EP1055011A1 - Austenitic stainless steel including columbium - Google Patents

Abstract

An austenitic stainless steel of the 201 series includes, in weight percent, greater than 0.003 % Cb. Also disclosed is a method for providing a high strength 201 series stainless steel wherein the method includes preparing a heat of a 201 series stainless steel and maintaining the Cb in the heat at a level, in weight percent, greater than 0.003 %.

Description

TITLE

Austenitic Stainless Steel Including Columbium

INVENTORS

James W. Underkofler, a citizen of the United States residing at 545 Center Church

Road, McMurray, PA 15317; William W. Timmons, a citizen of the United States residing at

1356 Timberwood Drive, Pittsburgh, PA 15241 ; and Ronald E. Bailey, a citizen of the United States residing at 313 Oak Forest Drive, Pittsburgh, PA 15216.

CROSS-REFERENCE TO RELATED APPLICATIONS The present application claims priority from United States provisional patent

application Serial No. 60/068,541, filed December 23, 1997.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

BACKGROUND OF THE INVENTION Field of the Invention

This invention relates generally to stainless steel alloys and more particularly to the

T201LN stainless steel alloy, and still more particularly to strengthening the T201LN alloy through the addition of columbium (Cb). Description of the Prior Art

Materials which are used at sub-zero temperatures should have good ductility, toughness and strength, which are all properties that are achievable with most of the

austenitic stainless steels. The T201LN alloy was specifically designed for such applications and is unique in that it is designated as an acceptable material for applications in which high

yield and ultimate strengths are specified. The T201LN alloy, which is disclosed in United

States Patent No. 4,568,387 to Ziemianski, the entire disclosure of which is incorporated

herein by reference, is an austenitic stainless steel having good low temperature properties of

austenitic stability, elongation and strength. As described in the '387 patent, the compositionally-balanced T201LN alloy consists essentially of, in weight percent, 0.03% carbon max., 6.4 to 7.5% manganese, up to 1.0% silicon, 16 to 17.5% chromium, 4.0 to 5.0%

nickel, up to 1.0% copper, 0.13 to 0.20% nitrogen, and the balance iron. The T201LN alloy

is characterized by austenitic stability, high room temperature strength, minimized

sensitization to welding, and high strength and ductility at low temperatures.

Although the T201LN alloy has been successfully used in sub-zero applications, the

strength requirements cannot always be achieved in all gages to satisfy the specifications of

some cryogenic applications. Therefore, it would be desirable to develop methods to reliably increase the strength of the T201LN alloy so that it may more reliably exceed the mechanical

requirements of material specified for cryogenic applications. Recent interest has also

surfaced in increasing the strength of the T201LN alloy to expand its use in structural

applications where it may possible be used to replace carbon steel in the production of truck

frames and other applications.

Industry attempts to produce high strength 201 series stainless steel have until now

involved simply evaluating the alloy to determine how much, if any, of the alloy meets the strength requirements. Modifying the amount of nitrogen during melt has also been attempted. In any event, alloys are milled and the strength characteristics are tested. Alloys

which do not meet the strength requirement would be scrapped. Extremely high scrap rates

were anticipated based on prior production, to a lower 38,000 psi yield strength. Therefore, a more reliable means of producing higher strength 201 series stainless steel is needed.

SUMMARY OF THE INVENTION

The present invention relates to methods for reliably producing high strength 201

series stainless steel. The method focuses on the influence of Cb on the mechanical

properties of the T201LN alloy. Laboratory heats of T201LN alloy, which were significantly alloyed with nitrogen (~0.15%) to stabilize the austenite, were made with varying amounts of

Cb (as low as possible up to approximately 0.20%) to determine the influence the Cb would

have on the mechanical properties of the alloy. It was found that a significant increase of at

least 5 k.s.i. is obtained in both the yield and ultimate strengths as the Cb level is increased

above 0.075%, and approximately 10 k.s.i. at Cb levels above 0.150%. The percent

elongation is decreased from about 55% to 48%. measured hardness is increased from about

89 Rb to about 98 Rb, and grain size is decreased from about ASTM 6.5 to about ASTM 10

as Cb content is increased from about 0.003% to about 0.210%).

