EP2277180A1 - Procédé de fabrication de matériaux à base de métal pour le refroidissement magnétique ou pour pompes à chaleur - Google Patents

Procédé de fabrication de matériaux à base de métal pour le refroidissement magnétique ou pour pompes à chaleur

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Publication number
EP2277180A1
EP2277180A1 EP09738093A EP09738093A EP2277180A1 EP 2277180 A1 EP2277180 A1 EP 2277180A1 EP 09738093 A EP09738093 A EP 09738093A EP 09738093 A EP09738093 A EP 09738093A EP 2277180 A1 EP2277180 A1 EP 2277180A1
Authority
EP
European Patent Office
Prior art keywords
metal
solid
range
cooling
based material
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.)
Granted
Application number
EP09738093A
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German (de)
English (en)
Other versions
EP2277180B1 (fr
Inventor
Ekkehard BRÜCK
Thanh Trung Nguyen
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.)
Technology Foundation - STW
Stichting voor de Technische Wetenschappen STW
Universiteit Van Amsterdam
Original Assignee
Technology Foundation - STW
Stichting voor de Technische Wetenschappen STW
Universiteit Van Amsterdam
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 Technology Foundation - STW, Stichting voor de Technische Wetenschappen STW, Universiteit Van Amsterdam filed Critical Technology Foundation - STW
Priority to EP09738093.5A priority Critical patent/EP2277180B1/fr
Publication of EP2277180A1 publication Critical patent/EP2277180A1/fr
Application granted granted Critical
Publication of EP2277180B1 publication Critical patent/EP2277180B1/fr
Active 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
    • 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
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1028—Controlled cooling
    • 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
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2200/00—Crystalline structure
    • C22C2200/04—Nanocrystalline
    • 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

