EP2137742A1 - Nouveaux composés intermétalliques, leur utilisation et leur procédé de préparation - Google Patents

Nouveaux composés intermétalliques, leur utilisation et leur procédé de préparation

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Publication number
EP2137742A1
EP2137742A1 EP08718355A EP08718355A EP2137742A1 EP 2137742 A1 EP2137742 A1 EP 2137742A1 EP 08718355 A EP08718355 A EP 08718355A EP 08718355 A EP08718355 A EP 08718355A EP 2137742 A1 EP2137742 A1 EP 2137742A1
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European Patent Office
Prior art keywords
chosen
comprised
magnetocaloric
group
rare earth
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EP08718355A
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German (de)
English (en)
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Thomas Mazet
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Universite de Lorraine
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Universite Henri Poincare Nancy I
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Priority to EP08718355A priority Critical patent/EP2137742A1/fr
Priority claimed from PCT/EP2008/053807 external-priority patent/WO2008122535A1/fr
Publication of EP2137742A1 publication Critical patent/EP2137742A1/fr
Withdrawn legal-status Critical Current

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Definitions

  • the present invention relates to new intermetallic compounds, their use and a process for preparing the same.
  • the magnetic refrigeration is expected to become competitive with conventional gas compression in a near future because of its higher efficiency and its lower environmental impact (Gschneidner K. A. et al, Annu. Rev. Mater. ScL, 30, 387, 2000; Tishin A. M. et al, The magnetocaloric effect and its applications, Institute of physics Publishing, Bristol, 2003; Gschneidner K. A. et al., Rep. Prog., Phys. 68, 1479, 2005) and the magnetocaloric effect (MCE), widely speaking the adiabatic temperature change (AT ac ⁇ ) or the isothermal magnetic entropy change (AS M ) of a solid in a varying magnetic field, is the heart of this cooling technique.
  • AT ac ⁇ adiabatic temperature change
  • AS M isothermal magnetic entropy change
  • Giant magnetocaloric properties are generally connected to first-order magnetic transitions (FOMT) which yield an intense but sharp response by opposition with the broader and less intense peak produced by second-order magnetic transitions (SOMT).
  • the phase transition can be a first-order phase transition which exhibits a discontinuity in the first derivative of the free energy with a thermodynamic variable, or a second-order phase transition which have a discontinuity in a second derivative of the free energy.
  • US patent N° 5,362,339 discloses magnetocaloric compounds having the following general formula Ln 3 A b M c wherein Ln is a rare earth element selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb, A is Al or Ga and M is selected from the group consisting of Fe, Co, Ni, Cu and Ag.
  • magnetocaloric compounds have two major drawbacks, a high cost due to the presence of expensive elements such as Gd and a temperature of use which is too low to be applicable near or above room temperature, i.e. from about 200 to about 600K.
  • the temperature of use is too limited and not compatible with various industrial systems. Furthermore, at the transition phase in La(Fe,Si)i3 type of alloys, a volume change of 1,5% is also observed (Wang et al, J. Phys. Condens Matter, 15, 5269- 5278, 2003). If this volume change is performed very frequently the material definitely becomes very brittle and may break into even smaller grains. This can have a distinct influence on the corrosion resistance of the material and thus on the life time of a refrigerator (Briick E., J. Phys. D: Appl. Phys. 38, R381-R391, 2005). The only way to circumvent this limited temperature of use is to make a composition comprising two compounds having different transitions temperatures and therefore leading to a broadened temperature of use.
  • intermetallic manganese(Mn)-based compounds are now especially studied because they often order near or above room temperature and are comparatively cheap.
  • the more outstanding behaviours have been found in FeMnP 1-x As x (WO 2003/012801, WO 2004/068512) and MnAsi_ x Sb x (WO 03/009314) that exhibit a GMCE comparable to that of Gd 5 Si 2 Ge 2 around room temperature.
  • MnAsi_ x Sb x WO 03/009314
  • the hysteresis loss i.e. systems that do not return completely to their original state: that is, systems the states of which depend on their immediate history, is a phenomena inherent in FOMT magnetic and ferromagnetic materials.
  • FOMT fast-cycling refrigerators
  • the slow kinetic also inherent in FOMT, may reduce the actual efficiency of the GMCE materials in fast-cycling refrigerators (Gschneidner K. A. et al., Rep. Prog., Phys. 68, 1479, 2005; Provenzano V. et al., Nature, 429, 853, 2004).
  • one of the subjects of the invention is to provide magnetic compounds, being in the form of an alloy, allowing a temperature of use greatly increased, presenting no hysteresis loss and having an almost constant response over the overall temperature use, i.e. near the room temperature, as a magnetocaloric agent, in particular for magnetic refrigeration.
