JP4950918B2 - Magnetic material for magnetic refrigeration equipment, heat exchange container and magnetic refrigeration equipment - Google Patents
Magnetic material for magnetic refrigeration equipment, heat exchange container and magnetic refrigeration equipment Download PDFInfo
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- 238000005057 refrigeration Methods 0.000 title claims description 97
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- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052689 Holmium Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
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Classifications
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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
- F25B21/00—Machines, plants or systems, using electric or magnetic effects
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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
- F25B2321/00—Details of machines, plants or systems, using electric or magnetic effects
- F25B2321/002—Details of machines, plants or systems, using electric or magnetic effects by using magneto-caloric effects
- F25B2321/0021—Details of machines, plants or systems, using electric or magnetic effects by using magneto-caloric effects with a static fixed magnet
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
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- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Hard Magnetic Materials (AREA)
Description
本発明は、磁気熱量効果を有する磁気冷凍装置用磁性材料およびこれを用いた熱交換容器、磁気冷凍装置に関する。 The present invention relates to a magnetic material for a magnetic refrigeration apparatus having a magnetocaloric effect, a heat exchange container using the same, and a magnetic refrigeration apparatus.
現在、人間の日常生活に密接に関係する室温域の冷凍技術、たとえば冷蔵庫、冷凍庫、室内冷暖房などの大半は、気体の圧縮膨張サイクルを使用している。しかし、気体の圧縮膨張サイクルに基づく冷凍技術に関しては、特定フロンガスの環境排出に伴う環境破壊が大きな問題となり、代替フロンガスについてもその環境への影響が懸念されている。このような背景から、環境リスクの低い自然冷媒(CO2、アンモニアなど)やイソブタンなどを用いた取り組みも行われており、作業ガスの廃棄に伴う環境破壊の問題がない、安全でクリーンで且つ効率の高い冷凍技術の実用化が求められている。 Currently, most of room temperature refrigeration technologies closely related to human daily life, such as refrigerators, freezers, and indoor air-conditioners, use a gas compression / expansion cycle. However, with regard to the refrigeration technology based on the gas compression / expansion cycle, environmental destruction due to the environmental discharge of the specific chlorofluorocarbon gas becomes a major problem, and there is a concern about the influence of the alternative chlorofluorocarbon on the environment. Against this background, efforts are being made using natural refrigerants (CO 2 , ammonia, etc.) and isobutane with low environmental risks, and there is no problem of environmental destruction associated with the disposal of working gas, and it is safe and clean. There is a need for practical use of highly efficient refrigeration technology.
このような環境配慮型で且つ効率の高い冷凍技術の一つとして、磁気冷凍への期待が高まり、室温域を対象とした磁気冷凍技術の研究開発が活発化してきている。磁気冷凍技術は、1881年にWarburgによって見出された鉄(Fe)における磁気熱量効果を基本原理としている。磁気熱量効果とは、断熱状態で磁性物質に対して外部印加磁場を変化させると、その磁性物質の温度が変化する現象である。1900年代前半には磁気熱量効果を有するGd2(SO4)3・8H2O、Gd3Ga5O12に代表される常磁性塩および常磁性化合物を用いた冷凍システムが開発されたが、これは20K以下の極低温領域に適用されるものが中心であり、超伝導磁石による10T程度の磁場が必要であった。 As one of such environmentally friendly and highly efficient refrigeration technologies, expectations for magnetic refrigeration have increased, and research and development of magnetic refrigeration technologies for room temperature regions have become active. The magnetic refrigeration technology is based on the magnetocaloric effect in iron (Fe) discovered by Warburg in 1881. The magnetocaloric effect is a phenomenon in which, when an externally applied magnetic field is changed with respect to a magnetic substance in an adiabatic state, the temperature of the magnetic substance changes. In the first half of the 1900s, a refrigeration system using paramagnetic salts and paramagnetic compounds represented by Gd 2 (SO 4 ) 3 · 8H 2 O, Gd 3 Ga 5 O 12 having a magnetocaloric effect was developed. This was mainly applied to a cryogenic region of 20K or less, and a magnetic field of about 10 T by a superconducting magnet was required.
1970年代以降になると高温領域での磁気冷凍の実現にむけて強磁性物質における常磁性状態と強磁性状態間の磁気転移を利用した研究が盛んに行われ、今日に至っている。これらの研究の結果としてPr、Nd、Dy、Er、Tm、Gdなどのランタン系列の希土類元素単体、Gd−Y、Gd−Dyのような二種類以上の希土類合金系材料、RAl2及びRNi2(R:希土類元素)、GdPdなどの希土類金属間化合物などの磁性材料が提案されている。 Since the 1970s, researches using magnetic transition between a paramagnetic state and a ferromagnetic state in a ferromagnetic material have been actively conducted to realize magnetic refrigeration in a high temperature region, and have reached today. As a result of these studies, lanthanum-based rare earth elements such as Pr, Nd, Dy, Er, Tm, and Gd, two or more rare earth alloy-based materials such as Gd-Y and Gd-Dy, RAl 2 and RNi 2 Magnetic materials such as (R: rare earth elements) and rare earth intermetallic compounds such as GdPd have been proposed.
常温域を対象とした磁気冷凍のシステムとしては、1982年に磁気冷凍材料に磁気熱量効果に加えて蓄熱効果も同時に担わせるAMR(“Active Magnetic Regenerative Refrigeration”)方式が米国のBarclayによって提案された(特許文献1参照)。このAMR方式は、従来室温域における磁気冷凍にとって阻害要因と位置づけられていた格子エントロピーをむしろ積極的に利用しようとするものである。 As a magnetic refrigeration system for the normal temperature range, an AMR (“Active Magnetic Regenerative Refrigeration”) method was proposed by Barclay in the United States in 1982, in which in addition to the magnetocaloric effect, the magnetic refrigeration material also has a heat storage effect. (See Patent Document 1). This AMR system intends to actively utilize lattice entropy, which has been conventionally regarded as an impediment to magnetic refrigeration at room temperature.
AMR方式による磁気冷凍は以下のようなステップで行われている。
(1)磁気冷凍作業物質に磁場を印加する。
(2)(1)により発生した温熱を冷媒により一端から他端へ輸送する。
(3)磁気冷凍作業物質の磁場を取り除く。
(4)(3)により発生した冷熱を(2)で熱を輸送した方とは逆の一端に輸送する。
(1)〜(4)の熱サイクルを繰り返すことにより、磁気冷凍作業室内部では磁気冷凍材料で生まれた熱が熱輸送媒体を介して一方向に輸送されることになり、熱流方向に温度勾配が生成し、両端では大きな温度差が生じることにより冷凍作業が行われる。
Magnetic refrigeration by the AMR method is performed in the following steps.
(1) A magnetic field is applied to the magnetic refrigeration material.
(2) The heat generated in (1) is transported from one end to the other end by the refrigerant.
(3) Remove the magnetic field of the magnetic refrigeration material.
(4) The cold generated by (3) is transported to one end opposite to the one where heat was transported in (2).
By repeating the heat cycle of (1) to (4), the heat generated from the magnetic refrigeration material is transported in one direction through the heat transport medium in the magnetic refrigeration chamber, and the temperature gradient in the heat flow direction. Is generated and a large temperature difference occurs between both ends, so that the freezing operation is performed.
