US20090217674A1 - Magnetic material for magnetic refrigeration apparatus, amr bed, and magnetic refrigeration apparatus - Google Patents

Magnetic material for magnetic refrigeration apparatus, amr bed, and magnetic refrigeration apparatus Download PDF

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Publication number
US20090217674A1
US20090217674A1 US12/393,849 US39384909A US2009217674A1 US 20090217674 A1 US20090217674 A1 US 20090217674A1 US 39384909 A US39384909 A US 39384909A US 2009217674 A1 US2009217674 A1 US 2009217674A1
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Prior art keywords
magnetic
magnetic particles
particles
amr bed
blended
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Abandoned
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US12/393,849
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English (en)
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Shiori Kaji
Akiko Saito
Tadahiko Kobayashi
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Toshiba Corp
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Assigned to KABUSHIKI KAISHA TOSHIBA reassignment KABUSHIKI KAISHA TOSHIBA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KAJI, SHIORI, KOBAYASHI, TADAHIKO, SAITO, AKIKO
Publication of US20090217674A1 publication Critical patent/US20090217674A1/en
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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
    • 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
    • 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
    • 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]

Definitions

  • the present invention relates to a magnetic material having a magnetocaloric effect and used for a magnetic refrigeration apparatus, AMR bed using the magnetic material, and the magnetic refrigeration apparatus.
  • a refrigeration technology in a room temperature region which closely relates to a human daily life, for example, a refrigerator, a freezer, a room air conditioner, and the like, almost employs a gas compression/expansion cycle.
  • a serious problem of environmental destruction is caused by specific freon gases discharged into the environment, and CFC's substitutes also have a problem of an adverse affect to the environment.
  • researches on the use of natural refrigerants (CO 2 , ammonia, and the like) and isobutane which have little environmental risk and the like are carried out.
  • it is required to put the refrigeration technologies, which have no environmental problems and work safety and efficiency, to practice use.
  • a magnetic refrigeration is one of the promising technology, in terms of environment-friendliness and high efficiency. And a magnetic refrigeration technology in a room temperature region is actively researched and developed.
  • the magnetic refrigeration technology uses a magnetocaloric effect that Warburg discovered on iron (Fe) in 1881.
  • the magnetocaloric effect is a phenomenon that the temperature of magnetic material changes according to changing of external magnetic field in an adiabatic state.
  • the refrigeration system using paramagnetic salts and compounds represented by Gd 2 (SO 4 ) 3 .8H 2 O or Gd 3 Ga 5 O 12 which show the magnetocaloric effect, was developed.
  • Gd 2 (SO 4 ) 3 .8H 2 O or Gd 3 Ga 5 O 12 which show the magnetocaloric effect, was developed.
  • Gd 2 (SO 4 ) 3 .8H 2 O or Gd 3 Ga 5 O 12 which show the magnetocaloric effect
  • Magnetic refrigeration is carried out by the AMR system using the following steps:
  • a magnetic field is applied to a magnetic refrigeration working material
  • a magnetic material for a magnetic refrigeration apparatus using a liquid refrigerant of an embodiment of the present invention includes at least two kinds of magnetic particles having different magnetic transition temperatures and blended approximately uniformly, wherein, the magnetic particles exhibit an approximately spherical shape with a maximum diameter of 0.3 mm or more to 2 mm or less.
  • the magnetic material includes at least two kinds of magnetic particles having different magnetic transition temperatures and blended approximately uniformly, and the magnetic particles exhibit an approximately spherical shape with a maximum diameter of 0.3 mm or more to 2 mm or less.
  • a magnetic refrigeration apparatus using a liquid refrigerant of an embodiment of the present invention has AMR bed filled with a magnetic material, a magnetic field generation device for applying and removing a magnetic field to and from the magnetic material, a cooling block, a radiating block, and a refrigerant flow path connected to the AMR bed, the cooling block and the radiating block configured to circulate the liquid refrigerant, wherein the magnetic material includes at least two kinds of magnetic particles having different magnetic transition temperatures and blended approximately uniformly, and the magnetic particles exhibit an approximately spherical shape with a maximum diameter of 0.3 mm or more to 2 mm or less.
