Metallic crucibles and methods of forming the same
View Patent ↗In various embodiments, a precursor powder is pressed into an intermediate volume and chemically reduced, via sintering, to form a metallic shaped article.
1. A method of fabricating a shaped article having a target set of final dimensions and consisting essentially of at least one metal, the method comprising:
pressing a precursor powder into a volume having intermediate dimensions larger than the final dimensions along at least one direction, the precursor powder comprising a compound comprising (i) the at least one metal and (ii) a non-metallic chemical species; and
thereafter, sintering the pressed precursor powder to (i) chemically reduce the precursor powder, (ii) shrink the volume having intermediate dimensions into the shaped article having the final dimensions, and (iii) release a non-metallic by-product,
wherein sintering the pressed precursor powder comprises:
sintering at a first temperature selected from the range of approximately 450° C. to approximately 650° C. for a first time selected from the range of approximately 4 hours to approximately 6 hours;
thereafter, sintering at a second temperature selected from the range of approximately 500° C. to approximately 700° C. for a second time selected from the range of approximately 5 hours to approximately 7 hours;
thereafter, sintering at a third temperature selected from the range of approximately 800° C. to approximately 1000° C. for a third time selected from the range of approximately 1 hour to approximately 5 hours; and
thereafter, sintering at a fourth temperature selected from the range of approximately 1450° C. to approximately 1800° C. for a fourth time selected from the range of approximately 6 hours to approximately 25 hours.
2. The method of claim 1 , wherein the non-metallic species comprises at least one of oxygen or ammonium.
3. The method of claim 1 , wherein the at least one metal comprises molybdenum.
4. The method of claim 1 , wherein the precursor powder comprises ammonium dimolybdate.
5. The method of claim 1 , wherein the volume shrinkage from the intermediate dimensions to the final dimensions is within the range of approximately 50% to approximately 70%.
6. The method of claim 1 , wherein the precursor powder is pressed by cold isostatic pressing.
7. The method of claim 1 , wherein each of at least two of the sintering stages comprises chemical reduction of the pressed powder to a different intermediate product.
8. The method of claim 1 , wherein the shaped article has a density ranging between approximately 90% and approximately 95% after sintering.
9. The method of claim 1 , wherein the sintering is performed in an atmosphere comprising hydrogen.
10. The method of claim 1 , wherein the shaped article comprises a crucible.
11. The method of claim 1 , wherein the by-product comprises at least one of ammonia, oxygen, or water vapor.
12. The method of claim 1 , further comprising, after sintering the pressed precursor powder:
cooling the shaped article to a fifth temperature less than the fourth temperature and greater than 100° C.; and
holding the shaped article at the fifth temperature (i) for a fifth time selected from the range of approximately 1 hour to approximately 8 hours and (ii) within an ambient comprising hydrogen.
13. The method of claim 12 , further comprising, after holding the shaped article at the fifth temperature for the fifth time, holding the shaped article at a sixth temperature less than the fourth temperature and greater than 100° C. (i) for a sixth time selected from the range of approximately 1 hour to approximately 8 hours and (ii) within an ambient comprising nitrogen.
14. The method of claim 13 , wherein the fifth temperature is approximately equal to the sixth temperature.
15. The method of claim 1 , further comprising disposing an additive on at least one surface of the shaped article.
16. The method of claim 15 , further comprising annealing the shaped article, thereby at least one of alloying or mixing the additive with the at least one metal to form a treated article.
17. The method of claim 16 , wherein the treated article comprises (i) an inner layer comprising an alloy or mixture of the additive and the at least one metal, (ii) an outer layer consisting essentially of the at least one metal, and (iii) therebetween, a zone comprising a graded concentration of the alloy or mixture of the additive and the at least one metal.
18. The method of claim 16 , wherein the at least one surface of the treated article comprises an alloy of the at least one metal and the additive.
19. The method of claim 16 , wherein a concentration of the additive varies as a function of thickness of the treated article.
20. The method of claim 19 , wherein the concentration of the additive is graded.
21. The method of claim 16 , wherein a portion of a thickness of the treated article is substantially free of the additive.
22. The method of claim 16 , wherein a grain size of the treated article is approximately equal to a grain size of the shaped article.
