Abstract:
A duplex stainless steel containing, by mass%: C: not more than 0.03%, Si: not
more than 0.3%, Mn: not more than 3.0%, P: not more than 0.040%, S: not more than
0.008%, Cu: 0.2 to 2.0%, Ni: 5.0 to 6.5%, Cr: 23.0 to 27.0%, Mo: 2.5 to 3.5%, W: 1.5 to
4.0%o, and N: 0.24 to 0.40%, the balance being Fe and impurities, wherein a CT phase
susceptibility index X (= 2.2Si + 0.5Cu + 2.0Ni + Cr + 4.2Mo + 0.2W) is not more than
52.0; a strength index Y (= Cr + 1.5Mo + ION + 3.5W) is not less than 40.5; and a pitting
resistance equivalent PREW (= Cr + 3.3(Mo + 0.5W) + 16N) is not less than 40. This
duplex stainless steel is excellent in corrosion resistance and embrittlement cracking
resistance.
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c/o Sumitomo Metal Industries Ltd. 5 33 Kitahama 4 chome Chuo ku Osaka shi Osaka
5410041
Specification
[Document Name] Description ORIGINAL
[Title of Invention] DUPLEX STAINLESS STEEL
[Technical Field]
[0001]
The present invention relates to a duplex stainless steel consisting of a ferrite phase
and an austenite phase.
[Background Art]
[0002]
Duplex stainless steels are excellent in corrosion resistance and weldability, and in
particular excellent in sea-water corrosion resistance and strength compared to ferrite
stainless steels or austenitic stainless steels. Accordingly, duplex stainless steels have
been widely used for a long time as industrial materials for their easiness of reducing
thickness and economic efficiency. Particularly, high Cr-high Mo duplex stainless steels
are excellent in corrosion resistance and strength, and thus are used in various fields such
as line pipes, components of heat exchangers, process steel tubes and pipes for oil and
chemical industrial usage, and oil country tubular goods. Currently, because of
increasing deeper sea oil wells and reduction in thickness of materials, materials having
further higher strength are required in umbilical tubes for oil wells and others. Greater
contents of Cr and Mo in duplex stainless steels, however, more likely cause precipitation
of intermetallic compounds (a phase, % phase) that are hard and brittle in a temperature
range of about 800 to 1000°C. This is because of the following reasons.
[0003]
A solid billet of a duplex stainless steel is produced in such a manner that an ingot
is hot-forged or hot-rolled into a longer-length cast piece, and the cast piece is allowed to
cool, and thereafter the cast piece is subjected to machining such as cutting-off and cutting.
In a high Cr-high Mo duplex stainless steel, a a phase is likely to precipitate, in particular
during air cooling, which significantly hardens a material thereof, and is likely to cause
cracks, so that it becomes difficult to cut off or cut the material in various machining.
Hence, it is preferable to suppress precipitation of the a phase to be as small as possible in
production of the duplex stainless steel, and various suggestions have been made, such as
reduction in the contents of Cr and Mo, and modification of heat treatment conditions and
cooling conditions.
[0004]
For example, Patent Document 1 suggests a duplex stainless steel in which a phase
stability index PSI (= 3Si + Cr + 3.3Mo) is defined to be 40 or less. Patent Document 1
describes that no a phase or the like is formed under heating, heat treatment and welding
conditions during normal hot working of this duplex stainless steel.
[0005]
Patent Document 2 suggests a producing method of a duplex stainless steel that
heats a duplex stainless steel at a temperature of 1110°C or more, and subjects this steel to
hot working into a seamless steel tube, in which the steel is reheated so as to have a
temperature within a range satisfying 800 + 5Cr + 25Mo + 15W < T(°C) < 1150 after
finishing rolling, and thereafter rapidly cools the steel. Patent Document 2 describes that
it is possible to produce a high-strength duplex stainless steel tube having no precipitation
of the o phase, and excellent in corrosion resistance.
