CN105063450B - Big specific heat multiphase magnetic cold-storage material of high intensity and preparation method thereof - Google Patents
Big specific heat multiphase magnetic cold-storage material of high intensity and preparation method thereof Download PDFInfo
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Abstract
Big specific heat multiphase magnetic cold-storage material of high intensity of the present invention and preparation method thereof, the material is at least by two-phase or two-phase composition described above.According to the standard sample preparations of ASTM E9 09, experiment is compressed, compressive strength is more than 200Mpa;Within the temperature range of from 2K to 10K, unit volume specific heat of combustion and thermal capacitance value are all higher than Pb unit volumes specific heat of combustion and thermal capacitance value;Temperature range from 10K to 40K, unit volume specific heat of combustion and thermal capacitance value are respectively greater than the 83% of Pb unit volumes specific heat of combustion and thermal capacitance value.The use of the metal or salvage material of low-purity is raw material;Using deoxyprocess of the invention, high intensity big specific heat multiphase magnetic cold-storage material of the oxygen content less than raw material oxygen content is obtained.Very big specific heat is shown from 4 K to 40K, therefore Pb can be substituted to use.Prepared by the raw material of materials'use of the present invention rich oxygen content, reduce to material requirements, saves preparation cost, competitiveness of improving price.
Description
Technical field
The invention belongs to rareearth magnetic material technical field, in particular, provide one kind and obtain height using low-purity raw material
Multiphase magnetic cold-storage material of the big specific heat of intensity and preparation method thereof.
Background technology
Small-sized cold storage Gas Refrigerator is generally used for superconductor systems, NMR imaging instrument (NMR-CT), also applies
In cooling, the microelectronic device of the photoelectric remote-sensing instrument of the outer space, as indispensable in the modern life and scientific development
Technology.
What the refrigerating efficiency of small-sized cold storage Gas Refrigerator was mainly determined by regenerator packing material, the specific heat of filler
Rong Yue great, regenerator efficiency is higher.Because Pb has larger specific heat capacity, therefore always as low-temperature cold accumulation materials application.But,
The toxic and present environmental protection of Pb is runed counter to, and therefore wishes to find a kind of new environment-friendly materials instead of Pb materials as cold-storage
Material.Patent US20080104967A1 proposes a kind of Bi alloys cool storage material and substitutes Pb, and Bi alloys, will not be to ring without poison
There is pollution in border.But the specific heat of the alloy is much smaller than Pb in below 20K, and the efficiency of refrigeration machine can be reduced after replacement Pb.
In addition, simultaneously when temperature drop to below 15K, as the specific heat of combustion of the decline Pb of temperature is quickly reduced, particularly
When temperature is to below 10K, the specific heat of combustion of Pb is much smaller compared to refrigerant He, so that regenerator occurs hot saturation stopping
Work.It is general at present to select Er3Ni or HoCu2 as cool storage material.These materials have the ratio much larger than Pb in below 15K
Heat, can significantly improve the efficiency of refrigeration machine, reduce lowest refrigerating temperature.But because these materials are intermetallic compounds,
Highly brittle, compression strength is low, and long-term use occurs micro mist, dusty gas refrigeration machine in refrigeration machine.Cause Gas Refrigerator
Using needing to reprocess after the regular period.
Also there is patent around Er3Ni, it is proposed that a kind of compound non-crystalline material（CN103031501A）, below 15K's
Specific heat is more than Pb.But this material is less than lead in the specific heat of more than 15K, therefore be not suitable for substituting Pb.And preparation needs original
The purity of material in more than 99.9wt%, to obtain non crystalline structure.Cost is prepared can also be greatly improved.
Because rare earth material is easy to oxidation, therefore also it is easy to make it lose its work(because of oxidation in use
Can, cause rare earth material to be gone out of use after using several years.And notice that rare earth is tellurian scarce resource, it is right in the world at present
The exploitation of rare earths material is extremely paid attention to, therefore, cycling and reutilization rare earth material is also problem in urgent need to solve.
The content of the invention
For these problems, the present invention proposes the multiphase magnetic that a kind of utilization low-purity raw material obtain the big specific heat of high intensity
Property cool storage material.Multiphase magnetic cold-storage material of the invention has intensity very high, and plasticity also has improvement, therefore has very well
Processing characteristics.Further, since these materials are in low temperature range very wide, from 2 K to 40K, there is very big specific heat, therefore can be with
Pb is substituted to use.Also these materials are used obtained by the raw metal of low-purity or the reclaimed materials of rare earth alloy, are reduced
The requirement prepared to material.It is cheap novel magnetic cool storage material.
