TECHNICAL FIELD
[0001] The present disclosure relates to a steel pipe, and more particularly relates to
a duplex stainless steel pipe.
BACKGROUND ART
[0002] Oil wells and gas wells (hereinafter, oil wells and gas wells are collectively referred
to simply as "oil wells") are sometimes a corrosive environment containing a corrosive
gas. Here, the term "corrosive gas" means carbon dioxide gas and/or hydrogen sulfide
gas. Therefore, steel materials for use in oil wells are required to have excellent
corrosion resistance in a corrosive environment.
[0003] To date, as means for improving the corrosion resistance of a steel material, means
of forming a passive film mainly composed of Cr oxide on the surface of the steel
material by increasing the content of chromium (Cr) is known. Therefore, in an environment
where excellent corrosion resistance is required, in some cases a duplex stainless
steel material in which the content of Cr has been made high is used.
[0004] In recent years, furthermore, deep wells below sea level are being actively developed.
A steel material used in such deep wells is required to have high strength. Therefore,
there is a need for a duplex stainless steel material that can achieve both high strength
and excellent corrosion resistance as a steel material to be used in an oil well.
[0006] The duplex stainless steel material disclosed in Patent Literature 1 has a chemical
composition which contains, in mass%, C: 0.005 to 0.04%, Si: 0.2 to 1.0%, Mn: 0.1
to 2.0%, P: 0.040% or less, S: 0.010% or less, Ni: 3 to 7%, Cr: 23 to 28%, Mo: 0.5
to 1.5%, Cu: 2 to 4%, N: 0.10 to 0.35%, Al: 0.001 to 0.04%, W: 0 to 1.0%, Co: 0 to
1.0%, V: 0 to 1.0%, Nb: 0 to 0.2%, Ti: 0 to 0.2%, Ca: 0 to 0.02%, Mg: 0 to 0.02%,
B: 0 to 0.02%, and rare earth metal (REM): 0 to 0.2%, with the balance being Fe and
impurities, and which satisfies Formula (1) to Formula (3), and has a yield strength
YS of 655 MPa or more. Here, Formula (1) to Formula (3) are as follows.

[0007] It is described in Patent Literature 1 that in this duplex stainless steel material,
by adjusting the contents of the elements in the chemical composition and the yield
strength so as to satisfy Formula (1) to Formula (3), high strength and excellent
corrosion resistance are obtained.
[0008] The duplex stainless steel material disclosed in Patent Literature 2 has a chemical
composition containing, in mass%, C: 0.03% or less, Si: 0.3% or less, Mn: 3.0% or
less, P: 0.040% or less, S: 0.008% or less, 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%, with the balance
being Fe and impurities, in which a σ phase susceptibility index X (= 2.2Si + 0.5Cu
+ 2.0Ni + Cr + 4.2Mo + 0.2W) is 52.0 or less, a strength index Y (= Cr + 1.5Mo + 10N
+ 3.5W) is 40.5 or more, and a pitting resistance equivalent PREW (= Cr + 3.3(Mo +
0.5W) + 16N) is 40 or more. In the structure of the steel, in a cross section in the
thickness direction which is parallel to the rolling elongation direction, when a
straight line is drawn parallel to the thickness direction from the outer layer to
a depth of 1 mm, the number of boundaries between a ferrite phase and an austenite
phase which intersect with the straight line is 160 or more. It is described in Patent
Literature 2 that in this duplex stainless steel, high strength can be achieved without
loss of corrosion resistance.
CITATION LIST
PATENT LITERATURE
SUMMARY OF INVENTION
TECHNICAL PROBLEM
[0010] In the duplex stainless steel materials disclosed in Patent Literature 1 and Patent
Literature 2, high strength and excellent corrosion resistance are obtained. However,
high strength and excellent corrosion resistance may also be obtained by means other
than the means disclosed in Patent Literature 1 and Patent Literature 2.
[0011] An objective of the present disclosure is to provide a duplex stainless steel pipe
in which high strength and excellent corrosion resistance are obtained.
SOLUTION TO PROBLEM
[0012] A duplex stainless steel pipe according to the present disclosure consists of, in
mass%, C: 0.030% or less, Si: 0.20 to 1.00%, Mn: 0.5 to 7.0%, P: 0.040% or less, S:
0.020% or less, Al: 0.100% or less, Ni: 4.0 to 9.0%, Cr: 20.0 to 30.0%, Mo: 0.5 to
2.0%, Cu: 1.5 to 3.0%, N: 0.15 to 0.30%, V: 0.01 to 0.50%, Nb: 0.030 to 0.300%, Co:
0.10 to 0.50%, Sn: 0.001 to 0.050%, Ta: 0 to 0.100%, Ti: 0 to 0.100%, Zr: 0 to 0.100%,
Hf: 0 to 0.100%, W: 0 to 0.200%, Sb: 0 to 0.100%, Ca: 0 to 0.020%, Mg: 0 to 0.020%,
B: 0 to 0.020%, and rare earth metal: 0 to 0.200%, with the balance being Fe and impurities,
and has a microstructure that is composed of, in volume ratio, ferrite in an amount
of 35.0 to 65.0% and σ phase in an amount of 0 to less than 1.0%, with the balance
being austenite, wherein a content of undissolved Nb is 0.008% by mass or more, and
a ratio of the content of undissolved Nb to a content of undissolved Al is 1.0 or
more, and a yield strength is 655 MPa or more.
ADVANTAGEOUS EFFECTS OF INVENTION
[0013] In the duplex stainless steel pipe according to the present disclosure, high strength
and excellent corrosion resistance are obtained.
BRIEF DESCRIPTION OF DRAWINGS
[0014]
[FIG. 1] FIG. 1 is a schematic diagram of an example of a straightening machine.
[FIG. 2] FIG. 2 is a front view of the straightening machine illustrated in FIG. 1.
DESCRIPTION OF EMBODIMENTS
[0015] The present inventors conducted studies from the viewpoint of the chemical composition
with regard to a duplex stainless steel pipe in which high strength and excellent
corrosion resistance can be obtained. As a result, the present inventors have considered
that if a duplex stainless steel pipe consists of, in mass%, C: 0.030% or less, Si:
0.20 to 1.00%, Mn: 0.5 to 7.0%, P: 0.040% or less, S: 0.020% or less, Al: 0.100% or
less, Ni: 4.0 to 9.0%, Cr: 20.0 to 30.0%, Mo: 0.5 to 2.0%, Cu: 1.5 to 3.0%, N: 0.15
to 0.30%, V: 0.01 to 0.50%, Nb: 0.030 to 0.300%, Co: 0.10 to 0.50%, Sn: 0.001 to 0.050%,
Ta: 0 to 0.100%, Ti: 0 to 0.100%, Zr: 0 to 0.100%, Hf: 0 to 0.100%, W: 0 to 0.200%,
Sb: 0 to 0.100%, Ca: 0 to 0.020%, Mg: 0 to 0.020%, B: 0 to 0.020%, and rare earth
metal: 0 to 0.200%, with the balance being Fe and impurities, high strength and excellent
corrosion resistance can be obtained.
[0016] Therefore, the present inventors conducted further studies from viewpoints other
than the chemical composition with respect to means for obtaining even higher strength
in a duplex stainless steel pipe that satisfies the chemical composition described
above. First, the present inventors conducted studies regarding the microstructure
of a duplex stainless steel pipe. The microstructure of a duplex stainless steel pipe
having the chemical composition described above is mainly composed of ferrite and
austenite. The present inventors have found that if the microstructure of a duplex
stainless steel pipe having the chemical composition described above is made a structure
in which the ferrite volume ratio is 35.0 to 65.0% and the balance is substantially
austenite, strength and corrosion resistance can be stably increased.
[0017] In addition, the present inventors have considered that the strength of a duplex
stainless steel pipe can be further increased by causing Nb carbo-nitrides to precipitate
in the duplex stainless steel pipe. Nb carbo-nitrides are fine precipitates. Therefore,
the strength of a duplex stainless steel pipe is increased by precipitation strengthening
by Nb carbo-nitrides. However, σ phase also easily forms in a temperature range in
which Nb carbo-nitrides form during a process for producing a duplex stainless steel
pipe. The σ phase reduces the corrosion resistance of the duplex stainless steel pipe.
Therefore, the present inventors investigated the relation between the formed amount
of Nb carbo-nitrides, the formed amount of σ phase, and the strength and corrosion
resistance. The formed amount of Nb carbo-nitrides correlates with the content of
undissolved Nb. In a duplex stainless steel pipe satisfying the chemical composition
described above, if the content of undissolved Nb is 0.008% by mass or more, Nb carbo-nitrides
are sufficiently formed and the strength can be increased. In addition, even when
the content of undissolved Nb is 0.008% by mass or more, by a microstructure that
is composed of, in volume ratio, ferrite in an amount of 35.0 to 65.0% and σ phase
in an amount of 0 to less than 1.0%, with the balance being austenite, excellent corrosion
resistance can be maintained.
[0018] However, it has been revealed that even when duplex stainless steel pipes satisfied
the features described above, sufficient strength was still not obtained in some cases.
Therefore, the present inventors conducted further studies. As a result, it has newly
been revealed that in a duplex stainless steel pipe having the chemical composition
described above, Al nitrides are a factor that causes a reduction in strength.
[0019] In the chemical composition described above, in order to obtain high strength by
means of dissolved N, the content of N is higher than the content of C. It is considered
that in the case of such a chemical composition, the content of N in the Nb carbo-nitrides
is higher than the content of C. That is, in the chemical composition described above,
N not only contributes to solid-solution strengthening as dissolved N, but also contributes
to precipitation strengthening by means of Nb carbo-nitrides.
[0020] On the other hand, N also combines with Al to form Al nitrides. Al nitrides are coarser
precipitates than Nb carbo-nitrides. Therefore, Al nitrides make almost no contribution
to precipitation strengthening. Therefore, in a duplex stainless steel pipe having
the chemical composition described above, if the formed amount of Al nitrides is relatively
larger than the formed amount of Nb carbo-nitrides, a case will occur in which the
dissolved N and Nb nitrides are insufficient. In such case, the strength of the duplex
stainless steel pipe cannot be sufficiently increased.
[0021] Al nitrides correlate with the content of undissolved Al. Therefore, the present
inventors conducted further studies regarding the relation between the content of
undissolved Nb and content of undissolved Al and the strength and corrosion resistance.
As a result, the present inventors have discovered that if an undissolved Nb/Al ratio
that is a ratio of the content of undissolved Nb to the content of undissolved Al
is 1.0 or more, a sufficient amount of Nb nitrides and a sufficient amount of dissolved
N can be secured, and as a result, both high strength and excellent corrosion resistance
can be achieved.
[0022] Note that, there is also a possibility that in a duplex stainless steel pipe satisfying
the chemical composition and microstructure described above, by making the content
of undissolved Nb 0.008% by mass or more and making the undissolved Nb/Al ratio 1.0
or more, both a yield strength of 655 MPa or more and excellent corrosion resistance
are achieved by a mechanism that is different from the mechanism described above.
