EP2457239A1 - Utilisation de matériaux diamagnétiques pour concentrer des lignes de champ magnétiques - Google Patents

Utilisation de matériaux diamagnétiques pour concentrer des lignes de champ magnétiques

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Publication number
EP2457239A1
EP2457239A1 EP10737542A EP10737542A EP2457239A1 EP 2457239 A1 EP2457239 A1 EP 2457239A1 EP 10737542 A EP10737542 A EP 10737542A EP 10737542 A EP10737542 A EP 10737542A EP 2457239 A1 EP2457239 A1 EP 2457239A1
Authority
EP
European Patent Office
Prior art keywords
magnetic field
diamagnetic
field lines
use according
paramagnetic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10737542A
Other languages
German (de)
English (en)
Inventor
Georg Degen
Fabian Seeler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP10737542A priority Critical patent/EP2457239A1/fr
Publication of EP2457239A1 publication Critical patent/EP2457239A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • 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 invention relates to the use of diamagnetic materials for bundling magnetic field lines and shaped bodies of magnetocaloric materials for coolers, heat pumps or generators containing diamagnetic materials.
  • NdFeB magnets To generate strong magnetic fields, expensive magnetic materials such as NdFeB magnets are often used. To save costs and materials, the magnets are designed in such a way that the largest possible magnetic field can be generated with as little magnetic material as possible. Frequently, ferromagnetic materials are used to reinforce the field lines in a certain area of the magnetic field. However, such ferromagnetic materials can usefully be used only where the magnetic field is not intended to affect other materials, since they focus the field lines away from these materials and because of their ferromagnetic properties.
  • the object of the present invention is to provide materials or devices for focusing the magnetic field lines of a directional magnetic field to the area in which such a reinforcement is required.
  • the object is achieved by using diamagnetic materials in a magnetic field in which a paramagnetic material is introduced, as a focuser for focusing the magnetic field lines in the paramagnetic material.
  • the object is achieved by a molded body of magnetocaloric material for coolers, heat pumps or generators having channels for passing a heat transfer medium and has a suitable form for introduction into a magnetic field, wherein the shaped body of a diamagnetic material on the surfaces in the Are substantially parallel to the magnetic field lines, at least partially surrounded.
  • the channels for passing a heat transfer medium and has a suitable for introduction into a magnetic field form, characterized in that the shaped body extending in the direction of the magnetic field lines inclusions diamagnetic materials.
  • diamagnetics Materials that tend to move in an inhomogeneous magnetic field from locations of high to lower intensity fields are referred to as diamagnetics or diamagnetic materials. Substances that behave in the opposite direction, namely the tendency to migrate to a stronger field, are called paramagnetic.
  • the diamagnetism is caused by the interaction between magnetic fields and moving charged particles, in particular electrons. In amount it is small compared to paramagnetism.
  • the paramagnetism on the other hand is caused by spin moments and orbital torques of the electrons.
  • Diamagnetic are all substances whose atoms or molecules refer to closed electron shells, since in this case the magnetic single moments of the electrons cancel each other out and thus no external magnetic moment appears on the outside.
  • the diamagnetic substances include, for example, all noble gases and all substances with noble gas-like ions or atoms. These include, for example, most organic compounds.
  • Preferred diamagnetic materials used according to the invention are plastics, wood, metal oxides, ceramics, leather, textiles or mixtures thereof.
  • Plastics are preferably selected from polyethylene, polypropylene, polyurethane, polyamide, polystyrene, polyester, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyimide, polyacetal, polyphenylene ether, polyvinyl acetate, polyvinyl chloride and mixtures thereof.
  • a magnetic field which has already been amplified by the usual methods of magnet design, for example by the magnetic field being concentrated by ferromagnetic magnetic shoes, can be obtained by using diamagnetic materials in the areas where the magnetic field is not needed or in an area covering the area the magnetic field surrounds, in addition to be amplified.
