US2006065327A1PendingUtilityA1
Fine-grained martensitic stainless steel and method thereof
Est. expiryFeb 7, 2023(expired)· nominal 20-yr term from priority
Inventors:Robert F. Buck
C22C 38/02C22C 38/06C22C 38/54C21D 2211/004C21D 9/08C22C 38/48Y10T428/12764C22C 38/04C22C 38/46C22C 38/50C22C 38/44C21D 2211/008C21D 6/007C22C 1/06C21D 6/004C21D 6/005
46
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Claims
Abstract
A martensitic alloy in which the ASTM grain size number is at least 5, including (wt. %) up to about 0.5% C, at least about 5% Cr, at least about 0.5% Ni, up to about 15% Co, up to about 8% Cu, up to about 8% Mn, up to about 4% Si, up to about 6% (Mo+W), up to about 1.5% Ti, up to about 3% V, up to about 0.5% Al, and at least about 40% Fe.
Claims
exact text as granted — not AI-modified1 . A martensitic alloy in which the ASTM grain size number is at least 5, comprising (wt. %):
about 0.05% to about 0.15% C; about 7.5% to about 15% Cr; about 1% to about 7% Ni; up to about 10% Co; up to about 5% Cu; up to about 5% Mn; up to about 1.5% Si; up to about 4% (Mo+W); about 0.01% to about 0.75% Ti; up to about 2% V; up to about 1.7% Nb; up to about 0.29% Al; and at least about 40% Fe.
2 . The alloy of claim 1 , comprising at least about 0.005% (Al+Si+Ti).
3 . (canceled)
4 . (canceled)
5 . (canceled)
6 . (canceled)
7 . (canceled)
8 . (canceled)
9 . (canceled)
10 . The alloy of any of the preceding claims comprising at least about 2% Ni.
11 . The alloy of any of the preceding claims comprising about 1 to about 5% Ni.
12 . (canceled)
13 . The alloy of any of the preceding claims comprising up to about 1.5% Co.
14 . The alloy of any of the preceding claims comprising up to about 4% Co.
15 . (canceled)
16 . The alloy of any of the preceding claims comprising up to about 3% Cu.
17 . The alloy of any of the preceding claims comprising up to about 1.2% Cu.
18 . (canceled)
19 . The alloy of any of the preceding claims comprising up to about 3% Mn.
20 . The alloy of any of the preceding claims comprising up to about 1% Mn.
21 . (canceled)
22 . (canceled)
23 . The alloy of any of the preceding claims comprising up to about 1% Si.
24 . (canceled)
25 . The alloy of any of the preceding claims comprising up to about 3% (Mo+W).
26 . The alloy of any of the preceding claims comprising up to about 2% (Mo+W).
27 . (canceled)
28 . The alloy of any of the preceding claims comprising up to about 0.5% Ti.
29 . (canceled)
30 . (canceled)
31 . The alloy of any of the preceding claims comprising up to about 1% V.
32 . The alloy of any of the preceding claims comprising up to about 0.5% V.
33 . (canceled)
34 . The alloy of any of the preceding claims comprising up to about 0.1% Al.
35 . The alloy of any of the preceding claims comprising up to about 0.05% Al.
36 . The alloy of any of the preceding claims comprising at least about 50% Fe.
37 . The alloy of any of the preceding claims comprising at least about 60% Fe.
38 . The alloy of any of the preceding claims comprising at least about 80% Fe.
39 . The alloy of any of the preceding claims, comprising at least about 0.01% (Al+Si+Ti).
40 . The alloy of any of the preceding claims, comprising at least about 0.02% (Al+Si+Ti).
41 . The alloy of any of the preceding claims, comprising at least about 0.04% (Al+Si+Ti).
42 . The alloy of any of the preceding claims, wherein the ASTM grain size number is at least 7.
43 . The alloy of any of the preceding claims, wherein the ASTM grain size number is at least 10.
44 . The alloy of any of the preceding claims, wherein the ASTM grain size number is at least 12.
