CN1174200C - Cold-accumulating material and cold-accumulating refrigerator - Google Patents
Cold-accumulating material and cold-accumulating refrigerator Download PDFInfo
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- CN1174200C CN1174200C CNB988026708A CN98802670A CN1174200C CN 1174200 C CN1174200 C CN 1174200C CN B988026708 A CNB988026708 A CN B988026708A CN 98802670 A CN98802670 A CN 98802670A CN 1174200 C CN1174200 C CN 1174200C
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
- H01F1/015—Metals or alloys
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
- F25B9/14—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the cycle used, e.g. Stirling cycle
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/0009—Antiferromagnetic materials, i.e. materials exhibiting a Néel transition temperature
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B2309/00—Gas cycle refrigeration machines
- F25B2309/003—Gas cycle refrigeration machines characterised by construction or composition of the regenerator
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Abstract
A cold-accumulating material characterized by comprising a magnetic substance represented by the general formula: RCu1-xM1+x (wherein R is at least one rare earth element selected from among Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Ho, Tm and Yb; M is at least one element selected from among Ag, Au, Al, Ga, In, Ge, Sn, Sb, Si, Bi, Ni, Pd, Pt, Zn, Co, Rh, Ir, Mn, Fe, Ru, Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf, provided that simultaneous selection of both Ni and Ge is excepted; and x is an atomic ratio satisfying the relationship: -0.95</=X</=0.90). The cold-accumulating material can exert a remarkably high refrigerating capacity stably in a cryogenic temperature region over a prolonged period, and makes it possible to provide a cold-accumulating refrigerator and so on.
Description
Technical field
The invention relates to the cold storage refrigerator of cool storage material and this cool storage material of use, especially about the cool storage material that under 10K or the extremely low temperature below the 10K, can give full play to refrigerating capacity and the cold storage refrigerator that uses this cool storage material.
Background technology
In recent years, the superconductor technology development significantly is accompanied by the expansion of its Application Areas, and indispensable is the high performance small refrigerator of exploitation.Require this small frozen body light, small-sized, and the thermo-efficiency height.
For example, in superconducting MRI device and cryopump etc., used employing Ji Buaodao McMahon (Gifford MacMahon (GM)) mode and Si Ta to make the refrigerator of the freeze cycle of (Starling) mode etc.The high performance refrigerator of absolute demand more on the maglev type train.Particularly, in recent years, in the single crystal drawing device, also used high performance refrigerator as its major parts at superconducting energy storage device (SMES) or in magnetic field.
In such refrigerator, to have filled in the regenerator of cool storage material, working mediums such as compression He gas flow to a direction, its heat energy is supplied with cool storage material, and the expansible working medium flow round about, obtain heat energy from cool storage material.In such process, be accompanied by good heat exchange effect, improved the thermo-efficiency in the working medium circulation, so, can realize lower temperature.
As the cool storage material that uses in the above-mentioned refrigerator, in the past, mainly be to use Cu and Pb etc.Yet, such cool storage material, because under the extremely low temperature below the 20K, specific heat significantly diminishes, so, above-mentioned heat exchange effect can not be given full play to effect, when refrigerator was worked, under extremely low temperature, each circulation can not be stored sufficient heat energy in cool storage material, and working medium can not obtain sufficient heat energy from cool storage material.Resultant problem is to use the refrigerator of having assembled the regenerator composition of filling above-mentioned cool storage material not reach extremely low temperature.
Therefore, in recent years, in order to improve the heat exchange efficiency of above-mentioned regenerator under extremely low temperature, realizing more freezing temp near zero absolute temperature, thus consider to use in 20K or the extremely low temperature zone below it, have local maximum volume ratio calorific value and show big volume specific heat, as Er with this maximum value
3Ni, ErNi, ErNi
2, HoCu
2Intermetallic compound Deng rare earth element and transition metal formation is the magnetic cold-storage material that main body constitutes.By such magnetic cold-storage material is used for the GM refrigerator, realized under the minimum temperature of 4K, carrying out refrigeration operation.
Yet, though refrigerator as described above is applied in each system, more and more higher along with more specifically research to the technical requirements of the more extensive frozen material of cooling under state steady in a long-term, so also just require further to improve freezing performance (ability).
; the regenerator of final cooling section that generally has the cold storage refrigerator of several cooling sections; promptly; the 2nd section regenerator inside at 2 sections expanding type refrigerators; the formation temperature gradient; making the temperature of the high temperature side end that flows into working medium is about 30K, and the temperature of the low temperature side of low level (place of outlet) end reaches 4K.
Owing in above-mentioned broad like that temperature province, do not have the big cool storage material of volume specific heat, be actually, distribute according to the regenerator temperature inside, fill to have respectively and be suitable for the cool storage material of each temperature province, promptly than thermal property, at the regenerator low temperature side, for example fill as HoCu
2The cool storage material that only in the broad temperature province of low temperature side, has large volume specific heat of one class, and at high temperature side, for example lamination, filling are as Er
3The cool storage material that in the broad temperature province of high temperature side, has large volume specific heat of Ni one class.
Therefore, greatly influencing the major cause of freezing performance in the extremely low temperature zone of about 4K, is the cool storage material kind of filling at the regenerator low temperature side.Up to now, as the cool storage material that is filled into above-mentioned regenerator low temperature side, research has been tried out has ErNi
2, ErNi
0.9Co
0.1, ErNi
0.8Co
0.2, ErRh and HoCu
2Cool storage material etc. various compositions.When these cool storage materials are used for the 2nd section regenerator of 2 sections common expanding type GM refrigerators, under 4K, can make refrigerating capacity reach the extra high HoCu of being
2, but because HoCu
2Volume specific heat not ideal enough, so, do not reach significantly improving of refrigerating capacity.
Will be by ErNi
2, ErNi
0.9Co
0.1, ErNi
0.8Co
0.2Deng the cool storage material that kicker magnet constitutes, when being applied to the used refrigerator of superconductive system, the problem of existence is, is subjected to the leakage influence of magnetic field from superconducting magnet easily, and for example, magneticaction produces in the refrigerator member that eccentric wear decreases and distortion.
On the other hand, the cool storage material that is made of ErRh is an Antiferromagnetism, be difficult to be subjected to the influence in above-mentioned leakage magnetic field, strong point is opposite therewith, rhodium (Rh) as constituent is very expensive, as being used for the refrigerator cool storage material, when being applied to industry, exist extremely difficult problem with hundreds of gram magnitudes.
The objective of the invention is in order to solve problems such as above-mentioned, and provide a kind of can be in the extremely low temperature zone the remarkable refrigerating capacity of performance steady in a long-term cool storage material and use its cold storage refrigerator etc.And then other purpose of the present invention is by using above-mentioned cold storage refrigerator, is provided at can bring into play the MRI device of premium properties, superconducting magnet, cryopump and the externally-applied magnetic field formula single crystal drawing device that the maglev type train is used in long-term.
Disclosure of the Invention
The inventor in order to achieve the above object, preparation has various compositions and than the cool storage material of thermal property, be filled in the regenerator of refrigerator, above-mentioned by experiment composition and than thermal property to the refrigerating capacity of refrigerator, the life-span of cool storage material, the influence of weather resistance, compare research.
The result has obtained following discovery and knowledge.Promptly it is found that, near the ultimate temperature zone 4K, the cool storage material that large volume specific heat is arranged suitably be filled in material in the regenerator that the ratio thermal property of high temperature side is complementary, can improve the refrigerating capacity of refrigerator in the 4K temperature province significantly.For example, people learn and are using specific heat height under the 4K, and under the situation of the cool storage material that specific heat is low under 10K, consider that the regenerator temperature inside distributes, by only when regenerator low temperature one side is loaded above-mentioned cool storage material, use the cool storage material that high specific heat is arranged effectively under the 4K temperature, can increase substantially refrigerator performance (ability).
