TECHNICAL FIELD
[0001] The present invention relates to a duplex stainless steel and a method for producing
the same.
BACKGROUND ART
[0002] There is a need for a stainless steel that has excellent corrosion resistance for
use in applications in which corrosion in a high-temperature and high-concentration
chloride environment is a problem, such as in the chemical industry field.
[0003] A duplex stainless steel containing a large amount of Cr (first-generation duplex
stainless steel: SUS 329J4L or the like) exhibits excellent corrosion resistance in
comparison to conventional stainless steel as typified by SUS 304 or SUS 316L. However,
in recent years, the environments in which stainless steel is used have become more
severe, and it is no longer possible to exhibit satisfactory corrosion resistance
using the traditional duplex stainless steels.
[0004] Patent Document 1, Patent Document 2 and Patent Document 3 disclose duplex stainless
steels (second-generation duplex stainless steels) of which, as the increasing severity
of usage environments increases, corrosion resistance is accordingly improved by utilizing
Mo and N in accordance with pitting resistance equivalent (PRE, PREW) values represented
by the following formula (1) and formula (2) that are known as indices that indicate
the corrosion resistance of duplex stainless steel. However, even in the case of these
second-generation duplex stainless steels, corrosion resistance is insufficient in
a seawater environment.

[0005] Patent Document 4, Patent Document 5, Patent Document 6, Non-Patent Document 1 and
Non-Patent Document 2 disclose duplex stainless steels containing W (third-generation
duplex stainless steels). The third-generation duplex stainless steels have excellent
corrosion resistance to the traditional second-generation duplex stainless steels,
and are widely used in seawater environments.
LIST OF PRIOR ART DOCUMENTS
PATENT DOCUMENT
NON PATENT DOCUMENT
SUMMARY OF INVENTION
TECHNICAL PROBLEM
[0008] Even in the case of third-generation duplex stainless steels, corrosion resistance
is insufficient in a hot concentrated chloride environment that is more severe than
seawater, such as in the chemical industry field.
[0009] An objective of the present invention is to provide a duplex stainless steel that,
by improving the corrosion resistance of third-generation duplex stainless steel,
can solve a problem of corrosion under a hot concentrated chloride environment such
as in the chemical industry field, as well as a method for producing the duplex stainless
steel.
SOLUTION TO PROBLEM
[0010] Heretofore the influence of W on corrosion resistance and the action mechanism thereof
have been considered to be the same as the mechanism of Mo. However, as a result of
detailed studies conducted to examine the action mechanisms which contribute to corrosion
resistance of Mo and W, the present inventors found that there is a mistake in the
conventional findings with respect to the corrosion resistance under severe environments.
[0011] Figure 1 illustrates polarization curves of pure W and pure Mo under a corrosive
environment. As shown in Figure 1, even in a region in which Mo is eluted, almost
no W is eluted. Thus, it is expected that the influences of Mo and W on improving
corrosion resistance are significantly different.
[0012] Therefore, detailed studies were performed on the corrosion resistance of duplex
stainless steel for which the chemical composition of a third-generation duplex stainless
steel was adopted as a basis and which contained a large amount of W but did not contain
Mo. As a result, the following findings were obtained.
[0013]
- (a) By appropriately adjusting the chemical composition and production method to obtain
an α+γ duplex micro-structure in which there is no precipitation of an σ-phase or
a χ-phase, duplex stainless steel having excellent corrosion resistance under an environment
in which hot concentrated chloride is present is obtained. The corrosion resistance
at such time exceeds a corrosion resistance that is predicted from the relational
expression of PREW.
- (b) By appropriately adjusting the chemical composition and production method, a passivation
film that is formed under an environment in which hot concentrated chloride having
a low pH is present can be made a passivation film that is rich in W. A passivation
film that is rich in W dramatically improves corrosion resistance under the aforementioned
environment.