The present invention provides a kind of multiphase magnetic cold-storage material for obtaining the big specific heat of high intensity intensity；Its feature is as follows:
Within the temperature range of from 2K to 10K, unit volume specific heat of combustion and thermal capacitance value be all higher than Pb unit volumes specific heat of combustion and
Thermal capacitance value.Temperature range from 10K to 40K, unit volume specific heat of combustion and thermal capacitance value be respectively greater than Pb unit volumes specific heat of combustion and
The 83% of thermal capacitance value.
The compressive strength of the big specific heat multiphase magnetic cold-storage material of high intensity of the present invention is more than 200Mpa.
The present invention employs the different multiphase of crystal structure to reach raising strength of materials purpose first, and in order to not drop
It is low than hot property, employ the same element high of the specific heat of combustion near 20K and mutually improve intensity and replace harmful substance Pb.Due to
Most of in heterogeneous material of the invention have big specific heat in low temperature, thus material of the present invention Low Temperature Specific Heat substantially and
Pb is equal, even above Pb, therefore is good Pb alternative materials.
Other material of the present invention is due to heterogeneous structure so that the compression strength of material is greatly improved, and material
Plasticity also has improvement, is conducive to machine-shaping.
Two-phase or two-phase composition described above that the material is at least differed by crystal structure；The matter of each component of the material
Measuring percentage is：Rare earth element er weight ratio in the material is 91 wt%~97wt%；Ho, Dy, Gd and Tb of 0-1wt%
In at least one, transition element Ni weight in the material than 1 wt%~9wt%, weight than the Co for 0-1wt%, Cu,
At least one in Mn and Zn elements, oxygen content is less than or equal to 0.8wt% in above-mentioned material.
Further, the material is at least differed by crystal structure two-phase or two-phase composition described above；The material each
The mass percent of component is：Rare earth element Ho weight ratios in the material are 57wt%~70wt%；The Er of 0-1wt%, Dy,
At least one in Gd and Tb, than 29wt%~41wt%, weight ratio is 0-1wt% to transition element Cu weight in the material
At least one in Co, Mn, Zn element, oxygen content is less than or equal to 0.8wt%.
Material element content of the invention composition, it is ensured that material is many phase compositions, the material of the present invention of many phase compositions, no
The mechanical property of material can be only improved, it is also possible that the specific heat peak value at magnetic phase transition broadens, or even is occurred without obvious
Specific heat peak, but the specific heat of combustion near higher than specific heat peak temperature averagely increases.The physical property of heterogeneous material of the invention with
Corresponding monophase materialses are very different：The magnetic phase transition of material can change.Some can disappear because of the specific heat peak that phase transformation is produced.
Supposition should be that crystal electric field there occurs change, cause 4f electron energy level degeneracys to disappear under conditions of the presence of various crystal structures
Lose, showing as the specific heat at magnetic phase transition temperature does not have peak value, while the specific heat of combustion near higher than magnetic phase transition temperature has
Different degrees of rising, so maintains from 2K to 40K the overall height than heating curve in temperature range.And specific heat is accumulated to temperature
The thermal capacitance reduction got is nor apparent.
And, the rare earth element can be used the HoxCu (x of recovery>Or EryNi (y 0)>0) substitute, described recovery
HoxCu(x>Or Ery (y 0)>0) the mass fraction ratio of material gross weight shared by Ni is 50-100%, the HoxCu (x of described recovery
>Or EryNi (y 0)>0) oxygen content is less than 0.8wt% in.
Further, material of the invention, under conditions of raw material are smelted into the foundry alloy for having synthesized the material, is carried out
Following deoxyprocess：The foundry alloy of the material is placed on into the foundry alloy of melting can be from the crucible of bottom outflow, in Gao Zhen
Foundry alloy is melted after sky plus in the environment of argon gas, and at a temperature of the foundry alloy of fusing is placed higher than into 40 to 200 DEG C of fusing point
10 to 60 minutes, the foundry alloy of the material is then set to be flowed out from bottom, and will be oxygen-containing in the melting foundry alloy of the material
Amount liquation top high is stayed in crucible, obtains the material.