  • Another subject of the invention is to provide compositions of magnetic compounds wherein the association of two magnetic compounds yield to a larger temperature span, allowing their uses in various refrigeration systems.
  • Another subject of the invention is to provide a process of preparation of magnetic compounds.
  • the present invention relates to the use of at least one compound having the following general formula (I) and a crystalline structure of Ni 3 Sn 2 type:
  • T and T' are chosen among: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu,
  • X and X' are chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x, x', y and y' are comprised from 0 to 1, x + x' ⁇ 0.5, y + y' ⁇ 0.5, and x + x'+ y + y' ⁇ 1, as a magnetocaloric agent, in particular for magnetic refrigeration.
  • the compounds of formula (I) used herein are in the form of alloys.
  • magnetocaloric agent it is meant a compound able to exercise a magnetocaloric effect (MCE) such as defined above.
  • magnetic refrigerant refrigerant material
  • magnetic material magnetocaloric material
  • magnetocaloric agent magnetocaloric compound
  • This temperature change, ⁇ r a d (or variation of the adiabatic temperature) is usually called "MCE” and reach maxima (or minima) at the transition temperature (i.e. the Curie temperature, the temperature where the material undergoes a change from a paramagnetic state to a ferromagnetic state).
  • the "transition temperature” or the phase transition or magnetic phase transition or phase change is the transformation of a thermodynamic system from one phase to another at a temperature change called Tc (also referred to peak herein) and at a maximum isothermal magnetic entropy change called - ASTM X .
  • the alloys have a crystalline structure of Ni 3 Sn 2 type, i.e. orthorhombic Pnma, they exhibit at least two ferromagnetic transitions (Tci and Tc 2 ), each of them being a second-order magnetic transition (SOMT), therefore leading to an almost constant magnetocaloric response over a larger temperature range of use (or a temperature span), near the room temperature, and presenting no hysteresis loss.
  • SOMT second-order magnetic transition
  • the temperature span depends on the location of the two second-order peaks (Tci and Tc 2 ) and on the distance between said two peaks.
  • the occurrence of two magnetic entropy change maxima is not a common event, especially in the temperature range from 200K to 300K.
  • giant magnetocaloric properties are generally connected to first-order magnetic transitions (FOMT) which yield an intense but sharp response by opposition with the broader and less intense peak produced by second-order magnetic transitions (SOMT).
  • FOMT first-order magnetic transitions
  • SOMT second-order magnetic transitions
  • Another advantage of the invention is the low cost and the great availability of the major constituents, i.e. Mn and Sn of the compounds.
  • Still another advantage of the invention consists in the opportunity to obtain variations of Tci and Tc 2 in function of the chemical replacement of a part of Mn by T and T' and/or a part of Sn by X and X' and the respective proportion of T, T', X, X', leading thus to magnetocaloric materials adapted to various uses.
  • the invention relates to the use of at least one of the above defined compounds, said compound comprising at least two phase transitions, each of them being of second order and constituting a peak.
  • the invention relates to the use of at least one of the above defined compounds having the following general formula (I) and a crystalline structure of Ni 3 Sn 2 type: in which :
  • T and T' are chosen among: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd,
  • X and X' are chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x, x', y and y' are comprised from O to 1, and x, x', y and y' are all different from O, x + x' ⁇ 0.5, y + y' ⁇ 0.5, and x + y ⁇ l, as a magnetocaloric agent, in particular for magnetic refrigeration.
  • the compounds of formula (I) are alloys comprising six element. According to a more preferred embodiment, the invention relates to the use of at least one of the above defined compounds having the following general formula (II) and a crystalline structure of Ni 3 Sn 2 type:
  • T and T' are chosen among: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu, X is chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x, x', and y are comprised from 0 to 1, and x, x', y are all different from 0, x + x' ⁇ 0.5 and x + y ⁇ 1, as a magnetocaloric agent, in particular for magnetic refrigeration. Therefore, the compounds of formula (II) are alloys comprising five elements. According to another preferred embodiment, the invention relates to the use of at least one of the above defined compounds having the following general formula (III) and a crystalline structure OfNi 3 Sn 2 type:
  • T is chosen among: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd,
  • X and X' are chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x, y and y' are comprised from O to 1, x + x' ⁇ 0.5, y + y' ⁇ 0.5, and x + y ⁇ 1, and x, y, y' are all different from 0, as a magnetocaloric agent, in particular for magnetic refrigeration.
  • the compounds of formula (III) are alloys comprising five elements.
  • the invention relates to the use of at least one of the above defined compounds having the following general formula (IV) and a crystalline structure OfNi 3 Sn 2 type: Mn 3-x T x Sn 2-y X y (IV) in which :
  • T is chosen among: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu,
  • X is chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x and y are comprised from O to 1, x + y ⁇ 1, as a magnetocaloric agent, in particular for magnetic refrigeration.