However, the fact that in a duplex stainless steel pipe having the chemical composition
and microstructure described above, both a high yield strength of 655 MPa or more
and excellent corrosion resistance can be achieved by making the content of undissolved
Nb 0.008% by mass or more and making the undissolved Nb/Al ratio 1.0 or more has been
demonstrated by examples that are described later.
[0023] A duplex stainless steel pipe according to the present embodiment, which was completed
based on the findings described above, is as follows.
[0024] A duplex stainless steel pipe according to a first aspect has a chemical composition
consisting of, in mass%, C: 0.030% or less, Si: 0.20 to 1.00%, Mn: 0.5 to 7.0%, P:
0.040% or less, S: 0.020% or less, Al: 0.100% or less, Ni: 4.0 to 9.0%, Cr: 20.0 to
30.0%, Mo: 0.5 to 2.0%, Cu: 1.5 to 3.0%, N: 0.15 to 0.30%, V: 0.01 to 0.50%, Nb: 0.030
to 0.300%, Co: 0.10 to 0.50%, Sn: 0.001 to 0.050%, Ta: 0 to 0.100%, Ti: 0 to 0.100%,
Zr: 0 to 0.100%, Hf: 0 to 0.100%, W: 0 to 0.200%, Sb: 0 to 0.100%, Ca: 0 to 0.020%,
Mg: 0 to 0.020%, B: 0 to 0.020%, and rare earth metal: 0 to 0.200%, with the balance
being Fe and impurities. The microstructure of the aforementioned duplex stainless
steel pipe is composed of, in volume ratio, ferrite in an amount of 35.0 to 65.0%
and σ phase in an amount of 0 to less than 1.0%, with the balance being austenite.
In addition, in the aforementioned duplex stainless steel pipe, a content of undissolved
Nb is 0.008% by mass or more, and a ratio of the content of undissolved Nb to a content
of undissolved Al is 1.0 or more, and the yield strength is 655 MPa or more.
[0025] A duplex stainless steel pipe according to the second aspect is in accordance with
the duplex stainless steel pipe according to the first aspect, wherein the chemical
composition contains one or more types of element selected from a group consisting
of Ta: 0.001 to 0.100%, Ti: 0.001 to 0.100%, Zr: 0.001 to 0.100%, Hf: 0.001 to 0.100%,
W: 0.001 to 0.200%, Sb: 0.001 to 0.100%, Ca: 0.001 to 0.020%, Mg: 0.001 to 0.020%,
B: 0.001 to 0.020%, and rare earth metal: 0.001 to 0.200%.
[0026] Hereunder, the duplex stainless steel pipe according to the present embodiment is
described in detail. Note that, in the following description, the duplex stainless
steel pipe is also referred to simply as "steel pipe". Further, the symbol "%" in
relation to an element means mass percent unless otherwise stated.
[Features of duplex stainless steel pipe of present embodiment]
[0027] The duplex stainless steel pipe of the present embodiment satisfies the following
feature 1 to feature 4.
(Feature 1)
[0028] The chemical composition consists of, in mass%, C: 0.030% or less, Si: 0.20 to 1.00%,
Mn: 0.5 to 7.0%, P: 0.040% or less, S: 0.020% or less, Al: 0.100% or less, Ni: 4.0
to 9.0%, Cr: 20.0 to 30.0%, Mo: 0.5 to 2.0%, Cu: 1.5 to 3.0%, N: 0.15 to 0.30%, V:
0.01 to 0.50%, Nb: 0.030 to 0.300%, Co: 0.10 to 0.50%, Sn: 0.001 to 0.050%, Ta: 0
to 0.100%, Ti: 0 to 0.100%, Zr: 0 to 0.100%, Hf: 0 to 0.100%, W: 0 to 0.200%, Sb:
0 to 0.100%, Ca: 0 to 0.020%, Mg: 0 to 0.020%, B: 0 to 0.020%, and rare earth metal:
0 to 0.200%, with the balance being Fe and impurities.
(Feature 2)
[0029] The microstructure is composed of, in volume ratio, ferrite in an amount of 35.0
to 65.0% and σ phase in an amount of 0 to less than 1.0%, with the balance being austenite.
(Feature 3)
[0030] The content of undissolved Nb is 0.008% by mass or more, and a ratio of the content
of undissolved Nb to the content of undissolved Al is 1.0 or more.
(Feature 4)
[0031] The yield strength is 655 MPa or more.
[0032] Feature 1 to feature 4 are described hereunder.
[(Feature 1) Regarding chemical composition]
[0033] The chemical composition of the duplex stainless steel pipe according to the present
embodiment contains the following elements.
C: 0.030% or less
[0034] Carbon (C) is unavoidably contained. That is, the lower limit of the content of C
is more than 0%. C forms Cr carbides at grain boundaries and increases the corrosion
susceptibility at the grain boundaries. Therefore, if the content of C is more than
0.030%, the corrosion resistance of the steel pipe will decrease even if the contents
of other elements are within the range of the present embodiment. Therefore, the C
content is 0.030% or less.
[0035] The content of C is preferably as low as possible. However, excessive reduction of
the content of C will significantly increase the production cost. Therefore, when
industrial manufacturing is taken into consideration, a preferable lower limit of
the content of C is 0.001%, more preferably is 0.002%, and further preferably is 0.005%.
[0036] A preferable upper limit of the content of C is 0.029%, more preferably is 0.028%,
and further preferably is 0.027%.
Si: 0.20 to 1.00%
[0037] Silicon (Si) deoxidizes the steel. If the content of Si is less than 0.20%, the aforementioned
advantageous effect will not be sufficiently obtained even if the contents of other
elements are within the range of the present embodiment.
[0038] On the other hand, if the content of Si is more than 1.00%, toughness and hot workability
of the steel pipe will decrease even if the contents of other elements are within
the range of the present embodiment.
[0039] Therefore, the content of Si is 0.20 to 1.00%.
[0040] A preferable lower limit of the content of Si is 0.21%, more preferably is 0.22%,
further preferably is 0.25%, and further preferably is 0.30%.
[0041] A preferable upper limit of the content of Si is 0.95%, more preferably is 0.92%,
further preferably is 0.91%, and further preferably is 0.90%.
Mn: 0.5 to 7.0%
[0042] Manganese (Mn) deoxidizes the steel and desulfurizes the steel. Furthermore, Mn enhances
hot workability of the steel pipe. If the content of Mn is less than 0.5%, the aforementioned
advantageous effects will not be sufficiently obtained even if the contents of other
elements are within the range of the present embodiment.
[0043] On the other hand, Mn segregates to grain boundaries together with impurities such
as P and S. Therefore, if the content of Mn is more than 7.0%, even if the contents
of other elements are within the range of the present embodiment, the corrosion resistance
of the steel pipe in high temperature environments will decrease.
[0044] Therefore, the content of Mn is 0.5 to 7.0%.
[0045] A preferable lower limit of the content of Mn is 0.6%, more preferably is 0.8%, further
preferably is 1.0%, and further preferably is 1.2%.
[0046] A preferable upper limit of the content of Mn is 6.8%, more preferably is 6.5%, further
preferably is 6.3%, further preferably is 6.2%, and further preferably is 6.0%.
P: 0.040% or less
[0047] Phosphorus (P) is unavoidably contained. That is, the lower limit of the content
of P is more than 0%. P segregates to grain boundaries. Therefore, if the content
of P is more than 0.040%, the corrosion resistance of the steel pipe will decrease
even if the contents of other elements are within the range of the present embodiment.
Therefore, the content of P is 0.040% or less.
[0048] The content of P is preferably as low as possible. However, excessive reduction of
the content of P will significantly increase the production cost. Therefore, when
industrial manufacturing is taken into consideration, a preferable lower limit of
the content of P is 0.001%, more preferably is 0.002%, and further preferably is 0.003%.
[0049] A preferable upper limit of the content of P is 0.038%, more preferably is 0.036%,
further preferably is 0.035%, and further preferably is 0.030%.
S: 0.020% or less
[0050] Sulfur (S) is unavoidably contained. That is, a lower limit of the content of S is
more than 0%. S segregates to grain boundaries. Therefore, if the content of S is
more than 0.020%, toughness and hot workability of the steel pipe will decrease even
if the contents of other elements are within the range of the present embodiment.
Therefore, the content of S is 0.020% or less.
[0051] The content of S is preferably as low as possible. However, excessive reduction of
the content of S will significantly increase the production cost. Therefore, when
industrial manufacturing is taken into consideration, a preferable lower limit of
the content of S is 0.001%, more preferably is 0.002%, further preferably is 0.003%,
further preferably is 0.004%, and further preferably is 0.005%.
[0052] A preferable upper limit of the content of S is 0.018%, more preferably is 0.016%,
and further preferably is 0.014%.
Al: 0.100% or less
[0053] Aluminum (Al) is unavoidably contained. That is, the lower limit of the content of
Al is more than 0%. Al deoxidizes the steel. On the other hand, if the content of
Al is more than 0.100%, coarse oxide-based inclusions will form. Consequently, even
if the contents of other elements are within the range of the present embodiment,
the toughness of the steel pipe will decrease. Therefore, the content of Al is 0.100%
or less.
[0054] A preferable lower limit of the content of Al is 0.001%, more preferably is 0.005%,
further preferably is 0.007%, and further preferably is 0.010%.
[0055] A preferable upper limit of the content of Al is 0.095%, more preferably is 0.092%,
further preferably is 0.090%, and further preferably is 0.085%.
[0056] Note that, the content of Al in the chemical composition of the duplex stainless
steel pipe of the present embodiment means the content of "acid-soluble Al," that
is, the content of sol. Al.
Ni: 4.0 to 9.0%
[0057] Nickel (Ni) stabilizes the austenitic structure of the steel pipe. That is, Ni stabilizes
the duplex microstructure consisting of ferrite and austenite. Ni also enhances the
corrosion resistance of the steel pipe. If the content of Ni is less than 4.0%, the
aforementioned advantageous effects will not be sufficiently obtained even if the
contents of other elements are within the range of the present embodiment.
[0058] On the other hand, if the content of Ni is more than 9.0%, the volume ratio of austenite
will be too high. In such case, the strength of the steel pipe will decrease even
if the contents of other elements are within the range of the present embodiment.
[0059] Therefore, the content of Ni is 4.0 to 9.0%.
[0060] A preferable lower limit of the content of Ni is 4.1%, more preferably is 4.3%, and
further preferably is 4.5%.
[0061] A preferable upper limit of the content of Ni is 8.8%, more preferably is 8.6%, further
preferably is 8.4%, further preferably is 8.2%, and further preferably is 8.0%.
Cr: 20.0 to 30.0%
[0062] Chromium (Cr) forms a passive film as an oxide on the surface of the steel pipe and
thereby enhances the corrosion resistance of the steel pipe. Cr also increases the
volume ratio of the ferritic structure of the steel pipe. By obtaining a sufficient
ferritic structure, the corrosion resistance of the steel pipe is stabilized. If the
content of Cr is less than 20.0%, the aforementioned advantageous effects will not
be sufficiently obtained even if the contents of other elements are within the range
of the present embodiment.
[0063] On the other hand, if the content of Cr is more than 30.0%, hot workability of the
steel pipe will decrease even if the contents of other elements are within the range
of the present embodiment.
