WO2015133551A1

WO2015133551A1 - Austenitic heat-resistant alloy

Info

Publication number: WO2015133551A1
Application number: PCT/JP2015/056433
Authority: WO
Inventors: 剛夫宮村; 難波　茂信
Original assignee: 株式会社神戸製鋼所
Priority date: 2014-03-05
Filing date: 2015-03-04
Publication date: 2015-09-11
Also published as: US20170067139A1; CN106062230B; KR20160116344A; KR101770536B1; JP6289941B2; EP3115476A1; EP3115476A4; JP2015168834A; CN106062230A

Abstract

An austenitic heat-resistant steel containing, by mass, 0.05-0.16% of C, 0.1-1% of Si, 0.1-2.5% of Mn, 0.01-0.05% of P, less than 0.005% of S, 7-12% of Ni, 16-20% of Cr, 2-4% of Cu, 0.1-0.8% of Mo, 0.1-0.6% of Nb, 0.1-0.6% of Ti, 0.0005-0.005% of B, 0.001-0.15% of N, and 0.005% or less of Mg and/or 0.005% or less of Ca, the amounts of Nb and Ti being 0.3% or above in total, with the remainder being made up by Fe and unavoidable impurities. The cumulative number density of a precipitate has a particle diameter of over 0 nm to 100 nm being 0.1-2.0/μm2, the precipitate particle diameter corresponding to half of the cumulative number density in the distribution of the cumulative number density and the precipitate particle diameter is 70 nm or less, the average hardness is 160 Hv or less, and the grain size number is 7.5 or above.

Description

Austenitic heat resistant steel

The present invention relates to an austenitic heat resistant steel.

Generally, high-temperature processes of several hundred degrees or more are used in energy-related equipment such as boilers and reaction vessels, and heat-resistant materials having excellent creep strength even in high-temperature environments are required.

In this heat-resistant material, in order to obtain excellent creep strength in a high-temperature environment, an element that can be dissolved in steel in a high-temperature environment is added to obtain an effect of solid solution strengthening, and an element that precipitates in a high-temperature environment is added. There are a method of forming precipitates in a high temperature environment to obtain the effect of precipitation strengthening, and a method of coarsening crystal grains to suppress grain boundary sliding.

Among these, the method of coarsening the crystal grains inhibits the formation of the Cr ₂ O ₃ protective film, so that the steam oxidation resistance may be lowered.
Moreover, in order to make the solid solution strengthen work, it is necessary to increase the element addition amount. If the amount of element addition is increased, various basic characteristics other than creep strength may be adversely affected.
Further, when the amount of element addition is increased, the raw material cost increases, and there is a possibility that economic efficiency is impaired. For this reason, a method of obtaining a solid solution strengthening action in a heat resistant material is not desirable as a method of obtaining a desired strength.

On the other hand, it is known that the method of obtaining the effect of precipitation strengthening can strongly suppress the movement of dislocation accompanying deformation and can greatly improve the creep strength. Here, many heat-resistant members are manufactured in the order of softening heat treatment, cold working, and final heat treatment. In these treatments, in order to cause a large amount of precipitation in the actual high-temperature environment or during the creep test, the final heat treatment is performed by heating to a high temperature followed by a rapid cooling treatment in the actual use environment or in the creep test. It is necessary to previously dissolve the element that precipitates therein. Although it is necessary to carry out such a final heat treatment at as high a temperature as possible in order to dissolve a larger amount of the precipitated components, there is a risk of causing coarsening of crystal grains, resulting in a decrease in steam oxidation resistance. There is a possibility.

Under such circumstances, Patent Document 1 discloses an austenitic stainless steel containing one or two of Ti: 0.15 to 0.5 mass% and Nb: 0.3 to 1.5 mass%. In the cold working process, the final softening temperature is set to over 1200 ° C. to 1350 ° C. and heated. After cooling at a cooling rate of 500 ° C./hr or more, 20 to 90% of cold working is added. Next, by heating to a temperature of 1070 to 1300 ° C. and 30 ° C. lower than the final softening temperature, and performing a final heat treatment of cooling at a cooling rate of air cooling or higher, the creep strength is high, and the fine grain structure has good corrosion resistance. A method for producing austenitic stainless steel is disclosed.

In the method disclosed in Patent Document 1, a part of the element to be precipitated in an actual use environment or a creep test is precipitated in a small amount in the above-described final heat treatment stage, and crystallized due to the grain boundary pinning effect by the precipitate. This is to suppress grain coarsening. That is, the method disclosed in Patent Document 1 precipitates the difference in the amount of solid solution corresponding to this temperature difference by raising the softening heat treatment temperature before cold working to a certain level or more with respect to the final heat treatment. Thus, by devising two heat treatment temperatures, improvement in creep strength by high-temperature heat treatment and formation of a structure (fine crystal grain structure) containing a lot of fine crystal grains are achieved.