[0014] The present invention has been made based on the above findings, and the gist of
the present invention is a duplex stainless steel and a production method therefor
which are described hereunder.
[0015]
- (1) A duplex stainless steel having a chemical composition comprising, by mass%,
C: 0.03% or less,
Si: 1.0% or less,
Mn: 1.0% or less,
P: 0.04% or less,
S: 0.01% or less,
Cu: 0.1 to 1.0%,
Ni: 5.0 to 7.5%,
Cr: 22.0 to 26.0%,
W: 6.0 to 12.0%,
N: 0.20 to 0.32%,
Mo: 0.01% or less, and
balance: Fe and impurities, wherein,
a metal micro-structure contains, by area ratio, 0.40 to 0.60 of an α-phase, with
the balance of a γ-phase and 0.01 or less of other phases.
- (2) The duplex stainless steel according to the above (1), wherein a pitting potential
corresponding to 100 µA/cm2 when immersed in a 250 g/L NaCl aqueous solution that is held at 90°C is 600 mV (vs.
SCE) or more.
- (3) The duplex stainless steel according to the above (1) or (2), wherein a chemical
composition of an outermost surface of a passivation film after immersion for 24 hours
in a testing liquid having a pH of 1 satisfies formula (i) below:

where, each symbol of an element in the above formula represents a content (at%)
of each element in the outermost surface of the passivation film.
- (4) A method for producing a duplex stainless steel, including, with respect to a
steel having a chemical composition according to the above (1), performing a heat
treatment of heating to a temperature range of 1150 to 1300°C, and after holding the
steel in the temperature range, cooling at a cooling rate that is equal to or higher
than a cooling rate of water cooling.
[0016] Note that, in the present invention, the term "α-phase" refers to a ferritic phase
and the term "γ-phase" refers to an austenite phase.
ADVANTAGEOUS EFFECTS OF INVENTION
[0017] According to the present invention, a duplex stainless steel that has excellent corrosion
resistance is obtained. The duplex stainless steel is suited for use in the chemical
industry field and the like in which corrosion under a hot concentrated chloride environment
is a problem.
BRIEF DESCRIPTION OF DRAWINGS
[0018]
[Figure 1 Figure 1 is a view illustrating polarization curves of pure W and pure Mo
under a corrosive environment.
[Figure 2] Figure 2 is a view illustrating the relation between a value for W/(Fe+Cr)
at an outermost surface of a passivation film and pitting potential according to an
example.
DESCRIPTION OF EMBODIMENTS
[0019] An embodiment of the present invention is described hereunder. Hereinafter, the symbol
"%" as used with respect to the content of respective elements refers to "mass%."
1. Chemical Composition of Base Metal
C: 0.03% or less
[0020] C is an austenite former and is effective for stabilizing an austenite phase. However,
in stainless steel with a high Cr content such as in the present invention, if the
C content exceeds 0.03%, there is a risk that Cr carbides will precipitate and corrosion
resistance will deteriorate. Therefore, the C content is made 0.03% or less. Preferably,
the C content is 0.01% or less. The above effect will be achieved if even a trace
amount of C is contained, and hence the lower limit thereof is not particularly defined.
However, to adequately achieve the above effect, a C content of 0.003% or more is
preferable.
Si: 1.0% or less
[0021] Si is effective as a deoxidizing component of steel. However, if the Si content is
excessive, there is a concern that the Si will promote precipitation of an σ-phase
and a χ-phase. Therefore, the Si content is made 1.0% or less. Preferably, the Si
content is 0.5% or less. Although the Si content may be substantially zero if deoxidation
is to be performed with another element, it is preferable to contain 0.2% or more
of Si to adequately achieve the above effect.
