[0001] This invention relates to a method of making a high strength duplex stainless steel
and a product of this alloy in either cast or wrought form. The material of this invention
displays superior toughness, weldability and cracking resistance in H₂S bearing environments
compared to other duplex stainless steels of similar strength level.
[0002] In recent years, a considerable number of high strength austenitic/ferritic duplex
stainless steels have been introduced, and the range of applications for these materials
has expanded rapidly. The primary reason for this is that these alloys, as a class,
offer an attractive combination of strength and corrosion resistance. Typically, these
alloys exhibit yield strengths which are about twice those of "ordinary" stainless
steels (when compared in the solution treated condition). In terms of general corrosion
resistance, these alloys perform quite well in a wide variety of environments. They
also have good resistance to localized corrosion and stress corrosion cracking in
the presence of chlorides. In resisting these forms of corrosion, the performance
of duplex stainless steels often rivals that of far more expensive, more highly-alloyed
materials.
[0003] The high strength duplex stainless steels of the prior art, however, have had a number
of drawbacks. Cast grades generally exhibited only moderate impact toughness at room
temperature, and suffered marked losses in toughness as temperatures decreased. Duplex
grades were also susceptible to serious embrittlement in the heat affected zones (HAZs)
of welds. They also exhibited poor resistance to cracking in the sour (H₂S-bearing)
environments often encountered in oil industry applications. These deficiencies have
been major factors inhibiting even wider application of these materials.
[0004] Most high strength duplex stainless steels are designed to have a microstructure
consisting of about 50% ferrite and 50% austenite. It is this microstructure which
is responsible for the high strength and good corrosion resistance of these materials.
In the duplex stainless steels of the prior art, the desired ferrite:austenite ratio
was obtained only by controlling the composition. This prevented alloy designers from
using other techniques for improving the toughness of the ferrite phase which would
lead to improved toughness of the total alloy.
[0005] The current invention involves the realization that the ferrite-austenite ratio can
be adjusted not only by varying the composition, but also by varying the solution
treatment temperature.
[0006] By using this concept, it is possible to produce a high strength duplex stainless
steel having excellent mechanical properties in both cast and wrought forms.
[0007] According to the invention a duplex stainless steel having the following composition
Carbon |
0.001 to 0.08 Wt. % |
Manganese |
0.001 to 2.00 Wt. % |
Silicon |
0.001 to 1.50 Wt. % |
Chromium |
20.00 to 27.50 Wt. % |
Nickel |
8.00 to 11.00 Wt. % |
Molybdenum |
3.00 to 4.50 Wt. % |
Sulfur |
0.0001 to 0.050 Wt. % |
Phosphorus |
0.0001 to 0.050 Wt. % |
Nitrogen |
0.10 to 0.30 Wt. % |
Iron |
Balance |
is produced. The composition is balanced such that:
where:
Products of this material are then solution treated by heating to a temperature in
the range of 1107°C-1274°C (2050°F-2350°F) and then cooling rapidly as with a water
quench. For cast products, the desired yield strength is developed by solution treating
at a temperature selected according to the following approximate relationship:
Where:
- Sy =
- yield strength (0.2% offset) in KSI
- Cr =
- Ni =
[0008] It should be noted that the composition ranges of Patent No. 4,032,367 overlap those
of the inventive alloy. Certain compositions of this material combined with certain
solution treatment temperatures probably would give a good combination of strength
and toughness. However, Patent 4,032,367 does not recognize the relationships between
Creq: Nieq ratio, solution treatment temperature and mechanical properties necessary
to accomplish this. Obtaining a good combination of strength and toughness with the
information given in Patent 4,032,367 would simply be a matter of chance. Other patents
such as 4,500,351 and 4,055,448 disclose preferred Creq:Nieq relationships, but they
differ from those of this invention and are not directly tied to mechanical properties
or heat treatment.
[0009] Compared to high strength duplex stainless steels of the prior art, the inventive
material exhibits considerably greater impact toughness values, particularly at low
temperatures. It also exhibits considerably greater impact toughness values in the
HAZs of welds. Furthermore, the inventive material exhibits improved resistance to
cracking when tested in a simulated sour gas environment according to NACE (National
Association of Corrosion Engineers) Test Method TM-01-77.