Japanese Patent Publication No. 5-69885

However, the manufacturing equipment used in actual production has an upper limit temperature. When the softening heat treatment temperature is raised to the equipment upper limit temperature, in order to provide a difference between the two heat treatment temperatures as in the method disclosed in Patent Document 1, it is necessary to set the final heat treatment temperature lower than the equipment upper limit temperature. . However, the decrease in the final heat treatment temperature decreases the amount of precipitation formed in the actual use environment or during the creep test, and as a result, the creep strength may not be sufficiently improved. In particular, the invention disclosed in Patent Document 1 obtains excellent steam oxidation resistance by making a fine grain structure, and obtains a pinning effect of grain boundaries by precipitating a small amount of precipitates. It has a creep strength. However, as described above, lowering the final heat treatment temperature to obtain a pinning effect means that the deposits that should be formed in the actual use environment or during the creep test are used in advance and sacrificed. Conceivable.

In particular, in steel materials such as fire SUS321J1HTB steel and fire SUS321J2HTB steel using Ti as a precipitation element, the presence or absence of fine precipitation of Ti carbide greatly affects the high temperature strength. In the first place, in these steel materials, since the solid solution temperature range of Ti is high, the softening heat treatment temperature often reaches the upper limit due to equipment restrictions. Therefore, in order to provide a temperature difference between the temperature of the softening heat treatment and the final heat treatment temperature, the final heat treatment temperature must be lowered, and the solid solution amount of Ti deposited in the actual use environment or during the creep test cannot be secured. There is a case.

Thus, in principle, it is presumed that the conventional technology cannot sufficiently utilize the precipitation strengthening that can be obtained from the steel material components. In many of the heat-resistant members, the creep strength is a limiting factor that determines the thickness of the member. Therefore, if the creep strength is improved, the thickness can be reduced and the cost can be reduced. However, at present, it is difficult to say that austenitic heat-resistant steel has sufficient creep strength, and it can be said that it has not led to cost reduction.

Further, assuming that the structure of the austenitic heat-resistant steel has a fine grain structure in order to maintain the steam oxidation resistance, the final heat treatment temperature is lowered when the method disclosed in Patent Document 1 is applied. There must be. As described above, when the final heat treatment temperature is lowered, the solid solution amount of the precipitated element is lowered. Therefore, it is presumed that precipitation strengthening cannot be utilized to the maximum and the effect of improving the creep strength cannot be fully expressed.

This invention is made | formed in view of such a condition, and makes it a subject to provide the austenitic heat-resisting steel which has the outstanding creep strength, maintaining a fine grain structure.

Conventionally, the creep strength has been arranged focusing on the solid solution amount of the precipitated element depending on the temperature of the heat treatment. Therefore, generally, when the final heat treatment temperature is lowered, the amount of precipitated elements decreases, and the amount of fine precipitates newly precipitated in the actual use environment or during the creep test is reduced. Has been thought to be lower.

Under such circumstances, in the method disclosed in Patent Document 1, the temperature difference between the softening heat treatment and the final heat treatment is set to 30 ° C. or more, and the precipitation of some precipitation elements is suppressed by the final heat treatment, thereby suppressing the coarsening of crystal grains. is doing. However, as described above, the precipitate that is precipitated by this operation is a precipitate that is supposed to be deposited in the actual use environment or during the creep test and contribute to the improvement of the creep strength. That is, the austenitic stainless steel manufactured by the method disclosed in Patent Document 1 cannot sufficiently improve the creep strength by the amount of the precipitated element to suppress the coarsening of crystal grains. The possibility is high.

The present inventors have intensively studied whether or not the precipitate formed by this final heat treatment can directly affect the improvement of creep strength. As a result, the inventors of the present invention maintain specific amounts of precipitation elements added and solid solution amounts within a certain range, and within a certain range the precipitation particle size and precipitation amount contained in the steel. It was found that the precipitate obtained by performing the final heat treatment at a lower temperature than in the prior art can improve the creep strength.
That is, the present inventors have found that precipitates formed by performing final heat treatment under specific heat treatment conditions contribute to improvement of creep strength as fine precipitates as they are. This finding exceeds the concept of the prior art that the creep strength is superior to conventional precipitates obtained by heat treatment at high temperatures.
It was also found that the final heat treatment is performed under the specific heat treatment conditions described above (lower temperature than before), so that the fine grain structure can be maintained and the steam oxidation resistance can be maintained.

Even when the final heat treatment is performed under specific heat treatment conditions (even if the final heat treatment is performed at a temperature lower than that of the conventional heat treatment), the following reason can be considered as a reason why a good creep strength can be obtained.
The present inventors have now found that, in austenitic heat resistant steel, the precipitate formed by the final heat treatment suppresses creep deformation more effectively than the precipitate formed during the creep test. Usually, precipitates formed during a creep test on an austenitic heat resistant steel are formed along dislocations introduced with deformation. Since dislocations are concentrated in the vicinity of the grain boundaries, the distribution of precipitates becomes nonuniform.
On the other hand, the precipitate formed by the final heat treatment when manufacturing the austenitic heat resistant steel is uniformly formed in the grains. Therefore, it is considered that the precipitate formed by the final heat treatment can efficiently suppress the dislocation movement accompanying the creep deformation from the initial stage of deformation throughout the grain. For these reasons, it is presumed that good creep strength can be obtained when the final heat treatment is performed under specific heat treatment conditions as described above. This knowledge goes beyond the concept of the solid solution amount of the precipitation element depending on the temperature of the conventional heat treatment.

