Intermetallic compounds, their use and a process for preparing the same
The present invention relates to new intermetallic compounds having a crystalline structure of Ni 3 Sn 2 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.
1. A method for magnetic refrigeration comprising:
providing refrigeration using a magnetocaloric agent consisting of at least one compound having the following general formula (I) and a crystalline structure of Ni 3 Sn 2 type:
Mn 3-(x+x′) Fe x T′ x′ Sn 2-(y+y′) X y X′ y′ (I),
in which:
T′ is selected from the group consisting of: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, and a rare earth element selected from the group consisting of: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, and Lu,
X and X′ are selected from the group consisting of: Ga, Ge, Sb, In, Al, Cd, As, P, C, and Si,
0.5<x≦1,
x′≦0.5
0≦y≦0.5,
0≦y′≦0.5
y+y′≦1, and
x+x′+y+y′≦2.5.
2. The method for magnetic refrigeration according to claim 1 , wherein the at least one compound has the following general formula (II) and a crystalline structure of Ni 3 Sn 2 type:
Mn 3-x Fe x Sn 2-(y+y′) X y X′ y′ (II),
in which:
X and X′ are selected from the group consisting of: Ga, Ge, Sb, In, Al, Cd, As, P, C, and Si,
0.5<x≦1,
0≦y≦0.5,
0≦y′≦0.5,
y+y′≦1, and
x+y+y′ 2.0.
3. The method for magnetic refrigeration according to claim 1 , wherein the at least one compound has the following general formula (III) and a crystalline structure of Ni 3 Sn 2 type:
Mn 3-(x+x′) Fe x T′ x′ Sn 2-y X y (III),
in which:
T′ is selected from the group consisting of: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, and a rare earth element selected from the group consisting of: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, and Lu,
X is selected from the group consisting of: Ga, Ge, Sb, In, Al, Cd, As, P, C, and Si,
0.5<x≦1,
x′<0.5,
0≦y≦1, and
x+x′+y≦2.5.
4. The method for magnetic refrigeration according to claim 1 , wherein the at least one compound has the following general formula (IV) and a crystalline structure of Ni 3 Sn 2 type:
Mn 3-x Fe x Sn 2-y X y (IV),
in which:
X is selected from the group consisting of: Ga, Ge, Sb, In, Al, Cd, As, P, C, and Si,
0.5<x≦1,
0≦y≦1, and
x+y≦2.
5. The method for magnetic refrigeration according to claim 1 , wherein the at least one compound has the following general formula (V) and a crystalline structure of Ni 3 Sn 2 type:
Mn 3-(x+x′) Fe x T′ x′ Sn 2 (V),
in which:
T′ is selected from the group consisting of: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, and a rare earth element selected from the group consisting of: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, and Lu,
0.5<x≦1, and
x′<0.5.
6. The method for magnetic refrigeration according to claim 1 , wherein the at least one compound has the following general formula (VI) and a crystalline structure of Ni 3 Sn 2 type:
Mn 3-x Fe x Sn 2 (VI),
in which:
0.5<x≦1.
7. The method for magnetic refrigeration according to claim 1 , wherein the at least one compound has a cooling capacity q for a magnetic field applied from 0 to 5 T from 50 mJ/cm 3 to 5000 mJ/cm 3 .
8. The method for magnetic refrigeration according to claim 1 , wherein the at least one compound presents two transition temperature peaks which are in a temperature range from 50 K to 550 K.
9. The method for magnetic refrigeration according to claim 1 , wherein the at least one compound presents two transition temperature peaks which are in a temperature range from 50 K to 550 K, wherein the temperature range between at least two adjacent transition temperature peaks is from 20 K to 150 K.
10. A method for magnetic refrigeration comprising:
providing refrigeration using a composition having the following general formula (VII):
(A,B) (VII),
in which:
A is at least one compound as defined in claim 1 ,
B is at least a second magnetocaloric material having a transition temperature peak from 300 to 350 K.