And then learn, with respect to the content of rare earth element, the amount of copper component and the amount of other metal ingredient are adjusted in the suitable scope, and, when reducing the content of rare earth element relatively, can obtain to have good cool storage material than thermal property.
Above-mentioned this than thermal property in order to realize, up to now, the inventor still is conceived to have the HoCu of very high volume specific heat under the 4K extremely low temperature in the magnetic cold-storage material of practicability
2Magneticsubstance is learnt with other rare earth element and is replaced a part of Ho, during perhaps with element substitutions such as transition metal part Cu, has realized the ratio thermal property that purpose requires for the first time.Finished the present invention according to above-mentioned discovery.
That is, cool storage material of the present invention is characterized in that, this cool storage material contains the magnetic substance by following general formula:
RCu
1-xM
1+x---(1)
(in the formula, R represents it is at least a kind of rare earth element selecting from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Ho, Tm and Yb, M represents it is at least a element of selecting from Ag, Au, Al, Ga, In, Ge, Sn, Sb, Si, Bi, Ni, Pd, Pt, Zn, Co, Rh, Ir, Mn, Fe, Ru, Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf, wherein Ni and Ge can not choose simultaneously, and x is the atomic ratio that satisfies relational expression-0.95≤x≤0.90).
Another purpose of the present invention is about containing the cool storage material by the magnetic substance of following general formula:
Ho
1-xR
x(Cu
1-yM
y)
2 (2)
(R represents it is at least a kind of rare earth element selecting in the formula from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb, M represents it is at least a element of selecting from Ag, Au, Al, Ga, In, Ge, Sn, Sb, Si, Bi, Ni, Pd, Pt, Zn, Co, Rh, Ir, Mn, Fe, Ru, Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf, wherein x, y are for satisfying 0≤x≤0.5 respectively, 0≤y≤0.5, the atomic ratio of x+y ≠ 0).
And the magnetic substance of above-mentioned general formula (1) or (2) expression is characterized in that containing the hexagonal system or the rhombic crystalline texture of 50% (volume) or its above ratio.
The preferably antiferromagnetic gonosome of magnetic substance is arranged again.
Cold storage refrigerator of the present invention, it is characterized in that, has the cooling section that several are made of the regenerator of having filled cool storage material, flow into by the regenerator upper reaches high temperature side of cool storage material working medium from each cooling section, by working medium and cool storage material heat exchange, downstream side at regenerator obtains lower temperature, wherein is filled in the cool storage material in the above-mentioned regenerator, and at least a portion is made of the cool storage material that above-mentioned general formula (1) or general formula (2) are represented.Have, this cool storage material preferably is filled in the dirty low temperature side of regenerator (last cooling section) again.
And the MRI relevant with the present invention (magnetic resonance imaging) device, magnetic-levitation train is characterized in that any cold storage refrigerator of the present invention that all has with superconducting magnet, cryopump and externally-applied magnetic field formula single crystal drawing device.
Shown in this general formula, cool storage material of the present invention is to become component to become the magnetic substance of component to be constituted with M by suitably adjusted Cu with respect to the R composition, perhaps, has HoCu
2In the magnetic substance of essentially consist, replace one section H o composition, or constitute with the magnetic substance of M composition displacement one portion C u composition with the R composition.
Promptly, the invention provides a kind of cold storage refrigerator, this refrigerator comprises several cooling sections that is made of the regenerator of having loaded cool storage material, by the regenerator upstream high temperature side inflow working medium of cool storage material from each cooling section, heat exchange by working medium and cool storage material, obtain more low temperature in the regenerator downstream side, wherein at least a portion of the cool storage material of filling in the regenerator is made of a kind of cool storage material, and this cool storage material contains the magnetic substance by general formula (2) expression:
Ho
1-xR
x(Cu
1-yM
y)
2 (2)
R is at least a kind of rare earth element selecting from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb in the formula, M is at least a element of selecting from Ag, Au, Al, Ga, In, Ge, Sn, Sb, Si, Bi, Ni, Pd, Pt, Zn, Co, Rh, Ir, Mn, Fe, Ru, Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf, x, y are with atomic ratio measuring in the formula, satisfy 0≤x≤0.5 respectively, 0≤y≤0.5, x+y ≠ 0.
The present invention also provides a kind of superconducting magnet, this superconducting magnet comprises a kind of cold storage refrigerator, this refrigerator comprises several cooling sections that is made of the regenerator of having loaded cool storage material, by the regenerator upstream high temperature side inflow working medium of cool storage material from each cooling section, heat exchange by working medium and cool storage material, obtain more low temperature in the regenerator downstream side, wherein at least a portion of the cool storage material of filling in the regenerator is made of a kind of cool storage material, and this cool storage material contains the magnetic substance by general formula (2) expression:
Ho
1-xR
x(Cu
1-yM
y)
2 (2)
R is at least a kind of rare earth element selecting from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb in the formula, M is at least a element of selecting from Ag, Au, Al, Ga, In, Ge, Sn, Sb, Si, Bi, Ni, Pd, Pt, Zn, Co, Rh, Ir, Mn, Fe, Ru, Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf, x, y are with atomic ratio measuring in the formula, satisfy 0≤x≤0.5 respectively, 0≤y≤0.5, x+y ≠ 0.
The present invention also provides a kind of NMR-CT, this device comprises a kind of cold storage refrigerator, this refrigerator comprises several cooling sections that is made of the regenerator of having loaded cool storage material, by the regenerator upstream high temperature side inflow working medium of cool storage material from each cooling section, heat exchange by working medium and cool storage material, obtain more low temperature in the regenerator downstream side, wherein at least a portion of the cool storage material of filling in the regenerator is made of a kind of cool storage material, and this cool storage material contains the magnetic substance by general formula (2) expression:
Ho
1-xR
x(Cu
1-yM
y)
2 (2)
R is at least a kind of rare earth element selecting from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb in the formula, M is at least a element of selecting from Ag, Au, Al, Ga, In, Ge, Sn, Sb, Si, Bi, Ni, Pd, Pt, Zn, Co, Rh, Ir, Mn, Fe, Ru, Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf, x, y are with atomic ratio measuring in the formula, satisfy 0≤x≤0.5 respectively, 0≤y≤0.5, x+y ≠ 0.
The present invention also provides a kind of cryopump, this cryopump comprises a kind of cold storage refrigerator, this refrigerator comprises several cooling sections that is made of the regenerator of having loaded cool storage material, by the regenerator upstream high temperature side inflow working medium of cool storage material from each cooling section, heat exchange by working medium and cool storage material, obtain more low temperature in the regenerator downstream side, wherein at least a portion of the cool storage material of filling in the regenerator is made of a kind of cool storage material, and this cool storage material contains the magnetic substance by general formula (2) expression:
Ho
1-xR
x(Cu
1-yM
y)
2 (2)
R is at least a kind of rare earth element selecting from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb in the formula, M is at least a element of selecting from Ag, Au, Al, Ga, In, Ge, Sn, Sb, Si, Bi, Ni, Pd, Pt, Zn, Co, Rh, Ir, Mn, Fe, Ru, Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf, x, y are with atomic ratio measuring in the formula, satisfy 0≤x≤0.5 respectively, 0≤y≤0.5, x+y ≠ 0.
