Intermetallic compounds, their use and a process for preparing the same

1. A method of implementation of a magnetocaloric agent, introducing to a magnetic refrigeration system at least one compound having the following general formula (I) and a crystalline structure of Ni 3 Sn 2 type:

Mn 3-(x+x′) T x T′ x′ Sn 2-(y+y′) X y X′ y′   (I)

in which:

T and T′ are 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,

x, x′, y and y′ are from 0 to 1

x+x′≦0.5,

y+y′≦0.5,

x+y≦1, and

provided that x+x′+y+y′ is different from 0.

2. The method according to claim 1 , wherein said at least one compound has the following general formula (II) and a crystalline structure of Ni 3 Sn 2 type:

Mn 3-(x+x′) T x T′ x′ Sn 2−y X y   (II)

in which:

T and T′ are 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,

x, x′, y are all different from 0, and

x+x′≦0.5 and x+y≦1.

3. The method according to claim 1 , wherein said at least one compound has the following general formula (III) and a crystalline structure of Ni 3 Sn 2 type:

Mn 3-x T x Sn 2-(y+y′) X 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 and X′ are selected from the group consisting of: Ga, Ge, Sb, In, Al, Cd, As, P, C, and Si,

x+x′≦0.5, y+y′≦0.5, and x+y≦1, and

x, y, y′ are all different from 0.

4. The method according to claim 1 , wherein said at least one compound has the following general formula (II) and a crystalline structure of Ni 3 Sn 2 type:

Mn 3-x T x Sn 2-y X y   (IV)

in which:

T is selected from the group consisting of: 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: Ge, Sb, In, Al, Cd, C, and Si,

x+y≦1; and

x+y is different from 0.

5. The method according to claim 1 , wherein said at least one compound has the following general formula (IV) and a crystalline structure of Ni 3 Sn 2 type:

Mn 3-x T x Sn 2-y X y   (IV)

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,

x and y are different from 0,and

x+y≦1.

6. The method according to claim 1 , wherein said at least one compound has the following general formula (V) and a crystalline structure of Ni 3 Sn 2 type:

Mn 3-x T x Sn 2   (V)

in which:

T is selected from the group consisting of: Zr, Hf, Nb, Mo, and a rare earth element selected from the group consisting of: La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Sc, Y, and Lu, and

x is different from 0.

7. The method according to claim 1 , wherein said at least one compound has the following general formula (VI) and a crystalline structure of Ni 3 Sn 2 type:

Mn 3 Sn 2-y X y   (VI)

in which:

X is selected from the group consisting of: Ge, In, Al, Cd, As, P, C, and Si, and

y is different from 0.

8. The method according to claim 1 , wherein the said at least one compound has a cooling capacity q for a magnetic field applied from 0 to about 5 T is from about 50 mJ/cm 3 to about 5000 mJ/cm 3 .

9. The method according to claim 1 , wherein said at least one compound comprises two peaks which are in a temperature range from about 50 K to about 550 K.

10. A method of implementation of a magnetocaloric agent, introducing to a magnetic refrigeration system a composition having the following general formula (VII):

(A, B)  (VII)

in which:

A is at least one compound selected from the group consisting of:

a first magnetocaloric material having the following general formula (I) and a crystalline structure of Ni 3 Sn 2 type:

Mn 3-(x+x′) T x T′ x′ Sn 2-(y+y′) X y X′ y′   (I)

in which:

T and T′ are 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,

x, x′, y and y′ are 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 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-z Ge z , Gd 5 (Si 1-z Ge z ) 4 ,and MnFeP 1-z As z ,

z being from 0 to 1.

11. The method according to according to claim 10 , wherein the ratio (w/w) between A and B is from about 0.01 to about 99.

12. The method according to claim 10 , wherein the composition has a cooling capacity for a magnetic field applied from about 0 to about 5 T is from about 50 mJ/cm 3 to about 5000 mJ/cm 3 .

13. The method according to claim 10 , wherein said peaks are in a temperature range from about 50 K to about 600 K.

14. The method according to claim 10 , wherein the temperature range between at least two adjacent peaks is from about 50 K to about 100 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′) T x T′ x′ Sn 2-(y+y′) X y X′ y′   (I)

in which:

T and T′ are 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,

x, x′, y and y′ are 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.

16. The magnetocaloric material according to claim 15 , having the following general formula (I):

Mn 3-(x+x′) T x T′ x′ Sn 2-(y+Y′) X y X′ y′   (I)

in which:

T and T′ are 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,

x+x′≦0.5,

y+y′≦0.5,

x+x′+y+y′≦1, and

x, x′, y and y′ are all different from 0.

17. The magnetocaloric material according to claim 15 , having the following general structure (II):

Mn 3-(x+x′) T x T′ x ′Sn 2-y X y   (II)

in which:

T and T′ are 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,

x+x′≦0.5,

x+y≦1, and

x, x′, y are all different from 0.

