Method for fabricating a functionally-graded monolithic sintered working component for magnetic heat exchange and an article for magnetic heat exchange

• US 9,978,487 B2
• Filed: 08/17/2011
• Issued: 05/22/2018
• Est. Priority Date: 08/18/2010
• Status: Active Grant

• Current Assignee: Vacuumschmelze GmbH & Company KG (Vectra Corp.)
• Original Assignee: Vacuumschmelze GmbH & Company KG (Vectra Corp.)
• Inventors: Katter, Matthias, Barcza, Alexander, Zellmann, Volker
• Primary Examiner(s): Su, Xiaowei
• Application Number:
  US13/817,304
• Publication Number:
  US 20130187077A1
• Time in Patent Office: 2,470 Days
• CPC Class Codes: B23P 15/26 heat exchangers or the like making heat exchangers by methods covered by other subclasses B21D53/02
• CPC Class Codes: H01F 1/015 Metals or alloys
• CPC Class Codes: H01F 1/017 Compounds
• CPC Class Codes: Y10T 29/4935 Heat exchanger or boiler making
• CPC Class Codes: Y10T 428/24992 Density or compression of components

Abstract

An article for magnetic heat exchange includes a functionally-graded monolithic sintered working component including La_1-aR_a(Fe_1-x-yT_yM_x)₁₃H_zC_b with a NaZn₁₃-type structure. M is one or more of the elements from the group consisting of Si and Al, T is one or more of the elements from the group consisting of Mn, Co, Ni, Ti, V and Cr and R is one or more of the elements from the group consisting of Ce, Nd, Y and Pr. A content of the one or more elements T and R, if present, a C content, if present, and a content of M varies in a working direction of the working component and provides a functionally-graded Curie temperature. The functionally-graded Curie temperature monotonically decreases or monotonically increases in the working direction of the working component.

Claims

1. A method for fabricating a functionally-graded monolithic sintered working component for magnetic heat exchange, comprising:

providing powder comprising elements in amounts sufficient for forming a La_1-aR_a(Fe_1-x-yT_yM_x)₁₃H_zC_b phase with a NaZn₁₃ structure, wherein T is one or more of the elements selected from the group consisting of Mn, Co, Ni, Ti, V and Cr, M is one or more of the elements selected from the group consisting of Si and Al, and R is one or more of the elements selected from the group consisting of Ce, Nd, Y and Pr, wherein a is such that 0≤

a≤

0.5, b is such that 0≤

b≤

1.5, x is such that 0.05≤

x≤

0.2, y is such that 0≤

y≤

0.2, and z is such that 0≤

z≤

3;

forming the powder to provide a green body in which an amount of at least one element selected from the group consisting of T, R, C and M varies in a pre-determined direction of the green body,

heat treating the green body at a temperature T and for a time t selected to allow diffusion of one or more of the elements selected from the group consisting of T, R and C, and

the heat treating step including forming a sintered working component comprising a Curie temperature that monotonically increases or monotonically decreases in the pre-determined direction, wherein the temperature T and the time t are selected to provide the monotonically increasing or monotonically decreasing Curie temperature, and wherein the monotonically increasing or monotonically decreasing Curie temperature changes with a gradient that lies within +/−

50% of a linear function over 80% of a length of the working component, wherein the linear function is defined as the difference between the Curie temperature at one end of the working component and the Curie temperature at the opposing end of the working component divided by the distance between the two ends, and wherein nowhere along the length of the working component is there a gradient that exceeds 10°

C./0.5 mm of length.

2. The method according to claim 1, wherein the elements T, or C, or both, are present, and wherein the temperature T is selected to provide a diffusion rate of the elements T, or C, or both of at least 2×

10<sup>−

11</sup> m²/s.

3. The method according claim 1, wherein the element C is present, and wherein the temperature T is selected to provide a diffusion rate of the element C of at least 1×

10<sup>−

10</sup> m²/s.

4. The method according to claim 1, wherein the temperature T is 900°

C.≤

T≤

1200°

C.

5. The method according to claim 1, wherein the temperature T is 1050°

C.≤

T≤

1150°

C.

6. The method according to claim 1, wherein the time t is 1 h≤

t≤

100 h.

7. The method according to claim 1, further comprising forming the powder from a plurality of powders with each powder comprising different amounts of at least one element selected from the group consisting of R, T, M and C and each powder being selected to provide a different Curie temperature when heat treated to form the NaZn₁₃ structure.

8. The method according to claim 7, wherein layers of the plurality of powders are stacked such that the content of at least one element selected from the group consisting of R, T, M and C increases or decreases in a direction of the stack.

9. The method according to claim 7, wherein each of the powders is mixed with a liquid and optionally with a binder and/or a dispersant to form a slurry or paste.

10. The method according to claim 9, wherein the viscosity of the slurry or paste is between 200 mPas and 100,000 mPas.

11. The method according to claim 10, wherein the slurries or pastes are applied to a surface layer by layer to form a stack such that the content of at least one element selected from the group consisting of R, T, M and C increases or decreases in a direction of the stack.

