JPH0914774A - Cool storage unit - Google Patents
Cool storage unitInfo
- Publication number
- JPH0914774A JPH0914774A JP7164151A JP16415195A JPH0914774A JP H0914774 A JPH0914774 A JP H0914774A JP 7164151 A JP7164151 A JP 7164151A JP 16415195 A JP16415195 A JP 16415195A JP H0914774 A JPH0914774 A JP H0914774A
- Authority
- JP
- Japan
- Prior art keywords
- regenerator
- specific heat
- regenerator material
- content
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、低温で比熱の大きい蓄
冷材が充填された蓄冷器に関するもので、各種の冷凍機
に利用される。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a regenerator filled with a regenerator material having a high specific heat at a low temperature and is used in various refrigerators.
【０００２】[0002]
【従来の技術】スターリングサイクル、ＧＭ（ギフォー
ドマクマホン）サイクル、パルス管式等の各種の冷凍機
に用いられる蓄冷器には、冷凍能力の向上という点から
蓄冷材が充填されることが必須になる。この蓄冷器は、
一方向に流れる圧縮された作動ガスから熱を奪ってその
熱を蓄えると共に、反対方向に流れる膨張した作動ガス
に蓄えた熱を伝達するものである。2. Description of the Related Art A regenerator used in various refrigerators such as a Stirling cycle, a GM (Gifford McMahon) cycle, and a pulse tube type must be filled with a regenerator material from the viewpoint of improving the refrigerating capacity. . This regenerator
The heat is taken from the compressed working gas flowing in one direction to store the heat, and the heat stored in the expanded working gas flowing in the opposite direction is transferred.
【０００３】従来、蓄冷器内に充填される蓄冷材として
は、銅や鉛等の合金が多用されている。ところが、銅や
鉛からなる蓄冷材では、格子系の比熱しかもたないた
め、比熱は４０Ｋ以上では大きいものの、２０Ｋ以下の
極低温で過度に小さくなる。そのため、前記蓄冷材が充
填された蓄冷器を冷凍機（特に多段式の冷凍機）内で使
用した場合には、圧縮された作動ガスから充分に熱を吸
収することができず、又、膨張した作動ガスに充分に熱
を伝達することができなくなる。その結果、このような
蓄冷材が充填された蓄冷器を使用する冷凍機では、極低
温に到達させることができないという問題点があった。Conventionally, alloys such as copper and lead are often used as the regenerator material filled in the regenerator. However, since the regenerator material made of copper or lead has only the specific heat of the lattice system, the specific heat is large at 40 K or more, but becomes excessively small at an extremely low temperature of 20 K or less. Therefore, when the regenerator filled with the regenerator material is used in a refrigerator (particularly, a multistage refrigerator), heat cannot be sufficiently absorbed from the compressed working gas, and the expansion does not occur. The heat cannot be sufficiently transferred to the working gas. As a result, a refrigerator using a regenerator filled with such a regenerator material has a problem that it cannot reach an extremely low temperature.
【０００４】そこで、このような問題点を解決するため
に提案された蓄冷器としては、特開平１−３１０２６９
号公報に示されるものが知られている。その代表例とし
て、格子系の比熱だけでなくスピン系の比熱を持つＥｒ
3 Ｎｉからなる磁性体の蓄冷材が充填された蓄冷器が開
示されている。これは、２０Ｋ以下の極低温でその比熱
が銅や鉛からなる蓄冷材よりも大きいため、銅や鉛から
なる蓄冷材よりも２０Ｋ以下（特に１０Ｋ未満）の極低
温において蓄冷効率を向上できる。Therefore, as a regenerator proposed in order to solve such a problem, Japanese Patent Laid-Open No. 1-310269 has been proposed.
What is shown in Unexamined-Japanese-Patent No. 2000-222 is known. As a typical example thereof, Er having not only the specific heat of the lattice system but also the specific heat of the spin system
A regenerator filled with a magnetic regenerator material made of 3 Ni is disclosed. This is because at a cryogenic temperature of 20 K or less, the specific heat thereof is larger than that of the regenerator material made of copper or lead, so that the regenerator efficiency can be improved at a cryogenic temperature of 20 K or less (particularly less than 10 K) than the regenerator material made of copper or lead.