  • the field lines are repelled by the diamagnetic material and directed into the area adjacent to the material. It thus takes place an amplification of the field outside of the diamagnetic material and thus within the range in which the field is needed. For example, if a material A is to be introduced into a magnetic field to cause a physical effect, it is advantageous to surround this material A with a diamagnetic material B in order to concentrate the magnetic field lines within the material A.
  • a diamagnetic material into the magnetic field so as to concentrate the field lines even more strongly on the area in which a high field strength is required.
  • the orientation of the diamagnetic materials parallel to the magnetic field lines is particularly advantageous.
  • a diamagnetic material is thus used in combination with a paramagnetic material, whereby the magnetic field lines are deflected, focused or concentrated in the paramagnetic material.
  • the paramagnetic material may be surrounded by the diamagnetic material substantially along or parallel to the magnetic field lines.
  • the cuboid can be surrounded, for example, on four surfaces with the diamagnetic material, while the surfaces facing the magnetic poles, on which the magnetic field lines are perpendicular or substantially are vertical, not covered by diamagnetic material.
  • the term "substantially" along or parallel to the magnetic field lines allows for angular deviations of ⁇ 10 °, preferably ⁇ 5 °, in particular ⁇ 2 °.
  • the paramagnetic material may include inclusions of the diamagnetic material substantially along the magnetic field lines.
  • the inclusions may be in the form of rods which pass through the paramagnetic material parallel to the magnetic field lines. These rods can have a round, angular, polygonal, oval or other cross-section and preferably pass through the paramagnetic shaped body in straight, mutually parallel lines. The rods can be distributed evenly spaced apart in the paramagnetic material.
  • the space into which a paramagnetic material is introduced in a magnetic field is surrounded by a diamagnetic material substantially along or parallel to the magnetic field lines. This makes it possible that as far as possible all magnetic field lines pass through the paramagnetic material.
  • the paramagnetic material is a magnetocaloric material.
  • magnetocaloric material Such materials are known in principle and described for example in WO 2004/068512.
  • the alignment of randomly oriented magnetic moments with an external magnetic field results in heating of the material. This heat can be dissipated from the MCE material into the ambient atmosphere by heat transfer.
  • the magnetic field is then turned off or removed, the magnetic mo- again in a random arrangement, which leads to a cooling of the material below ambient temperature.
  • a heat transfer medium such as water is used for heat removal from the magne- tocaloral material. Accordingly, applications are available as heat pumps and generators.
  • Typical materials for the magnetic cooling are multimetal materials which often contain at least three metallic elements and optionally also non-metallic elements.
  • metal-based materials indicates that the majority of these materials are composed of metals or metallic elements, typically the proportion of the total material is at least 50% by weight, preferably at least 75% by weight, in particular at least 80% by weight Suitable metal-based materials are explained in more detail below:
  • the magnetocaloric or metal-based material is particularly preferably selected from
  • B Fe, Cr or Ni, C, D, E at least two of C, D, E are different from each other, have a non-vanishing concentration and are selected from P, B, Se, Ge, Ga, Si, Sn, N, As and Sb, wherein at least one of C, D and E is Ge, As or Si, ⁇ number in the range of - 0.1 to 0.1 w, x, y, z numbers in the range of 0 to 1, wherein w + x + z 1;
  • x number from 0.7 to 0.95 y is from 0 to 3, preferably from 0 to 2;
  • C, D and E are preferably identical or different and selected from at least one of P, Ge, Si, Sn and Ga.
  • the metal-based material of the general formula (I) is preferably selected from at least quaternary compounds which in addition to Mn, Fe, P and optionally Sb also Ge or Si or As or Ge and Si or Ge and As or Si and As or Ge, Si and As included.
  • At least 90% by weight, more preferably at least 95% by weight, of component A are Mn. At least 90% by weight, more preferably at least 95% by weight, of B Fe are preferred. At least 90% by weight are preferred, especially preferably at least 95% by weight of C P. Preference is given to at least 90% by weight, particularly preferably at least 95% by weight, of D Ge. At least 90% by weight, more preferably at least 95% by weight, of E Si are preferred.