  • a magnetic material for a magnetic refrigeration apparatus which improves magnetic refrigeration efficiency by the wide operation temperature range of it and the magnetic refrigeration apparatus using the magnetic material.
  • FIG. 1 is an explanatory view showing an operation of a magnetic material for a magnetic refrigeration apparatus of a first embodiment
  • FIG. 2 is a schematic view of a system of a magnetic refrigeration apparatus of a second embodiment
  • FIG. 3 is a sectional view showing an arrangement of a magnetic material in AMR bed of the second embodiment
  • FIG. 4 is a sectional view showing another arrangement of the magnetic material in AMR bed of a third embodiment
  • FIG. 5 is a graph showing a result of measurement of a refrigerating operation temperature range of examples and comparative examples.
  • FIG. 6 is a graph showing a result of measurement of the refrigerating operation temperature range of the examples and the comparative examples.
  • the inventors have found that when at least two kinds of magnetic particles having different magnetic transition temperatures (Tc) are approximately uniformly blended and AMR bed is filled with them, a magnetic refrigeration operation temperature range can be extended without outstandingly lowering a refrigeration capability.
  • Tc magnetic transition temperatures
  • a magnetic material for a magnetic refrigeration apparatus, AMR bed, and the magnetic refrigeration apparatus of embodiments of the present invention will be explained below referring to the drawings based on the above knowledge found by the inventors.
  • two kinds of magnetic particles have different magnetic transition temperatures means that the average values of the magnetic transition temperatures of respective magnetic particles are separated from each other 0.5 K or more.
  • a magnetic material for a magnetic refrigeration apparatus of a first embodiment is a magnetic material for a magnetic refrigeration apparatus using a liquid refrigerant. At least two kinds of magnetic particles having different magnetic transition temperatures (Tc) are approximately uniformly blended. The magnetic particles exhibit an approximately spherical shape with a maximum diameter of 0.3 mm or more to 2 mm or less.
  • two kinds of magnetic particles for example, Gd particles having a magnetic transition temperature 293 (K) and Gd 95 Y 5 particles having a magnetic transition temperature 283 (K), which is lower than that of the Gd particles, are approximately uniformly blended at a ratio of 1:1.
  • ⁇ Tc magnetic transition temperature difference
  • the two kinds of the magnetic particles exhibit the approximately spherical shape with the maximum diameter of 0.3 mm or more to 2 mm or less.
  • the maximum diameter of the magnetic particles can be visually measured with a calipers and the like, by direct observation under a microscope, or by a microscope photograph.
  • GdR shows rear earth elements other than Gd, Y, i.e., Sc, La, Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu
  • compounds composed of various kinds of rear earth elements and transition metal elements NiMnGa alloys, GdGeSi alloys, LaFe 13 compounds, LaFe 13 H, MnAsSb, and the like can be used.
  • FIG. 1 is an explanatory view showing an operation of the magnetic material for the magnetic refrigeration apparatus of the first embodiment.
  • An upper view of FIG. 1 is a graph showing the relation between the temperature of the magnetic material and a refrigeration temperature difference ( ⁇ T) of the magnetic material.
  • a lower view of FIG. 1 is a conceptual view showing how AMR bed is filled with magnetic materials and the magnetic refrigeration operation temperature ranges to the respective magnetic material by arrows in correspondence to a temperature axis of the upper view of FIG. 1 .
  • the refrigeration temperature difference ( ⁇ T) means a temperature difference caused to the magnetic material when a magnetic field is repeatedly applied and removed to and from the magnetic material and used as an index of the refrigeration capability of the magnetic material.
  • a reason why the refrigeration capability is not outstandingly lowered against prediction in the first embodiment is considered as described below. That is, at a certain temperature, a temperature change caused by application and removal of the magnetic field is determined depending on materials. Accordingly, it is considered that when all the materials are the same materials, the same temperature change ideally occurs all at once. However, when different materials exist, since dispersion occurs in the temperature change caused by application of the magnetic field, heat is transmitted between the magnetic materials. Since heat is secondarily generated and absorbed by the transmission of heat, a temperature change, which is not caused when the same kind of a material is used, occurs. As a result, it is considered that an effect of an increase of temperature, which cannot be predicted from measurement of the simple material appears. The operation temperature can be increased without outstandingly lowering the refrigeration capability by the addition of the above effect resulting from the blend.