Mn: 1.0% or less
[0022] Mn is an austenite former and contributes to stabilization of an austenite. However,
if the Mn content is excessive, there is a concern that MnS that acts as a corrosion
starting point will crystallize or precipitate. Therefore, the Mn content is made
1.0% or less. Preferably the Mn content is 0.5% or less. The above effect will be
achieved if even a trace amount of Mn is contained, and hence the lower limit thereof
is not particularly defined. However, to adequately achieve the above effect, an Mn
content of 0.1 % or more is preferable.
P: 0.04% or less
[0023] P is an impurity element that is unavoidable during the production process, and if
the content thereof is excessive there is a risk that workability will be reduced.
Therefore, the P content is made 0.04% or less. Preferably, the P content is 0.01%
or less.
S: 0.01% or less
[0024] S is an impurity element that is unavoidable during the production process, and if
the content thereof is excessive there is a risk that workability will be reduced.
There is also a concern that MnS which acts as a corrosion starting point will crystallize
or precipitate. Therefore, the S content is made 0.01% or less. Preferably, the S
content is 0.004% or less.
Cu: 0.1 to 1.0%
[0025] Cu is an austenite former, and is effective for improving resistance to sulfuric
acid. Cu is also effective for assisting the formation of a passivation film that
contains a large amount of W. Specifically, Cu has an effect of promoting a cathode
reaction, and accelerating the formation of a passivation film containing a large
amount of W. Therefore, the content of Cu is made 0.1% or more. However, if the content
of Cu is excessive, there is a concern that the excessive content may deteriorate
formability. Accordingly, the Cu content is set in a range of 0.1 to 1.0%. A preferable
lower limit is 0.4%, and a preferable upper limit is 0.6%.
Ni: 5.0 to 7.5%
[0026] Ni is an austenite former. In order to obtain an α+γ duplex micro-structure with
a desirable balance with respect to the relation with ferrite forming elements such
as Cr and W, an Ni content in the range of 5.0 to 7.5% is necessary. A preferable
lower limit is 6.0%, and a preferable upper limit is 6.8%.
Cr: 22.0 to 26.0%
[0027] Cr is a ferrite forming element and is also a basic element that is effective for
improving corrosion resistance. If the Cr content is insufficient or excessive, a
temperature range in which an α+γ duplex micro-structure can be stably obtained narrows.
Therefore, the Cr content is set in a range of 22.0 to 26.0%. A preferable lower limit
is 23.0%, and a preferable upper limit is 25.5%.
W: 6.0 to 12.0%
[0028] W is a ferrite forming element and is also an important element for developing excellent
corrosion resistance. If the W content is insufficient or is excessive, an α+γ duplex
micro-structure cannot be stably obtained. Therefore, the W content is set as a value
within a range of 6.0 to 12.0%. A preferable lower limit is 8.0%, and a preferable
upper limit is 11.0%.
N: 0.20 to 0.32%
[0029] N is an austenite former, and is an effective element for improving thermal stability
and corrosion resistance of a duplex stainless steel. To obtain an α+γ duplex micro-structure
with a desirable balance with respect to a relation with ferrite forming elements
such as Cr and W, an N content of 0.20% or more is necessary. However, if the N content
exceeds 0.32%, there is a risk that the toughness and corrosion resistance of the
steel will noticeably deteriorate due to the production of nitride. Therefore, the
N content is set in a range of 0.20 to 0.32%. A preferable lower limit is 0.24%, and
a preferable upper limit is 0.28%.
Mo: 0.01% or less
[0030] Mo is a ferrite forming element, similarly to Cr and W. However, when Mo is contained
in the chemical composition, the Mo decreases the solubility of W, and hence it is
necessary to make the Mo content as low as possible. Therefore, the Mo content is
made 0.01% or less, and preferably is 0.008% or less.
[0031] The chemical composition of the duplex stainless steel of the present invention contains
each of the aforementioned elements in the respectively defined ranges, with the balance
of Fe and impurities. The term "impurities" refers to components that are contained
in raw materials such as ore or scrap or that are mixed in due to other causes when
industrially producing the steel material.