45 . The alloy of any of the preceding claims, further comprising secondary MX particles having an average size less than about 400 nm.
46 . The alloy of any of the preceding claims, further comprising secondary MX particles having an average size less than about 200 nm.
47 . The alloy of any of the preceding claims, further comprising secondary MX particles having an average size less than about 100 nm.
48 . The alloy of any of the preceding claims, further comprising secondary MX particles having an average size less than about 50 nm.
49 . The alloy of any of the preceding claims, wherein the Ac1 temperature is between 500° C. and 820° C.
50 . The alloy of any of the preceding claims, wherein the alloy is in a hot worked condition.
51 . The alloy of any of the preceding claims, wherein the alloy is in a rolled condition.
52 . The alloy of any of the preceding claims, wherein the alloy is in a cast condition.
53 . The alloy of any of the preceding claims, wherein the alloy is in a forged condition.
54 . The alloy of any of the preceding claims, also comprising less than 6% copper, less than 5% manganese, less than 1.5% silicon, less than 2% zirconium, less than 4% tantalum, less than 4% hafnium, less than 1% niobium, less than 2% vanadium, less than 0.1% of each member of the group consisting of calcium, cerium, magnesium, scandium, yttrium, lanthanum, beryllium, and boron, and less than 0.1% of each member of the group consisting of sulfur, phosphorus, tin, antimony, and oxygen.
55 . The alloy of any of the preceding claims, wherein Cr+Ni is in the range 5.0% to 14.5%.
56 . The alloy of any of the preceding claims, wherein W+Si+Mo is less than 4%.
57 . The alloy of any of the preceding claims, wherein:
0.135<1.17Ti+0.6Nb+0.6Zr+0.31Ta+0.31Hf<1.0.
58 . The alloy of any of the preceding claims, wherein the structure contains less than 40% delta ferrite by volume.
59 . A method of producing an alloy comprising:
preparing an alloy comprising (wt. %):
about 0.05% to about 0.15% C;
about 7.5% to about 15% Cr.
about 1% to about 7% Ni;
up to about 10% Co;
up to about 5% Cu;
up to about 5% Mn;
up to about 1.5% Si;
up to about 4% (Mo+W);
about 0.01% to about 0.75% Ti;
up to about 2% V;
up to about 1.7% Nb;
up to about 0.2% Al; and
at least about 40% Fe;
hot working the alloy at a temperature greater than about 800° C. to impart a true strain of greater than about 0.075 (7.5%); and cooling the alloy to room temperature to obtain a fine-grained martensitic microstructure.
60 . (canceled)
61 . The method of any of the preceding claims, wherein the hot working temperature is at least about 900° C.
62 . The method of any of the preceding claims, wherein the hot working temperature is at least about 1000° C.
63 . The method of any of the preceding claims, wherein the hot working temperature is at least about 1200° C.
64 . The method of any of the preceding claims, wherein the true strain is greater than about 0.10 (10%).
65 . The method of any of the preceding claims, wherein the true strain is greater than about 0.15 (15%).
66 . The method of any of the preceding claims, wherein the true strain is greater than about 0.20 (20%).
67 . The method of any of the preceding claims, the alloy comprising at least about 0.005% (Al+Si+Ti).
68 . (canceled)
69 . (canceled)
70 . (canceled)
71 . (canceled)
72 . (canceled)
73 . (canceled)
74 . (canceled)
75 . The method of any of the preceding claims, the alloy comprising at least about 2% Ni.
76 . The method of any of the preceding claims, the alloy comprising about 1 to about 5% Ni.
77 . (canceled)
78 . The method of any of the preceding claims, the alloy comprising up to about 7.5% Co.
79 . The method of any of the preceding claims, the alloy comprising up to about 4% Co.
80 . (canceled)
81 . The method of any of the preceding claims, the alloy comprising up to about 3% Cu.
82 . The method of any of the preceding claims, the alloy comprising up to about 1.2% Cu.
83 . (canceled)
84 . The method of any of the preceding claims, the alloy comprising up to about 3% Mn.
85 . The method of any of the preceding claims, the alloy comprising up to about 1% Mn.