  • the compounds of formula (IV) are alloys comprising four, three or two elements, depending of the value of x and y.
  • the invention relates to the use of at least one of the above defined compounds having the following general formula (IV) and a crystalline structure of Ni 3 Sn 2 type:
  • T is chosen among: Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu
  • X is chosen among: Ga, Ge, In, Al, Cd, C, Si, x and y are comprised from O to 1 , x + y ⁇ 1 ; and x + y is different from O, as a magnetocaloric agent, in particular for magnetic refrigeration. Therefore, the compounds of formula (IV) are alloys comprising four or three elements, depending of the value of x and y. According to a more preferred embodiment, the invention relates to the use of at least one of the above defined compounds having the following general formula (IV) and a crystalline structure OfNi 3 Sn 2 type:
  • T is chosen among: Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu
  • X is chosen among: Ge, In, Al, Cd, C, Si, x and y are comprised from O to l x + y ⁇ l; and x + y is different from O, as a magnetocaloric agent, in particular for magnetic refrigeration. Therefore, the compounds of formula (IV) are alloys comprising four or three elements, depending of the value of x and y.
  • the invention relates to the use of at least one of the above defined compounds having the following general formula (IV) and a crystalline structure of Ni 3 Sn 2 type:
  • T is chosen among: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu
  • X is chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x and y are comprised from O to 1, x and y are different from O, and x + y ⁇ 1, as a magnetocaloric agent, in particular for magnetic refrigeration.
  • the compounds of formula (IV) are alloys comprising four elements.
  • the invention relates to the use of at least one of the above defined compounds having the following general formula (V) and a crystalline structure OfNi 3 Sn 2 type: Mn 3-x T x Sn 2 (V) in which :
  • T is chosen among: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu, in particular Zr, Hf, Nb, Mo or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy,
  • the compounds of formula (V) are alloys comprising three elements.
  • the invention relates to the use of at least one of the above defined compounds having the following general formula (VI) and a crystalline structure OfNi 3 Sn 2 type:
  • X is chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, in particular Ga, Ge, In, Al,
  • the compounds of formula (VI) are alloys comprising three elements.
  • the invention relates to the use of the above defined compound having the formula Mn 3 Sn 2 and a crystalline structure of Ni 3 Sn 2 type as a magnetocaloric agent, in particular for magnetic refrigeration.
  • Mn 3 Sn 2 has crystalline structure Of Ni 3 Sn 2 type, i.e. an orthorhombic Pnma structural type.
  • the orthorhombic structure Of Mn 3 Sn 2 is represented in figure 3.
  • Mn 2 _ z Sn is a compact hexagonal stack of Sn atoms in which octahedral sites and a part of bipyramidal sites are occupied by manganese atoms. This structure is intermediate between NiAs a Ni 2 In in which bipyramidal sites are respectively empty or full (figure 4).
  • the invention relates to the use of at least one of the above defined compounds wherein the cooling capacity q for a magnetic field applied from more than 0 to about 5T is comprised from about 50 mJ/cm to about 5000 mJ/cm 3 particularly from about 100 mJ/cm 3 to about 4000 mJ/cm 3 , more particularly from about 500 mJ/cm 3 to about 3000 mJ/cm 3 and more particularly from about 1000 mJ/cm 3 to about 2000 mJ/cm 3 .
  • the refrigerant capacity (RC) of a magnetic refrigerant that is the amount of heat which can be transferred in one thermodynamic cycle
  • RC refrigerant capacity
  • the maximum refrigerant capacity (MRC) is reached when -AS m AT cyc ⁇ is maximized, thus defining the hot and cold temperatures for which the material is the most effective (figure 1).
  • the refrigerant capacity (RC) which also takes into account the width and shape of AS M VS T curves, is a more relevant parameter when evaluating the technological interest of a refrigerant material. Based on this criterion, the gap between FOMT and SOMT materials becomes less impressive.
  • the refrigerant capacity of the above defined compounds has been determined by the above described method 1) and corresponds therefore to the cooling capacity q.
  • Figure 5 represents the results obtained with the three methods for M ⁇ Sn 2 and others magnetic refrigerants like Gd, Gd 5 Si 2 Ge 2 .
  • the invention relates to the use of at least one of the above defined compounds wherein the variation of the magnetic entropy (- ⁇ S M ) versus the temperature for a magnetic field applied from more than 0 to about 5T is comprised from about 5 mJ/cm 3 /K to about 100 mJ/cm 3 /K particularly between 10 mJ/cm 3 /K to about 50 mJ/cm 3 /K, more particularly from about 15 mJ/cm 3 /K to about 40 mJ/cm 3 /K and more particularly from about 20 mJ/cm /K to about 30 mJ/cm /K.