The present invention also provides a kind of externally-applied magnetic field formula single crystal drawing device, this device comprises a kind of cold storage refrigerator, this refrigerator comprises several cooling sections that is made of the regenerator of having loaded cool storage material, by the regenerator upstream high temperature side inflow working medium of cool storage material from each cooling section, heat exchange by working medium and cool storage material, obtain more low temperature in the regenerator downstream side, wherein at least a portion of the cool storage material of filling in the regenerator is made of a kind of cool storage material, and this cool storage material contains the magnetic substance by general formula (2) expression:
Ho
1-xR
x(Cu
1-yM
y)
2 (2)
R is at least a kind of rare earth element selecting from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb in the formula, M is at least a element of selecting from Ag, Au, Al, Ga, In, Ge, Sn, Sb, Si, Bi, Ni, Pd, Pt, Zn, Co, Rh, Ir, Mn, Fe, Ru, Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf, x, y are with atomic ratio measuring in the formula, satisfy 0≤x≤0.5 respectively, 0≤y≤0.5, x+y ≠ 0.
In magnetic substance with above-mentioned general formula (1) or (2) expression, the R composition is at least a kind of element selecting from the rare earth element of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Ho (formula is removed (2)), Tm and Yb, and the M composition is at least a element of selecting from Ag, Au, Al, Ga, In, Ge, Sn, Sb, Si, Bi, Ni, Pd, Pt, Zn, Co, Rh, Ir, Mn, Fe, Ru, Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf.Add these R compositions and M composition, for the temperature position of the volume ratio thermal spike that makes any magnetic substance moves to the lower side of temperature, and the width of ratio thermal peak is so that realize the effective specific heat feature of cool storage material.
In above-mentioned general formula (1),, be taken as-0.95～0.90 with the x of atomic ratio measuring with respect to the decrement that adds of R composition Cu composition and M composition.When the above-mentioned amount x of adjusting is lower than-0.95, RCu
1-xM
1+xIn fact approach simple binary system RCu
2, and surpass at 0.90 o'clock, in fact approach RM
2This moment is because the ratio thermal spike half-breadth value of magnetic substance is very narrow, so, can not keep very high specific heat in wide temperature province, simultaneously, also be difficult to the temperature position of control ratio thermal spike.So it is x is preferably-0.60≤x≤0.60, better in-0.40≤x≤0.40 scope.
In above-mentioned general formula (2), with respect to Ho and Cu, replacement amount x, the y of R composition and M composition with atomic ratio measuring, are taken as 0～0.5.When above-mentioned replacement amount x or y surpass 0.5, the temperature position of volume ratio thermal spike can be moved very big, can reduce the volume specific heat near the temperature province of desired 4K, perhaps, half-breadth value width than thermal spike is too expanded, peak height can reduce again, and the volume ratio thermal change of magnetic substance gets undesirablely in the extremely low temperature zone, has reduced its function again as cool storage material.
Therefore, in the magnetic substance of above-mentioned general formula (2) expression, when adding a kind of in R and the M composition in the magnetotropism body, the temperature position of volume ratio thermal spike can be moved to low temperature side, and effectively enlarges the half-breadth value width than thermal spike.Therefore, addition (replacement amount) x of above-mentioned R composition and M composition, the lower value of y, both sides all can be defined as zero, but the value of x and y can not be 0 simultaneously, promptly will satisfy the relational expression of x+y ≠ 0.
In the magnetic substance of above-mentioned general formula (1), (2) expression, as the R composition, though can use at least a kind in the above-mentioned various rare earth element, but wherein Ce, Pr, Nd, Er, Dy, Ho (formula is removed in (2)), Tb and Gd are most appropriate to improve the ratio thermal property of cool storage material, and Pr, Nd, Er, Dy, Ho (formula is removed in (2)) are special ideal.
And as the M composition, in the above-mentioned metallic element, particularly Ag, Al, Ni, Ga, In, Ge, Sn, Si are ideal, and Al, Ga, Ge, Sn are better.For the M composition, the same with the R composition, by selecting several elements, can control the ratio thermal spike half-breadth value width of magnetic substance and than the temperature position of thermal spike.
In the magnetic substance of above-mentioned general formula (1) or (2) expression, have the hexagonal system of at least 50% (volume) (50～99.99% (volume)) or the magnetic substance of rhombic system crystalline structure, desirable especially as cool storage material.Hexagonal system or rhombic system and isometric system are the low crystalline structure of symmetry relatively.The inventor confirms, the symmetry of crystalline structure, and the effect by the xln field produces greatly influence to the ratio thermal property of cool storage material.Past, it is generally acknowledged when demonstration is narrower than thermal spike half-breadth value width to have the high crystalline structure of this symmetry of steep isometric system than thermal spike trend, be ideal as cool storage material.
On the other hand, the inventor is conceived to this cliffy summit, compares thermal spike but be conceived to the wideer wide cut of half-breadth value width.That is,, be conceived to hexagonal system that symmetry is low or rhombic system magnetic substance as main body in wideer temperature province, realizing higher specific heat.
The crystal symmetry of hexagonal system is higher slightly than rhombic system, because its crystal symmetry that presents is between isometric system and the rhombic system, so the specific heat peakedness ratio is higher, half-breadth value width is also than broad.That is, owing to can in very wide temperature range, obtain the good ratio thermal property of balance, so, be special ideal.
And, magnetic substance with above-mentioned general formula (1) or (2) expression, can be easy to from the state graph that contains the rare earth element material analogize, so, be difficult to realize the single phase structure structure, normally by compound between the different several metal of ratio of components mutually with constituted mutually by the impurity of forming as oxide compound or carbide etc.This weave construction form (metal structure), even form under the identical situation in target, ambiance in the time of also can forming content, melt temperature, the fusion of trace impurities such as oxygen and carbon along with the mixing of raw material and setting rate are slightly different and change.Particularly the process of cooling in the high-temperature area from fusing point to solidus curve is woven with very sensitive influence to metal group, so extremely difficult controlled chilling process.
In the magnetic substance metal structure that constitutes cool storage material of the present invention, contain rare earth metal or its sosoloid, unsatisfactory.That is, rare earth metal or its sosoloid and the intermetallic compound that contains rare earth element relatively because lower than thermal property, are not preferably separated out in metal structure as much as possible.Therefore, above-mentioned metal structure of not separating out rare earth metal or its sosoloid can mix by the raw material in control feedstock production stage and form, and promptly reduces by 1 R composition slightly from target is formed, and just can realize.
Magnetic substance ratio with above-mentioned hexagonal system or rhombic system crystalline structure is preferably in 50% (volume) or greater than 50% (volume).When the ratio of this crystalline structure was lower than 50% (volume), specific heat was big, became undesirable, in addition, also became sharply than thermal spike, during as cool storage material, can reduce the cold-storage effect.Consider that from above-mentioned viewpoint the magnetic substance ratios with six upright crystallographic systems or rhombic system crystalline structure are preferably in 70% (volume) or more than it, 80% (volume) or it more than better.
As previously mentioned, constitute the metal structure form of magnetic substance, the influence of complicated factors such as ambiance when being easy to be subjected to mixing content, melt temperature, the fusion of the trace impurities such as fine difference, oxygen and carbon of composition and setting rate.Therefore, be difficult to determine that a kind of method realizes above-mentioned metal construction.Particularly, under the situation of ternary or its above multicomponent system, it is very complicated that phasor becomes, and is difficult to realize desired metal construction.
But,, proved the following fact according to present inventors' opinion.When preparing magnetic particle by raw material melt alloy, use fast quench methods such as centrifugal spraying method and gas atomization method, and, and the temperature of melt alloy is set at than the high 100～300K of raw material fusing point, then can be easy to obtain to have the above-mentioned metal construction that needs ratio.