1998年に米国のZimm,Gschneidner,Pecharskyらは、室温域における磁気冷凍材料としてGd(ガドリニウム)を用い、上記AMR方式を用いた磁気冷凍機に超伝導磁石により5Tまでの高磁場を印加することで、磁気冷凍サイクルの連続運転に成功した。 In 1998, Zimm, Gschneidner, Pecharsky et al. In the United States applied Gd (gadolinium) as a magnetic refrigeration material at room temperature and applied a high magnetic field of up to 5 T to a magnetic refrigerator using the AMR method with a superconducting magnet. So, we succeeded in continuous operation of the magnetic refrigeration cycle.
もっとも、磁気冷凍材料の磁気熱量効果は磁気転移温度近傍でのみ大きな効果が得られるため、その温度から乖離する物質の作業効率が落ちるという問題点がある。そこで、熱交換容器内部に生じる温度差に合わせて層状に異なる磁気転移温度を有する磁性材料を充填することにより、作業温度を広げる提案がなされている(特許文献2参照)。
本発明は、上記事情を考慮してなされたものであり、その目的とするところは、広い動作温度範囲を有することによって、磁気冷凍効率を向上させる磁気冷凍装置用磁性材料およびこれを用いた磁気冷凍装置を提供することにある。 The present invention has been made in view of the above circumstances, and the object of the present invention is to provide a magnetic material for a magnetic refrigeration apparatus that improves the magnetic refrigeration efficiency by having a wide operating temperature range, and a magnetic material using the same. It is to provide a refrigeration apparatus.
本発明の一態様の熱交換容器は、磁性材料が充填された液体冷媒を用いるAMR方式の磁気冷凍装置用熱交換容器であって、前記磁性材料が、異なる磁気転移温度を有する2種以上の磁性体粒子が略均一に混合されており、前記磁性体粒子は、最大径が0.3mm以上2mm以下の略球状を呈し、前記2種以上の磁性体粒子中、最も含有重量の多い第1の磁性体粒子と、次いで含有重量の多い第2の磁性体粒子との磁気転移温度の差が1K以上10K未満であって、前記第1の磁性体粒子と、前記第2の磁性体粒子とが、5:5から3:2の重量比で混合され、空隙率が、30%以上50%以下であることを特徴とする。
The heat exchange container of one embodiment of the present invention is an AMR type magnetic refrigeration apparatus heat exchange container using a liquid refrigerant filled with a magnetic material, wherein the magnetic material has two or more kinds of different magnetic transition temperatures. are mixed magnetic particles substantially uniformly, the magnetic particles, the maximum diameter and coloration of 2mm or less substantially spherical or 0.3 mm, the 2 or more of the magnetic particles, often the most weight content first The difference in magnetic transition temperature between one magnetic particle and the second magnetic particle having a large content is 1 K or more and less than 10 K, and the first magnetic particle and the second magnetic particle Are mixed at a weight ratio of 5: 5 to 3: 2, and the porosity is 30% or more and 50% or less .
本発明の一態様の熱交換容器は、磁性材料が充填された液体冷媒を用いるAMR方式の磁気冷凍装置用熱交換容器であって、前記磁性材料が、異なる磁気転移温度を有する2種以上の磁性体粒子が略均一に混合されており、前記磁性体粒子は、最大径が0.3mm以上2mm以下の略球状を呈し、前記2種以上の磁性体粒子中、最も含有重量の多い第1の磁性体粒子と、次いで含有重量の多い第2の磁性体粒子との磁気転移温度の差が1K以上10K未満であって、前記第1の磁性体粒子と、前記第2の磁性体粒子とが、5:5から3:2の重量比で混合され、空隙率が、30%以上50%以下であることを特徴とする。The heat exchange container of one embodiment of the present invention is an AMR type magnetic refrigeration apparatus heat exchange container using a liquid refrigerant filled with a magnetic material, wherein the magnetic material has two or more kinds of different magnetic transition temperatures. The magnetic particles are substantially uniformly mixed, the magnetic particles have a substantially spherical shape with a maximum diameter of 0.3 mm or more and 2 mm or less, and the first containing the largest amount of the two or more kinds of magnetic particles. The difference in magnetic transition temperature between the first magnetic particles and the second magnetic particles having a large content is 1 K or more and less than 10 K, and the first magnetic particles, the second magnetic particles, Are mixed at a weight ratio of 5: 5 to 3: 2, and the porosity is 30% or more and 50% or less.
ここで、前記磁性体粒子が、Gd(ガドリニウム)またはGdR合金(R:希土類元素)であることが望ましい。
Here, the magnetic particles, Gd (gadolinium) or GdR alloy (R: rare earth element) der Rukoto is desirable.
本発明の一態様の磁気冷凍装置は、液体冷媒を用いる磁気冷凍装置であって、磁性材料が充填された熱交換容器と、前記磁性材料への磁場の印加または除去を行う磁場発生手段と、冷却ユニットと、排熱ユニットと、前記熱交換容器、前記冷却ユニットおよび前記排熱ユニットを接続して形成され、前記液体冷媒を循環させる冷媒回路を備え、前記熱交換容器が、上記態様の熱交換容器であることを特徴とする。 A magnetic refrigeration apparatus according to one aspect of the present invention is a magnetic refrigeration apparatus using a liquid refrigerant, a heat exchange container filled with a magnetic material, and a magnetic field generation unit that applies or removes a magnetic field to the magnetic material, A cooling unit, an exhaust heat unit, the heat exchange container, the cooling unit, and the exhaust heat unit are connected to each other. The refrigerant circuit circulates the liquid refrigerant, and the heat exchange container has the heat of the above aspect. It is an exchange container.
本発明によれば、広い動作温度範囲を有することによって、磁気冷凍効率を向上させる磁気冷凍装置用磁性材料およびこれを用いた磁気冷凍装置を提供することが可能となる。 ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the magnetic material for magnetic refrigeration apparatuses which improves a magnetic refrigeration efficiency by having a wide operating temperature range, and a magnetic refrigeration apparatus using the same.
発明者らは、異なる磁気転移温度(Tc)を有する2種以上の磁性体粒子を略均一に混合させて、熱交換容器へ充填すると、冷凍能力を著しく低下させることなく、磁気冷凍動作温度範囲が拡大できることを見出した。以下、発明者らの見出した上記知見に基づく、本発明の実施の形態の磁気冷凍装置用磁性材料、熱交換容器および磁気冷凍装置について、図面を参照しつつ説明する。なお、本明細書中、2種の磁性体粒子が異なる磁気転移温度を有するとは、それぞれの磁性体粒子の磁気転移温度の平均値が、0.5K以上乖離している場合を意味するものとする。 When the inventors mixed two or more kinds of magnetic particles having different magnetic transition temperatures (Tc) substantially uniformly and filled in the heat exchange container, the magnetic refrigeration operating temperature range is not significantly reduced without significantly reducing the refrigeration capacity. Found that can be expanded. Hereinafter, a magnetic material for a magnetic refrigeration apparatus, a heat exchange container, and a magnetic refrigeration apparatus according to an embodiment of the present invention based on the above findings found by the inventors will be described with reference to the drawings. In the present specification, the two kinds of magnetic particles having different magnetic transition temperatures means that the average value of the magnetic transition temperatures of the respective magnetic particles is deviated by 0.5 K or more. And
(第1の実施の形態)
本実施の形態の磁気冷凍装置用磁性材料は、液体冷媒を用いる磁気冷凍装置用磁性材料である。そして、異なる磁気転移温度(Tc)を有する2種以上の磁性体粒子が略均一に混合されている。この磁性体粒子は、最大径が0.3mm以上2mm以下の略球状を呈している。
(First embodiment)
The magnetic material for a magnetic refrigeration apparatus of the present embodiment is a magnetic material for a magnetic refrigeration apparatus that uses a liquid refrigerant. Two or more kinds of magnetic particles having different magnetic transition temperatures (Tc) are mixed substantially uniformly. The magnetic particles have a substantially spherical shape with a maximum diameter of 0.3 mm to 2 mm.
