Article for magnetic heat exchange and method of fabricating an article for magnetic heat exchange
View Patent ↗An article for magnetic heat exchange comprising a magnetocalorically active phase with a NaZn 13 -type crystal structure is provided by hydrogenating a bulk precursor article. The bulk precursor article is heated from a temperature of less than 50° C. to at least 300° C. in an inert atmosphere and hydrogen gas only introduced when a temperature of at least 300° C. is reached. The bulk precursor article is maintained in a hydrogen containing atmosphere at a temperature in the range 300° C. to 700° C. for a selected duration of time, and then cooled to a temperature of less than 50° C.
1. A method of fabricating an article for magnetic heat exchange, comprising:
providing a bulk precursor article comprising a magnetocalorically active phase with a NaZn 13 crystal structure,
performing hydrogenation of the bulk precursor article by:
heating the bulk precursor article 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 bulk precursor article 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 bulk precursor article to a temperature of less than 50° C. to provide a hydrogenated article.
2. The method according to claim 1 , wherein the cooling of the bulk precursor article to a temperature of less than 50° C. is in a hydrogen-containing atmosphere.
3. The method according to claim 2 , wherein the selected duration of time is 1 minute to 4 hours.
4. The method according to claim 2 , wherein after the hydrogenation, the article comprises at least 0.21 wt % hydrogen.
5. The method according to claim 2 , wherein after the hydrogenation, the article comprises a magnetic phase transition temperature of in the range of −40° C. to +150° C.
6. The method according to claim 2 , wherein the bulk precursor article is cooled at a rate of 0.1K/min to 10K/min.
7. The method according to claim 1 , further comprising, before cooling the bulk precursor article to a temperature of less than 50° C., replacing the hydrogen gas by inert gas.
8. The method according to claim 7 , wherein the selected duration of time is 1 minute to 4 hours.
9. The method according to claim 7 , wherein after the hydrogenation, the article comprises a hydrogen content in the range of 0.02 wt % to 0.21 wt %.
10. The method according to claim 7 , wherein the cooling of the bulk precursor article is cooled at a rate of 1 K/min to 100 K/min.
11. The method according to claim 1 , wherein the cooling of the bulk precursor article to a temperature of less than 50° C. comprises cooling the bulk precursor article to a temperature in the range 300° C. to 150° C. in a hydrogen containing atmosphere, replacing the hydrogen by inert gas, and cooling the bulk precursor article to a temperature of less than 50° C.
12. The method according to claim 1 , wherein the bulk precursor article has initial outer dimensions before hydrogenation and the article after hydrogenation has final outer dimensions, wherein a difference between the initial outer dimensions and final outer dimensions is less than 10 volume %.
13. The method according to claim 1 , wherein the introducing of hydrogen gas is only when a temperature of 400° C. to 600° C. is reached.
14. The method according to claim 1 , wherein the bulk precursor article has at least one outer dimension greater than 5 mm.
15. The method according to claim 1 , wherein the bulk precursor article is polycrystalline.
16. The method according to claim 1 , wherein the bulk precursor article is sintered or reactive sintered.
17. The method according to claim 1 , wherein the magnetocalorically active phase is La 1-a R a (Fe 1-x-y T y M x ) 13 H z , wherein M is at least one element from the group consisting of Si and Al, T is at least one element from the group consisting of Co, Ni, Mn and Cr, R is at least one element from the group consisting of Ce, Nd and Pr, 0≦a≦0.5, 0.05≦x≦0.2, 0≦y≦0.2 and 0≦z≦3.