NEW INTERMETALLIC COMPOUNDS, THEIR USE AND A PROCESS FOR PREPARING THE SAME

• US 20100276627A1
• Filed: 03/31/2008
• Published: 11/04/2010
• Est. Priority Date: 04/05/2007
• Status: Active Grant

• Current Assignee: Universite De Lorraine (Government of France)
• Original Assignee: Universite Henri Poincare Nancy -1
• Inventors: Mazet, Thomas
• Granted Patent: US 8,293,030 B2
• Time in Patent Office: Days
• US Class Current: 252/62.55
• CPC Class Codes: F25B 21/00 Machines, plants or systems, using electric or magnetic effects
• CPC Class Codes: F25B 2321/002 by using magneto-caloric effects
• CPC Class Codes: H01F 1/015 Metals or alloys
• CPC Class Codes: H01F 1/017 Compounds
• CPC Class Codes: Y02B 30/00 Energy efficient heating, ventilation or air conditioning [HVAC]

Abstract

The present invention relates to new intermetallic compounds having a crystalline structure of Ni₃Sn₂ type for the magnetic refrigeration, their use and a process for preparing the same. The present invention further relates to new magnetocaloric compositions for the magnetic refrigeration and their use.

Claims

1-44. -44. (canceled)

45. Method of implementation of a magnetocaloric agent, in particular for magnetic refrigeration, by means of at least one compound having the following general formula (I) and a crystalline structure of Ni₃Sn₂ type:

Mn<sub>3-(x+x′

)</sub>T_xT′

_x′

Sn<sub>2-(y+y′

)</sub>X_yX′

_y′

 

 

(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, and x, x′

, y and y′

are all different from 0,

x+x′

≦

0.5, y+y′

≦

0.5, and x+y≦

1.

46. Method according to claim 45, by means of at least one compound having the following general formula (II) and a crystalline structure of Ni₃Sn₂ type:

Mn<sub>3-(x+x′

)</sub>T_xT′

_x′

Sn_2-yX_y  

 

(II)

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 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.

47. Method according to claim 45, by means of at least one compound having the following general formula (III) and a crystalline structure of Ni₃Sn₂ type:

Mn_3-xT_xSn<sub>2-(y+y′

)</sub>X_yX′

_y′

 

 

(III)

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 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, and x+y≦

1, and x, y, y′

are all different from 0.

48. Method according to claim 45, by means of at least one compound having the following general formula (II) and a crystalline structure of Ni₃Sn₂ type:

Mn_3-xT_xSn_2-yX_y  

 

(IV)

in which;

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, Sb, In, Al, Cd, C, Si,

x and y are comprised from 0 to 1 x+y≦

1; and

x+y is different from 0.

49. Method according to claim 45, by means of at least one compound having the following general formula (IV) and a crystalline structure of Ni₃Sn₂ type:

Mn_3-xT_xSn_2-yX_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 0 to 1, x and y are different from 0, and x+y≦

1.

50. Method according to claim 45, by means of at least one compound having the following general formula (V) and a crystalline structure of Ni₃Sn₂ type:

Mn_3-xT_xSn₂  

 

(V)

in which;

T is chosen among;

Zr, Hf, Nb, Mo, or a rare earth element selected from the group consisting in;

La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, Lu,

x is comprised from 0 to 1 and x is different from 0.

51. Method according to claim 45, by means of at least one compound having the following general formula (VI) and a crystalline structure of Ni₃Sn₂ type:

Mn₃Sn_2-yX_y  

 

(VI)

in which;

X is chosen among;

Ge, In, Al, Cd, As, P, C, Si,

y is comprised from 0 to 1 and y is different from 0.

52. Method according to claim 45, wherein the cooling capacity q for a magnetic field applied from 0 to about 5 T is comprised from about 50 mJ/cm³ to about 5000 mJ/cm³ particularly from about 100 mJ/cm³ to about 4000 mJ/cm³, more particularly from about 500 mJ/cm³ to about 3000 mJ/cm³ and more particularly from about 1000 mJ/cm³ to about 2000 mJ/cm³.

53. Method according to claim 45, wherein said compound comprises 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.

54. Method of implementation of a magnetocaloric agent, in particular for magnetic refrigeration, by means of a composition having the following general formula (VII):

(A , B)  

 

(VII)

in which;

A is at least one compound selected from the group consisted of;

a compound having the following general formula (I) and a crystalline structure of Ni₃Sn₂ type;

Mn<sub>3-(x+x′

)</sub>T_xT′

_x′

Sn<sub>2-(y+y′

)</sub>X_yX′

_y′

 

 

(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,

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, MgMn₆Sn₆, Mn₄Ga₂Sn, Gd₅Si_4-zGe_z, Gd₅(Si_1-zGe_z)₄, MnFeP_1-zAs_z,

z being comprised from 0 to 1.

55. Method according to according to claim 54, 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.

56. Method according to claim 54, wherein the cooling capacity for a magnetic field applied from about 0 to about 5 T is comprised from about 50 mJ/cm³ to about 5000 mJ/cm³ particularly from about 100 mJ/cm³ to about 4000 mJ/cm³, more particularly from about 500 mJ/cm³ to about 3500 mJ/cm³ and more particularly from about 1000 mJ/cm³ to about 3000 mJ/cm³.

