JP2011137632A - Cold storage medium, cold accumulator, and cryogenic cold storage type refrigerating machine - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a more environment-friendly and inexpensive cold storage medium easily turned into a spherical shape, having sufficient mechanical strength for use and having a superior thermal property when used for a refrigerating machine. <P>SOLUTION: The cold storage medium includes granular bodies of bismuth alone in which a rate of the granular bodies having &ge;0.14 mm and &le;1.6 mm of a grain size is set to be 70 wt.% or more with respect to the whole granular bodies and a rate of the granular bodies of which ratio of the major axis with respect to the minor axis is 5 or less is set to be 70 wt.% or more with respect to the whole granular bodies. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a regenerator material, a regenerator, and a cryogenic regenerator refrigerator, and in particular, a GM (Gifford McMahon) cycle refrigerator, a Stirling cycle refrigerator, a pulse tube refrigerator, a Birmier cycle refrigerator, and a Solvay cycle refrigerator. Regenerators, regenerators, cryogenic regenerators with improved refrigerating capacity using new regenerators, suitable for use in refrigeration systems, etc., used in the precooling stage, and the like The present invention relates to a refrigeration system, a superconducting magnet, a nuclear magnetic resonance imaging (MRI) apparatus, a cryopump, a cryogen purification apparatus, a superconducting element cooling apparatus, and the like.

  Currently, one of the refrigerators widely used in the cryogenic region is a regenerative refrigerator. This includes a heat storage type heat exchanger called a regenerator. This regenerator has a heat exchange material called a regenerator built in the container.

  A material having a large specific heat at the target temperature is used as the cold storage material. Since the refrigerator has a wide temperature range from room temperature to 4K, it is necessary to select a material having a specific heat as large as possible in the entire region. The specific heat is greatly different in temperature dependency depending on the material, and no single material can cope with the entire temperature region. For this reason, optimum materials are used in combination according to the temperature. Usually, wire mesh copper or stainless steel is used from room temperature to around 50K, and spherical lead is used at temperatures lower than that. Lead has been widely used because it has a specific heat higher than other materials, a certain degree of structural strength, and is inexpensive at a low temperature range of 50K or lower (see, for example, Patent Document 1).

  However, due to the impact on the environment, it has been considered that a directive prohibiting use in electrical products will be enforced in Europe in 2006. Lead is used in the solder of electrical products, and it has a strong aspect of dealing with environmental pollution by being left outdoors after disposal.

  The content of the regulation is to eliminate lead from most electrical products except for some military and space applications. Medical products are also included in the regulated products. At present, it is not clear whether or not lead used in refrigerators of MRI equipment will be regulated. It is necessary to secure some countermeasures.

  Patent Document 2 discloses an alloy of indium, bismuth, and a third material as a cold storage material replacing lead. Since indium has a specific heat after lead at a temperature of 50K or less, the idea is to make use of its characteristics.

JP-A-3-99162 JP 2004-225920 A

  However, since indium is a very soft metal, it can not be used as a cold storage material as it is, but it has been raised to the hardness required for the cold storage material by alloying with bismuth and other metals, but it is still used as a cold storage material Is not enough. Moreover, the price of indium is about three times that of lead, and there is a problem that it is too expensive to be used as a cold storage material.

  The present invention has been made to solve the above conventional problems, has low toxicity, is easily spheroidized, has sufficient mechanical strength to be used, is inexpensive, and is excellent when used in a refrigerator. It is an object to provide a regenerator material having excellent thermal properties.

  The present invention is a bismuth single particle, the proportion of particles having a particle size of 0.14 mm or more and 1.6 mm or less is 70% by weight or more with respect to all the particles, and the ratio of the major axis to the minor axis The problem is solved by a regenerator material characterized in that the ratio of the particles having a particle size of 5 or less is 70% by weight or more based on the total particles.

  The surface roughness of the granules is 100 μm or less on the basis of the maximum height Rmax.

  The present invention also provides the above-mentioned problem by using a regenerator material that is a bismuth-only granule and has a granule whose surface roughness is 100 μm or less on the basis of the maximum height Rmax. It has been solved.

  Further, the structure of the granular body contains an amorphous phase at least partially.

  Moreover, the ratio with respect to all the particles of the particle | grains which have a micro defect with a length of 10 micrometers or more in the said granule shall be 30 weight% or less.

  Further, the surface of the granule is not discolored by oxidation.