  • the invention relates to the use of at least one of the above defined compounds wherein the variation of the adiabatic temperature
  • ( ⁇ T a d) for a magnetic field applied from more than 0 to about 5T is comprised from about 0.5
  • K to about 10 K particularly from about 1 K to about 5 K and more particularly from about 1.5 K to about 3K.
  • the invention relates to the use of at least one of the above defined compounds comprising two peaks which are in a temperature range from about 50 K to about 550 K, particularly from about 100 K to about 400 K, more particularly from about 150 K to about 350 K and more particularly from about 200 K to about 300 K.
  • one of the advantages of the Invention is to provide compounds having a temperature span broadened due to the presence of two transitions peaks.
  • Figure 6 represent the variation of entropy versus the temperature of Mn 3 Sn 2 (upper slide) and Gd 5 Si 2 Ge 2 (US patent N° 6,589,366, lower slide).
  • the temperature span OfMn 3 Sn 2 is broadened by comparison with compounds with a giant effect like Gd 5 Si 2 Ge 2 (and the other FOMT) which extends no more than ⁇ 25 K from Tc.
  • the invention relates to the use of at least one compound wherein the temperature range between at least two adjacent peaks and particularly between all the adjacent peaks is comprised from about 50 K to about 100 K.
  • the difference of temperature is comprised from about 50 K to about 100 K.
  • Ti-Tc 2 (TCi-Tc 2 ) between two adjacent peaks must be comprised from about 5OK to about 10OK.
  • the difference of temperature is lower than 5OK, it does not provide a temperature of use sufficient to be adapted to various refrigerant systems. If the gap is more than 10OK, the compound becomes uninteresting because the response is no more constant.
  • the invention relates to a composition having the following general formula (VII): (A , B) (VII) in which:
  • A is at least one the above defined compounds
  • B is at least a second magnetocaloric material having a transition peak comprised from about 290 to about 340 K chosen from the group consisting of Gd, MgMn 6 Sn 6 ,
  • a composition can be made consisting in a mixture of at least one compound A and a material B, in order to still broaden the temperature span of the compounds A defined above.
  • B can be any identified material already known presenting at least a transition peak in the temperature range 290-340K, and particularly Gd, MgMn 6 Sn 6 , Mn 4 Ga 2 Sn, Gd 5 Si 2 Ge 2 , MnFePAs;
  • A is working in the low temperature range (200K - 290K) and B is working in the high temperature range (290K-340K).
  • the B material can be a FOMT or SOMT material.
  • composition can be made with a mixture of the powders of compound A and material B or a multi layer mixture of each constituent.
  • the invention relates to one of the above defined compositions wherein the ratio (w/w) between A and B is from about 0.01 to about 99, particularly from about 0.1 to about 10 and more particularly from about 0.5 to about 5.
  • the intensity of the magnetic entropy is proportional to the quantity of each compound. Therefore, the ratio OfMn 3 Sn 2 and MgMn 6 Sn 6 being 50/50 (w/w), the - ⁇ S M value of the three peaks has been lowered by a factor 2 (approximately 17 and 14 for Tci and Tc 2 respectively instead of approximately 30mJ/cm 3 /K (Tci and Tc 2 ) for Mn 3 Sn 2 and
  • the invention relates to the use of one of the above defined compositions wherein the cooling capacity q for a magnetic field applied from about 0 to about 5T is comprised from about 50 mJ/cm 3 to about 5000 mJ/cm 3 particularly from about 100 mJ/cm 3 to about 4000 mJ/cm 3 , more particularly from about 500 mJ/cm 3 to about 3500 mJ/cm 3 and more particularly from about 1000 mJ/cm 3 to about 3000 mJ/cm 3 .
  • the invention relates to the use of one of the above defined compositions wherein said peaks are in a temperature range from about 50 K to about 600 K, particularly from about 100 K to about 500 K, more particularly from about 150 K to about 400 K and more particularly from about 200 K to about 350 K.
  • compositions of the invention are to broaden the temperature of use of said compositions in comparison to the existing materials B or the compounds A defined above taken alone, while lowering the cost of the composition thanks to the lower quantity of material B introduced.
  • the invention relates to the use of at least one of the above defined compositions wherein the temperature range between at least two adjacent peaks and particularly between all the adjacent peaks is comprised from about 50 K to about 100 K.
  • the invention relates to a magnetocaloric material having the following general formula (I) and a crystalline structure of Ni 3 Sn 2 type: in which :
  • T and T' are chosen among: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd,
  • X and X' are chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x, x', y and y' are comprised from 0 to 1, x + x' ⁇ 0.5, y + y' ⁇ 0.5, and x + x'+ y + y' ⁇ 1, provided that x + x'+ y + y' are different from 0.