【０００５】[0005]
【発明が解決しようとする課題】ところが、上記したＥ
ｒ3 Ｎｉからなる蓄冷材では、磁気変態点（即ち磁気的
状態間の相転移）が８Ｋ付近に存在することから、比熱
が１０Ｋ未満で大きいものの、１０〜３０Ｋでは小さく
なる。このため、１０Ｋ未満の極低温では蓄冷効率が高
くなるものの、１０〜３０Ｋで蓄冷効率が不充分であ
り、例えばＨｅの液化を行おうとする場合に１０〜３０
Ｋで冷却効率が悪くなり、効率良くＨｅを液化するには
不充分である。また、上記したＥｒ3 Ｎｉからなる蓄冷
材では、１０〜３０Ｋの冷凍を発生する冷凍機には適用
し難いという問題点がある。However, the above-mentioned E
In the regenerator material composed of r 3 Ni, the magnetic transformation point (that is, the phase transition between magnetic states) exists near 8K, so the specific heat is large at less than 10K, but becomes small at 10 to 30K. Therefore, although the cold storage efficiency is high at an extremely low temperature of less than 10K, the cold storage efficiency is insufficient at 10 to 30K, and for example, 10 to 30 when liquefying He is attempted.
When K is used, the cooling efficiency is deteriorated, which is insufficient to efficiently liquefy He. In addition, the above-described cool storage material made of Er 3 Ni has a problem that it is difficult to apply it to a refrigerator that generates freezing at 10 to 30K.
【０００６】故に、本発明は、３０Ｋ以下で比熱が大き
く、特に３０Ｋ以下での蓄冷効率を向上させ得る蓄冷材
をもつ蓄冷器を提供することを、その技術的課題とする
ものである。[0006] Therefore, it is a technical object of the present invention to provide a regenerator having a regenerator material which has a large specific heat at 30 K or less and can improve the regenerator efficiency particularly at 30 K or less.
【０００７】[0007]
【課題を解決するための手段】上記技術的課題を解決す
るために本発明の請求項１において講じた技術的手段
は、蓄冷材が充填されてなる蓄冷器において、前記蓄冷
材は、次式（１） Ｒa Ａｇb Ｍc ・・・（１） で表され、Ｒは少なくともＣｅ，Ｐｒ，Ｎｄ，Ｇｄ，Ｄ
ｙ，Ｈｏ，Ｅｒ，Ｔｍの１種又は２種以上である希土類
元素であり、ＭはＢ，Ａｌ，Ｉｎ，Ｓｉ，Ｇｅ，Ｇａ，
Ｓｎ，Ａｕ，Ｍｇ，Ｚｎ，Ｐｄ，Ｐｔ，Ｒｅ，Ｃｓ，Ｉ
ｒ，Ｆｅ，Ｍｎ，Ｃｒ，Ｃｄ，Ｈｇ，Ｏｓ，Ｐ，Ｌａ，
Ｙの内の少なくとも１種の元素であり、前記Ｒの含有率
ａは２０ａｔ％≦ａ≦９５ａｔ％であり、前記Ｍの含有
率ｃは５ａｔ％≦ｃ≦２５ａｔ％であり、Ａｇと前記Ｍ
との合計の含有率ｂ＋ｃは５ａｔ％＜ｂ＋ｃ≦８０ａｔ
％であることを特徴とする蓄冷器としたことである。In order to solve the above technical problems, the technical means taken in claim 1 of the present invention is a regenerator filled with a regenerator material, wherein the regenerator material has the following formula: (1) R a Ag b M c ... Represented by (1), R is at least Ce, Pr, Nd, Gd, D
It is a rare earth element which is one or more of y, Ho, Er and Tm, and M is B, Al, In, Si, Ge, Ga,
Sn, Au, Mg, Zn, Pd, Pt, Re, Cs, I
r, Fe, Mn, Cr, Cd, Hg, Os, P, La,
It is at least one element of Y, the content a of R is 20 at% ≦ a ≦ 95 at%, the content c of M is 5 at% ≦ c ≦ 25 at%, and Ag and M are the same.
And the total content b + c is 5 at% <b + c ≦ 80 at
It is a regenerator characterized by being%.