The austenitic heat-resisting steel according to the present invention, which is made on the basis of the above findings and solves the above-mentioned problems, is C: 0.05 to 0.16% by mass, Si: 0.1 to 1% by mass, Mn: 0.0. 1 to 2.5 mass%, P: 0.01 to 0.05 mass%, S: 0.005 mass% or less (excluding 0 mass%), Ni: 7 to 12 mass%, Cr: 16 to 20 % By mass, Cu: 2-4% by mass, Mo: 0.1-0.8% by mass, Nb: 0.1-0.6% by mass, Ti: 0.1-0.6% by mass, B: 0 .0005 to 0.005 mass%, N: 0.001 to 0.15 mass%, and Mg: 0.005 mass% or less (excluding 0 mass%) and Ca: 0.005 mass% At least one of the following (not including 0% by mass), and the total content of Nb and Ti is not less than 0.3% by mass. , The balance being Fe and inevitable impurities, precipitation cumulative number particle size precipitates in the range of 100nm exceeds the 0nm density 0.1-2.0 units / [mu] m ^2, the distribution of the precipitated particles size and the cumulative number density In this case, the precipitation particle diameter corresponding to the half value of the cumulative number density is 70 nm or less, the average hardness is 160 Hv or less, and the crystal grain size number is 7.5 or more.

Since it has such a configuration, the austenitic heat-resisting steel according to the present invention can have precipitates that can be obtained by performing the final heat treatment under a specific heat treatment condition with the steel material component in the above-described range. This precipitate is one in which the particle diameter and the amount of precipitation contained in the steel fall within a certain range, and contributes to the improvement of the creep strength as a fine precipitate as it is after the precipitation. As described above, this fine precipitate can improve the creep strength as compared with the conventional precipitate formed by final heat treatment at a high temperature. In addition to this, since the final heat treatment is performed at specific heat treatment conditions, specifically at a lower temperature than before, the fine grain structure can be maintained and the steam oxidation resistance is excellent. can do.

The austenitic heat-resisting steel according to the present invention further includes Zr: 0.3% by mass or less (not including 0% by mass), rare earth elements: 0.15% by mass or less (not including 0% by mass), and W : It is preferable to contain at least one of 3% by mass or less (not including 0% by mass).

When the austenitic heat-resisting steel according to the present invention contains Zr in the above-described range, the high temperature strength can be improved by precipitation strengthening. Moreover, when the austenitic heat-resisting steel according to the present invention contains a rare earth element in the above-described range, the oxidation resistance of the stainless steel can be improved. Furthermore, when the austenitic heat-resisting steel according to the present invention contains W in the above-described range, the high temperature strength can be improved by solid solution strengthening.

The austenitic heat-resisting steel according to the present invention has the steel material component in the above-described range, and the precipitate particle diameter and the precipitation amount contained in the steel are within a certain range, so that it is excellent while maintaining a fine grain structure. Can have creep strength.

It is a graph explaining obtaining | requiring the precipitation particle diameter corresponded to the half value of the said accumulation number density in distribution of accumulation number density and precipitation particle diameter. The horizontal axis is the precipitated particle size (nm), and the vertical axis is the cumulative number density (pieces / μm ² ).

[Austenitic heat resistant steel]
Hereinafter, the form (embodiment) for implementing the austenitic heat-resisting steel concerning the present invention is explained in detail.
In the austenitic heat-resisting steel according to the present embodiment, the steel material components are C: 0.05 to 0.16 mass%, Si: 0.1 to 1 mass%, Mn: 0.1 to 2.5 mass%, P : 0.01 to 0.05 mass%, S: 0.005 mass% or less (excluding 0 mass%), Ni: 7 to 12 mass%, Cr: 16 to 20 mass%, Cu: 2 to 4 mass %, Mo: 0.1 to 0.8 mass%, Nb: 0.1 to 0.6 mass%, Ti: 0.1 to 0.6 mass%, B: 0.0005 to 0.005 mass%, N: 0.001 to 0.15 mass%, Mg: 0.005 mass% or less (not including 0 mass%) and Ca: 0.005 mass% or less (not including 0 mass%) The total of the Nb content and the Ti content is 0.3% by mass or more, and the balance is Fe and inevitable impurities.
In addition, the austenitic heat-resistant steel according to the present embodiment further includes Zr: 0.3% by mass or less (excluding 0% by mass), rare earth element: 0.15% by mass or less (not including 0% by mass), and It is preferable to contain at least one of W: 3 mass% or less (excluding 0 mass%).
As can be seen from the steel material components described above, the austenitic heat-resistant steel according to the present embodiment is a fire SUS321J2HTB steel (18 mass% Cr-10 mass% Ni-3 mass% Cu-Nb) using Ti as a precipitation element. , Ti steel).

The austenitic heat-resisting steel according to the present embodiment comprising the above-described steel material components has a cumulative number density of precipitates in the range of the precipitate particle diameter exceeding 0 nm and 100 nm, 0.1 to 2.0 pieces / μm ² , In the distribution of the cumulative number density and the precipitated particle size, the precipitated particle size corresponding to the half value of the cumulative number density is 70 nm or less, the average hardness is 160 Hv or less, and the crystal grain size number is 7.5 or more. In the present specification, the precipitated particle diameter refers to a value calculated as the equivalent-circle diameter of the precipitated particles (precipitate).

Here, in the means for solving the problem, it is possible to obtain a precipitate in which the precipitate particle size and the precipitation amount contained in the steel are within a certain range by performing the final heat treatment under specific heat treatment conditions. As stated. The above average hardness and grain size number can also be controlled by controlling the heat treatment temperature. Specific heat treatment conditions and heat treatment temperatures will be described later.