12. The method according to claim 11, wherein each layer in the stack of layers has a thickness of 10 μ

m to 60 μ

m.

13. The method according to claim 9, wherein before sintering, the liquid, binder and dispersant, if present, are removed at a temperature of 500°

C. or below.

14. The method according to claim 7, wherein varying proportions of the powders are mixed with one another before being arranged in a former such that the content of at least one element selected from the group consisting of R, T, M, and C of the powder in the former increases or decreases over a length of the former.

15. The method according to claim 7, wherein varying proportions of the powders are introduced in a former such that the content of at least one element selected from the group consisting of R, T, M and C increases or decreases in an insertion direction of the powder into the former.

16. The method according to claim 1, wherein the powder is formed into the green body by applying pressure.

17. The method according to claim 1, wherein the green body is sintered at a temperature of 900°

C. or greater to produce a density of 90% or more of a theoretical density of the La_1-aR_a(Fe_1-x-yT_yM_x)₁₃H_zC_b phase with the NaZn₁₃ structure.

18. The method according to claim 1, wherein M is Si and the amount of Si is selected according to Si_m=3.85−

0.0573×

Co_m−

0.045×

Mn_m²+0.2965×

Mn_m, wherein Si_m is the metallic weight fraction of silicon, Mn_m is the metallic weight fraction of manganese and Co_m is the metallic weight fraction of cobalt.

19. The method according to claim 1, wherein M is Si and the amount of Si is selected according to Si_m=3.85−

0.045×

Mn_m²+0.2965×

Mn_m+(0.198−

0.066×

Mn_m)×

Ce(MM)_m, wherein Si_m is the metallic weight fraction of silicon, Mn_m is the metallic weight fraction of manganese and Ce(MM)_m is the metallic weight fraction of cerium misch metal.

20. The method according to claim 1, further comprising hydrogenating the working component after the heat treating step.

21. The method according to claim 20, wherein the working component is hydrogenated to produce a working component comprising a hydrogen content z of at least 90% of the hydrogen saturation value, z_sat, of the NaZn₁₃-structure.

22. The method according to claim 20, wherein the working component is hydrogenated to produce a hydrogen content z of 1.4≤

z≤

3 in the La_1-aR_a(Fe_1-x-yT_yM_x)₁₃H_z phase.

23. The method according to claim 20, wherein the hydrogenating comprises heat treating under a H₂ partial pressure of 0.5 to 2 bar.

24. The method according to claim 20, wherein a H₂ partial pressure is increased during hydrogenating.

25. The method according to claim 20, wherein the hydrogenating comprises treating at a temperature in the range 0°

C. to 100°

C.

26. The method according to claim 25, wherein the hydrogenating comprises treating at a temperature in the range 15°

C. to 35°

C.

27. The method according to claim 20, wherein the hydrogenating comprises a dwell at a temperature T_hyd, wherein 300°

C.≤

T_hyd≤

700°

C.

28. The method according to claim 27, wherein the hydrogenating comprises a dwell at a temperature T_hyd, wherein 300°

C.≤

T_hyd≤

700°

C. followed by cooling in a hydrogen atmosphere to a temperature of less than 100°

C.

29. The method according to claim 20, wherein the hydrogenating comprises:

heating the working component from a temperature of less than 50°

C. to at least 300°

C. in an inert atmosphere,

introducing hydrogen gas only when a temperature of at least 300°

C. is reached,

maintaining the working component in a hydrogen containing atmosphere at a temperature in the range 300°

C. to 700°

C. for a selected duration of time, and

cooling the working component to a temperature of less than 50°

C.

30. The method of claim 29, wherein the working component is cooled to a temperature of less than 50°

C. in a hydrogen-containing atmosphere.

31. The method according to claim 20, wherein hydrogen gas is introduced after the heat treating step at a temperature of 400°

C. to 600°

C.

32. The method according to claim 20, wherein after the hydrogenating, the working component comprises at least 0.18 wt % hydrogen.

33. The method according to claim 29, wherein a hydrogen content of the working component is varied as a function of position along a working direction of the working component by introducing a varying amount of hydrogen into, or removing a varying amount of hydrogen, from the working component by heat treating the working component in the temperature gradient to produce the monotonically increasing or monotonically decreasing Curie temperature that increases or decreases monotonically in the pre-determined direction.

34. The method according to claim 1, wherein the monotonically increasing or monotonically decreasing Curie temperature changes with a gradient that lies within +/−

10% of the linear function over 80% of a length of the working component.

35. The method according to claim 1, wherein the monotonically increasing or monotonically decreasing Curie temperature changes with a gradient that lies within +/−

20% of the linear function over 80% of a length of the working component.

