JPH0151449B2 - - Google Patents
Info
- Publication number
- JPH0151449B2 JPH0151449B2 JP59205645A JP20564584A JPH0151449B2 JP H0151449 B2 JPH0151449 B2 JP H0151449B2 JP 59205645 A JP59205645 A JP 59205645A JP 20564584 A JP20564584 A JP 20564584A JP H0151449 B2 JPH0151449 B2 JP H0151449B2
- Authority
- JP
- Japan
- Prior art keywords
- eral
- magnetic
- cold storage
- heat capacity
- magnetic material
- 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.)
- Expired
Links
- 239000000696 magnetic material Substances 0.000 claims description 22
- 239000011232 storage material Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 11
- 230000007704 transition Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005057 refrigeration Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000002547 anomalous effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
- C01F17/34—Aluminates, e.g. YAlO3 or Y3-xGdxAl5O12
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Hard Magnetic Materials (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、蓄冷材用磁性体、特に20〜4.2K
領域で有効に使用しうる、気体冷凍機の蓄冷材用
磁性体に関するものである。[Detailed Description of the Invention] (Industrial Application Field) This invention relates to magnetic materials for cold storage materials, particularly 20 to 4.2K magnetic materials.
The present invention relates to a magnetic material for a cold storage material in a gas refrigerator, which can be effectively used in the field.
（従来の技術）
従来、He液化用冷凍機における冷凍効率は、
理想的なカルノー効率に比較すると、著しく低か
つた。その主な原因としては、理想的なカルノー
効率を満足するような冷凍サイクルを構成するの
に不可欠な蓄冷材がないことが挙げられる。(Conventional technology) Conventionally, the refrigeration efficiency of Helium liquefaction refrigerators is
It was significantly lower than the ideal Carnot efficiency. The main reason for this is that there is no regenerator material that is essential for constructing a refrigeration cycle that satisfies the ideal Carnot efficiency.
現在、一般に蓄冷材としては、Pbなどの固体
材料が用いられる。しかし、このような固体材料
は、低温になると、格子振動が著しく沈静化する
ので、第２図に示すように、この格子振動に基づ
く熱容量も、低温になるに従つて著しく小さくな
る。反対に、冷却すべき気体Heにおいては、低
温の加圧状態で、第２図に示すように、その熱容
量が著しい増大を示し、単位体積あたりの熱容量
は前記Pbなどの蓄冷材のそれに数倍する。 Currently, solid materials such as Pb are generally used as cold storage materials. However, in such a solid material, the lattice vibrations significantly subside when the temperature decreases, so as shown in FIG. 2, the heat capacity based on the lattice vibrations also decreases significantly as the temperature decreases. On the contrary, the heat capacity of the gas He to be cooled shows a significant increase in the pressurized state at low temperatures, as shown in Figure 2, and the heat capacity per unit volume is several times that of the regenerator material such as Pb. do.
したがつて、このような蓄冷材を、20〜4.2K
領域での気体冷凍機用熱交換媒体とした場合に
は、カルノー効率を満たすようなスターリング又
はエリクソン・サイクルを構成することは不可能
になる。このことは第３図からも明らかである。
この図は、蓄冷材の熱容量Crと被冷凍媒体の熱
容量Cgとの比（Cr／Cg）に対する、冷凍能力の
低下の関係を示す。この関係からも、比Cr／Cg
が４程度以上でなければ、高冷凍効率が期待でき
ないことがわかる。要するに、前記のような低温
における高冷凍効率を達成することは、Pbなど
のような格子振動に基づく熱容量を利用する、従
来の蓄冷材では不可能であるので、新たな物理的
現象に伴う異常比熱を有する物質を蓄冷材として
開発することが必要となつた。 Therefore, such a cold storage material can be used at a temperature of 20 to 4.2K.
When used as a heat exchange medium for a gas refrigerator in the region, it becomes impossible to construct a Stirling or Ericsson cycle that satisfies Carnot efficiency. This is also clear from FIG.
This figure shows the relationship between the reduction in refrigerating capacity and the ratio (Cr/Cg) between the heat capacity Cr of the cold storage material and the heat capacity Cg of the medium to be refrigerated. From this relationship, the ratio Cr/Cg
It can be seen that high refrigeration efficiency cannot be expected unless it is about 4 or more. In short, it is impossible to achieve high refrigeration efficiency at low temperatures as described above with conventional regenerator materials that utilize heat capacity based on lattice vibrations such as Pb. It became necessary to develop a substance with specific heat as a cold storage material.