本実施の形態の磁性材料では、例えば、磁気転移温度293(K)のGd粒子と、Gd粒子よりも低い磁気転移温度283(K)のGd95Y5粒子の2種の磁性体粒子が、1:1の割合で略均一に混合されている。なお、ここで2種の磁性体粒子の磁気転移温度の差を磁気転移温度差(ΔTc)と以後称する。 In the magnetic material of the present embodiment, for example, two kinds of magnetic particles, that is, Gd particles having a magnetic transition temperature 293 (K) and Gd 95 Y 5 particles having a magnetic transition temperature 283 (K) lower than the Gd particles, Almost uniformly mixed at a ratio of 1: 1. Here, the difference in magnetic transition temperature between the two kinds of magnetic particles is hereinafter referred to as a magnetic transition temperature difference (ΔTc).
そして、この2種の磁性体粒子は、最大径が0.3mm以上2mm以下の略球状を呈している。この磁性体粒子の最大径の測長は、目視下でのノギス等、あるいは、顕微鏡下での直接観察や顕微鏡写真での測定によることで評価可能である。 The two types of magnetic particles have a substantially spherical shape with a maximum diameter of 0.3 mm to 2 mm. The measurement of the maximum diameter of the magnetic particles can be evaluated by vernier calipers or the like under visual observation, or by direct observation under a microscope or measurement with a micrograph.
なお、磁性体粒子としては、上記のGd95Y5、Gd以外にも、GdとYが異なる組成比で化合した化合物、あるいはGdR(RはGd、Y以外の希土類元素、すなわち、Sc、La、Ce、Pr、Nd、Pm、Sm、Eu、Tb、Dy、Ho、Er、Tm、Yb、Lu)を用いることが可能である。また、その他にも、例えば、各種希土類元素と遷移金属元素からなる化合物、NiMnGa合金、GdGeSi合金、LaFe13系化合物、LaFe13H、MnAsSbなどを用いることも可能である。 In addition to the above Gd 95 Y 5 and Gd, the magnetic particles include compounds in which Gd and Y are combined at different composition ratios, or GdR (R is a rare earth element other than Gd and Y, that is, Sc, La , Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu). In addition, for example, compounds composed of various rare earth elements and transition metal elements, NiMnGa alloys, GdGeSi alloys, LaFe 13 compounds, LaFe 13 H, MnAsSb, and the like can also be used.
図1は、本実施の形態の磁気冷凍装置用磁性材料の作用を示す説明図である。図1上図は、磁性材料の温度と磁性材料の冷凍温度差(ΔT)の関係を示すグラフである。また図1下図は、熱交換容器に磁性材料が充填された様子およびそれぞれの磁性材料の磁気冷凍動作温度範囲を、図1上図の温度軸に対応させて矢印で示す概念図である。なお、ここで冷凍温度差(ΔT)とは、磁性材料に磁場を印加・除去を繰り返し行うことによって磁性材料に生ずる温度差をいい、磁性材料の冷凍能力の指標となる。 FIG. 1 is an explanatory view showing the action of the magnetic material for the magnetic refrigeration apparatus of the present embodiment. The upper diagram in FIG. 1 is a graph showing the relationship between the temperature of the magnetic material and the refrigeration temperature difference (ΔT) of the magnetic material. The lower diagram of FIG. 1 is a conceptual diagram showing the state in which the heat exchange container is filled with the magnetic material and the magnetic refrigeration operating temperature range of each magnetic material with arrows corresponding to the temperature axis of the upper diagram of FIG. Here, the refrigeration temperature difference (ΔT) refers to a temperature difference generated in the magnetic material by repeatedly applying and removing a magnetic field to the magnetic material, and serves as an index of the refrigeration capacity of the magnetic material.
図1上図で2本の破線でそれぞれの冷凍温度特性が表される2種の異なる磁気転移温度を有する磁性体粒子Aおよび磁性体粒子Bを混合すると、図1上図中実線(実測)で示されるように、冷凍能力を著しく低下させることなく、磁気冷凍動作温度が拡大する。一般に、2種の異なる磁気転移温度を有する磁性体粒子Aおよび磁性体粒子Bを混合すると、図1上図中一点鎖線(予測)で示されるように磁気冷凍動作温度が拡大するが、冷凍能力が低下することが予想される。 When magnetic particles A and magnetic particles B having two different magnetic transition temperatures, each of which is represented by two broken lines in the upper diagram of FIG. 1, are mixed, a solid line (actual measurement) in the upper diagram of FIG. As shown, the magnetic refrigeration operating temperature increases without significantly reducing the refrigeration capacity. In general, when magnetic particles A and magnetic particles B having two different magnetic transition temperatures are mixed, the magnetic refrigeration operating temperature increases as shown by the one-dot chain line (predicted) in FIG. Is expected to decline.
本実施の形態において、予測に反して冷凍能力の顕著な低下が見られない理由は、以下のように考えられる。すなわち、ある温度において磁場印加・除去に伴う温度変化は材料によって決まる。したがって、すべて同じ材料であれば理想的には等しい温度変化が一斉に起こると考えられる。しかし、異なる材料が存在すると、磁場印加に伴う温度変化にバラつきが生じ、磁性材料間で熱のやり取りが起こる。この熱のやりとりに伴う2次的な発熱・吸熱過程が加わり、同種の材料のみのときは生じなかった温度変化が生じ、結果として単体材料で行った測定からは予測されない増大の効果が現れたと考えられる。混合により生じるこの効果が加わることにより、冷凍能力を著しく低下させることなく動作温度を拡大できるのである。 In the present embodiment, the reason why the refrigerating capacity is not significantly reduced contrary to the prediction is considered as follows. That is, the temperature change accompanying the application / removal of the magnetic field at a certain temperature is determined by the material. Therefore, if all the materials are the same, ideally the same temperature change is considered to occur simultaneously. However, when different materials are present, temperature changes due to application of a magnetic field vary, and heat exchange occurs between magnetic materials. Secondary heat generation and endothermic processes associated with this heat exchange were added, resulting in a temperature change that did not occur when only the same type of material was used, resulting in an unexpected increase effect from measurements performed on a single material. Conceivable. By adding this effect caused by mixing, the operating temperature can be expanded without significantly reducing the refrigerating capacity.