  • the invention relates to one of the above defined magnetocaloric materials having the following general formula (I): in which :
  • T and T' are chosen among: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu,
  • X and X' are chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x, x', y and y' are comprised from 0 to 1, x + x' ⁇ 0.5, y + y' ⁇ 0.5, x + x'+ y + y' ⁇ 1, and x, x', y and y' are all different from 0.
  • the compounds of formula (I) are alloys comprising six elements.
  • the invention relates to one of the above defined magnetocaloric materials having he following general structure (II):
  • T and T' are chosen among: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd,
  • X is chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x, x', and y are comprised from 0 to 1, x + x' ⁇ 0.5, x + y ⁇ 1, and x, x', y are all different from 0. Therefore, the compounds of formula (II) are alloys comprising five elements.
  • the invention relates to one of the above defined magnetocaloric materials having he following general structure (III):
  • T is chosen among: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu, X and X' are chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x, y and y' are comprised from 0 to 1, x + x' ⁇ 0.5, y + y' ⁇ 0.5, x + y ⁇ 1, and x, y ,y' are all different from 0. Therefore, the compounds of formula (III) are alloys comprising five elements. According to another preferred embodiment, the invention relates to one of the above defined magnetocaloric materials having
  • T is chosen among: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu
  • X is chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x and y are comprised from O to 1 , x + y ⁇ 1, Therefore, the compounds of formula (IV) are alloys comprising four, three or two elements.
  • the invention relates to one of the above defined magnetocaloric materials having the following general formula (IV):
  • T is chosen among: Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu,
  • X is chosen among: Ga, Ge, In, Al, Cd, C, Si, x and y are comprised from O to 1 , x + y ⁇ 1 ; provided that x + y is different from 0. Therefore, the compounds of formula (IV) are alloys comprising four or three elements.
  • the invention relates to one of the above defined magnetocaloric materials having the following general formula (IV):
  • T is chosen among: Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu, X is chosen among: Ge, In, Al, Cd, C, Si, x and y are comprised from O to l x + y ⁇ l; provided that x + y is different from O. Therefore, the compounds of formula (IV) are alloys comprising four or three elements.
  • the invention relates to one of the above defined magnetocaloric materials having the following general formula (IV):
  • T is chosen among: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu
  • X is chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x and y are comprised from 0 to 1, x and y are different from 0, and x + y ⁇ 1. Therefore, the compounds of formula (IV) are alloys comprising four elements.
  • the invention relates to one of the above defined magnetocaloric materials having the following general formula (V):
  • T is chosen among:Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu, in particular Zr, Hf, Nb, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu, Therefore, the compounds of formula (V) are alloys comprising three elements. According to another preferred embodiment, the invention relates to one of the above defined magnetocaloric materials having the following general formula (VI) and a crystalline structure of Ni 3 Sn 2 type:
  • X is chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, in particular Ga, Ge, In, Al,
  • the compounds of formula (VI) are alloys comprising three elements.
  • the invention relates to one of the above defined magnetocaloric materials wherein the phase transition of said magnetocaloric material comprising at least two phase transitions, each of them being of second order and constituting a peak.
  • the invention relates to one of the above defined magnetocaloric materials wherein the cooling capacity for a magnetic field applied from 0 to about 5T is comprised from about 50 mJ/cm 3 to about 5000 mJ/cm 3 particularly from about 100 mJ/cm 3 to about 4000 mJ/cm 3 , more particularly from about 500 mJ/cm 3 to about 3000 mJ/cm 3 and more particularly from about 1000 mJ/cm 3 to about 2000 mJ/cm 3 .
  • the invention relates to one of the above magnetocaloric materials wherein the variation of the magnetic entropy (- ⁇ S M ) versus the temperature for a magnetic field applied from more than 0 to about 5T is comprised from about 5 mJ/cm 3 /K to about 50 mJ/cm 3 /K particularly between 10 mJ/cm 3 /K to about 40 mJ/cm 3 /K, more particularly from about 15 mJ/cm 3 /K to about 35 mJ/cm 3 /K and more particularly from about 20 mJ/cm 3 /K to about 30 mJ/cm 3 /K.
  • the invention relates to one of the above above defined magnetocaloric material wherein the variation of the adiabatic temperature
  • ( ⁇ T a d) for a magnetic field applied from 0 to about 5T is comprised from about 0.5 K to about 5 K, particularly from about 1 K to about 4 K and more particularly from about 1.5 K to about 3 K.
  • the invention relates to one of the above magnetocaloric materials wherein said two peaks are in a temperature range from about 50 K to about 550 K, particularly from about 100 K to about 400 K, more particularly from about 150 K to about 350 K and more particularly from about 200 K to about 300 K.