23. The method of claim 15 , wherein the additive comprises at least one of tungsten or copper.
24. The method of claim 15 , wherein the additive is a powder.
25. The method of claim 24 , wherein disposing the additive comprises at least one of sprinkling, applying a slurry, or spray deposition.
26. A method of fabricating a shaped article having a target set of final dimensions and consisting essentially of at least one metal, the method comprising:
pressing a precursor powder into a volume having intermediate dimensions larger than the final dimensions along at least one direction, the precursor powder comprising a compound comprising (i) the at least one metal and (ii) a non-metallic chemical species; and
thereafter, sintering the pressed precursor powder to (i) chemically reduce the precursor powder, (ii) shrink the volume having intermediate dimensions into the shaped article having the final dimensions, and (iii) release a non-metallic by-product,
wherein sintering the pressed precursor powder comprises:
sintering at a first temperature selected from the range of approximately 450° C. to approximately 650° C. for a first time selected from the range of approximately 4 hours to approximately 6 hours;
thereafter, sintering at a second temperature greater than the first temperature and less than approximately 700° C. for a second time selected from the range of approximately 5 hours to approximately 7 hours;
thereafter, sintering at a third temperature greater than the second temperature and less than approximately 1000° C. for a third time selected from the range of approximately 1 hour to approximately 5 hours; and
thereafter, sintering at a fourth temperature greater than the third temperature and less than approximately 1800° C. for a fourth time selected from the range of approximately 6 hours to approximately 25 hours.
27. The method of claim 26 , wherein the non-metallic species comprises at least one of oxygen or ammonium.
28. The method of claim 26 , wherein the at least one metal comprises molybdenum.
29. The method of claim 26 , wherein the precursor powder comprises ammonium dimolybdate.
30. The method of claim 26 , wherein the volume shrinkage from the intermediate dimensions to the final dimensions is within the range of approximately 50% to approximately 70%.
31. The method of claim 26 , wherein the precursor powder is pressed by cold isostatic pressing.
32. The method of claim 26 , wherein each of at least two of the sintering stages comprises chemical reduction of the pressed powder to a different intermediate product.
33. The method of claim 26 , wherein the shaped article has a density ranging between approximately 90% and approximately 95% after sintering.
34. The method of claim 26 , wherein the sintering is performed in an atmosphere comprising hydrogen.
35. The method of claim 26 , wherein the shaped article comprises a crucible.
36. The method of claim 26 , wherein the by-product comprises at least one of ammonia, oxygen, or water vapor.
37. The method of claim 26 , further comprising, after sintering the pressed precursor powder:
cooling the shaped article to a fifth temperature less than the fourth temperature and greater than 100° C.; and
holding the shaped article at the fifth temperature (i) for a fifth time selected from the range of approximately 1 hour to approximately 8 hours and (ii) within an ambient comprising hydrogen.
38. The method of claim 37 , further comprising, after holding the shaped article at the fifth temperature for the fifth time, holding the shaped article at a sixth temperature less than the fourth temperature and greater than 100° C. (i) for a sixth time selected from the range of approximately 1 hour to approximately 8 hours and (ii) within an ambient comprising nitrogen.
39. The method of claim 38 , wherein the fifth temperature is approximately equal to the sixth temperature.
40. The method of claim 26 , further comprising disposing an additive on at least one surface of the shaped article.
41. The method of claim 40 , further comprising annealing the shaped article, thereby at least one of alloying or mixing the additive with the at least one metal to form a treated article.
42. The method of claim 41 , wherein the treated article comprises (i) an inner layer comprising an alloy or mixture of the additive and the at least one metal, (ii) an outer layer consisting essentially of the at least one metal, and (iii) therebetween, a zone comprising a graded concentration of the alloy or mixture of the additive and the at least one metal.
43. The method of claim 41 , wherein the at least one surface of the treated article comprises an alloy of the at least one metal and the additive.
44. The method of claim 41 , wherein a concentration of the additive varies as a function of thickness of the treated article.
45. The method of claim 44 , wherein the concentration of the additive is graded.
46. The method of claim 41 , wherein a portion of a thickness of the treated article is substantially free of the additive.
47. The method of claim 41 , wherein a grain size of the treated article is approximately equal to a grain size of the shaped article.
