WO2004068512A1

WO2004068512A1 - A magnetic material with cooling capacity, a method for the manufacturing thereof and use of such material

Info

Publication number: WO2004068512A1
Application number: PCT/NL2003/000059
Authority: WO
Inventors: Ekkehard Hubertus BRÜCK; Ojiyed Tergusi; Frank Roelof De Boer
Original assignee: Stichting Voor De Technische Wetenschappen; Universiteit Van Amsterdam, Faculteit Der Natuurwetenschappen, Wiskunde En Informatica
Priority date: 2003-01-29
Filing date: 2003-01-29
Publication date: 2004-08-12
Also published as: ATE361535T1; EP1599884B1; US20060117758A1; ES2286514T3; CA2514773C; AU2003303840A8; JP4663328B2; DK1599884T3; DE60313671D1; BR0318065A; CA2514773A1; SI1599884T1; EP1599884A1; BR0318065B1; AU2003303840A1; US8211326B2; JP2006514158A; DE60313671T2

Abstract

The invention relates to a material that can be used for magnetic refrigeration, wherein the material substantially has the general formula (AYB1-Y) 2+δ CWDXEZ Wherein: A is selected from Mn and Co; B is selected from Fe and Cr; of C, D and E at least two are different, have a non-vanishing concentration and are selected from P, B, Se, Ge, Ga, Si, Sn and Sb; wherein at least one of C, D and E is Ge or Si; W, X, Y and Z each is a number in the range 0-1, and W+X+Z=1; and δ is a number from (-0.1) - (+0.1).

Description

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.

Such a material is known, for example, from the review "Recent Developments in Magnetic Refrigeration" by K.A. Gschneidner Jr. et al . in Materials Science Forum

Vols. 315-317 (1999), pp. 69-76. This article reports that a search for new materials with improved magnetocaloric properties has led to the discovery of a strong magneto- caloric effect (MCE) in Gd metal and in Gds (Si_xGeι-_x) ₄ alloys, among which Gd5(Si₂Ge2).

Such new materials make it possible to use magnetic refrigeration (MR) in refrigerated storage and refrigerated transportation of food, air conditioning in buildings and vehicles, etc. A great advantage of magnetic refrigeration is that it is an environmentally safe technology that does not use ozone layer-depleting chemicals such as CFC's, hazardous chemicals such as NH₃, greenhouse gasses, etc. Moreover, because of the expected energy-efficiency, the amount of energy consumed and consequently the emission of C0₂ will be reduced.

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 (SiχGeι-χ) 4 alloys are very expensive, which hinders their use on a large scale.

There is a continuous need for new materials that are useful for magnetic refrigeration.

It is an object of the present invention to avoid the above-mentioned draw-back and to fill the aforementioned need. According to the present invention, this goal is achieved with a material according to the preamble, wherein the material substantially has the general formula

(AyBl-y) 2+δCwD_XEz wherein :

A is selected from Mn and Co; B is selected from Fe and Cr; of C, D and E at least two are different, have a non-vanishing concentration and are selected from P, B, Se, Ge, Ga, Si, Sn, N and Sb; wherein at least one of C, D and E is Ge or Si; w, x, y and z each denotes a concentration and is a number in the range 0 - 1, and w + x + z = l; and δ is a number from (-0.1) - (+0.1). With such a composition it is possible to vary the working point from cryogenic temperatures to above room temperature. Furthermore, depending on the ^'composition, with these alloys one can obtain a magnetocaloric effect that is stronger than that obtained with pure Gd. This is absolutely unexpected, because the magnetic moments of Gd-materials are by a factor of 2 greater than those of transition metal alloys, for which reason strong magnetocaloric effects are only expected in Gd-materials. 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.

It is preferred that C, D and E are identical or different and are selected from at least one of P, Ge, Si, Sn and Ga.

Preferably in the material according to the present invention is that 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.

According to a further preferred embodiment, the material has the general formula MnFe (P_wGe_xSi_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.

Favourable results are also obtained when x is a number in the range from 0.3 - 0.7, w ≤ 1-x and z = 1-x-w. It is especially preferred that the material ac- cording to the invention is in the hexagonal Fe₂P structure.

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_yBι_ y)2+δC_wD_xE_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. Especially an alloy of the composition MnFeP_wGe_xSi_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. This is contrary to the general expectation because based on the usual models, strong magnetocaloric effects are only expected in rare earth materials, as the magnetic moments in these materials are by a factor 2 or even more greater than in transition metal alloys. However, those models apply only at low temperatures. At room temperature a stronger magnetocalo- ric effect may occur in suitable alloys based on transition metals according to the invention.