[0010] The invention will now be further described by way of example with reference to the
accompanying drawings, in which:
Fig.1 is a graph of the empirically derived relationship between composition, solution
treatment and temperature and yield strength;
Fig.2 is a graph of the relationship between Creq:Nieq ratio, test temperature and
impact toughness;
Fig.3 includes three graphs of the impact toughness of inventive alloy and other high
strength duplex stainless steels;
Fig.4 includes three graphs showing HAZ impact toughness of the inventive alloy and
other high strength duplex stainless steels; and
Fig.5 includes four graphs of the pitting resistance of inventive alloy and other
high strength duplex stainless steels in de-aerated 5% NaCl+0.01M HCl.
[0011] The invention will also be further described by way of example with reference to
the Tables at the end of this description, in which:
Table 1 is a tabulation of the effects of composition and solution treatment temperature
on yield strength;
Table II is a tabulation of the relationship between Creq:Nieq ratio and impact toughness;
Table III is a tabulation of the mechanical properties of the inventive alloy; and
Table IV is a tabulation of the preferred composition ranges of the inventive alloy.
[0012] In cast high strength duplex stainless steels, mechanical property behaviour, microstructure
and composition are related in the following manner:
(1) Strength is primarily related to ferrite content. Higher ferrite contents lead
to higher strength levels and lower ferrite contents lead to lower strength levels.
(2) In material which has been given an appropriate solution treatment, toughness
(as reflected by transition temperature) is primarily controlled by the percentage
of ferrite, its distribution and its inherent toughness.
(3) The ferrite content is controlled by the composition of the alloy and by the solution treatment temperature.
(4) The composition of the ferrite is controlled by the composition of the alloy and
by the solution treatment temperature.
(5) The inherent toughness of ferrite is controlled by its composition. As with ferritic
stainless steels, increasing the nickel content of the ferrite phase increases its
inherent toughness.
[0013] In the prior art, it has been the practice to solution treat high strength duplex
stainless steels at temperatures similar to those used for "ordinary" austenitic stainless
steels (e.g. 1083°C-1107°C i.e. 2000°F to 2050°F). The desired strength levels have
been obtained simply by adjusting the composition to achieve the necessary ferrite
content. Because of this practice, it has been necessary to maintain relatively high
ratios of ferrite forming elements (Cr, Si and Mo) to austenite forming elements (Ni,
Cu, C and N). Consequently, the nickel levels of available high strength duplex stainless
steels have been relatively low, generally in the range of 4% to 7%. This, in turn,
has resulted in low nickel contents in the ferrite and ultimately in poor low temperature
toughness in these materials.
[0014] This invention is based on the realization that the ferrite contents (strength levels)
of high strength duplex stainless steels can be effectively varied not only by adjusting
composition, but also by selective use of solution treatment temperature. By employing
higher solution treatment temperatures than those which have been commonly used for
high strength duplex stainless steels, it is possible to obtain the desired ferrite
contents (strength levels) using alloy compositions with higher nickel contents for
a given content of Cr+Mo+Si. This results in higher nickel contents in the ferrite.
Consequently, improvements in low temperature toughness, the toughness of HAZs and
resistance to sulfide stress cracking are realized.
[0015] In the practice of this invention, a heat of duplex stainless steel is produced to
the following composition:
Carbon |
0.001 to 0.08 Wt. % |
Manganese |
0.001 to 2.00 Wt. % |
Silicon |
0.001 to 1.50 Wt. % |
Chromium |
20.00 to 27.50 Wt. % |
Nickel |
8.00 to 11.00 Wt. % |
Molybdenum |
3.00 to 4.50 Wt. % |
Sulfur |
0.0001 to 0.050 Wt. % |
Phosphorus |
0.0001 to 0.050 Wt. % |
Nitrogen |
0.10 to 0.30 Wt. % |
Iron |
Balance |
The composition is balanced such that:
where:
[0016] A product of this material (cast or wrought) is then solution treated by heating
to a temperature in the range of 1107°C-1274°C (2050°F-2350°F), followed by rapid
cooling (as with a water quench) to prevent formation of deleterious precipitates
in the microstructure. For cast products, the specific composition and solution treatment
temperature is selected so as to provide the desired combination of yield strength,
impact toughness and corrosion resistance.
[0017] For cast material having a composition covered by this patent, it has been determined
empirically that yield strength, composition and solution treatment temperature are
related by the following approximate relationship:
Where:
- Sy =
- yield strength (0.2% offset) in KSI (1 KSI = 6.895 MPa)
- Cr =
- Ni =
This relationship is presented graphically in FIG. 1. The experimental data from
which this relationship was derived are shown in Table 1. This was done by the method
of least squares polynomial regression curve fitting. A reference describing this
is: Irwin Miller and John E. Freund,
Probability and Statistics for Engineers, 2nd ed., Prentice Hall, 1977.