Definitions

  • the invention relates to processes for the production of metal-based materials for magnetic cooling or heat pumps, such materials and their use.
  • the materials produced according to the invention are used in magnetic cooling, in heat pumps or air conditioning systems.
  • the magnetic cooling techniques are based on the magnetocaloric effect (MCE) and may be an alternative to the known steam-cycle cooling methods.
  • MCE magnetocaloric effect
  • the alignment of randomly oriented magnetic moments with an external magnetic field results in heating of the material. This heat can be dissipated by the MCE material into the ambient atmosphere through a heat transfer.
  • the magnetic field is then turned off or removed, the magnetic moments revert to a random arrangement, causing the material to cool to below ambient temperature.
  • a heat transfer medium such as water is used for heat removal from the magnetocaloric material.
  • the preparation of conventional materials is carried out by solid phase reaction of the starting materials 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.
  • Such a method is described, for example, in J. Appl. Phys. 99, 2006, 08Q107.
  • the starting elements are first induction-melted in an argon gas atmosphere and then sprayed in the molten state via a nozzle onto a rotating copper roller. This is followed by sintering at 1000 ° C. and slow cooling to room temperature.
  • the materials obtained by the known method often show a large thermal hysteresis.
  • compounds of the Fe 2 P type those with Germanium or silicon are substituted, large values for thermal hysteresis are observed in a wide range of 10 K or more. Thus, these materials are less suitable for magnetocaloric cooling.
  • the object of the present invention is to provide a method for producing metal-based materials for magnetic cooling, which leads to a reduction of the thermal hysteresis. At the same time, preferably a large magnetocaloric effect (MCE) should be achieved.
  • MCE magnetocaloric effect
  • the object is achieved by a method for producing metal-based materials for magnetic cooling or heat pumps, comprising the following steps
  • step d) quenching the sintered and / or tempered solid from step c) with a cooling rate of at least 100 K / s.
  • the thermal hysteresis can be significantly reduced if the metal-based materials are not slowly cooled to ambient temperature after sintering and / or annealing, but are quenched at a high cooling rate.
  • the cooling rate is at least 100 K / s.
  • the cooling rate is preferably 100 to 10,000 K / s, more preferably 200 to 1300 K / s. Especially preferred are cooling rates of 300 to 1000 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. Without being bound by theory, the reduced hysteresis can be attributed to smaller grain sizes for the quenched (quenched) compositions.
  • the rest of the preparation of the metal-based materials is less critical, as long as the quenching of the sintered and / or tempered solid takes place in the last step with the cooling rate of the invention.
  • the method can be applied to the production of any suitable metal-based materials for magnetic cooling.
  • Typical materials for the magnetic cooling are multimetal materials which often contain at least three metallic elements and optionally also non-metallic elements.
  • the term "metal-based materials" indicates that the majority of these materials is 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.
  • step (a) of the method 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 heating the elements and / or alloys together 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).
  • 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.
  • the Meltspinning a high processing speed is achieved because the subsequent sintering and annealing can be shortened. Especially on an industrial scale, the production of metal-based materials becomes much more economical. Spray drying also leads to a high processing speed. Particular preference is given to melt spinning (middle spinning).
  • 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.
  • 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.
  • Formkör- per / solid state sintering is particularly preferably at a temperature in the range 1000 to 1300 0 C, in particular from 1100 to 1300 0 C.
  • the heat can then be effected for example with 600 to 700 0
  • 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.
  • tempering 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 tempering, this results in an extreme time advantage.
  • stage c The sintering / tempering causes the grain boundaries to melt, so that the material continues to densify. By melting and rapid cooling in stage b), the time duration for stage c) can thus be considerably reduced. This also allows for continuous production of the metal-based materials.
  • step b) annealing the solid from step b) for a period of 10 seconds or 1 minute to 5 hours, preferably 30 minutes to 2 hours at a temperature in the range of 430 to 1200, preferably 800 to 1000 0 C.
  • step d) quenching the tempered solid from step c) with a cooling rate of 200 to 1300 K / s.
  • the method of the invention can be used for any suitable metal-based materials.
  • the metal-based material is selected from
  • 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,
  • 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. Preferably, at least 90 wt .-%, more preferably at least 95 wt .-% of C P. Preferred are at least 90 wt .-%, more preferably at least 95 wt .-% 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 MnFePo, 45 to o, 7, Ge o, 5 up to 5 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 . y Ge y 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.yGe 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.
  • compounds of the formula Mnn-xFei- ⁇ Pi y Ge y - z Si z are suitable with x number in the range of 0.3 to 0.5, y in the range of 0.1 to 0.66, z less than or equal to y and less than 0.6.
  • La and Fe-based compounds of the general formulas (II) and / or (III) and / or (IV) are La (Fe o, 9O Si Oi i O) i 3, La (Fe 01 SgSiO 1 Ii) Is, La (Fe 01 Ss 0 Si 01 I 20 ) Is, La (Fe ⁇ i 877Si o , i23) i3, L a F eii i8 Sii i2 , La (Fe ⁇ i 8sSi ⁇ i i2) i3H ⁇ i 5, La (Fe ⁇ i 8sSi ⁇ i i2) i3Hi i ⁇ , LaFeH 17 SiI 13 Hi 1 I, LaFeii i57 Sii i43 Hi i3 , La (Fe ⁇ i88 Si ⁇ i i2) Hi i5 , LaFeH 12 Co 017 SiI 1 I, LaFeH 15 AIi 15 Co 1 I, LaF
  • Suitable manganese-containing compounds are MnFeGe, MnFe 09 Co 0 iGe,
  • suitable Heusler alloys are, for example, Fe 2 MnSi 05 Ge 05, Ni 529 Mn 224 Ga 2417 N i 509 Mn 24 7 Ga 24i4, Ni 55i2 Mn 18 6 Ga 2 6 i2, Ni 51 6 Mn 247 Ga 2318
  • the invention also relates to a metal-based magnetic cooling material obtainable by a method as described above.
  • the invention relates to a metal-based material for magnetic cooling, as defined above by means of the composition, excluding As containing materials, with an average crystallite size in the range of 10 to 400 nm, more 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 becomes too small, the maximum magnetocaloric effect is reduced. if the crystallite size is too large, however, the hysteresis of the system increases.
  • 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 applications are heat pumps and air conditioning systems.
  • the metal-based materials produced by the process according to the invention may have any solid form. They may be present, for example, in the form of flakes, ribbons, wires, powders, as well as in the form of shaped bodies. Shaped bodies such as monoliths or honeycomb bodies can be produced, for example, by a hot extrusion process. For example, cell densities of 400 to 1600 CPI or more may be present. Also obtainable by rolling thin sheets are inventively preferred.
  • Advantageous are non-porous molded body made of molded thin material, eg. As tubes, plates, nets, grids or rods. Shaping by metal injection molding (MIM) is possible according to the invention.
  • MIM metal injection molding
  • Mn 1 1 Feo, 9Po, 8iGeo, i9; M and
  • the observed values for the thermal hysteresis are 7 K, 5 K, 2 K and 3 K for these samples in the order given. Compared to a slowly cooled sample which had a thermal hysteresis of more than 10 K, the thermal hysteresis could be greatly reduced become.
  • the thermal hysteresis was determined in a magnetic field of 0.5 Tesla.
  • Figure 1 shows the isothermal magnetization of Mn 1 , iFe o , 9B o , 78Ge o , 22 in the vicinity of the Curie temperature with increasing magnetic field. A field-induced transient behavior leading to a large MCE is observed for magnetic fields of up to 5 Tesla.
  • the Curie temperature can be adjusted by varying the Mn / Fe ratio and the Ge concentration, as well as the thermal hysteresis value.
  • the change in magnetic entropy calculated from the DC magnetization using the Maxwell relationship for a maximum field change of 0 to 2 Tesla for the first three samples is 14 J / kgK, 20 J / kgK and 12.7 J / kgK, respectively ,
  • the polycrystalline MnFeP (Ge, Sb) alloys were first prepared in a high energy ball mill and by solid phase reaction techniques as described in WO 2004/068512 and J. Appl. Phys. 99.08 Q107 (2006). The pieces of material were then placed in a quartz tube with a nozzle. The chamber was evacuated to a vacuum of 10 "2 mbar and then filled with argon gas of high purity. The samples were melted by high frequency and through the nozzle is sprayed by a pressure difference to a chamber with a rotating copper drum. The surface speed of the copper wheel was set and cooling rates of about 10 5 K / s were achieved, and then the spun ribbons were annealed at 900 ° C. for one hour.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Hard Magnetic Materials (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Abstract