Testing has shown that above a residual level of Cb (0.003%), impact energy

increases as Cb content increases to about .10% at the three temperatures tested. Impact

energy decreases at above about .10% Cb. Ductility remains relatively high at -50°F and

70°F. A decrease, but not a complete loss, of ductility occurs at a very low test temperature of -320°F. Accordingly, an object of the present invention is to reliably increase the strength of the T201LN alloy so that it may exceed the mechanical requirements of material specified for

cryogenic applications. In this regard, a .06%) to .10% addition of Cb to a slightly modified

version of studied T201LN alloy has been shown to improve the mechanical characteristics of

the alloy for applications in temperatures down to -320°F.

It is a further object of the present invention to reliably increase the strength of the T201LN alloy for temperatures above -50°F. In this regard, a .10% to .20% addition of Cb

has been shown to improve the mechanical characteristics of the alloy for applications in

temperatures above -50°F. In light of the foregoing, the present invention is directed to an austenitic stainless

steel of the 201 series that includes, in weight percent, greater than 0.003% Cb. The present

invention also is directed to a method for providing a high strength 201 series stainless steel wherein the method includes preparing a heat of a 201 series stainless steel and maintaining

the Cb in the heat at a level, in weight percent, greater than 0.003%). Other objects and advantages of the invention will become apparent from the

following description of certain presently preferred embodiments thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows ferrite maps made on V." thick slices, taken from the bottom of the

laboratory produced ingots, which were then polished and etched before measurements (FN) were obtained with the Magne-Gage;

FIG. 2 is a schematic illustration of the tensile and subsize Charpy specimens which

were used to obtain the mechanical data for this study (with all dimensions in inches); FIG. 3 is a plot of the yield strength (0.2%) offset), obtained from tensile specimens of the laboratory melted material of T201LN alloy, as a function of Cb;

FIG. 4 is a plot of the ultimate strength, obtained from tensile specimens of the

laboratory melted material of T201LN alloy, as a function of Cb; FIG. 5 is a plot of the ferrite content, as measured with the Magne-Gage, of the as-

tested laboratory material, on the tensile blanks;

FIG. 6 is a plot of the magnetic response as measured with the Magne-Gage on the

tensile samples after mechanical testing;

FIG. 7 is a plot of the % elongation, obtained from tensile specimens of the laboratory melted material of T201 LN alloy, as a function of Cb;

FIG. 8 is a plot of the hardness, obtained from tensile specimens of the laboratory

melted material of T201LN alloy, as a function of Cb;

FIG. 9 is a plot of the grain size as a function of Cb obtained by metallographic

examination of micros taken from laboratory melted material of T20ILN alloy;

FIG. 10 is a plot of the impact energies as a function of Cb content for the testing of

subsize Charpy samples (-0.180" except the data which are circled) at -320, -50 and 70°F; FIG. 11 is a plot of the percent shear as a function of Cb content for the testing of

subsize Charpy samples (-0.180" thick) at -320, -50 and 70°F; and

FIG. 12 is a plot of the lateral expansion as a function of Cb content for the testing of subsize Charpy samples (~0.180" thick) at -320, -50 and 70°F. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Initial testing was conducted which involved making Cb additions to T201LN

material to provide four heats comprising the following additions of carbon, nitrogen, and Cb.

The initial testing involved providing eleven groups of plates from the four heats as

follows:

All plates from all four heats showed excellent impact and lateral expansion values at

320°F. The standard composition had been marginal at times and was of concern to the

intended cryogenic tank fabricators. The pressure vessel code requires a minimum of 15 mils lateral expansion after welding. The average lateral expansion values of 201LN prior to this

trial were 31 mils. The average of the high Cb heat was 35 and the other heats averaged 39. This is the expected improvement due to the more austenitic compositions of this trial.