As described above, precipitates obtained by performing specific heat treatment conditions contribute to improvement of creep strength as fine precipitates. In addition, since specific heat treatment conditions are performed, a fine crystal grain structure with fine crystal grains can be maintained. Therefore, the austenitic heat-resistant steel according to the present embodiment is excellent in steam oxidation resistance.

Hereinafter, the steel material component of the austenitic heat-resisting steel according to the present embodiment, the reason for keeping the precipitated particle size and the precipitation amount contained in the steel within a certain range, and the like will be described.
As described above, the austenitic heat-resistant steel according to the present embodiment is similar to the fire SUS321J2HTB steel using Ti as a precipitation element. In the fire SUS321J2HTB steel, the following steel material components have the following effects, and if they deviate from the predetermined contents, the following problems may occur.

[C: 0.05 to 0.16% by mass]
C has the effect | action which forms a carbide | carbonized_material and improves high temperature strength. In this embodiment, in order to acquire the effect | action which improves high temperature strength, 0.05 mass% or more is contained. However, if the C content becomes excessive and exceeds 0.16% by mass, coarse carbides are formed, and the high-temperature strength cannot be improved.
The lower limit of the C content is preferably 0.08% by mass, and more preferably 0.09% by mass. The upper limit of the C content is preferably 0.15% by mass, and more preferably 0.13% by mass.

[Si: 0.1 to 1% by mass]
Si has a deoxidizing action in the molten steel and effectively acts to improve oxidation resistance. In the present embodiment, Si is contained in an amount of 0.1% by mass or more in order to obtain a deoxidizing action in molten steel and an action for improving oxidation resistance. However, if the Si content is excessive and exceeds 1% by mass, the steel material may be brittle, which is not preferable.
In addition, the lower limit of the Si content is preferably 0.2% by mass, and more preferably 0.3% by mass. The upper limit of the Si content is preferably 0.7% by mass, and more preferably 0.5% by mass.

[Mn: 0.1 to 2.5% by mass]
Mn has a deoxidizing action in molten steel. In this embodiment, in order to obtain a deoxidation action in molten steel, 0.1 mass% or more of Mn is contained. However, if the Mn content exceeds 2.5 mass%, it is not preferable because it promotes coarsening of carbide precipitation.
Note that the lower limit of the Mn content is preferably 0.2% by mass, and more preferably 0.3% by mass. The upper limit of the Mn content is preferably 2.0% by mass, and more preferably 1.8% by mass.

[P: 0.01 to 0.05% by mass]
P has the effect of improving the high temperature strength. In the present embodiment, 0.01 mass% or more of P is contained in order to improve the high temperature strength. However, if the P content becomes excessive and exceeds 0.05% by mass, the weldability may be impaired.
The lower limit of the P content is preferably 0.015% by mass, and more preferably 0.02% by mass. The upper limit of the P content is preferably 0.04% by mass, and more preferably 0.03% by mass.

[S: 0.005 mass% or less (excluding 0 mass%)]
S is an inevitable impurity. If the S content becomes excessive and exceeds 0.005% by mass, the hot workability is deteriorated. In the present embodiment, the S content is set to 0.005 mass% or less so as not to deteriorate the hot workability. The smaller the S content, the better.
Note that the upper limit of the S content is preferably 0.002% by mass, and more preferably 0.001% by mass.

[Ni: 7 to 12% by mass]
Ni has the effect of stabilizing the austenite phase. In the present embodiment, 7% by mass or more of Ni is contained in order to stabilize the austenite phase. However, when Ni content exceeds 12 mass%, the cost of steel materials will increase.
In addition, the lower limit of the Ni content is preferably 9% by mass, and more preferably 9.5% by mass. The upper limit of the Ni content is preferably 11.5% by mass, and more preferably 11% by mass.

[Cr: 16 to 20% by mass]
Cr has the effect of improving the oxidation resistance and corrosion resistance of the steel material. In this embodiment, in order to improve the oxidation resistance and corrosion resistance of the steel material, Cr is contained in an amount of 16% by mass or more. However, if the Cr content exceeds 20% by mass, the steel material becomes brittle.
The lower limit of the Cr content is preferably 17.5% by mass, and more preferably 18% by mass. The upper limit of the Cr content is preferably 19.5% by mass, and more preferably 19% by mass.

[Cu: 2 to 4% by mass]
Cu has the effect of forming precipitates in steel and improving high temperature strength. In this embodiment, in order to improve high temperature strength, 2 mass% or more of Cu is contained. However, if the Cu content becomes excessive and exceeds 4% by mass, the effect is saturated.
The lower limit of the Cu content is preferably 2.5% by mass, and more preferably 2.8% by mass. The upper limit of the Cu content is preferably 3.5% by mass, and more preferably 3.2% by mass.

[Mo: 0.1 to 0.8% by mass]
Mo has the effect | action which improves corrosion resistance. In this embodiment, in order to improve corrosion resistance, Mo is contained in an amount of 0.1% by mass or more. However, if the Mo content becomes excessive and exceeds 0.8% by mass, the steel material becomes brittle.
In addition, the lower limit of the Mo content is preferably 0.2% by mass, and more preferably 0.3% by mass. The upper limit of the Mo content is preferably 0.6% by mass, and more preferably 0.5% by mass.