Material of the invention, it is also possible under conditions of raw material are smelted into the foundry alloy for having synthesized the material, carry out
Following deoxyprocess：The foundry alloy of the material is melted foundry alloy after high vacuum plus in the environment of argon gas, and will fusing
Foundry alloy be placed higher than 40 to 200 DEG C of fusing point at a temperature of, stand 10 to 60 minutes after, the foundry alloy of the material is stayed in
Cooled down in former crucible, containing the top compared with polyoxide in the foundry alloy of the excision material, obtain the material.
For the material with rare earth Ho and Cu as essential element, preferably at a temperature of higher than 100 degree to 150 degree of fusing point
Deoxygenation is carried out, and for the material with rare earth Er and Ni as essential element, is preferably entered at a temperature of being spent higher than fusing point 40 to 120
Row deoxygenation.
The density of the rare earth oxide such as holimium oxide or erbium oxide and the density difference of material of the present invention are little, therefore this hair
Bright method is not so that oxide floats and purifies simply due to density relationship.Concrete reason needs further research.Push away
Disconnected is probably that, due to there is cavity in oxide, and the liquid of material molten of the invention does not infiltrate with its oxide so that aoxidized
Thing floats to top from the liquid of melting gradually.
The static time can not be oversize more than higher than fusing point, if the good leak tightness of crucible, quiescent time can be slightly long,
But no more than 60 minutes, the time of overlength can cause that melt liquid is further aoxidized, the work for removing oxide is not had
With.The especially material with Er and Ni as essential element, ultra-long time can cause that melt liquid moment becomes oxide.
Further, the material obtained after deoxygenation of the present invention is heat-treated in inert gas atmosphere, is evacuated down to
It is not less than 1*10-2In the state of Pa, at 700-860 DEG C, inert gas is argon gas or helium to heat treatment temperature, annealing time from
1 day to 5 days.The material for removing oxygen content is further carried out hot place by material of the present invention by the different many phase compositions of crystal structure
Reason, can cause that material composition is uniform, multiphase sharpness of border, and can cause that crystal grain is agglomerated into subsphaeroidal trend, increased
Anti-pressure ability.
Although HoxCu (the x of the recovery more than raw metal, impurity present invention uses low-purity>And Er 0)y(y>0)Ni
As raw material, but due in the preparation technology of material of the present invention, employing deoxyprocess, so using the original of elevated oxygen level
Prepared by material can also prepare multiphase magnetic cold-storage material of the oxygen content less than the big specific heat of high intensity of raw material, improve material
Quality, has obtained the material of high specific heat.
Material of the invention can use the HoxCu (x for reclaiming>Or Ery (y 0)>0) Ni is prepared as raw material, is so had
Beneficial to maximally utilizing for rare earth resources, and meet the requirement of current environmental protection.
The beneficial effects of the invention are as follows：Due to using above-mentioned technical proposal, use low-purity alloy proposed by the present invention is former
Expect the multiphase magnetic cold-storage material of the big specific heat of high intensity of preparation, also improved with high compressive strength feature, and plasticity,
Therefore there is good processing characteristics.Further, since material of the present invention, from 2 K to 40K, shows very in low temperature range very wide
Big specific heat, therefore Pb can be substituted use.Material also of the present invention allows to be prepared using the raw material of elevated oxygen level, reduces
The requirement prepared to material, can save preparation cost, competitiveness of improving price, according to ASTM E9-09 standard sample preparations,
Experiment is compressed, the compressive strength of the big specific heat multiphase magnetic cold-storage material of high intensity of the invention is more than 200Mpa.
Brief description of the drawings
Fig. 1 (a) is the back scattering figure of comparative example 1.
Fig. 1 (b) is the compression fracture figure of comparative example 1.
Fig. 2 is the specific heat of comparative example 1.
Fig. 3 is the compression experiment curve of comparative example 1.
Fig. 4 is the XRD diffraction patterns of comparative example 2.
Fig. 5 is the ratio heating curve of comparative example 2.
The back scattering figure of the sample of Fig. 6 inventions embodiment 1.
The compressive strength curve of the sample of Fig. 7 embodiment of the present invention 1.
The unit volume of the sample of Fig. 8 embodiment of the present invention 1 compares heating curve.
The back scattering figure of the sample of Fig. 9 embodiment of the present invention 2.
The compression curve of the sample of Figure 10 embodiment of the present invention 2.
The unit volume of the sample of Figure 11 embodiment of the present invention 2 compares heating curve.
The back scattering figure of the sample of Figure 12 embodiment of the present invention 3.