The three heats of .17% to .18% nitrogen without Cb did not have sufficiently high enough yield or tensile strength after processing from ingots. Several groups were marginal

and one plate failed with a 93,700 psi tensile versus 95,000 psi minimum. (Slip # 24010,

Heat 2C153, yield strength was 46,600 psi).

The fourth heat (Heat 2C078) as shown has acceptable strength, which appears to result from the .05% Cb addition, as is discussed later. Finer grain size also results from the

high Cb content. All plates with #6 grain size were shown by heat to separate that variable from the comparison.

During rolling, all plates had work below 1600° F. The first two heats had more reduction below 1500° F via a 1500° F hold in the reheat furnace at 150% of the final gage

except for one plate of 21302. This plate was direct rolled without reheat like the second two

heats (2C152 and 2C153). This plate still had work below 1500° F and compares favorably with the reheated plates.

Heat 2C078 shows considerably higher yield and tensile strength than the other heats

without as much Cb. Impact and lateral expansion values at -320° were also very good.

There is no restriction in the applicable specifications against the addition of Cb or other elements. The lower Cb (.03%) heat 2C077 does show that level of Cb to be insufficient.

Earlier 201LN sheet experience over .17%) nitrogen found blistering and porosity to

be a problem. None of the plates from the above heats showed any blistering or porosity.

Product checks found up to .198% nitrogen. If only nitrogen was used for strength, it would appear that more than .20 % nitrogen would be needed, but this has not been tried recently. There is reluctance to continuous cast over .16% nitrogen.

The initial rolling of 2200° F oxidizing atmosphere was changed to 2150° F reducing

atmosphere after seeing a rough surface due to heavy scale. No evidence of intergranular attack was seen after dip pickling. It was thought that the hot rolling roughness may have had

a deleterious effect on the test properties. Room temperature tensile samples were polished without improving the properties. However, for the -320° F tensile test, improvement was

seen in the elongations when a subsize round was used versus the flat sample which had several cracks starting at the hot rolled surface roughness.

There is no minimum tensile properties at -320° F currently, but earlier data show low elongations in certain 20 IL plates at -320° F.

Shown below are the -320°F and corresponding room temperature (R.T.) results:

Previous 201LN product was annealed at 2025° F with later plates using 1950° F. An

anneal study done on hot rolled samples from heat 2C078 showed 1950° F to be the best

choice. All plates in this study were annealed at 1950° F. Due to concerns about diminishing the impact properties, none of the plates were

stretcher leveled initially.

After plate 24010 failed the tensile strength, it was given a 2% stretch to evaluate the effects. The results shown after the first two roller levelled results show a large yield and

notable tensile increase. The impact properties were still acceptable after stretching. It is

clear that they were not greatly diminished, if at all. Impact testing recognizes that a test may

be low due to testing variance. This one sample with 40.5 ft. lbs. and 26 mils lateral expansion is still above acceptable values.

These increases in strength from stretching can be expected to be lost in the welded

joints of the tank and do not contribute to the true strengthening of the product as does a compositional change. Special weld procedures currently used by the largest 201LN

potential customer are adding to the total fabrication cost due to the need to preserve the marginal tensile properties of the standard 201LN plate. These improvements in the

composition for higher tensile strength would be of value.

As is described in greater detail below, additional testing was performed. Three laboratory heats of T201LN were melted with various additions of Cb in the range of 0.003-

0.210%. The material was hot rolled to -3/16" (4.76 mm) and annealed at 1950°F. Tensile

and subsize Charpy specimens were obtained from each of the plates for mechanical testing.

Measurements were made on the tensile specimens before and after testing to determine the

ferrite content of the plate and the stability of the austenite. Micros were also obtained from

the ends of the tensile specimens which were then polished and etched so that the grain size could be measured.