  The granule is sintered and processed into a block shape, a pellet shape, or a plate shape.

  The present invention also provides a regenerator that is filled with the regenerator material.

  Moreover, the present invention provides a regenerator characterized by having a laminated structure of two or more layers composed of the regenerator material and a magnetic regenerator material.

  The magnetic regenerator material is HoCu2, HoCu2 and Gd2O2S or GAP (GdAlO3), Er3Ni or Er3Co, or Er3Ni or Er3Co and Gd2O2S or GAP (GdAlO3).

  The present invention also provides a cryogenic regenerator having the above regenerator.

  Further, the regenerator is used for the lowest temperature cooling stage.

  Alternatively, the regenerator is used for the intermediate cooling stage, and another magnetic material having a large specific heat of 4K or less is used for the final cooling stage regenerator.

  According to the present invention, since bismuth alone is used as the cold storage material, the load on the environment is relatively low. In addition, cold storage, which is a condition required for cold storage materials, such as being easily spheroidized, having sufficient mechanical strength to be used, inexpensive, and having excellent thermal properties when used in a refrigerator. Satisfies the requirements for materials.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  In FIG. 1, the outline of the cool storage type cryogenic refrigerator of 1st Embodiment which concerns on this invention is shown typically. In this refrigerator, the present invention is applied to a two-stage GM refrigerator.

  In the refrigerator 1 of the present embodiment, as shown in the figure, a high-pressure refrigerant gas is supplied from a compressor 11 via a high-pressure gas pipe 12 and a high-pressure valve 13 and is recovered as low-pressure gas via a low-pressure valve 14 and a low-pressure gas pipe 15. The In the refrigerator 1, the first-stage regenerator 21 and the second-stage regenerator 31 are accommodated in the first-stage cylinder 2 and the second-stage cylinder 3, respectively, and both the regenerators 21 and 31 are driven by the drive motor 16 to move in the vertical direction. By reciprocating, the lower end side of each cooler is cooled.

  The first stage regenerator 21 and the second stage regenerator 31 are filled with a first stage regenerator 22 and a second stage regenerator 32, respectively. The first-stage regenerator material 22 is formed by laminating, for example, 970 metal meshes made of copper mesh 150.

  A two-stage regenerator (displacer) 31 has a laminated structure of two upper and lower layers in which a two-stage regenerator material 32 is partitioned at substantially the same amount by volume ratio as shown in the figure, and the second-layer low-temperature regenerator material 32B is filled with granular HoCu2, and the first layer of high-temperature side cold storage material 32A is filled with Bi (bismuth) or spherical Bi crushed in bulk.

  The cooling unit of the refrigerator 1 of the present embodiment is composed of a first-stage cooler 21 and a two-stage cooler 31 respectively accommodated in the first-stage cylinder 2 and the second-stage cylinder 3 that are integrally formed. The first stage cooling stage 23 at the lower end (low temperature end) of the first stage cylinder is cooled to about 40K, and the second stage cooling stage 33 at the lower end of the second stage cylinder is cooled to, for example, 7K or less. In addition, an electric heater (not shown) is attached to each of the first-stage cooling stage 23 and the second-stage cooling stage 33, and a heat load is applied by the electric input so that the refrigeration capacity of each stage can be measured. .

  In FIG. 1, 24 is a gas passage of the first-stage regenerator 21, 25 is a seal for airtightness with the first-stage cylinder 2, 26 is a first-stage expansion space, and 34 is a gas passage of the two-stage regenerator. , 36 is a two-stage expansion space, and the stroke of the displacer is 25 mm. However, the seal between the two-stage regenerator 31 and the two-stage cylinder 3 is omitted.

  In this embodiment, the granular bismuth filled as the high temperature side cold storage material 32A can have a purity of, for example, 99.99%, and its particle size is 0.14 to 1.6 mm, preferably 0.15. It is -1.4mm, More preferably, it is 0.22-1.3mm.

  An example of the relationship between the bismuth size (particle size) and the freezing capacity of 4.2K is shown in FIG.

  When the particle size is less than 0.14 mm, the density when filling the regenerator becomes too high, and the passage resistance of He gas, which is the cooling medium, rapidly increases. Moreover, when a particle size exceeds 1.6 mm, there exists a possibility that the heat exchange efficiency between a granule and a cooling medium may fall remarkably.

