CN105986310A - Rare earth magnetostriction material and preparation method thereof - Google Patents
Rare earth magnetostriction material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a rare earth magnetostriction material. The method comprises three processes of smelting, directional solidification and heat treatment. The directional solidification process comprises the following steps that 1, a magnetostriction alloy smelted solution obtained in a smelting crucible is poured into a quartz tube of a heat insulation device; 2, a pull-down process is started, and the quartz tube arranged on a base of a pull-down rod perpendicularly moves downwards along with the pull-down rod, wherein the downward moving process has three time periods, and different pull-down progresses are set in the different time periods; 3, in the downward moving process of the quartz tube, the alloy smelted solution in the quartz tube is gradually solidified, the pull-down process is finished after the quartz tube is completely moved out of the heat insulation device, and finally the alloy smelted solution forms a rare earth magnetostriction bar of a certain structure. In addition, the invention further provides the rare earth magnetostriction bar prepared through the method. The rare earth magnetostriction bar is good in crystallization property; meanwhile, the fluctuation range of magnetostriction coefficient of materials on upper, middle and lower different portions is small, and is 18ppm to the minimum.
Description
Technical field
The invention belongs to field of magnetic material, relate to a kind of for improve rare earth magnetostriction rod material consistency of performance preparation method and
Use rare earth giant magnetostrictive material prepared by the method.
Technical background:
Rare earth ultra-magnetostriction material (TbDyFe2) there is magnetostriction coefficient greatly, response speed is fast, energy density advantages of higher,
Have broad application prospects in auto industry, chemical industry, many fields such as mechanical and military, be increasingly subject to people and pay attention to widely.
Rare earth giant magnetostrictive material directional solidification technology of preparing currently mainly has mound carat Bielski method (Czochralski), floating region district to melt
Three kinds of methods such as method (Float Zone, FZ) and the graceful method of Bridges (Bridgman).Mound carat Bielski method is a kind of employing
The directional solidification processes of seed crystal, the crystal orientation of prepared material is consistent with the crystal orientation of seed crystal, therefore by controlling seed crystal
Crystal orientation, can obtain and have the magnetostriction materials that<111>or<112>are orientated, but this kind of pull rate is the slowest, typically only has
Several microns per second, not only efficiency is low, and rare earth element scaling loss is serious, REFe easily occurs3Phase and Wei Shi soma.Therefore,
Mound carat Bielski method is prepared rare earth giant magnetostrictive material and is not had practical significance in engineering.Floating region district is molten and the graceful method of Bridges is equal
Do not use seed crystal, the directional solidification processes of industrialized production that to be two kinds be suitable for.The molten bar that can only prepare minor diameter in floating region district,
It is usually no more than 10mm.
Chinese patent ZL99117820 announces a kind of method using zone-melting process to prepare rare-earth magnetostrictive, and the method is by foundry alloy
Rod is put in crucible, and crucible is placed in vacuum cavity, and vacuum cavity evacuation is filled with argon or helium, closes mother with induction coil
Gold rod is heated to uniform temperature, mobile crucible and foundry alloy rod.In moving process, the fusing of foundry alloy rod crystallographic orientation solidification obtain
Rare earth magnetostriction rod material.The graceful method of Bridges can be used to produce the bar of major diameter, and maximum diameter of rod reaches 100mm, is
The prevailing technology of preparation of industrialization rare earth magnetostriction rod material at present.
United States Patent (USP) US4770704 announces the technique using the graceful method of Bridges to prepare rare earth magnetostriction rod material, and this technique is mainly wrapped
Include by raw material after upper portion crucible is smelted into alloy molten solution, by the opening of melting kettle bottom, alloy molten solution is injected into bottom and protects
The crucible being positioned on refrigerating seat in temperature bucket, in heat-preserving container, the temperature of lower of crucible is relatively low so that alloy molten solution in heat-preserving container crucible
Gradually solidify, form directional solidification rod.
Chinese patent ZL01102811.4 discloses a kind of side using Bridges graceful method continuously producing macro magnetostriction material in large scale
Method and device, it uses the magnesium-yttrium-transition metals such as the rare earth metal such as terbium, dysprosium and ferrum to be raw material, with charging, die-filling pipe, smelts, waters
The concrete steps such as note, crystallographic orientation obtain this material.In the graceful method of traditional Bridges, alloy melting, crystal growth and heat treatment
Three critical processes complete at three platform independent equipment respectively, cause rare earth giant magnetostrictive material oxygen content, impurity content to occupy height not
Under, rare earth scaling loss is serious thus is difficult to control to rare earth composition, it is difficult to obtain high performance rare earth giant magnetostrictive material.Meanwhile, raw
Product cost is high, and equipment investment is big.
Chinese patent ZL03156926 discloses the method using one-step technology and equipment to prepare rare earth giant magnetostrictive material, should
Method has carried out bigger improvement to traditional preparation technology, by alloy melting, crystal growth, heat treatment three operation at an equipment
Completing, impurity, oxygen content are low, and rare earth scaling loss is low, alloying component precise control, improve the concordance of performance of material with steady
Qualitative.
In the downdraw process of directional solidification, along with the carrying out of process of setting, the thermograde of freezing interface can change, from
And affecting the process of setting of alloy, the organizational structure causing magnetostriction bar is uneven, thus it is bigger to cause material property to produce
Fluctuation.In terms of disclosed technical data, also there is not preferable solution for this problem.
Summary of the invention
In order to solve above-mentioned technical problem, the present invention provides the preparation method of a kind of rare earth giant magnetostrictive material, by orientation being coagulated
Gu downdraw process is divided into three different time periods, each time period sets different drop-down processes, overcomes in downdraw process liquid-solid
Material structure and performance are caused the adverse effect of larger fluctuation by the change of interface temperature gradient, improve rare earth magnetostriction rod material group
Knit the concordance with performance and stability.
