The present invention relates to high Cr-based austenitic stainless steel.
Background Art
[0002] There has been an advancing tendency since 1990s in Japan with respect to a boiler
toward high temperature and high pressure, and the current mainstream is an Ultra Super
Critical power (USC) boiler for a steam temperature beyond 600"C.
In other areas of the world, including Europe or China, highly efficient USC boilers
have been constructed one after another from the viewpoint of C02 reduction as a global
environmental countermeasure.
As a source material steel to be used for a heat exchanger tube to generate high
temperature high pressure steam in a boiler, and for a pipe of a boiler, a steel material with
superior high temperature strength has been demanded and various steel materials have been
developed recently.
[0003] For example, Patent Literature 1 discloses, as a high Cr-based austenitic stainless
steel, a high strength austenitic stainless steel superior in high temperature strength and
suitable for a material of a chemical plant vessel using petroleum and coal as a fuel, a material
of a heat exchanger, or a material of a high temperature component such as a boiler tube or a
fast reactor.
Patent Literature 2 discloses an austenitic stainless steel pipe superior in creep
rupture strength at a high temperature for a long time period, and suitable for a material to be
used in a high temperature and high pressure environment, such as a steel tube or pipe for a
boiler, or a high temperature pressure vessel.
[0004] Patent Literature 3 discloses a high temperature austenite stainless steel which is
superior in workability after long term use and is suitable for a material for a steel tube or pipe
to be used as a superheater pipe or a reheater pipe of a boiler, a reacting furnace pipe in a
chemical plant, etc, or as a material for a steel plate, a steel bar, a steel forging, etc. to be used
as a heat-resistant, and pressure-resistant component.
[0005] Patent Literature 4 discloses an austenite stainless steel, which is superior in high
temperature corrosion thermal fatigue cracking resistance, is able to withstand an environment
subjected to high temperature corrosion at 500"C or higher as well as repeated thermal fatigue,
1
and is suitable for a pipe, a plate, a bar, a forging, etc. to be used for a heat exchanger
component of a HRSG (Heat Recovery Steam Generator) or a next-generation solar power
generator, or a heat-resistant and pressure-resistant component for a power generation boiler,
a chemical plant, an atomic power plant, etc.
(0006] Patent Literature 5 discloses a high strength austenite stainless steel which is superior
in toughness after aging, is applicable to a high strength steel tube or pipe for a boiler, etc, and
is usable for ultra-supercritical coal fired power generation, integrated coal gasification
combined cycle power generation, etc.
Patent Literature 6 discloses a high strent,>th austenite stainless steel to be used for
ultra-supercritical coal fired power generation, integrated coal gasification combined cycle
power generation, or the like.
[0007]
Patent Literature I: Japanese Patent No. 2510206
Patent Literature 2: Japanese Patent Application Laid-Open (JP-A) No. 2002-212634
Patent Literature 3: Japanese Patent No. 4946758
Patent Literature 4: Japanese Patent No. 5029788
Patent Literature 5: Japanese Patent No. 5661001
Patent Literature 6: Japanese Patent No. 5670103
SUMMARY OF INVENTION
Technical Problem
(0008] Generally, in designing the chemical composition of a material steel to be used for a
heat exchanger tube used in a high temperature range, importance is placed on high
temperature strength (for example, creep strength), high temperature corrosion resistance,
steam oxidation resistance, thermal fatigue resistance, etc., and corrosion resistance in a
normal temperature range (for example, corrosion resistance in water) is less valued.
Further, in the case of a high Cr-based stainless steel with a Cr content of21.50% or
more by mass, it has been believed that stress corrosion cracking itself does not take place.
(0009] However, there arises recently a big problem that stress corrosion cracking occurs in
water in a range of room temperature to low temperature (approximately 350°C or less) due to
an inhomogeneous metallic structure or precipitation of a heterogeneous carbide, etc. at a
heating processed portion, such as a welded portion or a bending portion.
For example, during a hydrostatic pressure test of a boiler, or a shut-down of a boiler,
2
since water is stored for an extended period of time inside heat exchanger tubes, stress
corrosion cracking may occur remarkably.
[00 I 0] Stress corrosion cracking may occur, because a crystal grain boundary becomes
susceptible to selective corrosion due to precipitation of a Cr-based carbide or generation of a
zone with a low Cr concentration (Cr depleted zone) in the vicinity of a crystal grain
boundary.
[0011] As a method of preventing stress corrosion cracking of an 18Cr-based austenitic
stainless steel, heretofore:
a method of suppressing formation of a grain boundary Cr carbide by reduction of a
C amount (a low carbon addition method),
a method of suppressing formation of a grain boundary Cr carbide by addition ofNb
and Ti, which have higher capability of forming a carbide than Cr, to form a MC carbide to fix
C (a stabilizing heat treatment method),
a method of suppressing fonnation of a Cr depleted zone by addition ofCr at 21.50%
or more to suppress selective corrosion at a grain boundary (a method of adding a large
amount of Cr), or the like is known.
There is, however, a drawback in any of the methods.
[0012] An 18 Cr-based austenitic stainless steel obtained by the low carbon addition method
or the stabilizing heat treatment method cannot be utilized in a high temperature environment
of 750-c or higher, or a severe high temperature corrosive environment caused by a fuel to be
used, because the oxidation resistance, high temperature corrosion resistance, and high
temperature strength thereof are insufficient in such environments.
Consequently, an austenitic stainless steel to be used in such a high temperature
environment or a high temperature corrosive environment is required to contain Cr at 21.50%
or more by mass according to the method of adding a large amount of Cr.
[00 13] However, a problem has arisen recently with respect to stress corrosion cracking
occurring in the extreme environment (severe environment in terms of stress corrosion
cracking), which a conventional high Cr-based stainless steel, or a conventional art cannot
cope with.
Such stress corrosion cracking in an extreme environment (severe environment in
terms of stress corrosion cracking) occurs due to a cause, such as "sensitization of material"
(namely, a phenomenon in which a Cr-based carbonitride precipitates in the vicinity of crystal
grain boundaries, whereby the Cr concentration in the vicinity of crystal grain boundaries is
decreased, and consequently grain boundary corrosion is promoted), a special corrosive
3
environment factor (for example, entry of seawater into a pipe), or equipment not free from a
large residual strain (residual strain remaining after welding or processing).
[00 14] Such stress corrosion cracking of a high Cr-based austenitic stainless steel occurring
in the extreme environment (severe environment in terms of stress corrosion cracking) has
been heretofore not taken into consideration at all, and there has been no effective
conventional art thereon. Therefore, a proposal of a new material is demanded.
Superior high temperature strength is also required for high Cr-based austenitic
stainless steel.
[00 15] An object of the invention is to provide a high Cr-based austenitic stainless steel that
contains Cr in an amount of21.50% or more by mass, that is able to secure stress corrosion
cracking resistance even in an extreme environment (severe environment in tenns of stress
corrosion cracking), which was heretofore left out of consideration, and that is also superior in
high temperature strength.
Solution to Problem
[0016] The means for achieving the object includes the following aspects.
[0017] A high Cr-based austenitic stainless steel with a chemical composition
consisting of in terms of% by mass:
0.03 to 0.12% ofC,
0.10 to 1.00% of Si,
0.10 to 3.00% ofMn,
0.030% or less ofP,
0.020% or less of S,
21.50 to 28.00% ofCr,
more than 26.00 and not more than 35.00% ofNi,
more than 2.00 and not more than 5.00% ofW,
0.80% or less of Co,
0.0 I to 0. 70% ofV,
0.15 to 1.00% ofNb,
0.001 to 0.040% of AI,
0.0001 to 0.0100% ofB,
0.0 I 0 to 0.400% ofN,
0.001 to 0.200% of Zt~
0.00 I to 0.200% ofNd,
4
0.001 to 0.200% ofTa,
0.020 to 0.200% ofTa+0.8Nd+0.5Zr,
0.010% or less ofTi,
0.010% or less ofSn,
0.010% or less ofSb,
0.001% or less ofPb,
0.001% or less of As,
0.001% or less ofBi,
0.025% or less ofTi+Sn+Sb+Pb+As+Bi,
0.0090% or less of 0,
4.00% or less of Cu,
2.00% or less ofMo,
0.20% or less of Ca,
0.20% or less ofMg,
0.20% or less in total of one or more ofY, Sc, Hf, Re, or lantbanoid elements other than Nd,
and
a remainder consisting of Fe and impurities.