A significant increase of at least 5 k.s.i. is obtained in both the yield and ultimate

strengths as the Cb level is increased above 0.075%, and approximately 10 k.s.i at Cb levels above 0. 150%). The percent elongation is decreased from about 55% to 48%, measured hardness is increased from about 89 Rb to 98 Rb, and grain size is decreased from about

ASTM 6.5 to ASTM 10 as Cb content is increased from 0.003% to 0.210%. Above a residual level of Cb (0.003%), impact energy is increased slightly as Cb content increased at the three temperatures tested up to .10% Cb. Ductility remains relatively high at -50 and 70°F. A

decrease, but not complete loss, of ductility occurs at a very low test temperature of -320°F

above .10% Cb. The addition of Cb enhances the mechanical properties of the T201LN alloy.

Based on the data obtained on laboratory melted and processed material, an addition

of approximately .075%) Cb is sufficient to enhance the strength mechanical properties of this alloy without significantly degrading any of the other mechanical properties.

The specific procedure and results of the additional testing were as follows. Three

fifty pound VIM laboratory heats were melted to the general chemistry aims of the T201LN

alloy which is commercially produced. Table 1 contains the chemistries of the three

laboratory heats that were melted for this study along with the minimum, average and

maximum of the three commercial heats of T201LN which were previously melted. The first heat, RV #1184, was melted to examine the influence of Cb additions in the range 0.01-

0.10%) by weight on the mechanical properties of T201LN. However, the final chemistry of

this first heat was slightly off the commercial chemistry of T201LN. Therefore a second heat,

RV #1185, was melted. Later in the investigation, it was decided to examine the influence of

slightly higher Cb contents (up to 0.20%) on the mechanical properties of this alloy, so a third

and final heat, RV #1212, was melted. Once each heat was melted, it was cast into three

seventeen pound ingots with the Cb content adjusted to various levels in between the pouring of the three individual ingots/heat. The purpose of this was to have essentially three identical alloys from which the influence of the varying Cb content on the mechanical properties of the

alloy could be studied.

A half-inch slice was cut from the bottom of each ingot which was then polished and etched so that ferrite maps could be obtained on the as-cast material. The Ferrite Number

(FN) measurements were obtained along a half-inch by half-inch grid on each of the 2-3/8" square ingot slices with the Magne-Gage to ascertain the stability, with respect to austenite, of

these alloys. These ferrite maps are shown in Figure 1 for heats RV #184, RV #1185 and RV

#1212 respectively. The ingots were ground and heated to 2150°F (-1 hr TAT) for hot

working. They were cross rolled to obtain a width of seven inches and then hot rolled to an aim gage of- 0.1875". Each panel was then annealed at 1950°F for six minutes (TAT)

followed by grit blasting and pickling. Tensile specimens were cut and machined from each of the plate samples in both the longitudinal and transverse directions. Charpy v-notch

impact specimens were also cut and machined from each of the plate samples from the transverse direction. A schematic of the tensile and subsize Charpy specimens (0.394" x

thickness of the plate material) used in this study are shown in Figure 2.

Samples were cut from the ends of the tensile specimens for microstructure evaluation

after the mechanical tests were completed. These were mounted, polished and electrolytically

etched in 10%) oxalic acid at 6V for 20 - 30 seconds to reveal the general grain structure. The

grain size of each sample was estimated per ASTM E 112 using the comparison procedure with the following two exceptions. The first is that the photomicrographs were taken at a

magnification of 106X instead of 100X. The second is that the photomicrographs were

compared to standards from Plate I and not Plate II, which is the recommended standard for

austenitic stainless steels. Therefore, the grain sizes measured in this report should be used only to characterize and compare the material which is described within this report. However, it should be noted that these minor variations in the grain size measuring technique should not significantly alter the grain size and/or the trend (grain size as a function of Cb

content).

