Martensitic stainless steel strengthened by copper-nucleated nitride precipitates

1. A case hardened martensitic stainless steel alloy strengthened by copper-nucleated nitride precipitates, said alloy comprising, in combination by weight percent, about 10.0 to about 14.5 Cr, about 0.3 to about 7.5 Ni, Co up to about 17.0 Co, about 0.6 to about 1.5 Mo, about 0.25 to about 2.3 Cu, up to about 0.6 Mn, up to about 0.4 Si, about 0.05 to about 0.15 V, up to about 0.10 N, C up to about 0.2 C, up to about 0.01 W, and the balance Fe and incidental elements and impurities, said alloy having a microstructure substantially free of cementite carbides and comprising a martensite matrix with nanoscale copper particles and alloy nitride precipitates selected from the group consisting of alloy nitride precipitates enriched with a transition metal nucleated on the copper precipitates, said alloy nitride precipitates having a hexagonal structure, said alloy nitride precipitates including one or more alloying elements selected from the group Fe, Ni, Cr, Co and Mn coherent with the matrix, and said alloy nitride precipitates having two dimensional coherency with the matrix, said alloy substantially free of cementite carbide precipitates in the form of a case hardened article of manufacture.

2. The alloy of claim 1 , wherein the alloy has a core tensile yield strength of about 150 to 175 ksi, a core ultimate strength of about 190 to 225 ksi and a fracture toughness of about 50 to 115 ksi√in.

3. The alloy of claim 1 , wherein the alloy has a martensite start temperature of at least about 50° C.

4. The alloy of claim 1 , wherein the alloy comprises precipitates of a copper-based phase and nitride precipitates enriched with transition metals.

5. The alloy of claim 4 , wherein the nitride precipitates nucleate on the copper-based phase, and comprise at least one metal selected from a group consisting of chromium, molybdenum, and vanadium.

6. The alloy of claim 1 wherein the alloy has a case hardness greater than about 59 HRC.

7. The alloy of claim 6 wherein said case includes at least about 90% of by volume martensitic matrix.

8. The alloy of claim 1 wherein the N to C ratio is in the range of about 2 to 10.

9. A case hardenable stainless steel alloy strengthened by copper-nucleated precipitates, said alloy comprising, in combination by weight percent, a melt of about 10.0 to about 14.5 Cr, about 0.3 to about 7.5 Ni, Co up to about 17.0 Co, about 0.6 to about 1.5 Mo, about 0.25 to about 2.3 Cu, up to about 0.6 Mn, up to about 0.4 Si, about 0.05 to about 0.15 V, C up to about 0.2 C, up to about 0.01 W, and the balance Fe and incidental elements and impurities, and having a hardenable case effected by the addition of up to about 0.10 N with a resulting microstructure substantially free of cementite carbides and comprising a martensite matrix with nanoscale copper particles and alloy nitride precipitates selected from the group consisting of alloy nitride precipitates enriched with a transition metal nucleated on the copper precipitates, said alloy nitride precipitates having a hexagonal structure, said alloy nitride precipitates including one or more alloying elements selected from the group Fe, Ni, Cr, Co and Mn coherent with the matrix, wherein the N is incorporated in said alloy by at least one processing step selected from the group consisting of (a) inclusion in the melt, and (b) subsequent addition of N by solution treatment of the cast melt and tempering.

10. The alloy of claim 9 , wherein the alloy comprises precipitates of a copper-based phase and nitride precipitates enriched with transition metals.

11. The alloy of claim 10 , wherein the nitride precipitates nucleate on the copper-based phase, and comprise at least one metal selected from a group consisting of chromium, molybdenum, and vanadium.

12. The alloy of claim 9 wherein the alloy has a case hardness greater than about 59 HRC.

13. The alloy of claim 12 wherein said case includes at least about 90% of by volume martensitic matrix.

14. The alloy of claim 9 wherein the N to C ratio is in the range of about 2 to 10.

15. The alloy of claim 9 wherein said alloy has a case hardness of at least about 48 HRC at a case depth of 0.02 inches.

16. A case hardened martensitic, stainless steel alloy in the form of an article of manufacture strengthened by copper-nucleated nitride precipitates, said alloy comprising, in combination by weight percent, about 10.0 to about 14.5 Cr, about 0.3 to about 7.5 Ni, Co up to about 17.0 Co, about 0.6 to about 1.5 Mo, about 0.25 to about 2.3 Cu, up to about 0.6 Mn, up to about 0.4 Si, about 0.05 to about 0.15 V, up to about 0.10 N, C up to about 0.2 C, up to about 0.01 W, and the balance Fe and incidental elements and impurities, said alloy having a microstructure substantially free of cementite carbides and comprising a martensite matrix with nanoscale copper particles and alloy nitride precipitates selected from the group consisting of alloy nitride precipitates enriched with a transition metal nucleated on the copper precipitates, said alloy nitride precipitates having a hexagonal structure, said alloy nitride precipitates including one or more alloying elements selected from the group Fe, Ni, Cr, Co and Mn coherent with the matrix.

17. The alloy of claim 16 , wherein the alloy has a core tensile yield strength of about 150 to 175 ksi, a core ultimate strength of about 190 to 225 ksi and a fracture toughness of about 50 to 115 ksi√in.

18. The alloy of claim 16 , wherein the alloy has a martensite start temperature of at least about 50° C.

19. The alloy of claim 16 , wherein the alloy comprises precipitates of a copper-based phase and nitride precipitates enriched with transition metals.