[0018] The relationship described above makes use of a ratio of ferrite forming elements
(chromium equivalent) to austenite forming elements (nickel equivalent). It has been
found that this ratio can also be used to insure that good impact toughness is maintained.
[0019] FIG. 2 shows a computer-drawn representation of the relationship between chromium
equivalent: Nickel equivalent ratio, test temperature and impact toughness for cast
material given a 1190°C (2200°F) solution treatment. The experimental data used to
develop this diagram are presented in Table II. Inspection of the diagram clearly
shows that by maintaining low Creq:Nieq ratios, higher impact toughnesses can be realized.
[0020] The rationale for choosing the upper and lower Creq:Nieq ratio limits (3.50 and 4.00
respectively) can be understood by examining FIGS. 1 and 2. The lower limit was set
at 3.50 since this appears to be the lowest value at which a yield strength of 65KSI
can be guaranteed in cast material given the range of solution treatment temperatures
covered in this patent. For many applications where a duplex stainless steel such
as this would be used, a minimum yield strength of 448.2 MPa (65 KSI) is required.
The upper limit was set at 4.00 since beyond this level, impact toughness values deteriorate
markedly. Although the Creq and Nieq expressions of this patent were not specifically
devised to describe other high strength duplex stainless steels, it should be pointed
out that they are typically produced with much higher Creq:Nieq ratios than the inventive
alloy. This would tend to place them in the lower toughness regions of the diagram
in FIG. 2.
[0021] Mechanical properties of cast material from five heats of the inventive alloy are
shown in Table III. Also shown are mechanical properties from one heat of forged material.
The compositions of these heats may be found in Table I and in all cases, the solution
treatment temperature was 1190°C (2200°F). All five heats of the cast material as
well as the wrought material show an excellent combination of strength and toughness.
All testing was performed according to ASTM A 370-77.
[0022] The superior impact toughness of cast material of the inventive alloy can be appreciated
when it is compared to the toughness of other cast duplex stainless steels having
similar strength. Two such materials are Alloy 2205 and Ferralium Alloy 255*. The
impact toughness of these alloys and the inventive alloy are compared in Fig.3. It
can be easily seen that the inventive alloy possesses considerably greater impact
toughness, particularly at low temperatures. At -87.5°C (-100°F) the lowest impact
toughness value of the inventive alloy was about 121.5J (90 ft. lbs)**. The best value
of the other two alloys at -87.5°C (-100°F) was below 54J (40 ft. lbs). A level of
about 101.25J (75 ft.lbs) is distinctly advantageous over high strength duplex stainless
steels of the prior art. All of these data were obtained using standard charpy specimens
taken from cast keel bars. The inventive alloy material was solution treated at 1190°C
(2200°F) while the other alloys were solution treated at their recommended temperature
1107°C (2050°F). All tests were performed in accordance with ASTM A370-77.
* Registered Trademark of Bonar-Langley Alloys Ltd., United Kingdom.
** 1 ft. lb = 1.35J.
[0023] It should be pointed out that all of the impact toughness data presented for the
inventive alloy were obtained from air-melt induction heats. Other melting processes
which result in greater cleanliness (i.e. AOD or VOD refining) can be expected to
result in even greater toughness values. For example, two recent AOD-refined heats
of the inventive alloy had impact toughness values approximately 25% higher than air-melt
induction heats of similar Creq:Nieq ratio.
[0024] The inventive alloy also shows superior weldability. While high strength duplex stainless
steels of the prior art are known to suffer severe embrittlement in the HAZs of welds,
this invention produces material which is far more resistant to the problem. In order
to illustrate this, test welds were made in cast material from four heats of the inventive
alloy, four heats of Ferralium Alloy 255 and one heat of Alloy 2205. Prior to welding,
the inventive alloy material had been solution treated at 1190°C (2200°F), while the
other materials had been solution treated at 1107°C (2050°F). The welding procedure
employed was as follows:
Process - SMAW
Filler Material - Sandvik 22.9.3 (4mm Dia.)
Preheat - None
Current - 135 AMPS
Polarity - DCRP
Interpass Temp - 79°C (200°F) Max
Post Weld Heat Treatment - None
[0025] After welding, standard charpy impact specimens were removed from the welded plates
such that the specimen notches were located in the HAZs of the welds. The specimens
were then tested according to ASTM A370-77.