Table 2 contains the results which were obtained on or from the testing of the tensile

specimens. Table 3 contains the results obtained from testing of the Charpy specimens. The

results obtained from duplicate test specimens were averaged to simplify the graphical

representation of the data. Where both longitudinal and transverse specimens were tested, an

average of all the samples is also given. An example of this is the data which are plotted in Figures 3 and 4 of the yield (0.2% offset) and ultimate strengths, respectively, as a function of Cb content. As can be seen, both plots show an increase in the strength of T201LN as the Cb

content is increased from -0.003 to 0.210%. A significant increase of at least 5 k.s.i. is seen

in both the yield and ultimate strengths as the Cb level is increased above 0.075%). The

increase is approximately 10 k.s.i. at Cb levels above 0.150%. In Figure 3, there is an abnormally high yield strength associated with a low Cb level material (RV #1184 - Ingot A)

which does not conform to the trend shown by the rest of the data. However, it should be

noted that this material had the highest ferrite level (-2.5%) as measured on the tensile blanks, before testing.

Figure 5 is a plot of the ferrite content measured on the tensile blanks before testing.

Only three of the materials examined in this study had a significant amount of ferrite. The first two of these are from the laboratory heat RV #1184 (ingots A & B) which did not match

the commercially produced chemistry. The higher ferrite levels observed in this heat are due

to the higher chromium and molybdenum and lower nickel and manganese contents. The

cause of the higher-than-expected ferrite level in the material from ingot C of laboratory heat RV #1 185 is unknown but may be due to fluctuations in the heat treating process which reduces the ferrite level from that which is found in the as-cast material (shown in Figure 1 ) to that in the final product.

The magnetic response (FN) was also measured along the shaft of the tensile

specimens after testing to determine the presence of martensite which is a measure of the

austenite stability. These data are shown in Figure 6 for future reference. This measurement

is an indication of the amount of martensite in the material. However, the relationship

between this measurement and actual amount of martensite is not known and therefore should

only be used for comparison between these samples.

The elongation and hardness measurements obtained from the tensile testing and the

grain size obtained from the metallographic examination of micros cut from the tensile specimens (from the ends which were not deformed during testing) are shown in Figures 7, 8

and 9, respectively. The percent elongation decreases (Figure 7) and the measured hardness

(Figure 8) of the material increases as the Cb content of the material increases.

The data that were obtained from impact testing of the subsize Charpy specimens (i.e.

< 0.394" thick) included the impact energies (Figure 10), percent shear (Figure 1 1) and the lateral expansion of the samples (Figure 12) as a function of Cb for three different

temperatures (320°F, -50°F and 70°F). It should be noted that the data points in Figure 10

which are circled were obtained from the material of Heat RV #1212, ingot A, which was

accidentally rolled to a lighter gage (0.157") than that of the rest of the material which was

rolled to a gage of ~0.180 - 0.185". Due to the fact that the impact energy is dependent upon the cross-section of the sample being tested, these samples (from Heat RV#1212) would have

had at least 18% higher impact energy if they were the correct thickness (-0.180 - 0.185").

Therefore, these data were not considered when examining the impact energy, % shear and lateral expansion trends as a function of Cb content. The impact energies initially increase and then decrease as the Cb content increases. Very little, if any, loss of toughness was observed between the testing at 70 and -50°F.

However, the tests that were completed at -320°F showed a decrease in the toughness of the

material above .10% Cb. However, it should be noted that the impact properties at this temperature still show a respectable level of toughness.

The Cb addition up to .10%) was successful in increasing the strength of this alloy without significantly degrading any of the other mechanical properties tested. Examination

of the data suggests that about .075%) Cb is an appropriate addition to achieve the desired

mechanical properties. Due to the fact that Cb is a strong stabilizer (i.e., retards the formation chromium

carbides at grain boundaries), the addition of Cb to this alloy may allow the maximum carbon

content to be relaxed and still be acceptable from a corrosion standpoint. This addition of Cb

along with a slight increase in the carbon content may insure the enhanced mechanical

properties needed for these new markets (additional strength and toughness due to the

increased austenite stability). Therefore, a variation of the T201 grade (Cb 0.100% & C

0.060%) max.) may produce an acceptable product in the as-welded condition.