  • the magnetic particles exemplified above have different magnetic transition temperatures depending on the compositions thereof.
  • a wide range of the refrigeration operation temperature can be guaranteed by appropriately combining two kinds of magnetic particles having appropriate magnetic transition temperatures.
  • three kinds or more of magnetic particles may be blended.
  • the magnetic particles of the first embodiment exhibit the approximately spherical shape with the maximum diameter of 0.3 mm or more to 2 mm or less. It is important for the magnetic refrigeration apparatus to realize a high refrigeration capability in that a magnetic material with which the AMR bed is filled sufficiently exchanges its heat with a liquid refrigerant and realizes high heat exchange efficiency. For this purpose, it is preferable to increase the specific surface area of magnetic particles by increasing the particle diameter thereof. In contrast, when the particle diameter is too small, a refrigerant pressure loss is increased. Accordingly, the refrigeration capability of a magnetic refrigeration apparatus is improved by using the magnetic particles of the first embodiment whose maximum diameter is set to 0.3 mm or more to 2 mm or less.
  • the magnetic material of the first embodiment can extend the magnetic refrigeration operation temperature range without outstandingly lowering the refrigeration capability as compared with a magnetic material composed of simple magnetic particles. Further, when the magnetic material is combined with the liquid refrigerant, high heat exchange efficiency can be realized. Accordingly, the refrigeration capability of the refrigeration apparatus can be improved by filling the AMR bed with the magnetic material of the first embodiment and applying the AMR bed to the refrigeration apparatus.
  • the first embodiment it is preferable to blend magnetic particles, which make use of secondary magnetic transition without hysteresis, with each other. This is because it is considered that heat is effectively transmitted between magnetic materials and an effect of suppressing a lowering of the refrigeration capability can be increased.
  • a magnetic refrigeration apparatus of a second embodiment is a magnetic refrigeration apparatus using a liquid refrigerant.
  • the magnetic refrigeration apparatus has AMR bed filled with a magnetic material, a magnetic field generation means (device) for applying and removing a magnetic field to and from the magnetic material, a cooling block, and a radiating block. Further, the magnetic refrigeration apparatus has a refrigerant flow path formed by connecting the AMR bed, the cooling block and the radiating block configured to circulate the liquid refrigerant.
  • the magnetic material with which the AMR bed is filled is formed by approximately uniformly bending at least two kinds of magnetic particles having different magnetic transition temperatures, and the magnetic particles has a feature in that they exhibit an approximately spherical shape with a maximum diameter of 0.3 mm or more to 2 mm or less. Note that since the magnetic material with which the AMR bed is filled is the same as that described in the first embodiment, description of duplicate contents is omitted.
  • FIG. 2 is a schematic view of a system of the magnetic refrigeration apparatus of the second embodiment.
  • the magnetic refrigeration apparatus uses, for example, water as the liquid refrigerant.
  • the cooling block 20 is disposed to a low temperature end side of the AMR bed 10
  • the radiating block 30 is disposed to a high temperature end side thereof.
  • a switching means 40 is interposed between the cooling block 20 and the radiating block 30 to switch a direction in which the liquid refrigerant flow.
  • a refrigerant pump 50 as a refrigerant transport means is connected to the switching means 40 .
  • the AMR bed 10 , the cooling block 20 , the switching means 40 , and the radiating block 30 are connected by a pipe and form the refrigerant flow path for circulating the liquid refrigerant.
  • the AMR bed 10 is filled with the magnetic material 12 having a magnetocaloric effect.
  • a horizontally movable permanent magnet 14 is disposed to outside of the AMR bed 10 as a magnetic field generation means.
  • the cooling block 20 is composed of a low-temperature bath 22 , in which a low temperature side heat exchanger device 24 is disposed, and a cooling unit 26 .
  • the low temperature side heat exchanger device 24 is thermally connected to the cooling unit 26 .