【０００８】上記技術的課題を解決するために本発明の
請求項２において講じた技術的手段は、蓄冷材が充填さ
れてなる蓄冷器において、前記蓄冷材は、次式（２） Ｒa Ａｇb ＭC ・・・（２） で表され、Ｒは少なくともＣｅ，Ｐｒ，Ｎｄ，Ｇｄ，Ｄ
ｙ，Ｈｏ，Ｅｒ，Ｔｍの１種又は２種以上である希土類
元素であり、ＭはＳｂ，Ｂｉ，Ｔｅ，Ｚｒ，Ｔｉの内の
少なくとも１種の元素であり、前記Ｒの含有率ａは２０
ａｔ％≦ａ≦９５ａｔ％であり、前記Ｍの含有率ｃは０
ａｔ％＜ｃ≦２５ａｔ％であり、Ａｇと前記Ｍとの合計
の含有率ｂ＋ｃは５ａｔ％≦ｂ＋ｃ≦８０ａｔ％である
ことを特徴とする蓄冷器としたことである。In order to solve the above technical problems, the technical means taken in claim 2 of the present invention is a regenerator filled with a regenerator material, wherein the regenerator material is represented by the following formula (2) Ra Ag. b M C ... (2), R is at least Ce, Pr, Nd, Gd, D
y, Ho, Er, Tm is one or more rare earth elements, M is at least one element of Sb, Bi, Te, Zr and Ti, and the content a of R is 20
at% ≦ a ≦ 95 at%, and the content c of M is 0.
At% <c ≤ 25 at%, and the total content b + c of Ag and M is 5 at% ≤ b + c ≤ 80 at%.
【０００９】[0009]
【作用】上記第１の技術的手段における蓄冷材は、３０
Ｋ以下で比熱のピークを有することが確認されている。
これは、磁気変態点が３０Ｋ以下の範囲にあるためと考
えられるが、このことにより３０Ｋ以下での蓄冷効率が
向上する。The regenerator material in the first technical means is 30
It has been confirmed to have a peak of specific heat at K or less.
It is considered that this is because the magnetic transformation point is in the range of 30K or lower, which improves the cold storage efficiency at 30K or lower.
【００１０】上記第２の技術的手段における蓄冷材は、
３０Ｋ以下で比熱のピークを有することが確認されてい
る。これは、磁気変態点が３０Ｋ以下の範囲にあるため
と考えられるが、このことにより３０Ｋ以下での蓄冷効
率が向上する。The regenerator material in the second technical means is
It has been confirmed that it has a specific heat peak at 30 K or less. It is considered that this is because the magnetic transformation point is in the range of 30K or lower, which improves the cold storage efficiency at 30K or lower.
【００１１】[0011]
【実施例】以下に本発明の実施例を示す。Examples of the present invention will be described below.
【００１２】本実施例は、Ｅｒ−Ａｇ−Ｇａ系合金及び
Ｅｒ−Ａｇ−Ｔｉ系合金を主成分とする蓄冷材に関する
ものである。This embodiment relates to a regenerator material containing Er-Ag-Ga-based alloy and Er-Ag-Ti-based alloy as main components.
【００１３】まず、Ｅｒ−Ａｇ−Ｇａ系合金からなる蓄
冷材について説明する。First, a regenerator material made of Er-Ag-Ga alloy will be described.
【００１４】Ｅｒブロック６．２５３ｇ（５０ａｔ
％）、Ａｇブロック３．２２６ｇ（４０ａｔ％）、Ｇａ
ブロック０．５２１ｇ（１０ａｔ％）をアーク溶解炉に
配置し、アーク溶解炉を真空吸引した後、アルゴンガス
にて置換する。その後、アーク溶解してＥｒ50Ａｇ40Ｇ
ａ10からなる蓄冷材を製造し、５×５×７ｍｍに切断す
る。Er block 6.253 g (50 at)
%), Ag block 3.226 g (40 at%), Ga
0.521 g (10 at%) of a block is placed in an arc melting furnace, the arc melting furnace is vacuumed, and then replaced with argon gas. After that, arc melting and Er 50 Ag 40 G
A regenerator material consisting of a 10 is manufactured and cut into 5 × 5 × 7 mm.
【００１５】次に、上記の如く製造した蓄冷材の比熱を
Ｇｅ温度計を用いて断熱法により略３〜３０Ｋで測定し
た。ここで、断熱法とは、断熱条件下で試料（ここでは
インゴッド）にジュール熱ΔＱを加えたときの温度変化
ΔＴを測定して、ジュール熱ΔＱを温度変化ΔＴで割っ
た値を比熱ΔＣとする方法である。この比熱測定結果を
図１に実施例１として示す。図１には、上記組成の配合
比を変えて同様に製造したＥｒ50Ａｇ42Ｇａ8 （実施例
２）、Ｅｒ50Ａｇ39Ｇａ11（実施例３）、の比熱測定結
果、従来のＥｒ3 Ｎｉ（従来例１）、Ｐｂ（従来例
２）、Ｅｒ50Ａｇ50（参考例）の比熱測定結果も合わせ
て示す。Next, the specific heat of the regenerator material manufactured as described above was measured at about 3 to 30 K by the adiabatic method using a Ge thermometer. Here, the adiabatic method is to measure the temperature change ΔT when Joule heat ΔQ is applied to a sample (here, ingot) under adiabatic conditions, and divide the Joule heat ΔQ by the temperature change ΔT to obtain the specific heat ΔC. Is the way to do it. The specific heat measurement result is shown as Example 1 in FIG. FIG. 1 shows the specific heat measurement results of Er 50 Ag 42 Ga 8 (Example 2) and Er 50 Ag 39 Ga 11 (Example 3), which were produced in the same manner by changing the composition ratio of the above composition, and the conventional Er 3 The specific heat measurement results of Ni (conventional example 1), Pb (conventional example 2), and Er 50 Ag 50 (reference example) are also shown.