[0018] <2> The high Cr-based austenitic stainless steel according to <1 >, wherein the
chemical composition comprises, in terms of% by mass, 0.01 to 0.80% of Co.
<3> The high Cr-based austenitic stainless steel according to <1> or <2>, wherein the
chemical composition comprises, in terms of% by mass, one or more of: 0.01 to 4.00% ofCu,
0.01 to 2.00% ofMo, 0.0001 to 0.20% ofCa, or 0.0005 to 0.20% ofMg.
<4> The high Cr-based austenitic stainless steel according to any one of to <3>,
wherein the chemical composition comprises, in terms of% by mass, 0.001 to 0.20% in total
of one or more ofY, Sc, Hf, Re, or lanthanoid elements other than Nd.
<5> The high Cr-based austenitic stainless steel according to any one of to <4>,
wherein a creep rupture strength at 750°C and I 00,000 hours is 50 MPa or more.
Advantageous Effects ofinvention
[00 19] According to the invention a high Cr-based austenitic stainless steel that contains Cr
in an amount of 21.50% or more by mass, that is able to secure stress corrosion cracking
resistance even in an extreme environment (severe environment in terms of stress corrosion
cracking), which was heretofore left out of consideration, and that is also superior in high
temperature strength, is provided.
5
DESCRIPTION OF EMBODIMENTS
[0020] Embodiments ofthe invention will be described below.
A numerical range expressed by "x to y" herein includes the values of x and y in the
range as the lower and upper limit values, respectively.
The content of an element expressed by"%", the value of "Ta+0.8Nd+0.5Zr"
expressed by"%", and the value of "Ti+Sn+Sb+Pb+As+Bi" expressed by"%" mean herein
respectively"% by mass".
The content ofC (carbon) may be herein occasionally expressed as "C content".
The content of another element may be expressed similarly.
[0021] An austenitic stainless steel of the embodiment (hereinafter also referred to as the
"steel of the embodiment") is an austenitic stainless steel with a chemical composition
consisting of in terms of% by mass: 0.03 to 0.12% ofC, 0.10 to 1.00% of Si, 0.10 to 3.00%
ofMn, 0.030% or less ofP, 0.020% or less ofS, 21.50 to 28.00% ofCr, more than 26.00 and
not more than35.00% ofNi, more than 2.00 and not more than 5.00% ofW, 0.80% or less of
Co, 0.01 to 0.70% ofV, 0.15 to 1.00% ofNh, 0.001 to 0.040% of AI, 0.0001 to 0.0100% ofB,
0.010 to 0.400% ofN, 0.001 to 0.200% ofZr, 0.001 to 0.200% ofNd, 0.001 to 0.200% ofTa,
0.020 to 0.200% ofTa+0.8Nd+0.5Zr, 0.010% or less ofTi, 0.010% or less ofSn, 0.010% or
less of Sb, 0.001% or less ofPb, 0.001% or less of As, 0.001% or less ofBi, 0.025% or less of
Ti+Sn+Sb+Pb+As+Bi, 0.0090% or less ofO, 4.00% or less ofCu, 2.00% or less ofMo,
0.20% or less ofCa, 0.20% or less ofMg, 0.20% or less in total of one or more ofY, Sc, Hf,
Re, or lanthanoid elements other than Nd, and a remainder consisting of Fe and impurities.
[0022] The steel of the embodiment is a high Cr-based austenitic stainless steel containing
Cr in an amount of21.50% or more by mass.
As described above, there has been recently a problem of stress corrosion cracking
occurring in an extreme environment (severe environment in terms of stress corrosion
cracking), which a conventional high Cr-based stainless steel, or a conventional art cannot
cope with.
[0023] With the steel of the embodiment, stress corrosion cracking resistance can be secured
also in an extreme environment (severe environment in terms of stress corrosion cracking),
which has been heretofore not taken into consideration.
The reason of such an effect to be obtained with the steel of the embodiment is
presumed as follows, provided that the invention be not restricted in any way by the following
6
presumption.
[0024] Through investigations by the inventors, it has become clear that, when appropriate
amounts of 3 elements of Ta, Nd, and Zr are added combinedly to a highly purified high
Cr-based austenitic steel, the stress corrosion cracking resistance is remarkably improved
through a synergistic effect of the combined addition.
Although independent addition of any ofthe 3 elements, or partly combined addition
of the same has been heretofore known, combined addition of the 3 elements for improving
the stress corrosion cracking resistance of a high Cr-based austenitic stainless steel has not yet
been known.
[0025] Further, through investigations by the inventors, it has become clear that the
synergistic effect of the 3 elements is exhibited remarkably by treating Ti, which has been
heretofore treated as an effective addition element, as an impurity element, and limiting the
content of impurity elements including the Ti (specifically, Ti, Sn, Sb, Pb, As, Bi, 0, etc.) so
as to attain a high purity of a high Cr-based austenitic stainless steel.
[0026] Although addition of C and N is essential from the viewpoint of maintenance of the
strength in a high temperature environment of from 700'C to 750'C, precipitation of a
Cr-based carbonitride at a grain boundary will cause stress corrosion cracking.
In the steel of the embodiment, the amount ofTi, which creates a coarse carbonitride,
is reduced to the extent possible, and in conjunction therewith, the amount of an impurity
which may weaken grain boundaries and cause stress corrosion cracking is also reduced. As
a result, stress corrosion cracking caused by precipitation of a Cr-based carbonitride at a grain
boundary may be suppressed.
[0027] The steel ofthe embodiment is superior in high temperature strength (for example,
creep rupture strength).
The reason behind the superior high temperature strength of the steel of the
embodiment is presumed to be that fine dispersion of a stable carbonitride and precipitation
strengthening of a fine and stable Laves phase are achieved owing to actions of combined
addition of the 3 elements ofT a, Nd, and Zr, an appropriate amount ofW, and the like.
With the steel of the embodiment, for example, a strength that is at least 1.4 times
higher than a creep rupture strength at 750'C and I 00,000 hours of a conventional
general-purpose steel may be obtained.
[0028] The chemical composition of the steel of the embodiment and its preferable mode
will be described below.
[0029] C: 0.03 to 0.12%
7
C is an essential element for formation of a carbide, and stabilization of an austenitic
structure, as well as improvement of high temperature strength and stabilization of a metallic
structure at a high temperature.
However, when the C content is less than 0.03%, it is difficult for a high Cr-based
austenitic stainless steel to maintain its high temperature creep strength and a sound metallic
structure at a high temperature. Therefore, the C content is 0.03% or more, and is preferably
0.04% or more.
[0030] When the C content exceeds 0.12%, a coarse Cr-based carbide precipitates at a
crystal grain boundary, which may cause stress corrosion cracking or welding cracking to
reduce toughness. Therefore, the C content is 0.12% or less, and is preferably 0.10% or less.
[0031] Si:0.10to 1.00%
Si is an element which functions as a deoxidizing agent during steel making, and
prevents steam oxidation at a high temperature. However, when the Si content is less than
0.1 0%, the addition effect cannot be obtained adequately. Therefore, the Si content is 0.10%
or more, and is preferably 0.15% or more.
[0032] When the Si content exceeds 1.00%, the workability decreases, and a brittle phase
such as a a-phase precipitates at a high temperature. Therefore, the Si content is 1.00% or
less, and is preferably 0.60% or less.
[0033] Mn: 0.10 to 3.00%
Mn is an element which makes S harmless by forming MnS with S as an impurity
element to contribute to improvement of a hot workability, as well as to stabilization of a
metallic structure at a high temperature.
When N, which is essential for securing the strength, is added in a high Cr-based
austenitic stainless steel, addition ofMn is especially effective.
[0034] When the Mn content is less than 0.10%, the addition effect cannot be obtained
adequately. Therefore, the Mn content is 0.10% or more, and is preferably 0.30% or more.
When the Mn content exceeds 3.00%, the workability and weldability decrease.
Therefore, the Mn content is 3.00% or less, and is preferably 2. 70% or less.
[0035] P: 0.030% or less
Pis an impurity element, which disturbs workability and weldability.
When the P content exceeds 0.030%, the workability and weldability decrease
remarkably. Therefore, the P content is 0.030% or less, and is preferably 0.020%.