86 . (canceled)
87 . (canceled)
88 . The method of any of the preceding claims, the alloy comprising up to about 1% Si.
89 . (canceled)
90 . The method of any of the preceding claims, the alloy comprising up to about 3% (Mo+W).
91 . The method of any of the preceding claims, the alloy comprising up to about 2% (Mo+W).
92 . (canceled)
93 . The method of any of the preceding claims, the alloy comprising up to about 0.5% Ti.
94 . (canceled)
95 . (canceled)
96 . The method of any of the preceding claims, the alloy comprising up to about 1% V.
97 . The method of any of the preceding claims, the alloy comprising up to about 0.5% V.
98 . (canceled)
99 . The method of any of the preceding claims, the alloy comprising up to about 0.1% Al.
100 . The method of any of the preceding claims, the alloy comprising up to about 0.05% Al.
101 . The method of any of the preceding claims, the alloy comprising at least about 50% Fe.
102 . The method of any of the preceding claims, the alloy comprising at least about 60% Fe.
103 . The method of any of the preceding claims, the alloy comprising at least about 80% Fe.
104 . The method of any of the preceding claims, the alloy comprising at least about 0.01% (Al+Si+Ti).
105 . The method of any of the preceding claims, the alloy comprising at least about 0.02% (Al+Si+Ti).
106 . The method of any of the preceding claims, the alloy comprising at least about 0.04% (Al+Si+Ti).
107 . The method of any of the preceding claims, the alloy having an ASTM grain size number of at least 5.
108 . The method of any of the preceding claims, the alloy having an ASTM grain size number of at least 7.
109 . The method of any of the preceding claims, the alloy having an ASTM grain size number of at least 10.
110 . The method of any of the preceding claims, the alloy having an ASTM grain size number of at least 12.
111 . The method of any of the preceding claims, the alloy having secondary MX particles having an average size less than about 400 nm.
112 . The method of any of the preceding claims, the alloy having secondary MX particles having an average size less than about 200 nm.
113 . The method of any of the preceding claims, the alloy having secondary MX particles having an average size less than about 100 nm.
114 . The method of any of the preceding claims, the alloy having secondary MX particles having an average size less than about 50 nm.
115 . A fine-grained iron base alloy in which the ASTM grain size number is greater than or equal to 5, comprising (wt. %) about 0.09 C, 10.7 Cr, 2.9 Ni, 0.4 Mn, 0.5 Mo, 0.15 Si, 0.04 Al, 0.25 Ti, 0.12 V, 0.08 Nb, 0.002 B, and the balance essentially iron and impurities.
116 . A method of producing a fine-grained iron base alloy comprising:
preparing an Iron base alloy comprising (wt. %) about: 0.09 C, 10.7 Cr, 2.9 Ni, 0.4 Mn, 0.5 Mo, 0.15 Si, 0.04 Al, 0.25 Ti, 0.12 V, 0.06 Nb, 0.002 B, and the balance essentially iron and impurities, thermal mechanically treating by austenitizing it at a temperature above 1000° C., hot working the alloy at a temperature greater than 1000° C. to impart a true strain of greater than about 0.15 (15%), and cooling the alloy to room temperature to obtain a fine-grained martensitic microstructure in which the ASTM grain size number is greater than or equal to 5.
117 . An article of manufacture comprising an Iron based alloy, the alloy having an ASTM grain size of at least about 5, the alloy comprising (wt. %):
about 0.05% to about 0.15% C; about 7.5% to about 15% Cr; about 1% to about 7% Ni; up to about 10% Co; up to about 5% Cu; up to about 5% Mn; up to about 1.5% Si; up to about 4% (Mo+W); about 0.01% to about 0.75% Ti; up to about 2% V; up to about 1.7% Nb; up to about 0.2% Al; and at least about 40% Fe.
118 . The article of manufacture claimed in claim 117 wherein the alloy is in a cast condition.
119 . The article of manufacture claimed in claim 117 wherein the alloy is in a forged condition.