  • the radiating block 30 is composed of a hot bath 32 , in which a high temperature side heat exchanger device 34 is disposed, and a radiating unit 36 .
  • the high temperature side heat exchanger device 34 is thermally connected to the radiating unit 36 .
  • the magnetic refrigeration apparatus of the second embodiment is not particularly limited, it is, for example, a home freezer/refrigerator, a home air conditioner, an industrial freezer/refrigerator, a large frozen/refrigerated warehouse, a frozen chamber for reserving and transporting a liquefied gas, and the like.
  • the magnetic refrigeration apparatus is the home freezer/refrigerator
  • the cooling unit is a freezing/refrigerating chamber
  • the radiating unit 36 is, for example, a radiation plate.
  • FIG. 3 is a sectional view showing an arrangement of a magnetic material in the AMR bed.
  • the AMR bed 10 is filled with a magnetic material having the magnetocaloric effect.
  • the magnetic material is a magnetic material formed by approximately uniformly blending two kinds of magnetic particles, for example, Gd particles 16 and Gd 95 Y 5 particles 15 having a magnetic transition temperature lower than that of the Gd particles 16 . Openings are formed to both the ends of the AMR bed 10 so that a refrigerant is caused to flow in both right and left directions in the AMR bed 10 .
  • FIG. 2 An operation of the magnetic refrigeration apparatus of the second embodiment will be schematically explained using FIG. 2 .
  • the permanent magnet 14 When the permanent magnet 14 is disposed at a position confronting with the AMR bed 10 (position shown in FIG. 2 ), a magnetic field is applied to the magnetic material 12 in the AMR bed 10 . Accordingly, the magnetic material 12 having the magnetocaloric effect generates heat.
  • the liquid refrigerant is caused to circulate in the direction from the AMR bed 10 to the radiating block 30 by the operations of the refrigerant pump 50 and the switching means 40 . Hot heat is transported to the radiating block 30 by the liquid refrigerant whose temperature is increased by the heat generated by the magnetic material 12 .
  • the liquid refrigerant flows into the hot bath 32 in the radiating block 30 , and the hot heat transported by the refrigerant is absorbed by the high temperature side heat exchanger device 34 .
  • the absorbed hot heat is radiated to, for example, the outside air by the radiating unit 36 .
  • the permanent magnet 14 is moved from the position confronting with the AMR bed 10 , and the magnetic field applied to the magnetic material 12 is removed.
  • the magnetic material 12 absorbs heat.
  • the liquid refrigerant is caused to circulate in the direction from the AMR bed 10 to the cooling block 20 by the operations of the refrigerant pump 50 and the switching means 40 .
  • Cold heat is transported to the cooling block 20 by the liquid refrigerant that is cooled by the heat absorbed by magnetic material 12 .
  • the liquid refrigerant flows into the low-temperature bath 22 in the cooling block 20 , and the cold heat transported by the refrigerant is absorbed by the low temperature side heat exchanger device 24 .
  • the cooling unit 26 is cooled by the cold heat.
  • the cooling unit 26 can be continuously cooled by repeating application and removal of the magnetic field to and from the magnetic material 12 in the AMR bed 10 by repeatedly moving the permanent magnet 14 .
  • the magnetic refrigeration apparatus of the second embodiment can realize high heat exchange efficiency by using the magnetic material whose magnetic refrigerating operation temperature is increased without outstandingly lowering a refrigeration capability.
  • FIG. 4 is a sectional view showing another arrangement of the magnetic material in the AMR bed.
  • the AMR bed 10 is filled with a magnetic material, in which magnetic particles A and B having two kinds of different magnetic transition temperatures are blended, on the low temperature end side thereof.
  • the AMR bed 10 is filled with a magnetic material, in which magnetic particles C and D having two kinds of different magnetic transition temperatures are blended, on the high temperature end side thereof.
  • the magnetic material on the low temperature end side are separated from that on the high temperature end side by, for example, a lattice-shaped partition wall 18 in which a refrigerant can flow so that they are not blended with each other.
  • the magnetic particles A, the magnetic particles B, the magnetic particles C, the magnetic particles D, and the blend ratio thereof are determined so that the magnetic material on the low temperature side have a refrigeration operation temperature range lower than that of the magnetic material on the high temperature side.