11. The method for magnetic refrigeration according to claim 10 , wherein the ratio (w/w) between A and B is from 0.01 to 99.
12. The method for magnetic refrigeration according to claim 10 , wherein the composition has a cooling capacity for a magnetic field applied from 0 to 5 T from 50 mJ/cm 3 to 5000 mJ/cm 3 .
13. The method for magnetic refrigeration according to claim 10 , wherein said transition temperature peak is in a temperature range from 50 K to 600 K.
14. The method for magnetic refrigeration according to claim 10 , wherein said transition temperature peak is in a temperature range from 50 K to 600 K, and wherein the temperature range between at least two adjacent transition temperature peaks is from 20 K to 150 K.
15. A magnetocaloric material having the following general formula (I) and a crystalline structure of Ni 3 Sn 2 type:
Mn 3-(x+x′) Fe x T′ x′ Sn 2-(y+y′) X y X′ y′ (I),
in which:
T′ is selected from the group consisting of: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, and a rare earth element selected from the group consisting of: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, and Lu,
X and X′ are selected from the group consisting of: Ga, Ge, Sb, In, Al, Cd, As, P, C, and Si,
0.5<x≦1,
x′≦0.5,
0≦y≦0.5,
0≦y′≦0.5,
y+y′≦1, and
x+x′+y+y′≦2.5.
16. The magnetocaloric material according to claim 15 , having the following general structure (II):
Mn 3-x Fe x Sn 2-(y+y′) X y X′ y′ (II),
in which:
X and X′ are selected from the group consisting of: Ga, Ge, Sb, In, Al, Cd, As, P, C, and Si,
0.5<x≦1,
0≦y≦0.5,
0≦y′≦0.5,
y+y′≦1, and
x+y+y′≦2.0.
17. The magnetocaloric material according to claim 15 , having the following general structure (III):
Mn 3-(x+x′) Fe x T′ x′ Sn 2-y X y (III),
in which:
T′ is selected from the group consisting of: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, and a rare earth element selected from the group consisting of: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, and Lu,
X is selected from the group consisting of: Ga, Ge, Sb, In, Al, Cd, As, P, C, and Si,
0.5<x≦1,
x′<0.5,
0≦y≦1, and
x+x′+y≦2.5.
18. The magnetocaloric material according to claim 15 , having the following general structure (IV):
Mn 3-x Fe x Sn 2-y X y (IV)
in which:
X is selected from the group consisting of: Ga, Ge, Sb, In, Al, Cd, As, P, C, and Si,
0.5<x≦1,
0≦y≦1, and
x+y≦2.
19. The magnetocaloric material according to claim 15 , having the following general structure (V):
Mn 3-(x+x′) Fe x T′ x′ Sn 2 (V),
in which:
T′ is selected from the group consisting of: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, and a rare earth element selected from the group consisting of: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, and Lu,
0.5<x≦1, and
x′<0.5.
20. The magnetocaloric material according to claim 15 , having the following general structure (VI):
Mn 3-x Fe x Sn 2 (VI),
in which:
0.5<x≦1.
21. The magnetocaloric material according to claim 15 , wherein said magnetocaloric material present at least two phase transitions, each of them being of second order and constituting a transition temperature peak.
22. The magnetocaloric material according to claim 15 , wherein the magnetocaloric material has a cooling capacity q for a magnetic field applied 0 to 5 T from 50 mJ/cm 3 to 5000 mJ/cm 3 .
23. The magnetocaloric material according to claim 15 , comprising two transition temperature peaks which are in a temperature range from 50 K to 550 K.
24. The magnetocaloric material according to claim 15 , comprising two transition temperature peaks which are in a temperature range from 50 K to 550 K, wherein the temperature range between at least two adjacent transition temperature peaks is from 20 K to 150 K.