L'invention porte sur un procédé de fabrication de matériaux à base de métal pour le refroidissement magnétique ou pour pompes à chaleur, qui comprend les étapes suivantes : a) réaction en phase solide et/ou en phase liquide des éléments chimiques et/ou des alliages, dans une stoehiométrie qui correspond au matériau à base de métal, b) éventuellement conversion du produit de la réaction de l'étape a) en un solide, c) frittage et/ou recuit du solide provenant de l'étape a) ou b), d) trempe du solide fritté et/ou recuit de l'étape c) avec une vitesse de refroidissement d'au moins 100 K/s.
EP09738093.5A 2008-04-28 2009-04-27 Procédé de fabrication de matériaux à base de métal pour le refroidissement magnétique ou pour pompes à chaleur Active EP2277180B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09738093.5A EP2277180B1 (fr) 2008-04-28 2009-04-27 Procédé de fabrication de matériaux à base de métal pour le refroidissement magnétique ou pour pompes à chaleur

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08155259 2008-04-28
EP09738093.5A EP2277180B1 (fr) 2008-04-28 2009-04-27 Procédé de fabrication de matériaux à base de métal pour le refroidissement magnétique ou pour pompes à chaleur
PCT/EP2009/055024 WO2009133049A1 (fr) 2008-04-28 2009-04-27 Procédé de fabrication de matériaux à base de métal pour le refroidissement magnétique ou pour pompes à chaleur

Publications (2)

Publication Number Publication Date
EP2277180A1 true EP2277180A1 (fr) 2011-01-26
EP2277180B1 EP2277180B1 (fr) 2017-08-09

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Country Status (11)

Country Link
US (1) US20110061775A1 (fr)
EP (1) EP2277180B1 (fr)
JP (1) JP5855457B2 (fr)
KR (1) KR101553091B1 (fr)
CN (1) CN102017025B (fr)
AU (2) AU2009242216C1 (fr)
BR (1) BRPI0911771A2 (fr)
CA (1) CA2721621A1 (fr)
NZ (1) NZ588756A (fr)
TW (1) TWI459409B (fr)
WO (1) WO2009133049A1 (fr)

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KR101553091B1 (ko) 2015-09-14
AU2009242216B2 (en) 2014-03-20
JP5855457B2 (ja) 2016-02-09
NZ588756A (en) 2012-05-25
KR20110036700A (ko) 2011-04-08
AU2009242216A1 (en) 2009-11-05
TWI459409B (zh) 2014-11-01
BRPI0911771A2 (pt) 2015-10-06
TW201009855A (en) 2010-03-01
CN102017025A (zh) 2011-04-13
CN102017025B (zh) 2014-06-25
AU2009242216C1 (en) 2014-09-04
CA2721621A1 (fr) 2009-11-05
EP2277180B1 (fr) 2017-08-09
US20110061775A1 (en) 2011-03-17
JP2011523676A (ja) 2011-08-18
AU2014203376A1 (en) 2014-07-10
WO2009133049A1 (fr) 2009-11-05

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