  • the material has the general formula MnFe (P w Ge x Si z ).
  • x is a number in the range of 0.3 to 0.7, w is less than or equal to 1-x and z corresponds to 1-x-w.
  • the material preferably has the crystalline hexagonal Fe 2 P structure.
  • suitable structures are MnFeP 0 45 to 0.7, Ge o from 55 to 0.30 and MnFeP 0, 5 to 0.70, (Si / Ge) 0, 5 to
  • Suitable compounds are also M n n- x Fe 1 . x P 1 .yGey with x in the range of -0.3 to 0.5, y in the range of 0.1 to 0.6. Also suitable are compounds of the general formula Mni + ⁇ Fei. ⁇ Pi. y Ge y - z Sb z with x in the range of -0.3 to 0.5, y in the range of 0.1 to 0.6 and z smaller than y and smaller than 0.2. Furthermore, compounds of the formula Mnn-x Fe 1 . x P 1 - y Ge y .
  • La and Fe-based compounds of the general formulas (II) and / or (III) and / or (IV) are La (Fe Oi9 oSi Ol io) i3, La (Fe 01 SgSiO 1 Ii) Is, La (Fe 01 Ss 0 Si 01 I 20) Is, La (Fe ⁇ i 877Si o, i23) i3, Lafen, 8 Sii i2, La (Fe ⁇ i 8sSi ⁇ i i2) i3H ⁇ i 5, La (Fe ⁇ i 8sSi ⁇ i i2) i3Hi i ⁇ , LaFe H17 Si I13 Hi 1I , LaFe H157 Si I14S Hi 13 , La (Fe ⁇ i88 Si ⁇ i i 2
  • Suitable manganese containing compounds are MnFeGe, MnFe 0 9 Co 0 iGe, MnFe 0i8 Co 0i 2 Ge, MnFe 0i7 Co o , 3Ge, MnFe ⁇ i 6Co ⁇ i 4 Ge, MnFe o , 5 Co 0i5 Ge, MnFe ⁇ i 4Co ⁇ i6 Ge, MnFe o, 3 Co 0i7 Ge, MnFe 0i2 Co 0i8 Ge, MnFe 0i i 5 Co 0i85 Ge, MnFe o, iCo o, 9 Ge, MnCoGe, Mn 5 Ge 2i5 Si o, 5 , Mn 5 Ge 2 Si, Mn 5 Gei , 5 Sii , 5 , Mn 5 GeSi 2 , Mn 5 Ge 3 , Mn 5 Ge 2.9 Sb o, i, Mn 5 Ge 2.8 Sb 0
  • Heusler alloys suitable according to the invention are, for example, Fe 2 MnSi 0 5 Ge 0 5 , Ni 52i9 Mn 22i4 Ga 2 4, 7 , Ni 50i9 Mn 24i7 Ga 2 4.4, Ni 55i 2 Mni 8i6 Ga 26i 2 , Ni 5 i 16 Mn 24i7 Ga 23i8 ,
  • the average crystallite size is generally in the range from 10 to 400 nm, particularly preferably 20 to 200 nm, in particular 30 to 80 nm. The average crystallite size can be determined by X-ray diffraction. If the crystallite size is too small, the maximum magnetocalor
  • the preparation of conventional materials is carried out by solid phase reaction of the starting elements or starting alloys for the material in a ball mill, subsequent compression, sintering and annealing under an inert gas atmosphere and subsequent slow cooling to room temperature.
  • the starting elements are first induction-melted in an argon gas atmosphere and then sprayed in a molten state via a nozzle onto a rotating copper roll. This is followed by sintering at 1000 ° C. and slow cooling to room temperature.
  • the preparation of the metal-based materials for magnetic cooling or heat pumps or generators includes, for. A) conversion of chemical elements and / or alloys in a stoichiometry corresponding to the metal-based material into the solid and / or liquid phase, b) if appropriate conversion of the reaction product from stage a) into a solid, c) sintering and / or annealing the solid from step a) or b), d) quenching the sintered and / or annealed solid from step c) with a cooling rate of at least 100 K / s.
  • Quenching can be achieved by any suitable cooling method, for example by quenching the solid with water or aqueous liquids, for example, cooled water or ice / water mixtures.
  • the solids can be dropped, for example, in iced water. It is also possible to quench the solids with undercooled gases such as liquid nitrogen. Other quenching methods are known to those skilled in the art.
  • the advantage here is a controlled and rapid cooling.
  • step (a) of the process according to the invention the reaction of the elements and / or alloys contained in the later metal-based material takes place in a stoichiometry corresponding to the metal-based material in the solid or liquid phase.
  • the reaction in step a) is carried out by co-heating the elements and / or alloys in a closed container or in an extruder, or by solid-phase reaction in a ball mill.
  • a solid phase reaction is carried out, which takes place in particular in a ball mill.
  • powders of the individual elements or powders of alloys of two or more of the individual elements, which are present in the later metal-based material are typically powder-mixed in suitable proportions by weight. If necessary, additional grinding of the mixture can be carried out to obtain a microcrystalline powder mixture.
  • This powder mixture is preferably heated in a ball mill, which leads to a further reduction as well as good mixing and to a solid phase reaction in the powder mixture.
  • the individual elements are mixed in the selected stoichiometry as a powder and then melted.
  • the common heating in a closed container allows the fixation of volatile elements and the control of the stoichiometry. Especially with the use of phosphorus, this would easily evaporate in an open system.
