WO2013005579A1 - 磁気冷凍材料及び磁気冷凍デバイス - Google Patents
磁気冷凍材料及び磁気冷凍デバイス Download PDFInfo
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- WO2013005579A1 WO2013005579A1 PCT/JP2012/065953 JP2012065953W WO2013005579A1 WO 2013005579 A1 WO2013005579 A1 WO 2013005579A1 JP 2012065953 W JP2012065953 W JP 2012065953W WO 2013005579 A1 WO2013005579 A1 WO 2013005579A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/30—Ferrous alloys, e.g. steel alloys containing chromium with cobalt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/02—Magnetic
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
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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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- 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 refrigeration material suitably used for home appliances such as a freezer and a refrigerator, an air conditioner for automobiles, and the like, and a magnetic refrigeration device using the same.
- a magnetic refrigeration system has been proposed in place of the conventional gas refrigeration system that uses a chlorofluorocarbon-based gas that causes environmental problems such as global warming.
- this magnetic refrigeration system when the magnetic refrigeration material is a refrigerant and the magnetic order of the magnetic material is changed by the magnetic field in the isothermal state and the magnetic order of the magnetic material is changed by the magnetic field in the adiabatic state. Use the adiabatic temperature change that occurs. Therefore, according to this magnetic refrigeration system, refrigeration can be performed without using chlorofluorocarbon gas, and there is an advantage that the refrigeration efficiency is higher than that of the conventional gas refrigeration system.
- Gd-based materials such as Gd (gadolinium) and / or Gd-based compounds are known as magnetic refrigeration materials used in this magnetic refrigeration system. These Gd-based materials are known as materials having a wide operating temperature range, but have a drawback that the amount of change in magnetic entropy ( ⁇ S M ) is small. Gd is a rare and expensive metal among rare earth elements, and it is difficult to say that it is an industrially practical material.
- Non-Patent Document 1 discusses various substitution elements including cobalt (Co) substitution.
- Patent Document 1 a part of La and La 1-z Ce z (Fe x Si 1-x) 13 H y by absorbing substituted and hydrogen Ce, and devised a high temperature the Curie temperature is made Yes.
- Patent Document 2 is devised to expand the operating temperature range by adjusting the ratio of Co, Fe, and Si in La (Fe 1-xy Co y Si x ) 13 .
- Patent Document 3 discloses a method of solidifying by a roll quenching method
- Patent Document 4 discloses a method of conducting current heating and sintering while applying pressure treatment
- Patent Document 5 Has proposed a method of reacting an Fe—Si alloy with oxidized La.
- the LaFeSi material reported in Non-Patent Document 1 and Patent Document 1 increases the Curie temperature while maintaining the maximum value ( ⁇ S max ) of the magnetic entropy variation ( ⁇ S M ), but the Gd material Since the operating temperature range of the magnetic refrigeration material is narrower than that, it is necessary to configure the magnetic refrigeration system with a plurality of types of materials having different operating temperature ranges, and there is a problem that handling is difficult.
- a LaFeSi-based material has a Curie temperature of around 200K, and thus cannot be used as a magnetic refrigeration material for a room temperature range.
- RCP relative cooling power
- An object of the present invention is to provide a magnetic refrigeration material that has a Curie temperature of 250 K or higher and a magnetic refrigeration material that greatly exceeds the conventional refrigeration performance up to around 2 Tesla, where a magnetic field change by a permanent magnet is considered possible.
- Another object of the present invention is to provide a magnetic refrigeration material that not only has a large amount of magnetic entropy change ( ⁇ S M ) but also has a wide operating temperature range, that is, a large RCP.
- the formula La 1-f RE f (Fe 1-abcde Si a Co b X c Y d Z e) 13 (Wherein RE is at least one element selected from rare earth elements including Sc and Y, excluding La, X is at least one element of Ga and Al, and Y is a group consisting of Ge, Sn, B, and C) At least one element selected from Z, Z represents at least one element selected from the group consisting of Ti, V, Cr, Mn, Ni, Cu, Zn, and Zr, and a represents 0.03 ⁇ a ⁇ .
- an average crystal grain size of 0.01 ⁇ m to 3 ⁇ m, a Curie temperature of 250 K or more, and a magnetic entropy change in a magnetic field change up to 2 Tesla maximum value of the amount (- ⁇ S M) (- ⁇ S max) indicates the least 5 J / kgK
- Magnetic refrigeration material is provided characterized by having a sex.