上記例示したような磁性体粒子は、その組成により異なる磁気転移温度を有している。本実施の形態の磁性材料において、適当な磁気転移温度を有する2種の磁性体粒子を適切に組み合わせることによって、広い冷凍動作温度を保証することが可能となる。また、ここでは、異なる磁気転移温度を有する2種の磁性体粒子を混合する場合を例に説明したが、混合する粒子は3種以上であっても構わない。 The magnetic particles as exemplified above have different magnetic transition temperatures depending on their compositions. In the magnetic material of the present embodiment, a wide refrigeration operating temperature can be ensured by appropriately combining two kinds of magnetic particles having an appropriate magnetic transition temperature. Here, the case where two kinds of magnetic particles having different magnetic transition temperatures are mixed has been described as an example, but three or more kinds of particles may be mixed.
そして、上述のように、本実施の形態の磁性体粒子は、最大径が0.3mm以上2mm以下の略球状を呈している。磁気冷凍装置が高い冷凍能力を実現するためには、熱交換容器の内部に充填される磁性材料と液体冷媒の熱交換が十分に行われ、高い熱交換効率を実現することが重要である。そのためには、粒径を大きくして磁性体粒子の比表面積を大きくすることが好ましい。一方、粒径が小さすぎると冷媒の圧力損失が増大する。したがって、本実施の形態の磁性体粒子は、最大径が0.3mm以上2mm以下であることにより、これを用いた磁気冷凍装置の冷凍能力を向上させる。 As described above, the magnetic particles of the present embodiment have a substantially spherical shape with a maximum diameter of 0.3 mm to 2 mm. In order for the magnetic refrigeration apparatus to achieve a high refrigeration capacity, it is important that heat exchange between the magnetic material filled in the heat exchange container and the liquid refrigerant is sufficiently performed to achieve high heat exchange efficiency. For this purpose, it is preferable to increase the particle size to increase the specific surface area of the magnetic particles. On the other hand, if the particle size is too small, the pressure loss of the refrigerant increases. Therefore, the magnetic particles of the present embodiment have a maximum diameter of 0.3 mm or more and 2 mm or less, thereby improving the refrigeration capacity of a magnetic refrigeration apparatus using the magnetic particles.
このように、本実施の形態の磁性材料は、単体の磁性体粒子で構成される磁性材料に比べて、冷凍能力を著しく低下させることなく、磁気冷凍動作温度範囲を拡大することが可能となる。また、液体冷媒と組み合わせた場合、高い熱交換効率を実現できる。したがって、本実施の形態の磁性材料を熱交換容器に充填し、この熱交換容器を冷凍装置に適用することで、この冷凍装置の冷凍能力を向上させることが可能となる。 Thus, the magnetic material of the present embodiment can expand the magnetic refrigeration operating temperature range without significantly reducing the refrigeration capacity as compared with a magnetic material composed of a single magnetic particle. . Moreover, when combined with a liquid refrigerant, high heat exchange efficiency can be realized. Therefore, it is possible to improve the refrigerating capacity of the refrigeration apparatus by filling the heat exchange container with the magnetic material of the present embodiment and applying the heat exchange container to the refrigeration apparatus.
また、本実施の形態において、混合する磁性体粒子はそれぞれがヒステリシスのない2次の磁気転移を利用する磁性体粒子同士を混合するのが望ましい。なぜなら、これによって磁性材料間で熱のやり取りが効率的に行われ、冷凍能力低下の抑制効果が大きくなると考えられるからである。 In the present embodiment, the magnetic particles to be mixed are desirably mixed with each other using magnetic particles that utilize the second order magnetic transition without hysteresis. This is because heat is efficiently exchanged between the magnetic materials, and it is considered that the effect of suppressing a decrease in the refrigerating capacity is increased.
なお、本実施の形態において、本実施の形態の効果を発現する磁性体粒子以外の粒子が、磁性材料の全重量に対し数%程度不純物として含まれていても本実施の形態の効果を阻害するものではない。 In the present embodiment, even if particles other than magnetic particles that exhibit the effects of the present embodiment are contained as impurities of about several percent with respect to the total weight of the magnetic material, the effects of the present embodiment are inhibited. Not what you want.
(第2の実施の形態)
本実施の形態の磁気冷凍装置は、液体冷媒を用いる磁気冷凍装置である。そして、磁性材料が充填された熱交換容器と、磁性材料への磁場の印加および除去を行う磁場発生手段と、冷却ユニットと、排熱ユニットを備えている。さらに、熱交換容器、冷却ユニットおよび排熱ユニットを接続して形成され、液体冷媒を循環させる冷媒回路を備えている。そして、熱交換容器に充填された磁性材料が、異なる磁気転移温度を有する2種以上の磁性体粒子が略均一に混合されて形成されており、磁性体粒子は、最大径が0.3mm以上2mm以下の略球状を呈することを特徴とする。なお、熱交換容器に充填される磁性材料については、第1の実施の形態に記載した磁性材料と同様であるので、重複する内容の記載は省略する。
(Second Embodiment)
The magnetic refrigeration apparatus of the present embodiment is a magnetic refrigeration apparatus that uses a liquid refrigerant. A heat exchange container filled with the magnetic material, magnetic field generating means for applying and removing the magnetic field to and from the magnetic material, a cooling unit, and an exhaust heat unit are provided. Furthermore, a heat exchanger vessel, a cooling unit, and a heat exhaust unit are connected to form a refrigerant circuit that circulates the liquid refrigerant. And the magnetic material with which the heat exchange container was filled is formed by substantially uniformly mixing two or more kinds of magnetic particles having different magnetic transition temperatures. The magnetic particles have a maximum diameter of 0.3 mm or more. It has a substantially spherical shape of 2 mm or less. Since the magnetic material filled in the heat exchange container is the same as the magnetic material described in the first embodiment, the description of overlapping contents is omitted.
図2は、本実施の形態の磁気冷凍装置のシステム概略図である。この磁気冷凍装置は、液体冷媒として、例えば水を用いる。熱交換容器10の低温端側には冷却ユニット20が、高温端側には排熱ユニット30が設けられている。そして、冷却ユニット20と排熱ユニット30との間には、冷媒の流れる方向の切り替え手段40が設けられている。さらに冷媒輸送手段である冷媒ポンプ50が切り替え手段40に接続されている。そして、熱交換容器10、冷却ユニット20、切り替え手段40、排熱ユニット30は、配管によって接続され、液体冷媒を循環させる冷媒回路を形成している。
FIG. 2 is a system schematic diagram of the magnetic refrigeration apparatus of the present embodiment. This magnetic refrigeration apparatus uses, for example, water as a liquid refrigerant. A cooling
熱交換容器10には、磁気熱量効果を有する磁性材料12が充填されている。熱交換容器10の外側には、水平移動可能な永久磁石14が磁場発生手段として配置されている。冷却ユニット20は、内部に低温側熱交換器24が設けられた低温側貯水槽22と冷却部26で構成されている。低温側熱交換器24と冷却部26は熱的に接続されている。一方、排熱ユニット30は、内部に高温側熱交換器34が設けられた高温側貯水槽32と排熱部36で構成されている。高温側熱交換器34と排熱部36は熱的に接続されている。
The
ここで、本実施の形態の磁気冷凍装置は特に限定されるものではないが、例えば、家庭用冷凍冷蔵庫、家庭用空調機、産業用冷凍冷蔵庫、大型冷凍冷蔵倉庫、液化ガス貯蔵・運搬用冷凍庫等である。 Here, the magnetic refrigeration apparatus of the present embodiment is not particularly limited, but for example, a home refrigeration refrigerator, a home air conditioner, an industrial refrigeration refrigerator, a large-sized refrigeration warehouse, a liquefied gas storage / transportation freezer Etc.