120 . The article of manufacture as claimed in claim 117 wherein the alloy is in a hot worked condition.
121 . The article of manufacture as claimed in claim 117 wherein the alloy is in a rolled condition.
122 . The article of manufacture of any of the preceding claims, wherein the article of manufacture is used in the chemical or petrochemical industries.
123 . The article of manufacture of any of the preceding claims, wherein the article of manufacture is selected from the group consisting of boiler tubes, steam headers, turbine rotors, turbine blades, cladding materials, gas turbine discs, and gas turbine components.
124 . The article of manufacture of any of the preceding claims, wherein the article of manufacture comprises a tubular member.
125 . The article of manufacture of any of the preceding claims, wherein the article of manufacture comprises a tubular member installed in a borehole.
126 . A fine-grained iron base martensitic alloy in which the ASTM grain size number is greater than or equal to 5, consisting essentially of (wt. %): 0.05<C<0.15; 7.5<Cr<15; 1<Ni<7; Co<10, Cu<5; Mn<5; Si<1.5; (Mo+W)<4; 0.01<Ti<0.75; 0.135<(1.17Ti +0.6 Nb+0.6 Zr+0.31 Ta+0.31 Hf)<1; V<2; N<0.1; Al<0.2; (Al+Si+Ti)>0.1; each of B, Ce, Ca, Mg, Sc, Y, La, and Be less than 0.1; P<0.1; S<0.05; each of Sn, Sb, O, Pb and other impurities less than 0.1; and the balance essentially iron.
127 . A method of producing a fine-grained iron base alloy comprising:
preparing an iron base alloy consisting essentially of (wt. %): 0.05<C<0.15; 7.5<Cr<15; 1<Ni<7; Co<10, Cu<5; Mn<5; Si<1.5; (Mo+W)<4; 0.01<Ti<0.75; 0.135<(1.17 Ti+0.6 Nb+0.6Zr+0.31 Ta+0.31 Hf)<1; V<2; N<0.1; Al<0.2; (Al+Si+Ti)>0.01; each of B, Ce, Ca, Mg, Sc, Y, La, and Be less than 0.1; P<0.1; S<0.05; each of Sn, Sb, O, Pb and other impurities less than 0.1; and the balance essentially iron; thermal mechanically treating by austenitizing it at a temperature above 1000° C., hot working the alloy at a temperature greater than 1000° C. to impart a true strain of greater than 0.15 (15%); and cooling the alloy to room temperature to obtain a fine-grained martensitic microstructure in which the ASTM grain size number is greater than or equal to 5.
128 . The alloy of any of the claims 1 or 2 , comprising at least about 1.5% Ni.
129 . The alloy of any one of the claims 1 , 2 , 10 , 11 , 13 , 14 , 16 , 17 , 19 , 20 , 23 , 25 , 26 , 28 , 31 , 32 and 128 , comprising up to about 1% Nb.
130 . The alloy of any one of the claims 1 , 2 , 10 , 11 , 13 , 14 , 16 , 17 , 19 , 20 , 23 , 25 , 26 , 28 , 31 , 32 , 128 and 129 , comprising up to about 0.75% Nb.
131 . The alloy of any one of the claims 1 , 2 , 10 , 11 , 13 , 14 , 16 , 17 , 19 , 20 , 23 , 25 , 26 , 28 , 31 , 32 , 34 - 41 and 128 - 130 , comprising up to about 0.10% N.
132 . The alloy of any one of the claims 1 , 2 , 10 , 11 , 13 , 14 , 16 , 17 , 19 , 20 , 23 , 25 , 26 , 28 , 31 , 32 , 34 - 41 and 128 - 131 , comprising up to about 0.065% N.
133 . The alloy of any one of the claims 1 , 2 , 10 , 11 , 13 , 14 , 16 , 17 , 19 , 20 , 23 , 25 , 26 , 28 , 31 , 32 , 34 - 41 and 128 - 132 , comprising up to about 0.05% N.