【００１６】図１から明らかなように、実施例の蓄冷材
と、Ｅｒ3 Ｎｉを用いた蓄冷材（従来例１）及びＰｂを
用いた蓄冷材（従来例２）とを比較すると、Ｅｒ50Ａｇ
39Ｇａ11では３〜２５Ｋの測定域全域において比熱が大
きくなっていることが認められ、またＥｒ50Ａｇ40Ｇａ
10においても８〜２５Ｋの範囲において、比熱が大きく
なっていることが認められる。またＥｒ50Ａｇ50と本実
施例とを比較すると、Ｇａの含有量が増加するに従い、
比熱のピークは低温側へ移行する傾向が認めら＾る。こ
の原因は必ずしも明らかでないが、以下のように考えら
れる。As is apparent from FIG. 1, when the regenerator material of the embodiment is compared with the regenerator material using Er 3 Ni (conventional example 1) and the regenerator material using Pb (conventional example 2), Er 50 Ag
With 39 Ga 11 , it was observed that the specific heat increased over the entire measurement range of 3 to 25 K, and Er 50 Ag 40 Ga
It is recognized that in 10 as well, the specific heat is large in the range of 8 to 25K. Further, comparing Er 50 Ag 50 with this example, as the content of Ga increases,
The specific heat peak tends to shift to the low temperature side. The cause of this is not clear, but it is considered as follows.
【００１７】即ち、Ｅｒ50Ａｇ40Ｇａ10は、Ｅｒ50Ａｇ
50のＡｇを一部Ｇａで置き換えたものであり、またＧａ
は非磁性体であることからして磁気的な相互作用が大き
く変化することは考え難いが、ＡｇをＧａに置き換える
量が増加するに従い格子定数が小さくなることが判明し
ている。重希土類系の合金において格子定数が小さくな
るにつれ、磁気変態温度が低下する傾向が一般的にあ
り、この影響によってＧａの含有量が増加するに従い比
熱のピークが低温側に移行するものと考えられる。That is, Er 50 Ag 40 Ga 10 is Er 50 Ag
50 Ag is partially replaced by Ga.
Since it is a non-magnetic substance, it is difficult to think that the magnetic interaction changes greatly, but it has been found that the lattice constant becomes smaller as the amount of Ag replaced by Ga increases. In the heavy rare earth alloys, the magnetic transformation temperature generally tends to decrease as the lattice constant becomes smaller, and it is considered that due to this effect, the specific heat peak shifts to the low temperature side as the Ga content increases. .
【００１８】図２は、Ｅｒ50Ａｇ50-YＸY （Ｘ：Ｇｅ，
Ｇａ，Ａｌ）で示される合金で、Ｘの置換量Ｙを変えて
比熱ピークを示す温度を測定したものをグラフ上に示し
たものである。これによると、置換量Ｙが５ａｔ％以上
の領域では比熱ピークを示す温度が低下することがわか
る。また置換量Ｙが２５ａｔ％以上のものである場合は
５Ｋ以下に比熱のピークが移行し、しかもピーク比熱が
小さくなてしまう傾向にあるため、十分な蓄冷材とはし
がたい。従って、３０Ｋ以下において比熱ピークを有
し、この温度範囲で蓄冷効率を向上させるためには、Ｘ
の置換量を５〜２５ａｔ％とすることが望ましい。FIG. 2 shows that Er 50 Ag 50-Y XY (X: Ge,
Ga, Al), which is an alloy represented by Ga and Al) and whose temperature at which a specific heat peak is measured by changing the substitution amount Y of X is shown on the graph. According to this, it can be seen that the temperature at which the specific heat peak appears decreases in the region where the substitution amount Y is 5 at% or more. Further, when the substitution amount Y is 25 at% or more, the peak of the specific heat tends to shift to 5 K or less, and the peak specific heat tends to be small, so that it is difficult to obtain a sufficient regenerator material. Therefore, in order to improve the cold storage efficiency in this temperature range, there is a specific heat peak at 30 K or below.