2. Metal Micro-structure of Base Metal
[0032] The base metal has an α+γ duplex micro-structure in which the area ratio of the σ-phase
is from 0.40 to 0.60 and the balance is the γ-phase as well as other phases for which
the area ratio is 0.01 or less. In phases other than the σ-phase and γ-phase, particularly
in an σ-phase and a χ-phase, a Cr depleted zone is formed around the phase, and consequently
corrosion resistance is degraded. Therefore, although it is preferable that the total
area ratio of those phases is zero, a total area ratio of 0.01 or less is permissible.
Note that, since the corrosion resistance may be degraded if the proportion of the
γ-phase is large, preferably the area ratio of the γ-phase is made 0.58 or less.
3. Passivation Film
[0033] If the duplex stainless steel having the aforementioned chemical composition and
metal micro-structure is produced under appropriate conditions, a passivation film
formed under an environment in which hot concentrated chloride having a low pH is
present can be made a passivation film that is rich in W. Although Fe and Cr in a
passivation film undergo corrosion in a low pH environment, a passivation film that
contains a large amount of W that effectively contributes to corrosion resistance
is excellent in corrosion resistance.
[0034] Further, in a case where the chemical composition of an outermost surface of the
passivation film after immersion for 24 hours in a testing liquid having a pH of 1
satisfies the following formula (i), it is possible to dramatically improve the corrosion
resistance of the duplex stainless steel. The left-hand value in the following formula
(i) is more preferably set to 0.10% or more.

[0035] Where, each symbol of an element in the above formula represents a content (at%)
of each element in the outermost surface of the passivation film.
4. Method for Producing Duplex Stainless Steel
[0036] The duplex stainless steel of the present invention is made into a product by melting
under production conditions that are generally adopted, performing necessary processes
such as hot working and cold working, and finally performing a heat treatment including
heating in a temperature range of 1150 to 1300°C, and after holding the steel in this
temperature range, cooling at a cooling rate that is equal to or higher than a cooling
rate of water cooling.
[0037] This is because, if the aforementioned heat treatment temperature is less than 1150°C,
precipitation of the σ-phase or χ-phase is inevitable, while on the other hand, if
the aforementioned heat treatment temperature exceeds 1300°C, there is a risk that
an α+γ duplex micro-structure in which the area ratio of the σ-phase is from 0.4 to
0.6 and the balance is substantially a γ-phase cannot be obtained. Therefore, the
heat treatment is performed in a temperature range from 1150 to 1300°C. Although the
holding time will vary depending on the thickness of the duplex stainless steel, the
holding time may be appropriately selected within a range of 1 to 120 min.
[0038] If the cooling rate after the steel is held in the aforementioned temperature range
is excessively slow there is a risk that an σ-phase or a χ-phase will precipitate
during the cooling process, and therefore the steel is cooled at a cooling rate that
is equal to or higher than the cooling rate of water cooling. More specifically, it
is sufficient to perform cooling at a cooling rate of 40°C/s or more.
[0039] Hereunder, the present invention is described specifically by way of an example,
although the present invention is not limited to the following example.
EXAMPLE 1
[0040] Ingots having the chemical compositions shown in Table 1 were melted in a 17-kg vacuum
furnace, and then subjected to hot rolling to a thickness of 4 to 8 mm. Each of the
steels was adjusted so that a pitting resistance equivalent PREW value defined by
the following formula was around 43 to 44.

[0041] Where, each symbol of an element in the above formula represents a content (mass%)
of the element in the steel.
[0042] Thereafter, after heating and holding at the temperatures shown in Table 1, the respective
steels were subjected to water cooling and specimens were obtained. Commercially available
stainless steels having the chemical compositions shown in Table 2 were also prepared
as specimens. With respect to these specimens, observation of the metal micro-structure
of the base metal, measurement of corrosion resistance, and component analysis of
a passivation film were performed.