18. The magnetocaloric material according to claim 15 , having he following general structure (III):

Mn 3-x T x Sn 2-(y+y′) X 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 and X′ are selected from the group consisting of: Ga, Ge, Sb, In, Al, Cd, As, P, C, and Si,

x+x′≦0.5,

y+y′≦0.5,

x+y≦1, and

x, y, y′ are all different from 0.

19. The magnetocaloric material according to claim 15 , having the following general formula (IV):

Mn 3-x T x Sn 2-y X y   (IV)

in which:

T is selected from the group consisting of: 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: Ge, In, Al, Cd, C, and Si,

x+y≦1; provided that x+y is different from 0.

20. The magnetocaloric material according to claim 15 , having the following general formula (IV):

Mn 3-x T x Sn 2-y X y   (IV)

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,

x and y are different from 0, and

x+y≦1.

21. The magnetocaloric material according to claim 15 , having the following general formula (V):

Mn 3-x T x Sn 2   (V)

in which:

T is selected from the group consisting of: Zr, Hf, Nb,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, and

x is different from 0.

22. The magnetocaloric material according to claim 15 , having the following general formula (VI) and a crystalline structure of Ni 3 Sn 2 type:

Mn 3 Sn 2-y X y   (VI)

in which:

X is selected from the group consisting of: Ge, In, Al, Cd, As, P, C, and Si, and

y is different from 0.

23. The magnetocaloric material according to claim 15 having a formula chosen from the group consisting of:

Mn 3-x Fe x Sn 2-y Ga y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Fe x Sn 2-y Ge y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Fe x Sn 2-y In y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Fe x Sn 2-y Sb y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Co x Sn 2-y Ga y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Co x Sn 2-y Ge y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Co x Sn 2-y In y wherein 0≦x≦0.5 and 0≦0.5,

Mn 3-x Cr x Sn 2-y In y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Co x Sn 2-y Sb y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Ni x Sn 2-y Ga y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Ni x Sn 2-y Ge y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Ni x Sn 2-y In y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Ni x Sn 2-y Sb y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Nb x Sn 2-y Ga y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Nb x Sn 2-y Ge y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Nb x Sn 2-y In y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Nb x Sn 2-y Sb y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Zn x Sn 2-y Ga y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Zn x Sn 2-y Ge y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Zn x Sn 2-y In y wherein 0≦x≦0.5 and 0≦y≦0.5, and

Mn 3-x Zn x Sn 2-y Sb y wherein 0≦x≦0.5 and 0≦y≦0.5.

Mn 3-x Fe x Sn 2-(y+y′) As y P y′ wherein 0≦x≦0.5 and 0≦y≦0.5, and 0≦y′≦0.5.

24. The magnetocaloric material according to claim 15 , having a formula chosen from the group consisting of:

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.

Mn 3-x Co x Sn 2-y In y wherein 0≦x≦0.5 and 0≦y≦0.5,

Mn 3-x Cr x Sn 2-y In y wherein 0≦x≦0.5 and 0≦y≦0.5, and

Mn 3-x Fe x Sn 2-(y+′) As y P y′ wherein 0≦x≦0.5 and 0≦y≦0.5, and 0≦y′≦0.5.

25. The magnetocaloric composition having the following general formula (VII):

(A, B)  (VII)

in which:

A is at least one first magnetocaloric material selected from the group consisted of:

a compound having the following general formula (I) and a crystalline structure of Ni 3 Sn 2 type:

Mn 3-(x+x′) T x T′ x′ Sn 2-(y+y′) X y X′ y′   (I)

in which:

T and T′ are 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,

x, x′, y and y′ are 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, MgMn 6 Sn 6 , Mn 4 Ga 2 Sn, Gd 5 Si 4-z Ge z , Gd 5 (Si 1-z Ge z ) 4 ,and MnFeP 1-x As z ,

z being comprised from 0 to 1.

26. The magnetocaloric composition according to claim 25 , wherein the ratio (w/w) between A and B is from about 0.01 to about 99.

27. The magnetocaloric composition according to claim 25 , said A and B, respectively, 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-z Ge z , Gd 5 (Si 1-z Ge z ) 4 ,

Mn 3 Sn 2 and MnFeP 1-z As z ,

Mn 3-x Fe 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 ) 4 ,

Mn 3-x Fe x Sn 2 and Gd 5 Si 4-z Ge z , and

Mn 3-x Fe x Sn 2 and MnFeP 1-z As z ,

x and z being as previously defined.

28. The method according to claim 1 , wherein said at least one compound has the following general formula (I) and a crystalline structure of Ni 3 Sn 2 type:

Mn 3-(x+x′) T x T′ x′ Sn 2-(y+y′) X y X′ y′   (I)

in which:

T and T′ are 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,

x, x′, y and y′ are all different from 0,

x+x′≦0.5,

y+y′≦0.5, and

x+y≦1.