[0064] Therefore, the content of Cr is 20.0 to 30.0%.
[0065] A preferable lower limit of the content of Cr is 20.2%, more preferably is 20.5%,
further preferably is 21.0%, and further preferably is 21.5%.
[0066] A preferable upper limit of the content of Cr is 29.8%, more preferably is 29.6%,
further preferably is 29.5%, further preferably is 29.0%, and further preferably is
28.5%.
Mo: 0.5 to 2.0%
[0067] Molybdenum (Mo) enhances the corrosion resistance of the steel pipe. Mo also dissolves
in the steel and increases the strength of the steel pipe. If the content of Mo is
less than 0.5%, the aforementioned advantageous effects will not be sufficiently obtained
even if the contents of other elements are within the range of the present embodiment.
[0068] On the other hand, if the content of Mo is more than 2.0%, hot workability of the
steel pipe will decrease even if the contents of other elements are within the range
of the present embodiment.
[0069] Therefore, the content of Mo is 0.5 to 2.0%.
[0070] A preferable lower limit of the content of Mo is 0.6%, more preferably is 0.7%, and
further preferably is 0.8%.
[0071] A preferable upper limit of the content of Mo is 1.9%, more preferably is 1.8%, further
preferably is 1.7%, further preferably is 1.6%, and further preferably is 1.5%.
Cu: 1.5 to 3.0%
[0072] Copper (Cu) precipitates in the steel pipe and increases the strength of the steel
pipe. If the content of Cu is less than 1.5%, the aforementioned advantageous effect
will not be sufficiently obtained even if the contents of other elements are within
the range of the present embodiment.
[0073] On the other hand, if the content of Cu is more than 3.0%, hot workability of the
steel pipe will decrease even if the contents of other elements are within the range
of the present embodiment.
[0074] Therefore, the content of Cu is 1.5 to 3.0%.
[0075] A preferable lower limit of the content of Cu is 1.6%, more preferably is 1.8%, and
further preferably is 2.0%.
[0076] A preferable upper limit of the content of Cu is 2.9%, more preferably is 2.8%, and
further preferably is 2.7%.
N: 0.15 to 0.30%
[0077] Nitrogen (N) dissolves in the steel pipe and increases the strength of the steel
pipe. N also combines with Nb to form Nb carbo-nitrides, thereby increasing the strength
of the steel pipe by precipitation strengthening. In addition, N stabilizes the austenitic
structure of the steel pipe. If the content of N is less than 0.15%, the aforementioned
advantageous effects will not be sufficiently obtained even if the contents of other
elements are within the range of the present embodiment.
[0078] On the other hand, if the content of N is more than 0.30%, toughness and hot workability
of the steel pipe will decrease even if the contents of other elements are within
the range of the present embodiment.
[0079] Therefore, the content of N is 0.15 to 0.30%.
[0080] A preferable lower limit of the content of N is 0.16%, more preferably is 0.18%,
and further preferably is 0.20%.
[0081] A preferable upper limit of the content of N is 0.29%, more preferably is 0.28%,
further preferably is 0.27%, further preferably is 0.26%, and further preferably is
0.25%.
V: 0.01 to 0.50%
[0082] Vanadium (V) increases the strength of the steel pipe. If the content of V is less
than 0.01%, the aforementioned advantageous effect will not be sufficiently obtained
even if the contents of other elements are within the range of the present embodiment.
[0083] On the other hand, if the content of V is more than 0.50%, even if the contents of
other elements are within the range of the present embodiment, the strength of the
steel pipe will be too high and the toughness and hot workability of the steel pipe
will decrease.
[0084] Therefore, the content of V is 0.01 to 0.50%.
[0085] A preferable lower limit of the content of V is 0.02%, more preferably is 0.03%,
further preferably is 0.05%, further preferably is 0.07%, and further preferably is
0.10%.
[0086] A preferable upper limit of the content of V is 0.48%, more preferably is 0.47%,
further preferably is 0.45%, further preferably is 0.42%, and further preferably is
0.40%.
Nb: 0.030 to 0.300%
[0087] Niobium (Nb) forms carbo-nitrides and thereby increases the strength of the steel
pipe. If the content of Nb is less than 0.030%, the aforementioned advantageous effect
will not be sufficiently obtained even if the contents of other elements are within
the range of the present embodiment.
[0088] On the other hand, if the content of Nb is more than 0.300%, even if the contents
of other elements are within the range of the present embodiment, the strength of
the steel pipe will be too high and the toughness of the steel pipe will decrease.
[0089] Therefore, the content of Nb is 0.030 to 0.300%.
[0090] A preferable lower limit of the content of Nb is 0.031%, more preferably is 0.033%,
further preferably is 0.035%, further preferably is 0.037%, and further preferably
is 0.040%.
[0091] A preferable upper limit of the content of Nb is 0.294%, more preferably is 0.290%,
further preferably is 0.280%, and further preferably is 0.250%.
Co: 0.10 to 0.50%
[0092] Cobalt (Co) forms a coating on the surface of the steel pipe and enhances the corrosion
resistance of the steel pipe. Co also increases hardenability of the steel pipe and
stabilizes the strength. If the content of Co is less than 0.10%, the aforementioned
advantageous effects will not be sufficiently obtained even if the contents of other
elements are within the range of the present embodiment.
[0093] On the other hand, if the content of Co is more than 0.50%, the production cost will
increase considerably even if the contents of other elements are within the range
of the present embodiment.
[0094] Therefore, the content of Co is 0.10 to 0.50%.
[0095] A preferable lower limit of the content of Co is 0.11%, more preferably is 0.13%,
and further preferably is 0.15%.
[0096] A preferable upper limit of the content of Co is 0.48%, more preferably is 0.45%,
further preferably is 0.40%, and further preferably is 0.35%.
Sn: 0.001 to 0.050%
[0097] Tin (Sn) enhances the corrosion resistance of the steel pipe. If the content of Sn
is less than 0.001%, the aforementioned advantageous effect will not be sufficiently
obtained even if the contents of other elements are within the range of the present
embodiment.
[0098] On the other hand, if the content of Sn is more than 0.050%, even if the contents
of other elements are within the range of the present embodiment, liquation cracking
will occur at grain boundaries, which will decrease the hot workability of the steel
pipe.
[0099] Therefore, the content of Sn is 0.001 to 0.050%.
[0100] A preferable lower limit of the content of Sn is 0.002%, more preferably is 0.003%,
further preferably is 0.005%, further preferably is 0.006%, further preferably is
0.008%, and further preferably is 0.010%.
[0101] A preferable upper limit of the content of Sn is 0.048%, more preferably is 0.045%,
further preferably is 0.043%, and further preferably is 0.040%.
[0102] The balance of the chemical composition of the duplex stainless steel pipe according
to the present embodiment is Fe and impurities. Here, the term "impurities" with respect
to the chemical composition refers to substances which are mixed in from ore or scrap
as the raw material or from the production environment or the like when industrially
producing the duplex stainless steel pipe, and which are permitted within a range
that does not adversely affect the duplex stainless steel pipe according to the present
embodiment.
[Regarding optional elements]
[0103] The chemical composition of the duplex stainless steel pipe described above may further
contain, in lieu of a part of Fe, one or more types of element selected from the group
consisting of Ta: 0 to 0.100%, Ti: 0 to 0.100%, Zr: 0 to 0.100%, Hf: 0 to 0.100%,
W: 0 to 0.200%, Sb: 0 to 0.100%, Ca: 0 to 0.020%, Mg: 0 to 0.020%, B: 0 to 0.020%,
and rare earth metal: 0 to 0.200%.
[0104] These optional elements are described hereunder.
[First group (Ta, Ti, Zr, Hf, and W)]
[0105] The duplex stainless steel pipe of the present embodiment may contain one or more
types of element selected from the group consisting of Ta, Ti, Zr, Hf, and W in lieu
of a part of Fe. Each of these elements is an optional element, and increases the
strength of the steel pipe.
Ta: 0 to 0.100%
[0106] Tantalum (Ta) is an optional element, and does not have to be contained. That is,
the content of Ta may be 0%.
[0107] When contained, that is, when the content of Ta is more than 0%, Ta forms carbo-nitrides
and increases the strength of the steel pipe. If even a small amount of Ta is contained,
the aforementioned advantageous effect will be obtained to a certain extent.
[0108] However, if the content of Ta is more than 0.100%, even if the contents of other
elements are within the range of the present embodiment, the strength of the steel
pipe will be too high and the toughness of the steel pipe will decrease.
[0109] Therefore, the content of Ta is 0 to 0.100%.
[0110] A preferable lower limit of the content of Ta is 0.001 %, more preferably is 0.002%,
further preferably is 0.003%, further preferably is 0.005%, further preferably is
0.010%, and further preferably is 0.015%.
[0111] A preferable upper limit of the content of Ta is 0.080%, more preferably is 0.070%,
further preferably is 0.060%, further preferably is 0.050%, and further preferably
is 0.040%.
Ti: 0 to 0.100%
[0112] Titanium (Ti) is an optional element, and does not have to be contained. That is,
the content of Ti may be 0%.
[0113] When contained, that is, when the content of Ti is more than 0%, Ti forms carbo-nitrides
and increases the strength of the steel pipe. If even a small amount of Ti is contained,
the aforementioned advantageous effect will be obtained to a certain extent.
[0114] However, if the content of Ti is more than 0.100%, even if the contents of other
elements are within the range of the present embodiment, the strength of the steel
pipe will be too high and the toughness of the steel pipe will decrease.
[0115] Therefore, the content of Ti is 0 to 0.100%.
[0116] A preferable lower limit of the content of Ti is 0.001%, more preferably is 0.002%,
further preferably is 0.003%, further preferably is 0.005%, further preferably is
0.010%, and further preferably is 0.015%.
[0117] A preferable upper limit of the content of Ti is 0.098%, more preferably is 0.095%,
further preferably is 0.090%, further preferably is 0.085%, further preferably is
0.080%, further preferably is 0.075%, and further preferably is 0.070%.
Zr: 0 to 0.100%
[0118] Zirconium (Zr) is an optional element, and does not have to be contained. That is,
the content of Zr may be 0%.
[0119] When contained, that is, when the content of Zr is more than 0%, Zr forms carbo-nitrides
and increases the strength of the steel pipe. If even a small amount of Zr is contained,
the aforementioned advantageous effect will be obtained to a certain extent.
[0120] However, if the content of Zr is more than 0.100%, even if the contents of other
elements are within the range of the present embodiment, the strength of the steel
pipe will be too high and the toughness of the steel pipe will decrease.
[0121] Therefore, the content of Zr is 0 to 0.100%.
[0122] A preferable lower limit of the content of Zr is 0.001%, more preferably is 0.002%,
further preferably is 0.003%, further preferably is 0.005%, further preferably is
0.010%, and further preferably is 0.015%.
[0123] A preferable upper limit of the content of Zr is 0.090%, more preferably is 0.080%,
further preferably is 0.070%, further preferably is 0.060%, and further preferably
is 0.050%.
Hf: 0 to 0.100%
[0124] Hafnium (Hf) is an optional element, and does not have to be contained. That is,
the content of Hf may be 0%.