25. The magnetocaloric material according to claim 15 , selected from the group consisting of:
Mn 3-x Fe x Sn 2 ,
Mn 3-x Fe x Sn 2-y Ge y and
Mn 3-x Fe x Sn 2-y In y ,
wherein 0.5<x≦1, 0≦y≦1, and x+y≦2.
26. The magnetocaloric material according to claim 15 , selected from the group consisting of:
Mn 3-x Fe x Sn 2 where 0.5<x≦0.1.
27. A magnetocaloric composition having the following general formula (VII):
(A,B) (VII),
in which:
A is at least one compound as defined in claim 1 ,
B is at least a second magnetocaloric material having a transition temperature peak from 300 to 350 K.
28. The magnetocaloric composition according to claim 27 , wherein the ratio (w/w) between A and B is from 0.01 to 99.
29. The magnetocaloric composition according to claim 27 , selected from the group consisting of:
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 Gd 5 (Si 1-z Ge z ) 4 , and Mn 3-x Fe x Sn 2 and MnFeP 1-z As z , and
x being 0.5<x≦1,and
z being 0 to 1.
30. A process of preparation of the compound of formula (I) having a crystalline structure of Ni 3 Sn 2 type:
Mn 3-(x+x′) Fe x T′ x′ Sn 2-(y+y′) X y X′ y′ (I),
in which:
T′ is selected from the group consisting of: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, and a rare earth element selected from the group consisting of: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, and Lu,
X and X′ are selected from the group consisting of: Ga, Ge, Sb, In, Al, Cd, As, P, C, and Si,
0.5<x≦1,
x′≦0.5,
0≦y≦0.5,
0≦y′≦0.5,
y+y′≦1, and
x+x′+y+y′≦2.5,
comprising a first step of annealing a homogenized mixture of the elements Mn, Fe, T′, Sn, X and X′, in an appropriate amount, at a temperature from 550° C. to 850° C., grinding the mixture thus obtained and a second step of annealing at a temperature below 480° C., said homogenised mixture being prepared by sintering a mixture of the elements Mn, Fe, T′, Sn, X and X′, in an appropriate amount, X and X′ being pure elements, at a temperature range from 300 to 600° C.
31. The process of preparation according to claim 30 , wherein said homogenized mixture prepared by sintering a mixture of the elements Mn, Fe, T′, Sn, X, and X′, is first ground to obtain an amorphous or micro-crystalline mixture.
32. The process of preparation according to claim 30 , to obtain a compound of formula (I) in which:
T′ is selected from the group consisting of: Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ru, Zr, Hf, Nb, Mo, and a rare earth element selected from the group consisting of: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, and Lu,
X and X′ selected from the group consisting of: Ga, Ge, Sb, In, Al, Cd, As, P, and C,
0.5<x≦1,
x′≦0.5
0≦y≦0.5,
0≦y′≦0.5,
y+y′≦1, and
x+x′+y+y′≦2.5,
comprising:
a) optionally grinding a mixture of the elements Mn, Fe, T′, Sn, X and X′, in an appropriate amount to obtain an amorphous or micro-crystalline mixture,
b) sintering said amorphous or micro-crystalline mixture at a temperature from 300 to 600° C. to obtain a homogenized mixture,
c) crushing and compacting said homogenized mixture to obtain a crushed and compacted mixture,
d) annealing said crushed and compacted mixture in a first step at a temperature from 650° C. to 750° C., grinding the mixture thus obtained and annealing in a second step at a temperature below 480° C.
33. The method for magnetic refrigeration according to claim 10 , wherein,
B is selected from the group consisting of Gd, MgMn 6 Sn 6 , Mn 4 Ga 2 Sn, Gd 5 (Si 1-z Ge z ) 4 , and MnFeP 1-z As z , and
0≦z≦1.
34. The magnetocaloric composition according to claim 27 , wherein,
B is selected from the group consisting of Gd, MgMn 6 Sn 6 , Mn 4 Ga 2 Sn, Gd 5 (Si 1-z Ge z ) 4 , and MnFeP 1-z As z , and
0≦z≦1.