The unit volume of the sample of Figure 13 embodiment of the present invention 3 compares heating curve.
The unit volume of Figure 14 the present embodiment 4 of the present invention compares heating curve.
The remelting method of Figure 15 the present embodiment 5 of the present invention.
The ingot casting of Figure 16 the present embodiment 5 of the present invention.
In figure：
1. bulk granular, 2. quartz ampoule, 3. ingot casting, 4. oxide, 5. dark areas I, 6. dark areas II.
Specific embodiment
Technical scheme is described further with reference to comparing embodiment and specific embodiment.
Comparative example 1：
Er3Ni alloys are prepared for electric arc furnaces.Fig. 1 is the back scattering figure and compression fracture figure of comparative example 1.As can be seen that
Comparative example 1 only has the phase compositions of Er3Ni mono-.Fig. 2 is the specific heat of comparative example 1, has used what American Bureau of Standards (ABS) (nist) announced in figure
The ratio dsc data of lead is compared.As can be seen that the unit volume specific heat of comparative example 1 is more than Pb in below 20K, in more than 20K and
Pb is essentially identical.Fig. 3 is the compression experiment curve of comparative example 1, and compressive strength is 58MPa, also finds out that compression fracture is allusion quotation from Fig. 1
The rock-candy structure of type.Therefore comparative example 1 belongs to fragile material.It is difficult to.
Comparative example 2:
HoCu2 alloys are prepared for electric arc furnaces.Fig. 4 for comparative example 2 XRD diffraction patterns, from Fig. 4 can, comparative example 2 is
Homogeneous structure.The compressive strength of HoCu2 alloys is 200Mpa.Fig. 5 is the ratio heating curve of comparative example 2, and U.S.'s mark has been used in figure
The ratio dsc data of the lead that quasi- office (nist) is announced is compared.Although as can be seen that the unit volume specific heat of comparative example 2 20K with
It is more than Pb down, but in more than 20K less than the 83% of Pb.Therefore comparative example 2 can not substitute Pb and use.
Embodiment 1：
The Er raw metals of 0.32wt% are up to oxygen content, using preparation technology of the invention, foundry alloy crucible is placed into
It is interior, 5*10 is evacuated to before heating-3Pa, then imports in crucible argon gas, and argon pressure is 0.06MPa, then melts foundry alloy
After change, at 1100 DEG C, 30 minutes are stood, flowed out from the crucible with hole, and cause to leave the mother of elevated oxygen level in crucible
Alloy surplus.The percentage by weight of Er is obtained for 92wt%, the percentage by weight of Ni is 7.9%, and oxygen content is the reality of 0.1wt%
Apply the sample of example 1.Then the material is put into vacuum annealing furnace, be evacuated down to 8*10-3In the state of Pa, 700 DEG C are heated to,
The argon gas of 0.05MPa is then introduced into, regulation temperature is annealed 3 days to 830 degree.Although the oxygen content in Er raw metals is very high,
It is by deoxyprocess of the invention so that the sample oxygen content only 0.1wt% of the embodiment of the present invention 1 for finally obtaining.Fig. 6 is
The back scattering figure of the sample of the embodiment of the present invention 1.It can be seen that the matrix of the present embodiment is Er3Ni, but wherein also deposit
In crystal boundary sharpness of border, round and smooth Er phases.The Er phases of this form are embedded in matrix phase, improve the sample of the embodiment of the present invention 1
The mechanical property of product.Fig. 7 is the compressive strength change curve of the sample of the embodiment of the present invention 1.The compression of the sample of the embodiment of the present invention 1
Intensity is 437.5 Mpa.Compared with comparative example 1, the compression strength of the embodiment of the present invention is increased substantially.Fig. 8 is real for the present invention
The unit volume for applying the sample of example 1 compares heating curve.The ratio dsc data of the lead of American Bureau of Standards (ABS) (nist) announcement has been used to oppose in figure
Than.From the influence that be can be seen that than heating curve due to multiphase, the ratio heating curve of the sample of the embodiment of the present invention 1 is in Single Phase Metal Er
Do not occur peak value at magnetic phase transition point 18K, 22K（Bibliography 1）.But higher than magnetic phase transition point, specific heat is more than theory
Value, illustrates that the crystal field in the heterogeneous material of the embodiment of the present invention 1 there occurs change, is not that simple two-phase is added.So, originally
Specific heat and thermal capacitance value of the specific heat of combustion of inventive embodiments 1 from 2K to 40K are both greater than Pb.It is extraordinary Pb alternative materials.