[0125] When contained, that is, when the content of Hf is more than 0%, Hf forms carbo-nitrides
and increases the strength of the steel pipe. If even a small amount of Hf is contained,
the aforementioned advantageous effect will be obtained to a certain extent.
[0126] However, if the content of Hf is more than 0.100%, even if the contents of other
elements are within the range of the present embodiment, the strength of the steel
pipe will be too high and the toughness of the steel pipe will decrease.
[0127] Therefore, the content of Hf is 0 to 0.100%.
[0128] A preferable lower limit of the content of Hf is 0.001 %, more preferably is 0.002%,
further preferably is 0.003%, further preferably is 0.005%, further preferably is
0.010%, and further preferably is 0.015%.
[0129] A preferable upper limit of the content of Hf is 0.095%, more preferably is 0.090%,
further preferably is 0.085%, further preferably is 0.080%, further preferably is
0.070%, further preferably is 0.060%, and further preferably is 0.050%.
W: 0 to 0.200%
[0130] Tungsten (W) is an optional element, and does not have to be contained. That is,
the content of W may be 0%.
[0131] When contained, that is, when the content of W is more than 0%, W forms carbo-nitrides
and increases the strength of the steel pipe. If even a small amount of W is contained,
the aforementioned advantageous effect will be obtained to a certain extent. However,
if the content of W is more than 0.200%, even if the contents of other elements are
within the range of the present embodiment, the strength of the steel pipe will be
too high and the toughness of the steel pipe will decrease.
[0132] Therefore, the content of W is 0 to 0.200%.
[0133] A preferable lower limit of the content of W is 0.001%, more preferably is 0.003%,
further preferably is 0.005%, further preferably is 0.010%, and further preferably
is 0.015%.
[0134] A preferable upper limit of the content of W is 0.180%, more preferably is 0.150%,
further preferably is 0.130%, further preferably is 0.100%, further preferably is
0.080%, and further preferably is 0.050%.
[Second group: Sb]
[0135] The chemical composition of the duplex stainless steel pipe of the present embodiment
may further contain Sb in lieu of a part of Fe.
[0137] Antimony (Sb) is an optional element, and does not have to be contained. That is,
the content of Sb may be 0%.
[0138] When contained, that is, when the content of Sb is more than 0%, Sb enhances the
corrosion resistance of the steel pipe. If even a small amount of Sb is contained,
the aforementioned advantageous effect will be obtained to a certain extent.
[0139] However, if the content of Sb is more than 0.100%, even if the contents of other
elements are within the range of the present embodiment, the high-temperature ductility
of the steel pipe will decrease and hot workability of the steel pipe will decrease.
[0140] Therefore, the content of Sb is 0 to 0.100%.
[0141] A preferable lower limit of the content of Sb is 0.001 %, more preferably is 0.003%,
further preferably is 0.005%, further preferably is 0.010%, and further preferably
is 0.015%.
[0142] A preferable upper limit of the content of Sb is 0.090%, more preferably is 0.085%,
further preferably is 0.080%, further preferably is 0.070%, further preferably is
0.060%, and further preferably is 0.050%.
[Third group (Ca, Mg, B, and rare earth metal)]
[0143] The chemical composition of the duplex stainless steel pipe of the present embodiment
may further contain, in lieu of a part of Fe, one or more types of element selected
from the group consisting of Ca, Mg, B, and rare earth metal.
[0144] Each of these elements is an optional element, and increases hot workability of the
steel pipe.
Ca: 0 to 0.020%
[0145] Calcium (Ca) is an optional element, and does not have to be contained. That is,
the content of Ca may be 0%.
[0146] When contained, that is, when the content of Ca is more than 0%, Ca immobilizes S
in the steel pipe as a sulfide and thereby increases hot workability of the steel
pipe. If even a small amount of Ca is contained, the aforementioned advantageous effect
will be obtained to a certain extent.
[0147] However, if the content of Ca is more than 0.020%, oxides in the steel pipe will
coarsen. Consequently, even if the contents of other elements are within the range
of the present embodiment, the toughness of the steel pipe will decrease.
[0148] Therefore, the content of Ca is 0 to 0.020%.
[0149] A preferable lower limit of the content of Ca is 0.001%, more preferably is 0.002%,
further preferably is 0.003%, and further preferably is 0.005%.
[0150] A preferable upper limit of the content of Ca is 0.018%, more preferably is 0.016%,
further preferably is 0.014%, further preferably is 0.012%, and further preferably
is 0.010%.
Mg: 0 to 0.020%
[0151] Magnesium (Mg) is an optional element, and does not have to be contained. That is,
the content of Mg may be 0%.
[0152] When contained, that is, when the content of Mg is more than 0%, Mg immobilizes S
in the steel pipe as a sulfide and thereby increases hot workability of the steel
pipe. If even a small amount of Mg is contained, the aforementioned advantageous effect
will be obtained to a certain extent.
[0153] However, if the content of Mg is more than 0.020%, oxides in the steel pipe will
coarsen. Consequently, even if the contents of other elements are within the range
of the present embodiment, the toughness of the steel pipe will decrease.
[0154] Therefore, the content of Mg is 0 to 0.020%.
[0155] A preferable lower limit of the content of Mg is 0.001%, more preferably is 0.002%,
further preferably is 0.003%, further preferably is 0.005%, and further preferably
is 0.006%.
[0156] A preferable upper limit of the content of Mg is 0.018%, more preferably is 0.016%,
and further preferably is 0.015%.
B: 0 to 0.020%
[0157] Boron (B) is an optional element, and does not have to be contained. That is, the
content of B may be 0%.
[0158] When contained, that is, when the content of B is more than 0%, B suppresses segregation
of S in the steel pipe to grain boundaries and thereby increases hot workability of
the steel pipe. If even a small amount of B is contained, the aforementioned advantageous
effect will be obtained to a certain extent.
[0159] However, if the content of B is more than 0.020%, boron nitride (BN) will be formed.
Consequently, even if the contents of other elements are within the range of the present
embodiment, the toughness of the steel pipe will decrease.
[0160] Therefore, the content of B is 0 to 0.020%.
[0161] A preferable lower limit of the content of B is 0.001%, more preferably is 0.002%,
further preferably is 0.003%, and further preferably is 0.005%.
[0162] A preferable upper limit of the content of B is 0.018%, more preferably is 0.016%,
further preferably is 0.014%, further preferably is 0.012%, and further preferably
is 0.010%.
Rare earth metal: 0 to 0.200%
[0163] Rare earth metal (REM) is an optional element, and does not have to be contained.
That is, the content of REM may be 0%.
[0164] When contained, that is, when the content of REM is more than 0%, REM immobilizes
S in the steel pipe as a sulfide and thereby increases hot workability of the steel
pipe. If even a small amount of REM is contained, the aforementioned advantageous
effect will be obtained to a certain extent.
[0165] However, if the content of REM is more than 0.200%, oxides in the steel pipe will
coarsen. Consequently, even if the contents of other elements are within the range
of the present embodiment, the toughness of the steel pipe will decrease.
[0166] Therefore, the content of REM is 0 to 0.200%.
[0167] A preferable lower limit of the content of REM is 0.001%, more preferably is 0.005%,
further preferably is 0.008%, further preferably is 0.010%, and further preferably
is 0.020%.
[0168] A preferable upper limit of the content of REM is 0.180%, more preferably is 0.160%,
further preferably is 0.140%, further preferably is 0.120%, further preferably is
0.100%, further preferably is 0.080%, further preferably is 0.060%, and further preferably
is 0.050%.
[0169] Note that, in the present description the term "REM" means one or more elements
selected from the group consisting of scandium (Sc) which is the element with atomic
number 21, yttrium (Y) which is the element with atomic number 39, and the elements
from lanthanum (La) with atomic number 57 to lutetium (Lu) with atomic number 71 that
are lanthanoids. Further, in the present description, the term "content of REM" means
the total content of these elements.
[(Feature 2) Regarding microstructure]
[0170] The microstructure of the duplex stainless steel pipe of the present embodiment is
composed of, in volume ratio, ferrite in an amount of 35.0 to 65.0% and σ phase in
an amount of 0 to less than 1.0%, with the balance being austenite. In the microstructure,
structures other than ferrite, austenite, and σ phase are negligibly small. Specifically,
the microstructure of the duplex stainless steel pipe according to the present embodiment
may contain minute amounts of precipitates, inclusions and the like, in addition to
ferrite and austenite. However, with respect to the chemical composition of the duplex
stainless steel pipe according to the present embodiment, the volume ratios of precipitates
and inclusions and the like are negligibly small as compared with the volume ratios
of ferrite, austenite, and σ phase.
[0171] In the microstructure of the duplex stainless steel pipe of the present embodiment,
the volume ratio of ferrite is 35.0 to 65.0%. If the volume ratio of ferrite is too
low, the yield strength and/or corrosion resistance of the steel pipe may decrease
in some cases. On the other hand, if the volume ratio of ferrite is too high, the
toughness and/or hot workability of the steel pipe may decrease in some cases.
[0172] Therefore, in the microstructure of the duplex stainless steel pipe of the present
embodiment, the volume ratio of ferrite is 35.0 to 65.0%.
[0173] A preferable lower limit of the volume ratio of ferrite is 36.0%, and more preferably
is 37.0%.
[0174] A preferable upper limit of the volume ratio of ferrite is 64.0%, and more preferably
is 63.0%.
[0175] In the microstructure of the duplex stainless steel pipe of the present embodiment,
σ phase reduces corrosion resistance. Therefore, it is preferable that the volume
ratio of σ phase is small. If the volume ratio of σ phase is 1.0% or more, the corrosion
resistance of the duplex stainless steel pipe will decrease. Therefore, the volume
ratio of σ phase is 0 to less than 1.0%.
[0176] A low volume ratio of σ phase is preferable, and most preferably the volume ratio
of σ phase is 0%. However, if the volume ratio of σ phase is excessively lowered,
the production cost will significantly increase. Therefore, a preferable lower limit
of the volume ratio of σ phase is more than 0%, and more preferably is 0.1%.
[0177] The balance of the microstructure is austenite. When the microstructure is composed
of, in volume ratio, ferrite in an amount of 35.0 to 65.0% and σ phase in an amount
of 0 to less than 1.0%, with the balance being austenite, on the precondition that
the other features, i.e. feature 1, feature 3, and feature 4, are satisfied, high
strength and excellent corrosion resistance are obtained.
[Method for measuring ferrite volume ratio and σ-phase volume ratio]
[0178] The volume ratio of ferrite in the duplex stainless steel pipe can be determined
by a method in accordance with ASTM E562 (2019).
[0179] Specifically, a test specimen for microstructure observation having an observation
surface with dimensions of 5 mm in the pipe axis direction and 5 mm in the pipe circumferential
direction is taken from a central portion of the wall thickness of the duplex stainless
steel pipe. In the present description, the pipe circumferential direction of the
steel pipe means the direction that is perpendicular to the pipe axis direction and
the pipe diameter direction. Note that, the size of the test specimen is not particularly
limited as long as the aforementioned observation surface is obtained.
[0180] The observation surface of the test specimen is mirror-polished. The mirror-polished
observation surface is electrolytically etched in a 7% potassium hydroxide etching
reagent to reveal the microstructure. The observation surface on which the microstructure
has been revealed is observed in 10 visual fields using an optical microscope. The
area of each visual field is set to 1.00 mm
2 (magnification of 100×). In each visual field, ferrite and austenite are identified
based on contrast. In a case where the observation surface is electrolytically etched
in a 7% potassium hydroxide etching reagent, a region in which the brightness is low
corresponds to ferrite, and a region in which the brightness is high corresponds to
austenite. Therefore, a person skilled in the art can easily identify ferrite and
austenite based on contrast.
[0181] The area fraction of the identified ferrite is measured by a point counting method
in accordance with ASTM E562 (2019). The arithmetic average value of the area fractions
(10 area fractions in total) of ferrite obtained in the respective visual fields is
defined as the volume ratio (%) of ferrite. A value to the first decimal place obtained
by rounding off the second decimal place of the obtained numerical value is taken
as the volume ratio (%) of ferrite.
[0182] The volume ratio of σ phase in the duplex stainless steel pipe is determined by the
following method.
[0183] The aforementioned observation surface on which the microstructure has been revealed
is observed in five visual fields using an optical microscope. The area of each visual
field is set to 0.0625 mm
2 (magnification of 400×; 250 µm × 250 µm). In each visual field, σ phase is identified
based on contrast. On the observation surface that has been electrolytically etched
in a 7% potassium hydroxide etching reagent, σ phase can be identified as a black
region with a lower brightness compared to other structures. Note that, in each visual
field, element concentration analysis (EDS analysis) may be performed to identify
σ phase. In the case of performing element concentration analysis, σ phase is identified
by the following method. In each visual field, particles are identified based on contrast.
The identified particles are subjected to EDS analysis. In the EDS analysis, the acceleration
voltage is set to 20 kV, and the EDS analysis is conducted for quantification of N,
Mo, Al, Si, P, S, Ca, Ti, Cr, Mn, Fe, Cu, and Nb as elements to be analyzed. Based
on the EDS analysis result for each particle, if the content of Cr is 35.0% by mass
or more and the content of Mo is 3.0% by mass or more in a particle, the relevant
particle is identified as σ phase.
[0184] The area of the identified σ phase is determined. The area fraction (%) of σ phase
is determined based on the total area of σ phase in the five visual fields and the
total area of the five visual fields. The determined area fraction (%) of σ phase
is regarded as the volume ratio (%) of σ phase. In the present embodiment, a value
to the first decimal place obtained by rounding off the second decimal place of the
obtained numerical value is taken as the volume ratio (%) of σ phase.
[(Feature 3) Regarding content of undissolved Nb and undissolved Nb/Al ratio]
[0185] In the duplex stainless steel pipe of the present embodiment, the content of undissolved
Nb is 0.008% by mass or more, and an undissolved Nb/Al ratio that is a ratio of the
content of undissolved Nb to the content of undissolved Al is 1.0 or more. These matters
are described hereunder.
[Regarding content of undissolved Nb]
[0186] Undissolved Nb is Nb which does not dissolve in the base metal and is contained in
precipitates. In the duplex stainless steel pipe of the present embodiment, a high
yield strength of 655 MPa or more is obtained by sufficiently forming Nb carbo-nitrides
in the steel pipe. When the content of undissolved Nb is less than 0.008% by mass,
Nb carbo-nitrides are not sufficiently formed in the steel pipe. Consequently, sufficient
yield strength cannot be obtained. Therefore, the content of undissolved Nb is 0.008%
by mass or more.
[0187] A preferable lower limit of the content of undissolved Nb is, in percent by mass,
0.009%, more preferably is 0.010%, further preferably is 0.012%, further preferably
is 0.015%, further preferably is 0.020%, and further preferably is 0.025%.
[0188] The upper limit of the content of undissolved Nb is not particularly limited. In
the case of a chemical composition which satisfies feature 1, the upper limit of the
content of undissolved Nb is for example, 0.300%, or for example is 0.250%.
[Regarding undissolved Nb/Al ratio]
[0189] The undissolved Nb/Al ratio which is a ratio of the content of undissolved Nb to
the content of undissolved Al can be defined by the following equation.
Undissolved Nb/Al ratio = content of undissolved Nb (mass%)/content of undissolved
Al (mass%)

[0190] The undissolved Nb/Al ratio is an index of the ratio of the formed amount of Nb carbo-nitrides
in the steel pipe to the formed amount of Al nitrides in the steel pipe. As mentioned
above, Nb carbo-nitrides in the steel pipe increase the strength of the steel pipe
by precipitation strengthening. On the other hand, Al nitrides are coarse in comparison
to Nb carbo-nitrides and do not contribute substantially to precipitation strengthening.
Al nitrides also reduce the amount of dissolved N in the steel pipe and reduce the
amount of dissolved N that is utilized for formation of Nb carbo-nitrides. Therefore,
even if Nb carbo-nitrides form to a certain extent, if Al nitrides excessively form
relative to the formed amount of Nb carbo-nitrides, a sufficient amount of dissolved
N and a sufficient formed amount of Nb carbo-nitrides will not be obtained in the
steel pipe. Consequently, in some cases sufficient strength will not be obtained in
the duplex stainless steel pipe.
[0191] In a duplex stainless steel pipe that satisfies feature 1 and feature 2, if the content
of undissolved Nb is 0.008% or more and the undissolved Nb/Al ratio is 1.0 or more,
a sufficient formed amount of Nb carbo-nitrides and a sufficient dissolved N amount
can be secured in the steel pipe. As a result, the yield strength of the duplex stainless
steel pipe can be raised to 655 MPa or more.
[0192] A preferable lower limit of the undissolved Nb/Al ratio is 1.1, more preferably is
1.2, further preferably is 1.5, further preferably is 2.0, further preferably is 2.5,
and further preferably is 3.0.
[0193] The upper limit of the undissolved Nb/Al ratio is not particularly limited. In the
case of a chemical composition which satisfies feature 1, the upper limit of the undissolved
Nb/Al ratio is for example, 70.0, or for example, 65.0.
[Method for measuring content of undissolved Nb and undissolved Nb/Al ratio]
[0194] The content of undissolved Nb and the undissolved Nb/Al ratio are determined by the
following method.
[0195] A cylindrical test specimen having a diameter of 8 mm and a length of 50 mm is taken
from the duplex stainless steel pipe. Specifically, a cylindrical test specimen that
has the central portion of the wall thickness of the steel pipe as the central axis
thereof is prepared. The axial direction of the cylindrical test specimen is to be
the pipe axis direction of the steel pipe.
[0196] The cylindrical test specimen is subjected to constant current electrolysis using
a 10% AA-based solution (a solution containing, in volume fraction, 10% acetylacetone,
1% tetramethylammonium chloride, and 89% methanol solution).
[0197] First, pre-electrolysis is performed to remove deposits (surface scale and impurities)
from the surface of the cylindrical test specimen. In the pre-electrolysis, a region
from the surface of the scale to a position at a depth of approximately 100 µm is
electrolyzed at normal temperature (25°C) with a current of 1000 mA. After the pre-electrolysis,
the cylindrical test specimen is immersed in an alcohol solution. The cylindrical
test specimen immersed in the alcohol solution is subjected to ultrasonic cleaning
to remove deposits from the surface of the cylindrical test specimen. The mass of
the cylindrical test specimen from which the deposits have been removed, that is,
the mass of the cylindrical test specimen before constant current electrolysis is
measured.
[0198] Next, the cylindrical test specimen is subjected to constant current electrolysis.
Specifically, a new 10% AA-based solution is prepared. Then, using the new 10% AA-based
solution, electrolysis in which the current density is maintained at 20 mA/cm
2 is performed at normal temperature. After the constant current electrolysis, the
cylindrical test specimen is immersed in an alcohol solution and then the cylindrical
test specimen is subjected to ultrasonic cleaning to remove deposits on the surface
of the cylindrical test specimen. The mass of the cylindrical test specimen from which
the deposits have been removed is measured, and the measured value is taken as the
mass of the cylindrical test specimen after constant current electrolysis.
[0199] The 10% AA-based solution used in the constant current electrolysis, and the alcohol
solution used in the ultrasonic cleaning thereafter are suction filtered through a
filter with a mesh size of 0.2 µm to extract residue.
[0200] The extracted residue is subjected to chemical elemental analysis. Specifically,
the residue is dissolved in acid to obtain a solution. The solution is subjected to
chemical elemental analysis using ICP-AES to perform quantitative analysis of Nb and
Al. Based on the Nb mass and Al mass obtained by the quantitative analysis, and the
difference in the mass of the cylindrical test specimen between before and after the
constant current electrolysis, the content of Nb (mass%) in the residue and the content
of Al (mass%) in the residue are determined. The determined content of Nb in the residue
is taken as the content of undissolved Nb (mass%). The determined content of Al in
the residue is taken as the content of undissolved Al (mass%). The undissolved Nb/Al
ratio is determined based on the content of undissolved Nb and the content of undissolved
Al.
[(Feature 4) Regarding yield strength]
[0201] The yield strength of the duplex stainless steel pipe according to the present embodiment
is 655 MPa or more (95 ksi or more). The duplex stainless steel pipe of the present
embodiment satisfies feature 1 to feature 3. As a result, excellent corrosion resistance
is obtained, and a high yield strength of 655 MPa or more is also obtained.
[0202] A preferable lower limit of the yield strength of the duplex stainless steel pipe
according to the present embodiment is 660 MPa or more, more preferably is 665 MPa,
further preferably is 670 MPa, and further preferably is 675 MPa.
[0203] Although not particularly limited, the upper limit of the yield strength of the duplex
stainless steel pipe according to the present embodiment is, for example, 800 MPa.
[Method for measuring yield strength]
[0204] The yield strength of the duplex stainless steel pipe of the present embodiment is
determined by conducting a tensile test by a method in accordance with ASTM E8/E8M
(2022).
[0205] Specifically, an arc-shaped test specimen is taken from the duplex stainless steel
pipe of the present embodiment. For example, the arc-shaped test specimen has a thickness
that is the same as the wall thickness of the steel pipe, and has a width of 25.4
mm and a gage length of 50.8 mm. The longitudinal direction of the arc-shaped test
specimen is to be parallel to the pipe axis direction of the steel pipe.
[0206] A tensile test is carried out at normal temperature (25°C) in air using the arc-shaped
test specimen. In the present embodiment, the 0.2% offset proof stress obtained by
the tensile test is defined as the yield strength (MPa). In the present embodiment,
an integer obtained by rounding off the first decimal place of the obtained numerical
value is adopted as the yield strength (MPa).
[Advantageous effects of duplex stainless steel pipe of present embodiment]
[0207] The duplex stainless steel pipe of the present embodiment satisfies feature 1 to
feature 4. Therefore, in the duplex stainless steel pipe of the present embodiment,
a high yield strength of 655 MPa or more (95 ksi or more) is obtained, and in addition,
excellent corrosion resistance is obtained.
[Regarding corrosion resistance]
[0208] In the present embodiment, the corrosion resistance of the duplex stainless steel
pipe is evaluated by the following method.
[Corrosion resistance evaluation method]
[0209] A test specimen for a four-point bending test is taken from the duplex stainless
steel pipe of the present embodiment. The size of the test specimen is, for example,
2 mm in thickness × 10 mm in width × 75 mm in length. The test specimen is prepared
from the central portion of the wall thickness of the steel pipe. In this case, the
longitudinal direction of the test specimen is to be parallel to the pipe axis direction
of the steel pipe.
[0210] A 20% by mass sodium chloride aqueous solution adjusted to pH 4.0 is used as the
test solution. In accordance with ASTM G39-99 (2021), stress corresponding to 90%
of the actual yield stress is applied to the test specimen by four-point bending.
The test specimen to which stress has been applied is enclosed in an autoclave together
with the test jig. The test solution is poured into the autoclave so as to leave a
vapor phase portion, and this is adopted as a test bath. After the test bath is degassed,
a gaseous mixture of H
2S gas at 0.2 bar and CO
2 gas at 30 bar is charged under pressurization into the autoclave, and the test bath
is stirred to cause the gaseous mixture to saturate. After sealing the autoclave,
the test bath is stirred for 720 hours at 90°C.
[0211] In the present embodiment, after 720 hours elapse in the test environment described
above, observation using a magnifying glass with a magnification of 10× is performed
to check for the presence or absence of a crack. If the occurrence of a crack is suspected
as a result of the observation with the magnifying glass, observation using an optical
microscope with a magnification of 100× is further performed to confirm the presence
or absence of a crack. If a crack is not confirmed, it is evaluated that "excellent
corrosion resistance is obtained".
[Shape of duplex stainless steel pipe]
[0212] The duplex stainless steel pipe of the present embodiment may be a welded tube or
may be a seamless steel pipe. Preferably, the duplex stainless steel pipe according
to the present embodiment is a seamless steel pipe.
[Production method]
[0213] One example of a method for producing the duplex stainless steel pipe of the present
embodiment composed as described above will now be described. Note that, a method
for producing the duplex stainless steel pipe according to the present embodiment
is not limited to the production method described hereunder.
[0214] A method for producing the duplex stainless steel pipe of the present embodiment
includes the following steps.
(Step 1) Starting material preparation step
(Step 2) Hot working step
(Step 3) Solution treatment step
(Step 4) Straightening step
(Step 5) Aging heat treatment step
Each step is described hereunder.
[(Step 1) Starting material preparation step]
[0215] In the starting material preparation step, a starting material having a chemical
composition that satisfies feature 1 is prepared. The starting material may be prepared
by producing the starting material, or may be prepared by purchasing the starting
material from a third party. That is, a method for preparing the starting material
is not particularly limited.
[0216] In the case of producing the starting material, for example, the starting material
is produced by the following method. A molten steel having the chemical composition
described above is produced. A cast piece (a slab, a bloom, or a billet) is produced
by a continuous casting process using the molten steel. An ingot may also be produced
by an ingot-making process using the molten steel. As required, a slab, a bloom, or
an ingot may be subjected to blooming to produce a billet. The starting material is
produced by the above process.
[(Step 2) Hot working step]
[0217] In the hot working step, the starting material prepared in the aforementioned starting
material preparation step is subjected to hot working to produce a hollow shell. The
hot working may be hot forging, may be hot extrusion, or may be hot rolling. The hot
working method is not particularly limited, and it suffices to use a well-known method.
[0218] As the hot working method, for example, hot extrusion such as the Ugine-Sejournet
process or the Ehrhardt push bench process may be performed, or piercing-rolling according
to the Mannesmann process, which is one type of hot rolling, may be performed. Note
that, hot working may be performed only one time or may be performed multiple times.
For example, after performing the aforementioned piercing-rolling on the starting
material, the aforementioned hot extrusion may be performed. For example, in addition,
after performing the aforementioned piercing-rolling on the starting material, elongating,
which is one type of hot rolling, may be performed. That is, in the hot working step,
hot working is performed by a well-known method to produce a hollow shell. Note that,
the heating temperature during hot working is, for example, 1000 to 1280°.
[(Step 3) Solution treatment step]
[0219] In the solution treatment step, a solution treatment is performed on the hollow shell
after the hot working step. Specifically, the hollow shell is loaded into a heat treatment
furnace to heat the hollow shell. Then, after being held at a desired temperature
(solution treatment temperature), the hollow shell is rapidly cooled. In the solution
treatment, the following conditions are satisfied.
(Condition 1)
[0220] An average heating rate HR1 from 700 to 900°C when heating the hollow shell is to
be 0.25°C/sec or more.
(Condition 2)
[0221] A solution treatment temperature T1 is to be within the range of 980 to 1 100°C.
[0222] Each condition is described hereunder.
(Regarding Condition 1)
[0223] During heating in the solution treatment, Al nitrides are easily formed in the temperature
range of 700 to 900°C. By making the residence time in the temperature range of 700
to 900°C as short as possible, formation of Al nitrides in the hollow shell is suppressed,
and as a result, the undissolved Nb/Al ratio in the produced hollow shell increases.
If the average heating rate HR1 from 700 to 900°C is 0.25°C/sec or more, the undissolved
Nb/Al ratio in the produced hollow shell can be sufficiently increased. The upper
limit of the average heating rate HR1 is, for example, 0.60°C/sec.
(Regarding Condition 2)
[0224] The solution treatment temperature T1 influences the ferrite volume ratio in the
microstructure of the steel pipe. If the solution treatment temperature T1 is too
low, in some cases the ferrite volume ratio in the duplex stainless steel pipe will
be less than 35.0% and the strength and/or corrosion resistance of the produced duplex
stainless steel pipe will decrease. On the other hand, if the solution treatment temperature
T1 is too high, in some cases the volume ratio of ferrite in the duplex stainless
steel pipe after the solution treatment will be 65.0% or more and the corrosion resistance
of the steel pipe will, on the contrary, decrease. If the solution treatment temperature
T1 is 980 to 1100°C, the ferrite volume ratio of the duplex stainless steel pipe will
be in an appropriate range.
[0225] Note that, a holding time t1 at the solution treatment temperature T1 is, for example,
10 to 180 minutes. Here, the term "solution treatment temperature T1" means the temperature
(°C) of the heat treatment furnace for performing the solution treatment. The phrase
"holding time t1 at the solution treatment temperature T1" means the time (mins) for
which the hollow shell is held at the solution treatment temperature.
[(Step 4) Straightening step]
[0226] In the straightening step, the hollow shell subjected to the aforementioned solution
treatment step is subjected to straightening at normal temperature. Imparting strain
to the hollow shell by straightening causes a sufficient amount of Nb carbo-nitrides
to be formed in the aging heat treatment step that is the next step.
[0227] FIG. 1 is a schematic diagram of a rotary straightener that is one example of a straightening
machine. Referring to FIG. 1, the rotary straightener includes a plurality of stands
ST1 to STn (n is a natural number of 3 or more). In FIG. 1, the rotary straightener
has four stands. However, the number of stands is not particularly limited as long
as the number of stands is three or more. For example, straightening may be performed
using three stands, or straightening may be performed using five or more stands. Each
stand includes a pair of skew rolls. The stands are arranged in one row along a pass
line PL along which the hollow shell passes. Among the plurality of stands, the skew
rolls of the stands other than a stand ST2 are arranged on the pass line PL, and the
skew rolls of the stand ST2 are arranged at a position that deviates from the pass
line PL.
[0228] FIG. 2 is a front view of the straightening machine illustrated in FIG. 1. The view
on the left side of FIG. 2 is a cross-sectional view perpendicular to the axial direction
of the hollow shell before performing straightening. The view on the right side of
FIG. 2 is a front view of a stand that has a smallest roll gap DB. Crush straightening
is performed as the straightening according to the present embodiment. The term "crush
straightening" means straightening in which the hollow shell is subjected to rolling
reduction to deform the hollow shell into an elliptical shape. Referring to FIG. 2,
the roll draft with respect to the hollow shell at the stand that has the smallest
roll gap DB is defined as a crush amount δc (mm). The crush amount δc can be calculated
by subtracting the roll gap DB at the stand that has the smallest roll gap DB from
the outer diameter DA of the hollow shell before straightening.
[0229] In the straightening step, the following condition is satisfied.
(Condition 3)
[0230] The crush amount δc is to be 3 mm or more.
(Regarding Condition 3)
[0231] If the crush amount δc in the straightening is too small, strain will not be introduced
sufficiently into the hollow shell before the aging heat treatment. Consequently,
a sufficient amount of Nb carbo-nitrides will not form in the aging heat treatment
step that is the next step. If the crush amount δc is 3 mm or more, strain will be
introduced sufficiently into the hollow shell. As a result, in the duplex stainless
steel pipe after the aging heat treatment step, a sufficient amount of Nb carbo-nitrides
will be formed and a sufficient content of undissolved Nb will be obtained. Note that,
the upper limit of the crush amount is, for example, 8 mm.
[(Step 5) Aging heat treatment step]
[0232] In the aging heat treatment step, the hollow shell is subjected to an aging heat
treatment. In the aging heat treatment step of the present embodiment, when the aging
heat treatment is performed, a sufficient amount of Nb carbo-nitrides is formed while
suppressing the formation of σ phase. The aging heat treatment satisfies the following
conditions.
(Condition 4)
[0233] An aging heat treatment temperature T2 satisfies the following Formula (A).

[0234] Where, the content of the corresponding element in percent by mass in the duplex
stainless steel pipe is substituted for each symbol of an element in Formula (A).
(Condition 5)
[0235] A holding time t2 at the aging heat treatment temperature T2 satisfies the following
Formula (B).

[0236] Where, the aging heat treatment temperature T2 (°C) is substituted for T2 in Formula
(B), and the content of Nb in percent by mass in the duplex stainless steel pipe is
substituted for Nb in Formula (B).
[0237] Each condition is described hereunder.
(Regarding Condition 4)
[0238] FnA is defined as follows.
FnA = 700 - (0.5Cr + 0.3Mn + 3Mo + 1.5Si + 8Nb + Ni - 0.6Cu - 4Co - 10Sn)2

[0239] FnA means the lower limit of a temperature (°C) that promotes formation of σ phase.
In FnA, the elements Cr, Mn, Mo, Si, and Nb promote formation of σ phase. On the other
hand, the elements Ni, Cu, Co, and Sn suppress formation of σ phase. If the aging
heat treatment temperature T2 is equal to or higher than FnA, formation of σ phase
will be promoted in the hollow shell during the aging heat treatment. As a result,
the volume ratio of σ phase will be excessively high in the produced duplex stainless
steel pipe. If the aging heat treatment temperature T2 is less than FnA, formation
of σ phase will be sufficiently suppressed in the hollow shell during the aging heat
treatment. As a result, the volume ratio of σ phase will be sufficiently reduced in
the produced duplex stainless steel pipe.
(Regarding Condition 5)
[0240] FnB is defined as follows.