このような異常比熱を示すものに磁性体があ
る。磁生体におけるスピン系の秩序−無秩序相転
移、例えば、常磁性−強磁性相転移の際には、大
きなエントロピー変化があり、それに伴う大きな
異常磁気比熱が観測される。このような現象に注
目した蓄冷材として、希土類元素−Rh系蓄冷材
が知られる。（カー・ハー・イエー・バシヨウ
（K.H.J.Buschow）ら、クライオジエニツクス
（Cryogenics）1975年５月、p261〜264）。 Magnetic materials exhibit such abnormal specific heat. During an order-disorder phase transition of a spin system in a magnetic body, for example, a paramagnetic-ferromagnetic phase transition, there is a large entropy change, and a large anomalous magnetic specific heat associated with it is observed. A rare earth element-Rh based regenerator material is known as a regenerator material that focuses on such a phenomenon. (KHJ Buschow et al., Cryogenics, May 1975, p. 261-264).
第４図は、前記希土類元素−Rh系の系列の若
干の化合物について、比熱の温度依存性を示し、
20〜4.2K領域でさえ、大きな比熱が得られるこ
とを示す。 FIG. 4 shows the temperature dependence of specific heat for some compounds of the rare earth element-Rh series,
It shows that even in the 20-4.2K region, a large specific heat can be obtained.
（発明が解決しようとする問題点）
しかしながら、前記希土類元素−Rh系蓄冷材
は、Rhを使用するため、極めて高価であり、到
底実用的といえない。(Problems to be Solved by the Invention) However, since the rare earth element-Rh based regenerator material uses Rh, it is extremely expensive and cannot be said to be practical at all.
この発明の目的は、大きな異常磁気比熱を有す
るとともに、安価にして実用的な、気体冷凍機の
蓄冷材用磁性体、特に20〜4.2K領域で有効に使
用しうる前記磁性体を提供することである。 An object of the present invention is to provide a magnetic material that has a large abnormal magnetic specific heat, is inexpensive and practical, and can be used as a cold storage material for a gas refrigerator, and in particular can be effectively used in the 20 to 4.2 K range. It is.
（問題点を解決するための手段）
本発明者は、前記問題について鋭意研究を重ね
た結果、意外にも前記希土類元素−Rh系の代り
に、特定の組成範囲を有するEr−Al系及びEr−
Al−Ｏ系磁性体により、前記目的に適合するこ
とを確かめ、この発明を達成するに至つた。(Means for Solving the Problems) As a result of extensive research into the above-mentioned problems, the inventors of the present invention unexpectedly found that instead of the rare earth element-Rh system, an Er-Al system having a specific composition range and an Er-Al system with a specific composition range were used. −
It was confirmed that the Al--O magnetic material was suitable for the above purpose, and the present invention was achieved.
すなわち、この発明は、式
ErAl2-〓Ox （）
（式中、０δ＜0.2及び０ｘ＜0.2である）
で表される磁性体及び式
ErAl3±〓Oy （）
（式中、０γ＜0.2及び０ｙ＜0.2である）
で表される磁性体よりなる群の中から選ばれてな
る蓄冷材用磁性体である。 That is, the present invention provides a magnetic material represented by the formula ErAl 2- 〓O x () (wherein 0δ<0.2 and 0x<0.2) and a magnetic material represented by the formula ErAl 3± 〓O y () (wherein 0γ <0.2 and 0y<0.2) This is a magnetic material for cold storage material selected from the group consisting of magnetic materials represented by
この発明の磁性体であるErAl2-〓Ox（）及び
ErAl3±〓Oy（）は、例えば、真空又はアルゴン
のような不活性ガスふん囲気中で、化学量論比を
満たすように混合したEr−Al系とEr−Ｏ試料を
アーク溶解してつくることができる。このように
してつくつた磁性体の均質性をあげるためには、
これを粉砕し、再溶解するという手続きを数回繰
り返す。 ErAl 2- 〓O x () and
ErAl 3± 〓O y () is obtained by arc melting Er-Al and Er-O samples mixed to satisfy the stoichiometric ratio in vacuum or in an atmosphere of an inert gas such as argon. You can make it. In order to improve the homogeneity of the magnetic material produced in this way,
This process of crushing and redissolving is repeated several times.