[Nb: 0.1 to 0.6% by mass]
[Ti: 0.1 to 0.6% by mass]
[Total of Nb content and Ti content is 0.3 mass% or more]
Nb and Ti can be precipitated as carbonitrides (carbides, nitrides or carbonitrides) to improve the high-temperature strength. Moreover, this precipitate suppresses the coarsening of crystal grains and promotes the diffusion of Cr. It can be said that it is a part of the most important element in the present invention because it exerts a secondary effect of improving corrosion resistance (water vapor oxidation resistance) by diffusion of Cr.
In the present embodiment, Nb and Ti precipitates are formed to improve the high-temperature strength and to exert the effect of improving the steam oxidation resistance, so that Nb is 0.1% by mass or more and Ti is 0.1%. It is contained by mass% or more. By simultaneously containing Nb and Ti, the contribution to the improvement of the high temperature strength of the precipitate can be further increased.
However, if these are not contained so that the total of the Nb content and the Ti content is 0.3% by mass or more, it is impossible to ensure the minimum necessary precipitation amount.

In addition, it is preferable that the minimum of Nb content shall be 0.2 mass%. The lower limit of the Ti content is preferably 0.15% by mass. The lower limit of the total content of Nb and Ti is preferably 0.35% by mass.
On the other hand, if the Nb content is excessive and exceeds 0.6% by mass, or the Ti content is excessive and exceeds 0.6% by mass, the precipitates become coarse in both cases, and the toughness is increased. Will be reduced.
In addition, it is preferable that the upper limit of content of Nb and Ti is respectively 0.4 mass%, and it is more preferable to set it as 0.3 mass%.

[B: 0.0005 to 0.005 mass%]
B has the effect of promoting the formation of M ₂₃ C ₆ type carbide (M is a carbide forming element) and improving the high temperature strength. In this embodiment, in order to improve high temperature strength, 0.0005 mass% or more of B is contained. However, if the B content becomes excessive and exceeds 0.005% by mass, the weldability is deteriorated.
The lower limit of the B content is preferably 0.001% by mass, and more preferably 0.0015% by mass. The upper limit of the B content is preferably 0.004% by mass, and more preferably 0.003% by mass.

[N: 0.001 to 0.15% by mass]
N has the effect of improving the high-temperature strength by solid solution strengthening. In the present embodiment, N is added in an amount of 0.001% by mass or more in order to improve the high temperature strength. However, if the N content becomes excessive and exceeds 0.15% by mass, the formation of coarse Ti nitrides or Nb nitrides may be caused and the toughness may be deteriorated.
The lower limit of the N content is preferably 0.002% by mass, more preferably 0.003% by mass. The upper limit of the N content is preferably 0.08% by mass, and more preferably 0.04% by mass.

[Mg: at least one of 0.005% by mass or less (not including 0% by mass) and Ca: 0.005% by mass or less (not including 0% by mass)]
Mg and Ca act as desulfurization / deoxidation elements and have an effect of improving the hot workability of the steel material. Depending on the content of S contained as an inevitable impurity, Ca and Mg may be contained in a range of 0.005% by mass or less.
The upper limit of Ca and Mg is preferably 0.002% by mass.

[Zr: 0.3% by mass or less (excluding 0% by mass)]
Zr is an optional component and has the effect of improving the high-temperature strength by precipitation strengthening. However, if the Zr content becomes excessive and exceeds 0.3% by mass, a coarse intermetallic compound is formed, resulting in a decrease in hot ductility.
In addition, it is preferable that the upper limit of Zr content shall be 0.25 mass%.
However, since inclusion of Zr increases the cost of the steel material, it may be included as necessary.

[Rare earth element: 0.15% by mass or less (excluding 0% by mass)]
Rare earth elements are optional components and have the effect of improving the oxidation resistance of stainless steel.
That is, the generation of oxide scale can be suppressed by arbitrarily containing rare earth elements. However, if the content of the rare earth element becomes excessive and exceeds 0.15% by mass, a part of the grain boundary is melted in a high temperature environment and hot workability is hindered.
The upper limit of the rare earth element content is preferably 0.1% by mass, and more preferably 0.05% by mass.
Here, the rare earth element is one or more elements selected from a total of 17 elements including Sc and Y and 15 lanthanoid elements represented by La, Ce, and Nd. The rare earth element content is a total content of one or more elements selected from 17 elements.

[W: 3% by mass or less (excluding 0% by mass)]
W is an optional component and has the effect of improving the high temperature strength by solid solution strengthening. However, if the W content is excessive and exceeds 3% by mass, a coarse intermetallic compound is formed, resulting in a decrease in high temperature ductility.
The upper limit of the W content is preferably 2.5% by mass, and more preferably 2.0% by mass.

The steel material component described above exhibits the above-described action by being contained, but at the same time increases the cost. Therefore, what is necessary is just to set content according to a required reinforcement | strengthening amount and allowable cost.