[0241] FnB means the lower limit of the holding time (mins) required for formation of a
sufficient amount of Nb carbo-nitrides. Because the content of Nb in the steel pipe
significantly influences formation of Nb carbo-nitrides, Nb is included in FnB. If
the holding time t2 at the aging heat treatment temperature T2 is equal to or less
than FnB, a sufficient amount of Nb carbo-nitrides will not be formed in the produced
duplex stainless steel pipe. Consequently, a sufficient content of undissolved Nb
will not be obtained. If the holding time t2 is longer than FnB, a sufficient amount
of Nb carbo-nitrides will be formed in the produced duplex stainless steel pipe. Therefore,
a sufficient content of undissolved Nb will be obtained.
[Other steps]
[0242] The production method of the present embodiment may also include other production
steps in addition to the production steps described above. For example, the duplex
stainless steel pipe after the aging heat treatment step may be subjected to a pickling
treatment step. In such case, the pickling treatment step is not particularly limited,
and it suffices to perform the pickling treatment step according to a well-known method.
Note that, in the production method of the present embodiment a cold rolling step
needs not to be performed at a timing that is after the hot working step and is before
the solution treatment step. Even if the cold rolling step is omitted, a duplex stainless
steel pipe having sufficient strength will be obtained.
[0243] The duplex stainless steel pipe of the present embodiment can be produced by performing
the steps described above. Note that, the method for producing the duplex stainless
steel pipe described above is one example, and the duplex stainless steel pipe of
the present embodiment may also be produced by another method. Hereunder, the duplex
stainless steel pipe of the present embodiment is described in further detail by way
of examples.
EXAMPLES
[0244] Duplex stainless steel pipes that were seamless steel pipes having the chemical compositions
shown in Table 1A and Table 1B were produced.
[Table 1A]
[0245]
TABLE 1A
| Steel Symbol |
Chemical Composition (unit is mass%; balance is Fe and impurities) |
| C |
Si |
Mn |
P |
S |
Al |
Ni |
Cr |
Mo |
Cu |
N |
v |
Nb |
| A |
0.028 |
0.91 |
2.2 |
0.001 |
0.017 |
0.036 |
5.3 |
25.2 |
1.1 |
2.6 |
0.22 |
0.06 |
0.051 |
| B |
0.017 |
0.35 |
0.5 |
0.005 |
0.017 |
0.050 |
4.5 |
27.7 |
0.6 |
3.0 |
0.20 |
0.31 |
0.111 |
| C |
0.030 |
0.43 |
4.8 |
0.001 |
0.017 |
0.052 |
7.3 |
25.6 |
0.5 |
1.8 |
0.28 |
0.30 |
0.033 |
| D |
0.006 |
0.32 |
5.5 |
0.010 |
0.020 |
0.007 |
8.6 |
21.4 |
0.7 |
2.1 |
0.24 |
0.35 |
0.059 |
| E |
0.009 |
0.57 |
2.4 |
0.031 |
0.011 |
0.012 |
5.8 |
29.6 |
0.7 |
2.5 |
0.21 |
0.47 |
0.284 |
| F |
0.028 |
0.86 |
5.4 |
0.019 |
0.016 |
0.053 |
6.7 |
23.9 |
1.9 |
2.7 |
0.30 |
0.28 |
0.198 |
| G |
0.027 |
0.78 |
4.1 |
0.004 |
0.012 |
0.055 |
7.9 |
25.7 |
2.0 |
2.4 |
0.29 |
0.28 |
0.141 |
| H |
0.028 |
0.68 |
1.2 |
0.027 |
0.005 |
0.070 |
7.1 |
27.7 |
1.7 |
2.9 |
0.27 |
0.07 |
0.294 |
| I |
0.028 |
0.66 |
2.5 |
0.030 |
0.014 |
0.075 |
7.8 |
21.5 |
1.5 |
2.5 |
0.20 |
0.46 |
0.155 |
| J |
0.010 |
0.62 |
4.5 |
0.021 |
0.003 |
0.070 |
5.6 |
24.8 |
0.9 |
1.7 |
0.27 |
0.36 |
0.041 |
| K |
0.003 |
0.35 |
1.5 |
0.036 |
0.007 |
0.092 |
7.2 |
23.7 |
2.0 |
2.5 |
0.15 |
0.08 |
0.244 |
| L |
0.029 |
0.28 |
5.5 |
0.029 |
0.012 |
0.076 |
4.5 |
24.0 |
1.8 |
2.1 |
0.26 |
0.46 |
0.121 |
| M |
0.017 |
0.22 |
6.2 |
0.032 |
0.006 |
0.034 |
5.0 |
27.3 |
0.8 |
2.0 |
0.21 |
0.32 |
0.185 |
| N |
0.007 |
0.88 |
1.6 |
0.016 |
0.003 |
0.085 |
8.4 |
23.6 |
0.7 |
2.7 |
0.16 |
0.23 |
0.138 |
| O |
0.026 |
0.82 |
1.1 |
0.012 |
0.003 |
0.034 |
7.4 |
21.4 |
0.9 |
2.2 |
0.26 |
0.43 |
0.232 |
| P |
0.001 |
0.22 |
2.2 |
0.025 |
0.002 |
0.052 |
7.5 |
25.3 |
0.9 |
1.6 |
0.24 |
0.26 |
0.264 |
| Q |
0.010 |
0.65 |
6.3 |
0.025 |
0.001 |
0.062 |
8.0 |
20.2 |
1.2 |
2.3 |
0.30 |
0.03 |
0.051 |
| R |
0.003 |
0.62 |
4.1 |
0.024 |
0.017 |
0.020 |
8.5 |
22.0 |
0.8 |
2.9 |
0.21 |
0.13 |
0.461 |
| S |
0.025 |
0.56 |
4.1 |
0.019 |
0.009 |
0.023 |
7.1 |
25.1 |
1.7 |
1.9 |
0.24 |
0.37 |
0.011 |
| T |
0.014 |
0.63 |
0.6 |
0.023 |
0.001 |
0.045 |
6.8 |
22.8 |
1.9 |
1.7 |
0.16 |
0.07 |
0.063 |
[Table 1B]
[0246]
TABLE 1B
| Steel Symbol |
Chemical Composition (unit is mass%; balance is Fe and impurities) |
| Co |
Sn |
Ta |
Ti |
Zr |
Hf |
w |
Sb |
Ca |
Mg |
B |
REM |
| A |
0.23 |
0.032 |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
| B |
0.29 |
0.007 |
0.034 |
- |
- |
- |
- |
- |
- |
- |
- |
- |
| C |
0.17 |
0.046 |
- |
0.079 |
- |
- |
- |
- |
- |
- |
- |
- |
| D |
0.45 |
0.006 |
- |
- |
0.056 |
- |
- |
- |
- |
- |
- |
- |
| E |
0.19 |
0.029 |
- |
- |
- |
0.043 |
- |
- |
- |
- |
- |
- |
| F |
0.20 |
0.033 |
- |
- |
- |
- |
0.048 |
- |
- |
- |
- |
- |
| G |
0.13 |
0.044 |
- |
- |
- |
- |
- |
0.023 |
- |
- |
- |
- |
| H |
0.36 |
0.014 |
- |
- |
- |
- |
- |
- |
0.018 |
- |
- |
- |
| I |
0.25 |
0.036 |
- |
- |
- |
- |
- |
- |
- |
0.014 |
- |
- |
| J |
0.38 |
0.021 |
- |
- |
- |
- |
- |
- |
- |
- |
0.010 |
- |
| K |
0.10 |
0.025 |
- |
- |
- |
- |
- |
- |
- |
- |
- |
0.042 |
| L |
0.22 |
0.028 |
0.045 |
- |
- |
- |
- |
0.048 |
- |
- |
- |
- |
| M |
0.45 |
0.047 |
- |
0.098 |
- |
- |
- |
- |
0.010 |
- |
- |
- |
| N |
0.28 |
0.050 |
- |
- |
0.073 |
- |
- |
- |
- |
0.006 |
- |
- |
| O |
0.17 |
0.045 |
- |
- |
- |
0.092 |
- |
- |
- |
- |
0.009 |
- |
| P |
0.33 |
0.032 |
- |
- |
- |
- |
0.130 |
- |
- |
- |
- |
0.008 |
| Q |
0.38 |
0.032 |
- |
- |
- |
- |
- |
0.084 |
0.011 |
- |
- |
- |
| R |
0.49 |
0.047 |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
| S |
0.22 |
0.042 |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
| T |
0.11 |
0.003 |
- |
- |
- |
- |
0.190 |
- |
- |
- |
0.018 |
0.187 |
[0247] Specifically, molten steels were melted using a 50 kg vacuum furnace. The molten
steels were used to produce ingots by an ingot-making process. Note that, the symbol
"-" in Table 1B means that the content of the corresponding element was at an impurity
level. For example, the symbol "-" means that the content of Ta, the content of Ti,
the content of Zr, the content of Hf, the content of W, the content of Sb, the content
of Ca, the content of Mg, the content of B, and the content of REM of steel A were
each 0% when rounded off to the third decimal place.
[0248] Each ingot was subjected to hot working (hot extrusion) to produce a hollow shell.
The heating temperature during the hot working was in the range of 1000 to 1280°C.
The hollow shell of each test number on which hot working had been performed was then
subjected to a solution treatment. In the solution treatment, the average heating
rate HR1 (°C/sec) from 700 to 900°C, the solution treatment temperature T1 (°C), and
the holding time t1 (mins) at the solution treatment temperature T1 were as shown
in Table 2.