[0036] Preferably the P content is as low as possible, and may be even 0%.
However, P may inevitably get mixed in from steel raw materials (raw material ore,
8
scrap, etc.), and reduction of the P content to below 0.001% will increase the production cost
greatly. Therefore, the P content may be 0.001% or more from the viewpoint of production
cost.
[0037] S: 0.020%% or less
S is an impurity element, which disturbs workability, weldability, and stress
corrosion cracking resistance.
When the S content exceeds 0.020%, the workability, weldability, and stress
corrosion cracking resistance decrease remarkably. Therefore the S content is 0.020% or
less.
Even in a case in which S is added for improvement of molten metal flow in welding,
S is added at a content of 0.020% or less. The S content is preferably 0.0 I 0% or less.
[0038) Preferably the S content is as low as possible, and may be even 0%.
However, S may inevitably get mixed in from steel source materials (raw material
ore, scrap, etc.) and reduction of the S content to below 0.001% will increase the production
cost greatly. Therefore, the S content may be 0.001% or more rrom the viewpoint of
production cost.
[0039) Cr: 21.50 to 28.00%
Cr is a major element of a high Cr-based austenitic stainless steel, which contributes
to improvement of high temperature corrosion resistance and stress corrosion cracking
resistance, as well as to improvement of the strength and stabilization of a metallic structure
with a Cr carbonitride.
Especially, in a case in which importance is placed on high temperature corrosion
resistance and stress corrosion cracking resistance, when the Cr content is less than 21.50%,
adequate high temperature corrosion resistance and stress corrosion cracking resistance
cannot be obtained. Therefore, the Cr content is 21 .50% or more, and is preferably 22.00%
or more.
[0040) When the Cr content exceeds 28.00%, a brittle phase such as a a-phase is formed to
deteriorate the high temperature strength, toughness, workability, and weldability. Therefore,
the Cr content is 28.00%, and is preferably 27.00% or less, more preferably 26.00% or less,
and particularly preferably 26.50% or less.
[0041) Ni: more than 26.00 and not more than 35.00%
Ni is a major element of an austenitic stainless steel, which contributes to
improvement of high temperature strength and workability as well as to stabilization of a
metallic structure at a high temperature. Especially, in the case of an austenite stainless steel
9
with a high Cr content, a considerable amount ofNi is required to be added for stabilizing a
metallic structure at a high temperature, and suppressing precipitation of a brittle phase.
[0042] When the Ni content is 26.00% or less, the addition effect cannot be obtained
adequately. Therefore, the Ni content is more than 26.00%, and preferably 28.00% or more.
When the Ni content exceeds 35.00%, the high temperature strength, weldability, and
economic efficiency are decreased. Therefore, the Ni content is 35.00% or less, and is
preferably 34.00% or less, more preferably 33.00% or less, and particularly preferably
32.00% or less.
[0043] W: more than 2.00 and not more than 5.00%
Since W is slow in diffusion at a high temperature, it is an element, which maintains
a stable metallic structure, and a strength in a high temperature range for a long time period to
contribute to improvement of stress corrosion cracking resistance, and high temperature
strength.
When theW content is 2.00% or less, adequate stress corrosion cracking resistance
and high temperature strength cannot be secured. Therefore, theW content is more than
2.00%, and is preferably 2.20% or more.
[0044] When the W content exceeds 5.00%, a brittle phase is increased, whereby the
workability, strength, and weldability are decreased. Therefore, the W content is 5.00% or
less, and is preferably 4.80% or less.
[0045] Co: 0.80% or less
Co is an element, which stabilizes a metallic structnre to contribute to improvement
of high temperature strength. Co is an optional element, and the Co content may be 0%.
From the viewpoint of obtaining the effect of Co more effectively, the Co content is
preferably 0.01% or more, and more preferably 0.03% or more.
When the content exceeds 0.80%, the addition effect is saturated, and the Co content
becomes high in producing another steel. Therefore, the Co content is 0.80% or less, and is
preferably 0.60% or less.
[0046] V: 0.01 to 0.70%
Vis an element contributing to improvement of high temperature strength by
forming a fine carbonitride together with Nb. When the V content is less than 0.01 %, a
combined effect of combined addition with Nb cannot be obtained. Therefore, the V content
is 0.01% or more, and is preferably 0.03% or more.
When the V content exceeds 0. 70%, the strength or stress corrosion cracking
resistance decreases. Therefore, the V content is 0.70% or less, and is preferably 0.60% or
10
less.
[004 7] Nb: 0.15 to 1.00%
Nb is an element contributing to improvement of high temperature strength by
forming a fine carbonitride together with V, and contributing also to improvement of stress
corrosion cracking resistance through suppression of precipitation of a Cr-based carbonitride
at a crystal grain boundary by fixing C. Nb is also an element contributing to improvement of
the high temperature strength due to precipitation of a fine Laves phase.
[0048] When the Nb content is less than 0.15%, the addition effect is not obtained
adequately. Therefore, the Nb content is 0.15% or more, and is preferably 0.20% or more.
When the Nb content exceeds 1.00%, a clumpy precipitate is precipitated to decrease
the strength, toughness, and stress corrosion cracking resistance. Therefore, the Nb content
is 1.00% or less, and is preferably 0.90% or less, more preferably 0.80% or less, and further
preferably 0. 70% or less.
[0049] AI: 0.001 to 0.040%
AI is an element which functions as a deoxidizing element in steel making to purifY a
steel.
When the AI content is less than 0.001 %, purification of a steel cannot be achieved
adequately. Therefore, the AI content is 0.001% or more, and is preferably 0.003% or more.
[0050] When the AI content exceeds 0.040%, a large amount of nonmetallic inclusion is
formed, whereby the stress corrosion cracking resistance, high temperature strength,
workability, toughness, and stability of a metallic structure at a high temperature are
decreased. Therefore, the AI content is 0.040% or less, and is preferably 0.030% or less, and
more preferably 0.020% or less.
[0051] B: 0.0001 to 0.0100%
B is an essential element for improvement of the high temperature strength and stress
corrosion cracking resistance. Namely, B is an element not only to contribute to
improvement of the high temperature strength through segregation at a crystal grain boundary,
but also to contribute to formation of a carbonitride, micronization of a Laves phase, and
stabilization of a metallic structure, which are effective for improvement of the high
temperature strength.
B is also an element, which contributes to improvement of the stress corrosion
cracking resistance through a synergistic effect of combined addition with Ta, etc.
[0052] When the B content is less than 0.0001%, the addition effect cannot be obtained
adequately. Therefore the B content is 0.0001% or more, and is preferably 0.003% or more.
11
When the B content exceeds 0.0 I 00% the workability, weldability, and high
temperature strength decrease remarkably. Therefore the B content is 0.0 I 00% or less, and
is preferably 0.0070% or less.
[0053] N: 0.010 to 0.400%
N is an element essential for securing a high temperature strength with respect to a
high Cr-based austenitic stainless steel through solid solution strengthening and precipitation
strengthening with a carbonitride.
N is an essential element for suppressing a brittle phase or stabilizing a metallic
structure with respect to a high Cr-based austenitic stainless steel together with Ni, Mn, etc.
[0054] When theN content is less than 0.010%, the addition effect cannot be obtained
adequately. Therefore, theN content is 0.010% or more, and is preferably 0.050% or more.
When theN content exceeds 0.400%, a blowhole defect is formed in a steel, and a
clumpy nitride precipitates at a high temperature, whereby stress corrosion cracking resistance
is deteriorated. Therefore theN content is 0.400% or less, and is preferably 0.300% or less.
[0055] Zr: 0.00 I to 0.200%
Zr is an element, which contributes to improvement of stress corrosion cracking
resistance, and high temperature strength by addition of only a trace amount thereof. A Zr
nitride or a Zr oxide constitutes a precipitation nucleus for a fine carbonitride in a high
Cr-based austenitic stainless steel, such that the stress corrosion cracking resistance is
improved.
[0056] When the Zr content is less than 0.001%, the addition effect cannot be obtained
adequately. Therefore, the Zr content is 0.001% or more, and is preferably 0.003% or more.
When the Zr content exceeds 0.200%, a large amount of Zr nitride or Zr oxide is
formed to deteriorate the toughness, workability, corrosion resistance, and weldability.