  In addition, the ratio of the maximum diameter to the minimum diameter (aspect ratio) of the bismuth regenerator material of this embodiment is 5 or less, preferably 3 or less, more preferably 2 or less, and spherical as much as possible in any three-dimensional direction. It is preferable to approach. When the aspect ratio exceeds 5, mechanical deformation is likely to occur, and it is difficult to fill with high density, so that the cooling efficiency is lowered.

  In an experiment using a 4.2K refrigerator having a refrigeration capacity of 1 W according to this embodiment shown below, the bismuth regenerator material has a purity of 99.99% or more, a particle size of 0.3 to 0.5 mm, and an aspect ratio of 5 or less. Unless otherwise specified, the operation cycle by the motor 16 is 60 rpm, and the displacer stroke is 30 mm.

  First, in FIG. 3, the characteristic of volume specific heat in the low temperature region of bismuth used as a material for the regenerator material in the present invention is shown in comparison with a material used as another regenerator material. Bismuth Bi is also used in cosmetic materials, so it has high safety, is considered to be free from environmental pollution, and is inexpensive. In general, the regenerator material is required to have a large volume specific heat in the intended cryogenic temperature range, but bismuth does not reach lead Pb as far as FIG. 3 is seen. However, in the region of 5K or more, it has a feature that almost coincides with HoCu2 that is a magnetic regenerator material. In the figure, GOS is an abbreviation for Gd2O2S.

  Table 1 shows the hardness measurement results of the regenerator material evaluated in Example 1.

  In Vickers hardness, bismuth spheres can be said to be equivalent to lead. Although the hardness of the B lot whose surface is black is lower than that of the A lot whose surface is gold, there is a possibility that it is due to the effect of surface oxidation. Regarding the strength, when the compressive strength was measured, deformation due to compression was less in bismuth than in lead, and no cracking of the material was observed. From this, it was found that bismuth has the same strength as lead.

  Next, lead and bismuth were filled in the two-stage regenerator 31, and the refrigerating capacity was compared. The regenerator configuration is shown in FIG. Both lead and bismuth having a particle size of 0.4 to 0.5 mm were used. Bismuth was used after sieving from a spherical powder whose surface was not oxidized. Although the filling amount of lead and bismuth is different, the experiment was conducted with the filling volume being equal.

  The rotation speed dependency of the minimum temperature is shown in FIG. The two-stage temperature T2 is almost the same, but the first-stage temperature T1 is about 2K lower than that of lead (◯ mark) when bismuth (Δ mark) is used in the entire rotation speed region.

  FIG. 6 shows the rotation speed dependency of the two-stage refrigeration capacity at the first stage no load. At any rotational speed tested, bismuth (Δ mark) shows higher refrigerating capacity than lead (◯ mark). The highest refrigeration capacity was obtained at 48 rpm. The refrigeration capacity diagram at 60 rpm is shown in FIG. As shown in FIG. 5, bismuth was lower than the case where the first stage temperature was lead. Reflecting the result, it can be seen that even when a load is applied to one stage, bismuth (Δ mark) shows a lower temperature than lead (◯ mark).

  FIG. 8 shows a comparison of the two-stage refrigeration capacity when a load is applied to the first stage. Bismuth (Δ mark) shows higher refrigerating capacity than lead (◯ mark) at any one stage temperature. The difference is larger as the first stage temperature is higher, and a large difference of about 10% is seen in the second stage refrigeration capacity of 4.2K near 45K.

  Next, the difference in refrigerating capacity due to the difference in surface condition and particle size was evaluated. Bismuth spheres were sieved in 0.1 mm increments. The evaluated classification is shown in Table 2. The low temperature side was filled with HoCu 2110 g + GOS 93.7 g as in FIG.

  FIG. 9 shows the first-stage temperature dependence of the two-stage refrigeration capacity with the bismuth condition as a parameter. Black dots correspond to B lot, and white dots correspond to A lot. The difference between lots is larger than the difference due to the particle size in the same lot. In particular, it can be seen that the difference between lots is larger in the range where the first stage temperature T1 is higher than 40K.

  The difference in the two-stage refrigeration capacity depending on the particle size of bismuth is shown in FIG. The first stage temperature T1 is drawn in increments of 5K from 25K to 45K. Black dots correspond to B lot, and white dots correspond to A lot. Comparison between lots is possible when the particle size is 0.4-0.5 mm, but the difference is larger as the first stage temperature is higher. On the other hand, it can be seen that there is little difference in refrigeration capacity depending on the particle size in the same lot.