Embodiment 2：
The Ho raw metals of 0.48wt% are up to oxygen content.Using preparation technology of the invention, foundry alloy is placed into crucible
It is interior, 7*10 is evacuated to before heating-3Pa, then imports in crucible argon gas, and argon pressure is 0.5Pa, then melts foundry alloy
Afterwards, at 1120 DEG C, then the foundry alloy after cooling is cut away interior hyperoxia by the static cooling in alumina crucible after standing 20 minutes
The top of content, has obtained the percentage by weight of Ho for 65.8wt%, and the percentage by weight of Cu is 34.14%, and oxygen content is
The sample of embodiment 2 of 0.06wt%.Then the material is put into vacuum annealing furnace, be evacuated down to 8*10-3In the state of Pa,
760 DEG C are heated to, the argon gas of 0.03MPa is then introduced into, regulation temperature is annealed 2 days to 860 DEG C.Fig. 9 is the embodiment of the present invention 2
The back scattering figure of sample.It can be seen that have the round and smooth HoCu phases in first separate out, border in the present embodiment, and eutectic
HoCu2 and HoCu phases.The heterogeneous structure of this form improves the mechanical property of the sample of the embodiment of the present invention 2.Figure 10 is this
The compression curve of the sample of inventive embodiments 2.Knowable to compression curve, the compressive strength of the present embodiment is 911MPa, and is compressed
There is obvious yield point on curve.Illustrate that the material has plasticity feature.Figure 11 is bent for the unit volume specific heat of the sample of embodiment 2
Line.The ratio dsc data of the lead of American Bureau of Standards (ABS) (nist) announcement has been used to compare in figure.From than heating curve can be seen that due to
The influence of multiphase, the ratio heating curve of the present embodiment specific heat peak at the 27K of the antiferromagnetic phase transformation of single-phase CuHo phases is not obvious（With reference to
Document 2）.But within the temperature range of the specific heat of the sample of embodiment 2 is from 2K to 20K, unit volume specific heat of combustion and thermal capacitance value are big
In or equal to Pb unit volumes specific heat of combustion and thermal capacitance value.Temperature range from 20K to 40K, unit volume specific heat of combustion and thermal capacitance
Value is respectively greater than the 88% of Pb unit volumes specific heat of combustion and thermal capacitance value.It is extraordinary Pb alternative materials.
Embodiment 3
With the rare earth Er raw material that oxygen content is 0.4wt%, and using 30wt%, oxygen content be the Er3Ni's of 0.8wt%
Reclaimed materials preparation, the foundry alloy for smelting into embodiment 3.Foundry alloy is placed in crucible, 7*10 is evacuated to before heating-3Pa, so
Afterwards by argon gas import crucible in, argon pressure is 0.06MPa, then make foundry alloy melt after, will melt foundry alloy at 1350 DEG C,
Flowed out from the crucible with hole after standing 11 minutes, elevated oxygen level surplus is left in crucible.The weight percent of Er is obtained
Than being 95.6wt%, the percentage by weight of Ni is 4.2%, and oxygen content is the sample of embodiment 3 of 0.2wt%.Then it is put into the material
In vacuum annealing furnace, 8*10 is being evacuated down to-3In the state of Pa, 740 degree are heated to, are then introduced into the argon gas of 0.05MPa, adjusted
Temperature is annealed 5 days to 840 degree.Figure 12 is the back scattering figure of the sample of embodiment 3.It can be seen that the sample of embodiment 3
Matrix is Er3Ni, but wherein also there is approximate circle Er.Approximate circle Er phases are embedded in matrix phase, improve reality
Apply the mechanical property of the sample of example 3.The compressive strength for measuring the sample of embodiment 3 is 456 Mpa.Compared with comparative example 1, the present invention is real
The compression strength for applying the sample of example 3 is increased substantially.Figure 13 compares heating curve for the unit volume of the sample of embodiment 3.Used in figure
The ratio dsc data of the lead that American Bureau of Standards (ABS) (nist) announces is compared.From than heating curve again it can be seen that due to the shadow of multiphase
Ring, the ratio heating curve of the sample of embodiment 3 does not occur peak value at Single Phase Metal Er magnetic phase transition points 18K, 22K（Bibliography
1）.But higher than magnetic phase transition point, specific heat is more than theoretical value, illustrates the crystalline substance in the heterogeneous material of the sample of the embodiment of the present invention 3
Lattice there occurs change, not be that simple two-phase is added.Specific heat and heat of the specific heat of the sample of example 3 from 2K to 40K is implemented
Capacitance is both greater than Pb.It is extraordinary Pb alternative materials.