  • the reaction is followed by sintering and / or tempering of the solid, wherein one or more intermediate steps may be provided.
  • the solid obtained in step a) can be pressed before it is sintered and / or tempered.
  • the pressing is known per se and can be carried out with or without pressing aids. In this case, any suitable shape can be used for pressing. By pressing, it is already possible to produce shaped bodies in the desired three-dimensional structure.
  • the pressing may be followed by sintering and / or tempering step c) followed by quenching step d).
  • sintering and / or tempering step c) followed by quenching step d).
  • Melt spinning processes are known per se and described for example in Rare Metals, Vol. 25, October 2006, pages 544 to 549 as well as in WO 2004/068512.
  • the composition obtained in step a) is melted and sprayed onto a rotating cold metal roller.
  • This spraying can be achieved by means of positive pressure in front of the spray nozzle or negative pressure behind the spray nozzle.
  • a rotating copper drum or roller is used which, if desired, may be cooled.
  • the copper drum preferably rotates at a surface speed of 10 to 40 m / s, in particular 20 to 30 m / s.
  • the liquid composition is cooled at a rate of preferably 10 2 to 10 7 K / s, more preferably at a rate of at least 10 4 K / s, in particular at a rate of 0.5 to 2 x 10 6 K / s.
  • the melt spinning can be carried out as well as the reaction in step a) under reduced pressure or under an inert gas atmosphere.
  • step b) a spray cooling may be carried out, in which a melt of the composition from step a) is sprayed into a spray tower.
  • the spray tower can be additionally cooled, for example. In spray towers cooling rates in the range of 10 3 to 10 5 K / s, in particular about 10 4 K / s are often achieved.
  • the sintering and / or tempering of the solid takes place in stage c), preferably first at a temperature in the range from 800 to 1400 ° C. for sintering and subsequently at a temperature in the range from 500 to 750 ° C. for tempering.
  • a temperature in the range from 800 to 1400 ° C. for sintering preferably first at a temperature in the range from 800 to 1400 ° C. for sintering and subsequently at a temperature in the range from 500 to 750 ° C. for tempering.
  • These values apply in particular to shaped bodies, while for powders lower sintering and tempering temperatures can be used.
  • the sintering at a temperature in the range of 500 to 800 0 C take place.
  • moldings / solids sintering is particularly preferably carried out at a temperature in the range of 1000 to 1300 0 C, in particular from 1100 to 1300 0 C.
  • the annealing can then be carried out for example at 600 to 700
  • the sintering is preferably carried out for a period of 1 to 50 hours, more preferably 2 to 20 hours, especially 5 to 15 hours.
  • the annealing is preferably carried out for a time in the range of 10 to 100 hours, particularly preferably 10 to 60 hours, in particular 30 to 50 hours. Depending on the material, the exact time periods can be adapted to the practical requirements.
  • sintering can often be dispensed with, and tempering can be greatly shortened, for example, for periods of 5 minutes to 5 hours, preferably 10 minutes to 1 hour. Compared to the usual values of 10 hours for sintering and 50 hours for annealing, this results in an extreme time advantage.
  • the sintering / tempering causes the grain boundaries to melt, so that the material continues to densify.
  • the metal-based materials according to the invention are preferably used in the magnetic cooling, as described above.
  • a corresponding refrigerator has in addition to a magnet, preferably permanent magnets, metal-based materials, as described above.
  • the cooling of computer chips and solar power generators is also considered. Further fields of application are heat pumps and air conditioning systems as well as generators.
  • the magnetocaloric materials When the magnetocaloric materials are introduced into a magnetic field, it is desirable to concentrate the magnetic field on the areas in which the magnetocaloric material is located. Therefore, according to the invention, the magnetocaloric materials can be surrounded with a diamagnetic material (except for the end faces that are perpendicular to the magnetic field lines). It is also possible, for example, to introduce rods of diamagnetic material into corresponding longitudinal bores in the magnetocaloric molded body, so that the rods run parallel to the magnetic field lines. As a result, the field line density in the magnetocaloric material can be increased.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Hard Magnetic Materials (AREA)