Based upon the results obtained on laboratory produced material, the addition of Cb

acts as a grain refiner and enhances the mechanical properties of the T201LN alloy. It was

concluded that a significant increase of at least 5 k.s.i. is obtained in both the yield and

ultimate strengths as the Cb level is increased above about 0.075%, and an approximately 10

k.s.i. increase is obtained at Cb levels above 0.150%). Further, the percent elongation is

decreased from about 55%> to 48%>, measured hardness is increased from about 89 Rb to 98

Rb and grain size is decreased from ASTM 6.5 to ASTM 10 as Cb content is increased from 0.003% to 0.210%. In addition, above the residual level of Cb (-0.003%), the impact energy is increased as Cb content is increased up to about .10%) at the three temperatures tested. Ductility remains relatively high at -50 and 70°F. At above about .10% Cb. a decrease, but

still acceptable ductility occurs at the low test temperature of -320°F.

While certain presently preferred embodiments have been shown and described, it is

distinctly understood that the invention is not limited thereto but may be otherwise embodied within the scope of the following claims.

1 able 1

** Range ol chemistries obtained from the three heats of I 201 i N which were melted in 1994

Table 2

-17- Table 2 (continued)

-18- Table 3

Table 3 (continued)

20

Claims

What is claimed:

1. An austenitic stainless steel, the austenitic stainless steel having a chemical

composition of the 201 series and comprising, in weight percent, greater than 0.003%

columbium.

2. The austenitic stainless steel of claim 1, wherein said columbium is present in an

amount of at least 0.06%

3. The austenitic stainless steel of claim 2, wherein said columbium is present in an amount of at least 0.10%

4. The austenitic stainless steel of claim 1 , wherein said columbium is present in an

amount not greater than 0.21%.

5. The austenitic stainless steel of claim 1, comprising 0.06% carbon max. and 0.10% columbium.

6. The austenitic stainless steel of claim 1 , comprising, in weight percent, 0.15

carbon max., 5.4 to 7.5 manganese, up to 1.0 silicon, 16.0 to 18.0 chromium, 3.5 to 5.5

nickel, 0.25 nitrogen max., and greater than 0.003% columbium.

7. The austenitic stainless steel of claim 6, wherein said columbium is present in an amount of at least 0.06%

8. The austenitic stainless steel of claim 6. further comprising, in weight percent, 0.060 phosphorous max. and 0.030 sulfur max.

9. An austenitic stainless steel comprising, in weight percent, 0.03% carbon max.,

6.4 to 7.5% manganese, up to 1.0% silicon, 16 to 17.5% chromium, 4.0 to 5.0% nickel, up to 1.0% copper, 0.13 to 0.20% nitrogen, and greater than 0.003% columbium.

10. The austenitic stainless steel of claim 9, wherein said columbium is present in an

amount of at least 0.06%.

11. The austenitic stainless steel of claim 9, wherein said columbium is present in an

amount of at least 0.075%.

12. The austenitic stainless steel of claim 9, wherein said columbium is present in an

amount not greater than 0.21%.

13. The austenitic stainless steel of claim 9, consisting essentially of, in weight percent, 0.03% carbon max., 6.4 to 7.5% manganese, up to 1.0% silicon, 16 to 17.5%

chromium, 4.0 to 5.0% nickel, up to 1.0% copper, 0.13 to 0.20% nitrogen, greater than

0.003% columbium, and the balance iron.

14. The austenitic stainless steel of claim 9, characterized by at least 100,000 psi

tensile strength and at least 50,000 psi yield strength at room temperature.

15. The austenitic stainless steel of claim 14, further characterized by an ASTM grain size of 6 or higher.

16. In an austenitic stainless steel of the 201 series, the improvement comprising including in the steel greater than 0.003% columbium.