[0006]
Patent Document 3 suggests a duplex stainless steel having ferrite amount and a
PRE value that are adjusted to be within a predetermined range. Patent Document 3
describes that it is possible to produce a duplex stainless steel excellent in sea-water
resistance through this configuration. Patent Document 4 suggests a duplex stainless steel
whose Mo content is reduced so as to suppress formation of the a phase, and having ferrite
amount and a PREW value that are adjusted to be within respective predetermined ranges.
Patent Document 4 describes that it is possible to produce a duplex stainless steel excellent
in warm workability, crevice corrosion resistance, and structural stability through this
configuration.
[0007]
Patent Documents 5 and 6 suggest duplex stainless steels having ferrite amount,
respective PREW values of an austenite phase and a ferrite phase, and a ratio therebetween
that are adjusted to be within respective predetermined ranges. Both Patent Documents 5
and 6 describe that it is possible to produce a duplex stainless steel excellent in corrosion
resistance and structural stability.
[Citation List]
[Patent Documents]
[0008]
[Patent Document 1] JP5-132741A
[Patent Document 2] JP9-241746A
[Patent Document 3] JP2002-529599A
[Patent Document 4] JP2003-503596A
[Patent Document 5] JP2005-501969A
[Patent Document 6] JP2005-501970A
[Summary of Invention]
[Technical Problem]
[0009]
As mentioned above, decrease in the contents of Cr and Mo that are element
enhancing corrosion resistance deteriorates corrosion resistance and strength required in a
duplex stainless steel. On the other hand, in a steel whose contents of Cr and Mo are
increased, the a phase is likely to precipitate during air cooling, welding, and hot bending
after hot forging or hot rolling. This tendency becomes significant particularly in large
sized steel materials such as billets. Hence, precipitation of the a phase cannot be
• * °
suppressed by simply controlling chemical compositions, microstructure states, heat
treatment conditions or the like of steels in the above prior arts.
[0010]
An object of the present invention, which has been made in order to solve the
problems according to the conventional art, is to provide a duplex stainless steel without
deteriorating corrosion resistance required in the duplex stainless steel, capable of attaining
high strengthening, suppressing cracks due to a thermal history during air cooling or
welding of a billet by suppressing precipitation of the cr phase, and also excellent in
machinability in various machining.
[Solution to Problem]
[0011]
In order to solve the above problems, the present inventors have investigated
influences of various elements on the a phase susceptibility, that is, impact values after
aging treatment (900°C x 600 seconds) simulating a thermal history during air cooling and
welding of each billet of various duplex stainless steels, and have studied precipitation
noses of the a phase and cooling curves during air cooling of the billets. As a result, it
has been found that it is useful to adjust the chemical composition such that an a phase
susceptibility index X, which is comprehensively represented by Si, Cu, Ni, Cr, Mo, and W
that are elements causing influences on the a phase susceptibility, satisfies a predetermined
condition.
[0012]
The present inventors have studied influences on strength of each element, and as a
result of this, it has been found that it is useful to adjust the chemical composition such that
a strength index Y represented by Cr, Mo, W, and N, which are elements contributing to
high strengthening, satisfies a predetermined condition. It is possible to provide a highstrength
duplex stainless steel that suppresses the precipitation of the a phase by adjusting
the above indexes X and Y to satisfy the respective predetermined conditions at the same
time.
[0013]
The present invention has been accomplished based on the aforementioned findings,
and the gist of the present invention is described by the duplex stainless steel in the
following (a) and (b).