Abstract

L'invention porte sur l'utilisation de matériaux diamagnétiques dans un champ magnétique dans lequel on introduit un matériau paramagnétique, en tant que moyen de focalisation pour concentrer les lignes de champ magnétique dans le matériau paramagnétique.
EP10737542A 2009-07-23 2010-07-22 Utilisation de matériaux diamagnétiques pour concentrer des lignes de champ magnétiques Withdrawn EP2457239A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10737542A EP2457239A1 (fr) 2009-07-23 2010-07-22 Utilisation de matériaux diamagnétiques pour concentrer des lignes de champ magnétiques

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09166175 2009-07-23
EP10737542A EP2457239A1 (fr) 2009-07-23 2010-07-22 Utilisation de matériaux diamagnétiques pour concentrer des lignes de champ magnétiques
PCT/EP2010/060602 WO2011009904A1 (fr) 2009-07-23 2010-07-22 Utilisation de matériaux diamagnétiques pour concentrer des lignes de champ magnétiques

Publications (1)

Publication Number Publication Date
EP2457239A1 true EP2457239A1 (fr) 2012-05-30

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EP10737542A Withdrawn EP2457239A1 (fr) 2009-07-23 2010-07-22 Utilisation de matériaux diamagnétiques pour concentrer des lignes de champ magnétiques

Country Status (10)

Country Link
US (1) US20110018662A1 (fr)
EP (1) EP2457239A1 (fr)
JP (1) JP2013501907A (fr)
KR (1) KR20120041225A (fr)
CN (1) CN102473497A (fr)
AU (1) AU2010275203A1 (fr)
BR (1) BR112012001245A2 (fr)
RU (1) RU2012106080A (fr)
TW (1) TW201120924A (fr)
WO (1) WO2011009904A1 (fr)

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Also Published As

Publication number Publication date
CN102473497A (zh) 2012-05-23
JP2013501907A (ja) 2013-01-17
TW201120924A (en) 2011-06-16
AU2010275203A1 (en) 2011-12-15
BR112012001245A2 (pt) 2016-02-10
KR20120041225A (ko) 2012-04-30
US20110018662A1 (en) 2011-01-27
WO2011009904A1 (fr) 2011-01-27
RU2012106080A (ru) 2013-08-27

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