  • the invention relates to one of the above magnetocaloric materials wherein the temperature range between at least two adjacent peaks and particularly between all the adjacent peaks is comprised from about 50 K to about 100 K.
  • the invention relates to one of the above magnetocaloric material chosen from the group consisting of:
  • Mn 3 _ x Zn x Sn 2 _ y Sb y wherein 0 ⁇ x ⁇ 0.5 and 0 ⁇ y ⁇ 0.5.
  • y P y ' wherein 0 ⁇ x ⁇ 0.5 and 0 ⁇ y ⁇ 0.5, and 0 ⁇ y' ⁇ 0.5
  • the invention relates to one of the above magnetocaloric materials chosen from the group consisting of: Mn 3 _ x Fe x Sn 2 where 0 ⁇ x ⁇ 0.5, Mn 3 _ x Cu x Sn 2 where 0 ⁇ x ⁇ 0.1 ,
  • Mn 3 _ x Co x Sn 2 where 0 ⁇ x ⁇ 0.5, Mn 3 _ x Ni x Sn 2 where 0 ⁇ x ⁇ 0.5, Mn 3 Sn 2 _ y Ga y where 0 ⁇ y ⁇ 0.1 , Mn 3 Sn 2 - y Ge y where 0 ⁇ y ⁇ 0.5, Mn 3 _ x Nb x Sn 2 where 0 ⁇ x ⁇ 0.5, Mn 3 . x Y x Sn 2 where 0 ⁇ x ⁇ 0.5.
  • the invention relates to a magnetocaloric composition having the following general formula (VII):
  • A is at least one of the above defined compounds
  • B is at least a second magnetocaloric material having a transition peak comprised from about 290 to about 340 K chosen from the group consisting of Gd, MgMn 6 Sn 6 , Mn 4 Ga 2 Sn, Gd 5 Si 4 -ZGeZ 1 Gd 5 (SiLzGeZ) 4 , MnFePi_ z As z , z is comprised from 0 to 1.
  • the invention relates to the use of a magnetocaloric composition wherein the ratio (w/w) between A and B is from about 0.01 to about 99, particularly from about 0.1 to about 10, and more particularly from about 0.5 to about 5.
  • the invention relates to the use of one of the above defined magnetocaloric composition chosen from the group consisting of:
  • Mn 3 Sn 2 and Gd Mn 3 Sn 2 and MgMn 6 Sn 6 , Mn 3 Sn 2 and Mn 4 Ga 2 Sn, Mn 3 Sn 2 and Gd 5 Si 4 -ZGeZ 1 Gd 5 (SiLzGeZ) 4 , Mn 3 Sn 2 and MnFePi_ z As z ,
  • Mn 3 _ x Fe x Sn 2 and Gd Mn 3 _ x Fe x Sn 2 and MgMn 6 Sn 6 , Mn 3 _ x Fe x Sn 2 and Mn 4 Ga 2 Sn, Mn 3 _ x Fe x Sn 2 and GdsSLt-zGez, Mn 3 _ x Fe x Sn 2 and Gd 5 (Sii_ z Ge z ) 4 , Mn 3 Sn 2 and MnFePi. zASz, x being as above defined above.
  • the invention also relates to a process of preparation of the compound of formula (I) having a crystalline structure OfNi 3 Sn 2 type Mn 3-(X+X > ) T X T VSn 2 W) X y XV (I) in which :
  • T and T' are chosen among: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu, X and X' are chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x , x', y and y' are comprised from 0 to 1, x + x' ⁇ 0.5, y + y' ⁇ 0.5, and x + x'+ y + y' ⁇ 1, comprising at least a step of annealing, at a temperature below 480 0 C, preferably from about 450 0 C to about 480 0 C, a homogenized mixture prepared by sintering a mixture of the elements Mn, T, T', Sn,
  • the sintering step is carried out to combine and homogenize the mixture of the elements.
  • the invention relates to a process of preparation of the compound of formula (I) having a crystalline structure OfNi 3 Sn 2 type
  • T and T' are chosen among: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu,
  • X and X' are chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x, x', y and y' are comprised from 0 to 1, x + x' ⁇ 0.5, y + y' ⁇ 0.5, and x + x'+ y + y' ⁇ 1, comprising one step of annealing, at a temperature below 480 0 C, preferably from about 450 0 C to about 480 0 C, a homogenized mixture prepared by sintering a mixture of the elements Mn, T, T', Sn, X and X', in an appropriate amount, T, T', X and X' being as above defined, in particular pure elements, at a temperature range from 300 to 600 0 C.