[The balance is Fe and inevitable impurities]
The balance is Fe and other inevitable impurities. Examples of other inevitable impurities include Al, Sn, Zn, Pb, As, Bi, Sb, Te, Se, and In.
Inevitable impurities are preferably reduced as much as possible. As a guideline, Al is 0.01% by mass or less, Sn is 0.005% by mass or less, Zn is 0.01% by mass or less, and Pb is 0.002%. Mass% or less, As is 0.01 mass% or less, Bi is 0.002 mass% or less, Sb is 0.002 mass% or less, Te is 0.01 mass% or less, Se is 0.002 mass% or less, In is It is recommended that the content be 0.002% by mass or less.

[Average hardness is 160Hv or less]
In the present embodiment, the average hardness (Vickers hardness) is set to 160 Hv or less in order to secure the solid solution amount of the elements that are deposited in the actual use environment or the creep test after the above-described component range. If the average hardness exceeds 160 Hv, the solid solution amount of the element that precipitates in the actual use environment or during the creep test cannot be secured, so the creep strength decreases. In order to set the average hardness to 160 Hv or less, although depending on the above-described component composition, it can be easily obtained by performing a heat treatment at a temperature of 1150 ° C. or higher and cooling by water cooling, for example.
The upper limit of the average hardness is preferably 140 Hv. The lower limit of the average hardness is preferably 100 Hv, more preferably 110 Hv.
In addition, Vickers hardness can be measured based on JISZ2244: 2009, for example.

[Cumulative density of precipitates having a particle diameter exceeding 0 nm and in a range of 100 nm is 0.1 to 2.0 / μm ² ]
[In the distribution of cumulative number density and precipitated particle size, the precipitated particle size corresponding to half the cumulative number density is 70 nm or less]
The cumulative number density of precipitates having a particle diameter exceeding 0 nm and in the range of 100 nm is 0.1 to 2.0 / μm ² , and the distribution of the cumulative number density and the precipitated particle diameter When the precipitated particle diameter corresponding to the half value is 70 nm or less, the creep strength can be improved.
That is, with respect to the precipitates formed by the final heat treatment, the precipitate particle diameter corresponding to half the cumulative number density is kept as fine as 70 nm or less while forming a certain amount of precipitates of 100 nm or less, thus improving the creep strength. Can be made.
The lower limit of the cumulative number density mentioned above is preferably of a 0.3 / μm ^2, and more preferably set to 0.4 / μm ^2.
The upper limit of the precipitated particle diameter corresponding to the half value of the cumulative number density is preferably 60 nm, and more preferably 50 nm. In addition, the lower limit of the precipitated particle diameter corresponding to the half value of the cumulative number density exceeds 0 nm.
The method for measuring the precipitated particle diameter and the cumulative number density will be described later.

[Grain size number is 7.5 or more]
If the crystal grain size number is 7.5 or more, the metal structure is in a sufficiently fine state and can be referred to as a fine crystal grain structure. Therefore, the steam oxidation resistance can be maintained.
In order to set the grain size number to 7.5 or more, the final heat treatment may be performed under specific heat treatment conditions described later.

[Final heat treatment under specific heat treatment conditions]
In order to keep the precipitation particle size and precipitation amount contained in the steel within a certain range and the crystal grain size number to be 7.5 or more, on the premise of the steel material component and the hardness range, The final heat treatment may be performed under the condition that the coarsening factor is 2000 ° C. · min or less. This “condition that the coarsening factor of the precipitate is 2000 ° C./min or less” is the specific heat treatment condition described above.

The coarsening factor of the precipitate is an index representing the influence of heat on the coarsening of the precipitate, and is a value obtained by integrating over time a temperature of 900 ° C. or higher at which the growth of the precipitate proceeds with respect to the temperature history during the heat treatment. is there. Note that this coarsening factor must include not only the heat treatment holding time but also the heating time and cooling time of 900 ° C. or higher. Incidentally, the coarsening factor of a conventional austenitic heat resistant steel that contains Ti as a precipitation element and has sufficiently increased high-temperature strength, such as fire SUS321J2HTB steel, is about 3000 to 7000 ° C./min. On the other hand, in the austenitic heat resistant steel according to this embodiment, as described above, the coarsening factor is set to 2000 ° C. · min or less. The lower limit of the coarsening factor is preferably larger than 473 ° C./min, more preferably 500 ° C./min or more, and even more preferably 821 ° C./min or more.

If the above-mentioned coarsening factor is satisfied, the maximum temperature reached and the holding time can be adjusted according to the constraints of the equipment. Here, in order to form precipitates as in the prior art, it is necessary to carry out the softening heat treatment at a temperature higher by 30 ° C. or more than the final heat treatment to dissolve the precipitated elements. That is, the temperature lower by 30 ° C. than the softening heat treatment is the upper limit temperature of the final heat treatment.

[Measuring method of precipitated particle size and cumulative number density]
In order to determine whether the coarsening factor satisfies the above-described conditions, it is necessary to quantify the number density and size distribution of the precipitates. This can be obtained by collecting a micro image capturing a state in which precipitates are dispersed in a cross section of the steel material, and quantifying this by image analysis. A micro image can be obtained by, for example, photographing a surface of an electropolished steel material with a scanning electron microscope. When the precipitate is fine, a transmission electron microscope may be used instead of the scanning electron microscope. In addition, from the viewpoint of quantitative accuracy, at least 200 precipitates are quantified, and 100 nm exceeding 0 nm may be arranged by a histogram for every 10 nm.