- the magnetic refrigeration device using the said magnetic refrigeration material and also the magnetic refrigeration system are provided.
- the magnetic refrigeration having the physical property that the maximum value ( ⁇ S max ) of the magnetic entropy change amount ( ⁇ S M ) at a Curie temperature of 250 K or higher and a magnetic field change up to 2 Tesla is 5 J / kgK or higher.
- ⁇ S max the maximum value of the magnetic entropy change amount
- ⁇ S M magnetic entropy change amount
- the present invention provides a magnetic refrigeration material having not only a large magnetic entropy change amount ( ⁇ S M ) but also a wide operating temperature range at a Curie temperature of 250 K or higher, that is, a physical refrigeration material that greatly exceeds the refrigeration performance obtained with conventional materials can do. Furthermore, by using the magnetic refrigeration material of the present invention, a magnetic refrigeration system can be configured with fewer types of materials than before. Moreover, by selecting the magnetic refrigeration material of the present invention having different Curie temperatures, it is possible to configure a magnetic refrigeration system according to different applications such as a home air conditioner and an industrial refrigerator-freezer.
- Magnetic refrigeration material of the present invention is a composition represented by the formula La 1-f RE f (Fe 1-abcde Si a Co b X c Y d Z e) 13, the specific average grain size and the specific Curie An alloy having a temperature is used.
- RE is at least one element selected from rare earth elements including Sc and Y, excluding La
- X is at least one element of Ga and Al
- Y is a group consisting of Ge, Sn, B, and C.
- At least one element selected, Z represents at least one element selected from the group consisting of Ti, V, Cr, Mn, Ni, Cu, Zn and Zr.
- a is 0.03 ⁇ a ⁇ 0.17
- b is 0.003 ⁇ b ⁇ 0.06
- c is 0.02 ⁇ c ⁇ 0.10
- d is 0 ⁇ d ⁇ 0.04
- e is 0 ⁇ e ⁇ 0.04
- f is 0 ⁇ f ⁇ 0.50.
- a part of La in the alloy can be replaced with the RE.
- f represents the content of the element RE that replaces part of La.
- f is 0 ⁇ f ⁇ 0.50.
- La and RE elements can adjust the Curie temperature, the operating temperature range, and the RCP. However, when f exceeds 0.50, the magnetic entropy change amount ( ⁇ S M ) decreases.
- a represents the content of Si element. a is 0.03 ⁇ a ⁇ 0.17.
- Si can adjust the Curie temperature, the operating temperature range, and the RCP. In addition, there are effects such as adjusting the melting point of the compound and increasing the mechanical strength. When a is smaller than 0.03, the Curie temperature decreases. On the other hand, when a is larger than 0.17, the magnetic entropy change amount ( ⁇ S M ) decreases.
- b represents the content of Co element.
- b is 0.003 ⁇ b ⁇ 0.06.
- Co is an element that is effective in adjusting the Curie temperature and the amount of change in magnetic entropy ( ⁇ S M ).
- ⁇ S M the magnetic entropy change amount
- b exceeds 0.06, the half width of the temperature curve in the magnetic entropy change amount ( ⁇ S M ) becomes narrow.
- c represents the content of the X element. c is 0.02 ⁇ c ⁇ 0.10. X is an element that is effective in adjusting the operating temperature range. When c is smaller than 0.02, the half-value width of the temperature curve in the magnetic entropy change amount ( ⁇ S M ) becomes narrow. On the other hand, when c is larger than 0.10, the magnetic entropy change amount ( ⁇ S M ) decreases.
- d represents the content of the Y element.
- d is 0 ⁇ d ⁇ 0.04.
- Y can adjust the Curie temperature, the operating temperature range, and the RCP.
- there are effects such as adjusting the melting point of the compound and increasing the mechanical strength.
- d is larger than 0.04, the magnetic entropy change amount ( ⁇ S M ) decreases, or the half width of the temperature curve at the magnetic entropy change amount ( ⁇ S M ) becomes narrow.
- e represents the content of the Z element. e is 0 ⁇ e ⁇ 0.04. Z can suppress the precipitation of ⁇ -Fe, control the Curie temperature, and improve the durability of the powder. However, if it is out of the predetermined range, a compound phase having a desired amount of NaZn 13 type crystal structure phase cannot be obtained, and the magnetic entropy change amount ( ⁇ S M ) decreases. When e is larger than 0.04, the magnetic entropy change amount ( ⁇ S M ) decreases, or the half width of the temperature curve at the magnetic entropy change amount ( ⁇ S M ) becomes narrow.
- 1-abbcde is the content of Fe.
- 1-abbcde is preferably 0.75 ⁇ 1-abbcde ⁇ 0.947.
- Fe affects the generation efficiency of a compound phase having a NaZn 13 type crystal structure phase.
- the average crystal grain size of the magnetic refrigeration material of the present invention is 0.01 ⁇ m or more and 3 ⁇ m or less.
- particles having a crystal grain size in the above range are present equiaxed, and each particle has a different crystal orientation.
- the crystal grain size can be confirmed using an electron microscope such as SEM or TEM, and the crystal grain size is an average value of the minor axis and major axis of the particle that can be confirmed in the visual field.
- the average crystal grain size was the average value of the crystal grain sizes of 100 particles that could be confirmed in the visual field.
- the length in the long axis direction of the crystal is small, the length in the long axis direction is large, and crystal grains with uniform orientation are not preferable.
- the average crystal grain size is smaller than 0.01 ⁇ m, the magnetization in the magnetic field becomes small and the magnetic entropy change becomes small. Also, when the average crystal grain size is larger than 3 ⁇ m, the magnetic entropy change is small.
- the alloy represented by the above formula preferably has a small content of oxygen, nitrogen and inevitable impurities in the raw material, but may be contained in a trace amount.
- the method for producing the magnetic refrigeration material of the present invention is not particularly limited as long as the crystal grain size can be refined.
- an alloy in an amorphous state is temporarily formed by a rapid quenching method using a roll such as a melt span.
- the master alloy is prepared by a method of obtaining fine crystals by recrystallization heat treatment, single roll casting methods such as arc melting method, die casting method, strip casting and atomizing method, and then in a specific temperature range
- the HDDR method in which fine crystals are obtained by absorbing and releasing hydrogen gas, and the sintering method in which the mother alloy is pulverized so that the average particle size is 3 ⁇ m or less and then sintered under the condition that no grain growth occurs are preferable.
- the obtained alloy is coarsely pulverized, it is preferably classified by, for example, a sieve of 18 mesh to 30 mesh to form a powder.
- the half-value width of the temperature curve in the magnetic entropy change amount ( ⁇ S M ), the RCP indicating the magnetic refrigeration capacity, and the magnetic entropy change amount ( ⁇ S M ) is obtained by the following method.
- the amount of magnetic entropy change (- ⁇ S M ) is measured using a SQUID magnetometer (product name: MPMS-7, manufactured by Quantum Design Co., Ltd.) under an applied magnetic field with a constant intensity up to 2 Tesla in a specific temperature range. From the obtained magnetization-temperature curve, it can be obtained using the Maxwell relational expression shown below.
- M magnetization
- T temperature
- H an applied magnetic field
- RCP of a magnetic refrigeration capacity magnetic entropy change obtained in the maximum value of (- ⁇ S M) and (- ⁇ S max), by the product of the half-value width of the temperature curve of the magnetic entropy change (- ⁇ S M) can be calculated from the following equation.
- RCP - ⁇ S max ⁇ ⁇ T
- - ⁇ S max represents the maximum value of - ⁇ S M
- ⁇ T denotes a half-value width of the peak of - ⁇ S M.
- the half width is the half width at half the maximum value ( ⁇ S max ) of the magnetic entropy change amount ( ⁇ S M ) on the temperature curve in the magnetic entropy change amount ( ⁇ S M ), that is, the maximum value. It means an index indicating the extent of the mountain-shaped curve with the peak at.
- the magnetic refrigeration material of the present invention has a temperature that shows the maximum value ( ⁇ S max ) of the amount of change in magnetic entropy ( ⁇ S M ) as compared with the conventional magnetic refrigeration material of NaZn 13 type La (FeSi) 13 series compound.
- the Curie temperature can be increased.
- the magnetic refrigeration material of the present invention can be used in a high temperature range of Curie temperature of 250K or higher. Furthermore, since the half-value width of the temperature curve in the magnetic entropy change amount ( ⁇ S M ) is wide, it is possible to configure a magnetic refrigeration system with less material than conventional materials.
- the magnetic refrigeration material of the present invention has the physical property that the maximum value (- ⁇ S max ) of the magnetic entropy change amount ( ⁇ S M ) (J / kgK) in the magnetic field change up to 2 Tesla is 5 J / kgK or more.
- the maximum value ( ⁇ S max ) of the magnetic entropy change amount ( ⁇ S M ) is lower than 5 J / kgK, the magnetic refrigeration performance is insufficient and the efficiency of the magnetic refrigeration decreases.
- the magnetic refrigeration material of the present invention preferably has the physical property that the half-value width (K) of the temperature curve in the magnetic entropy change ( ⁇ S M ) measured and calculated in the magnetic field change up to 2 Tesla is 40K or more.
- K half-value width
- ⁇ S M magnetic entropy change
- the magnetic refrigeration material of the present invention has a physical property in which RCP indicating magnetic refrigeration ability in a magnetic field change up to 2 Tesla is 300 J / kg or more.
- RCP has physical properties of 300 J / kg or more, the refrigerating capacity of the magnetic refrigeration material is high, and the amount of magnetic refrigeration material used can be reduced.
- the magnetic refrigeration device of the present invention and the magnetic refrigeration system use the magnetic refrigeration material of the present invention.
- the magnetic refrigeration material of the present invention can be processed into various shapes. Examples include a shape machined into a strip shape, a powder shape, and a shape obtained by sintering powder.
- the magnetic refrigeration device and the magnetic refrigeration system are not particularly limited depending on the type. For example, a heat exchange medium introduction pipe is provided at one end of the magnetic refrigeration work chamber and a heat is provided at the other end so that the heat exchange medium flows through the surface of the magnetic refrigeration material of the present invention disposed in the magnetic refrigeration work chamber.
- An exchange medium discharge pipe is provided, a permanent magnet is disposed in the vicinity of the magnetic refrigeration chamber, and a drive device is provided for applying and removing a magnetic field by changing the relative position of the permanent magnet with respect to the magnetic refrigeration material of the present invention. Those are preferred.
- the main action of the preferred magnetic refrigeration device or system is that, for example, when the drive unit is operated to change the relative position between the magnetic refrigeration chamber and the permanent magnet, a magnetic field is applied to the magnetic refrigeration material of the present invention.
- the entropy moves from the crystal lattice to the electron spin, and the entropy of the electron spin system increases.
- the temperature of the magnetic refrigeration material of the present invention is lowered and transmitted to the heat exchange medium, and the temperature of the heat exchange medium is lowered.
- the heat exchange medium whose temperature has been lowered in this manner is discharged from the magnetic refrigeration chamber through the discharge pipe and can supply the refrigerant to the external low-temperature consumption facility.
- Manufacturing method 2 After weighing various raw materials, it was melted in an argon gas atmosphere in a high-frequency melting furnace to obtain an alloy melt. Subsequently, this alloy melt was poured into a copper mold to obtain an alloy having a thickness of 10 mm. The obtained alloy was heat-treated at 1150 ° C. for 120 hours in an argon gas atmosphere, and then coarsely pulverized with a mortar. The pulverized powder was classified with a sieve of 18 mesh to 30 mesh to obtain an alloy powder.
- Manufacturing method 3 An alloy powder was obtained in the same manner as in Production Method 1 except that the recrystallization heat treatment was performed at 500 ° C. for 20 minutes.
- alloy powder for magnetic refrigeration material was produced by the above production method 1.
- the compositions of the obtained magnetic powders for magnetic refrigeration materials are shown in Tables 1 to 9.
- the average crystal grain size of the obtained alloy powder, the Curie temperature using the alloy powder, the maximum magnetic entropy change amount ( ⁇ S max ) in the magnetic field change up to 2 Tesla, the magnetic entropy change amount ( ⁇ S M The half-width and RCP of the temperature curve in) were evaluated according to the method described above. The results are shown in Table 2.
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Abstract
Description
この磁気冷凍方式では、磁気冷凍材料を冷媒とし、等温状態で磁性材料の磁気秩序を磁場で変化させた際に生じる磁気エントロピー変化および断熱状態で磁性材料の磁気秩序を磁場で変化させた際に生じる断熱温度変化を利用する。したがって、この磁気冷凍方式によれば、フロンガスを使用せずに冷凍を行なうことができ、従来の気体冷凍方式に比べて冷凍効率が高いという利点がある。
また、これらの材料を製造するための手段として、例えば、特許文献3には、ロール急冷法により凝固させる方法、特許文献4には、加圧処理しつつ通電加熱焼結する方法、特許文献5には、Fe-Si合金と酸化Laとを反応させる方法が提案されている。
また特許文献2には、磁気冷凍性能を示す指標として相対冷却力(Relative Cooling Power,以下RCP)が提示されている。この指標で判断するとこれらに記載されている磁気冷凍材料では、磁気エントロピー変化量(-ΔSM)の最大値は大きいが動作温度範囲が狭い、もしくは動作温度範囲が広くなるが磁気エントロピー変化量(-ΔSM)の最大値(-ΔSmax)が減少傾向にあるため、RCPはGd系材料とほぼ同等であり、性能を大きく上回る磁気冷凍材料とは言い難い。
本発明の課題は、キュリー温度が250K以上であり、かつ永久磁石による磁場変化が可能と考えられる2テスラ付近までで、従来の冷凍性能を大幅に超える磁気冷凍材料を提供することにある。
本発明の別の課題は、磁気エントロピー変化量(-ΔSM)が大きいだけでなく動作温度範囲も広い、即ち、RCPが大きい磁気冷凍材料を提供することにある。
(式中、REはLaを除く、Sc及びYを含む希土類元素から選ばれる少なくとも1種の元素、XはGa及びAlの少なくとも1種の元素、YはGe、Sn、B及びCからなる群より選択される少なくとも1種の元素、ZはTi、V、Cr、Mn、Ni、Cu、Zn及びZrからなる群より選択される少なくとも1種の元素を示す。aは0.03≦a≦0.17、bは0.003≦b≦0.06、cは0.02≦c≦0.10、dは0≦d≦0.04、eは0≦e≦0.04、fは0≦f≦0.50である。)で表される組成からなり、平均結晶粒径が0.01μm以上3μm以下、キュリー温度が250K以上であり、かつ2テスラまでの磁場変化における磁気エントロピー変化量(-ΔSM)の最大値(-ΔSmax)が5J/kgK以上を示す物性を有することを特徴とする磁気冷凍材料が提供される。
また本発明によれば、前記磁気冷凍材料を用いた磁気冷凍デバイス、さらには磁気冷凍システムが提供される。
更に本発明によれば、キュリー温度250K以上で、かつ2テスラまでの磁場変化における磁気エントロピー変化量(-ΔSM)の最大値(-ΔSmax)が5J/kgK以上を示す物性を有する磁気冷凍材料を製造するための、上記式で表される組成であり、平均結晶粒径が0.01μm以上3μm以下であり、キュリー温度が250K以上である合金の使用が提供される。
本発明の磁気冷凍材料は、式La1-fREf(Fe1-a-b-c-d-eSiaCobXcYdZe)13で表される組成であり、特定の平均結晶粒径及び特定のキュリー温度を有する合金を用いる。
式中、REはLaを除く、Sc及びYを含む希土類元素から選ばれる少なくとも1種の元素、XはGa及びAlの少なくとも1種の元素、YはGe、Sn、B及びCからなる群より選択される少なくとも1種の元素、ZはTi、V、Cr、Mn、Ni、Cu、Zn及びZrからなる群より選択される少なくとも1種の元素を示す。aは0.03≦a≦0.17、bは0.003≦b≦0.06、cは0.02≦c≦0.10、dは0≦d≦0.04、eは0≦e≦0.04、fは0≦f≦0.50である。
磁気冷凍材料の合金組織は、上記範囲の結晶粒径を持つ粒子が等軸的に存在しており、それぞれの粒子は異なる結晶方位を持っている。結晶粒径は、SEMまたはTEM等の電子顕微鏡を用いて確認することができ、結晶粒径は視野内に確認できる粒子の短径と長径の平均値である。平均結晶粒径は、視野内に確認できる粒子100個の結晶粒径の平均値とした。