For steadily being flowed into, working mediums (cooling agent) such as helium loaded in the regenerator of cool storage material, simultaneously, for improving the heat exchanger effectiveness between above-mentioned working medium and the cool storage material, and for the stable maintenance hot-swap feature, above-mentioned cool storage material preferably is made of the spherical magnetic particle of particle diameter unanimity.Specifically, in all magnetic particles that constitute above-mentioned cool storage material, the ratio of the preferred line of apsides (shape than) is below 5, and preferable particle size is that the magnetic particle ratio of 0.01～3mm is controlled at 70% (weight) or more than it.
The grain size of magnetic particle is the individual factor that produces a very large impact for the refrigerating function and the heat transfer characteristic of particle intensity, refrigerator, when grain size during less than 0.01mm, when in regenerator, loading, density can be too high, cooling agent (heat-eliminating medium) He gas is sharply increased by resistance (pressure-losses), along with mobile He gas cut is gone in the compressor, component parts is worn prematurely, cause its life-span to descend.
On the other hand, when grain size surpasses 3mm, produce segregation in the crystalline structure of granule, become fragile, simultaneously, the heat transfer area between magnetic particle and the heat-eliminating medium He gas diminishes, and heat transfer efficiency is significantly reduced.When this oversize particle surpasses 30% (weight), will cause the cold-storage performance to reduce.Therefore, the median size size is set between 0.01～3mm, is preferably between 0.05～1.0mm, more preferably between 0.1～0.5mm.
In the practical application, for refrigerating function and the intensity of giving full play to cool storage material, for whole magnetic cold-storage material particles, the particle with above-mentioned particle diameter is at least in 70% (weight), be preferably in 80% (weight) or bigger, be more preferably and account for 90% (weight) or bigger.
, be preferably in below 3 below 5 according to the ratio of the line of apsides of magnetic particle of the present invention (shape than), better below 2, it is especially good to be set in below 1.3.The shape of magnetic particle comparison particle intensity and filling density and homogeneity when loading in regenerator produce very big influence, when the shape ratio surpasses 5, be subjected to mechanical effect, be easy to cause the deformation failure of magnetic particle, simultaneously, be difficult to evenly, and in regenerator, load to high-density, make the space form homogeneous,, will cause the reduction of cold-storage efficient when this particle accounts for 30% (weight) of the total particle of cool storage material when above.
When utilizing molten metal quenching legal system to be equipped with magnetic particle, the deviation of the ratio of the deviation of its particle diameter and the line of apsides relatively, reduces, so the magnetic particle ratio outside the above-mentioned particle size range is very little when being equipped with the plasma jet legal system of using routine greatly.Even the generation deviation is easy to that also it is carried out suitable classification and is used.At this moment, be filled in all magnetic particles of regenerator inside, shape is set in 70% or bigger than the magnetic particle ratio in above-mentioned scope, is preferably in 80% or bigger, better 90% or bigger, so that obtain fully durable cool storage material.
Magnetic particle average crystalline particle diameter by the preparation of molten metal quenching method is set in 0.5mm or littler, and perhaps at least a portion of alloy structure makes the amorphism material, then can form the long lifetime magnetic particle of very high strength.
The surfaceness of magnetic particle also is the resistance that passes through to physical strength, cooling characteristic, heat-eliminating medium, the factor that cold-storage efficient etc. produces a very large impact, and according to the regulation of JIS (Japanese Industrial Standards) B 0601, concavo-convex maximum height R
MaxGenerally at 10 μ m or below it, be preferably in 5 μ m or below it, better be set in 2 μ m or below it.Its surfaceness can utilize scanning tunnel microscope (STM roughmeter) to measure.
As surfaceness R
MaxWhen surpassing 10 μ m, on particle, form destructive and cause point, easily produce hair line, simultaneously, the resistance that passes through of heat-eliminating medium rises, and increases the load of compressor, and particularly contact area increases between the magnetic particle of Tian Zhuaning, cold and hot conductivity change between magnetic particle strengthens, and cold-storage efficient is reduced.
To the magnetic particle that the physical strength of magnetic particle exerts an influence with the tiny flaw more than the length 10 μ m, account for whole ratio and be 30% or below it, better below 20%, better should be during application 10% or below it.
The manufacture method of above-mentioned magnetic cold-storage material particle does not have particular determination, can use the manufacture method of various widely used alloy particles.For example, according to the centrifugal spraying method, gas atomization method, rotating electrode method etc. also can use the melt alloy that disperses to have the regulation composition to carry out the method that fast quench solidifies simultaneously.
When the melt alloy is handled in above-mentioned quenching, Cu proportioning in the adjusting melt alloy composition is multiple spot slightly, or suitably control setting rate, the metal construction of magnetic cold-storage material particle inside can be transformed into antiferromagnetic gonosome and heterogeneous metal structure by above-mentioned general formula (1) or (2) expression.
When particularly forming the magnetic cold-storage material particle that constitutes by antiferromagnetic gonosome,, also can obtain the effect that influenced by the superconducting magnet stray field even when this particle is used as superconductive system with the cool storage material of refrigerator.
Magnetic cold-storage material particle with metal construction of this Cu metallographic phase formation, its physical strength height.Therefore, the excessive stresses that generates even the impact force action that the operating vibration of refrigerator etc. produce when cool storage material, is perhaps loaded in regenerator is done the time spent, also can be not destroyed or pulverize.
Therefore, can prevent effectively that hermetic unit that the cool storage material powder is invaded refrigerator in company with working medium from causing the refrigerator damage that damage etc. and solid efflorescence cause.
Cold storage refrigerator of the present invention, its formation be, in the regenerator of the final cooling section of the refrigerator with several cooling sections, at least a portion is filled with above-mentioned magnetic cold-storage material particle.For example, under the situation of 2 sections expanding type refrigerators, low-temperature end one side that is located at the 2nd section regenerator is filled cool storage material of the present invention.And in the occasion of 3 sections expanding type refrigerators, low-temperature end one side at the regenerator of the 3rd section setting, load cool storage material of the present invention, and the space that other cool storage material is loaded, should load and have other cool storage material that the temperature distribution than thermal property and regenerator is complementary.
In the regenerator of above-mentioned final cooling section, in weight ratio, the amount of fill of magnetic cold-storage material particle of the present invention is too small, and little to 1% (weight) or more hour, does not think that the cold-storage efficient of refrigerator has raising.On the other hand, when amount of fill is big, and greatly to 80% (weight) or when bigger, the shortcoming of magnetic cold-storage material particle of the present invention becomes clearly, causes cold-storage efficient to reduce equally.
That is, the temperature province of volume specific heat beyond the temperature of Cheng Feng, particularly in the high temperature side temperature province, the volume ratio thermal change gets smaller, can produce detrimentally affect to whole regenerator, and the result causes cold-storage efficient to reduce.Therefore, for the particle gross weight of loading in the regenerator of above-mentioned final cooling section, the amount of fill of magnetic cold-storage material particle of the present invention in 1-80% (weight) scope, but is preferably in 2～70% (weight), better between 3～50% (weight).
According to the cool storage material of above-mentioned formation, suitably adjust the consumption of Cu and M composition for the R composition, perhaps, the HoCu that in the extremely low temperature zone, has sharp-pointed volume ratio thermal spike with displacements such as other rare earth element or transition metal
2Part in the magneticsubstance constituent so the temperature position of volume ratio thermal spike can be displaced to more low temperature place, simultaneously, has enlarged the half-breadth value than thermal spike, obtains the cool storage material better than thermal property.Equally,, can be provided at refrigerating capacity height in the temperature 4K zone by low-temperature end one side in the regenerator that this cool storage material is filled in the final cooling section of refrigerator, and can the long-time interior refrigerator that keeps stablizing freezing performance.