In other words, as shown in the graph of FIG. 1, by plotting the cumulative number density (number / μm ² ) every 10 nm on the vertical axis and the precipitated particle diameter (nm) on the horizontal axis, The “cumulative number density of precipitates having a diameter exceeding 0 nm and in the range of 100 nm” can be understood from numerical values with a horizontal axis of 90 to 100 nm. In addition, regarding “precipitation particle diameter corresponding to half the cumulative number density of precipitates in the range where the precipitation particle diameter exceeds 0 nm and 100 nm”, in the example in the figure, the point of 50 to 60 nm and the point of 60 to 70 nm are It can be understood from the numerical value on the horizontal axis that intersects with the half value of the numerical value of 90 to 100 nm.

Since the austenitic heat-resisting steel according to the present embodiment described above has the steel material component in the above-described range and the precipitated particle diameter and precipitation amount contained in the steel are within a certain range, the fine grain structure is While maintaining, it can have excellent creep strength.
Therefore, conventionally, the grain size has been reduced while sacrificing the amount of precipitation formed in the actual use environment or during the creep test. However, in the austenitic heat-resisting steel according to the present embodiment, it has been conventionally sacrificed. Precipitation can also contribute to the improvement of creep strength. Therefore, the precipitation strengthening action can be maximized even when the upper limit temperature of the heat treatment exists due to equipment restrictions and the like. Thereby, in the austenitic heat-resistant steel using Ti as a precipitation element, it is possible to provide a heat-resistant stainless steel having a further improved creep strength while having a fine grain structure. Since the austenitic heat-resistant steel according to the present embodiment can improve the creep strength, the thickness of the heat-resistant member can be made thinner than before, and the cost reduction as a heat-resistant component can be realized.

Next, the content of the present invention will be described in detail with reference to examples that achieve the effects of the present invention and comparative examples that do not.

Steel component No. shown in Table 1 Various steel materials shown in A to F were melted, and a 20 kg ingot melted in a vacuum melting furnace (VIF) was hot forged into a size of 130 mm width × 20 mm thickness.
Thereafter, softening heat treatment was performed at 1250 ° C., and the base material was processed by cold rolling to a thickness of 13 mm. No. 1 shown in Table 1 Among the steel materials A to F, No. A to E are similar to the so-called fire SUS321J2HTB steel, and are steel materials that satisfy the chemical composition defined in the present invention. In contrast, no. F is a steel material that deviates from the chemical composition defined in the present invention.
In Table 1, numerical values represented by underlines and italics indicate that the requirements of the present invention are not satisfied.

For each of the base materials, the heat treatment temperature and time were changed in the range of 1040 to 1215 ° C. and 0.5 to 10 minutes, that is, the coarsening factor [° C./min] of the precipitate was changed, and Table 2 No. Steel materials shown in 1-31 were prepared. In these steel materials, the Vickers hardness, the cumulative number density of precipitates in the range of more than 0 nm to 100 nm and the distribution of the cumulative number density and the precipitated particle diameter, the precipitated particle diameter corresponding to half the cumulative number density. The grain size number and the creep rupture time were measured as follows. These measurement results are shown in Table 2 together with the coarsening factor.
In Table 2, numerical values represented by underlines and italics indicate that the requirements of the present invention are not satisfied.

(1) Vickers hardness [Hv]
The Vickers hardness is No. A Vickers hardness test was performed on each of the steel materials 1 to 31 in accordance with JIS Z 2244: 2009, and the hardness was measured. The load in the Vickers hardness test was measured at 10 kg. Those having a Vickers hardness of 160 Hv or less were evaluated as being excellent in average hardness, and those having a Vickers hardness exceeding 160 Hv were evaluated as being inferior in average hardness.

(2) Accumulated number density [μm / cm ² ] of precipitates having a particle diameter exceeding 0 nm and in the range of 100 nm
(3) Precipitated particle diameter [μm] corresponding to half the cumulative number density in the distribution of cumulative number density and precipitated particle diameter
The deposited particle size corresponding to the cumulative number density of (2) and the half value of the cumulative number density of (3) was obtained by taking an image of 6000 times from the surface of the electropolished steel material using a scanning electron microscope. Image analysis of 200 or more precipitates was performed, and the graph as shown in FIG. 1 was created to calculate the distribution of cumulative number density and precipitated particle size.
At this time, an image capable of recognizing an object of 20 nm at a magnification of 6000 times was obtained, and it was confirmed by a transmission electron microscope that no finer precipitates existed in this example.

(4) Crystal grain size number
The grain size number is No. With respect to each of the steel materials shown in 1-31, the structure was observed with a microscope in accordance with JIS G 0551: 2013, and the crystal grain size number was measured. Those having a crystal grain size number of 7.5 or more were accepted and those less than 7.5 were rejected.

(5) Creep rupture time [hours]
The creep rupture time is no. Test pieces were prepared from the steel materials shown in 1 to 31 in accordance with JIS Z 2271: 2010, and were tested and measured. Those having a creep rupture time of 650 hours or more were evaluated as being excellent in creep strength, and those having a creep rupture time of less than 650 hours were evaluated as being inferior in creep strength.

