Surface modified stainless steels for PEM fuel cell bipolar plates
View Patent ↗A nitridation treated stainless steel article (such as a bipolar plate for a proton exchange membrane fuel cell) having lower interfacial contact electrical resistance and better corrosion resistance than an untreated stainless steel article is disclosed. The treated stainless steel article has a surface layer including nitrogen-modified chromium-base oxide and precipitates of chromium nitride formed during nitridation wherein oxygen is present in the surface layer at a greater concentration than nitrogen. The surface layer may further include precipitates of titanium nitride and/or aluminum oxide. The surface layer in the treated article is chemically heterogeneous surface rather than a uniform or semi-uniform surface layer exclusively rich in chromium, titanium or aluminum. The precipitates of titanium nitride and/or aluminum oxide are formed by the nitriding treatment wherein titanium and/or aluminum in the stainless steel are segregated to the surface layer in forms that exhibit a low contact resistance and good corrosion resistance.
1. An article comprising:
stainless steel having a surface layer including nitrogen-modified chromium-base oxide and precipitates of chromium nitride, wherein oxygen is present in the surface layer at a greater concentration than nitrogen,
wherein the article includes surface grains of precipitates of chromium nitride.
2. The article of claim 1 wherein:
the surface layer is 1 micron thick or less.
3. The article of claim 1 wherein:
the surface layer is 100 nanometers thick or less.
4. The article of claim 1 wherein:
the surface layer further includes precipitates of titanium nitride, and
the nitrogen-modified chromium-base oxide is present in the surface layer at a greater concentration than the precipitates of chromium nitride and the precipitates of titanium nitride combined.
5. The article of claim 4 wherein:
the surface layer further includes precipitates of aluminum oxide, and
the nitrogen-modified chromium-base oxide and the precipitates of aluminum oxide are present in the surface layer at a greater concentration than the precipitates of chromium nitride and the precipitates of titanium nitride combined.
6. The article of claim 1 wherein:
the surface layer further includes precipitates of a transition metal nitride.
7. The article of claim 1 wherein:
the stainless steel comprises nickel at a level of less than 5 weight percent based on the total weight of the stainless steel.
8. The article of claim 7 wherein:
the stainless steel is ferritic.
9. The article of claim 1 wherein:
the stainless steel comprises greater than 20 weight percent nickel based on the total weight of the stainless steel.
10. The article of claim 9 wherein:
the stainless steel is austenitic.
11. The article of claim 1 wherein:
the stainless steel comprises titanium at a level of 1 weight percent or less based on the total weight of the stainless steel.
12. The article of claim 1 wherein:
the surface layer is a chemically heterogeneous surface and not a uniform or semi-uniform surface layer exclusively rich in chromium.
13. A proton exchange membrane fuel cell comprising the article of claim 1 as a bipolar plate.
14. A sensor comprising the article of claim 1 as a bipolar plate.
15. A process for increasing the corrosion resistance and decreasing the interfacial contact electrical resistance of a stainless steel article, the process comprising:
(a) providing an article comprising stainless steel having a surface layer including chromium-base oxide;
(b) exposing the surface layer to an atmosphere comprising nitrogen without prior removal of the surface layer to introduce nitrogen into the chromium-base oxide and to form precipitates of chromium nitride in the surface layer; and
(c) ceasing exposure of the surface layer to the atmosphere before the volume of precipitates of chromium nitride degrades the corrosion resistance.
16. The process of claim 15 wherein:
the atmosphere consists of nitrogen or a nitrogen-hydrogen mixture.
17. The process of claim 15 wherein:
the atmosphere is free from oxygen.
18. The process of claim 15 wherein:
step (b) is conducted at a temperature in the range of 800° C. to 1200° C.
19. The process of claim 15 wherein:
step (c) comprises ceasing exposure of the surface layer to the atmosphere when nitrogen uptake for the surface layer exceeds 1 mg/cm 2 .
20. The process of claim 15 wherein:
step (c) comprises ceasing exposure of the surface layer to the atmosphere when nitrogen uptake for the surface layer is in the range of 0.05 mg/cm 2 to 0.75 mg/cm 2 .
21. The process of claim 15 wherein:
step (c) comprises ceasing exposure of the surface layer to the atmosphere when nitrogen uptake for the surface layer is in the range of 0.25 mg/cm 2 to 0.5 mg/cm 2 .