[Table 1]
Table 1
| Steel No. |
Chemical composition (by mass%, balance: Fe and impurities) |
PREW |
Heat treatment temperature (°C) |
Cooling rate (°C/s) |
| C |
Si |
Mn |
P |
S |
Cu |
Ni |
Cr |
N |
W |
Mo |
| 1 |
0.003 |
0.26 |
0.48 |
<0.001 |
0.001 |
0.49 |
6.96 |
25.04 |
0.26 |
8.44 |
<0.01 |
43.0 |
1200 |
45 |
| 2 |
0.004 |
0.26 |
0.49 |
<0.001 |
0.001 |
0.49 |
6.96 |
25.07 |
0.26 |
8.46 |
<0.01 |
43.1 |
43 |
| 3 |
0.003 |
0.27 |
0.49 |
<0.001 |
0.001 |
0.49 |
6.97 |
25.02 |
0.25 |
8.46 |
<0.01 |
43.2 |
50 |
| 4 |
0.003 |
0.26 |
0.48 |
<0.001 |
0.001 |
0.49 |
6.96 |
25.04 |
0.26 |
8.44 |
<0.01 |
43.0 |
1150 |
49 |
| 5 |
0.004 |
0.26 |
0.49 |
<0.001 |
0.001 |
0.49 |
6.96 |
25.07 |
0.26 |
8.46 |
<0.01 |
43.1 |
42 |
| 6 |
0.003 |
0.27 |
0.49 |
<0.001 |
0.001 |
0.49 |
6.97 |
25.02 |
0.25 |
8.46 |
<0.01 |
43.2 |
44 |
| 7 |
0.003 |
0.26 |
0.48 |
<0.001 |
0.001 |
0.49 |
6.96 |
25.04 |
0.26 |
8.44 |
<0.01 |
43.0 |
1050 # |
40 |
| 8 |
0.004 |
0.26 |
0.49 |
<0.001 |
0.001 |
0.49 |
6.96 |
25.07 |
0.26 |
8.46 |
<0.01 |
43.1 |
42 |
| 9 |
0.003 |
0.27 |
0.49 |
<0.001 |
0.001 |
0.49 |
6.97 |
25.02 |
0.25 |
8.46 |
<0.01 |
43.2 |
39 |
| 10 |
0.003 |
0.26 |
0.48 |
<0.001 |
0.001 |
0.49 |
6.96 |
25.04 |
0.26 |
8.44 |
<0.01 |
43.0 |
950 # |
37 |
| 11 |
0.004 |
0.26 |
0.49 |
<0.001 |
0.001 |
0.49 |
6.96 |
25.07 |
0.26 |
8.46 |
<0.01 |
43.1 |
41 |
| 12 |
0.003 |
0.27 |
0.49 |
<0.001 |
0.001 |
0.49 |
6.97 |
25.02 |
0.25 |
8.46 |
<0.01 |
43.2 |
38 |
| 13 |
0.003 |
0.26 |
0.48 |
<0.001 |
0.001 |
0.49 |
6.96 |
25.04 |
0.26 |
8.44 |
<0.01 |
43.0 |
850 # |
33 |
| 14 |
0.004 |
0.26 |
0.49 |
<0.001 |
0.001 |
0.49 |
6.96 |
25.07 |
0.26 |
8.46 |
<0.01 |
43.1 |
31 |
| 15 |
0.003 |
0.27 |
0.49 |
<0.001 |
0.001 |
0.49 |
6.97 |
25.02 |
0.25 |
8.46 |
<0.01 |
43.2 |
34 |
| 16 |
0.012 |
0.29 |
0.49 |
0.027 |
0.001 |
0.50 |
6.97 |
25.53 |
0.30 |
1.95* |
3.21 * |
44.1 |
1100 # |
40 |
| 17 |
0.013 |
0.29 |
0.47 |
0.025 |
0.001 |
0.49 |
6.97 |
25.50 |
0.30 |
1.94* |
3.23 * |
44.1 |
38 |
| 18 |
0.010 |
0.30 |
0.48 |
0.024 |
0.001 |
0.49 |