17. The improvement of claim 16, wherein the steel comprises, in weight percent, 0.15 carbon max., 5.4 to 7.5 manganese, up to 1.0 silicon, 16.0 to 18.0 chromium, 3.5 to 5.5

nickel, and 0.25 nitrogen max.

18. In an austenitic stainless steel comprising, in weight percent, 0.03% carbon max.,

6.4 to 7.5% manganese, up to 1.0% silicon, 16 to 17.5% chromium, 4.0 to 5.0% nickel, up to 1.0% copper, and 0.13 to 0.20% nitrogen, the improvement comprising including in the steel

greater than 0.003% columbium

19. An article of manufacture comprising an austenitic stainless steel, said steel

having a chemical composition of the 201 series and comprising, in weight percent, greater than 0.003% columbium.

20. The article of manufacture of claim 19, wherein said austenitic stainless steel

comprises columbium in an amount of at least 0.06%.

21. The article of manufacture of claim 19, wherein the article of manufacture is

selected from the group consisting of a plate, a tank, and a pressure vessel.

22. The article of manufacture of claim 19, wherein said austenitic stainless steel

comprises, in weight percent, 0.03% carbon max., 6.4 to 7.5% manganese, up to 1.0% silicon,

16 to 17.5% chromium, 4.0 to 5.0% nickel, up to 1.0% copper, 0.13 to 0.20% nitrogen, and greater than 0.003% columbium.

23. The article of manufacture of claim 22, wherein said austenitic stainless steel is

characterized by at least 100,000 psi tensile strength and at least 50,000 psi yield strength at room temperature.

24. A method for providing a high strength stainless steel, the method comprising preparing a heat comprising, in weight percent, 0.15 carbon max., 5.4 to 7.5 manganese, up

to 1.0 silicon, 16.0 to 18.0 chromium, 3.5 to 5.5 nickel, 0.25 nitrogen max., and greater than

0.003% columbium.

25. The method of claim 24, wherein the heat comprises columbium in an amount of

at least 0.06%

26. The method of claim 24, wherein the heat comprises, in weight percent 0.03%

carbon max., 6.4 to 7.5% manganese, up to 1.0% silicon, 16 to 17.5% chromium, 4.0 to 5.0% nickel, up to 1.0% copper, 0.13 to 0.20% nitrogen, and greater than 0.003% columbium.

27. A method for providing an article of manufacture comprising a high strength

stainless steel, the method comprising processing at least a portion of an alloy comprising, in

weight percent, 0.15 carbon max., 5.4 to 7.5 manganese, up to 1.0 silicon, 16.0 to 18.0

chromium, 3.5 to 5.5 nickel, 0.25 nitrogen max., and greater than 0.003%) columbium.

28. The method of claim 27, wherein the alloy includes columbium in an amount of at

least 0.06%

29. The method of claim 27, wherein the alloy comprises, in weight percent, 0.03%

carbon max., 6.4 to 7.5% manganese, up to 1.0% silicon, 16 to 17.5% chromium, 4.0 to 5.0%

nickel, up to 1.0% copper, 0.13 to 0.20% nitrogen, and greater than 0.003% columbium.

30. The method of claim 27, wherein the act of processing comprises hot rolling at

least a portion of the alloy at less than 2200° F in a reducing atmosphere.

31. The method of claim 27, wherein the act of processing comprises hot rolling the least a portion of the alloy at approximately 2150° F in a reducing atmosphere.

32. The method of claim 30, further comprising annealing at least a portion of the alloy at approximately 1950° F.

33. The method of claim 27, wherein the article of manufacture is a plate.

34. An austenitic stainless steel alloy comprising, in weight percent, 0.03% carbon

max., 6.4 to 7.5% manganese, up to 1.0% silicon, 16 to 17.5% chromium, 4.0 to 5.0% nickel, up to 1.0% copper, 0.13 to 0.20% nitrogen, and at least 0.06% columbium, the alloy

characterized by at least 100,000 psi tensile strength and at least 50,000 psi yield strength at room temperature.