A kind of preparation method of the rare earth giant magnetostrictive material of the present invention, including melting, directional solidification and three processes of heat treatment,
It is characterized in that directional solidification includes following process:
(1) magnetostriction alloy liquation melted in melting kettle is poured in the quartz ampoule in attemperator；
(2) starting drop-down motor, the quartz ampoule being placed on lower link base moves vertically downward with water-cooling subbase, moves down process
It is made up of three time periods, in each time period, sets different drop-down processes.
(3) quartz ampoule is during moving down, and the alloy molten solution in quartz ampoule gradually solidifies, when quartz ampoule is fully removed insulation
After device, downdraw process completes, and final alloy molten solution forms the rare earth magnetostriction rod material with certain texture.
Wherein, in above-mentioned steps (2), the initial drop-down speed of the first time period of three time periods is V1s, end drop-down speed
For V1t, fall times is t1；The initial drop-down speed of the second time period is V2s, the drop-down speed that ends is V2t, fall times is
t2；The initial drop-down speed of the 3rd time period is V3s, the drop-down speed that ends is V3t, fall times is t3；Condition is V1s≥V1t,
V2s≥V2t, V3s≥V3t, and V1s-V3t≥30mm/h；T simultaneously1=0.2-1 hour, t2=0.8-5 hour, t3=0.5-3 hour.
Further preferably V1s-V3t>=50mm/h, further preferably V1s-V3t>=60mm/h, more further preferably V1s-V3t≥70
Mm/h, and most preferably V1s-V3t≥80mm/h。
Further, V1t≥V2s-10mm/h, and V2t≥V3s-10mm/h.Further preferred, V1t≥V2s, and V2t
≥V3s-10mm/h；Or, V1t≥V2s-10mm/h, and V2t≥V3s.Most preferably, V1t≥V2s, and V2t≥V3s。
Advantageously, in each time period, initial drop-down speed and end and be changed to linear change between drop-down speed.
In a detailed description of the invention, the initial drop-down speed of the first time period of three time periods in above-mentioned steps (2)
V1s=150-100mm/h, end drop-down speed V1t=150-80mm/h, fall times t1=0.2-1 hour.
In a detailed description of the invention, the initial drop-down speed of second time period of three time periods in above-mentioned steps (2)
V2s=120-60mm/h, end drop-down speed V2t=120-40mm/h, fall times t2=0.8-5 hour.
In a detailed description of the invention, the initial drop-down speed of the 3rd time period of three time periods in above-mentioned steps (2)
V3s=100-40mm/h, end drop-down speed V3t=100-30mm/h, fall times t3=0.5-3 hour.
Further, in described process (1), attemperator is heat-preserving container, and temperature is between 1300-1600 DEG C.
In a detailed description of the invention, in the present invention, the heat treatment process of magnetostriction bar uses two sections of heat treatments, first paragraph
Technique is: heat treatment temperature is 900-1000 DEG C, and heat treatment time is 1-4 hour；Second segment technique is: heat treatment temperature is
500-700 DEG C, heat treatment time is 0.5-2 hour, is then cooled to room temperature.The type of cooling is furnace cooling.
In another embodiment, the stretch heat treatment process of bar of magnetostriction can use magnetic-field heat treatment, added
Magnetic field intensity is 180-480KA/m, heat treatment temperature 400-800 DEG C, and heat treatment time 10-120 minute is then cooled to room
Temperature.The type of cooling is any one of furnace cooling, air cooling or shrend.
Rare earth magnetostriction rod material composition out prepared by the present invention is RE (Fe, M)2-x, wherein, RE is for comprising Y and Sc
One or more of 17 kinds of rare earth elements, M be in Mn, Co, Ni, Al one or both, 0≤x≤0.1.
Further, RE is the one or two kinds of in terbium and dysprosium, M be in Mn, Co, Ni, Al one or both, 0≤x≤
0.1.In a detailed description of the invention, rare earth magnetostriction rod material composition is TbmDy1-m(Fe,M)2-x, wherein, M be Mn,
In Co, Ni, Al one or both, 0.25≤m≤0.35,0≤x≤0.1.In another embodiment, Rare-Earth Magnetic
Causing flexible bar composition is TbmDy1-mFe2-x, wherein, 0.25≤m≤0.35,0≤x≤0.1.
On the other hand, present invention also offers a kind of rare earth magnetostriction rod material, it is characterised in that: obtain according to above-mentioned preparation method
Arrive.
Rare earth magnetostriction rod material prepared by the present invention has<110>or<112>texture of axial orientation.
Rare earth magnetostriction rod material prepared by the present invention is less than in the fluctuation of upper, middle and lower different parts material magnetostriction coefficient
50ppm, is further preferably no larger than 40ppm, the most preferably smaller than 25ppm, and more preferably less than 18ppm.
In the present invention, position, the middle part performance of rare earth magnetostriction rod material is best, and upper and lower performance is less than middle part performance, rod
The upper, middle and lower section different parts of material refers to directional solidification rod is divided into three sections, and top refers to that upper surface is to away from upper surface 1/3
Locating one section, middle part is that bottom is away from lower surface at span upper surface 2/3 to one section at upper surface 2/3 at span upper surface 1/3
One section.On the basis of the middle part of rare earth magnetostriction rod material, the magnetostriction coefficient on bar top and middle part magnetostriction coefficient
Difference is the fluctuation numerical value on magnetostriction bar top；The magnetostriction coefficient of bar bottom and the difference of middle part magnetostriction coefficient
Value is the fluctuation numerical value of magnetostriction bar bottom.The magnetostriction system of rare earth magnetostriction rod material upper, middle and lower different parts
Number is gained of averaging after taking, from the every section in upper, middle and lower portion, the sample test that three specifications are Φ 8mm × 10mm.