Embodiment 4
With rare earth Ho and Gd raw materials that oxygen content is 0.6wt%, it is 0.8wt%'s to add the recovery of 70wt%, oxygen content
HoCu2, has prepared Ho raw material weights percentage for 61.8wt%, and Gd raw material weights percentage is 0.8wt%, Cu raw material weight percentages
Than the raw material foundry alloy for 37.4%, above-mentioned foundry alloy is placed in crucible, 5*10 is evacuated to before heating-3Pa, then by argon gas
Import crucible in, argon pressure is 0.03MPa, then make foundry alloy melt after, will melt the present embodiment foundry alloy at 1000 DEG C,
Flowed out from the crucible with hole after standing 30 minutes, the surplus of elevated oxygen level is left in crucible, having obtained oxygen content is
The sample of the embodiment 4 of 0.09wt%.There is the CuHo phases for first separating out, and CuHo and Cu in the sample of the embodiment of the present invention 42Ho's is total to
Crystalline phase.The compressive strength of the sample of embodiment 4 is 800MPa.Figure 14 compares heating curve for the unit volume of the sample of embodiment 4.Make in figure
The ratio dsc data of the lead announced with American Bureau of Standards (ABS) (nist) is compared.Temperature model of the specific heat of the present embodiment from 2K to 10K
In enclosing, unit volume specific heat of combustion and thermal capacitance value are all higher than Pb unit volumes specific heat of combustion and thermal capacitance value.Temperature model from 10K to 40K
Enclose, unit volume specific heat of combustion and thermal capacitance value are respectively greater than the 83% of Pb unit volumes specific heat of combustion and thermal capacitance value.It is that extraordinary Pb is replaced
For material.
Embodiment 5
With rare earth Ho and Er raw materials that oxygen content is 0.6wt%, it is 0.8wt%'s to add the recovery of 50wt%, oxygen content
HoCu2, has prepared the percentage by weight of Ho raw materials for 68wt%, and the percentage by weight of Er raw materials is 1 wt%, the weight of Cu raw materials
Percentage is 31% sample.Foundry alloy is placed in crucible, 5*10 is evacuated to before heating-3Pa, then imports crucible by argon gas
Interior, argon pressure is 0.03MPa, then make foundry alloy melt after, will melt the present embodiment foundry alloy at 1100 DEG C, stand 40 points
Flowed out in crucibles of the Zhong Houcong with hole, the surplus of elevated oxygen level is left in crucible, obtained the reality that oxygen content is 0.09wt%
Apply the sample of example 5.There is the CuHo phases for first separating out, and CuHo and Cu in the sample of the embodiment of the present invention 52The eutectic phase of Ho.Embodiment 5
The compressive strength of sample is 920MPa.Within the temperature range of the specific heat of the present embodiment is from 2K to 10K, unit volume specific heat of combustion and heat
Capacitance is all higher than Pb unit volumes specific heat of combustion and thermal capacitance value.Temperature range from 10K to 40K, unit volume specific heat of combustion and thermal capacitance
Value is respectively greater than the 83% of Pb unit volumes specific heat of combustion and thermal capacitance value.It is extraordinary Pb alternative materials.
Embodiment 6
Prepared with rare earth Er that oxygen content is 0.4wt% and Ho raw materials, smelt into the foundry alloy of embodiment 6.Foundry alloy is put
Put in crucible, 7*10 is evacuated to before heating-3Pa, then imports in crucible argon gas, and argon pressure is 0.05MPa, then makes mother
After alloy melting, the foundry alloy that will be melted flows out, crucible after standing 10 minutes in 1300 DEG C of temperature from the crucible with hole
Inside leave elevated oxygen level surplus.The percentage by weight of Er has been obtained for the percentage by weight of 93.5wt%, Ho is 0.5wt%, Ni
Percentage by weight is 5.8%, and oxygen content is the sample of embodiment 6 of 0.2wt%.The compressive strength of the sample of embodiment 6 is 440MPa.This
Within the temperature range of the specific heat of embodiment is from 2K to 10K, unit volume specific heat of combustion and thermal capacitance value are all higher than Pb unit volume specific heats
Value and thermal capacitance value.Temperature range from 10K to 40K, unit volume specific heat of combustion and thermal capacitance value are respectively greater than Pb unit volume specific heats
The 83% of value and thermal capacitance value.It is extraordinary Pb alternative materials.