Therefore, the Zr content is 0.200% or less, and is preferably 0.150% or less. Zr is added in
an appropriate amount combinedly with Ta and Nd, and the aspect will be described below.
[0057] Nd: 0.001 to 0.200%
Nd is an essential element for improving the stress corrosion cracking resistance
through a synergistic effect of combined addition with Ta and Zr.
With respect to the steel of the embodiment, as described above, the stress corrosion
cracking resistance is improved by micronizing a carbonitride and a Laves phase, by securing
the long term stability, and by strengthening a crystal grain boundary through combined
addition ofNd and B. However, even when Nd in a form of metal Nd is added, if it
precipitates as a clumpy oxide or nitride, Nd is consumed uselessly.
12
[0058] When the Nd content is less than 0.001%, the addition effect is not obtained
adequately. Therefore, the Nd content is 0.00 I% or more, and is preferably 0.003% or more.
When the Nd content exceeds 0.200%, the addition effect is saturated, and an
inclusion based on an oxide or a nitride is fanned, whereby the stress corrosion cracking
resistance, high temperature strength, and weldability are decreased. Therefore, the Nd
content is 0.200% or less, and is preferably 0.170% or less, and more preferably 0.150% or
less. Nd is added in an appropriate amount combinedly with Ta and Zr, and the aspect will
be described below.
[0059] Ta: 0.00 I to 0.200%
Ta is an element, which contributes to improvement of stress corrosion cracking
resistance by addition of only a trace amount thereof. Namely, Ta is an element, which
contributes to micronization of a carbonitride, improvement of a long term strength at a high
temperature, stabilization of a metallic structure, etc. in a high Cr-based austenitic stainless
steel, and from which an excellent effect may be expected by combined addition with Nd and
Zr.
[0060] When the Ta content is less than 0.001%, the addition effect is not obtained
adequately. Therefore, theTa content is 0.001% or more, and is preferably 0.003% or more.
When the Ta content exceeds 0.200%, an inclusion based on an oxide increases,
whereby the stress corrosion cracking resistance, high temperature strength, workability, and
weldability are deteriorated. Therefore, the Ta content is 0.200% or less, and is preferably
0.180% or less, and more preferably 0.150% or less. Ta is added in an appropriate amount
combinedly with Nd and Zr, and the aspect will be described below.
[0061] Ta+0.8Nd+0.5Zr: 0.020 to 0.200%
When Ta, Nd, and Zr are added in appropriate amounts combinedly in a high
Cr-based austenitic stainless steel, which contains from 21.50 to 28.00% ofCr, and in which
trace amounts of impurity elements including Ti (an impurity element in the case of the steel
of the embodiment) are restricted strictly, the stress corrosion cracking resistance is improved
remarkably owing to a synergistic effect of the 3 elements.
[0062] The synergistic effect is an effect not attainable through independent addition of each
element ofTa, Nd, and Zr, but attainable only by combined addition of the 3 elements ofTa,
Nd, and Zr.
The synergistic effect of combined addition of the 3 elements is a novel effect
discovered by the inventors.
[0063] The synergistic effect of combined addition of the 3 elements is:
13
(a) an effect by which precipitation of a coarse carbonitride causing stress cotTosion
cracking at a crystal grain boundary is suppressed by combined addition of the 3 elements in
an appropriate amount (suppression of sensitization), as a result of which a carbonitride is
precipitated in a state finely dispersed in a crystal grain and the stress corrosion cracking
resistance is improved;
(b) an effect by which a carbonitride stable for a long time period at a high temperature
is formed by combined addition of the 3 elements in an appropriate amount, as a result of
which the high temperature creep strength at 700"C or higher is improved; and
(c) an effect by which a W-based Laves phase contributing greatly to a high temperature
strength is precipitated finely, and stabilized in a high temperature range, as a result of which
a high strength not obtainable with a conventional steel is achieved.
[0064] According to the embodiment, in order to rate the action effect of each element ofT a,
Nd, and Zr equally, and to evaluate fairly a synergistic effect of combined addition thereof,
the amount of "Ta+0.8Nd+0.5Zr" (each element symbol represents the content(% by mass) of
each element) is used as an index.
In "Ta+0.8Nd+0.5Zr", the Nd content is multiplied with the atomic weight ratio with
respect to Ta, namely 0.8 ("'144(Nd)/18l(Ta)), to get "0.8Nd"; the Zr content is multiplied
with the atomic weight ratio with respect to Ta, namely 0.5 ("'ll(Zr)/181(Ta)), to get "0.5Zr";
and the "0.8Nd" and "0.5Zr" are added to theTa content.
[0065] When "Ta+0.8Nd+0.5Zr" is less than 0.020%, the synergistic effect cannot he
obtained adequately. Therefore, "Ta+0.8Nd+0.5Zr" is 0.020% or more, and is preferably
0.050% or more, and more preferably 0.080% or more.
[0066] When "Ta+0.8Nd+0.5Zr" exceeds 0.200%, the addition effect is saturated, and an
inclusion based on an oxide is increased to deteriorate the strength, toughness, weldability,
and workability. Therefore, "Ta+0.8Nd+0.5Zr" is 0.200% or less, and is preferably 0.195%
or less, more preferably 0.170% or less, and particularly preferably 0.140% or less.
[0067] In the steel of the embodiment, for securing the synergistic effect of from 0.020 to
0.200% of "Ta+0.8Nd+0.5Zr", the steel of the embodiment is highly purified by restricting
strictly the contents of impurity elements, namely Ti, Sn, Sb, Ph, As, Bi, and 0.
Although Ti is ordinarily treated as an effective addition element, it is treated as an
impurity element in the steel of the embodiment.
[0068] Ti: 0.010% or less
Ti forms a clumpy Ti nitride in an austenitic stainless steel containing a required
amount ofN. The Ti nitride reduces a synergistic effect of combined addition ofT a, Nd, and
14
Zr and deteriorate remarkably stress cracking resistance, high temperature strength,
workability, and weldability.
Consequently, Ti is restricted as an impurity element to the extent possible in the
steel ofthe embodiment. Specifically, the Ti content is limited to 0.010% or less, although it
may get mixed inevitably from a steel source material such as a scrap. The Ti content is
preferably 0.005% or-less.
Since the Ti content is preferably as low as possible, the Ti content may be even 0%.
[0069] Sn: 0.010% or less
Sb: 0.010% or less
Sn and Sb, which are impurity elements, may get mixed inevitably from a steel
source material such as a scrap, and, once mixed, are hardly removed in a refining process.
For securing superior stress corrosion cracking resistance, both the Sn content and
the Sb content should be reduced to the extent possible. Therefore, both ofthe Sn content
and the Sb content are limited to 0.010% or less. The Sn content and the Sb content are
preferably 0.005% or less respectively.
Since both the Sn content and the Sb content are preferably as low as possible, the Sn
content and the Sb content may be respectively even 0%.
[0070] Pb: 0.001% or less
As: 0.001% or less
Pb and As, which are impurity elements, may get mixed inevitably from a steel
source material such as a scrap, and, once mixed, are hardly removed in a refining process.
For securing superior stress corrosion cracking resistance, both the Pb content and
the As content should be reduced to the extent possible. Therefore, both of the Pb content
and the As content are limited to 0.001% or less. The Pb content and the As content are
preferably 0.0005% or less respectively.
Since Pb and As are preferably as low as possible, the Pb content and the As content
may be respectively even 0%.
[0071] Bi: 0.001% orless
Bi, which is an impurity element, is an element that does not get mixed ordinarily,
but may get mixed inevitably from a steel source material such as a scrap. Since Bi is an
element harmful to high temperature strength or stress corrosion cracking resistance, its
content should be reduced to the extent possible. Therefore, the Bi content is limited to
0.001% or less, and is preferably 0.0005% or less.
Since the Bi content is preferably as low as possible, the Bi content may be even 0%.
15
I
[0072] Ti+Sn+Sb+Pb+As+Bi: 0.025% or less
For securing effectively a synergistic effect of combined addition ofT a, Nd, and Zr in
the steel of the embodiment, it is necessary to purify highly a steel not only by limiting the
contents of6 impurity elements (specifically, 6 elements ofTi, Sn, Sb, Pb, As, and Bi)
individually, but also by limiting the total content of the 6 impurity elements (namely,
Ti+Sn+Sb+Pb+As+Bi).