57. Method according to claim 54, 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.

58. Method according to claim 54, 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.

59. Magnetocaloric material having the following general formula (I) and a crystalline structure of Ni₃Sn₂ type:

Mn<sub>3-(x+x′

)</sub>T_XT′

_x′

Sn<sub>2-(y+y′

)</sub>X_yX′

_y′

 

 

(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,

provided that x+x′

+y+y′

is different from 0.

60. Magnetocaloric material according to claim 59, having the following general formula (I):

Mn<sub>3-(x+x′

)</sub>T_XT′

_x′

Sn<sub>2-(y+y′

)</sub>X_yX′

_y′

 

 

(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.

61. Magnetocaloric material according to claim 59, having the following general structure (II):

Mn<sub>3-(x+x′

)</sub>TxT′

x′

Sn_2-yX_y  

 

(II)

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 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.

62. Magnetocaloric material according to claim 59, having he following general structure (III):

Mn_3-xT_xSn<sub>2-(y+y′

)</sub>X_yX′

_y′

 

 

(III)

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 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.

63. Magnetocaloric material according to claim 59, having the following general formula (IV):

Mn_3-xT_xSn_2-yX_y  

 

(IV)

in which;

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 0 to 1, x+y≦

1;

provided that x+y is different from 0.

64. Magnetocaloric material according to claim 59, having the following general formula (IV):

Mn_3-xT_xSn_2-yX_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 0 to 1, x and y are different from 0, and x+y≦

1.

65. Magnetocaloric material according to claim 59, having the following general formula (V):

Mn_3-xT_xSn₂  

 

(V)

in which;

T is chosen among;

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, x is comprised from 0 to 1 and x is different from 0.

66. Magnetocaloric material according to claim 59, having the following general formula (VI) and a crystalline structure of Ni₃Sn₂ type:

Mn₃Sn_2-yX_y  

 

(VI)

in which;

X is chosen among;

Ge, In, Al, Cd, As, P, C, Si,

y is comprised from 0 to 1 and y is different from 0.

67. Magnetocaloric material according to claim 59 to, chosen from the group consisting of:

Mn_3-xFe_xSn_2-yGa_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xFe_xSn_2-yGe_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xFe_xSn_2-yIn_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xFe_xSn_2-ySb_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xCo_xSn_2-yGa_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xCo_xSn_2-yGe_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xCo_xSn_2-yIn_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xCr_xSn_2-yIn_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xCo_xSn_2-ySb_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xNi_xSn_2-yGa_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xNi_xSn_2-yGe_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xNi_xSn_2-yIn_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xNi_xSn_2-ySb_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xNb_xSn_2-yGa_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xNb_xSn_2-yGe_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xNb_xSn_2-yIn_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xNb_xSn_2-ySb_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xZn_xSn_2-yGa_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xZn_xSn_2-yGe_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xZn_xSn_2-yIn_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xZn_xSn_2-ySb_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5.

Mn_3-xFe_xSn<sub>2-(y+y′

)</sub>As_yP_y′

wherein 0≦

x≦

0.5 and 0≦

y≦

0.5, and 0≦

y′

≦

0.5.

68. Magnetocaloric material according to claim 59, chosen from the group consisting of:

Mn₃Sn_2-yGe_y where 0≦

y≦

0.5,

Mn_3-xNb_xSn₂ where 0≦

x≦

0.5,

Mn_3-xY_xSn₂ where 0≦

x≦

0.5.

Mn_3-xCo_xSn_2-yIn_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xCr_xSn_2-yIn_y wherein 0≦

x≦

0.5 and 0≦

y≦

0.5,

Mn_3-xFe_xSn<sub>2-(y+y′

)</sub>As_yP_y′

wherein 0≦

x≦

0.5 and 0≦

y≦

0.5, and 0≦

y′

≦

0.5.

69. Magnetocaloric composition having the following general formula (VII):

(A , B)  

 

(VII)

in which;

A is at least one compound selected from the group consisted of;

a compound having the following general formula (I) and a crystalline structure of Ni₃Sn₂ type;

Mn<sub>3-(x+x′

)</sub>T_xT′

_x′

Sn<sub>2-(y+y′

)</sub>X_yX′

_y′

 

 

(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,

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, MgMn₆Sn₆, Mn₄Ga₂Sn, Gd₅Si_4-zGe_z, Gd₅(Si_1-zGe_z)₄, MnFeP_1-zAs_z, z being comprised from 0 to 1.

70. Magnetocaloric composition according to claim 69, 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.

71. Magnetocaloric composition according to claim 69, chosen from the group consisting of:

Mn₃Sn₂ and Gd, Mn₃Sn₂ and MgMn₆Sn₆, Mn₃Sn₂ and Mn₄Ga₂Sn, Mn₃Sn₂ and Gd₅Si_4-zGe_z, Gd₅(Si_1-zGe_z)₄, Mn₃Sn₂ and MnFeP_1-zAs_z,

Mn_3-xFe_xSn₂ and Gd, Mn_3-xFe_xSn₂ and MgMn₆Sn₆, Mn_3-xFe_xSn₂ and Mn₄Ga₂Sn, Mn_3-xFe_xSn₂ and Gd₅(Si_1-zGe_z)₄, Mn_3-xFe_xSn₂ and Gd₅Si_4-zGe_z, Mn_3-xFe_xSn₂ and MnFeP_1-zAs_z,

x and z being as previously defined.