Embodiment 7
With rare earth β-diketone complex and Ho raw materials that oxygen content is 0.7wt%, it is 0.8wt%'s to add the recovery of 70wt%, oxygen content
HoCu1.6, has prepared the weight ratio of Ho for 63.8wt%, and the weight ratio of Dy is 0.2 wt%, and the weight of Cu is than the sample for 36%.
Foundry alloy is placed in crucible, 5*10 is evacuated to before heating-3Pa, then imports in crucible argon gas, and argon pressure is
0.04MPa, then after melting foundry alloy, the present embodiment foundry alloy that will be melted is after static 30 minutes of 1060 degree of temperature in oxygen
Change static cooling in aluminium crucible, then the foundry alloy after cooling is cut away the top of interior elevated oxygen level, obtain the sample of embodiment 6
Product.Then the material is put into vacuum annealing furnace, be evacuated down to 5*10-3In the state of Pa, 720 DEG C are heated to, then led
Enter the argon gas of 0.03MPa, regulation temperature is annealed 4 days to 820 degree.There is the CuHo phases for first separating out in the sample of the embodiment of the present invention 7,
With CuHo and Cu2The eutectic phase of Ho.The compressive strength of the sample of embodiment 7 is 850MPa.The specific heat of the present embodiment is from 2K to 10K
In temperature range, unit volume specific heat of combustion and thermal capacitance value are all higher than Pb unit volumes specific heat of combustion and thermal capacitance value.From 10K to 40K
Temperature range, unit volume specific heat of combustion and thermal capacitance value are respectively greater than the 83% of Pb unit volumes specific heat of combustion and thermal capacitance value.It is very good
Pb alternative materials.
Embodiment 8
With the HoCu2 for reclaiming, oxygen content is 0.8wt%, and the weight for having prepared Ho is 1 than the weight ratio for 59wt%, Er
The weight of wt%, Cu confirms the effect to method of purification of the invention than the sample for 40%：As shown in figure 15, it is first same by two parts
The foundry alloy of quality is respectively put into quartz ampoule A and B, is evacuated to 5*10-3Pa, then after pouring the argon gas less than an atmospheric pressure
, then vertically be placed in heating furnace quartz ampoule by closed quartz tube A and B, foundry alloy is solidified after melting, and obtains the He of ingot casting 1
2.Ingot casting 1 and 2 is more than bottom in the rare earth oxide content of the upper position of quartz ampoule A and B.Again by the two ingot casting top and the bottom
It is placed into after reverse in an internal diameter and quartz ampoule A and B identical quartz ampoule C long so that rare earth oxide high before thawing
Part is respectively positioned at the bottom and middle part of quartz ampoule C.Quartz ampoule C is evacuated to 5*10-3Pa, then pour less than an atmospheric pressure
Argon gas rear enclosed quartz ampoule C, then by quartz ampoule C, heating causes that two ingot castings of the inside melt vertically, then solidifies it.It is solidifying
Gu after ingot casting is broken vertically, be made metallographic sample.Result is as shown in figure 16.Figure 16 (a) is, hair static 8 minutes at 970 degree
Although the oxide at existing bottom and middle part has all moved up distance, originally in the black impurity of bottom is located at ingot casting
Portion, it is impossible to effectively remove these impurity.Figure 16 (b) is static 45 minutes at 1040 degree, is found original in middle part and bottom
Black impurity is had moved near top, has purified the material of the embodiment of the present invention 5.Figure 16 (c) is at 1100 degree static 30
Minute, it is found that the original black impurity at middle part and bottom has moved to top, effectively purify the embodiment of the present invention 5
Material.The density of holimium oxide is 8.36, and the density 9.2 of HoCu2 is more or less the same, thus the inventive method be not it is simple by
In density relationship so that oxide floats and purifies.Deduction is probably that, due to there is cavity in oxide, and material of the invention is molten
The liquid for melting does not infiltrate with its oxide so that oxide floats to top from the liquid of melting gradually.At the top of ingot casting
Tissue this can be substantially one of reason with tentative confirmation than the tissue looseness of bottom.Concrete reason needs further research.