During directional solidification, the tissue of magnetostriction bar and performance are decided by the crystal growth pattern of liquid-solid boundary, work as liquid
When the ratio of the thermograde of liquid/solid interface and drop-down speed is more than marginal value, the crystal growth pattern of liquid-solid boundary is that plane is brilliant or born of the same parents' shape
Crystals growth mode, when the thermograde of liquid-solid boundary is less than marginal value with the ratio of drop-down speed, the growth pattern of liquid-solid boundary is
Dendrite growth mode, when liquid-solid boundary grows in dendrite mode, the degree of orientation of rare earth magnetostriction rod is deteriorated, serious shadow
Ring the performance of material.At tradition directional solidification processes, typically use single directional solidification rates, during directional solidification,
The thermograde of liquid-solid boundary depends on the hot-fluid of directional solidification rod solid phase end and derives condition.Downdraw process at directional solidification rod
In, the thermograde of liquid-solid boundary is in during constantly reducing, thus cause liquid-solid boundary thermograde and drop-down speed it
Be constantly in change than also, therefore, the growth pattern of liquid-solid boundary crystal also in being continually changing, directional solidification rod tissue
Fluctuation with performance is bigger.
The present invention according to the length of prepared directional solidification rod in the range of 200-350mm, the directional solidification rod that application is set up
SOLIDIFICATION MODEL, directional solidification rod is divided into three sections, every section according to calculate thermograde delta data set different
Drop-down speed.Downdraw process is divided into three sections by the present invention, main reason is that different time sections, calculates institute according to SOLIDIFICATION MODEL
There is bigger difference in the drop-down process mode set, uses one section of pull-down pattern relatively difficult to achieve in technique.
In first paragraph downdraw process, owing to the thermograde of liquid-solid boundary is higher, higher drop-down speed, temperature can be used
Gradient is more than marginal value with the ratio of drop-down speed, and now, liquid-solid boundary crystal growth pattern is plane crystalline substance or cellular crystal growth side
Formula.
When entering second segment, directional solidification rod pull-out distance and rod length increase, the temperature ladder near directional solidification rod liquid-solid boundary
Degree tapers into, and therefore, in the downdraw process of second stage, needs suitably to adjust drop-down speed so that liquid-solid boundary temperature
The ratio of gradient and drop-down speed, still greater than marginal value, keeps the crystal growth pattern of liquid-solid boundary to keep plane brilliant or cellular crystal
Growth pattern so that solidified structure keeps stable, it is ensured that the stability of material property and concordance.
When downdraw process enters the 3rd section, the thermograde of liquid-solid boundary declines further, adapts with this, need to adjust further
The drop-down speed of whole rare earth magnetostriction rod material, to continue to keep liquid-solid boundary to grow with plane or cellular crystal mode, so that
Whole bar obtains stable tissue and performance.
Applicant have surprisingly discovered that, the technological parameter of three time periods is advantageously following condition: V1s≥V1t, V2s≥V2t, V3s
≥V3t, and V1s-V3t≥30mm/h；T simultaneously1=0.2-1 hour, t2=0.8-5 hour, t3=0.5-3 hour.Finally give
Crystal property is good, and at the less rare earth magnetostriction rod of the fluctuation of upper, middle and lower different parts material magnetostriction coefficient
Material.
Compared with prior art, the rare earth magnetostriction rod material of the present invention has the advantages that
(1) the rare earth magnetostriction rod material crystal property that prepared by the inventive method is good；Upper, middle and lower different parts material mangneto simultaneously
The fluctuation range of coefficient of dilatation is less, minimum only 18ppm；
(2) the preparation method technological process of the present invention is short, production cost is low, production efficiency is high, is suitable for industrialized production major diameter
High-performance rare-earth magnetostriction bar.
Accompanying drawing explanation
Fig. 1: position, rare earth magnetostriction rod material upper, middle and lower schematic diagram
Detailed description of the invention
Hereinafter by embodiment, the invention will be further described.Scope is not restricted by the embodiments.
Embodiment 1
Stoichiometrically formula Tb0.3Dy0.7Fe1.95Composition proportion, wherein Dy excess 3%, by load weighted alloy raw material Tb,
Dy, Fe put into melting kettle, and in stove, vacuum is evacuated to 1.0 × 10-2Below Pa, is filled with argon, and argon pressure is 0.05Mpa.
Opening intermediate frequency power supply and carry out melting, monitor system is 60kW, and smelting time is 25 minutes, after raw material is completely melt, refine
5 minutes.Then, being poured in the quartz ampoule in heat-preserving container by running gate system by alloy molten solution, quartz ampoule specification is Φ 30mm
× 200mm, now, the temperature of heat-preserving container is 1450 DEG C.After alloy molten solution is poured into quartz ampoule completely, start lower pull system,
The quartz ampoule being on lower link base moves vertically downwardly together with lower link, progressively removes heat-preserving container.Drop-down process is set as
Three time periods, first time period, initial drop-down speed is 150mm/h, and the drop-down speed that ends is 120mm/h, and the time is 10
Minute；Second time period, initial drop-down speed is 110mm/h, and the drop-down speed that ends is 90mm/h, and the time is 1 hour；
3rd time period, initial drop-down speed is 80mm/h, and end drop-down speed 70mm/h, and fall times is 1 hour 10 minutes,
Initial drop-down and end drop-down between velocity variations be linear change.Drop-down complete after, by rare earth magnetostriction rod material, again
In feeding heat-preserving container, in heat-preserving container, carry out heat treatment, use two sections of Technologies for Heating Processing.First paragraph heat treatment temperature is 900 DEG C,
Heat treatment time is 2 hours；Second segment heat treatment temperature is 600 DEG C, and heat treatment time is 1 hour；Subsequently, furnace cooling.