36. A method for fabricating a functionally-graded monolithic sintered working component for magnetic heat exchange, comprising:

providing a plurality of powders comprising elements in amounts sufficient for forming a La_1-aR_a(Fe_1-x-yT_yM_x)₁₃H_zC_b phase with a NaZn₁₃ structure, wherein T is one or more of the elements selected from the group consisting of Mn, Co, Ni, Ti, V and Cr, M is one or more of the elements selected from the group consisting of Si and Al, and R is one or more of the elements selected from the group consisting of Ce, Nd, Y and Pr, wherein a is such that 0≤

a≤

0.5, b is such that 0≤

b≤

1.5, x is such that 0.05≤

x≤

0.2, y is such that 0≤

y≤

0.2, and z is such that 0≤

z≤

3;

mixing the powders with a liquid and optionally with a binder and/or a dispersant to form a green body in the form of a slurry or paste in which an amount of at least one element selected from the group consisting of T, R, C and M varies in a pre-determined direction,

heat treating the green body at a temperature T and for a time t selected to allow diffusion of one or more of the elements selected from the group consisting of T, R and C, and

forming a working component from the green body comprising a Curie temperature that monotonically increases or monotonically decreases in the pre-determined direction, and wherein a gradient of the increase or decrease does not exceed 10°

C./0.5 mm anywhere in the working component.

37. A method for fabricating a functionally-graded monolithic sintered working component for magnetic heat exchange, comprising:

providing a plurality of powders comprising elements in amounts sufficient for forming a La_1-aR_a(Fe_1-x-yT_yM_x)₁₃H_zC_b phase with a NaZn₁₃ structure, wherein T is one or more of the elements selected from the group consisting of Mn, Co, Ni, Ti, V and Cr, M is one or more of the elements selected from the group consisting of Si and Al, and R is one or more of the elements selected from the group consisting of Ce, Nd, Y and Pr, wherein a is such that 0≤

a≤

0.5, b is such that 0≤

b≤

1.5, x is such that 0.05≤

x≤

0.2, y is such that 0≤

y≤

0.2, and z is such that 0≤

z≤

3;

mixing the powders with a liquid and optionally with a binder and/or a dispersant to form a green body in the form of a slurry or paste in which an amount of at least one element selected form the group consisting of T, R, C and M varies in a pre-determined direction, the slurry or paste having a viscosity between 200 mPas and 100,000 mPas,

heat treating the green body at a temperature T and for a time t selected to allow diffusion of one or more of the elements selected from the group consisting of T, R and C,

forming a working component from the green body comprising a Curie temperature that monotonically increases or monotonically decreases in the pre-determined direction.

38. A method for fabricating a functionally-graded monolithic sintered working component for magnetic heat exchange, comprising:

providing a plurality of powders comprising elements in amounts sufficient for forming a La_1-aR_a(Fe_1-x-yT_yM_x)₁₃H_zC_b phase with a NaZn₁₃ structure, wherein T is one or more of the elements selected from the group consisting of Mn, Co, Ni, Ti, V and Cr, M is one or more of the elements selected from the group consisting of Si and Al, and R is one or more of the elements selected from the group consisting of Ce, Nd, Y and Pr, wherein a is such that 0≤

a≤

0.5, b is such that 0≤

b≤

1.5, x is such that 0.05≤

x≤

0.2, y is such that 0≤

y≤

0.2, and z is such that 0≤

z≤

3;

mixing the powders with a liquid and optionally with a binder and/or a dispersant to form a green body in the form of a slurry or paste in which an amount of at least one element selected from the group consisting of T, R, C and M varies in a pre-determined direction,

applying the slurry or paste to a surface layer by layer to form a stack such that the content of at least one element selected from the group consisting of R, T, C and M increases or decreases in a direction of the stack,

heat treating the green body at a temperature T and for a time t selected to allow diffusion of one or more of the elements selected from the group consisting of T, R and C,

forming a working component from the green body comprising a Curie temperature that monotonically increases or monotonically decreases in the pre-determined direction, and wherein a gradient of the increase or decrease does not exceed 10°

C./0.5 mm anywhere in the working component.

39. A method for fabricating a functionally-graded monolithic sintered working component for magnetic heat exchange, comprising:

providing powder comprising elements in amounts sufficient for forming a La_1-aR_a(Fe_1-x-yT_yM_x)₁₃H_zC_b phase with a NaZn₁₃ structure, wherein T is one or more of the elements selected from the group consisting of Mn, Co, Ni, Ti, V and Cr, M is one or more of the elements selected from the group consisting of Si and Al, and R is one or more of the elements selected from the group consisting of Ce, Nd, Y and Pr, wherein a is such that 0≤

a≤

0.5, b is such that 0≤

b≤

1.5, x is such that 0.05≤

x≤

0.2, y is such that 0≤

y≤

0.2, and z is such that 0≤

z≤

3;

mixing the powders with a liquid and optionally with a binder and/or a dispersant to form a green body in the form of a slurry or paste in which an amount of at least one element selected from the group consisting of T, R, C and M varies in a pre-determined direction,

applying the slurry or paste to a surface layer by layer to form a stack, each layer in the stack having a thickness of 10 μ

m to 60 μ

m,

heat treating the green body at a temperature T and for a time t selected to allow diffusion of one or more of the elements selected from the group consisting of T, R and C, and

forming a working component comprising a Curie temperature that monotonically increases or monotonically decreases in the pre-determined direction.