δ及びｘの値を前記範囲内にすることにより、
前記磁性体（）の転移温度をErAl2の転移温度
である約20Kから約10Kまで連続的に変化させる
ことができる。しかも、この温度範囲において、
前記ErAl2-〓Ox（）は、その体積あたりの熱容
量が加圧He（10〜30気圧）の単位体積あたりの熱
容量、約0.5J／cm3に匹敵する大きさであるので、
20K〜4.2Kの領域における、気体冷凍機の蓄冷材
用磁性体にじゆうぶん使用することができる。 By setting the values of δ and x within the above range,
The transition temperature of the magnetic material ( ) can be continuously changed from about 20K, which is the transition temperature of ErAl 2 , to about 10K. Moreover, in this temperature range,
The heat capacity per unit volume of ErAl 2- 〓O x () is comparable to the heat capacity per unit volume of pressurized He (10 to 30 atmospheres), about 0.5 J/cm 3 .
It can be used as a magnetic material for cold storage material in gas refrigerators in the range of 20K to 4.2K.
δ及びｘの値が前記範囲を満足しない場合は、
試料の合成が困難であり、その特性は不明であ
る。 If the values of δ and x do not satisfy the above range,
The sample is difficult to synthesize and its properties are unknown.
この発明の他の磁性体であるErAl3±〓Oy（）
においては、転移温度、すなわちネール点TNは、
ErAl3自体のそれである約6Kから、ErAl3±〓Oy
（）のγ及びｙを前記範囲内で変化させること
により、±3K程度の幅で変化させることが可能で
あり、しかもそのグラム当りの熱容量も、前記
ErAl2-〓Ox（）とほとんど同程度の値を有する。
したがつて、この磁性体は、ErAl2-〓Ox（）と
ともに、20〜4.2K領域での、気体冷凍機の蓄冷
材となる。なお、γ及びｙの値が前記範囲を満足
しない場合については、前記のErAl2-〓Ox（）
の場合と同様に合成が困難である。 ErAl 3± 〓O y () which is another magnetic material of this invention
, the transition temperature, i.e., the Neel point T N , is
From about 6K, that of ErAl 3 itself, ErAl 3± 〓O y
By changing γ and y in () within the above range, it is possible to change it within a range of about ±3K, and the heat capacity per gram is also the same as above.
It has almost the same value as ErAl 2- 〓O x ().
Therefore, this magnetic material, together with ErAl 2- 〓O x (), becomes a regenerator material for a gas refrigerator in the 20 to 4.2 K range. In addition, if the values of γ and y do not satisfy the above range, the above ErAl 2- 〓O x ()
As in the case of , synthesis is difficult.
（実施例）
以下に、この発明を実施例によりさらに詳細に
説明する。(Examples) The present invention will be explained in more detail below using examples.
ErAl2化学量論比よりAlを過剰にしたEr0.9Al1.9
粉末201.8重量部、ErO粉末18.3重量部をじゆうぶ
ん混合し、次いでこの混合物をアルゴンガスふん
囲気中でアーク溶解し、冷却して、ErAl1.9O0.1の
組成の固溶体を調整した。この物質及びErAl2の
熱容量は、通常の定常法による、低温比熱の測定
により求めた。結果を第１図に示し。この図に示
すように、ErAl2の転移温度は約20Kにあるが、
ErAl1.9O0.1の転移温度はこれより低温側に移り、
約11Kにあり、その熱容量の大きさは、約0.5J／
cm3・Ｋで、加圧He（10〜30気圧）の熱容量に匹敵
する大きさである。 ErAl 2 Excess Al from stoichiometric ratio Er 0.9 Al 1.9
201.8 parts by weight of powder and 18.3 parts by weight of ErO powder were thoroughly mixed, and then this mixture was arc melted in an argon gas atmosphere and cooled to prepare a solid solution having a composition of ErAl 1.9 O 0.1 . The heat capacities of this material and ErAl 2 were determined by measuring low-temperature specific heat using the usual steady-state method. The results are shown in Figure 1. As shown in this figure, the transition temperature of ErAl 2 is around 20K,
The transition temperature of ErAl 1.9 O 0.1 shifts to the lower temperature side,
It is located at about 11K, and its heat capacity is about 0.5J/
cm 3 ·K, which is comparable to the heat capacity of pressurized He (10 to 30 atmospheres).