  The case of the first stage refrigeration capacity is shown in FIG. 11, but it can be seen that there is practically no difference between lots. This is in contrast to the obvious particle size dependence seen with lead.

  From these results, it can be considered that the bismuth particle size has no influence on the refrigerating capacity in the evaluated range. If there is no problem in reliability or the like, the purchase unit price can be reduced if the particle size range to be used is wide. On the other hand, the surface oxidation state may affect the refrigerator performance, and Table 3 shows the results of examining the difference in the refrigerating capacity at 4.2 K depending on the surface oxidation state.

  As a result of evaluating bismuth as a cold storage material instead of lead, it was shown that bismuth showed better performance than lead for 4K refrigerators. There is a possibility that the price of the material can be made cheaper than lead since the particle size may be widely taken. However, if the surface is oxidized, the performance may decrease.

  For practical use, not only the refrigeration capacity but also the material strength is important, but the hardness test and compression test showed that bismuth has hardness and strength higher than lead. From the above, bismuth may be used in place of lead.

  Next, bismuth characteristics in a temperature region of 10K or higher were evaluated using a 4.2K machine having a refrigeration capacity of 0.5 W.

  So far, experimental results focusing on the effect of bismuth in the 4K region have been described. However, as a use of the GM refrigerator, there is a region of 10K or more such as a cryopump other than 4K. Conventionally, all lead is used as a cold storage material in this temperature range. When all the lead was replaced with bismuth, the refrigeration capacity was reduced by 30% or more in the temperature range of 10K or higher. Therefore, when lead-free becomes indispensable, there are cases where it is not possible to replace all lead with bismuth due to insufficient freezing capacity. Therefore, an experiment was conducted to find out how to use bismuth to achieve a refrigerating capacity equivalent to that of lead.

  One possible measure is to hybridize bismuth and other cold storage materials. Therefore, materials having excellent specific heat characteristics at around 15K were selected and evaluated from the cold storage materials tried so far. First, HoCu2 used at 4K and Er0.7Ho0.3Ni having a specific heat peak at 15K were evaluated. As shown in FIG. 3, Er0.7Ho0.3Ni has a large specific heat peak in the vicinity of 15K. GOS was excluded from the evaluation because the specific heat was drastically decreased at a temperature higher than the specific heat peak near 5K.

  The refrigerator used is a 4.2K machine having a refrigeration capacity of 0.5 W, and the cylinder dimensions are a first stage inner diameter of 52 mm, a length of 191.5 mm, a second stage inner diameter of 25 mm, and a length of 165 mm. The stroke was 25 mm, the filling pressure was 19 kgf / cm @ 2 G, and the displacer motor rotation speed was 60 rpm. The single-stage regenerator is filled with 900 pieces of 150 mesh copper mesh. The operating frequency of the compressor was 50 Hz.

  The configuration of the regenerator compared in this example is shown in FIG. 12, and the difference in refrigeration capacity due to the difference in regenerator configuration is shown in FIG.

  The lowest temperature reached in the second stage was 4K or less only when HoCu2 was filled. The lowest temperature is 2.78 K in the case of the regenerator 2, which is greatly different from 6.14 K in the case of the regenerator 3 made entirely of bismuth. On the other hand, the lowest temperature was achieved in the case of the regenerator 3 in which the first stage was made of bismuth.

  In order to compare the refrigeration capacities, the refrigeration capacities at the second stage temperatures of 10K, 15K, and 20K and the first stage temperatures of 50K, 60K, and 70K were obtained and compared from the refrigeration capacity diagrams by interpolation. FIG. 14 shows the two-stage capability, and FIG. 15 shows the one-stage capability.

  The two-stage capacity shown in FIG. 14 is lower in the case of bismuth (cold regenerator 3) than lead (cold regenerator 1), but the low temperature side 1/4 of bismuth is reduced to HoCu2 (cold regenerator 5) or Er0. It can be seen that by replacing with 7Ho0.3Ni (the regenerator 6), it is recovered to almost the same as lead.

  On the other hand, the first-stage refrigeration capacity shown in FIG. 15 is improved by bismuth. That is, when all are made of bismuth (the regenerator 3), the value of the first stage refrigerating capacity is particularly large when the second stage temperature T2 is a low temperature around 10K. However, the effect that the two-stage temperature has on the first-stage refrigeration capacity is large. When the temperature is as high as 20 K, the first-stage refrigeration capacity is equal to or rather inferior to that of the hybrid regenerator. Overall, the combination of bismuth and HoCu2 is excellent as a regenerator configuration replacing lead.