22. The process of claim 15 wherein:
nitrogen modified chromium-base oxide is present in the surface layer at a greater concentration than the precipitates of chromium nitride in the surface layer after ceasing exposure of the surface layer to the atmosphere.
23. The process of claim 15 wherein:
the stainless steel comprises titanium at a level of 1 weight percent or less based on the total weight of the stainless steel, and
the surface layer includes precipitates of titanium nitride after exposing the surface layer to the atmosphere.
24. The process of claim 23 wherein:
the surface layer further includes precipitates of aluminum oxide after exposing the surface layer to the atmosphere, and
chromium-base oxide and the precipitates of aluminum oxide are present in the surface layer at a greater concentration than the precipitates of chromium nitride and the precipitates of titanium nitride combined.
25. The process of claim 15 wherein:
the interfacial contact electrical resistance of the article is 50 milliohms/cm 2 or less at a contact force of 100-150 N/cm 2 after ceasing exposure of the surface layer to the atmosphere.
26. The process of claim 15 wherein:
the interfacial contact electrical resistance of the article is 30 milliohms/cm 2 or less at a contact force of 150 N/cm 2 after ceasing exposure of the surface layer to the atmosphere.
27. The process of claim 15 wherein:
the interfacial contact electrical resistance of the article is 20 milliohms/cm 2 or less at a contact force of 150 N/cm 2 after ceasing exposure of the surface layer to the atmosphere.
28. The process of claim 15 wherein:
oxygen is present in the surface layer at a greater concentration than nitrogen after ceasing exposure of the surface layer to the atmosphere.
29. The process of claim 15 wherein:
the article is a bipolar plate of a fuel cell.
30. The process of claim 15 wherein:
the article is a bipolar plate of a sensor.
31. A proton exchange membrane fuel cell comprising:
a bipolar plate comprising stainless steel having a surface layer including nitrogen-modified chromium-base oxide and precipitates of chromium nitride, wherein oxygen is present in the surface layer at a greater concentration than nitrogen.
32. The proton exchange membrane fuel cell of claim 31 wherein:
the surface layer is 1 micron thick or less.
33. The proton exchange membrane fuel cell of claim 31 wherein:
the surface layer further includes precipitates of titanium nitride, and
the nitrogen-modified chromium-base oxide is present in the surface layer at a greater concentration than the precipitates of chromium nitride and the precipitates of titanium nitride combined.
34. The proton exchange membrane fuel cell of claim 31 wherein:
the surface layer further includes precipitates of aluminum oxide, and
the nitrogen-modified chromium-base oxide and the precipitates of aluminum oxide are present in the surface layer at a greater concentration than the precipitates of chromium nitride and the precipitates of titanium nitride combined.
35. The proton exchange membrane fuel cell of claim 31 wherein:
the stainless steel comprises nickel at a level of less than 5 weight percent based on the total weight of the stainless steel.
36. The proton exchange membrane fuel cell of claim 31 wherein:
the stainless steel comprises greater than 20 weight percent nickel based on the total weight of the stainless steel.
37. A sensor comprising:
a bipolar plate comprising stainless steel having a surface layer including nitrogen-modified chromium-base oxide and precipitates of chromium nitride, wherein oxygen is present in the surface layer at a greater concentration than nitrogen.
38. The sensor of claim 37 wherein:
the surface layer is 1 micron thick or less.
39. The sensor of claim 37 wherein:
the surface layer further includes precipitates of titanium nitride, and
the nitrogen-modified chromium-base oxide is present in the surface layer at a greater concentration than the precipitates of chromium nitride and the precipitates of titanium nitride combined.
40. The sensor of claim 37 wherein:
the surface layer further includes precipitates of aluminum oxide, and
the nitrogen-modified chromium-base oxide and the precipitates of aluminum oxide are present in the surface layer at a greater concentration than the precipitates of chromium nitride and the precipitates of titanium nitride combined.
41. The sensor of claim 37 wherein:
the stainless steel comprises nickel at a level of less than 5 weight percent based on the total weight of the stainless steel.
42. The sensor of claim 37 wherein:
the stainless steel comprises greater than 20 weight percent nickel based on the total weight of the stainless steel.