[0026] The HAZ impact toughness results are presented in graphical form in Fig.4. While
the inventive material did show some loss of toughness (see Table II), the HAZs of
the other alloys were seriously degraded in toughness. The inventive alloy had HAZ
impact toughness values above 67.5J (50 ft. lbs) at -87.5°C (-100°F) while the other
two alloys gave values less than 27J (20 ft.lbs) at the same temperatures.
[0027] In many environments, the corrosion resistance of the inventive alloy is similar
to that of high strength duplex stainless steels of the prior art. For chloride-containing
environments, this has been established electrochemically. Specimens of the inventive
alloy and other duplex stainless steels have been subjected to rapid scan potentio-dynamic
tests in a deaerated solution of water plus 5% sodium chloride plus 0.01M hydrochloric
acid. The results of this comparison testing are presented in graph form in FIG. 5.
Clearly, the test results of the inventive alloy are at least as good as those of
any of the other alloys examined. It is appreciated that electrochemical corrosion
resistance data are highly dependent upon technique and the specific test method.
However, the tests performed were consistent so as to obtain data that were as comparable
as possible.
[0028] Compared to other cast high strength duplex stainless steels, the material of this
invention has superior resistance to cracking in sour (H₂S-bearing) environments.
In evaluating materials for service in sour environments, it is common to employ tests
conducted according to NACE Standard TM-01-77. This test involves stressing tensile
specimens of the material being studied in a solution simulating conditions in sour
oil wells. The solution consists of water, sodium chloride and acetic acid through
which hydrogen sulfide and carbon dioxide gases are bubbled. Specimens are stressed
to various percentages of their yield strengths in order to determine the highest
stress level at which fracture does not occur. The higher this stress level, the better
the material's cracking resistance.
[0029] Specimens from three heats of the inventive alloy (71545, 72497 and 72847) have been
tested. These have survived 720 hours (the duration of the standard test) unbroken
at stress levels up to and including 80% of their yield strengths. In addition, specimens
containing welds in their gage lengths (both as welded and resolution treated) have
passed the test at 80% of the base metal's yield strength. As far as is known, no
other cast duplex stainless steels of similar strength level have been able to perform
this well.
[0030] Depending upon the characteristics desired, certain narrower preferred ranges of
alloying elements can be utilized. These are shown in Table IV. For example, when
superior corrosion resistance in chloride-containing environments is desired, composition"C"
is advantageously employed. If maximum toughness is desired, composition "A" is preferred.
Composition "A" is also preferred for thick-section parts since it is more resistant
to formation of deleterious precipitates. Composition "B" offers a combination of
improved corrosion resistance compared to Composition "A", but with improved toughness
with respect to Composition "C". For further clarification, consider the following
examples:
Example 1.
[0031] Suppose it was desired to produce a small valve body having good-to-excellent corrosion
resistance in the presence of chlorides, a minimum yield strength of 448.2 MPa (65
KSI) and a minimum impact toughness of 101.25J (75 ft/lbs) at -87.5°C (-100°F). Since
the size of the casting is small and the degree of corrosion resistance must be high,
composition "C" would be selected. A heat of the inventive alloy would be produced
having a composition falling within the limits of "C". An example of such a heat is
Heat 72497, which had the following actual composition:
C |
0.039% |
Mn |
0.54 |
Si |
1.05 |
Cr |
24.59 |
Ni |
9.83 |
Mo |
3.51 |
Cu |
0.11 |
N |
0.198 |
Fe |
Balance |
The Creq:Nieq ratio would then be calculated. For heat 72497, this was 3.66. A solution
treatment temperature would then be chosen so as to obtain the desired yield strength.
For Heat 72497, an appropriate temperature would be 1190°C (2200°F). When material
from Heat 72497 was solution treated at 1190°C (2200°F), the resulting yield strength
was 67.9 KSI. The resulting average impact toughness at -87.5°C (-100°F) was 135J
(100 ft-lbs). These values would readily satisfy the requirements listed above.
Example 2
[0032] Suppose it was desired to produce a large pump casting requiring excellent toughness
in relatively heavy sections. A yield strength of 70 KSI minimum and moderate corrosion
resistance in the presence of chlorides. Since thick sections are involved and extreme
corrosion resistance is not required, composition "A" would be selected. As in the
previous example, a heat of the inventive alloy would be produced and solution treated
at a temperature selected to give the desired yield strength level.