そして、冷却部26は、例えば、磁気冷凍装置が家庭用冷凍冷蔵庫である場合は冷却される冷凍・冷蔵室であり、排熱部36は、例えば、放熱板である。
The cooling
図3は、熱交換容器内の磁性材料の構成を示す断面図である。図に示すように熱交換容器10内には、磁気熱量効果を有する磁性材料が充填されている。この磁性材料は、例えば、Gd粒子16とGd粒子16よりも低い磁気転移温度を有するGd95Y5粒子15の2種の磁性体粒子が、略均一に混合された磁性材料である。そして、熱交換容器10の両端には、熱交換容器10内で左右両方向に冷媒を流すための開口部が設けられている。
FIG. 3 is a cross-sectional view showing the configuration of the magnetic material in the heat exchange vessel. As shown in the figure, the
次に、図2を用いて本実施の形態の磁気冷凍装置の動作の概略を説明する。熱交換容器10に対向する位置(図2に示す位置)に永久磁石14が配置されると、熱交換容器10内の磁性材料12に対して磁場が印加される。このため、磁気熱量効果を有する磁性材料12が発熱する。この時、冷媒ポンプ50と切り替え手段40の動作により、液体冷媒を熱交換容器10から排熱ユニット30に向かう方向に循環させる。磁性材料12の発熱により温度の上昇した液体冷媒により、温熱が排熱ユニット30に輸送される。そして、液体冷媒は排熱ユニット30内の高温側貯水槽32に流入し、高温側熱交換器34によって冷媒の輸送した温熱が吸収される。そして、吸収された温熱が排熱部36で、例えば外気に放出される。
Next, the outline of the operation of the magnetic refrigeration apparatus of the present embodiment will be described with reference to FIG. When the
その後、永久磁石14を熱交換容器10に対向する位置から移動し、磁性材料12に対する磁場を除去する。磁場を除去することで、磁性材料12は吸熱する。この時、冷媒ポンプ50と切り替え手段40を動作により、液体冷媒を熱交換容器10から冷却ユニット20に向かう方向に循環させる。磁性材料12の吸熱により冷却された液体冷媒により、冷熱が冷却ユニット20に輸送される。液体冷媒は冷熱ユニット20内の低温側貯水槽22に流入し、低温側熱交換器24によって冷媒の輸送した冷熱が吸収される。吸収された冷熱により冷却部26が冷却される。
Thereafter, the
永久磁石14の移動を繰り返し、熱交換容器10内の磁性材料12に対する磁場の印加・除去を繰り返すことにより、冷却部26の冷却を継続することが可能となる。
By repeatedly moving the
本実施の形態の磁気冷凍装置は、冷凍能力を著しく低下させることなく磁気冷凍動作温度の拡大した磁性材料を用いることで、高い熱交換効率を実現することができる。 The magnetic refrigeration apparatus of the present embodiment can achieve high heat exchange efficiency by using a magnetic material having an increased magnetic refrigeration operating temperature without significantly reducing the refrigeration capacity.
なお、熱交換容器内の磁性材料の構成は、必ずしも図3に示す構成に限らない。図4は、熱交換容器内の磁性材料の別の構成を示す断面図である。図4に示すように、熱交換容器10の低温端側には、2種の異なる磁気転移温度を有する磁性体粒子Aおよび磁性体粒子Bを混合した磁性材料を充填する。そして、高温端側には、2種の異なる磁気転移温度を有する磁性体粒子Cおよび磁性体粒子Dを混合した磁性材料を充填する。低温端側の磁性材料と、高温端側の磁性材料は互いに混合しないよう、冷媒が流通可能な、例えば格子状の隔壁18で隔てられる。
The configuration of the magnetic material in the heat exchange container is not necessarily limited to the configuration shown in FIG. FIG. 4 is a cross-sectional view showing another configuration of the magnetic material in the heat exchange vessel. As shown in FIG. 4, the low temperature end side of the
ここで、低温側の磁性材料が、高温側の磁性材料よりも低い冷凍動作温度範囲を有するように磁性体粒子A、磁性体粒子B、磁性体粒子Cおよび磁性体粒子Dと、それらの混合比が決定されている。 Here, the magnetic particles A, the magnetic particles B, the magnetic particles C, and the magnetic particles D are mixed so that the low temperature side magnetic material has a lower refrigeration operating temperature range than the high temperature side magnetic material. The ratio has been determined.
図4に示す熱交換容器内の磁性材料の構成を採用することで、一層、磁気冷凍動作温度の拡大が拡大し、さらに高い熱交換効率を実現する磁気冷凍装置を提供することが可能となる。 By adopting the configuration of the magnetic material in the heat exchange container shown in FIG. 4, the expansion of the magnetic refrigeration operating temperature is further expanded, and it is possible to provide a magnetic refrigeration apparatus that realizes higher heat exchange efficiency. .
なお、図4では熱交換容器内の磁性材料を2層の積層構造にする場合を示したが、3層以上の積層構造にすることにより、さらに磁気冷凍動作温度の拡大を図ることも可能である。 Although FIG. 4 shows a case where the magnetic material in the heat exchange container has a two-layer structure, it is possible to further increase the magnetic refrigeration operating temperature by using a three-layer structure. is there.
また、磁性材料が充填された熱交換容器の空隙率が、30%以上50%以下であることが望ましい。液体冷媒を用いる磁気冷凍装置用の磁性体粒子が充填された熱交換容器においては、熱交換容器内での液体冷媒の流れを妨げないように、流体が流れるのに十分な空隙があることが望ましい。空隙率が30%未満であると、圧力損失が大きくなりすぎ、冷凍効率が低下するおそれがある。また、空隙率が50%を超えると、冷凍動作に寄与する磁性体粒子が少なくなり、十分な冷凍能力が得られないおそれがある。なお、ここで、空隙率は熱交換容器容積に相当する磁性材料の質量と、充填された磁性材料の質量との質量比で定義される値である。 Moreover, it is desirable that the porosity of the heat exchange container filled with the magnetic material is 30% or more and 50% or less. In a heat exchange container filled with magnetic particles for a magnetic refrigeration apparatus using a liquid refrigerant, there may be a sufficient gap for the fluid to flow so as not to hinder the flow of the liquid refrigerant in the heat exchange container. desirable. If the porosity is less than 30%, the pressure loss becomes too large, and the refrigeration efficiency may be reduced. On the other hand, if the porosity exceeds 50%, the number of magnetic particles contributing to the freezing operation decreases, and there is a possibility that sufficient freezing capacity may not be obtained. Here, the porosity is a value defined by the mass ratio between the mass of the magnetic material corresponding to the heat exchange vessel volume and the mass of the filled magnetic material.