  • the magnetic refrigerating operation temperature can be more increased and a magnetic refrigeration apparatus that realizes higher heat exchange efficiency can be provided by employing the arrangement of the magnetic materials in the AMR bed shown in FIG. 4 .
  • the magnetic refrigerating operation temperature can be more increased by providing a layered structure having three or more layers.
  • the void ratio of the AMR bed filled with the magnetic materials is preferably 30% or more to 50% or less.
  • AMR bed filled with magnetic particles for a magnetic refrigeration apparatus using a liquid refrigerant it is preferable to form a sufficient amount of void space through which a fluid flows so that the flow of the liquid refrigerant is not inhibited in the AMR bed.
  • the void ratio is less than 30%, since a pressure loss is excessively increased, there is a possibility that refrigeration efficiency is lowered.
  • the void ratio exceeds 50%, since the magnetic particles that contribute to a refrigerating operation are reduced, there is possibility that a sufficient refrigeration capability cannot be obtained.
  • the void ratio is a value defined by the mass ratio of the mass of a magnetic material equivalent to the volume of AMR bed and the mass of a magnetic material with which the AMR bed is filled.
  • the magnetic transition temperature of the Gd 95 Y 5 particles was 283 K
  • the magnetic transition temperature of the Gd particles was 293 K
  • a magnetic transition temperature difference ( ⁇ Tc) was 10 K.
  • the refrigeration temperature difference ( ⁇ T) was evaluated by the following method.
  • the AMR bed was filled with the specimen so that the specimen did not easily move.
  • a thermocouple was inserted into the specimen vessel through a 0.8 mm ⁇ hole formed to an upper lid of the vessel so that it was positioned in a central portion of the specimen vessel.
  • the specimen vessel was entirely covered with a heat insulating material and fixed to a specimen holder in a constant temperature bath.
  • the specimen holder was located at a position at which it was possible to apply and remove a magnetic field by the operation of yoke magnet,and it was possible to adjust the internal temperature of the constant temperature bath from the outside. After the inside of the constant temperature bath was shut off from the outside, the temperature of the inside thereof was adjust, and it was waited that the inside temperature thereof was made uniform.
  • the magnetic field was repeatedly applied and removed to and from the specimen by operating the yoke magnet, and ⁇ T was measured by a temperature difference at the time. Subsequently, after the temperature in the constant temperature bath was adjusted, ⁇ T at the respective temperatures of the specimen was evaluated by repeating a process of measuring the temperature dependence of ⁇ T by applying and removing the magnetic field to and from the specimen.
  • the temperature range which satisfies ⁇ T ⁇ 1.6 K was set as the magnetic refrigeration operation temperature range of the specimen.
  • the condition of ⁇ T ⁇ 1.6 K is a condition by which the superiority of the magnetic material is verified by the refrigeration test performance in the AMR system obtained up to that time. Table 1 shows an obtained result.
  • FIG. 5 is a graph in which the results of the examples 1 to 3 and the comparative example 1 are plotted.
  • the magnetic transition temperature difference ( ⁇ Tc) was 10 K
  • the Gd ratio was 25% to 75%
  • the weight ratio of first magnetic particles, which have a heaviest weight in contained magnetic materials, and second magnetic particles, which have a next heaviest weight in contained materials was 5:5 to 3:1
  • a particularly wide refrigeration operation temperature range could be obtained.
  • FIG. 6 is a graph in which the results of the examples 4 to 8 and the comparative example 2 are plotted.
  • ⁇ Tc magnetic transition temperature difference

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JP2008047663A JP4950918B2 (ja) 2008-02-28 2008-02-28 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

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US20120222427A1 (en) * 2009-09-17 2012-09-06 Materials And Electrochemical Research (Mer) Corporation Flow-synchronous field motion refrigeration
US20120222428A1 (en) * 2009-11-11 2012-09-06 Serdar Celik Combined-loop magnetic refrigeration system
US20120324908A1 (en) * 2011-06-27 2012-12-27 Ludtka Gerard M Apparatus and method for magnetically processing a specimen
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