As shown in Table 2, No. 1 having the desired effect of the present invention is obtained. 4, 5, 7, 8, 11, 12, 14, 16, 17, 18, 20, 21, 23, 25, 26, 28, the creep rupture time is 650 hours or more, It was confirmed that creep rupture strength superior to that of the comparative example was obtained with the components. In addition, these No. Steel materials shown in 4, 5, 7, 8, 11, 12, 14, 16, 17, 18, 20, 21, 23, 25, 26, and 28 all have fine crystal grains (with a fine crystal grain structure). It was confirmed (all were Examples).
In addition, it is guessed that these examples which are fine crystal grain structures can obtain favorable steam oxidation resistance.

In particular, no. 4 and 7, no. 11 and 14, no. 16 and 18, no. 20 and 23, no. Nos. 25 and 28 are examples in which the latter number is lower than the former number in the heat treatment temperature. 4 and 7, no. 11 and 14, no. Nos. 25 and 28 are examples in which the temperature was lowered by 20 ° C. Nos. 16 and 18 are examples in which the temperature is lowered by 10 ° C. 20 and 23 are examples in which the temperature was lowered by 30 ° C.
Of these, no. 16 and 18, no. 20 and 23, no. From the results of 25 and 28, it was found that the creep rupture time was increased in the latter number compared to the former number heat-treated at high temperature. This finding may be due to an action different from the conventional finding focusing on the solid solution amount of the precipitated element that the effect of improving the creep strength obtained in the present invention is “the higher the heat treatment temperature, the higher the creep strength”. It is shown that.

On the other hand, as shown in Table 2, no. The steel materials shown in 1, 2, 19, and 24 are comparative examples in which crystal grains are coarsened because the heat treatment conditions (the coarsening factor of precipitates) are inappropriate. That is, these steel materials could not be made into a fine grain structure that has been achieved by conventional techniques (for example, the invention described in Patent Document 1). Therefore, these No. It is presumed that the steel materials shown in 1, 2, 19, and 24 cannot obtain good steam oxidation resistance.

Also, No. The steel material shown in No. 9 is a comparative example in which the precipitation component could not be sufficiently dissolved because the coarsening factor of the precipitate was too low. The No. Although the steel material shown in No. 9 had a fine grain structure, it was confirmed that the Vickers hardness (average hardness) deviated from the definition of the present invention and the creep rupture time was reduced.

No. The steel materials shown in 29 to 31 are comparative examples in which the chemical composition deviates from the definition of the present invention.
Of these, No. Although the steel materials shown in 29 and 30 have coarse grains and include elements desirable for creep strength, the creep strength of all the steel materials is less than 650 hours, and an insufficient strength can be obtained as compared with the examples. It was.
No. The steel material shown in No. 31 has a crystal grain size number of 7.5 and a good fine grain structure is obtained, but the creep strength is less than 650 hours, and only an insufficient strength is obtained as compared with the examples. There wasn't.

No. The steel materials shown in 3, 6, 10, 13, 15, 22, and 27 have a good fine crystal grain structure with a crystal grain size number of 7.5 or more. However, these No. The steel materials shown in 3, 6, 10, 13, 15, 22, and 27 are, in the distribution of the cumulative number density of precipitates and the number of precipitated particles in the range of the precipitate particle diameter exceeding 0 nm and 100 nm, The creep rupture time was inferior when compared with the examples (both were comparative examples) because at least one of the precipitate particle diameters corresponding to the half value of the cumulative number density was not satisfied.

From the above, the steel material satisfying the provisions of the present invention (steel material according to the embodiment) has a fine grain structure compared with the steel material not satisfying the provisions of the present invention (steel material according to the comparative example). Was confirmed to be excellent.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on March 5, 2014 (Japanese Patent Application No. 2014-042889), the contents of which are incorporated herein by reference.

Since the austenitic heat-resistant steel of the present invention exhibits excellent creep strength even in a high temperature environment, it is useful for energy-related equipment such as boilers and reaction vessels. Excellent creep strength even in high temperature environments.

Claims

C: 0.05 to 0.16% by mass,
Si: 0.1 to 1% by mass,
Mn: 0.1 to 2.5% by mass,
P: 0.01 to 0.05% by mass,
S: 0.005 mass% or less (excluding 0 mass%),
Ni: 7 to 12% by mass,
Cr: 16 to 20% by mass,
Cu: 2 to 4% by mass,
Mo: 0.1 to 0.8 mass%,
Nb: 0.1 to 0.6% by mass,
Ti: 0.1 to 0.6% by mass,
B: 0.0005 to 0.005 mass%,
N: 0.001 to 0.15% by mass, and
Mg: at least one of 0.005 mass% or less (excluding 0 mass%) and Ca: 0.005 mass% or less (not including 0 mass%),
The total of the Nb content and the Ti content is 0.3 mass% or more,
The balance consists of Fe and inevitable impurities,
The cumulative number density of precipitates having a particle diameter exceeding 0 nm and in the range of 100 nm is 0.1 to 2.0 / μm 2 ,
In the distribution of cumulative number density and precipitated particle size, the precipitated particle size corresponding to half the cumulative number density is 70 nm or less,
The average hardness is 160 Hv or less, and
The grain size number is 7.5 or more
An austenitic heat-resistant steel characterized by this.
Furthermore, Zr: 0.3% by mass or less (not including 0% by mass), rare earth elements: 0.15% by mass or less (not including 0% by mass), and W: 3% by mass or less (not including 0% by mass) The austenitic heat-resisting steel according to claim 1, characterized in that it contains at least one of