以上、具体例を参照しつつ本発明の実施の形態について説明した。上記、実施の形態はあくまで、例として挙げられているだけであり、本発明を限定するものではない。また、実施の形態の説明においては、磁気冷凍装置用磁性材料、熱交換容器、磁気冷凍装置等で、本発明の説明に直接必要としない部分等については記載を省略したが、必要とされる磁気冷凍装置用磁性材料、磁気冷凍装置等に関わる要素を適宜選択して用いることができる。 The embodiments of the present invention have been described above with reference to specific examples. The above embodiment is merely given as an example, and does not limit the present invention. In the description of the embodiment, the description of the magnetic material for the magnetic refrigeration apparatus, the heat exchange container, the magnetic refrigeration apparatus, etc. that is not directly necessary for the description of the present invention is omitted, but is required. Elements related to the magnetic material for the magnetic refrigeration apparatus, the magnetic refrigeration apparatus, and the like can be appropriately selected and used.
その他、本発明の要素を具備し、当業者が適宜設計変更しうる全ての磁気冷凍装置用磁性材料、熱交換容器、磁気冷凍装置は、本発明の範囲に包含される。本発明の範囲は、特許請求の範囲およびその均等物の範囲によって定義されるものである。 In addition, all magnetic materials for a magnetic refrigeration apparatus, heat exchange containers, and magnetic refrigeration apparatuses that include elements of the present invention and that can be appropriately modified by those skilled in the art are included in the scope of the present invention. The scope of the present invention is defined by the appended claims and equivalents thereof.
以下、本発明の実施例を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
(実施例1)
直径0.3mm以上2mm以下で球状のGd95Y5粒子とGd粒子を、重量比3:1(Gd比率=25%)で混合した試料を空隙率30〜50%で熱交換容器(以下、試料容器ともいう)に充填し、冷凍温度差(ΔT)を評価した。なお、Gd95Y5粒子の磁気転移温度は283K、Gd粒子の磁気転移温度は293Kであり、磁気転移温度差(ΔTc)は、10Kである。
冷凍温度差(ΔT)は、以下の方法で評価した。
Example 1
A sample in which spherical Gd 95 Y 5 particles having a diameter of 0.3 mm or more and 2 mm or less and Gd particles are mixed at a weight ratio of 3: 1 (Gd ratio = 25%) with a porosity of 30 to 50% (hereinafter, (Also referred to as a sample container) and the freezing temperature difference (ΔT) was evaluated. The magnetic transition temperature of Gd 95 Y 5 particles is 283 K, the magnetic transition temperature of Gd particles is 293 K, and the magnetic transition temperature difference (ΔTc) is 10 K.
The freezing temperature difference (ΔT) was evaluated by the following method.
試料を熱交換容器に試料が容易に動くことがないよう充填した。次に熱電対を試料容器中央部に来るように容器上蓋中央部に開けた0.8mmΦの穴より熱電対を挿入した。さらに試料容器全体を断熱材で覆い、恒温槽中の試料ホルダーに固定した。試料ホルダーはヨーク磁石の稼働により磁場の印加・除去が可能な位置にあり、恒温層は外部より内部温度を調整することが可能である。恒温槽内を外界と遮断後、温度調整を行い、恒温槽内部の温度が一様になるまで待つ。その後ヨーク磁石を稼働させ試料に磁場を印加・除去を繰り返し、その際の温度差でΔTを測定した。続いて恒温槽内の温度を調整後、試料の磁場の印加・除去に伴う温度差ΔTを測定する過程を繰り返し、試料の各温度でのΔTを評価した。 The sample was filled into a heat exchange vessel so that the sample did not move easily. Next, a thermocouple was inserted from a 0.8 mmφ hole opened in the center of the container upper lid so that the thermocouple was in the center of the sample container. Further, the entire sample container was covered with a heat insulating material and fixed to the sample holder in the thermostat. The sample holder is in a position where a magnetic field can be applied and removed by operation of the yoke magnet, and the constant temperature layer can adjust the internal temperature from the outside. After shutting off the inside of the thermostatic chamber from the outside, the temperature is adjusted and waits until the temperature inside the thermostatic bath becomes uniform. Thereafter, the yoke magnet was operated, and the magnetic field was repeatedly applied to and removed from the sample, and ΔT was measured by the temperature difference at that time. Subsequently, after adjusting the temperature in the thermostat, the process of measuring the temperature difference ΔT accompanying the application / removal of the magnetic field of the sample was repeated, and ΔT at each temperature of the sample was evaluated.
そして、測定の結果、ΔT≧1.6Kを満たす温度範囲をその試料の有する磁気冷凍動作温度範囲とした。ΔT≧1.6Kの条件は、これまで得られたAMR方式での冷凍試験性能により、磁性材料としての優位性が実証されている条件である。得られた結果は表1に示す。 As a result of the measurement, the temperature range satisfying ΔT ≧ 1.6K was set as the magnetic refrigeration operating temperature range of the sample. The condition of ΔT ≧ 1.6K is a condition in which superiority as a magnetic material has been demonstrated by the refrigeration test performance in the AMR method obtained so far. The results obtained are shown in Table 1.
(実施例2)
Gd95Y5粒子とGd粒子を、重量比1:1(Gd比率=50%)で混合した試料を準備する以外は実施例1と同様の評価を行った。
(Example 2)
The same evaluation as in Example 1 was performed except that a sample in which Gd 95 Y 5 particles and Gd particles were mixed at a weight ratio of 1: 1 (Gd ratio = 50%) was prepared.
(実施例3)
Gd95Y5粒子とGd粒子を、重量比1:3(Gd比率=75%)で混合した試料を準備する以外は実施例1と同様の評価を行った。
(Example 3)
The same evaluation as in Example 1 was performed except that a sample in which Gd 95 Y 5 particles and Gd particles were mixed at a weight ratio of 1: 3 (Gd ratio = 75%) was prepared.
(比較例1)
Gd95Y5粒子単体の試料を準備する以外は実施例1と同様の評価を行った。
(Comparative Example 1)
The same evaluation as in Example 1 was performed except that a sample of Gd 95 Y 5 particles alone was prepared.
(実施例4)
Gd97Y3粒子とGd粒子を、重量比3:1(Gd比率=25%)で混合した試料を準備する以外は実施例1と同様の評価を行った。なお、Gd97Y3粒子の磁気転移温度は287K、Gd粒子の磁気転移温度は293Kであり、磁気転移温度差(ΔTc)は、6Kである。
Example 4
The same evaluation as in Example 1 was performed except that a sample in which Gd 97 Y 3 particles and Gd particles were mixed at a weight ratio of 3: 1 (Gd ratio = 25%) was prepared. The magnetic transition temperature of Gd 97 Y 3 particles is 287 K, the magnetic transition temperature of Gd particles is 293 K, and the magnetic transition temperature difference (ΔTc) is 6 K.