Finally, the maximum magnetostriction coefficient of test rare earth magnetostriction rod material upper, middle and lower different parts, is 1650ppm respectively,
1685ppm and 1645ppm, rare-earth magnetostrictive coefficient undulating value is 40ppm.
Embodiment 2
Stoichiometrically formula Tb0.3Dy0.7(Fe0.9Al0.1)1.95Composition proportion, wherein Dy excess 3%, by load weighted conjunction
Gold raw material Tb, Dy, Fe put into melting kettle, and in stove, vacuum is evacuated to 1.0 × 10-2Below Pa, is filled with argon, argon pressure
For 0.03Mpa.Opening intermediate frequency power supply and carry out melting, monitor system is 60kW, and smelting time is 25 minutes, treats that raw material is complete
After fusing, refine 5 minutes.Then, being poured in heat-preserving container in quartz ampoule by alloy molten solution by running gate system, quartz ampoule is advised
Lattice are Φ 30mm × 200mm, and now, the temperature of heat-preserving container is 1450 DEG C.After alloy molten solution is poured into quartz ampoule completely,
Starting lower pull system, the quartz ampoule being on lower link base moves vertically downwardly together with lower link, progressively removes heat-preserving container.
Drop-down process is set as three time periods, first time period, and initial drop-down speed is 110mm/h, and the drop-down speed that ends is
110mm/h, the time is 20 minutes；Second time period, initial drop-down speed is 110mm/h, and the drop-down speed that ends is 80mm/h,
Time is 1 hour 30 minutes；3rd time period, initial drop-down speed is 80mm/h, and end drop-down speed 50mm/h, under
Drawing the time is 1 hour 20 minutes.Drop-down complete after, by rare earth magnetostriction rod material, be re-fed in heat-preserving container, insulation
Carry out heat treatment in Tong, use two sections of Technologies for Heating Processing.First paragraph heat treatment temperature is 1000 DEG C, and heat treatment time is 1 hour；
Second segment heat treatment temperature is 600 DEG C, and heat treatment time is 2 hours；Subsequently, furnace cooling.Finally, detection magnetostriction
The maximum magnetostriction coefficient of bar upper, middle and lower different parts, is 1640ppm, 1665ppm and 1655ppm respectively, rare earth
Magnetostriction undulating value is 25ppm.
Embodiment 3
Stoichiometrically formula Tb0.3Dy0.7(Fe0.85Mn0.15)1.95Composition proportion, wherein Dy excess 3%, by load weighted alloy
Raw material Tb, Dy, Fe put into melting kettle, and in stove, vacuum is evacuated to 1.0 × 10-2Below Pa, is filled with argon, and argon pressure is
0.03Mpa.Opening intermediate frequency power supply and carry out melting, monitor system is 60kW, and smelting time is 25 minutes, treats that raw material is the most molten
After change, then refine 5 minutes.Then, alloy molten solution is poured in the quartz ampoule in heat-preserving container by running gate system, quartz ampoule
Specification is Φ 50mm × 300mm, and now, the temperature of heat-preserving container is 1450 DEG C.After alloy molten solution is poured into quartz ampoule completely,
Starting lower pull system, the quartz ampoule being on lower link base moves vertically downwardly together with lower link, progressively removes heat-preserving container.
Drop-down process is set as three time periods, first time period, and initial drop-down speed is 120mm/h, and the drop-down speed that ends is
100mm/h, the time is 20 minutes；Second time period, initial drop-down speed is 100mm/h, and the drop-down speed that ends is 70mm/h,
Time is 3 hours；3rd time period, initial drop-down speed is 70mm/h, and end drop-down speed 40mm/h, and fall times is
50 minutes, initial drop-down and end drop-down between velocity variations be linear change.Drop-down complete after, by rare earth magnetostriction rod
Material, is re-fed in heat-preserving container, carries out heat treatment in heat-preserving container, uses two sections of Technologies for Heating Processing.First paragraph heat treatment temperature
Being 900 DEG C, heat treatment time is 2 hours；Second segment heat treatment temperature is 500 DEG C, and heat treatment time is 2 hours；Subsequently,
Furnace cooling.Finally, the maximum magnetostriction coefficient of detection magnetostriction bar upper, middle and lower different parts, is 1620ppm respectively,
1645ppm and 1635ppm, the undulating value of magnetostriction coefficient is 25ppm.
Embodiment 4
Stoichiometrically formula Tb0.3Dy0.7Fe1.95Composition proportion, wherein Dy excess 3%, by load weighted alloy raw material Tb,
Dy, Fe put into melting kettle, and in stove, vacuum is evacuated to 1.0 × 10-2Below Pa, is filled with argon, and argon pressure is 0.06Mpa.
Opening intermediate frequency power supply and carry out melting, monitor system is 60kW, and smelting time is 25 minutes, after raw material is completely melt, then essence
Refine 5 minutes.Then, being poured in the quartz ampoule in heat-preserving container by running gate system by alloy molten solution, quartz ampoule specification is Φ 70mm
× 350mm, now, the temperature of heat-preserving container is 1450 DEG C.After alloy molten solution is poured into quartz ampoule completely, start lower pull system,
The quartz ampoule being on lower link base moves vertically downwardly together with lower link, progressively removes heat-preserving container.Drop-down process is set as
Three time periods, first time period, initial drop-down speed is 100mm/h, and the drop-down speed that ends is 80mm/h, and the time is 30
Minute；Second time period, initial drop-down speed is 90mm/h, and the drop-down speed that ends is 60mm/h, and the time is 3 hours；The
Three time periods, initial drop-down speed is 60mm/h, and end drop-down speed 50mm/h, and fall times is 1 hour 50 minutes,
Initial drop-down and end drop-down between velocity variations be linear change.Drop-down complete after, by rare earth magnetostriction rod material, again
In feeding heat-preserving container, in heat-preserving container, carry out heat treatment, use two sections of Technologies for Heating Processing.First paragraph heat treatment temperature is 900 DEG C,
Heat treatment time is 2 hours；Second segment heat treatment temperature is 600 DEG C, and heat treatment time is 1 hour；Subsequently, furnace cooling.