134 . The alloy of any one of the claims 1 , 2 , 10 , 11 , 13 , 14 , 16 , 17 , 19 , 20 , 23 , 25 , 26 , 28 , 31 , 32 , 34 - 41 and 128 - 133 , comprising up to about 0.02% N.
135 . The alloy of any one of the claims 1 , 2 , 10 , 11 , 13 , 14 , 16 , 17 , 19 , 20 , 23 , 25 , 26 , 28 , 31 , 32 , 34 - 57 and 128 - 134 , wherein:
0.135<1.17Ti+0.6Zr+0.31Ta+0.31Hf<1.0.
136 . The method of any one of the claims 59 and 61 - 67 , the alloy comprising at least about 1.6% Ni.
137 . The method of any one of the claims 59 , 61 - 67 , 75 , 76 , 78 , 79 , 81 , 82 , 84 , 85 , 88 , 90 , 91 , 93 , 96 , 97 and 136 , the alloy comprising up to about 1% Nb.
138 . The method of any one of the claims 59 , 61 - 67 , 75 , 76 , 78 , 79 , 81 , 82 , 84 , 85 , 88 , 90 , 91 , 93 , 96 , 97 , 136 and 137 , the alloy comprising up to about 0.75% Nb.
139 . The method of any one of the claims 59 , 61 - 67 , 75 , 76 , 78 , 79 , 81 , 82 , 84 , 85 , 88 , 90 , 91 , 93 , 96 , 97 , 99 - 106 and 136 - 138 , the alloy comprising up to about 0.10% N.
140 . The method of any one of the claims 59 , 61 - 67 , 75 , 76 , 78 , 79 , 81 , 82 , 84 , 85 , 88 , 90 , 91 , 93 , 96 , 97 , 99 - 106 and 136 - 139 , the alloy comprising up to about 0.065% N.
141 . The method of any one of the claims 59 , 61 - 67 , 75 , 76 , 78 , 79 , 81 , 82 , 84 , 85 , 88 , 90 , 91 , 93 , 96 , 97 , 99 - 106 and 136 - 140 , the alloy comprising up to about 0.05% N.
142 . The method of any one of the claims 59 , 61 - 67 , 75 , 76 , 78 , 79 , 81 , 82 , 84 , 85 , 88 , 90 , 91 , 93 , 96 , 97 , 99 - 106 and 136 - 141 , the alloy comprising up to about 0.02% N.
143 . The iron base alloy of claim 126 , wherein the alloy is in a hot worked condition.
144 . The iron base alloy of claim 126 , wherein the alloy is in a hot rolled condition and formed into a tubular product.
145 . The iron base alloy of claim 126 , wherein the alloy is in a hot worked condition and formed into a tubular product.
146 . The method of claim 127 , wherein hot working the iron base alloy comprises hot rolling the iron base alloy at a temperature above about 1000° C. to impart the true strain of greater than 0.15 (15%).
147 . The method of claim 127 , wherein hot rolling the iron base alloy further comprises forming the iron base alloy into a tubular product.
148 . The method of claim 127 , wherein hot working the iron base alloy further comprises forming the iron base alloy into tubular product.
149 . The method of claim 127 , further comprising heat treating the iron base alloy after the iron base alloy is cooled to room temperature and retaining a fine grain size in which the ASTM grain size number is greater than or equal to 5.
150 . The method of claim 149 , wherein heat treating the iron base alloy after the iron base alloy is cooled to room temperature further comprises tempering the iron base alloy.
151 . The method of claim 149 , wherein heat treating the iron base alloy after the iron base alloy is cooled to room temperature further comprises austenitizing, quenching and tempering the iron base alloy.
152 . The method of claim 149 , wherein heat treating the iron base alloy after the iron base alloy is cooled to room temperature further comprises normalizing and tempering the iron base alloy.
153 . The method of claim 149 , wherein heat treating the iron base alloy after the iron base alloy is cooled to room temperature further comprises normalizing the iron base alloy.
154 . The method of claim 149 wherein heat treating the iron base alloy after the iron base alloy is cooled to room temperature further comprises austenitizing and quenching the iron base alloy.Join the waitlist — get patent alerts
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