[0014]
(a) A duplex stainless steel containing, by mass%:
C: not more than 0.03%, Si: not more than 0.3%, Mn: not more than 3.0%, P: not
more than 0.040%, S: not more than 0.008%, Cu: 0.2 to 2.0%, Ni: 5.0 to 6.5%, Cr: 23.0 to
27.0%, Mo: 2.5 to 3.5%, W: 1.5 to 4.0%, and N: 0.24 to 0.40%; the balance being Fe and
impurities,
wherein a a phase susceptibility index X represented by the following Formula (1)
is not more than 52.0;
a strength index Y represented by the following Formula (2) is not less than 40.5;
and
a pitting resistance equivalent PREW represented by the following Formula (3) is
not less than 40:
X = 2.2Si + 0.5Cu + 2.0Ni + Cr + 4.2Mo + 0.2W (1)
Y = Cr+1.5Mo+10N + 3.5W (2)
PREW = Cr + 3.3(Mo + 0.5W)+16N (3)
where a symbol of each element in the Formulas (1), (2), and (3) denotes a content
(mass%) of the element.
[0015]
(b) The duplex stainless steel according to (a), further containing, by mass%, one or
more elements selected from among Ca: not more than 0.02%, Mg: not more than 0.02%,
B: not more than 0.02%, and rare earth elements: not more than 0.2%, in lieu of part of Fe.
-/^
[Advantageous Effect of Invention]
[0016]
According to the present invention, the precipitation of the o phase is suppressed,
and thus it is possible to provide a duplex stainless steel capable of suppressing cracks
during air cooling of a billet, and having excellent machinability of various machining.
[Brief Description of Drawings]
[0017]
[Figure 1] Figure 1 is a drawing showing a relation between the a phase susceptibility
index X and the impact value after aging at 900°C and 60D seconds.
[Figure 2] Figures 2 are drawings showing precipitation noses of the a phase estimated
based on the impact value evaluation, and cooling curves during air cooling of solid billets
having an outer diameter of 180 mm.
[Figure 3] Figure 3 is a drawing showing a relation between the outer diameter of each
billet and the maximum depth from the surface of each billet where precipitation of the a
phase is suppressed during air cooling.
[Figure 4] Figure 4 is a drawing showing a relation between the strength index Y and the
0.2% yield stress YS.
[Description of Embodiment]
[0018]
C: not more than 0.03%
C is effective in stabilizing an austenite phase. The excessive C content, however,
is likely to cause precipitation of carbide, and deteriorates corrosion resistance.
Accordingly, the C content is set to be not more than 0.03%. The preferable upper limit
thereof is 0.02%.
[0019]
Si: not more than 0.3%
Si is effective in deoxidation of the steel. However, Si is an element that
encourages formation of the a phase with its excessive content. Accordingly, the Si
content is set to be not more than 0.3%. The preferable upper limit thereof is 0.25%.
The above effect can be attained by a slight amount of Si, but the preferable Si content is
not less than 0.01%, in particular if Si is added as a deoxidizer.
[0020]
Mn: not more than 3.0%
Mn is effective in desulfurization and deoxidation during melting the steel, and also
effective in stabilizing the austenite phase. Mn is an element contributing to enhancement
of hot workability. Mn also has effect of increasing solubility of N. The excessive Mn
content, however, deteriorates corrosion resistance. Accordingly, the Mn content is set to
be not more than 3%. The preferable upper limit thereof is set to be 2.5%. The above
effect can be attained by a slight amount of Mn, but it is preferable to contain Mn of not
less than 0.01%, in particular if Mn is added for the purpose of desulfurization and
deoxidation.
[0021]
P: not more than 0.040%
P is an impurity element inevitably mixed in the steel, and the excessive P content
significantly deteriorates corrosion resistance and toughness. Accordingly, the P content
is restricted to be not more than 0.040%. The preferable upper limit thereof is 0.030%.
[0022]
S: not more than 0.008%
S is an impurity element inevitably mixed in the steel, as similar to P, and
deteriorates hot workability of the steel. Sulfide becomes initiation of pitting, and
deteriorates pitting resistance. Accordingly, the S content is preferably suppressed to be
as small as possible, and the S content of not more than 0.008% practically causes no
problem. The preferable upper limit thereof is 0.005%.