[0073] As per tests by the inventors, when "Ti+Sn+Sb+Pb+As+Bi" (each element symbol
represents the content(% by mass) of each element) exceeds 0.025%, the synergistic effect of
combined addition ofTa, Nd, and Zr is reduced remarkably (see, for example, Comparative
Steel 25 below).
Therefore, for the steel of the embodiment, "Ti+Sn+Sb+Pb+As+Bi" is limited to
0.025% or less. "Ti+Sn+Sb+Pb+As+Bi" is preferably 0.020% or less, and more preferably
0.015% or Jess.
[0074] 0: 0.0090% or less
0 (oxygen) remaining inevitably after refining a molten steel is an element used as
an index of the content of a nonmetallic inclusion. When the 0 content exceeds 0.0090%,
Ta, Nd, and Zr are consumed to form oxides, as a result of which the improvement effect on
stress corrosion cracking resistance (synergistic effect of combined addition) does not develop,
and the high temperature strength, weldability, workability, and toughness decrease.
Therefore, the 0 content is limited to 0.0090% or less, and is preferably 0.0060% or less,
more preferably 0.0030% or less.
[0075] Since the 0 content is preferably as !low as possible, the 0 content may be 0%.
However, 0 may occasionally remain after refining inevitably at 0.0001% or so. Therefore,
from the viewpoint of production cost, the 0 content may be even 0.0001% or more.
[0076] The chemical composition of the steel of the embodiment may include in addition to
the above elements one or more ofCu, Mo, Ca, or Mg; and/or one or more ofY, Sc, Ht; Re, or
lanthanoid elements except Nd.
Any of the elements is an optional element, and therefore each of the contents thereof
maybe 0%.
[0077] Cu: 4.00% or less
Cu is an optional element, and the Cu content may be also 0%.
Cu is an element, which precipitates as a fine Cu phase stable at a high temperature,
and contributes to improvement of a long term strength in a high temperature range of 650°C
or less. When the steel of the embodiment contains Cu, the Cu content is preferably 0.01%
16
or more from the viewpoint of obtaining the above effect further effectively, and more
preferably 0.10% or more.
[0078] When the Cu content exceeds 4.00%, the workability, creep ductility, and strength
decrease. Therefore, the Cu content is 4.00% or less, and is preferably 3.50% or less.
[0079] Mo: 2.00% or less
Mo is an optional element, and the Mo content may be 0%.
Moisan element effective for improvement of the high temperature strength,
corrosion resistance, and stress corrosion cracking resistance. Mo is an element contributing
to formation of a Laves phase or a carbide stable for a long time period at a high temperature
through a synergistic effect of combined addition with W. In a case in which the steel of the
embodiment contains Mo, from the viewpoint of obtaining the effect more effectively, the Mo
content is preferably 0.01% or more, and more preferably 0.02% or more.
[0080] When the Mo content exceeds 2.00%, a brittle phase is formed extensively, and the
workability, high temperature strength, and toughness are deteriorated. Therefore, the Mo
content is 2.00% or less, and is preferably 1.50% or less.
[0081] Ca: 0.20% or less
Ca is an optional element, and the Ca content may be 0%.
Ca may be added as a finishing element for deoxidation. Since the steel of the
embodiment contains Nd, it is preferable that the steel is deoxidized by Cain a refining
process. When the steel of the embodiment contains Ca, from the viewpoint of obtaining
more effectively a deoxidation effect, theCa content is preferably 0.0001% or more, and more
preferably 0.0010% or more.
[0082] When the Ca content exceeds 0.20%, the amount of a nonmetallic inclusion increases
to lower the high temperature strength, stress corrosion cracking resistance, and toughness.
Therefore theCa content is 0.20% or less, and is preferably 0.15% or less.
[0083] Mg: 0.20% or less
Mg is an optional element, and the Mg content may be 0%.
Mg is an element, which contributes to improvement of high temperature strength or
corrosion resistance hy addition of a trace amount thereof. When the steel of the
embodiment contains Mg, from the viewpoint of obtaining more effectively the effect, the Mg
content is preferably 0.0005% or more, and more preferably 0.0010% or more.
[0084] When the Mg content exceeds 0.20%, the strength, toughness, corrosion resistance,
and weldability decrease. Therefore the Mg content is 0.20% or less, and is preferably
0.15% or less.
17
(0085] Total of one or more ofY, Sc, Hf, Re, and lanthanoid elements other than Nd: 0.20%
or less
Any ofY, Sc, Hf, Re and lanthanoid elements other than Nd (namely, La, Ce, Pr, Pm,
Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) is an optional element, and the total content of
the elements may be 0%.
Although Y, Sc, Hf, Re, and lanthanoid elements other than Nd are expensive, they
are elements acting to enhance a synergistic effect of combined addition of Ta, Nd, and Zr.
When the steel of the embodiment contains one or more of the elements, the total content of
the elements is preferably 0.001% or more, and more preferably 0.005% or more.
[0086] When the total content exceeds 0.20%, the amount of a nonmetallic inclusion
increases, whereby the workability, strength, toughness, corrosion resistance, and weldability
decrease. Therefore the total content is 0.20% or less, and is preferably 0.15% or less.
(0087] A remainder excluding other than the aforementioned elements from the chemical
composition of the steel of the embodiment is Fe and impurities.
The impurities referred to herein mean one or more of elements other than the
aforementioned elements. The contents of the elements (impurities) other than the
aforementioned elements are preferably limited to 0.010% or less respectively, and more
preferably to 0.001% or less.
(0088] The steel of the embodiment is superior in high temperature strength (especially,
creep rupture stren1,>th) as described above.
There is no particular restriction on the specific range of the high temperature
strength of the steel of the embodiment. The creep rupture strength at 750'C and I 00,000
hours of the steel of the embodiment is preferably 50 MPa or more.
In this regard, the "creep rupture strength at 750'C and I 00,000 hours" means a value
estimated as an average creep rupture strength at 750'C and I 00,000 hours.
(0089] A high temperature strength of 50 MPa or more in terms of a creep rupture strength
at 750'C and I 00,000 hours is a high temperature strength that is remarkably superior to the
high temperature strength of ASME SA213 TP31 OHCbN steel, which is used widely in the
world as a conventional 25 Cr austenitic stainless steel having the highest temperature
strength (see, for example, Inventive Steels I to 18, and Comparative Steel 19 in Table 3
below).
(0090] The strength less than 50 MPa in terms of a creep rupture strength at 750"C and
100,000 hours can be attained by an extension of the conventional art. However a high
temperature strength of 50 MPa or more in terms of the creep rupture strength can be hardly
18
attained by an extension of the conventional art.
In contrast, in the case of the steel of the embodiment, the creep rupture strength can
be attained, for example, through a synergistic effect of combined addition with Ta, Nd, and
Zr, restriction on a chemical composition, and higher degree of purification by restriction on
an impurity element content.
[0091) There is no particular restriction on a method of producing the steel of the
embodiment, and a publicly known method of producing an austenitic stainless steel may be
appropriately adopted.
The steel of the embodiment may be the heat-treated steel plate or the heat-treated
steel tube or pipe.
From the viewpoint of easy formation of a coarse grain structure and easy
improvement of the high temperature strength (for example, creep rupture strength), the
heating temperature of the heat treatment is preferably from 1050 to 1250'C, more preferably
from 1150'C to 1250'C.
Although there is no particular restriction on the mode of cooling after the heating
during the heat treatment, and either of quenching (for example, water cooling) and air
cooling is acceptable, quenching is preferable, and water cooling is more preferable.
[0092) The heat-treated steel plate or the heat-treated steel tube or pipe is obtained for
example by preparing a steel plate or a steel tube or pipe having a chemical composition of
the aforementioned steel of the embodiment, then heating the prepared steel plate or the
prepared steel tube or pipe at, for example, from 1050 to 1250'C (preferably from 1 150'C to
1250'C), and thereafter cooling the same.
The steel plate or the steel tube or pipe having the chemical composition (a steel
plate or a steel tube or pipe before a heat treatment) may be prepared according to an ordinary
method.
A steel tube or pipe having the chemical composition may be prepared, for example,
by casting a molten steel having the chemical composition to form a steel ingot or a steel
billet, and performing at least one kind of a processing selected from the group consisting of
hot extrusion, hot rolling, hot forging, cold drawing, cold rolling, cold forging, and cutting, on
the obtained steel ingot, or steel billet.