（発明の効果）
以上のように、この発明は、それぞれ特定の組
成範囲を有するErAl2-〓Ox（）及びErAl3±〓Oy
（）を気体冷凍機の蓄冷材用磁性体として提供
し、これにより性能的には、従来の蓄冷材である
鉛のような固定蓄冷材では、その熱容量が極めて
小さかつた20〜4.2K領域でも、じゆうぶんな熱
容量を有し、しかも異常磁気比熱を利用する、従
来の、高価な希土類元素−Rh系蓄冷材と比べて
も、性能的にこれに匹敵するばかりでなく、価格
的にじゆうぶんな実用性を有する点で優れてお
り、これにより、従来実用的な蓄冷材が存在しな
かつた、20〜4.2K領域で有効な、気体冷凍機の
蓄冷材用磁性体を提供することができる。(Effects of the Invention) As described above, the present invention provides ErAl 2- 〓O x () and ErAl 3± 〓O y each having a specific composition range.
() is provided as a magnetic material for regenerator material in gas refrigerators, which improves performance in the range of 20 to 4.2K, where conventional regenerator materials such as fixed regenerator materials, such as lead, have an extremely small heat capacity. However, compared to conventional, expensive rare earth element-Rh based regenerator materials that have sufficient heat capacity and utilize anomalous magnetic specific heat, it is not only comparable in performance, but also in terms of price. It is superior in that it has sufficient practicality, and as a result, it provides a magnetic material for a regenerator material for gas refrigerators that is effective in the 20 to 4.2 K range, where no practical regenerator material existed in the past. be able to.
第１図はこの発明のErAl2-〓Ox（）系蓄冷材
用磁性体の熱容量の温度依存性を示すグラフ、第
２図は加圧ヘリウムガス、鉛及びステンレスの熱
容量の温度依存性を示すグラフ、第３図は蓄冷材
の比熱対ガスの比熱の比と冷凍機の冷凍能力低下
率との相関を示すグラフ、第４図は希土類元素−
Rh系の系列の若干の化合物における比熱の温度
依存性を示すグラフである。
Figure 1 is a graph showing the temperature dependence of the heat capacity of the ErAl 2- 〓O x ()-based magnetic material for cold storage materials of this invention, and Figure 2 is a graph showing the temperature dependence of the heat capacity of pressurized helium gas, lead, and stainless steel. Figure 3 is a graph showing the correlation between the ratio of the specific heat of the cold storage material to the specific heat of the gas and the cooling capacity reduction rate of the refrigerator.
1 is a graph showing the temperature dependence of specific heat in some compounds of the Rh series.
Claims (1)
る蓄冷材用磁性体。 ２ 式 ErAl3±〓Oy （式中、０γ＜0.2及び０ｙ＜0.2である） で表される磁性体よりなる群の中から選ばれてな
る蓄冷材用磁性体。[Claims] 1. A magnetic material for a cold storage material selected from the group consisting of magnetic materials represented by the formula ErAl 2- 〓O x (where 0δ<0.2 and 0x<0.2). 2 A magnetic material for a cold storage material selected from the group consisting of magnetic materials represented by the formula ErAl 3± 〓O y (wherein, 0γ<0.2 and 0y<0.2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59205645A JPS6186420A (en) | 1984-10-02 | 1984-10-02 | Magnetic material for cold storage material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59205645A JPS6186420A (en) | 1984-10-02 | 1984-10-02 | Magnetic material for cold storage material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6186420A JPS6186420A (en) | 1986-05-01 |
| JPH0151449B2 true JPH0151449B2 (en) | 1989-11-02 |
Family
ID=16510320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59205645A Granted JPS6186420A (en) | 1984-10-02 | 1984-10-02 | Magnetic material for cold storage material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6186420A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0816214B2 (en) * | 1991-12-19 | 1996-02-21 | 株式会社東芝 | Regenerator material and regenerator |
-
1984
- 1984-10-02 JP JP59205645A patent/JPS6186420A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6186420A (en) | 1986-05-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |