WO2004068512A1 - A magnetic material with cooling capacity, a method for the manufacturing thereof and use of such material - Google Patents
A magnetic material with cooling capacity, a method for the manufacturing thereof and use of such material Download PDFInfo
- Publication number
- WO2004068512A1 WO2004068512A1 PCT/NL2003/000059 NL0300059W WO2004068512A1 WO 2004068512 A1 WO2004068512 A1 WO 2004068512A1 NL 0300059 W NL0300059 W NL 0300059W WO 2004068512 A1 WO2004068512 A1 WO 2004068512A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- material according
- temperature
- mixture
- range
- formula
- Prior art date
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Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/5154—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on phosphides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/405—Iron group metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/428—Silicon
-
- 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
-
- 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
- a magnetic material with cooling capacity a method for the manufacturing thereof and use of such material
- the invention relates to a material that can be used for magnetic refrigeration.
- MR magnetic refrigeration
- a draw-back of the known materials that can be used for magnetic refrigeration is that they are not optimally applicable in the temperature range from approxi- mately 200 to 600 K. Also, the known materials that are suitable for magnetic refrigeration such as the above- mentioned Gds (Si ⁇ Ge ⁇ - ⁇ ) 4 alloys are very expensive, which hinders their use on a large scale.
- the cooling capacity of the materials according to the present invention may therefore be higher than that of the best Gd-based materials referred to in the article by Gschneidner Jr. et al . . (see above). Moreover, the maximum cooling capacity covers a much more useful range of temperature with regard to the application in, for example, an air conditioner.
- a further advantage of the materials according to the present invention is that they are comprised of widely occurring elements, so that large-scale application is possible.
- the magnetocaloric effect is so strong that it becomes possible to work with a magnetic field generated by permanent magnets instead of (optionally superconductive) electromagnets.
- a further advantage is that the materials according to the present invention do not or not readily dissolve in water.
- C, D and E are identical or different and are selected from at least one of P, Ge, Si, Sn and Ga.
- At least 90%, preferably at least 95% of A is Mn; at least 90%, preferably at least 95% of B is Fe; at least 90%, preferably at least 95% of C is P; at least 90%, preferably at least 95% of D is Ge; and at least 90%, preferably at least 95% of E is Si.
- the material has the general formula MnFe (P w Ge x Si z ) • This material produces a high cooling capacity in the temperature range of 200 - 600 K, preferably 280 - 500 K. It has an exceptionally strong magnetocaloric effect. If there is a possibility that the compound according to the invention comes into contact with the environment, the compound is also preferred, because no poisonous compounds can develop during decomposition.
- the present invention also relates to a method for the manufacture of the material as indicated above, characterized by performing the steps of mixing powders of each of the elements A, B, C, D and E as indicated in claim 1, in suitable weight proportions to produce a powder mixture that complies with the general formula (A y B ⁇ _ y)2+ ⁇ C w D x E z , if necessary grinding said mixture so as to obtain an amorphous or micro-crystalline powder mixture, sintering said obtained mixture under an inert atmosphere at a temperature of at least 700 °C, preferably 700-1100 °C, more preferably 800-1050 °C, and annealing said sintered mixture at a temperature of from 600-700 °C, preferably 630-680 °C, more preferably 640-660 °C.
- a particularly preferable method starts out from pure elements in suitable weight proportions, these are mixed, the powder mixture is melted, and the resulting al- loy is finally annealed.
- the starting materials may, for example, be treated in a ball mill to produce an alloy. This alloy is subsequently sintered under an inert atmosphere and then annealed, for example, in a suitable furnace.
- an alloy of the composition MnFeP w Ge x Si z preferably MnFePo.45-0. loGeo.55-0.30 and more preferably having the formula MnFePo.5-0.70 (Si/Ge) 0.5-0.30 will exhibit a magnetocaloric effect at room temperature that is stronger than the one found when using pure Gd.
- the powder mixture Prior to melting, the powder mixture is preferably first compressed into a pill or any other desired shape. This reduces the chance of material loss when the material is being melted (sintered) .
- this inert atmosphere When melting the powder mixture under an inert atmosphere, it has been shown to be advantageous for this inert atmosphere to be an argon atmosphere. This reduces the occurrence of contaminants in the material during melting.
- the present invention relates to the application of the material according to the invention with magnetic refrigeration in the 200 - 600 K range.
- the material according to the present invention may be used, among other things, for food refrigerators, air conditioners, computers, etc.
- these elements are ground under a protective atmosphere until an amorphous or micro- crystalline product is obtained.
- Dependent on the proper- ties of the mill, such a product may be obtained within 20 minutes until a few hours.
- the powder is subsequently heated in a closed ampoule in a protected atmosphere until a temperature is obtained of from 800 to 1050 °C. Subsequently the same is annealed at a temperature of about 650 °C.
- these elements are ground under a protective atmosphere until an amorphous or micro- crystalline product is obtained.
- Dependent on the properties of the mill such a product may be obtained withir> 20 minutes until a few hours.
- the powder is subsequently heated in a closed ampoule in a protected atmosphere until a temperature is ob- tained of from 800 to 1050 °C. Subsequently the same is annealed at a temperature of about 650 °C.
- these elements are ground under a protective atmosphere until an amorphous or micro- crystalline product is obtained.
- Dependent on the properties of the mill such a product may be obtained within 20 minutes until a few hours.
- the powder is subsequently heated in a closed ampoule in a protected atmosphere until a temperature is obtained of from 800 to 1050 °C. Subsequently the same is annealed at a temperature of about 650 °C.
- the alloys obtained by the fore-mentioned examples 1, 2 and 3 all crystallise in a hexagonal F ⁇ 2P structure.
- the alloy of Example 3 has a high magnetocaloric effect at and near the critical temperature, as shown in the appended Figure 1.
- An alternative embodiment of the invention is obtained by starting out from alloys of the starting elements, instead of the pure elements; such is especially functional if Si is used in the alloy. Although the reason for this is not sure, it probably is due to the fact that FeSi alloys are very stable and are obtained if pure Fe and Si are available in the mill.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Structural Engineering (AREA)
- Power Engineering (AREA)
- Soft Magnetic Materials (AREA)
- Hard Magnetic Materials (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
Claims
Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/543,673 US8211326B2 (en) | 2003-01-29 | 2003-01-29 | Magnetic material with cooling capacity, a method for the manufacturing thereof and use of such material |
DE60313671T DE60313671T2 (en) | 2003-01-29 | 2003-01-29 | MAGNETIC MATERIAL WITH COOLABILITY, METHOD FOR THE PRODUCTION AND USE OF SUCH A MATERIAL |
AU2003303840A AU2003303840A1 (en) | 2003-01-29 | 2003-01-29 | A magnetic material with cooling capacity, a method for the manufacturing thereof and use of such material |
ES03815615T ES2286514T3 (en) | 2003-01-29 | 2003-01-29 | MAGNETIC MATERIAL WITH REFRIGERANT CAPACITY, PROCEDURE FOR THE MANUFACTURE OF THE SAME AND USE OF SUCH MATERIAL. |
AT03815615T ATE361535T1 (en) | 2003-01-29 | 2003-01-29 | MAGNETIC MATERIAL HAVING COOLING CAPACITY, METHOD FOR PRODUCING SAME AND USE OF SUCH MATERIAL |
PCT/NL2003/000059 WO2004068512A1 (en) | 2003-01-29 | 2003-01-29 | A magnetic material with cooling capacity, a method for the manufacturing thereof and use of such material |
CA2514773A CA2514773C (en) | 2003-01-29 | 2003-01-29 | A magnetic material with cooling capacity, a method for the manufacturing thereof and use of such material |
DK03815615T DK1599884T3 (en) | 2003-01-29 | 2003-01-29 | Magnetic material with cooling capacity, method of making it and use of such material |
BRPI0318065-4A BR0318065B1 (en) | 2003-01-29 | 2003-01-29 | MATERIAL THAT CAN BE USED FOR MAGNETIC REFRIGERATION, AND METHOD FOR MANUFACTURING AND APPLYING THEM |
EP03815615A EP1599884B1 (en) | 2003-01-29 | 2003-01-29 | A magnetic material with cooling capacity, a method for the manufacturing thereof and use of such material |
SI200330894T SI1599884T1 (en) | 2003-01-29 | 2003-01-29 | A magnetic material with cooling capacity, a method for the manufacturing thereof and use of such material |
JP2004567588A JP4663328B2 (en) | 2003-01-29 | 2003-01-29 | Magnetic material having cooling capacity, method for producing the material, and method for using the material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/NL2003/000059 WO2004068512A1 (en) | 2003-01-29 | 2003-01-29 | A magnetic material with cooling capacity, a method for the manufacturing thereof and use of such material |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004068512A1 true WO2004068512A1 (en) | 2004-08-12 |
Family
ID=32822836
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL2003/000059 WO2004068512A1 (en) | 2003-01-29 | 2003-01-29 | A magnetic material with cooling capacity, a method for the manufacturing thereof and use of such material |
Country Status (12)
Country | Link |
---|---|
US (1) | US8211326B2 (en) |
EP (1) | EP1599884B1 (en) |
JP (1) | JP4663328B2 (en) |
AT (1) | ATE361535T1 (en) |
AU (1) | AU2003303840A1 (en) |
BR (1) | BR0318065B1 (en) |
CA (1) | CA2514773C (en) |
DE (1) | DE60313671T2 (en) |
DK (1) | DK1599884T3 (en) |
ES (1) | ES2286514T3 (en) |
SI (1) | SI1599884T1 (en) |
WO (1) | WO2004068512A1 (en) |
Cited By (75)
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EP2107575A1 (en) | 2008-03-31 | 2009-10-07 | Université Henri Poincaré - Nancy 1 | New intermetallic compounds, their use and a process for preparing the same |
WO2009133047A2 (en) * | 2008-04-28 | 2009-11-05 | Basf Se | Thermomagnetic generator |
WO2010108883A2 (en) | 2009-03-24 | 2010-09-30 | Basf Se | Printing method for producing thermomagnetic form bodies for heat exchangers |
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WO2011009904A1 (en) | 2009-07-23 | 2011-01-27 | Basf Se | Use of diamagnetic materials for focusing magnetic field lines |
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WO2011020826A1 (en) | 2009-08-18 | 2011-02-24 | Technology Foundation Stw | Polycrystalline magnetocaloric materials |
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US7914628B2 (en) * | 2005-03-24 | 2011-03-29 | Kabushiki Kaisha Toshiba | Magnetic refrigeration material and method of manufacturing thereof |
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WO2011083446A1 (en) * | 2010-01-11 | 2011-07-14 | Basf Se | Magnetocaloric materials |
US8109100B2 (en) | 2005-09-29 | 2012-02-07 | Karl Sandeman | Magnetocaloric refrigerant |
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WO2014088774A1 (en) * | 2012-12-07 | 2014-06-12 | General Electric Company | Novel magnetic refrigerant materials |
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Also Published As
Publication number | Publication date |
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EP1599884B1 (en) | 2007-05-02 |
BR0318065B1 (en) | 2014-12-23 |
DK1599884T3 (en) | 2007-09-10 |
CA2514773A1 (en) | 2004-08-12 |
US8211326B2 (en) | 2012-07-03 |
SI1599884T1 (en) | 2007-12-31 |
JP2006514158A (en) | 2006-04-27 |
CA2514773C (en) | 2012-10-09 |
US20060117758A1 (en) | 2006-06-08 |
AU2003303840A1 (en) | 2004-08-23 |
AU2003303840A8 (en) | 2004-08-23 |
ATE361535T1 (en) | 2007-05-15 |
BR0318065A (en) | 2005-12-06 |
ES2286514T3 (en) | 2007-12-01 |
DE60313671D1 (en) | 2007-06-14 |
DE60313671T2 (en) | 2008-01-17 |
JP4663328B2 (en) | 2011-04-06 |
EP1599884A1 (en) | 2005-11-30 |
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