  • the invention relates to a process of preparation to obtain a compound of formula (I) in which: T and T' are chosen among: Zr, Hf, Nb, Mo, X and X' are chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x and y are comprised from 0 to 1 and x + y ⁇ 1 ; comprising a first step of annealing a homogenized mixture of the elements Mn, T, T', Sn, X and X', in an appropriate amount, at a temperature from about 550 0 C to about 850 0 C, particularly at a temperature from about 600 0 C to about 800 0 C and more particularly from 650 0 C to about 750 0 C, and a second step of annealing at a temperature below 480 0 C, preferably from about 450 0 C to about 480 0 C, said homogenised mixture being prepared by sintering a mixture of
  • the invention relates to a process of preparation wherein said homogenized mixture prepared by sintering a mixture of the elements Mn, T, T', Sn, X, X', is first ground to obtain an amorphous or micro-crystalline mixture.
  • the grinding is realised to obtain a homogenized powder in the form of an amorphous or micro-crystalline mixture.
  • the invention relates to a process of preparation to obtain a compound of formula (I) in which:
  • T and T' are chosen among: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, or a rare earth element selected from the group consisting in: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu,
  • X and X' chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x and y are comprised from 0 to 1 and x + y ⁇ 1 ; comprising:
  • the invention relates to a process of preparation to obtain a compound of formula (I) in which: T and T' are chosen among: Zr, Hf, Nb, Mo, X and X' chosen among: Ga, Ge, Sb, In, Al, Cd, As, P, C, Si, x and y are comprised from 0 to 1 and x + y ⁇ 1 ; comprising: a) optionally grinding a mixture of the elements Mn, T, T', Sn, X and X', in an appropriate amount to obtain an amorphous or micro-crystalline mixture,
  • the above defined compounds can be used for magnetic refrigeration in systems such as near room temperature magnetic refrigerators (figure 17 and 18), freezers, conditioned air, gas liquefaction, cooling of electronic components, heat pump (figure 17).
  • Figure 1 represents the thermal variation of the magnetic entropy versus temperature Of Mn 3 Sn 2 . On this figure are also indicated - AS ⁇ , ⁇ T FWHM /2 , T co u, Ikot and MRC as defined in the specification.
  • Figure 2 represents the binary phase diagram of Mn and Sn (Stange M. et al, Journal of alloys and compounds, 259(1-2), 140-144, 1997).
  • Figure 3 represents the orthorhombic structure of Mn 3 Sn 2 showing the Ni 3 Sn 2 structural type (Pnma) adopted (upper slide (A)) and the crystal parameters of the Ni 3 Sn2- type (Pnma) Mn 3 Sn 2 compound (lower slide (B)).
  • Figure 4 represent the NiAs type of structure (P6 3 /mmc), the Ni 2 In type of structure (P6 3 /mmc) (left (A) and right (B) upper slide respectively) and the crystal parameters of the lacunary Ni 2 ln-type (P6 3 /mmc) Mn 2 _ x Sn compounds (C).
  • Figure 5 represents the results obtained with the different methods of evaluating the refrigerant capacity (RC) for Mn 3 Sn 2 and known magnetocaloric compounds:
  • Figure 6 represents the compared thermal variation of the magnetic entropy versus temperature of Mn 3 Sn 2 and Gd 5 Si 2 Ge 2 at different applied fields (upper slide (A) : Mn 3 Sn 2 and lower slide (B): Gd 5 Si 2 Ge 2 ).
  • Figure 7 represents the thermal variation of the magnetic entropy versus temperature of the Mn 3 Sn 2 and MgMn 6 Sn 6 composition (50/50, w/w) for field changes of 5T, 3T, 2T and IT.
  • Figure 8 represents the thermal variation of the magnetic entropy versus temperature OfMgMn 6 Sn 6 alone for a field change of 5T.
  • Figure 10 represents the thermal variation of the magnetic entropy versus temperature of Mn 2.9 Cuo . iSn 2 for field changes of 5T, 3T and IT.
  • Figure 11 represents the thermal variation of the magnetic entropy versus temperature ofMn 3 .
  • x Fe x Sn 2 for a field change of 5T for x 0.1 (A), 0.2 (B), 0.5 (C).
  • Figure 12 represents the thermal variation of the magnetic entropy versus temperature of Mn 2.9 Y d Sn 2 for a field change of 5T.
  • Figure 13 represents the thermal variation of the magnetic entropy versus temperature of Mn 2. gNbo . iSn 2 for a field change of 5T.
  • Figure 14 represents the thermal variation of the magnetic entropy versus temperature of Mn 2 .8Feo. 2 Sni. 8 Aso.iPo.i for a field change of 5T.
  • Figure 15 represents the thermal variation of the magnetic entropy versus temperature OfMn 2-8 COc 2 Sn 1-8 In 0-2 for a field change of 5T, 3T and IT.
  • Figure 16 represents the thermal variation of the magnetic entropy versus temperature of Mn2.9Cr o .iSni.8lno.2 for a field change of 5T, 3T and IT.