Bibliography 1 Doon Gibbs, Jakob Bohr, and J. D. Axe, PHYSICAL B, VOLUME
34, NUMBER 11,8182(1986)
K. Shashikala, Seemita Banerjee, R. Kulkarni, the S.K. Dhar of bibliography 2,
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Claims (5)
1. the multiphase magnetic cold-storage material of the big specific heat of a kind of high intensity, it is characterised in that:The multiphase magnetic cold-storage material from 2K to
Within the temperature range of 10K, unit volume specific heat of combustion and thermal capacitance value are all higher than Pb unit volumes specific heat of combustion and thermal capacitance value, from 10K to
The temperature range of 40K, unit volume specific heat of combustion and thermal capacitance value are respectively greater than the 83% of Pb unit volumes specific heat of combustion and thermal capacitance value；Should
The compressive strength of multiphase magnetic cold-storage material is more than 200Mpa；Two-phase or two-phase that the material is at least differed by crystal structure
Composition described above；The percentage by weight of each component of the material is：The percentage by weight of rare earth element er be 91 wt%~
97wt%；Percentage by weight is at least one in Ho, Dy, Gd and Tb of 0-1wt%, and transition element Ni is in the material
Percentage by weight 1wt%~9wt%, percentage by weight is at least one in Co, Cu, Mn and Zn element of 0-1wt%, above-mentioned
Oxygen content is less than or equal to 0.8wt% in material.
2. the multiphase magnetic cold-storage material of the big specific heat of a kind of high intensity, it is characterised in that:The multiphase magnetic cold-storage material from 2K to
Within the temperature range of 10K, unit volume specific heat of combustion and thermal capacitance value are all higher than Pb unit volumes specific heat of combustion and thermal capacitance value, from 10K to
The temperature range of 40K, unit volume specific heat of combustion and thermal capacitance value are respectively greater than the 83% of Pb unit volumes specific heat of combustion and thermal capacitance value；Should
The compressive strength of multiphase magnetic cold-storage material is more than 200Mpa；Two-phase or two-phase that the material is at least differed by crystal structure
Composition described above；The percentage by weight of each component of the material is：The percentage by weight of rare earth element Ho is 57wt%~70wt%；
Percentage by weight is at least one in Er, Dy, Gd and Tb of 0-1wt%, transition element Cu weight hundred in the material
Divide than 29wt%~41wt%, percentage by weight is at least one in 0-1wt%Co, Mn, Zn element, oxygen content in above-mentioned material
Less than or equal to 0.8wt%.
3. a kind of side of the multiphase magnetic cold-storage material of the big specific heat of high intensity prepared as described in claim 1-2 any one
Method, it is characterised in that specifically include following steps：
Step 1：To carry out melting and obtain foundry alloy according to being designed to distribution and putting weigh each raw material；
Step 2：Step 1 is obtained into foundry alloy to place in crucible, 7*10 is evacuated to-3Pa, is passed through argon gas, and the pressure of argon gas is
0.03-0.06MPa, heating is to melt foundry alloy, and 10-60 points is stood at a temperature of 40-200 DEG C of the fusing point higher than foundry alloy
Clock, makes oxide floating top set in foundry alloy, wherein containing less oxide foundry alloy is from crucible bottom outflow or cuts off the material
Containing the top compared with polyoxide in the foundry alloy of material, that is, obtain the multiphase magnetic cold-storage material of the big specific heat of high intensity.
4. the preparation method of the multiphase magnetic cold-storage material of the big specific heat of high intensity as claimed in claim 3, it is characterised in that should
Method also includes Technology for Heating Processing, and the concrete technology of the heat treatment is, by the multiphase magnetic cold-storage material of the big specific heat of high intensity
It is put into vacuum annealing furnace, is evacuated down to and is not less than 1*10-2In the state of Pa, import inert gas, inert gas be argon gas or
Person's helium, is 700-860 DEG C in temperature, and annealing time is 1-5 days.
5. the preparation method of the multiphase magnetic cold-storage material of the big specific heat of high intensity according to claim 3, it is characterised in that
Raw material in the step 1 can be used the HoxCu of recovery, x>0 or EryNi, y>0 substitutes, the HoxCu, x of described recovery>0 or
EryNi, y>The mass ratio of material gross weight shared by 0 is 50-100wt%, remaining for rare earth element er or Ho, described recovery
HoxCu, x>0 or EryNi, y>Oxygen content is less than 0.8wt% in 0.
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