Equally, MRI device, cryopump, magnetic-levitation train superconducting magnet and externally-applied magnetic field formula single crystal drawing device, the performance of any refrigerator can both about each the device performance, so the MRI device of the present invention, cryopump, magnetic-levitation train that use above-mentioned refrigerator be with superconducting magnet and externally-applied magnetic field formula single crystal drawing device, anyly bring into play good performance in can both be between long-term.
The accompanying drawing simple declaration
Fig. 1 is the formation sectional drawing of the cold storage refrigerator of the present invention (GM refrigerator) major portion.
Fig. 2 be in embodiment and the comparative example cool storage material than the comparison synoptic diagram of thermal property.
Fig. 3 is the brief configuration schematic cross-sectional views of superconducting MRI device according to one embodiment of the present invention.
Fig. 4 is the brief configuration signal oblique drawing of superconducting magnet (using on the magnetic-levitation train) integral part according to one embodiment of the present invention.
Fig. 5 is the brief configuration schematic cross-sectional views of cryopump according to one embodiment of the present invention.
Fig. 6 is the brief configuration signal oblique drawing of the major portion of externally-applied magnetic field formula single crystal drawing device according to one embodiment of the present invention.
Implement optimised form of the present invention
Specify embodiment of the present invention below with reference to following embodiment.
Mix various raw metals, utilize the high-frequency melting method to prepare respectively and have each mother alloy of forming shown in the left hurdle of table 1.Each mother alloy of fusion under than the temperature of the high approximately 150K of each mother alloy composition fusing point prepares various melt alloys, is in the Ar gas atmosphere of 90KPa with each melt alloy at pressure again, drips with 1.5 * 10
4On the rotating disk of the speed rotation of rpm, its quenching is solidified, make the magnetic substance particle respectively.
By resulting magnetic substance particle, carry out the Shape Classification classification after, sieve out L/D ratio 1.2 or particle below it, the spherical magnetic substance particle that filters out 200g particle diameter 0.2～0.3mm respectively constitutes the cool storage material of embodiment 1～12.
Mix various raw metals, utilize the high-frequency melting method respectively raw materials mixed to be carried out fusion again, preparation has each mother alloy of forming shown in the left hurdle of table 1, each mother alloy of fusion under the temperature of about 1350K, preparing each melt alloy is in the He gas atmosphere of 90KPa with every kind of melt alloy at pressure again, drops in 1 * 10
4It is solid to carry out quench condensation on the disk of rpm speed rotation, makes the magnetic substance particle respectively.The magnetic substance particle that obtains is classified by the shape classification, sieve out L/D ratio and be 1.2 or its following particle, the spherical magnetic substance particle that filters out the 200g particle diameter respectively and be 0.2～0.3mm constitutes the cool storage material of embodiment 13～23.
Utilize the crystalline structure of X-ray diffraction method evaluation as the various cool storage materials of the embodiment 1～23 of above-mentioned preparation.Each crystalline structure have a ratio, calculate by the integrated intensity at X-ray diffraction peak.Calculation result is shown in table 1.
On the other hand, in order to estimate each cool storage material characteristic of above-mentioned preparation, prepare 2 sections expanding type GM refrigerators shown in Figure 1.In addition, 2 segmentation GM refrigerators 10 shown in Figure 1 are embodiments of refrigerator of the present invention.
2 segmentation GM refrigerators 10 shown in Figure 1 have be provided with large diameter the 1st cylinder 11 with the vacuum vessel 13 of the 2nd cylinder 12 of the 1st cylinder 11 coaxial minor diameters that are connected.In the 1st cylinder 11, dispose the 1st regenerator 14 that can back and forth move freely, in the 2nd cylinder 12, also dispose the 2nd regenerator 15 that can back and forth move freely.Between the 1st cylinder 11 and the 1st regenerator 14, between the 2nd cylinder 12 and the 2nd regenerator 15, dispose wear ring 16,17 respectively.
Cu net grade in an imperial examination 1 cool storage material 18 is packed in the 1st regenerator 14.Utmost point low temperature usefulness cool storage material of the present invention pack into as the 2nd cool storage material 19 at the downside of the 2nd regenerator 15.The 1st regenerator 14 and the 2nd regenerator 15 have the path of the working mediums (cooling agent) such as He gas that are located at the 1st cool storage material 18 and utmost point low temperature usefulness cool storage material 19 gap locations respectively.
Between the 1st regenerator 14 and the 2nd regenerator 15, be provided with the 1st expansion chamber 20.Between the end wall of the 2nd regenerator 15 and the 2nd cylinder 12, be provided with the 2nd expansion chamber 21.And, form the 1st cooling section 22 in the bottom of the 1st expansion chamber 20, and at the bottom formation temperature of the 2nd expansion chamber 21 2nd cooling section 23 lower than the 1st cooling section 22.
In the GM of above-mentioned 2 segmentations refrigerator 10, infeed high-pressure working medium (for example He gas) by compressor 24.The working medium that infeeds arrives the 1st expansion chamber 20 by being contained in the 1st cool storage material 18 in the 1st regenerator 14, by being contained in the utmost point low temperature cool storage material (the 2nd cool storage material) 19 in the 2nd regenerator 15, arrives the 2nd expansion chamber 21 again.At this moment, working medium is supplied with each cool storage material 18,19 with heat energy and is cooled off.
By the working medium of each cool storage material 18,19, in each expansion chamber 20,21, expand, produce cold atmosphere, make each cooling section 22,23 cooling.The expansible working medium flows to 18,19 of each cool storage materials in the opposite direction.Working medium is discharged after each cool storage material 18,19 receives heat energy.In such process, along with the heat exchange effect improves, working medium round-robin thermo-efficiency has improved, thereby has realized the lower temperature of refrigerator.
Equally,, be filled in the low temperature side of the 2nd regenerator of above-mentioned 2 sections expanding type GM refrigerators, and then load 150g Er at the high temperature side of the 2nd regenerator with the cool storage material among each embodiment 1～23 of the above-mentioned preparation of 200g
3The Ni cool storage material is assembled into the refrigerator of embodiment 1～23 respectively, implements freezing test, and each refrigerator operation is continuously measured its refrigerating capacity after 3000 hours.
Refrigerating capacity among these embodiment is defined as when refrigerator moves, and to the 2nd cooling section supply thermal load, makes the temperature of the 2nd cooling section rise the thermal load when stopping at 4.2K by well heater.
Comparative example 1～3
1,2 prepare the conventional (Er of composition respectively as a comparative example
3Ni, ErNi
2) mother alloy.And as a comparative example 3, do not add R composition and M composition, mix Ho, Cu raw metal, prepare raw mix thus, utilize high-frequency melting method fused raw material mixture again, preparation contains HoCu thus
2.0The mother alloy of forming.Making these mother alloys carry out fusion under the temperature than the high 350K of fusing point of composition, with each alloy solution that obtains, is in the Ar gas atmosphere of 90KPa at pressure, and each alloy solution is dropped in 1 * 10
4It is solid to carry out quench condensation on the rotating disk of rpm speed rotation, makes each magnetic substance particle.
The magnetic substance particle that obtains is carried out by after the Shape Classification classification, sieve out L/D ratio 1.2 or particle below it, choosing the 200g particle diameter is the cool storage material that the spherical magnetic substance particle of 0.2～0.3mm constitutes each comparative example 1～3.