  As described above, the regenerator material made of bismuth of the present embodiment is superior to lead in terms of environmental friendliness, and is used in combination with, for example, a magnetic regenerator material such as HoCu2, Gd2O2S, and other types of regenerator materials. It becomes possible to utilize as a cool storage material more than the conventional lead by giving this device.

  The magnetic regenerator material used together with HoCu2 is not limited to Gd2O2S, but GAP (GdAlO3), general formula RxO2S or (R1-yR'y) xO2S (R, R 'is at least one kind of rare earth element, 0 .Ltoreq.x.ltoreq.9, 0.ltoreq.y.ltoreq.1). In this case, the elements R and R ′ are yttrium Y, lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium. Tm or ytterbium Yb may be used. Further, Er3Co can be used instead of Er3Ni.

  In the above embodiment, the case where the regenerator material is made of granular material (powder) of bismuth alone is shown. However, the regenerator material of the present invention is not limited to bismuth alone, but an alloy containing bismuth as a main component. There may be. As an alloy component, there is antimony (Sb), which may be contained up to about 5 to 10%, for example, and there is an advantage that the hardness can be increased by using such an alloy.

  The granular regenerator material made of bismuth or an alloy containing bismuth as a main component is manufactured by a molten metal quenching method in which a molten metal is rapidly cooled simultaneously with granulation using a rotating disk, a roll, a rotating nozzle or the like. Alternatively, it may be produced by an arbitrary production method such as a plasma spray method or a gas atomization method.

  Next, FIG. 16 shows a second embodiment of the present invention which is an MRI apparatus using the two-stage GM refrigerator of the first embodiment.

  In the MRI apparatus 4 of this embodiment, a superconducting magnet 45 is used to create a magnetic field space 48. The superconducting magnet 45 is immersed in liquid helium 44 and cooled to a superconducting state. There is a heat shield 42 outside the liquid helium vessel 43 and a vacuum vessel 41 outside. Liquid helium is injected from the inlet 46, but the vaporized helium is returned to the liquid again by the condensing unit 47 provided in the liquid helium container 43, and operation can be performed without supplying helium for a long period of time.

  The condensing unit 47 is thermally coupled to the two-stage cooling stage 33 of the GM refrigerator 1 and is continuously supplied with cold. The heat shield 42 is cooled by the one-stage cooling stage 23 of the GM refrigerator 1.

  In this embodiment, since the refrigerating capacity of the GM refrigerator 1 is improved by the cold storage material according to the present invention, the recondensation of the liquid helium 44 can be performed more efficiently, and the MRI with a larger helium evaporation amount. It becomes possible to correspond to the device.

  In the present embodiment, the refrigerator 1 is used for recondensing the liquid helium 44. However, the liquid helium can be eliminated, and the refrigerator 1 can be configured to directly cool the superconducting magnet 45 by heat conduction. . Further, by adding a heat shield, the first-stage cooling stage 23 and the second-stage cooling stage 33 can be of a so-called shield cooling type in which different heat shields are cooled.

  In the above embodiment, the present invention is applied to the GM cycle refrigerator, but the application target of the present invention is not limited to this, and a pulse tube refrigerator, a Stirling cycle refrigerator, a Birmier cycle refrigerator, a Solvey It is clear that the present invention can be applied to other regenerative cryogenic refrigerators such as cycle refrigerators.

  The system using the regenerator type cryogenic refrigerator according to the present invention is not limited to the MRI apparatus of the second embodiment, but includes an NMR apparatus, a superconducting magnet apparatus, a cryopump, a Josephson voltage standard apparatus, a cryogen product It is obvious that the present invention can be similarly applied to a device, a superconducting element cooling device, a helium recondensing device, and the like.

  Further, the shape of the regenerator material is not limited to the granular material, and can be filled into the regenerator after being sintered and processed into a block shape, a pellet shape, or a plate shape. Alternatively, the regenerator material may be formed in a net shape having an opening of 0.01 mm to 1 mm, or may be formed by applying or plating on the surface of a metal net having an opening of 0.01 mm to 1 mm.

  As described above, according to the present invention, it is possible to provide a cryogenic regenerator material having excellent performance made of an environmentally friendly material, a cryogenic regenerator filled with the regenerator material, and the regenerator. It is possible to provide a cryogenic refrigerator equipped with a refrigerator, and it is also possible to provide various systems using the refrigerator.