[0093) Hereinabove the steel of the embodiment has been described.
There is no particular restriction on an application of the steel of the embodiment,
and the steel of the embodiment may be applied to any application demanding securement of
high temperature strength and stress corrosion cracking resistance.
19
The steel of the embodiment is a material steel suitable for, for example, a
heat-resistant and pressure-resistant heat exchanger tube or a pipe for a boiler, a chemical
plant, or the like; a heat-resistant forged product; a heat-resistant steel bar; or a heat-resistant
steel plate.
The steel of the embodiment is a material steel especially suitable for a heat-resistant
and pressure-resistant heat exchanger tube to be placed inside a boiler (for example, a
heat-resistant and pressure-resistant heat exchanger tube with an outer diameter of from 30 to
70 mm, and a thickness of from 2 to 15 mm), or a pipe of boiler (for example, a pipe with an
outer diameter of from 125 to 850 mm, and a thickness of from 20 to 100 mm).
EXAMPLES
[0094] Next, Examples of the invention will be described, but conditions in the Examples
are just examples of conditions adopted for confirming the feasibility and effectiveness of the
invention, and the invention is not limited to such condition examples. Indeed, many
alternative conditions may be adopted for the invention, insofar as the object of the invention
is achieved without departing from the spirit and scope of the invention.
[0095] In the Examples, 32 kinds of steels, whose chemical compositions are shown in Table
1 and Table 2 (Continuation of Table I), were produced by melting.
In Table I and Table 2, Steels I to 18 are Inventive Steels which are examples of the
invention (hereinafter also referred to as "Inventive Steels I to 18" respectively), and Steels
19 to 32 are Comparative Steels which are comparative examples (hereinafter also referred to
as "Comparative Steels 19 to 32" respectively).
In this regard, Comparative Steel l 9 is a steel corresponding to existing ASME
SA213 TP31 OHCbN, and is a standard material for comparison between the prior art and
Inventive Steels 1 to 18.
[0096] In melt-producing Inventive Steels I to 18, as a Fe source, high purity Fe obtained by
smelting in a blast furnace and a converter and secondary refining by a vacuum oxygen
degassing process was used, and as an alloy element, a high purity alloy element analyzed in
advance was used. Further, before melt-producing any ofinventive Steels I to 18, the
furnace for melt-producing Inventive Steels l to 18 was washed adequately, and special care
was taken so as to prevent contamination with impurities.
Under the above special control, in producing Inventive Steels l to 18, the 6 impurity
elements (specifically, Ti, Sn, Sb, Pb, As, and Bi) content, the 0 content, and the like were
limited, and theTa content, the Nd content, and the Zr content were regulated within an
20
appropriate range.
[0097] In melt-producing Comparative Steels 19 to 32, the high purity Fe source was used
also. Further, in melt-producing Comparative Steels 19 to 32, the chemical compositions
were adjusted as follows.
In melt-producing Comparative Steels 19, 21, 24, 25, 27, and 28 at least one of the 6
impurity elements, or 0 (oxygen) was added intentionally.
ln melt-producing Comparative Steels 19 to 23, and 29 to 31, at least one ofZr, Nd,
or Tawas not added.
In melt-producing Comparative Steels 27, and 28, the addition amount of Zr or Nd
was made excessive.
In melt-producing Comparative Steels 19, 20, 22, 24, 26, 27, and 32, the addition
amount of an alloy element of Cr, Ni, or W was made excessive or insufficient.
[0098]
[Table I]
21
Class Steel c Si Mn p s Cr Ni Co w v Nb A1 B N
1 0.08 0.40 1.00 0.020 0.001 22.05 26.03 0.25 2.10 0.22 0.60 0.011 0.0030 0.170
2 0.05 0.15 1.85 0.005 <0.001 23.00 29.55 0.22 3.45 0.68 0.41 0.008 0.0042 0.220
3 0.10 0.23 0.23 0.017 <0.001 23.45 30.70 0.32 4.75 0.05 0.88 0.013 0.0039 0.170
4 0.07 0.35 1.03 0.011 0.002 25.30 28.75 0.20 2.50 0.34 0.52 0.023 0.0028 0.180
5 0.08 0.50 0.89 0.008 0.001 26.73 32.04 0.26 3.47 0.40 0.75 0.027 0.0037 0.210
6 0.04 0.3 I 2.50 0.004 0.002 25.42 33.20 0.31 2.90 0.69 0.29 0.025 0.0040 0.230
7 0.07 0.29 0.57 0.0\9 0.003 27.40 34.50 0.24 4.10 0.02 0.41 0.007 0.0028 0.190
8 0.05 0.45 2.05 0.013 0.001 24.19 31.00 0.20 3.97 0.55 0.64 0.003 0.0021 0.220
Inventive 9 0.08 0.33 0.86 0.015 0.004 23.31 30.01 0.28 2.87 0.32 0.60 0.011 0.0035 0.190
Steel 10 0.09 0.43 1.60 0.010 <0.00\ 23.78 29.88 0.21 2.71 0.45 0.65 0.002 0.0045 0.200
II 0.07 0.50 1.11 0.004 <0.001 22.99 28.60 0.26 2.68 0.30 0.90 0.013 0.0024 0.180
12 0.10 0.32 0.38 0.005 <0.001 22.04 31.04 0.55 2.80 0.27 0.71 0.008 0.0020 0.150
13 0.08 0.44 0.88 0.006 0.001 22.80 29.85 0.39 3.1 I o. 18 0.75 0.019 0.0023 0.190
14 0.06 0.48 1.31 0.010 0.002 23.47 27.41 0.21 2.45 0.66 0.45 0.014 0.0035 0.170
15 0.04 0.37 2.63 0.017 0.001 24.10 32.04 0.23 2.99 0.38 0.28 0.007 0.0052 0.280
16 0.06 0.28 2.10 0.011 <0.001 25.30 30.14 0.30 2.67 0.47 0.42 0.012 0.0033 0.110
17 0.07 0.20 1.04 0.016 <0.001 25.78 30.09 0.22 2.86 0.22 0.55 0.022 0.0022 0.220
18 0.06 0.39 1.31 0.015 0.002 26.40 31.02 0.40 3.07 0.36 0.43 0.015 0.0040 0.240
19 0.06 0.45 1.23 0.015 0.001 25.01 19.87 0 Q Q 0.45 0.021 Q 0.260
20 0.06 0.89 0.23 0.023 0.002 27.56 30.01 0.02 ill 0.23 0.15 0.008 0.0060 0.020
21 0.07 0.23 0.15 0.021 0.003 22.75 27.85 0.12 2.D4 0.20 0.30 0.012 0.0032 0.110
22 0.08 0.71 0.60 0.019 0.001 20.30 26.40 0.09 3.04 0.30 0.17 0.032 0.0041 0.380
23 0.11 0.36 0.52 0.028 0.003 25.63 26.05 0.18 2.53 0.45 0.20 0.024 0.0050 0.090
24 0.12 0.65 1.36 0.030 0.001 28.70 25.53 0.07 2.20 0.08 0.15 0.015 0.0024 0.170
Comparative 25 0.10 0.42 1.07 0.019 0.001 26.30 27.82 0.17 2.90 0.17 0.21 0.009 0.0008 0.200
Steel 26 0.04 0.26 0.92 0.022 0.002 30.05 26.34 0.05 3.10 0.32 0.16 0.001 0.0035 0.260
27 0.05 0.31 0.80 0.020 0.005 22.85 25.84 0.09 L2Q 0.36 0.20 0.027 0.0028 0.170
28 0.10 0.33 0.47 0.024 0.001 23.65 29.33 0.10 3.45 0.47 0.30 0.025 0.0041 0.240
29 0.03 0.32 0.55 0.028 0.008 22.00 26.20 0.02 2.08 0.05 0.16 0.002 0.0050 O.Dl5
30 0.05 0.25 0.35 0.027 0.005 23.75 27.00 0.05 3.14 0.07 0.17 0.015 0.0074 0.024
31 0.09 0.15 0.20 0.015 0.015 25.40 26.15 0.02 2.78 0.20 0.30 0.025 0.0008 0.030
32 0.04 0.74 0.63 0.023 0.005 27.50 27.31 0.05 1.85 0.35 0.50 0.032 0.0042 0.120
22
[0099]
[Table 2]
23
(Continuation of Table I)
Class Steel Zr Nd Ta Ta+D.8Nd+D.5Zr Ti Sn Sb Pb As Bl
Sub-total 0 Others
(X)
t 0.002 0.015 0.010 0.023 0.005 <0.001 <0.001 <0.001 <0.001 <0.001 0.005 0.0052
2 0.002 0.050 0.002 0.043 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 0 0.0027
3 0.050 0.020 0.050 0.091 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 0 0.0045