[Table 2]
[0249]
TABLE 2
| Test Number |
Steel Symbol |
Solution Treatment |
Straightening |
Aging Heat Treatment |
| Average Heating Rate HR1 (°C/sec) |
Solution Treatment Temperature T1 (°C) |
Holding Time t1 (mins) |
Crush Amount δc (mm) |
FnA(°C) |
FnB (mins) |
Aging Heat Treatment Temperature T2 (°C) |
Holding Time t2 (mins) |
| 1 |
A |
0.37 |
1000 |
20 |
3 |
595 |
60 |
590 |
65 |
| 2 |
B |
0.49 |
990 |
20 |
3 |
606 |
36 |
600 |
55 |
| 3 |
C |
0.31 |
1050 |
30 |
3 |
649 |
42 |
640 |
50 |
| 4 |
D |
0.34 |
1060 |
30 |
3 |
686 |
25 |
680 |
30 |
| 5 |
E |
0.59 |
1010 |
20 |
3 |
546 |
25 |
520 |
30 |
| 6 |
F |
0.56 |
1080 |
20 |
4 |
539 |
39 |
535 |
45 |
| 7 |
G |
0.57 |
1060 |
40 |
5 |
554 |
82 |
505 |
90 |
| 8 |
H |
0.27 |
1090 |
20 |
3 |
550 |
25 |
515 |
60 |
| 9 |
I |
0.28 |
1060 |
20 |
4 |
643 |
36 |
570 |
45 |
| 10 |
J |
0.34 |
1080 |
20 |
5 |
612 |
61 |
595 |
70 |
| 11 |
K |
0.43 |
1020 |
20 |
5 |
569 |
30 |
530 |
35 |
| 12 |
L |
0.45 |
1030 |
100 |
3 |
517 |
94 |
505 |
120 |
| 13 |
M |
0.51 |
1040 |
20 |
6 |
573 |
64 |
500 |
80 |
| 14 |
N |
0.29 |
1040 |
20 |
6 |
673 |
22 |
630 |
30 |
| 15 |
O |
0.46 |
1030 |
20 |
3 |
651 |
23 |
560 |
30 |
| 16 |
P |
0.39 |
1060 |
20 |
6 |
630 |
21 |
550 |
30 |
| 17 |
Q |
0.33 |
1060 |
20 |
6 |
667 |
41 |
630 |
50 |
| 18 |
T |
0.30 |
1000 |
30 |
4 |
591 |
93 |
540 |
100 |
| 19 |
R |
0.36 |
1060 |
20 |
6 |
657 |
2 |
640 |
10 |
| 20 |
S |
0.43 |
1080 |
130 |
6 |
595 |
133 |
540 |
180 |
| 21 |
A |
0.38 |
1000 |
20 |
6 |
595 |
31 |
660 |
40 |
| 22 |
L |
0.31 |
1030 |
20 |
6 |
517 |
56 |
550 |
70 |
| 23 |
A |
0.39 |
1000 |
20 |
4 |
595 |
161 |
500 |
70 |
| 24 |
L |
0.27 |
1030 |
20 |
4 |
517 |
94 |
505 |
40 |
| 25 |
A |
0.14 |
1000 |
20 |
5 |
595 |
73 |
570 |
75 |
| 26 |
C |
0.19 |
1050 |
30 |
5 |
649 |
42 |
640 |
60 |
| 27 |
A |
0.26 |
1000 |
20 |
2 |
595 |
73 |
570 |
75 |
| 28 |
C |
0.30 |
1050 |
30 |
1 |
649 |
42 |
640 |
50 |
[0250] The hollow shell after the solution treatment was subjected to straightening using
a rotary straightener equipped with three stands. The crush amount δc (mm) during
straightening was as shown in Table 2. An aging heat treatment was performed on the
hollow shell after the straightening. The aging heat treatment temperature T2 (°C)
and the holding time t2 (mins) in the aging heat treatment were as shown in Table
2. Note that, FnA (°C) and FnB (mins) of each test number are also shown in Table
2. A duplex stainless steel pipe of each test number was produced by the above production
process.
[Evaluation tests]
[0251] The duplex stainless steel pipe of each test number was subjected to the following
evaluation tests.
(Test 1) Test to measure ferrite volume ratio and σ-phase volume ratio
(Test 2) Test to measure content of undissolved Nb and undissolved Nb/Al ratio
(Test 3) Yield strength measurement test
(Test 4) Corrosion resistance test
Hereunder, each test is described.
[(Test 1) Test to measure ferrite volume ratio and σ-phase volume ratio]
[0252] The ferrite volume ratio (%) and the σ-phase volume ratio (%) of the duplex stainless
steel pipe of each test number were determined in accordance with the method described
above in the section [Method for measuring ferrite volume ratio and σ-phase volume
ratio]. The determined ferrite volume ratio (%) and σ-phase volume ratio (%) are shown
in Table 3.
[Table 3]
[0253]
TABLE 3
| Test Number |
Steel Symbol |
Microstructure |
YS (MPa) |
Corrosion Resistance |
Remarks |
| Ferrite Volume Ratio (%) |
σ-Phase Volume Ratio (%) |
Content of Undissolved Nb (mass%) |
Content of Undissolved Al (mass%) |
Undissolved Nb/Al Ratio |
| 1 |
A |
43.1 |
0.1 |
0.031 |
0.005 |
6.2 |
683 |
NO SSC |
Inventive Example |
| 2 |
B |
44.4 |
0.0 |
0.070 |
0.010 |
7.0 |
718 |
NO SSC |
Inventive Example |
| 3 |
C |
59.4 |
0.0 |
0.012 |
0.010 |
1.2 |
670 |
NO SSC |
Inventive Example |
| 4 |
D |
56.6 |
0.0 |
0.041 |
0.001 |
41.0 |
697 |
NO SSC |
Inventive Example |
| 5 |
E |
48.3 |
0.0 |
0.211 |
0.005 |
42.2 |
738 |
NO SSC |
Inventive Example |
| 6 |
F |
39.8 |
0.4 |
0.135 |
0.011 |
12.3 |
711 |
NO SSC |
Inventive Example |
| 7 |
G |
35.7 |
0.8 |
0.118 |
0.011 |
10.7 |
690 |
NO SSC |
Inventive Example |
| 8 |
H |
61.0 |
0.3 |
0.217 |
0.035 |
6.2 |
752 |
NO SSC |
Inventive Example |
| 9 |
I |
59.4 |
0.2 |
0.109 |
0.038 |
2.9 |
711 |
NO SSC |
Inventive Example |
| 10 |
J |
51.3 |
0.0 |
0.024 |
0.014 |
1.7 |
704 |
NO SSC |
Inventive Example |
| 11 |
K |
49.0 |
0.1 |
0.171 |
0.013 |
13.2 |
745 |
NO SSC |
Inventive Example |
| 12 |
L |
44.7 |
0.2 |
0.084 |
0.010 |
8.4 |
697 |
NO SSC |
Inventive Example |
| 13 |
M |
63.5 |
0.0 |
0.091 |
0.017 |
5.4 |
676 |
NO SSC |
Inventive Example |
| 14 |
N |
39.0 |
0.0 |
0.083 |
0.043 |
1.9 |
718 |
NO SSC |
Inventive Example |
| 15 |
O |
60.5 |
0.0 |
0.076 |
0.004 |
19.0 |
684 |
NO SSC |
Inventive Example |
| 16 |
P |
64.6 |
0.0 |
0.204 |
0.013 |
15.7 |
759 |
NO SSC |
Inventive Example |
| 17 |
Q |
50.0 |
0.1 |
0.041 |
0.016 |
2.6 |
669 |
NO SSC |
Inventive Example |
| 18 |
T |
49.9 |
0.1 |
0.029 |
0.019 |
1.5 |
703 |
NO SSC |
Inventive Example |
| 19 |
R |
47.7 |
0.0 |
0.313 |
0.004 |
78.3 |
835 |
SSC |
Comparative Example |
| 20 |
s |
39.4 |
0.0 |
0.002 |
0.002 |
1.0 |
614 |
NO SSC |
Comparative Example |
| 21 |
A |
42.1 |
4.2 |
0.038 |
0.005 |
7.6 |
752 |
SSC |
Comparative Example |
| 22 |
L |
43.1 |
3.0 |
0.084 |
0.019 |
4.4 |
766 |
SSC |
Comparative Example |
| 23 |
A |
42.4 |
0.1 |
0.005 |
0.005 |
1.0 |
621 |
NO SSC |
Comparative Example |
| 24 |
L |
46.0 |
0.1 |
0.003 |
0.002 |
1.5 |
615 |
NO SSC |
Comparative Example |
| 25 |
A |
42.3 |
0.1 |
0.018 |
0.021 |
0.9 |
625 |
NO SSC |
Comparative Example |
| 26 |
C |
58.6 |
0.1 |
0.021 |
0.033 |
0.6 |
631 |
NO SSC |
Comparative Example |
| 27 |
A |
40.9 |
0.1 |
0.011 |
0.018 |
0.6 |
629 |
NO SSC |
Comparative Example |
| 28 |
C |
58.9 |
0.1 |
0.009 |
0.013 |
0.7 |
640 |
NO SSC |
Comparative Example |
[(Test 2) Test to measure content of undissolved Nb and undissolved Nb/Al ratio]
[0254] The content of undissolved Nb (mass%) and the undissolved Nb/Al ratio of the duplex
stainless steel pipe of each test number were determined in accordance with the method
described above in the section [Method for measuring content of undissolved Nb and
undissolved Nb/Al ratio]. The determined content of undissolved Nb (mass%), content
of undissolved Al (mass%), and undissolved Nb/Al ratio are shown in Table 3.
[(Test 3) Yield strength measurement test]
[0255] The yield strength (MPa) of the duplex stainless steel pipe of each test number was
determined in accordance with the method described above in the section [Method for
measuring yield strength]. Note that, each arc-shaped test specimen had a thickness
that was the same as the wall thickness of the steel pipe, had a width of 25.4 mm,
and had a gage length of 50.8 mm. The determined yield strength (MPa) is shown in
the column "YS (MPa)" in Table 3.
[(Test 4) Corrosion resistance test]
[0256] The corrosion resistance of the duplex stainless steel pipe of each test number was
evaluated in accordance with the method described above in the section [Corrosion
resistance evaluation method]. Note that, the size of the test specimen was 2 mm in
thickness × 10 mm in width × 75 mm in length. For test specimens in which a crack
was not confirmed after 720 hours elapsed, it was determined that excellent corrosion
resistance was obtained. The test numbers in which excellent corrosion resistance
was obtained are indicated by the description "NO SSC" in the column "Corrosion Resistance"
in Table 3. On the other hand, for test specimens in which a crack was confirmed after
720 hours elapsed, it was determined that excellent corrosion resistance was not obtained.
The test numbers in which excellent corrosion resistance was not obtained are indicated
by the description "SSC" in the column "Corrosion Resistance" in Table 3.
[Evaluations results]
[0257] Referring to Table 1A, Table 1B, Table 2, and Table 3, the duplex stainless steel
pipes of Test Nos. 1 to 18 satisfied feature 1 to feature 4. Therefore, in these seamless
steel pipes, a high yield strength of 655 MPa or more was obtained. In addition, excellent
corrosion resistance was obtained. In other words, in the duplex stainless steel pipes
of Test Nos. 1 to 18, a high yield strength of 655 MPa or more and excellent corrosion
resistance were both achieved.
[0258] On the other hand, in Test No. 19, the content of Nb was too high. Consequently,
excellent corrosion resistance was not obtained.
[0259] In Test No. 20, the content of Nb was too low. Consequently, the content of undissolved
Nb was too low. As a result, the yield strength was less than 655 MPa, which was low.
[0260] In Test Nos. 21 and 22, in the aging heat treatment, the aging heat treatment temperature
T2 was equal to or higher than FnA, and thus Formula (A) was not satisfied. Consequently,
the σ-phase volume ratio was 1.0% or more, which was high. As a result, excellent
corrosion resistance was not obtained.
[0261] In Test Nos. 23 and 24, in the aging heat treatment, the holding time t2 at the aging
heat treatment temperature T2 was shorter than FnB, and thus Formula (B) was not satisfied.
Consequently, the content of undissolved Nb was too low. As a result, the yield strength
was less than 655 MPa, which was low.
[0262] In Test Nos. 25 and 26, in the solution treatment, the average heating rate HR1 from
700 to 900°C was too slow. Consequently, the undissolved Nb/Al ratio was low. As a
result, the yield strength was less than 655 MPa, which was low.
[0263] In Test Nos. 27 and 28, in the straightening, the crush amount δc was too small.
Consequently, the undissolved Nb/Al ratio was low. As a result, the yield strength
was less than 655 MPa, which was low.
[0264] An embodiment of the present disclosure has been described above. However, the embodiment
described above is merely an example for carrying out the present disclosure. Therefore,
the present disclosure is not limited to the embodiment described above, and can be
implemented by appropriately modifying the above-described embodiment within a range
that does not depart from the gist thereof.