Finally, the maximum magnetostriction coefficient of detection magnetostriction bar upper, middle and lower different parts, is 1615ppm, 1635ppm respectively
And 1625ppm, the undulating value of magnetostriction coefficient is 25ppm.
Embodiment 5
Stoichiometrically formula Tb0.3Dy0.7Fe1.95Composition proportion, wherein Dy excess 3%, by load weighted alloy raw material Tb,
Dy, Fe put into melting kettle, and in stove, vacuum is evacuated to 1.0 × 10-2Below Pa, is filled with argon, and argon pressure is 0.02Mpa.
Opening intermediate frequency power supply and carry out melting, monitor system is 60kW, and smelting time is 25 minutes, after raw material is completely melt, then essence
Refine 5 minutes.Then, being poured in the quartz ampoule in heat-preserving container by running gate system by alloy molten solution, quartz ampoule specification is Φ 80mm
× 350mm, now, the temperature of heat-preserving container is 1600 DEG C.After alloy molten solution is poured into quartz ampoule completely, start lower pull system,
The quartz ampoule being on lower link base moves vertically downwardly together with lower link, progressively removes heat-preserving container.Drop-down process is set as
Three time periods, first time period, initial drop-down speed is 100mm/h, and the drop-down speed that ends is 80mm/h, and the time is 30
Minute；Second time period, initial drop-down speed is 80mm/h, and the drop-down speed that ends is 50mm/h, and the time is 4 hours；The
Three time periods, initial drop-down speed is 50mm/h, and drop-down speed 30mm/h fall times of ending is 1 hour 30 minutes,
Initial drop-down and end drop-down between velocity variations be linear change.Drop-down complete after, by rare earth magnetostriction rod material, again send
Enter in heat-preserving container, in heat-preserving container, carry out heat treatment, use two sections of Technologies for Heating Processing.First paragraph heat treatment temperature is 1000 DEG C,
Heat treatment time is 1 hour；Second segment heat treatment temperature is 500 DEG C, and heat treatment time is 2 hours；Subsequently, furnace cooling.
Finally, the maximum magnetostriction coefficient of detection magnetostriction bar upper, middle and lower different parts, is 1575ppm, 1595ppm respectively
And 1580ppm, the undulating value of magnetostriction coefficient is 20ppm.
Embodiment 6
Stoichiometrically formula Tb0.3Dy0.7Fe1.95Composition proportion, wherein Dy excess 3%, by load weighted alloy raw material Tb,
Dy, Fe put into melting kettle, and in stove, vacuum is evacuated to 1.0 × 10-2Below Pa, is filled with argon, and argon pressure is 0.03Mpa.
Opening intermediate frequency power supply and carry out melting, monitor system is 60kW, and smelting time is 25 minutes, after raw material is completely melt, then essence
Refine 5 minutes.Then, being poured in the quartz ampoule in heat-preserving container by running gate system by alloy molten solution, quartz ampoule specification is Φ
100mm × 350mm, now, the temperature of heat-preserving container is 1600 DEG C.After alloy molten solution is poured into quartz ampoule completely, under startup
Pull system, the quartz ampoule being on lower link base moves vertically downwardly together with lower link, progressively removes heat-preserving container.Under draw in
Journey is set as three time periods, first time period, and initial drop-down speed is 100mm/h, and the drop-down speed that ends is 80mm/h,
Time is 30 minutes；Second time period, initial drop-down speed is 90mm/h, and the drop-down speed that ends is 40mm/h, and the time is 5
Hour；3rd time period, initial drop-down speed is 40mm/h, and drop-down speed 30mm/h fall times of ending is 1 hour 10
Minute, initial drop-down and end drop-down between velocity variations be linear change.Drop-down complete after, by rare earth magnetostriction rod material,
It is re-fed in heat-preserving container, in heat-preserving container, carries out heat treatment, use two sections of Technologies for Heating Processing.First paragraph heat treatment temperature is 900
DEG C, heat treatment time is 4 hours；Second segment heat treatment temperature is 600 DEG C, and heat treatment time is 1 hour；Subsequently, with stove
Cooling.Finally, the maximum magnetostriction coefficient of detection magnetostriction bar upper, middle and lower different parts, is 1567ppm respectively,
1585ppm and 1570ppm, the undulating value of magnetostriction coefficient is 18ppm.
Embodiment 7
Stoichiometrically formula Tb0.3Dy0.7Fe1.95Composition proportion, wherein Dy excess 3%, by load weighted alloy raw material Tb,
Dy, Fe put into melting kettle, and in stove, vacuum is evacuated to 1.0 × 10-2Below Pa, is filled with argon, and argon pressure is 0.05Mpa.