It is desirable to set the substitution amount of 5 to 25 at%.
【００１９】次に、Ｅｒ−Ａｇ−Ｔｉ系合金からなる蓄
冷材について説明する。Next, the regenerator material composed of Er-Ag-Ti alloy will be described.
【００２０】Ｅｒブロック６．１２５ｇ（５０ａｔ
％）、Ａｇブロック３．６０７ｇ（４５ａｔ％）、Ｔｉ
ブロック０．１７８ｇ（５ａｔ％）をアーク溶解炉に配
置し、アーク溶解炉を真空吸引した後、アルゴンガスに
て置換する。その後、アーク溶解してＥｒ50Ａｇ45Ｔｉ
5 からなる蓄冷材を製造し、５×５×７ｍｍに切断す
る。Er block 6.125 g (50 at)
%), Ag block 3.607 g (45 at%), Ti
0.178 g (5 at%) of a block is placed in an arc melting furnace, the arc melting furnace is vacuumed, and then replaced with argon gas. After that, arc melting and Er 50 Ag 45 Ti
A regenerator material consisting of 5 is manufactured and cut into 5 × 5 × 7 mm.
【００２１】比熱の測定方法については、上記Ｅｒ−Ａ
ｇ−Ｇａ系合金の場合と同様であるため、説明を省略す
る。As to the method for measuring the specific heat, the above-mentioned Er-A is used.
The description is omitted because it is similar to the case of the g-Ga alloy.
【００２２】第３図に上記方法により作製したＥｒ50Ａ
ｇ45Ｔｉ5 の比熱特性（実施例４）を、従来のＥｒ3 Ｎ
ｉ（従来例１）、Ｐｂ（従来例２）と共に示す。図３に
おいて、実施例４と従来例１とを比較すると、１１〜２
５Ｋの領域にて比熱が大きくなっていること認められ、
また従来例２と比較すると、３〜２５Ｋの測定域全域に
おいて比熱が大きくなっていることが認められる。Ｅｒ
−Ａｇに対するＴｉの添加効果が実施例１，２，３のＧ
ａの添加効果と同様にあるものと考えられる。FIG. 3 shows the Er 50 A prepared by the above method.
g 45 Ti 5 specific heat properties (Example 4), a conventional Er 3 N
i (conventional example 1) and Pb (conventional example 2) are shown. In FIG. 3, comparing Example 4 with Conventional Example 1, 11 to 2
It was recognized that the specific heat was large in the 5K region,
Further, as compared with Conventional Example 2, it is recognized that the specific heat is large in the entire measurement range of 3 to 25K. Er
-The effect of adding Ti to Ag is G in Examples 1, 2, and 3.
It is considered to have the same effect as the addition effect of a.
【００２３】〔従来例１〕Ｅｒブロック８．９５ｇ（７
５ａｔ％）とＮｉブロック１．０５ｇ（２５ａｔ％）と
をアーク溶解炉に配置したこと以外は、実施例と同様で
ある。ここで、従来例１の蓄冷材は、Ｅｒ3 Ｎｉ（磁気
変態点８Ｋ）であり、その比熱を実施例１と同様に測定
し、その測定結果を実施例による合金と同時に図１に示
す。[Conventional Example 1] Er block 8.95 g (7
5 at%) and Ni block 1.05 g (25 at%) were placed in the arc melting furnace, and the same as the example. Here, the regenerator material of Conventional Example 1 was Er 3 Ni (magnetic transformation point 8K), and its specific heat was measured in the same manner as in Example 1, and the measurement results are shown in FIG.
【００２４】図１から明らかなように、従来例１の蓄冷
材は、８Ｋ以下での比熱は大きいが、８Ｋ以上での比熱
は実施例と比較して小さくなっている。これは、Ｅｒ3
Ｎｉの磁気変態点が８Ｋに存在し、比熱のピークが７Ｋ
付近に存在するためであると考えられる。As is apparent from FIG. 1, the regenerator material of Conventional Example 1 has a large specific heat at 8 K or less, but the specific heat at 8 K or more is smaller than that of the embodiment. This is Er 3
The magnetic transformation point of Ni exists at 8K and the peak of specific heat is 7K.
It is thought to be because it exists in the vicinity.
【００２５】〔従来例２〕Ｐｂ１０ｇを溶解して蓄冷材
を製造したもので、この蓄冷材の比熱を実施例１と同様
に測定し、その測定結果を実施例による合金と同時に図
１に示す。[Conventional Example 2] A regenerator material was manufactured by melting 10 g of Pb. The specific heat of this regenerator material was measured in the same manner as in Example 1, and the measurement results are shown in FIG. .