Utilize X-ray diffraction method to identify the crystalline structure of the cool storage material of each comparative example, calculate the ratio that exists of this crystalline structure by the X-ray diffraction peak, calculation result is shown in table 1.Can confirm ErNi in the comparative example 2
242% (volume) of cool storage material is to be made of rhombic system, and all the other 58% (volumes) are to be made of isometric system.
Comparative example 4
Utilize the high-frequency melting method to make the mother alloy that has with embodiment 1 same composition (HoCuAl).The mother alloy that obtains is pulverized with beater grinder, made the powder that particle diameter is 0.2～0.3mm.Then,, in Ar gas atmosphere, utilize the plasma body spray method to fuse dispersion, be processed into spherical powder the powder that obtains.In this plasma body spraying was handled, last Ar atmospheric pressure reached 180KPa.To this spherical particle, the same crystalline structure and have ratio measured with embodiment the results are shown in table 1.
Comparative example 5
Under the condition identical with embodiment 1, with the ratio of components of atom % (at.%), preparation Ho
42Cu
29Al
29Spherical particle.Utilize X-ray diffraction method to identify the spherical particle crystalline structure that obtains, the results are shown in table 1.When utilizing the observable particle of EPMA method, confirm to have the Ho layer on the particle surface.
Then, with each the comparative example 1-5 cool storage material 200g that obtains, be filled in the 2nd regenerator low temperature side of 2 sections expanding type GM refrigerators shown in Figure 1.Load 150g Er at the high temperature side of the 2nd regenerator again
3The Ni cool storage material is assembled into the refrigerator of each comparative example 1-5, implements freezing test, measures the refrigerating capacity of the refrigerator of operation after 3000 hours continuously.
The refrigerating capacity measurement result of each refrigerator is shown in table 1.
Table 1
| Specimen coding | Cool storage material is formed (atomic ratio) | Hexagonal system or rhombic ratio | Refrigerating capacity under 4.2K (w) |
| Embodiment 1 | HoCuAl | 94(h) | 1.26 |
| Embodiment 2 | HoCu 1.2Al 0.8 | 88(h) | 1.29 |
| Embodiment 3 | HoCu 0.7Al 1.3 | 76(h) | 1.21 |
| Embodiment 4 | DyCuSn | 93(h) | 1.07 |
| Embodiment 5 | HoCuSn | 94(h) | 1.25 |
| Embodiment 6 | ErCuSn | 89(h) | 1.10 |
| Embodiment 7 | NdCuGe | 94(h) | 1.06 |
| Embodiment 8 | DyCuGe | 85(h) | 1.00 |
| Embodiment 9 | HoCuGe | 91(h) | 1.07 |
| Embodiment 10 | ErCuGe | 96(h) | 1.09 |
| Embodiment 11 | Ho 0.5Er 0.5CuSn | 90(h) | 1.29 |
| Embodiment 12 | HoCuSn 0.9Ge 0.1 | 87(h) | 1.32 |
| Embodiment 13 | Ho 0.9Pr 0.1Cu 2 | 95(o) | 1.16 |
| Embodiment 14 | Ho 0.7Nd 0.3Cu 2 | 88(o) | 1.20 |
| Embodiment 15 | Ho 0.8Er 0.2Cu 2 | 96(o) | 1.18 |
| Embodiment 16 | Ho 0.6Ce 0.4Cu 2 | 91(o) | 1.09 |
| Embodiment 17 | Ho 0.95Dy 0.05Cu 2 | 86(o) | 1.06 |
| Embodiment 18 | Ho 0.99Gd 0.01Cu 2 | 90(o) | 1.11 |
| Embodiment 19 | Ho 0.85Tb 0.15Cu 2 | 96(o) | 1.07 |
| Embodiment 20 | HoCu 1.9Ni 0.1 | 91(o) | 1.17 |
| Embodiment 21 | HoCu 1.4Al 0.6 | 86(o) | 1.16 |
| Embodiment 22 | HoCu 1.8Ag 0.2 | 97(o) | 1.25 |
| Embodiment 23 | Ho 0.9Nd 0.1Cu 1.9Ag 0.1 | 90(o) | 1.22 |
| Comparative example 1 | Er 3Ni | 90(o) | 0.52 |
| Comparative example 2 | ErNi 2 | 42(o) | 0.37 |
| Comparative example 3 | HoCu 2.0 | 84(o) | 0.81 |
| Comparative example 4 | HoCuAl | 44(h) | 0.53 |
| Comparative example 5 | Ho 42Cu 29Al 29(at.％) | 65(h) | 0.55 |
Annotate: in hexagonal system or rhombic ratio, (h) expression hexagonal system, (o) expression rhombic system.
Known to from result shown in the above-mentioned table 1, suitably adjusting Cu for the R composition becomes component, replaces a part of Ho or with each refrigerator of the cool storage material of each embodiment that antiferromagnetic gonosome constituted of a part of Cu of displacement such as transition metal with other rare earth element with M, with the refrigerator of comparative example relatively, can confirm that the such refrigerating capacity of any one refrigerator in the 4K zone all want high 1.2～3.5 times.And then as can be known, used the refrigerator of each embodiment cool storage material, owing to improved the physical strength of cool storage material, and it is rotten that cool storage material can not worsened, even refrigerator long-time continuous operation work, the reduction of refrigerating capacity is little, can keep stable refrigerating capacity.
Fig. 2 has HoCu
1.2Al
0.8The cool storage material of the embodiment 2 that forms and have HoCu
2.0The ratio thermal property of comparative example 3 cool storage materials of forming is synoptic diagram relatively.Compare with the cool storage material of comparative example 3, as can be known because embodiment 2 cool storage materials specific heat in low-temperature region is big, so when the cool storage material of embodiment 2 being filled in the regenerator of refrigerator, can increase refrigerating capacity, the rising of freezing operation is also good.
The cool storage material of comparative example 4, owing to be to prepare with conventional plasma jet method, with regard to its crystalline texture itself, with solidify the cool storage material of the present invention that legal system is equipped with quenching, come down to different, because it is very little to form the crystalline structure ratio of hexagonal system, so do not reach competent refrigerating capacity.
On the other hand, in the cool storage material of comparative example 5,, form two second phases or the parafacies that much contain rare earth metal and its sosoloid owing to improved the amount of rare earth composition (R) relatively.So the cold-storage effect is not in full use.
In contrast, in the cool storage material of each embodiment, reduced the amount of rare earth composition relatively.Owing to do not separate out rare earth metal, outside the removal of impurity, all form intermetallic compound, so this material demonstrates good ratio thermal property, given play to high refrigerating capacity.
Below superconducting MRI device of the present invention, magnetic-levitation train are described with the embodiment of superconducting magnet, cryopump and externally-applied magnetic field formula single crystal drawing device.
Fig. 3 is to use the concise and to the point schematic cross-sectional views of superconducting MRI apparatus structure of the present invention.Superconducting MRI device 30 shown in Fig. 3, its formation comprises: it is even that human body is added the space, the superconduction static magnetic field coil 31 of stable static magnetic field, compensation produce the compensation coil (omitting among the figure) of magnetic field bump on time, give the gradient magnetic field coil 32 of field gradient and the transmitter 33 of transmitting-receiving electric wave etc. to measuring the zone.And, as the refrigerator of cooling superconduction static magnetic field coil 31, can use the cold storage refrigerator 34 of the invention described above.In addition, among the figure, numeral 35 expression cryostats, numeral 36 expression radiation disrupters.