[0023]
^
Cu: 0.2 to 2.0%
Cu is particularly effective in enhancing corrosion resistance in a low-pH
environment which is considered to have low reducibility, such as an environment of
H2SO4 or hydrogen sulfide. In order to attain this effect, the Cu content should be not
less than 0.2%. The excessive Cu content, however, deteriorates hot workability, and
encourages formation of the cr phase. Accordingly, the Cu content is set to be not more
than 2.0%. The preferable lower limit thereof is 0.3%, and the more preferable lower
limit thereof is 0.4%. On the other hand, the preferable upper limit thereof is 1.5%, and
the more preferable upper limit thereof is 0.8%.
[0024]
Ni: 5.0 to 6.5%
Ni is an essential element to stabilize austenite. If the Ni content is excessively
small, the amount of ferrite becomes excessively great, which hinders characteristics of the
duplex stainless steel. Solubility of N into ferrite becomes too small, and nitride is likely
to precipitate, resulting in deterioration of corrosion resistance. Accordingly, the Ni
content is set to be not less than 5.0%. On the other hand, the excessive Ni content is
likely to cause precipitation of the a phase, and deteriorates toughness. Accordingly, the
Ni content is set to be not more than 6.5%. The preferable lower limit thereof is 5.3%.
On the other hand, the preferable upper limit thereof is 6.0%.
[0025]
Cr: 23.0 to 27.0%
Cr is an essential basic component for securing corrosion resistance and strength.
The excessively small Cr content cannot secure corrosion resistance enough for a so-called
super duplex stainless steel. Accordingly, the Cr content is set to be not less than 23.0%.
On the other hand, the excessive Cr content causes significant precipitation of the a phase,
which deteriorates corrosion resistance as well as hot workability and weldability.
Accordingly, the Cr content is set to be not more than 27.0%. The preferable lower limit
thereof is 25.0%. The preferable upper limit thereof is 26.0%.
[0026]
Mo: 2.5 to 3.5%
Mo is effective in enhancing corrosion resistance, as similar to Cr, and in particular
effective in enhancing pitting resistance and crevice corrosion resistance. Mo is also
effective in high strengthening. Accordingly, the Mo content should be not less than
2.5%. On the other hand, the excessive Mo content is likely to cause precipitation of the
a phase. Accordingly, the Mo content is set to be not more than 3.5%. The Mo content
is preferably set to be not less than 2.7%. The Mo content is also preferably set to be not
more than 3.2%, and more preferably set to be less than 3.0%.
[0027]
W: 1.5 to 4.0%
W forms fewer intermetallic compounds such as the a phase, compared to Mo, and
is an element of enhancing corrosion resistance, particularly enhancing pitting resistance
and crevice corrosion resistance. W is also effective in high strengthening. The
appropriate W content secures high corrosion resistance without increasing the contents of
Cr, Mo, and N. However, the excessive W content rather saturates its advantageous
effect of enhancing corrosion resistance. Accordingly, the W content is set to be 1.5 to
4.0%. The preferable lower limit thereof is 1.8%, and the more preferable lower limit
thereof is 2.0%. The preferable upper limit thereof is 3.8%.
[0028]
N: 0.24 to 0.40%
N is a strong austenite forming element, and effective in enhancing thermal stability
and corrosion resistance as well as high strengthening of the duplex stainless steel. In
order to attain an appropriate balance between the ferrite phase and austenite phase, an
appropriate amount of N should be contained on the relation with the contents of Cr and
Mo that are ferrite forming elements. N also has effect of enhancing corrosion resistance
of alloy, as similar to Cr, Mo, and W. Hence, the N content should be not less than
0.24%. On the other hand, the excessive N content causes defects due to generation of
to
blowholes, nitride formation due to thermal influences during welding or the like, resulting
in deterioration of toughness and corrosion resistance of the steel. Accordingly, the N
content is set to be not more than 0.40%. The N content is preferably set to be more than
0.30%, and more preferably set to be more than 0.32%.
[0029]
One of the duplex stainless steels according to the present invention contains the
above described elements within the above described ranges, and its balance is Fe and
impurities. The impurities denote components that are mixed during industrially
manufacturing the duplex stainless steel due to various factors, including raw materials
such as minerals and scraps, as well as manufacturing processes, and are contained within
an acceptable range of causing no bad influences to the present invention.
[0030]
The other of the duplex stainless steels according to the present invention contains
one or more elements selected from among Ca: not more than 0.02%, Mg: not more than
0.02%, B: not more than 0.02%, and rare earth elements: not more than 0.2% by mass%, in
addition to the above elements.
[0031]
Each of Ca, Mg, B, and the rare earth elements is an element for suppressing
segregation of S as an impurity to the crystal grain boundaries, and enhancing hot
workability; thus they may be contained in the duplex stainless steel according to the
present invention. Their excessive contents, however, form more sulfide, oxide, carbide,
and nitride that work as initiation of putting in the steel, which deteriorates corrosion
resistance. Accordingly if one or more of the above elements is contained, each content
of Ca, Mg, and B is preferably set to be not more than 0.02 %, and the content of the rare
earth elements is preferably set to be not more than 0.2%. Significant effect of enhancing
hot workability can be achieved by a content of not less than 0.0003% of Ca, Mg, or B, or
a content of not less than 0.01% of the rare earth elements. Only one or a combination of
more than one of the Ca, Mg, B, and the rare earth elements may be contained. The total
\content of these elements is preferably set to be not more than 0.25% if more than one of
these elements are added.
[0032]
The rare earth elements (REM) collectively denote a total of 17 elements including
Sc and Y in addition to lanthanide series, and one or more selected from these elements
may be contained in the steel. The REM content denotes the total amount of the above
elements.
[0033]
The a phase susceptibility index X: not more than 52.0
Among the above chemical components, Si, Cu, Ni, Cr, Mo, and W are elements
that easily form the a phase, so that the contents of these elements should be within their
predetermined ranges, and the a phase susceptibility index X represented by the Formula
(1) below should be not more than 52;0. Adjustment of the chemical composition such
that the a phase susceptibility index X becomes not more than 52.0 makes it easy to set the
impact value (JIS Z 2242: 2005) after aging at 900°C and 600 seconds to be not less than
20 J/cm2, thereby attaining excellent embrittlement cracking resistance. The a phase
susceptibility index X is preferably set to be not more than 51.0.
X = 2.2Si + 0.5Cu + 2.0Ni + Cr + 4.2Mo + 0.2W (1)
where a symbol'of each element in the Formula (1) denotes a content (mass%) of
the element.
[0034]
Strength index Y: not less than 40.5
Among the above chemical components, Cr, Mo, W, and N are solid-solution
strengthening elements for contributing to high strengthening, so that the contents of these
elements should be within their predetermined ranges, and the strength index Y
represented by the Formula (2) below should be not less than 40.5. Adjustment of the
chemical composition such that the strength index Y becomes not less than 40.5 sets the
0.2% yield stress YS to be 620 MPa, thereby achieving the high strengthening. The
-yrstrength
index Y is preferably set to be not less than 41.5 in order to attain sufficient high
strengthening effect.
Y = Cr+1.5Mo+10N + 3.5W (2)
where a symbol of each element in the Formula (2) denotes a content (mass%) of
the element.
[0035]
Pitting resistance equivalent PREW: not less than 40
Among the above chemical components, the contents of the elements of Cr, Mo, W
and N should be within their predetermined ranges, and in order to enhance corrosion
resistance, particularly sea-water corrosion resistance of the duplex stainless steel of the
present invention, the pitting resistance equivalent PREW represented by the Formula (3)
below should be not less than 40. In general, the pitting resistance equivalent PREW is
adjusted to be not less than 35, but in the duplex stainless steel of the present invention, the
contents of Cr, Mo, and N are increased such that PREW becomes not less than 40.
Through this configuration, it is possible to attain significantly excellent corrosion
resistance.
PREW = Cr + 3.3(Mo + 0.5W) + 16N (3)
where a symbol of each element in the Formula (3) denotes a content (mass%) of
the element.
[Example 1]
[0036]
The duplex stainless steels of 10 kg having the chemical compositions shown in
Table 1 were melted in a VIM melting furnace, and the cast pieces were retained at a
temperature of 1250°C for two hours, and thereafter, were hot-forged into plate materials
having a thickness of 30mm. Subsequently, the produced plate materials were subjected
to solution heat treatment at a temperature of 1110°C for 30 minutes, and then were waterquenched.
[0037]
\3
The CT phase susceptibility was evaluated based on the impact value after aging at
900°C and 600 seconds. Specifically, V-notch test specimens collected from the plate
materials after the solution heat treatment were aged, and thereafter, the impact value for
each test specimen was measured in compliance with JIS Z 2242 (2005). With respect to
corrosion resistance (sea-water corrosion resistance), a critical pitting temperature CPT
was measured for each test specimen by conducting a pitting test on each plate material;
after the solution heat treatment. The pitting test was carried out in compliance with the
pitting test method using ferric chloride specified by ASTM G48. With respect to
strength, No. 10 test specimens of JIS Z2201(1998) were collected from the plate materials
after the solution heat treatment, and a tensile test was conducted on each test specimen at
a normal temperature. These results are shown in Table 2.
[0038]
[Table 1]
Table 1
Division
Inventive Comparative examples examples
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Chemical composition (mass% Balance: Fe and impurities)
c
0.015
0.015
0.015
0.015
0.016
0.016
0.016
0.014
0.016
0.014
0.015
0.016
0.018
0.015
Si
0.21
0.26
0.25
0.22
0.22
0.23
0.23
0.24
0.22
0.30
0.22
0.97*
0.29
0.14
Mn
0.99
0.99
1.00
0.49
0.49
0.49
0.49
1.96
0.49
0.47
0.49
0.49
0.52
0.49
P
0.020
0.020
0.021
0.020
0.020
0.017
0.017
0.019
0.019
0.021
0.023
0.019
0.019
0.018
S
0.0017
0.0016
0.0010
0.0008
0.0009
0.0009
0.0009
0.0017
0.0009
0.0012
0.0015
0.0011
0.0014
0.0014
Cu
0.46
0.45
0.46
0.45
0.44
0.45
0.44
0.46
0.46
0.46
0.47
0.47
4.92*
0.47
Ni
5.87
5.83
5.89
5.97
5.98
6.27
6.31
5.30
6.25
6.70*
6.15
7.60*
6.76*
5.86
Cr
25.0
25.4
26.1
26.1
25.6
25.1
25.0
25.0
25.2
25.1
25.2
25.2
24.9
25.0
Mo
2.97
2.87
2.88
2.86
2.87
2.63
2.58
3.20
3.01
3.16
3.21
3.15
3.01
3.19
W
2.19
2.20
2.17
2.50
3.02
3.48
3.96
2.07
3.44
2.19
2.07
2.08
1.95
2.09
N
0.355
0.344
0.356
0.349
0.323
0.309
0.311
0.388
0.310
0.280
0.266
0.246
0.246
0.261
Ca
-
-
-
0.0014
-
0.0017
-
0.0028
-
-
-
-
-
-
B
-
-
-
-
0.0031
0.0025
-
0.0018
-
-
-
-
-
-
Nd
-
-
-
-
-
-
-
-
0.02
-
-
-
-
-
The mark * indicates out of the scope of the invention
[0039]
[Table 2]
Table 2
Division
Inventive Comparative examples examples
1
2
3
4
5
6
7
8
9
10
11
12
13
14