(実施例5)
Gd97Y3粒子とGd粒子を、重量比3:2(Gd比率=40%)で混合した試料を準備する以外は実施例1と同様の評価を行った。
(Example 5)
The same evaluation as in Example 1 was performed except that a sample in which Gd 97 Y 3 particles and Gd particles were mixed at a weight ratio of 3: 2 (Gd ratio = 40%) was prepared.
(実施例6)
Gd97Y3粒子とGd粒子を、重量比1:1(Gd比率=50%)で混合した試料を準備する以外は実施例1と同様の評価を行った。
(Example 6)
The same evaluation as in Example 1 was performed except that a sample in which Gd 97 Y 3 particles and Gd particles were mixed at a weight ratio of 1: 1 (Gd ratio = 50%) was prepared.
(実施例7)
Gd97Y3粒子とGd粒子を、重量比2:3(Gd比率=60%)で混合した試料を準備する以外は実施例1と同様の評価を行った。
(Example 7)
The same evaluation as in Example 1 was performed except that a sample in which Gd 97 Y 3 particles and Gd particles were mixed at a weight ratio of 2: 3 (Gd ratio = 60%) was prepared.
(実施例8)
Gd97Y3粒子とGd粒子を、重量比1:3(Gd比率=75%)で混合した試料を準備する以外は実施例1と同様の評価を行った。
(Example 8)
The same evaluation as in Example 1 was performed except that a sample in which Gd 97 Y 3 particles and Gd particles were mixed at a weight ratio of 1: 3 (Gd ratio = 75%) was prepared.
(比較例2)
Gd97Y3粒子単体の試料を準備する以外は実施例1と同様の評価を行った。
(Comparative Example 2)
The same evaluation as in Example 1 was performed except that a sample of Gd 97 Y 3 particles alone was prepared.
(実施例9)
Gd98Y2粒子とGd粒子を、重量比3:2(Gd比率=40%)で混合した試料を準備する以外は実施例1と同様の評価を行った。なお、Gd98Y2粒子の磁気転移温度は289K、Gd粒子の磁気転移温度は293Kであり、磁気転移温度差(ΔTc)は、4Kである。
Example 9
The same evaluation as in Example 1 was performed except that a sample in which Gd 98 Y 2 particles and Gd particles were mixed at a weight ratio of 3: 2 (Gd ratio = 40%) was prepared. The magnetic transition temperature of Gd 98 Y 2 particles is 289 K, the magnetic transition temperature of Gd particles is 293 K, and the magnetic transition temperature difference (ΔTc) is 4 K.
(実施例10)
Gd98Y2粒子とGd粒子を、重量比1:1(Gd比率=50%)で混合した試料を準備する以外は実施例1と同様の評価を行った。
(Example 10)
The same evaluation as in Example 1 was performed except that a sample in which Gd 98 Y 2 particles and Gd particles were mixed at a weight ratio of 1: 1 (Gd ratio = 50%) was prepared.
(実施例11)
Gd98Y2粒子とGd粒子を、重量比2:3(Gd比率=60%)で混合した試料を準備する以外は実施例1と同様の評価を行った。
(Example 11)
The same evaluation as in Example 1 was performed except that a sample in which Gd 98 Y 2 particles and Gd particles were mixed at a weight ratio of 2: 3 (Gd ratio = 60%) was prepared.
(実施例12)
Gd98Y2粒子とGd粒子を、重量比1:3(Gd比率=75%)で混合した試料を準備する以外は実施例1と同様の評価を行った。
(Example 12)
The same evaluation as in Example 1 was performed except that a sample in which Gd 98 Y 2 particles and Gd particles were mixed at a weight ratio of 1: 3 (Gd ratio = 75%) was prepared.
(比較例3)
Gd98Y2粒子単体の試料を準備する以外は実施例1と同様の評価を行った。
(Comparative Example 3)
The same evaluation as in Example 1 was performed except that a sample of Gd 98 Y 2 particles alone was prepared.
(実施例13)
Gd98.5Y1.5粒子とGd粒子を、重量比1:1(Gd比率=50%)で混合した試料を準備する以外は実施例1と同様の評価を行った。なお、Gd98.5Y1.5粒子の磁気転移温度は290K、Gd粒子の磁気転移温度は293Kであり、磁気転移温度差(ΔTc)は、3Kである。
(Example 13)
The same evaluation as in Example 1 was performed except that a sample in which Gd 98.5 Y 1.5 particles and Gd particles were mixed at a weight ratio of 1: 1 (Gd ratio = 50%) was prepared. The magnetic transition temperature of Gd 98.5 Y 1.5 particles is 290 K, the magnetic transition temperature of Gd particles is 293 K, and the magnetic transition temperature difference (ΔTc) is 3 K.
(比較例4)
Gd98.5Y1.5粒子単体の試料を準備する以外は実施例1と同様の評価を行った。
(Comparative Example 4)
Evaluation similar to Example 1 was performed except preparing a sample of Gd 98.5 Y 1.5 particles alone.
実施例1〜3、比較例1の結果より、Gd95Y5粒子単体では10.7KにとどまるΔT≧1.6Kの冷凍動作温度範囲が、Gd粒子を加えることにより8K程度拡大されることが明らかになった。図5は、実施例1〜3、比較例1の結果をプロットしたグラフである。磁気転移温度差(ΔTc)が10Kの実施例1〜3の場合、Gd比率が25〜75%、すなわち、磁性材料中、最も含有重量の多い第1の磁性体粒子と、次いで含有重量の多い第2の磁性体粒子との重量比が5:5から3:1の場合に、特に広い冷凍動作温度範囲が得られた。 From the results of Examples 1 to 3 and Comparative Example 1, the refrigeration operating temperature range of ΔT ≧ 1.6 K, which remains at 10.7 K with the Gd 95 Y 5 particles alone, can be expanded by about 8 K by adding Gd particles. It was revealed. FIG. 5 is a graph in which the results of Examples 1 to 3 and Comparative Example 1 are plotted. In Examples 1 to 3 where the magnetic transition temperature difference (ΔTc) is 10 K, the Gd ratio is 25 to 75%, that is, the first magnetic particles having the largest content in the magnetic material, and then the most content. A particularly wide refrigeration operating temperature range was obtained when the weight ratio with the second magnetic particles was 5: 5 to 3: 1.
実施例4〜8、比較例2の結果より、Gd97Y3粒子単体では13.1KにとどまるΔT≧1.6Kの冷凍動作温度範囲が、Gd粒子を加えることにより、最大6.5K程度拡大されることが明らかになった。図6は、実施例4〜8、比較例2の結果をプロットしたグラフである。磁気転移温度差(ΔTc)が6Kの実施例4〜8の場合、Gd比率が40〜60%、すなわち、磁性材料中、最も含有重量の多い第1の磁性体粒子と、次いで含有重量の多い第2の磁性体粒子との重量比が5:5から3:2の場合に、特に広い冷凍動作温度範囲が得られた。 From the results of Examples 4 to 8 and Comparative Example 2, the refrigeration operating temperature range of ΔT ≧ 1.6K, which remains at 13.1K with Gd 97 Y 3 particles alone, is expanded by about 6.5K at the maximum by adding Gd particles. It became clear that 6 is a graph in which the results of Examples 4 to 8 and Comparative Example 2 are plotted. In Examples 4 to 8 in which the magnetic transition temperature difference (ΔTc) is 6K, the Gd ratio is 40 to 60%, that is, the first magnetic particles having the largest content weight in the magnetic material, and then the most content weight. A particularly wide refrigeration operating temperature range was obtained when the weight ratio with the second magnetic particles was 5: 5 to 3: 2.