Used the superconducting MRI device 30 of the cold storage refrigerator 34 of the present invention, owing to can guarantee in long-time that the working temperature of superconduction static magnetic field coil 31 is stable, so it is even to obtain the space in for a long time, stable static magnetic field on the time.Therefore, can bring into play the performance of superconducting MRI device 30 steadily in the long term.
Fig. 4 has been to use the structural representation oblique drawing of the magnetic-levitation train of the cold storage refrigerator of the present invention with the superconducting magnet integral part, and magnetic-levitation train superconducting magnet 40 parts are shown.Magnetic-levitation train shown in Fig. 4 comprises with the formation of superconducting magnet 40: superconducting coil 41, cool off the liquid helium jar 42 of this superconducting coil 41, anti-liquid helium jar evaporable liquid nitrogen container 43 and cold storage refrigerator 44 of the present invention etc.In addition, among the figure, numeral 45 is expression lamination lagging materials, and numeral 46 is apparent source lead-in wires, and numeral 47 is permanent electric current switches.
The magnetic-levitation train of the cold storage refrigerator 44 of use the present invention is with in the superconducting magnet 40, because the working temperature of superconducting coil 41 can guarantee long-term stability, so the floating and propelling for the magnetic of train can obtain necessary magnetic field steady in a long-term.Particularly, the superconducting magnet 40 that magnetic-levitation train is used can be subjected to the effect of acceleration, but cold storage refrigerator 44 of the present invention is even be subjected under the situation of acceleration effect, owing to can keep long good refrigerating capacity, so for long-term stable very big contributions of having made such as magneticstrengties.Therefore, used the magnetic-levitation train of this superconducting magnet 40, can make its reliability in long-time, obtain performance.
Fig. 5 has been to use the cryopump brief configuration sectional schematic diagram of the cold storage refrigerator of the present invention.Cryopump 50 shown in Fig. 5, its structure comprises: condense or the annular plate 51 of adsorption gas molecule, the cold storage refrigerator 52 of extremely cryogenic the present invention that this annular plate 51 is cooled to stipulate, be arranged on the sealing baffle 53 between them, be located at the baffle plate 54 of suction opening and change the ring 55 etc. of exhaust velocities such as argon, nitrogen, hydrogen.
In the cryopump 50 that has used the cold storage refrigerator 52 of the present invention, can guarantee the working temperature long-term stability of annular plate 51.Therefore, cryopump 50 can be brought into play its stable performance in long-time.
Fig. 6 has been to use the brief configuration stravismus synoptic diagram of the externally-applied magnetic field formula single crystal drawing device of the cold storage refrigerator of the present invention.Externally-applied magnetic field formula single crystal drawing device 60 shown in Figure 6, its formation comprises: have crucible that fused raw material uses, well heater, crystal-pulling mechanism etc. crystal-pulling part 61, raw material melt is added the superconducting coil 62 of static magnetic field and the hoisting appliance 63 of crystal-pulling part 61 etc.And, as the freezing plant of cooling superconducting coil 62 usefulness, still use the cold storage refrigerator 64 of the invention described above.In addition, numeral 65 is current terminals, the 66th among the figure, heat seal baffle plate, the 67th, helium vessel.
In having used the externally-applied magnetic field formula single crystal drawing device 60 of the cold storage refrigerator 64 of the present invention, owing to can guarantee the working temperature long-term stability of superconducting coil 62, so, can obtain to suppress the magnetic field of crystal raw material melt convection for a long time.Therefore, the performance that can in long-time, play stably of externally-applied magnetic field formula single crystal drawing device 60.
The possibility of industrial application
As mentioned above, according to cool storage material of the present invention, owing to the amount of suitably having adjusted copper and other metal ingredient with respect to rare earth composition, perhaps, owing to replaced a part has high volume ratio thermal spike in the extremely low temperature zone HoCu with other rare earth element or transition metal etc.2The constituent of magnetic material, so, make the temperature position of volume ratio thermal spike move to the lower example of temperature, enlarge simultaneously the half-breadth value width than thermal spike, thereby obtained the good cool storage material of Specific Heat Capacity.
And, by low temperature one side in the regenerator that this cool storage material is filled in the last cooling section of refrigerator, thus can provide a kind of in the 4K temperature province refrigerating capacity high, and, can be in long-time maintenance stablize the refrigerator of freezing performance.
Therefore, used this utmost point low temperature with the refrigerator of the present invention of cool storage material, can make good freezing performance in long-time, keep good repeatability. Have again, have MRI device of the present invention, cryogenic pump, magnetic-levitation train superconducting magnet and the externally-applied magnetic field formula single crystal drawing device of this refrigerator, can in long-time, bring into play good performance.
Claims (8)
1. a cool storage material is characterized in that, this cool storage material contains the magnetic substance by general formula (2) expression:
Ho
1-xR
x(Cu
1-yM
y)
2 (2)
R is at least a kind of rare earth element selecting from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb in the formula, M is at least a element of selecting from Ag, Au, Al, Ga, In, Ge, Sn, Sb, Si, Bi, Ni, Pd, Pt, Zn, Co, Rh, Ir, Mn, Fe, Ru, Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf, x, y are with atomic ratio measuring in the formula, satisfy 0≤x≤0.5 respectively, 0≤y≤0.5, x+y ≠ 0.
2. according to the cool storage material of claim 1, wherein said magnetic substance has the hexagonal system or the rhombic crystalline structure of 50% volume or its above ratio.
3. according to the cool storage material of claim 1 or 2, wherein said magnetic substance is antiferromagnetic gonosome.
4. cold storage refrigerator, this refrigerator comprises several cooling sections that is made of the regenerator of having loaded cool storage material, by the regenerator upstream high temperature side inflow working medium of cool storage material from each cooling section, heat exchange by working medium and cool storage material, obtain more low temperature in the regenerator downstream side, wherein at least a portion of the cool storage material of filling in the regenerator is made of a kind of cool storage material, and this cool storage material contains the magnetic substance by general formula (2) expression:
Ho
1-xR
x(Cu
1-yM
y)
2 (2)
R is at least a kind of rare earth element selecting from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb in the formula, M is at least a element of selecting from Ag, Au, Al, Ga, In, Ge, Sn, Sb, Si, Bi, Ni, Pd, Pt, Zn, Co, Rh, Ir, Mn, Fe, Ru, Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf, x, y are with atomic ratio measuring in the formula, satisfy 0≤x≤0.5 respectively, 0≤y≤0.5, x+y ≠ 0.
5. superconducting magnet, this superconducting magnet comprises a kind of cold storage refrigerator, this refrigerator comprises several cooling sections that is made of the regenerator of having loaded cool storage material, by the regenerator upstream high temperature side inflow working medium of cool storage material from each cooling section, heat exchange by working medium and cool storage material, obtain more low temperature in the regenerator downstream side, wherein at least a portion of the cool storage material of filling in the regenerator is made of a kind of cool storage material, and this cool storage material contains the magnetic substance by general formula (2) expression:
Ho
1-xR
x(Cu
1-yM
y)
2 (2)
R is at least a kind of rare earth element selecting from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb in the formula, M is at least a element of selecting from Ag, Au, Al, Ga, In, Ge, Sn, Sb, Si, Bi, Ni, Pd, Pt, Zn, Co, Rh, Ir, Mn, Fe, Ru, Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf, x, y are with atomic ratio measuring in the formula, satisfy 0≤x≤0.5 respectively, 0≤y≤0.5, x+y ≠ 0.