【００２６】図１から明らかなように、従来例２の蓄冷
材は、２５Ｋ以下での比熱は実施例と比較して小さくな
っている。これは、格子振動に基づく格子系の比熱が温
度降下と共に著しく低下すると共にスピン系の比熱をも
たないためであると考えられる。As is apparent from FIG. 1, the specific heat of the regenerator material of Conventional Example 2 at 25 K or less is smaller than that of the embodiment. It is considered that this is because the specific heat of the lattice system due to the lattice vibration is remarkably lowered with the temperature drop and does not have the specific heat of the spin system.
【００２７】尚実施例に係る蓄冷材が充填された蓄冷器
は、３０Ｋ以下の冷凍を発生するスターリングサイク
ル，ＧＭサイクル，パルス管式の各種の冷凍機に適用で
きる。The regenerator filled with the regenerator material according to the embodiment can be applied to various Stirling cycle, GM cycle, and pulse tube type refrigerators that generate refrigeration at 30K or less.
【００２８】又、多段冷凍機の温度に合わせて、各段に
用いることも可能である。It is also possible to use each stage according to the temperature of the multistage refrigerator.
【００２９】[0029]
【発明の効果】本発明は、以下の如く効果を有する。The present invention has the following effects.
【００３０】本発明の請求項１によれば、蓄冷材を、次
式（１） Ｒa Ａｇb Ｍc ・・・（１） で表され、Ｒは少なくともＣｅ，Ｐｒ，Ｎｄ，Ｇｄ，Ｄ
ｙ，Ｈｏ，Ｅｒ，Ｔｍの１種又は２種以上である希土類
元素であり、ＭはＢ，Ａｌ，Ｉｎ，Ｓｉ，Ｇｅ，Ｇａ，
Ｓｎ，Ａｕ，Ｍｇ，Ｚｎ，Ｐｄ，Ｐｔ，Ｒｅ，Ｃｓ，Ｉ
ｒ，Ｆｅ，Ｍｎ，Ｃｒ，Ｃｄ，Ｈｇ，Ｏｓ，Ｐ，Ｌａ，
Ｙの内の少なくとも１種の元素であり、前記Ｒの含有率
ａは２０ａｔ％≦ａ≦９５ａｔ％であり、前記Ｍの含有
率ｃは５ａｔ％≦ｃ≦２５ａｔ％であり、Ａｇと前記Ｍ
との合計の含有率ｂ＋ｃは５ａｔ％＜ｂ＋ｃ≦８０ａｔ
％であるものとした。このため、３０Ｋ以下での蓄冷効
率を向上させることができ、極低温に到達可能な蓄冷器
を提供することができ、また３０Ｋ以下の冷凍を発生す
る冷凍機に適用可能となる。According to claim 1 of the [0030] present invention, the cold storage material, represented by the following formula (1) R a Ag b M c ··· (1), R is at least Ce, Pr, Nd, Gd, D
It is a rare earth element which is one or more of y, Ho, Er and Tm, and M is B, Al, In, Si, Ge, Ga,
Sn, Au, Mg, Zn, Pd, Pt, Re, Cs, I
r, Fe, Mn, Cr, Cd, Hg, Os, P, La,
It is at least one element of Y, the content a of R is 20 at% ≦ a ≦ 95 at%, the content c of M is 5 at% ≦ c ≦ 25 at%, and Ag and M are the same.
And the total content b + c is 5 at% <b + c ≦ 80 at
%. Therefore, the cold storage efficiency at 30 K or less can be improved, a regenerator capable of reaching a cryogenic temperature can be provided, and it can be applied to a refrigerator that generates refrigeration at 30 K or less.
【００３１】本発明の請求項２によれば、蓄冷材を、次
式（２） Ｒa Ａｇb ＭC ・・・（２） で表され、Ｒは少なくともＣｅ，Ｐｒ，Ｎｄ，Ｇｄ，Ｄ
ｙ，Ｈｏ，Ｅｒ，Ｔｍの１種又は２種以上である希土類
元素であり、ＭはＳｂ，Ｂｉ，Ｔｅ，Ｚｒ，Ｔｉの内の
少なくとも１種の元素であり、前記Ｒの含有率ａは２０
ａｔ％≦ａ≦９５ａｔ％であり、前記Ｍの含有率ｃは０
ａｔ％＜ｃ≦２５ａｔ％であり、Ａｇと前記Ｍとの合計
の含有率ｂ＋ｃは５ａｔ％≦ｂ＋ｃ≦８０ａｔ％である
ものとした。このため、３０Ｋ以下での蓄冷効率を向上
させることができ、極低温に到達可能な蓄冷器を提供す
ることができ、また３０Ｋ以下の冷凍を発生する冷凍機
に適用可能となる。According to claim 2 of the present invention, the regenerator material is represented by the following formula (2): Ra ag b M C (2), where R is at least Ce, Pr, Nd, Gd, D.