6.95 |
25.55 |
0.30 |
2.02* |
3.22 * |
44.2 |
39 |
| 19 |
0.019 |
0.51 |
0.46 |
0.024 |
<0.001 |
0.44 |
6.69 |
25.15 |
0.26 |
2.07 * |
3.09 * |
43.0 |
39 |
| 20 |
0.015 |
0.49 |
0.49 |
0.025 |
<0.001 |
0.46 |
6.67 |
25.31 |
0.26 |
2.09 * |
3.08 * |
43.1 |
39 |
| 21 |
0.016 |
0.47 |
0.48 |
0.024 |
<0.001 |
0.50 |
6.70 |
25.30 |
0.26 |
2.06 * |
3.11 * |
43.2 |
39 |
| 22 |
0.003 |
0.26 |
0.48 |
<0.001 |
0.001 |
0.49 |
6.96 |
25.04 |
0.26 |
8.44 |
<0.01 |
43.0 |
38 |
| 23 |
0.004 |
0.26 |
0.49 |
<0.001 |
0.001 |
0.49 |
6.96 |
25.07 |
0.26 |
8.46 |
<0.01 |
43.1 |
39 |
| 24 |
0.003 |
0.27 |
0.49 |
<0.001 |
0.001 |
0.49 |
6.97 |
25.02 |
0.25 |
8.46 |
<0.01 |
43.2 |
38 |
| 25 |
0.003 |
0.26 |
0.48 |
<0.001 |
0.001 |
<0.01 * |
6.96 |
25.42 |
0.27 |
8.52 |
<0.01 |
43.8 |
1200 |
50 |
| 26 |
0.007 |
0.30 |
0.48 |
<0.001 |
<0.001 |
<0.01 * |
6.89 |
25.13 |
0.26 |
8.58 |
<0.01 |
43.5 |
45 |
| 27 |
0.008 |
0.29 |
0.49 |
<0.001 |
0.001 |
<0.01 * |
7.12 |
25.10 |
0.27 |
8.49 |
<0.01 |
43.4 |
45 |
| 28 |
0.003 |
0.26 |
0.48 |
<0.001 |
0.001 |
0.49 |
6.96 |
25.04 |
0.26 |
8.44 |
<0.01 |
43.0 |
1150 |
0.05 # |
| 29 |
0.003 |
0.26 |
0.48 |
<0.001 |
0.001 |
<0.01 * |
6.96 |
25.42 |
0.27 |
8.52 |
<0.01 |
43.8 |
0.1 # |
* indicates that conditions do not satisfy those defined by the present invention.
# indicates that production conditions do not satisfy the preferrable conditions described
in the present invention. |
[Table 2]
Table 2
| Steel No. |
Chemical composition (by mass%, balance: Fe and impurities) |
PREW |
Heat treatment temperature (°C) |
Cooling rate (°C/s) |
| C |
Si |
Mn |
P |
S |
Cu |
Ni |
Cr |
N |
W |
Mo |
| 30 |
0.019 |
0.40 |
0.75 |
0.025 |
0.001 |
<0.01 * |
6.39 |
24.530 |
0.17 |
<0.01 * |
3.22 |
37.9 |
1100 # |
41 |
| 31 |
0.011 |
0.41 |
0.77 |
0.021 |
0.001 |
<0.01 * |
6.34 |
24.550 |
0.17 |
<0.01 * |
3.24 |
38.0 |
42 |
| 32 |
0.013 |
0.39 |
0.71 |
0.024 |
0.001 |
<0.01 * |
6.45 |
24.810 |
0.19 |
<0.01 * |
3.23 |
38.5 |
39 |
* indicates that conditions do not satisfy those defined by the present invention.