Explanatory drawing which shows typically the outline | summary of the cryogenic refrigerator of 1st Embodiment which concerns on this invention. Diagram showing an example of the relationship between bismuth size and 4.2K refrigerating capacity Diagram showing volume specific heat of material constituting cold storage material (A) Cross-sectional view of a main part of a two-stage regenerator showing the configuration of a conventional lead regenerator and (B) a bismuth regenerator according to the present invention. The diagram which shows the rotation speed dependence of the minimum temperature at the time of no load in Example 1 of this invention Similarly, a diagram showing the rotational speed dependence of the two-stage refrigeration capacity when there is no first stage load Refrigeration capacity diagram for 60rpm Similarly, a diagram showing the temperature dependence of the second stage refrigeration capacity at 4.2K when the first stage is loaded. Similarly, a diagram showing the temperature dependence of the first stage of the second stage refrigeration capacity at 4.2K with the bismuth condition as a parameter. Similarly, a diagram showing the bismuth particle size dependence of the two-stage refrigeration capacity at 4.2K Similarly, a diagram showing the bismuth particle size dependence of the first stage refrigerating capacity Sectional drawing which shows the principal part structure of the two-stage regenerator compared in Example 2 The diagram which compares and shows the refrigerating capacity by the difference in the cool storage structure in Example 2. Diagram showing comparison of two-stage refrigeration capacity Diagram showing comparison of first-stage refrigeration capacity The schematic sectional drawing which shows the whole structure of 2nd Embodiment which applied the refrigerator of this invention to the MRI apparatus.

DESCRIPTION OF SYMBOLS 1 ... Refrigerator 2 ... 1 stage cylinder 3 ... 2 stage cylinder 21 ... 1 stage cool storage 22 ... 1 stage cool storage material 23 ... 1 stage cooling stage 31 ... 2 stage cool storage 32 ... 2 stage cool storage 32A ... high temperature side cool storage material 32B ... Low-temperature side regenerator 33 ... Two-stage cooling stage

Claims (16)

  Bismuth single particles, the proportion of particles having a particle size of 0.14 mm or more and 1.6 mm or less is 70% by weight or more with respect to the whole particles, and the ratio of the major axis to the minor axis is 5 or less. A regenerator material comprising a granule in which the proportion of a certain granule is 70% by weight or more based on the total granule.   The regenerator material according to claim 1, wherein the surface roughness of the granules is 100 μm or less on the basis of the maximum height Rmax.   Bismuth-only particles, the proportion of particles having a particle size of 0.14 mm or more and 1.6 mm or less is 70% by weight or more with respect to the whole particles, and the surface roughness of the particles is the highest. A cold storage material comprising particles having a thickness Rmax of 100 μm or less.   The cold storage material according to any one of claims 1 to 3, wherein the grain structure includes an amorphous phase at least in part.   The regenerator material according to any one of claims 1 to 3, wherein a ratio of particles having microdefects having a length of 10 µm or more to all particles in the granule is 30 wt% or less.   The regenerator material according to any one of claims 1 to 3, wherein the surface of the granule is not discolored by oxidation.   The regenerator material according to any one of claims 1 to 6, wherein the granule is sintered and processed into a block shape, a pellet shape, or a plate shape.   A regenerator that is filled with the regenerator material according to claim 1.   A regenerator having a laminated structure of two or more layers constituted of the regenerator material according to any one of claims 1 to 7 and a magnetic regenerator material.   The regenerator according to claim 9, wherein the magnetic regenerator material is HoCu 2.   The regenerator according to claim 9, wherein the magnetic regenerator material is HoCu 2 and Gd 2 O 2 S or GAP (GdAlO 3).   The regenerator according to claim 9, wherein the magnetic regenerator material is Er3Ni or Er3Co.   The regenerator according to claim 9, wherein the magnetic regenerator material is Er3Ni or Er3Co and Gd2O2S or GAP (GdAlO3).   A cryogenic regenerator having the regenerator according to any one of claims 8 to 13.   The cryogenic regenerative refrigerator according to claim 14, wherein the regenerator is used in a lowest temperature cooling stage.   The cryogenic regenerative refrigerator according to claim 14, wherein the regenerator is used for an intermediate cooling stage, and another magnetic material having a large specific heat of 4K or less is used for the final cooling stage regenerator.

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