4 0.030 0.100 0.100 0.195 0.007 0.006 <0.001 <0.001 <0.001 <0.001 0.013 0.0065
5 0.002 0.010 0.180 0.189 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 0 0.0033
6 0.100 0.170 0.005 0.191 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 0 0.0021
7 0.030 0.011 0.003 0.027 0.009 <0.001 <0.001 <0.001 <0.001 <0.001 0.009 0.0070
8 0.007 0.080 0.110 0.178 0.005 0.005 <0.001 <0.001 <0.001 <0.001 0.010 0.0085 Ca: 0.005, Ce: 0.01
Inventive 9 0.010 0.004 0.130 0.138 <0.001 0.005 0.002 <0.001 <0.001 <0.001 0.007 0.0028 Mo: 0.53
Steel 10 0.003 0.040 0.008 0.042 <0.001 <0.001 <0.001 <0.001 <0.001 <0,001 0.000 0.0025 Y: 0.01
11 0.110 0.050 0.090 0.185 0.005 0.008 0.001 <0,001 <0.001 <0,001 0.014 0.0060 HI: 0.002
12 0.002 0.070 0.120 0.177 <0.001 0.008 <0.001 <0.001 <0.001 <0.001 0.008 0.0088 Cu: 3.50
13 0.150 0.005 0.090 0.169 0.009 0.001 <0.001 <0.001 <0.001 <0.001 0.010 0.0074 Cu: 2.30, Re: 0.005
14 0.070 0.090 0.060 0.167 <0.001 0.001 0.001 <0.001 <0.001 <0.001 0.002 0.0055 Mo: 1 .50, Cu: 3.00, La: 0.002
15 0.003 0.004 0.030 0.035 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 0 0.0038 Sc 0.005
16 0.075 0.060 0.002 0.088 0.008 <0.001 <0.001 <0.001 <0.001 <0.001 0.008 0.0020 Mg: 0.001
17 0.030 0.120 0.080 0.191 0.005 0.003 <0.001 <0.001 <0.001 <0.001 0.008 0.0075 Y: 0.02, Ce: 0.01
18 0.002 0.080 0.120 0.185 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 0 0.0073
19 <0.001 <0.001 <0.001 Q 0.015 0.040 0.010 0.001 <0.001 <0.001 0.066 0.0085
20 <0.001 <0.001 0.150 0.150 <0.001 <0.001 0.009 <0.001 <0.001 <0.001 0.009 0.0089
21 <0.001 0.020 0.005 0.021 0.008 0.009 0.001 0.002 <0.001 <0.001 0.020 0.0075
22 <0.001 0.030 <0.001 0.024 0.007 <0.001 <0.001 <0.001 <0.001 <0.001 0.007 0.0080
23 0.150 <0.001 <0.001 0.075 0.006 0.005 <0.001 <0.001 <0.001 <0.001 0.011 0.0090
24 0.010 0.005 0.020 0.029 0.015 <0.001 <0.001 <0.001 <0.001 <0.001 0.015 0.0081
Comparative 25 0.120 0.001 0.130 0.191 0.009 0.009 0.007 0.001 0.001 0.001 0.028 0.0077
Steel 26 0.002 0.003 0.080 0.083 0.003 0.005 0.008 <0.001 <0.001 <0.001 0.016 0.0056
27 0.002 0.250 0.001 0.202 0.001 0.008 <0.001 <0.001 <0.001 <0.001 0.009 0.0120
28 0.210 0.001 0.002 0.108 <0.001 <0.001 0.008 0.001 0.001 <0.001 0.010 0.0150
29 <0.001 0.002 0.035 0.037 0.005 0.004 <0.001 <0.001 <0.001 <0.001 0.009 0.0085
30 0.055 0.003 <0.001 0.030 0.003 0.006 0.001 0.001 <0.001 <0.001 0.011 0.0079
31 0.020 <0.001 0.020 0.030 0.001 0.009 0.003 0.001 0.001 <0.001 0.015 0.0088
32 0.010 0.003 0.100 0.107 0.008 0.003 0.010 0.001 0.001 <0,001 0.023 0.0075
24
[01 00] -Explanation of Table I and Table 2-
A numerical value represents the content of each element(% by mass).
An underlined numerical value is a value outside the range of the chemical
composition of the embodiment.
A remainder of each steel excluding the elements listed in Table 1 and Table 2 is Fe
and impurities.
In a calculation of "Ta+0.8Nd+0.5Zr", "Ta+0.8Nd+0.5Zr" was calculated by
regarding the content as 0% with respect to an element which content is less than 0.001%
(written in Table 2 as "<0.001 ").
Sub-total (X) shows the total content(% by mass) of the 6 impurity elements
(specifically, Ti, Sn, Sb, Pb, As, and Bi). In this regard, for an element with a content ofless
than 0.001% (written as "<0.00 1" in Table 2), the sub-total (X) was calculated by regarding
the content of the element as 0%.
[0 10 I]
A steel having an chemical composition shown in Table 1 and Table 2 was produced
by melting by vacuum melting and cast to obtain a 50 kg-steel ingot.
By hot forging the obtained steel ingot, a 15 mm-thick steel plate was obtained.
By cutting a surface ofthe obtained 15 mm-thick steel plate, an approximately 12
mm-thick steel plate was obtained.
By performing cold rolling on the obtained approximately 12 mm-thick steel plate at
a cross-section reduction rate of approximately 30%, an approximately 8 mm-thick platy test
material was obtained.
A heat treatment at 1200'C was performed on the test material by heating the test
material to 1200'C, then keeping test material at 1200'C for 15 min, and thereafter cooling
the test material with water. By the heat treatment, both the metallic structures of a test
material of an Inventive Steel and a test material of a Comparative Steel were converted to a
coarse grain structure with anASTM grain size number (ASTM El12) of7 or less.
[01 02]
A corrosion test piece with a width of I 0 mm x a thickness of 4 mm x a length of 40
mm was sliced out from the heat-treated test material. The sliced out corrosion test piece is
hereinafter called as a "base material".
The base material was subjected to a thermal aging treatment at 650'C for I 00 hours
for execution of a corrosion cracking evaluation under a severe condition.
A Strauss test (ASTM A262, Practice E: Sensitization evaluation) was performed as a
25
stress corrosion cracking test on the base material after the thermal aging treatment, and the
crack depth and the cracking state were observed.
The results are shown in Table 3.
[0103] A stress corrosion cracking test after a thennal aging treatment under the above
conditions is a severe test, which has been heretofore not performed quantitatively with
respect to a high Cr-based austenitic stainless steel.
[0104]
A corrosion test piece with a width of I 0 mm x a thickness of 4 mm x a length of 40
mm was sliced out from the heat-treated test material.
The sliced-out test piece was heated at 950'C for 25 sec using a Greeble tester (Joule
heating in vacuum). A weld HAZ equivalent material (i.e. a weld heat affected zone
equivalent material) was obtained by blowing He for cooling after the heating.
A thermal aging treatment similar to the thermal aging treatment on a base material
was conducted on the obtained weld HAZ equivalent material in order to perform a corrosion
cracking evaluation under a severe condition as in the case of a base material.
A Strauss test (ASTM A2622, Practice E: Sensitization evaluation) was conducted as
a stress corrosion cracking test on a weld HAZ equivalent material after the thermal aging
treatment, as on a base material, and the crack depth and the cracking state were observed.
The results are shown in Table 3.
[01 05]
A creep rupture test piece with a size of 6 mm~ and a length of the parallel portion of
30 mm was cut out from the heat-treated test material, whose longitudinal direction was the
longitudinal direction of the test piece. The creep rupture test piece was subjected to a long
term creep rupture test at 750'C for 10,000 hours or longer, and an average creep rupture
strength (MPa) at 750'C and I 00,000 hours was estimated as a high temperature strength.
The results are shown in Table 3.