# indicates that production conditions do not satisfy the preferrable conditions described
in the present invention. |
<Observation of metal micro-structure of base metal>
[0043] A cross-section of each specimen was observed under an optical microscope at a magnification
of 500, and the area ratios of the σ-phase and the γ-phase were measured. In addition,
the presence/absence of an σ-phase and a χ-phase was verified, and steel in which
there was no σ-phase or χ-phase precipitation was marked with "O", while steel in
which precipitation of at least one of σ-phase and χ-phase was observed was marked
with "x", and the total area ratios of these phases were measured.
<Measurement of corrosion resistance>
[0044] A disk-like test specimen having a diameter of 15 mm and a plate thickness of 2 mm
was cut out from each specimen, and the surface was finished by #600 wet polishing.
Testing was performed in accordance with JIS G 0577 (2014), and a pitting potential
V'C100 corresponding to 100 µA/cm
2 was measured. Note that, since an environment in which hot concentrated chloride
is present was assumed, a 250 g/L NaCl aqueous solution that was kept at 90°C was
used as the aqueous solution.
<Component Analysis of Passivation Film>
[0045] Some of the specimens were immersed for 24 hours in a testing liquid having a pH
of 1, and thereafter measurement of each main metal element in the passivation film
was performed by X-ray photoelectron spectroscopy and a value of W/(Fe+Cr) in the
outermost surface of the passivation film was calculated.
[0046] The results of the above measurements are summarized in Table 3.
[Table 3]
Table 3
| Test No. |
Steel No. |
Metal micro-structure |
Left-hand value in formula (i)† |
Petting potential (mV vs. SCE) |
|
| Ratio of σ-phase |
Ratio of γ-phase |
Presence/ absence of σ, χ-phase |
Total ratio of σ, χ-phase |
| 1 |
1 |
0.55 |
0.45 |
○ |
- |
0.10 |
663 |
Inventive example |
| 2 |
2 |
0.55 |
0.45 |
○ |
- |
0.10 |
661 |
| 3 |
3 |
0.52 |
0.48 |
○ |
- |
0.10 |
701 |
| 4 |
4 |
0.57 |
0.43 |
○ |
- |
0.09 |
630 |
| 5 |
5 |
0.46 |
0.54 |
○ |
- |
0.10 |
685 |
| 6 |
6 |
0.44 |
0.56 |
○ |
- |
0.11 |
722 |
| 7 |
7 |
0.38 * |
0.60 |
× |
0.02 * |
0.03 |
188 |
Comparative example |
| 8 |
8 |
0.43 |
0.55 |
× |
0.02 * |
0.02 |
152 |
| 9 |
9 |
0.35 * |
0.63 |
× |
0.02 * |
0.03 |
218 |
| 10 |
10 |
0.34 * |
0.62 |
× |
0.04 * |
0.03 |
220 |
| 11 |
11 |
0.29 * |
0.66 |
× |
0.05 * |
0.03 |
238 |
| 12 |
12 |
0.42 |
0.54 |
× |
0.04 * |
0.04 |
308 |
| 13 |
13 |
0.38 * |
0.55 |
× |
0.07 * |
0.01 |
-4 |
| 14 |
14 |
0.37 * |
0.56 |
× |
0.07 * |
0.01 |
12 |
| 15 |
15 |
0.43 |
0.51 |
× |
0.06 * |
0.01 |
44 |
| 16 |
16 * |
0.48 |
0.52 |
○ |
- |
0.07 |
416 |
| 17 |
17 * |
0.51 |
0.49 |
○ |
- |
0.06 |
404 |
| 18 |
18 * |
0.48 |
0.52 |
○ |
- |
0.06 |
433 |
| 19 |
19 * |
0.55 |
0.45 |
○ |
- |
0.06 |
378 |
| 20 |
20 * |
0.52 |
0.48 |
○ |
- |
0.06 |
404 |
| 21 |
21 * |
0.51 |
0.49 |
○ |
- |
0.06 |
411 |
| 22 |
22 |
0.34 * |
0.66 |
○ |
- |
0.08 |
574 |
| 23 |
23 |
0.31 * |
0.69 |
○ |
- |
0.07 |
509 |
| 24 |
24 |
0.33 * |
0.65 |
× |
0.02 * |
0.03 |
294 |
| 25 |
25 * |
0.55 |
