Nd0.09(Fe0.9Co0.1)1.93The section micro-structure diagram of material.It may be seen that Substantial amounts of column crystal is had to be formed along cooling direction.Fig. 3 is Tb0.253Dy0.657Nd0.09(Fe0.9Co0.1)1.93Column crystal bulk Compose with x-ray diffractogram of powder.X ray diffracting spectrum shows, the direction of these column crystals should be<110>orientation. Fig. 5 is that conventional melting mode obtains the No yield point that x span is 0≤x≤0.20 (Tb0.27Dy0.73)1-x(Nd0.9Tb0.1)x(Fe0.9Co0.1)1.93Magnetostriction and crystal anisotropy constant K1Absolute value Ratio.It may be seen that x=0.1 i.e. materials chemistry formula is Tb0.253Dy0.657Nd0.090(Fe0.9Co0.1)1.93Material represent Go out the magnetoelastic properties of optimum.Fig. 6 is Tb0.253Dy0.657Nd0.09(Fe0.9Co0.1)1.93Column crystal and No yield point alloy Magnetostriction contrasts.By contrast, stretch it will be seen that column crystal material not only effectively raises mangneto in low field Contracting performance, 1.5T outer after the match, stroke has reached about 1450ppm.
Embodiment 2
Being Tb, Dy, Pr of 99.9% by purity, Fe, Co simple substance of 99% according to stoichiometric equation is (Tb0.27Dy0.73)1-x(Pr0.9Tb0.1)x(Fe0.9Co0.1)1.93(atomic ratio) proportioning, x span is 0≤x≤0.35.Fig. 1 Rare earth component (Tb, Dy, Pr) phasor (shade represents composition) for polynary giant magnetostriction material.Will preparation Good raw material loads in the copper crucible of electric arc melting, and copper crucible is adopted first by conventional water circulating cooling, uses electric arc melting to add The mode melt back of electromagnetic agitation 4 times, obtains composition uniform alloy mother metal.Recirculated water is shifted to frozen water pattern, i.e. Using temperature is that the frozen water of 0 degree Celsius is as recirculated water;The alloy material that high speed electromagnetic stirring is melted, maintains 15 seconds, Close rapidly arc current, and maintain high speed electromagnetic to stir 10 seconds, until room temperature is down to by alloy, load material into true Empty annealing furnace carries out vacuum annealing 5 days.Fig. 4 is that x=0.3 i.e. materials chemistry formula is Tb0.219Dy0.511Pr0.27(Fe0.9Co0.1)1.93The X ray diffracting spectrum of material.XRD shows these column crystal materials <110>strengthened with<111>diffraction maximum.
The present invention uses light rare earth base to compensate system trace and substitutes traditional rare earth compensation system, simultaneously by transition metal Fe position substitutes and optimizes, and is prepared for the multielement rare earth giant magnetostriction material that anisotropy is relatively low, and uses supercool melting technique One step obtains partially oriented alloy, and the preparation of traditional vertical area fusion method preparing monocrystalline or oriented crystal Journey generally requires substantial amounts of power consumption and time.
The above is only the preferred embodiment of the present invention, it is noted that for those skilled in the art For, some improvement can also be made under the premise without departing from the principles of the invention, these improvement also should be regarded as the present invention's Protection domain.

Claims (2)

1. the preparation technology of the giant magnetostriction material of a light rare earth modulation, it is characterised in that comprise the steps:
1). preparation of raw material: employing purity is one or several in rare earth Tb, Dy, Ho, Pr, Nd of 99.9% With one or several in the transition-metal Fe that purity is 99.9%, Co, Ni, Mn according to stoichiometric equation (RR’)1-x(LR0.9Tb0.1)x(Fe1-yMy)zAtomic ratio proportioning, and wherein (RR ') it is Tb0.27Dy0.73、Tb0.14Ho0.86Tradition Magnetocrystalline anisotropy compensates system, and LR is light rare earth Pr or Nd, and M is VIIB, VIIIB of Ni, Co, Mn The one of race's element or composition, wherein 0≤x≤0.35,0≤y≤0.2,1.85≤z≤2.1;
2). conventional vacuum arc melting: by step 1) metal simple-substance that obtains puts into the copper of vacuum arc melting furnace intracavity In crucible, use rare earth under, transition metal is at upper modes of emplacement;Close furnace chamber, take out in advance with mechanical pump and add molecular pump The continuous mode taken out, until vacuum arrives 10 in furnace chamber-5Below Pa, is filled with argon shield gas to subatmospheric 0.06-0.09MPa;Use conventional melting repeated multiple times, until alloying component is uniform;
3). rapid cooling melting: recirculated water shifts to frozen water pattern, i.e. using temperature is that the frozen water of 0 degree Celsius is as recirculated water; Electric arc melting alloy, to molten condition, the alloy material that high speed electromagnetic stirring is melted, maintains 10-20 second, closes rapidly Arc current, and maintain high speed electromagnetic to stir 5-10 second, treat that material is cooled to room temperature;
4). vacuum annealing: material is taken out and carries out the 1-15 days time of vacuum annealing at 300-1000 degree Celsius, annealing After obtain the columnar orientation crystalline substance giant magnetostriction material of well-crystallized.
2. the preparation technology of the giant magnetostriction material of light rare earth modulation as claimed in claim 1, it is characterised in that: institute Stating giant magnetostriction material has substantial amounts of column crystal to be formed along cooling direction.
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CN111940750B (en) * 2019-05-15 2022-02-22 刘丽 Preparation method of alloy powder material
CN110423932A (en) * 2019-08-23 2019-11-08 南京信息职业技术学院 A kind of magnetostriction materials and preparation method of light rare earth Pr doping
CN111057959A (en) * 2019-12-05 2020-04-24 南京信息职业技术学院 Magnetostrictive material and preparation process thereof
CN111378906A (en) * 2020-04-14 2020-07-07 聊城大学 Ultrahigh hypersensitive 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

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