y, Ho, Er, Tm is one or more rare earth elements, M is at least one element of Sb, Bi, Te, Zr and Ti, and the content a of R is 20
at% ≦ a ≦ 95 at%, and the content c of M is 0.
It is assumed that at% <c ≦ 25 at% and the total content b + c of Ag and M is 5 at% ≦ b + c ≦ 80 at%. Therefore, the cold storage efficiency at 30 K or less can be improved, a regenerator that can reach a cryogenic temperature can be provided, and it can be applied to a refrigerator that generates refrigeration at 30 K or less.
【図１】本発明の実施例１、２、３及び従来例１、２、
参考例の低温での比熱特性を示すグラフである。FIG. 1 is a first example of the present invention, a second example, and a third example of the related art.
It is a graph which shows the specific heat characteristic in the low temperature of a reference example.
【図２】本発明の請求項１に係る合金において、添加物
の配合比率を変えて比熱ピークを示す温度を測定したも
のをグラフ上に示したものである。FIG. 2 is a graph showing an alloy according to claim 1 of the present invention, in which a temperature at which a specific heat peak is measured by changing a compounding ratio of an additive.
【図３】本発明の実施例４及び従来例１、２の低温での
比熱特性を示すグラフである。FIG. 3 is a graph showing the specific heat characteristics at low temperature of Example 4 of the present invention and Conventional Examples 1 and 2.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 水 谷 宇一郎 愛知県名古屋市南区外山２丁目12−６ (72)発明者 星 野 善 樹 愛知県丹羽郡扶桑町高木473 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Uichiro Mizutani 2-6-6 Sotoyama, Minami-ku, Aichi Prefecture Nagoya City (72) Inventor Yoshiki Hoshino 473 Takagi, Fuso-cho, Niwa-gun, Aichi Prefecture
Claims (2)
て、 前記蓄冷材は、次式（１） Ｒa Ａｇb Ｍc ・・・（１） で表され、Ｒは少なくともＣｅ，Ｐｒ，Ｎｄ，Ｇｄ，Ｄ
ｙ，Ｈｏ，Ｅｒ，Ｔｍの１種又は２種以上である希土類
元素であり、ＭはＢ，Ａｌ，Ｉｎ，Ｓｉ，Ｇｅ，Ｇａ，
Ｓｎ，Ａｕ，Ｍｇ，Ｚｎ，Ｐｄ，Ｐｔ，Ｒｅ，Ｃｓ，Ｉ
ｒ，Ｆｅ，Ｍｎ，Ｃｒ，Ｃｄ，Ｈｇ，Ｏｓ，Ｐ，Ｌａ，
Ｙの内の少なくとも１種の元素であり、前記Ｒの含有率
ａは２０ａｔ％≦ａ≦９５ａｔ％であり、前記Ｍの含有
率ｃは５ａｔ％≦ｃ≦２５ａｔ％であり、Ａｇと前記Ｍ
との合計の含有率ｂ＋ｃは５ａｔ％＜ｂ＋ｃ≦８０ａｔ
％であることを特徴とする蓄冷器。1. A regenerator filled with a regenerator material, wherein the regenerator material is represented by the following formula (1) R a Ag b M c (1), and R is at least Ce, Pr, Nd. , Gd, D
It is a rare earth element which is one or more of y, Ho, Er and Tm, and M is B, Al, In, Si, Ge, Ga,
Sn, Au, Mg, Zn, Pd, Pt, Re, Cs, I
r, Fe, Mn, Cr, Cd, Hg, Os, P, La,
It is at least one element of Y, the content a of R is 20 at% ≦ a ≦ 95 at%, the content c of M is 5 at% ≦ c ≦ 25 at%, and Ag and M are the same.
And the total content b + c is 5 at% <b + c ≦ 80 at
A regenerator characterized by being%.