Opening intermediate frequency power supply and carry out melting, monitor system is 60kW, and smelting time is 25 minutes, after raw material is completely melt, then essence
Refine 5 minutes.Then, being poured in the quartz ampoule in heat-preserving container by running gate system by alloy molten solution, quartz ampoule specification is Φ 30mm
× 200mm, now, the temperature of heat-preserving container is 1300 DEG C.After alloy molten solution is poured into quartz ampoule completely, start lower pull system,
The quartz ampoule being on lower link base moves vertically downwardly together with lower link, progressively removes heat-preserving container.Drop-down process is set as
Three time periods, first time period, initial drop-down speed is 140mm/h, and the drop-down speed that ends is 120mm/h, and the time is 20
Minute；Second time period, initial drop-down speed is 120mm/h, and the drop-down speed that ends is 80mm/h, and the time is 1 hour 30
Minute；3rd time period, initial drop-down speed is 80mm/h, and drop-down speed 70mm/h fall times of ending is 40 minutes,
Initial drop-down and end drop-down between velocity variations be linear change.Drop-down complete after, by rare earth magnetostriction rod material from orientation
Consolidation furnace is taken out, puts in core magnetic field annealing furnace, close door of annealing furnace, be evacuated to 1.0 × 10-3Pa, then, is passed through
Argon, ar pressure is 0.05Mpa, and furnace temperature rises to 400 DEG C, is incubated 10 minutes, adds magnetic field to 180kA/m, subsequently, with
Stove is slowly cooled to room temperature.Finally, the maximum magnetostriction coefficient of detection magnetostriction bar upper, middle and lower different parts, point
Being not 1690ppm, 1715ppm and 1696ppm, the undulating value of magnetostriction coefficient is 25ppm.
Embodiment 8
Stoichiometrically formula Tb0.3Dy0.7(Fe0.9Co0.1)1.95Composition proportion, wherein Dy excess 3%, by former for load weighted alloy
Material Tb, Dy, Fe put into melting kettle, and in stove, vacuum is evacuated to 1.0 × 10-2Below Pa, is filled with argon, and argon pressure is
0.03Mpa.Opening intermediate frequency power supply and carry out melting, monitor system is 60kW, and smelting time is 25 minutes, treats that raw material is the most molten
After change, then refine 5 minutes.Then, alloy molten solution is poured in the quartz ampoule in heat-preserving container by running gate system, quartz ampoule
Specification is Φ 50mm × 300mm, and now, the temperature of heat-preserving container is 1400 DEG C.After alloy molten solution is poured into quartz ampoule completely,
Starting lower pull system, the quartz ampoule being on lower link base moves vertically downwardly together with lower link, progressively removes heat-preserving container.
Drop-down process is set as three time periods, first time period, and initial drop-down speed is 120mm/h, and the drop-down speed that ends is
100mm/h, the time is 20 minutes；Second time period, initial drop-down speed is 100mm/h, and the drop-down speed that ends is 70mm/h,
Time is 2 hours 30 minutes；3rd time period, initial drop-down speed is 70mm/h, and drop-down speed 40mm/h that ends is drop-down
Time is 1 hour 40 minutes, initial drop-down and end drop-down between velocity variations be linear change.Drop-down complete after, will
Rare earth magnetostriction rod material takes out from directional solidification furnace, puts in core magnetic field annealing furnace, closes door of annealing furnace, is evacuated to 1.0
×10-3Pa, then, is passed through argon, and ar pressure is 0.05Mpa, and furnace temperature rises to 700 DEG C, is incubated 120 minutes, adds magnetic
Field, to 480kA/m, subsequently, is cooled to room temperature in atmosphere.Finally, detection magnetostriction bar upper, middle and lower different parts
Maximum magnetostriction coefficient, be 1650ppm, 1675ppm and 1665ppm respectively, the undulating value of magnetostriction coefficient is 25ppm.
Embodiment 9
Stoichiometrically formula Tb0.3Dy0.7Fe1.95Composition proportion, wherein Dy excess 3%, by load weighted alloy raw material Tb,
Dy, Fe put into melting kettle, and in stove, vacuum is evacuated to 1.0 × 10-2Below Pa, is filled with argon, and argon pressure is 0.03Mpa.
Opening intermediate frequency power supply and carry out melting, monitor system is 60kW, and smelting time is 25 minutes, after raw material is completely melt, then essence
Refine 5 minutes.Then, being poured in the quartz ampoule in heat-preserving container by running gate system by alloy molten solution, quartz ampoule specification is Φ 70mm
× 350mm, now, the temperature of heat-preserving container is 1450 DEG C.After alloy molten solution is poured into quartz ampoule completely, start lower pull system,
The quartz ampoule being on lower link base moves vertically downwardly together with lower link, progressively removes heat-preserving container.Drop-down process is set as
Three time periods, first time period, initial drop-down speed is 110mm/h, and the drop-down speed that ends is 100mm/h, and the time is 30
Minute；Second time period, initial drop-down speed is 90mm/h, and the drop-down speed that ends is 60mm/h, and the time is 3 hours 30
Minute；3rd time period, initial drop-down speed is 70mm/h, and drop-down speed 50mm/h fall times of ending is 1 hour,
Initial drop-down and end drop-down between velocity variations be linear change.Drop-down complete after, rare earth magnetostriction rod material is solidifying from orientation
Gu stove takes out, put in core magnetic field annealing furnace, close door of annealing furnace, be evacuated to 1.0 × 10-3Pa, then, is passed through argon
Gas, ar pressure is 0.05Mpa, and furnace temperature rises to 600 DEG C, is incubated 60 minutes, adds magnetic field to 360kA/m, subsequently, at sky
Gas is cooled to room temperature.Finally, the maximum magnetostriction coefficient of detection magnetostriction bar upper, middle and lower different parts, respectively
Being 1627ppm, 1645ppm and 1635ppm, magnetostriction coefficient undulating value is 18ppm.