6. NMR-CT, this device comprises a kind of cold storage refrigerator, this refrigerator comprises several cooling sections that is made of the regenerator of having loaded cool storage material, by the regenerator upstream high temperature side inflow working medium of cool storage material from each cooling section, heat exchange by working medium and cool storage material, obtain more low temperature in the regenerator downstream side, wherein at least a portion of the cool storage material of filling in the regenerator is made of a kind of cool storage material, and this cool storage material contains the magnetic substance by general formula (2) expression:
Ho
1-xR
x(Cu
1-yM
y)
2 (2)
R is at least a kind of rare earth element selecting from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb in the formula, M is at least a element of selecting from Ag, Au, Al, Ga, In, Ge, Sn, Sb, Si, Bi, Ni, Pd, Pt, Zn, Co, Rh, Ir, Mn, Fe, Ru, Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf, x, y are with atomic ratio measuring in the formula, satisfy 0≤x≤0.5 respectively, 0≤y≤0.5, x+y ≠ 0.
7. cryopump, this cryopump comprises a kind of cold storage refrigerator, this refrigerator comprises several cooling sections that is made of the regenerator of having loaded cool storage material, by the regenerator upstream high temperature side inflow working medium of cool storage material from each cooling section, heat exchange by working medium and cool storage material, obtain more low temperature in the regenerator downstream side, wherein at least a portion of the cool storage material of filling in the regenerator is made of a kind of cool storage material, and this cool storage material contains the magnetic substance by general formula (2) expression:
Ho
1-xR
x(Cu
1-yM
y)
2 (2)
R is at least a kind of rare earth element selecting from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb in the formula, M is at least a element of selecting from Ag, Au, Al, Ga, In, Ge, Sn, Sb, Si, Bi, Ni, Pd, Pt, Zn, Co, Rh, Ir, Mn, Fe, Ru, Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf, x, y are with atomic ratio measuring in the formula, satisfy 0≤x≤0.5 respectively, 0≤y≤0.5, x+y ≠ 0.
8. externally-applied magnetic field formula single crystal drawing device, this device comprises a kind of cold storage refrigerator, this refrigerator comprises several cooling sections that is made of the regenerator of having loaded cool storage material, by the regenerator upstream high temperature side inflow working medium of cool storage material from each cooling section, heat exchange by working medium and cool storage material, obtain more low temperature in the regenerator downstream side, wherein at least a portion of the cool storage material of filling in the regenerator is made of a kind of cool storage material, and this cool storage material contains the magnetic substance by general formula (2) expression:
Ho
1-xR
x(Cu
1-yM
y)
2 (2)
R is at least a kind of rare earth element selecting from Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb in the formula, M is at least a element of selecting from Ag, Au, Al, Ga, In, Ge, Sn, Sb, Si, Bi, Ni, Pd, Pt, Zn, Co, Rh, Ir, Mn, Fe, Ru, Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf, x, y are with atomic ratio measuring in the formula, satisfy 0≤x≤0.5 respectively, 0≤y≤0.5, x+y ≠ 0.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP287200/97 | 1997-10-20 | ||
| JP287200/1997 | 1997-10-20 | ||
| JP28720097 | 1997-10-20 |
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|---|---|
| CN1248319A CN1248319A (en) | 2000-03-22 |
| CN1174200C true CN1174200C (en) | 2004-11-03 |
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ID=17714369
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB988026708A Expired - Fee Related CN1174200C (en) | 1997-10-20 | 1998-10-20 | Cold-accumulating material and cold-accumulating refrigerator |
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| Country | Link |
|---|---|
| EP (1) | EP0947785B1 (en) |
| CN (1) | CN1174200C (en) |
| DE (1) | DE69813767T2 (en) |
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|---|---|---|---|---|
| JP4551509B2 (en) * | 1998-12-28 | 2010-09-29 | 株式会社東芝 | Cold storage material and cold storage type refrigerator |
| JP5010071B2 (en) * | 2000-07-18 | 2012-08-29 | 株式会社東芝 | Cold storage material, manufacturing method thereof, and refrigerator using the cold storage material |
| WO2003081145A1 (en) * | 2002-03-22 | 2003-10-02 | Sumitomo Heavy Industries, Ltd. | Cryogenic temperature cool storage device and refrigerator |
| CN100458310C (en) * | 2004-08-25 | 2009-02-04 | 爱发科低温泵株式会社 | Coolness storage unit and cryopump |
| JP2006242484A (en) * | 2005-03-03 | 2006-09-14 | Sumitomo Heavy Ind Ltd | Cold accumulating material, cold accumulator and cryogenic cold accumulating refrigerator |
| GB0519843D0 (en) * | 2005-09-29 | 2005-11-09 | Univ Cambridge Tech | Magnetocaloric refrigerant |
| CN103773995B (en) * | 2014-02-13 | 2017-09-15 | 北京科技大学 | A kind of magnetic cold-storage material |
| JP6608835B2 (en) * | 2014-09-25 | 2019-11-20 | 株式会社東芝 | Rare earth regenerator particles, refrigerators using them, superconducting magnets, inspection devices and cryopumps |
| WO2018199278A1 (en) * | 2017-04-28 | 2018-11-01 | 株式会社三徳 | Hocu-based cold-storage material, and cold-storage device and refrigerating machine each equipped therewith |
| CN108981217A (en) * | 2018-06-04 | 2018-12-11 | 中船重工鹏力（南京）超低温技术有限公司 | Cool storage material and the cold storage Cryo Refrigerator for using the cool storage material |
| CA3112908A1 (en) * | 2018-09-28 | 2020-04-02 | Kabushiki Kaisha Toshiba | Cold storage material, refrigerator, device incorporating superconducting coil, and method of manufacturing cold storage material |
| CN110440475A (en) * | 2019-07-23 | 2019-11-12 | 中船重工鹏力（南京）超低温技术有限公司 | Anti-oxidant cool storage material and the cold storage Cryo Refrigerator for using the cool storage material |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07101134B2 (en) * | 1988-02-02 | 1995-11-01 | 株式会社東芝 | Heat storage material and low temperature heat storage |
| JPH0796974B2 (en) * | 1988-11-09 | 1995-10-18 | 三菱電機株式会社 | Multi-stage regenerative refrigerator and cooling device incorporating the same |
| JPH0784957B2 (en) * | 1989-05-30 | 1995-09-13 | 株式会社東芝 | Low temperature regenerator |
| JP2790549B2 (en) * | 1991-06-10 | 1998-08-27 | 三菱電機株式会社 | Superconducting magnet device for crystal pulling device |
| JP2837795B2 (en) * | 1992-11-11 | 1998-12-16 | 住友重機械工業株式会社 | Cryogenic regenerator |
| US5593517A (en) * | 1993-09-17 | 1997-01-14 | Kabushiki Kaisha Toshiba | Regenerating material and refrigerator using the same |
| KR100305249B1 (en) * | 1996-02-22 | 2001-09-24 | 니시무로 타이죠 | Cryogenic refrigerant and refrigerator using the same |
-
1998
- 1998-10-20 EP EP98947963A patent/EP0947785B1/en not_active Expired - Lifetime
- 1998-10-20 CN CNB988026708A patent/CN1174200C/en not_active Expired - Fee Related
- 1998-10-20 DE DE69813767T patent/DE69813767T2/en not_active Expired - Fee Related
- 1998-10-20 WO PCT/JP1998/004749 patent/WO1999020956A1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| EP0947785A4 (en) | 2000-06-07 |
| EP0947785B1 (en) | 2003-04-23 |
| CN1248319A (en) | 2000-03-22 |
| EP0947785A1 (en) | 1999-10-06 |
| WO1999020956A1 (en) | 1999-04-29 |
| DE69813767D1 (en) | 2003-05-28 |
| DE69813767T2 (en) | 2004-02-12 |
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