0.45 |
○ |
- |
0.05 |
523 |
| 26 |
26 * |
0.50 |
0.50 |
○ |
- |
0.05 |
526 |
| 27 |
27 * |
0.53 |
0.47 |
○ |
- |
0.05 |
514 |
| 28 |
28 |
0.56 |
0.33 |
× |
0.11 * |
0.01 |
-44 |
| 29 |
29 * |
0.57 |
0.30 |
× |
0.13 * |
0.01 |
-68 |
| 30 |
30 * |
0.68 * |
0.32 |
○ |
- |
- |
219 |
| 31 |
31 * |
0.66 * |
0.34 |
○ |
- |
- |
230 |
| 32 |
32 * |
0.66 * |
0.34 |
○ |
- |
- |
248 |
* indicates that conditions do not satisfy those defined by the present invention.
† W/(Fe+Cr) ≥ 0.09 ... (i) |
[0047] As shown in Table 3, in test Nos. 1 to 6 in which the chemical composition and metal
micro-structure satisfied the specification of the present invention, the pitting
potential was 600 mV or more and favorable corrosion resistance was exhibited.
[0048] In contrast, the results showed that the corrosion resistance was inferior in test
Nos. 16 to 21, 25 to 27 and 29 to 32 in which at least the chemical composition deviated
from the range specified by the present invention and in test Nos. 7 to 15, 22 to
24 and 28 in which at least the metal micro-structure deviated from the range specified
by the present invention.
[0049] As shown in Figure 2, there is a constant correlation between the value of W/(Fe+Cr)
in the outermost surface of the passivation film and the pitting potential, and it
is possible to make the pitting potential 600 mV or more when the value for W/(Fe+Cr)
is 0.09 or more.
INDUSTRIAL APPLICABILITY
[0050] According to the present invention, a duplex stainless steel having excellent corrosion
resistance is obtained. The duplex stainless steel is suitable for use in the chemical
industry field and the like in which corrosion under a hot concentrated chloride environment
is a problem.
1. A duplex stainless steel having a chemical composition comprising, by mass%,
C: 0.03% or less,
Si: 1.0% or less,
Mn: 1.0% or less,
P: 0.04% or less,
S: 0.01% or less,
Cu: 0.1 to 1.0%,
Ni: 5.0 to 7.5%,
Cr: 22.0 to 26.0%,
W: 6.0 to 12.0%,
N: 0.20 to 0.32%,
Mo: 0.01% or less, and
balance: Fe and impurities, wherein,
a metal micro-structure contains, by area ratio, 0.40 to 0.60 of an α-phase, with
the balance of a γ-phase and 0.01 or less of other phases.
2. The duplex stainless steel according to claim 1, wherein a pitting potential corresponding
to 100 µA/cm2 when immersed in a 250 g/L NaCl aqueous solution that is held at 90°C is 600 mV (vs.
SCE) or more.
3. The duplex stainless steel according to claim 1 or 2, wherein a chemical composition
of an outermost surface of a passivation film after immersion for 24 hours in a testing
liquid having a pH of 1 satisfies formula (i) below:

where, each symbol of an element in the formula represents a content (at%) of each
element in the outermost surface of the passivation film.
4. A method for producing a duplex stainless steel, including, with respect to a steel
having a chemical composition according to claim 1, performing a heat treatment of
heating to a temperature range of 1150 to 1300°C, and after holding the steel in the
temperature range, cooling at a cooling rate that is equal to or higher than a cooling
rate of water cooling.