Embodiment 10
Stoichiometrically formula Tb0.3Dy0.7(Fe0.95Ni0.05)1.95Composition proportion, wherein Dy excess 3%, by former for load weighted alloy
Material Tb, Dy, Fe put into melting kettle, and in stove, vacuum is evacuated to 1.0 × 10-2Below Pa, is filled with argon, and argon pressure is
0.05Mpa.Opening intermediate frequency power supply and carry out melting, monitor system is 60kW, and smelting time is 25 minutes, treats that raw material is the most molten
After change, then refine 5 minutes.Then, alloy molten solution is poured in the quartz ampoule in heat-preserving container by running gate system, quartz ampoule
Specification is Φ 100mm × 350mm, and now, the temperature of heat-preserving container is 1500 DEG C.After alloy molten solution is poured into quartz ampoule completely,
Starting lower pull system, the quartz ampoule being on lower link base moves vertically downwardly together with lower link, progressively removes heat-preserving container.
Drop-down process is set as three time periods, first time period, and initial drop-down speed is 130mm/h, and the drop-down speed that ends is
110mm/h, the time is 20 minutes；Second time period, initial drop-down speed is 100mm/h, and the drop-down speed that ends is 50mm/h,
Time is 3 hours 10 minutes；3rd time period, initial drop-down speed is 60mm/h, and drop-down speed 30mm/h that ends is drop-down
Time is 1 hour 30 minutes, initial drop-down and end drop-down between velocity variations be linear change.Drop-down complete after, will
Rare earth magnetostriction rod material takes out from directional solidification furnace, puts in core magnetic field annealing furnace, closes door of annealing furnace, is evacuated to 1.0
×10-3Pa, then, is passed through argon, and ar pressure is 0.05Mpa, and furnace temperature rises to 800 DEG C, is incubated 60 minutes, adds magnetic field
To 460kA/m, subsequently, water is cooled to room temperature.Finally, detection magnetostriction bar upper, middle and lower different parts is
Big magnetostriction coefficient, is 1577ppm, 1595ppm and 1585ppm respectively, and magnetostriction coefficient undulating value is 18ppm.
Comparative example 1
Stoichiometrically formula Tb0.3Dy0.7Fe1.95Composition proportion, wherein Dy excess 3%, by load weighted alloy raw material Tb,
Dy, Fe put into melting kettle, and in stove, vacuum is evacuated to 1.0 × 10-2Below Pa, is filled with argon, and argon pressure is 0.05Mpa.
Opening intermediate frequency power supply and carry out melting, monitor system is 60kW, and smelting time is 25 minutes, after raw material is completely melt, then essence
Refine 5 minutes.Then, being poured in the quartz ampoule in heat-preserving container by running gate system by alloy molten solution, quartz ampoule specification is Φ 30mm
× 200mm, now, the temperature of heat-preserving container is 1300 DEG C.After alloy molten solution is poured into quartz ampoule completely, start lower pull system,
The quartz ampoule being on lower link base moves vertically downwardly together with lower link, progressively removes heat-preserving container.Whole drop-down process is protected
Hold constant drop-down speed 140mm/h, fall times 2 hours 30 minutes.Drop-down complete after, by rare earth magnetostriction rod material
Take out from directional solidification furnace, put in core magnetic field annealing furnace, close door of annealing furnace, be evacuated to 1.0 × 10-3Pa, then,
Being passed through argon, ar pressure is 0.05Mpa, and furnace temperature rises to 400 DEG C, is incubated 10 minutes, adds magnetic field to 180kA/m, subsequently,
It is slowly cooled to room temperature with stove.Finally, the maximum magnetostriction coefficient of detection magnetostriction bar upper, middle and lower different parts,
Being 1608ppm, 1695ppm and 1623ppm respectively, the undulating value of magnetostriction coefficient is 87ppm.
Comparative example 2
Stoichiometrically formula Tb0.3Dy0.7Fe1.95Composition proportion, wherein Dy excess 3%, by load weighted alloy raw material Tb,
Dy, Fe put into melting kettle, and in stove, vacuum is evacuated to 1.0 × 10-2Below Pa, is filled with argon, and argon pressure is 0.05Mpa.
Opening intermediate frequency power supply and carry out melting, monitor system is 60kW, and smelting time is 25 minutes, after raw material is completely melt, then essence
Refine 5 minutes.Then, being poured in the quartz ampoule in heat-preserving container by running gate system by alloy molten solution, quartz ampoule specification is Φ 30mm
× 200mm, now, the temperature of heat-preserving container is 1300 DEG C.After alloy molten solution is poured into quartz ampoule completely, start lower pull system,
The quartz ampoule being on lower link base moves vertically downwardly together with lower link, progressively removes heat-preserving container.Whole drop-down process is protected
Hold constant drop-down speed 70mm/h, fall times 2 hours 30 minutes.Drop-down complete after, by rare earth magnetostriction rod material from
Directional solidification furnace takes out, puts in core magnetic field annealing furnace, close door of annealing furnace, be evacuated to 1.0 × 10-3Pa, then,
Being passed through argon, ar pressure is 0.05Mpa, and furnace temperature rises to 400 DEG C, is incubated 10 minutes, adds magnetic field to 180kA/m, subsequently,
It is slowly cooled to room temperature with stove.Finally, the maximum magnetostriction coefficient of detection magnetostriction bar upper, middle and lower different parts,
Being 1616ppm, 1708ppm and 1627ppm respectively, the undulating value of magnetostriction coefficient is 92ppm.
Result is it can be seen that the rare earth magnetostriction rod material crystal property prepared of the inventive method is good；Upper, middle and lower are different simultaneously
The rare earth magnetostriction rod material that the fluctuation range of part material magnetostriction coefficient is prepared significantly lower than comparative example 1-2 method.