48. The method of claim 40 , wherein the additive comprises at least one of tungsten or copper.
49. The method of claim 40 , wherein the additive is a powder.
50. The method of claim 49 , wherein disposing the additive comprises at least one of sprinkling, applying a slurry, or spray deposition.
51. A method of fabricating a shaped article having a target set of final dimensions and consisting essentially of at least one metal, the method comprising:
pressing a precursor powder into a volume having intermediate dimensions larger than the final dimensions along at least one direction, the precursor powder comprising a compound comprising (i) the at least one metal and (ii) a non-metallic chemical species; and
thereafter, sintering the pressed precursor powder to (i) chemically reduce the precursor powder, (ii) shrink the volume having intermediate dimensions into the shaped article having the final dimensions, and (iii) release a non-metallic by-product,
wherein the pressed precursor powder is sintered at a first temperature, and further comprising, after sintering the pressed precursor powder:
cooling the shaped article to a second temperature less than the first temperature and greater than 100° C.; and
holding the shaped article at the second temperature (i) for a first time selected from the range of approximately 1 hour to approximately 8 hours and (ii) within an ambient comprising hydrogen.
52. The method of claim 51 , further comprising, after holding the shaped article at the second temperature for the first time, holding the shaped article at a third temperature less than the first temperature and greater than 100° C. (i) for a second time selected from the range of approximately 1 hour to approximately 8 hours and (ii) within an ambient comprising nitrogen.
53. The method of claim 52 , wherein the second temperature is approximately equal to the third temperature.
54. The method of claim 51 , wherein the non-metallic species comprises at least one of oxygen or ammonium.
55. The method of claim 51 , wherein the at least one metal comprises molybdenum.
56. The method of claim 51 , wherein the precursor powder comprises ammonium dimolybdate.
57. The method of claim 51 , wherein the volume shrinkage from the intermediate dimensions to the final dimensions is within the range of approximately 50% to approximately 70%.
58. The method of claim 51 , wherein the precursor powder is pressed by cold isostatic pressing.
59. The method of claim 51 , wherein sintering the pressed precursor powder comprises a plurality of heating stages each at a different maximum temperature.
60. The method of claim 59 , wherein each of at least two of the heating stages comprises chemical reduction of the pressed powder to a different intermediate product.
61. The method of claim 51 , wherein the shaped article has a density ranging between approximately 90% and approximately 95% after sintering.
62. The method of claim 51 , wherein the sintering is performed in an atmosphere comprising hydrogen.
63. The method of claim 51 , wherein the shaped article comprises a crucible.
64. The method of claim 51 , wherein the by-product comprises at least one of ammonia, oxygen, or water vapor.
65. The method of claim 51 , wherein sintering the pressed precursor powder comprises:
sintering at a third temperature less than approximately 1000° C. for at least 2 hours; and
thereafter, sintering at the first temperature for at least 6 hours, the first temperature being selected from the range of approximately 1450° C. to approximately 1800° C.
66. The method of claim 51 , further comprising disposing an additive on at least one surface of the shaped article.
67. The method of claim 66 , further comprising annealing the shaped article, thereby at least one of alloying or mixing the additive with the at least one metal to form a treated article.
68. The method of claim 67 , wherein the treated article comprises (i) an inner layer comprising an alloy or mixture of the additive and the at least one metal, (ii) an outer layer consisting essentially of the at least one metal, and (iii) therebetween, a zone comprising a graded concentration of the alloy or mixture of the additive and the at least one metal.
69. The method of claim 67 , wherein the at least one surface of the treated article comprises an alloy of the at least one metal and the additive.
70. The method of claim 67 , wherein a concentration of the additive varies as a function of thickness of the treated article.
71. The method of claim 70 , wherein the concentration of the additive is graded.
72. The method of claim 67 , wherein a portion of a thickness of the treated article is substantially free of the additive.
73. The method of claim 67 , wherein a grain size of the treated article is approximately equal to a grain size of the shaped article.
74. The method of claim 66 , wherein the additive comprises at least one of tungsten or copper.
75. The method of claim 66 , wherein the additive is a powder.
76. The method of claim 75 , wherein disposing the additive comprises at least one of sprinkling, applying a slurry, or spray deposition.