磁気冷凍材料の合金を製造するあたり、比較的遅い速度で鋳造を行った場合、合金組織は柱状晶となる。しかし、そのような組織では、結晶の短軸方向の長さは小さくても長軸方向の長さが大きくなり、方位の揃った結晶粒となり好ましくない。平均結晶粒径が0.01μmより小さいと、磁場中での磁化が小さくなり、磁気エントロピー変化が小さくなる。また、平均結晶粒径が3μmより大きい場合も、磁気エントロピー変化が小さくなる。
まず磁気エントロピー変化量(-ΔSM)は、SQUID磁束計(カンタムデザイン社製、商品名MPMS-7)を用いて特定温度範囲において2テスラまでの一定強度の印加磁場のもとで磁化を測定した磁化-温度曲線から、下記に示すMaxwellの関係式を用いて求めることができる。
RCP=-ΔSmax×δT
但し、-ΔSmaxは-ΔSMの最大値を示し、δTは-ΔSMのピークの半値幅を示す。ここで半値幅とは、磁気エントロピー変化量(-ΔSM)における温度曲線での磁気エントロピー変化量(-ΔSM)の最大値(-ΔSmax)の半分の値における半値半幅、即ち、最大値をピークとした山形曲線の広がりの程度を示す指標を意味する。
本発明の磁気冷凍材料は、キュリー温度250K以上という高い温度域において使用することが可能である。さらに磁気エントロピー変化量(-ΔSM)における温度曲線の半値幅が広いため、従来の材料よりも少ない材料で磁気冷凍システムを構成することが可能である。
製法1
各種原料を秤量した後、高周波溶解炉にてアルゴンガス雰囲気中で溶解し、合金溶融物とした。続いて、この合金溶融物を、周速度40m/sで回転する銅製ロールに注湯して厚み約50μmの合金リボンを得た。その後、得られた合金をアルゴンガス雰囲気中において850℃、20分間で再結晶化熱処理を行ない、その後乳鉢により粉砕を行った。粉砕した粉末を、18メッシュ~30メッシュのふるいで分級して合金粉末を得た。
各種原料を秤量した後、高周波溶解炉にてアルゴンガス雰囲気中で溶解し、合金溶融物とした。続いて、この合金溶融物を、銅製金型に注湯して厚み10mmの合金を得た。得られた合金をアルゴンガス雰囲気中において1150℃、120時間で熱処理を行ない、その後乳鉢により粗粉砕を行った。粉砕した粉末を18メッシュ~30メッシュのふるいで分級して合金粉末を得た。
再結晶化熱処理の条件を500℃、20分間とした以外は製法1と同様にして合金粉末を得た。
表1に示す組成1~9の合金原料を用い、上記製法1により、磁気冷凍材料用合金粉末を作製した。得られた磁気冷凍材料用合金粉末の組成を表1の1~9に示す。次に、得られた合金粉末の平均結晶粒径及び該合金粉末を用いてキュリー温度、2テスラまでの磁場変化における磁気エントロピー変化量最大値(-ΔSmax)、磁気エントロピー変化量(-ΔSM)における温度曲線の半値幅およびRCPを上述の方法に従って評価した。結果を表2に示す。
表1に示す組成2~7、9~14の合金原料を用い、それぞれ表1に示す上記製法1~3により、磁気冷凍材料用合金粉末を作製した。得られた磁気冷凍材料用合金粉末の組成を表1に示す。次、得られた合金粉末について、実施例1~9と同様に各評価を行った。結果を表2に示す。
Claims (3)
- 式La1-fREf(Fe1-a-b-c-d-eSiaCobXcYdZe)13
(式中、REはLaを除く、Sc及びYを含む希土類元素から選ばれる少なくとも1種の元素、XはGa及びAlの少なくとも1種の元素、YはGe、Sn、B及びCからなる群より選択される少なくとも1種の元素、ZはTi、V、Cr、Mn、Ni、Cu、Zn及びZrからなる群より選択される少なくとも1種の元素を示す。aは0.03≦a≦0.17、bは0.003≦b≦0.06、cは0.02≦c≦0.10、dは0≦d≦0.04、eは0≦e≦0.04、fは0≦f≦0.50である。)で表される組成からなり、平均結晶粒径が0.01μm以上3μm以下、キュリー温度が250K以上であり、かつ2テスラまでの磁場変化における磁気エントロピー変化量(-ΔSM)の最大値(-ΔSmax)が5J/kgK以上を示す物性を有する磁気冷凍材料。 - 2テスラまでの磁場変化における磁気冷凍能力を示す相対冷却力が300J/kg以上を示す物性を有する請求項1記載の磁気冷凍材料。
- 請求項1又は2記載の磁気冷凍材料を用いた磁気冷凍デバイス。
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