Claims (18)
1. the method preparing rare earth magnetostriction rod material, including melting, directional solidification and three processes of heat treatment, its feature exists
Following process is included in: described directional solidification:
(1) magnetostriction alloy liquation melted in melting kettle is poured in the quartz ampoule in attemperator；
(2) start downdraw process, the quartz ampoule being placed on lower link base moves vertically downward with lower link, move down process by
Three time period compositions, set different drop-down processes in each time period；
(3) quartz ampoule is during moving down, and the alloy molten solution in quartz ampoule gradually solidifies, when quartz ampoule is fully removed insulation
After device, downdraw process completes, and final alloy molten solution forms the rare earth magnetostriction rod material with certain texture.
Preparation method the most according to claim 1, wherein, in above-mentioned steps (2), the first time period of three time periods rises
The drop-down speed that begins is V1s, the drop-down speed that ends is V1t, fall times is t1；The initial drop-down speed of the second time period is
V2s, the drop-down speed that ends is V2t, fall times is t2；The initial drop-down speed of the 3rd time period is V3s, lower pulling rate of ending
Rate is V3t, fall times is t3；Condition is V1s≥V1t, V2s≥V2t, V3s≥V3t, and V1s-V3t≥30mm/h；
T simultaneously1=0.2-1 hour, t2=0.8-5 hour, t3=0.5-3 hour.
Preparation method the most according to claim 2, wherein, V1t≥V2s-10mm/h, and V2t≥V3s-10mm/h。
4. according to the preparation method described in Claims 2 or 3, wherein, the first time period of three time periods in described process (2)
Initial drop-down speed be V1s=150-100mm/h, the drop-down speed that ends is V1t=150-80mm/h, fall times is
t1=0.2-1 hour.
5. according to the preparation method described in Claims 2 or 3, wherein, second time period of three time periods in described process (2)
Initial drop-down speed be V2s=120-60mm/h, the drop-down speed that ends is V2t=120-40mm/h, fall times is
t2=0.8-5 hour.
6. according to the preparation method described in Claims 2 or 3, wherein, the 3rd time period of three time periods in described process (2)
Initial drop-down speed be V3s=100-40mm/h, the drop-down speed that ends is V3t=100-30mm/h, fall times is
t3=0.5-3 hour.
Preparation method the most according to claim 1, wherein, in described process (1), attemperator temperature is at 1300-1600 DEG C
Between.
Preparation method the most according to claim 1, wherein, in described process (1), the specification of quartz ampoule is diameter of phi 30-100mm,
A length of 200-350mm.
Preparation method the most according to claim 1, wherein, heat treatment two sections of heat treatments of employing of magnetostriction bar, first
Segment process is: heat treatment temperature is 900-1000 DEG C, and heat treatment time is 1-4 hour；Second segment technique is: heat treatment temperature
Degree is for 500-700 DEG C, and heat treatment time is 0.5-2 hour, is then cooled to room temperature.
Preparation method the most according to claim 8, wherein, the described type of cooling is furnace cooling.
11. preparation methoies according to claim 1, wherein, magnetostriction stretch bar heat treatment use magnetic-field heat treatment,
Added magnetic field intensity is 180-480KA/m, heat treatment temperature 400-800 DEG C, heat treatment time 10-120 minute, subsequently
It is cooled to room temperature.
12. preparation methoies according to claim 11, wherein, the described type of cooling is furnace cooling, air cooling or three kinds of sides of shrend
The one of formula.
13. according to described in claims 1 preparation method, wherein, described rare earth magnetostriction rod material composition is RE (Fe, M)2-x,RE
For comprising one or more of 17 kinds of rare earth elements of Y and Sc, M be in Mn, Co, Ni, Al one or both,
0≤x≤0.1。
14. according to described in claims 13 preparation method, wherein, described rare earth magnetostriction rod material composition is
TbmDy1-m(Fe,M)2-x, wherein, M be in Mn, Co, Ni, Al one or both, 0.25≤m≤0.35,0≤x≤
0.1。
15. according to described in claims 13 preparation method, wherein, rare earth magnetostriction rod material composition is TbmDy1-mFe2-x,
Wherein, 0.25≤m≤0.35,0≤x≤0.1.
16. 1 kinds of rare earth magnetostriction rod materials, it is characterised in that: obtain according to the preparation method of any one of claim 1-15.
17. rare earth magnetostriction rod materials according to claim 16, wherein, described rare earth magnetostriction rod material has and axially takes
To<110>or<112>texture.
18. according to the rare earth magnetostriction rod material described in claim 16 or 17, wherein, described rare earth magnetostriction rod material upper,
In, the fluctuation of lower different parts material magnetostriction coefficient is less than 50ppm.
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| CN1490435A (en) * | 2003-09-15 | 2004-04-21 | 北京有色金属研究总院 | Rareearth supermagnetostrictive material one step preparation and apparatus and products thereof |
| CN101308718A (en) * | 2007-05-18 | 2008-11-19 | 北京有色金属研究总院 | Rare earth - iron super magnetostriction material and preparing method thereof |
| CN101388433A (en) * | 2007-09-14 | 2009-03-18 | 有研稀土新材料股份有限公司 | Cementing magnetostrictive material and preparation thereof |
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| US4770704A (en) * | 1987-03-13 | 1988-09-13 | Iowa State University Research Foundation, Inc. | Continuous method for manufacturing grain-oriented magnetostrictive bodies |
| CN1285421A (en) * | 1999-08-21 | 2001-02-28 | 甘肃天星稀土功能材料有限公司 | Method and apparatus for producing rare-earth big magnetostriction material |
| CN1364943A (en) * | 2001-01-12 | 2002-08-21 | 甘肃天星稀土功能材料有限公司 | Method and device for continuously producing macro magnetostriction material in large scale |
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