[01 06]
[Table 3]
Class
Inventive
Steel
Steel
1
2
3
4
5
6
7
Stress corrosion cracking test
(Observation results of cracking state and maximum crack depth)
Base material Weld HAZ equivalent material
Grain boundary cracking< 10~m Grain boundary cracking < 1 O~m
Grain boundary cracking< 10~m Grain boundary cracking < 1 O~m
Grain boundary cracking < 1 O~m Grain boundary cracking< 1 O~m
Grain boundary cracking < 1 O~m Grain boundary cracking < 1 O~m
Grain boundary cracking < 1 O~m Grain boundary cracking< 10~m
Grain boundary cracking< 10~m Grain boundary cracking< 10~m
Grain boundary cracking< 10~m Grain boundary cracking < 1 OjJm
26
High temperature strength
(Creep rupture strength at
750"C and 100,000 hours)
IMPa)
59
65
70
59
62
63
58
8 Grain boundary cracking< 10~m Grain boundary cracking < 1 O~m 59
9 Grain boundary cracking < 1 O~m Grain boundary cracking< 1 O~m 60
10 Grain boundary cracking< 1 O~m Grain boundary cracking< 1 O~m 68
11 Grain boundary cracking< 1 O~m Grain boundary cracking < 1 D11m 72
12 Grain boundary cracking < 1 O!Jm Grain boundary cracking < 101Jm 69
13 Grain boundary cracking < 1 Oj.Jm Grain boundary cracking < 1 O!Jm 61
14 Grain boundary cracking < 1 01Jm Grain boundary cracking < 1 Oj.Jm 63
15 Grain boundary crac-king< 1 01Jm Grain boundary cracking< 1 OjJm 65
16 Grain boundary cracking< 1 D11m Grain boundary cracking< 1 01Jm 59
17 Grain boundary cracking< 1 O!Jm Grain boundary cracking< 10j.Jm 62
18 Grain boundary crackino < 1 Dum Grain boundary crackin0 < 10um 60
19 Many cracks of 2 to 3mm Many cracks of 3 mm or deeper 42
20 Many cracks of 3 mm or deeper Through cracking 30
21 Many cracks of 2 to 3mm Many cracks of 3 mm or deeper 47
22 Many cracks of 3 mm or deeper Through cracking 55
23 Many cracks of 3 mm or deeper Through cracking 50
24 Through cracking Through cracking 51
Comparative 25 Many cracks of 3 mm or deeper Through cracking 52
Steel 26 Many cracks of 3 mm or deeper Many cracks of 3 mm or deeper 35
27 Many cracks of 2 to 3mm Many cracks of 3 mm or deeper 38
28 Many cracks of 2 to 3mm Many cracks of3 mm or deeper 33
29 Many cracks of 2 to 3mm Many cracks of 3 mm or deeper 58
30 Many cracks of 2 to 3mm Many cracks of 3 mm or deeper 55
31 Many cracks of 2 to 3mm Many cracks of 3 mm or deeper 59
32 Grain boundary crackin~ < 1 Dum Grain boundary cracking< 1 D11m 28
[0107] As shown in Table 3, in Inventive Steels 1 to 18, stress corrosion cracking was
suppressed remarkably compared to Comparative Steels 19 to 31, such that merely grain
boundary cracking with a depth of less than 10 J.lm appeared in the base material and the weld
HAZ equivalent materiaL
From this result, it has been demonstrated that Inventive Steels 1 to 18 exhibit
superior stress corrosion cracking resistance even in a severely corrosive enviromnent.
[0108] In contrast to Inventive Steels I to 18, in a steel cotTesponding to a conventional
general-purpose steel TP347HCbN (Comparative Steell9), many large cracks with a depth of
2 mm or more were generated in both the base material and the weld HAZ equivalent
material.
Similarly, in Comparative Steels 20 to 31 as well, many large cracks with a depth of
2 mm or more, or through cracking, which is more serious cracking, was generated in both the
base material and the weld HAZ equivalent material.
[0 1 09] From a comparison of Comparative Steels 1 to 1 8,
with Comparative Steel20, in which theTa content was appropriate, but Nd and Zr
were insufficient, as well as Comparative Steels 21 to 23, and 27 to 31, in which at least one
ofNd, Ta, or Zr was insufficient or excessive,
it bas been demonstrated that it is necessary for suppressing stress corrosion cracking
under a severe condition to control Ta, Nd, Zr, and Ta+0.8Nd+0.5Nd to appropriate contents.
[0 11 0] From a comparison of inventive Steels I to 1 8,
27
with Comparative Steels 24 and 25, in which the contents ofTa, Nd, Zr, and
Ta+0.8Nd+0.5Nd were appropriate, but Ti as one of the 6 impurity elements, or the total of
the 6 impurity elements (sub-total (X)) was excessive,
it has been demonstrated that it is necessary for suppressing stress corrosion cracking
under a severe condition not only to control Ta, Nd, Zr, and Ta+0.8Nd+0.5Nd to appropriate
contents, but also to limit the contents of the 6 impurity elements.
[OJ 1 1] As shown in Table 3, Inventive Steels 1 to 18 exhibited a superior high temperature
strength of 58 MPa or more. The high temperature strength of Inventive Steels 1 to 18 was
about 1.4 times higher or more than the high temperature strength of Comparative Steel 19
(general-purpose steel TP3l OHCbN steel).
In contrast, the high temperature strengths of, for example, Comparative Steels 19 to
21, 26 to 28, and 32 were 47 MPa or less, and inferior to the high temperature strengths of
Inventive Steels 1 to 18.
Especially, from a comparison oflnventive Steels 1 to 18 with Comparative Steels 20,
27, and 32, in which W was insufficient or excessive, it has been demonstrated that it is
necessary for improving a high temperature strength to control the W content to an
appropriate level.
[0112] The entire contents of the disclosures by Japanese Patent Application No.
2015-120592 are incorporated herein by reference.
All documents, patent applications, and technical standards described in this
specification are herein incorporated by reference to the same extent as if each individual
document, patent application, or technical standard was so specifically and individually
indicated to be incorporated by reference.

CLAIMS
l. A high Cr-based austenitic stainless steel with a chemical composition consisting of
in terms of% by mass:
0.03 to 0.12% of C,
0.10 to 1.00% of Si,
0.10 to 3.00% ofMn,
0.030% or less ofP,
0.020% or less of S,
21.50 to 28.00% ofCr,
more than 26.00 and not more than 35.00% ofNi,
more than 2.00 and not more than 5.00% ofW,
0.80% or less of Co,
0.01 to 0.70% ofV,
0.15 to 1.00% ofNb,
0.001 to 0.040% of AI,
0.0001 to 0.0100% ofB,
0.010 to 0.400% ofN,
0.001 to 0.200% ofZr,
0.001 to 0.200% ofNd,
0.001 to 0.200% ofTa,
0.020 to 0.200% ofTa+0.8Nd+0.5Zr,
0.010% or less ofTi,
0.0 l 0% or less of Sn,
0.0 l 0% or less of Sb,
0.001% or less ofPb,
0.00 I% or less of As,
0.001% or less ofBi,
0.025% or less ofTi+Sn+Sb+Pb+As+Bi,
0.0090% or less of 0,
4.00% or less of Cu,
2.00% or less ofMo,
0.20% or less of Ca,
0.20% or less ofMg,
29
0.20% or less in total of one or more of Y, Sc, Hf, Re, or lanthanoid elements other than Nd,
and
a remainder consisting of Fe and impurities.
2. The high Cr-based austenitic stainless steel according to claim 1, wherein the
chemical composition comprises, in terms of% by mass, 0.01 to 0.80% of Co.
3. The high Cr-based austenitic stainless steel according to claim 1 or 2, wherein the
chemical composition comprises, in terms of% by mass, one or more of: 0.01 to 4.00% of Cu,
0.01 to 2.00% ofMo, 0.0001 to 0.20% ofCa, or 0.0005 to 0.20% of Mg.
4. The high Cr-based austenitic stainless steel according to any one of claims 1 to 3,
wherein the chemical composition comprises, in terms of% by mass, 0.001 to 0.20% in total
of one or more ofY, Sc, Hf, Re, or lanthanoid elements other than Nd.
5. The high Cr-based austenitic stainless steel according to any one of claims I to 4,
wherein a creep rupture strength at 750"C and I 00,000 hours is 50 MPa or more.