て、 前記蓄冷材は、次式（２） Ｒa Ａｇb ＭC ・・・（２） で表され、Ｒは少なくともＣｅ，Ｐｒ，Ｎｄ，Ｇｄ，Ｄ
ｙ，Ｈｏ，Ｅｒ，Ｔｍの１種又は２種以上である希土類
元素であり、ＭはＳｂ，Ｂｉ，Ｔｅ，Ｚｒ，Ｔｉの内の
少なくとも１種の元素であり、前記Ｒの含有率ａは２０
ａｔ％≦ａ≦９５ａｔ％であり、前記Ｍの含有率ｃは０
ａｔ％＜ｃ≦２５ａｔ％であり、Ａｇと前記Ｍとの合計
の含有率ｂ＋ｃは５ａｔ％≦ｂ＋ｃ≦８０ａｔ％である
ことを特徴とする蓄冷器。2. A regenerator filled with a regenerator material, wherein the regenerator material is represented by the following formula (2) R a Ag b M C (2), and R is at least Ce, Pr, Nd. , Gd, D
y, Ho, Er, Tm is one or more rare earth elements, M is at least one element of Sb, Bi, Te, Zr and Ti, and the content a of R is 20
at% ≦ a ≦ 95 at%, and the content c of M is 0.
The regenerator characterized in that at% <c ≦ 25 at% and the total content b + c of Ag and M is 5 at% ≦ b + c ≦ 80 at%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16415195A JP3677818B2 (en) | 1995-06-29 | 1995-06-29 | Regenerator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16415195A JP3677818B2 (en) | 1995-06-29 | 1995-06-29 | Regenerator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0914774A true JPH0914774A (en) | 1997-01-17 |
| JP3677818B2 JP3677818B2 (en) | 2005-08-03 |
Family
ID=15787717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16415195A Expired - Fee Related JP3677818B2 (en) | 1995-06-29 | 1995-06-29 | Regenerator |
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| Country | Link |
|---|---|
| JP (1) | JP3677818B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004225920A (en) * | 2002-11-27 | 2004-08-12 | Aisin Seiki Co Ltd | Cool accumulator |
| JP2017058079A (en) * | 2015-09-17 | 2017-03-23 | 株式会社東芝 | Cold storage material for cryogenic refrigeration machine, cryogenic regenerator, cold storage type cryogenic refrigeration machine and system with cryogenic cold storage type cryogenic refrigeration machine |
| US10101061B2 (en) | 2016-08-19 | 2018-10-16 | Kabushiki Kaisha Toshiba | Cryogenic regenerator material, regenerative cryocooler, and system including regenerative cryocooler |
| WO2020067356A1 (en) | 2018-09-28 | 2020-04-02 | 株式会社東芝 | Cold storage material, refrigerator, device incorporating superconducting coil, and method of manufacturing cold storage material |
| WO2022039150A1 (en) * | 2020-08-18 | 2022-02-24 | 株式会社 東芝 | Cold storage material particles, cold storage device, refrigerating machine, cryopump, superconducting magnet, nuclear magnetic resonance imaging apparatus, nuclear magnetic resonance apparatus, magnetic field application type single crystal pulling apparatus, and mehod for producing cold storage material particles |
-
1995
- 1995-06-29 JP JP16415195A patent/JP3677818B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004225920A (en) * | 2002-11-27 | 2004-08-12 | Aisin Seiki Co Ltd | Cool accumulator |
| JP2017058079A (en) * | 2015-09-17 | 2017-03-23 | 株式会社東芝 | Cold storage material for cryogenic refrigeration machine, cryogenic regenerator, cold storage type cryogenic refrigeration machine and system with cryogenic cold storage type cryogenic refrigeration machine |
| US10393412B2 (en) | 2015-09-17 | 2019-08-27 | Kabushiki Kaisha Toshiba | Cryocooler regenerator material, cryogenic regenerator, regenerative cryocooler and system comprising regenerative cryocooler |
| US10101061B2 (en) | 2016-08-19 | 2018-10-16 | Kabushiki Kaisha Toshiba | Cryogenic regenerator material, regenerative cryocooler, and system including regenerative cryocooler |
| WO2020067356A1 (en) | 2018-09-28 | 2020-04-02 | 株式会社東芝 | Cold storage material, refrigerator, device incorporating superconducting coil, and method of manufacturing cold storage material |
| WO2022039150A1 (en) * | 2020-08-18 | 2022-02-24 | 株式会社 東芝 | Cold storage material particles, cold storage device, refrigerating machine, cryopump, superconducting magnet, nuclear magnetic resonance imaging apparatus, nuclear magnetic resonance apparatus, magnetic field application type single crystal pulling apparatus, and mehod for producing cold storage material particles |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3677818B2 (en) | 2005-08-03 |
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