実施例9〜12、比較例3の結果より、Gd98Y2粒子単体では15.9KにとどまるΔT≧1.6Kの冷凍動作温度範囲が、Gd粒子を加えることにより、最大2.1K程度拡大されることが明らかになった。また、磁気転移温度差(ΔTc)が4Kの実施例9〜12の場合、Gd比率が40〜60%、すなわち、磁性材料中、最も含有重量の多い第1の磁性体粒子と、次いで含有重量の多い第2の磁性体粒子との重量比が5:5から3:2の場合に、特に広い冷凍動作温度範囲が得られた。 From the results of Examples 9 to 12 and Comparative Example 3, the refrigeration operating temperature range of ΔT ≧ 1.6 K, which remains at 15.9 K with the Gd 98 Y 2 particles alone, is expanded by about 2.1 K at the maximum by adding Gd particles. It became clear that Further, in Examples 9 to 12 where the magnetic transition temperature difference (ΔTc) is 4K, the Gd ratio is 40 to 60%, that is, the first magnetic particles having the largest content in the magnetic material, and then the content A particularly wide refrigeration operating temperature range was obtained when the weight ratio of the second magnetic particles to the second magnetic material particles with a large amount was 5: 5 to 3: 2.
実施例13、比較例4の結果より、Gd98Y2粒子単体では17.2KにとどまるΔT≧1.6Kの冷凍動作温度範囲が、Gd粒子を加えることにより、2.8K程度拡大されることが明らかになった。また、磁気転移温度差(ΔTc)が3Kの実施例13の場合、Gd比率が50%、すなわち、磁性材料中、最も含有重量の多い第1の磁性体粒子と、次いで含有重量の多い第2の磁性体粒子との重量比が5:5の場合に、冷凍動作温度範囲の拡大が得られた。 From the results of Example 13 and Comparative Example 4, the refrigeration operating temperature range of ΔT ≧ 1.6K, which remains at 17.2K with Gd 98 Y 2 particles alone, is expanded by about 2.8K by adding Gd particles. Became clear. Further, in Example 13 in which the magnetic transition temperature difference (ΔTc) is 3K, the Gd ratio is 50%, that is, the first magnetic particles having the largest content in the magnetic material, and the second mass having the second largest content. When the weight ratio to the magnetic particles was 5: 5, expansion of the refrigeration operating temperature range was obtained.
以上のように、本実施例により本発明の効果が確認された。 As described above, the effect of the present invention was confirmed by this example.
10 熱交換容器
12 磁性材料
14 永久磁石
15 Gd95Y5粒子
16 Gd粒子
18 隔壁
20 冷熱ユニット
22 低温側貯水槽
24 低温側熱交換器
26 冷却部
30 排熱ユニット
32 高温側貯水槽
34 高温側熱交換機
36 排熱部
40 切り替え手段
50 冷媒ポンプ
DESCRIPTION OF
Claims (4)
前記磁性材料が、
異なる磁気転移温度を有する2種以上の磁性体粒子が略均一に混合されており、
前記磁性体粒子は、最大径が0.3mm以上2mm以下の略球状を呈し、
前記2種以上の磁性体粒子中、最も含有重量の多い第1の磁性体粒子と、次いで含有重量の多い第2の磁性体粒子との磁気転移温度の差が1K以上10K未満であって、
前記第1の磁性体粒子と、前記第2の磁性体粒子とが、5:5から3:2の重量比で混合され、
空隙率が、30%以上50%以下であることを特徴とする熱交換容器。 A heat exchange container for an AMR magnetic refrigerating apparatus using a liquid refrigerant filled with a magnetic material,
The magnetic material is
Two or more kinds of magnetic particles having different magnetic transition temperatures are substantially uniformly mixed,
The magnetic particles has a maximum diameter and coloration of 2mm or less substantially spherical or 0.3 mm,
Among the two or more kinds of magnetic particles, the difference in magnetic transition temperature between the first magnetic particles having the highest content weight and the second magnetic particles having the second highest content weight is 1K or more and less than 10K,
The first magnetic particles and the second magnetic particles are mixed at a weight ratio of 5: 5 to 3: 2.
A heat exchange container having a porosity of 30% to 50% .
前記磁性材料が、
異なる磁気転移温度を有する2種以上の磁性体粒子が略均一に混合されており、
前記磁性体粒子は、最大径が0.3mm以上2mm以下の略球状を呈し、
前記2種以上の磁性体粒子中、最も含有重量の多い第1の磁性体粒子と、次いで含有重量の多い第2の磁性体粒子との磁気転移温度の差が10K以上15K以下であって、
前記第1の磁性体粒子と、前記第2の磁性体粒子とが、5:5から3:1の重量比で混合され、
空隙率が、30%以上50%以下であることを特徴とする熱交換容器。 A heat exchange container for an AMR magnetic refrigerating apparatus using a liquid refrigerant filled with a magnetic material,
The magnetic material is
Two or more kinds of magnetic particles having different magnetic transition temperatures are substantially uniformly mixed,
The magnetic particles have a substantially spherical shape with a maximum diameter of 0.3 mm to 2 mm,
Among the two or more kinds of magnetic particles, the difference in magnetic transition temperature between the first magnetic particles having the highest content weight and the second magnetic particles having the second highest content weight is 10K or more and 15K or less,
The first magnetic particles and the second magnetic particles are mixed in a weight ratio of 5: 5 to 3: 1 ;
A heat exchange container having a porosity of 30% to 50% .
磁性材料が充填された熱交換容器と、
前記磁性材料への磁場の印加および除去を行う磁場発生手段と、
冷却ユニットと、
排熱ユニットと、
前記熱交換容器、前記冷却ユニットおよび前記排熱ユニットを接続して形成され、前記液体冷媒を循環させる冷媒回路を備え、
前記熱交換容器が、請求項1ないし請求項3いずれか一項に記載の熱交換容器であることを特徴とする磁気冷凍装置。
A magnetic refrigeration apparatus using a liquid refrigerant,
A heat exchange container filled with magnetic material;
Magnetic field generating means for applying and removing a magnetic field to the magnetic material;
A cooling unit;
An exhaust heat unit;
A refrigerant circuit that is formed by connecting the heat exchange container, the cooling unit, and the exhaust heat unit, and circulates the liquid refrigerant,
The magnetic refrigeration apparatus, wherein the heat exchange container is the heat exchange container according to any one of claims 1 to 3 .
Priority Applications (2)
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JP2008047663A JP4950918B2 (en) | 2008-02-28 | 2008-02-28 | Magnetic material for magnetic refrigeration equipment, heat exchange container and magnetic refrigeration equipment |
US12/393,849 US20090217674A1 (en) | 2008-02-28 | 2009-02-26 | Magnetic material for magnetic refrigeration apparatus, amr bed, and magnetic refrigeration apparatus |
Applications Claiming Priority (1)
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