  • Figure 17 is a schematic view illustrating an embodiment of a refrigeration system utilizing a magnetocaloric material according to the present invention.
  • Figure 18 represents a schematic view of the arrangement of a magnetic refrigeration system (WO 2005/043052).
  • the alloys and compounds with general composition Mn3_( x+X ')T x T' X 'Sn2-(y + y')X y X' y are prepared by mixing the pure commercially available elements, having a quality 3N, in suitable weight proportion.
  • the mixtures can be mixed by hand or ball-milled to obtain an amorphous or micro-crystalline mixture in order to reduce the annealing time.
  • the resulting mixtures are compressed into pills using for instance a steel die.
  • the pellets are then enclosed into silica tubes sealed under inert atmosphere (e.g. 300 mm Hg of purified argon) to avoid any oxidization during the thermal treatment.
  • the sintering stage i.e.
  • the final thermal treatment must be conducted below 480 0 C (preferably between 450 and 480 0 C) for at least one weak whatever the composition to be sure to stabilize the Ni 3 Sn 2 type of structure and not the lacunary Ni2ln-type which is formed at higher temperatures. Indeed, that is the Ni3Sn2-type which yields the desired and unusual two-peak magnetocaloric effect whereas compounds which crystallize in the lacunary Ni2ln-type only display a single peak. After this final heating, the samples are quenched in ice/water.
  • powders of the A and B compounds can be mixed by hand (or ball-milled) or can be arranged into layers in necessary order (i.e. the compound with the higher ordering temperature near the hot end, the compound with the lower ordering temperature near the cold end).
  • Figure 17 illustrates a working principle of the magnetic refrigeration using a magnetocaloric material according to the present invention. It concerns an example of a magnetic refrigeration system in which the magnetocaloric material 2J_ (MCE material) according to the invention is adapted for operation.
  • This magnetic refrigeration system is characterized by a linear displacement of the magnetocaloric material 2J_ between two positions. Into the first position, the magnetocaloric material 2J_ is magnetized thanks to a permanent magnet 22 surrounding said magnetocaloric material 2J_. Whereas, into a second position, as depicted in dotted line in figure 17, the magnetocaloric material 2J_ is demagnetized as it is out of the permanent magnet 22.
  • the temperature is then exchanged with the hot heat exchanger 24, allowing the magnetocaloric material 2J_ to return to the initial temperature.
  • the magnetocaloric material 2J_ is demagnetized by switching off the applied field, causing an alignment of the material moments and thus a decrease of the temperature below the room temperature.
  • the temperature is then exchanged with a cold heat exchanger 25 . (refrigerator).
  • the working principle of the heat pump is the same as above, except the hot and cold sources are switched.
  • FIG. 5 Arrangement of a magnetic refrigeration system An example of magnetic refrigeration system using the magnetocaloric compounds or compositions of the present invention is represented in figure 18.
  • This system 1 is composed of a thermic flux generator Jj) comprising twelve thermic parts 11 forming a circle and containing the magnetocaloric compound or the compositions of the invention (50Og- lkg)J_2.
  • Each thermic part H is connected to a thermically conductor element 1_3 which transmits the hot (or cold) heat from J_2 to H, depending if the field is applied or not by means of magnet elements 102, 103 fixed on a mobile support 104.
  • Thermic parts H are fixed on a plate 18 and separated by a seal Jj ⁇ Both plate and seal are pierced allowing the exchange with a heat transfer fluid.
  • the magnetocaloric compounds or the compositions of the invention introduced in J_2 can be under the form of a powder, a multi layer powder, a pill, a block.

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Abstract

La présente invention concerne de nouveaux composés intermétalliques ayant une structure cristalline de type Ni3Sn2 pour la réfrigération magnétique, leur utilisation et leur procédé de préparation. La présente invention concerne également de nouvelles compositions magnétocaloriques pour la réfrigération magnétique et leur utilisation.
EP08718355A 2007-04-05 2008-03-31 Nouveaux composés intermétalliques, leur utilisation et leur procédé de préparation Withdrawn EP2137742A1 (fr)

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EP08718355A EP2137742A1 (fr) 2007-04-05 2008-03-31 Nouveaux composés intermétalliques, leur utilisation et leur procédé de préparation

Applications Claiming Priority (3)

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EP2007053405 2007-04-05
EP08718355A EP2137742A1 (fr) 2007-04-05 2008-03-31 Nouveaux composés intermétalliques, leur utilisation et leur procédé de préparation
PCT/EP2008/053807 WO2008122535A1 (fr) 2007-04-05 2008-03-31 Nouveaux composés intermétalliques, leur utilisation et leur procédé de préparation

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EP2137742A1 true EP2137742A1 (fr) 2009-12-30

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