It has been shown that if the above-mentioned materials are prepared starting out from the pure materials Ge or Si, P, Fe and Mn, wherein part of Ge, or all of Ge, is replaced by Sn or Ga, the resulting materials do indeed also exhibit a strong magnetocaloric effect.

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) .

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.

It is also preferable for the molten powder mixture to be annealed at a temperature in the 750 - 900°C range, e.g. 780°C. This results in a low concentration gradient in the material. Finally, 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.

The method according to the present invention will now be further elucidated with reference to a non- limiting exemplary embodiment.

Example 1

An alloy of 5g FeMnPo,7Geo.a, with a critical temperature of about 350 K is obtained by mixing the pure elements, having a quality of 3N, in the following amounts: Fe = l,81g, Mn = l,78g, P = 0,703g and Ge = 0,706g. In a closed ball mill, 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.

Example 2

An alloy of 5g FeMnPo,sGeo,5, having a critical temperature of about 600 K is obtained by mixing the pure elements, having a quality of 3N, in the following amounts: Fe = l,72g, Mn = l,69g, P = 0,476g and Ge = l,12g. In a closed ball mill, 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.

Example 3

An alloy of 5g FeMnPo,sGeo,ιSio,4 having a critical temperature of about 300 K is obtained by mixing the pure elements, having a quality of 3N, in the following amounts : Fe = l,93g, Mn = l,90g, P = 0,535, Ge = 0,251g and Si = 0,388g. In a closed ball mill, 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 alloys obtained by the fore-mentioned examples 1, 2 and 3 all crystallise in a hexagonal Fθ2P structure. The alloy of Example 3 has a high magnetocaloric effect at and near the critical temperature, as shown in the appended Figure 1.

A partial replacement of Ge by Sn or Ga is also possible, wherein alloys are obtained having a magmeto- caloric effect as indicated in the examples 1, 2 and 3.

Example 4

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.

An alloy of lOg Feo,86Mnι,ι₄Po,5Sio,₃5Geo,i5 having a critical temperature of 390 K is obtained, by mixing the pure elements having a quality of 3N and the alloy Fe₂P having a quality of 2N (Alpha Aesar 22951) , in the following amounts: Fe₂P = 4,18g, Mn = 4,26g, P = 0,148g, Si = 0,669 g and Ge = 0,742g. In a closed ball mill 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 is obtained within 20 minutes until a few hours. The powder is subsequently heated (sintered) 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 present invention is not limited to the embodiment shown in the figures and described in the exemplary embodiment. The amounts may be varied in numerous ways within the scope of protection established by the claims .

Claims

1. A material that can be used for magnetic refrigeration, characterized in that the material substantially has the general formula

(AyB_l-y) 2 + δC_wD_XE_z wherein :

A is selected from Mn and Co; B is selected from Fe and Cr; of C, D and E at least two are different, have a non-vanishing concentration and are selected from P, B, Se, Ge, Ga, Si, Sn, N and Sb; wherein at least one of C, D and E is Ge or Si; w, x, y and z each denotes a concentration and is a number in the range 0 - 1, and w + x + z = 1; and δ is a number from (-0.1) - (+0.1).

2. A material according to claim 1, characterized in that C, D and E are identical or different and are selected from at least one of P, Ge, Si, Sn and Ga.

3. A material according to claim 1, characterized in that 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.

4. A material according to any of the preceding claims, characterized in that the material has the general formula MnFe (P_wGe_xSi_z) .

5. A material according to any of the preceding claims, characterized in that x is a number in the range of from 0.3 - 0.7, w ≤ 1-x and z = 1-x-w.

6. A material according to any of the preceding claims, characterized in that it is in the crystalline hexagonal Fe₂P structure.

7. A method- for the manufacture of the material according to any of claims 1-6, 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_yBι-_y) 2+δC_wD_xE_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.

8. A method according to claim 7, characterized in that the sintering step substantially takes at least one hour and the annealing step takes substantially at least 24 hours.

9. A method according to any of claims 7 and 8, characterized in that the starting materials are mixed in quantities such as to provide a composition having the formula according to claim 1, preferably having the formula MnFePo.45-0.7oGeo.55-0.30 and more preferably having the formula MnFePo.5-0.70 (Si/Ge) 0.5-0.30.

10. A method according to any of claims 7-9, characterized in that prior to the sintering step, the powder mixture is compressed to a desired shape, for example a pill or the like.

11. A method according to any of claims 7-10, characterized in that the inert atmosphere is an argon atmosphere.

12. Application of the material according to any of claims 1-6 with magnetic refrigeration in the 200-600 K range, preferably 280 - 500 K.