WO2023238851A1 - Matériau d'alliage inoxydable austénitique - Google Patents

Matériau d'alliage inoxydable austénitique Download PDF

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WO2023238851A1
WO2023238851A1 PCT/JP2023/020959 JP2023020959W WO2023238851A1 WO 2023238851 A1 WO2023238851 A1 WO 2023238851A1 JP 2023020959 W JP2023020959 W JP 2023020959W WO 2023238851 A1 WO2023238851 A1 WO 2023238851A1
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alloy material
content
austenitic stainless
less
precipitates
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PCT/JP2023/020959
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English (en)
Japanese (ja)
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奈央 大瀧
友彰 浜口
孝裕 小薄
克樹 田中
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日本製鉄株式会社
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies

Definitions

  • the present disclosure relates to alloy materials, and more specifically to austenitic stainless steel alloy materials.
  • the austenitic stainless steel alloy material disclosed in Patent Document 2 has, in mass%, C: 0.03 to 0.12%, Si: 0.2 to 2%, Mn: 0.1 to 3%, P: 0.03% or less, S: 0.01% or less, Ni: more than 18% and less than 25%, Cr: more than 22% and less than 30%, Co: 0.04 to 0.8%, Ti: 0.002 % or more and less than 0.01%, Nb: 0.1 to 1%, V: 0.01 to 1%, B: more than 0.0005% and less than 0.2%, sol. It contains Al: 0.0005% or more and less than 0.03%, N: 0.1 to 0.35%, O (oxygen): 0.001 to 0.008%, and the remainder consists of Fe and impurities.
  • the alloy material disclosed in this document contains Ti, Nb, and V to generate precipitates when used in a high-temperature environment, thereby increasing creep strength.
  • the austenitic stainless steel alloy material according to the present disclosure is In mass%, C: 0.03-0.12%, Si: 0.05-2.00%, Mn: 0.05-3.00%, P: 0.03% or less, S: 0.010% or less, Ni: 18.0 to less than 25.0%, Cr: less than 22.0 to 30.0%, Co: 0.04-0.80%, Ti: 0.002 to 0.010%, Nb: 0.1-1.0%, V: 0.01-1.00%, Al: 0.001 to less than 0.030%, N: 0.10-0.35%, Mo: 0-1.00%, W: 0-1.00%, B: 0 to 0.010%, and Contains Ca: 0 to 0.0100%, the remainder consists of Fe and impurities, The number density of precipitates with an equivalent circle diameter of 0.5 to 2.0 ⁇ m is 5000 pieces/mm 2 or more.
  • the present inventors investigated an austenitic stainless steel alloy material that can have both excellent creep strength and excellent stress relaxation cracking resistance.
  • the present inventors attempted to achieve both excellent creep strength and excellent stress relaxation cracking resistance from the viewpoint of chemical composition.
  • C 0.03 to 0.12%
  • Si 0.05 to 2.00%
  • Mn 0.05 to 3.00%
  • P 0.03% or less
  • S 0.010% or less
  • Ni 18.0 to less than 25.0%
  • Cr 22.0 to less than 30.0%
  • Co 0.04 to 0.80%
  • Nb 0.1 to 1.0%
  • V 0.01 to 1.00%
  • Al 0.01 to less than 0.030%
  • N 0.10 to 0.35%
  • Mo 0 -1.00%
  • W 0-1.00%
  • B 0-0.010%
  • Ca 0-0.0100%
  • the balance is Fe and impurities.
  • the present inventors intentionally removed the fine precipitates from the austenitic stainless steel alloy material. We thought that by pre-existing it in stainless steel alloy materials, it would be possible to increase not only creep strength but also stress relaxation cracking resistance.
  • the present inventors have developed a method that can be used in high-temperature environments by reducing the amount of precipitates in the alloy material as much as possible, like the conventional austenitic stainless steel alloy materials such as Patent Document 1 and Patent Document 2.
  • a method that can be used in high-temperature environments by reducing the amount of precipitates in the alloy material as much as possible, like the conventional austenitic stainless steel alloy materials such as Patent Document 1 and Patent Document 2.
  • Patent Document 1 and Patent Document 2 We have discovered that it is possible to achieve both excellent creep strength and excellent stress relaxation cracking resistance by deliberately allowing 5000 or more fine precipitates/ mm2 to exist in the austenitic stainless steel alloy material, rather than increasing the creep strength of the material.
  • the austenitic stainless steel alloy material of this embodiment was completed.
  • the austenitic stainless steel alloy material of this embodiment which was completed based on the above technical idea, has the following configuration.
  • S 0.010% or less Sulfur (S) is unavoidably contained.
  • the S content is over 0%. S segregates at the grain boundaries of the alloy material. If the S content exceeds 0.010%, even if the contents of other elements are within the ranges of this embodiment, the above-mentioned segregation occurs and stress relaxation cracking resistance decreases. Therefore, the S content is 0.010% or less. It is preferable that the S content is as low as possible. However, excessive reduction in S content increases the manufacturing cost of the alloy material. Therefore, considering normal industrial production, the preferable lower limit of the S content is 0.001%. A preferable upper limit of the S content is 0.008%, more preferably 0.006%, still more preferably 0.004%, and still more preferably 0.003%.
  • a preferable upper limit of the Cr content is 29.9%, more preferably 29.8%, even more preferably 29.5%, still more preferably 29.0%, and even more preferably 28.5%. %, more preferably 28.0%, still more preferably 27.5%, even more preferably 27.0%.
  • the chemical composition of the austenitic stainless steel alloy material of this embodiment may further contain one or more selected from the group consisting of Mo and W in place of a part of Fe. These elements are optional elements, and all of them increase the creep strength of the austenitic stainless alloy material.
  • the preferable lower limit of the B content is more than 0%, more preferably 0.001%, and still more preferably 0.002%.
  • a preferable upper limit of the B content is 0.009%, more preferably 0.008%, still more preferably 0.007%, and still more preferably 0.006%.
  • the austenitic stainless steel alloy material of this embodiment may further contain Ca.
  • Ca 0 ⁇ 0.0100%
  • Calcium (Ca) is an optional element and may not be included. That is, the Ca content may be 0%.
  • Ca When Ca is contained, that is, when the Ca content is more than 0%, Ca fixes O (oxygen) and S (sulfur) as inclusions and improves the hot workability of the alloy material. If even a small amount of Ca is contained, the above effects can be obtained to some extent. However, if the Ca content exceeds 0.0100%, even if the contents of other elements are within the range of this embodiment, the cleanliness of the alloy material will decrease and the hot workability of the alloy material will decrease. . Therefore, the Ca content is 0 to 0.0100%, and if contained, the Ca content is 0.0100% or less.
  • fine precipitates With an equivalent circle diameter of 0.5 to 2.0 ⁇ m are defined as "fine precipitates".
  • the fine precipitates keep the crystal grains of the austenitic stainless alloy material fine due to the pinning effect. As a result, the grain boundary area of the austenitic stainless steel alloy material increases, and stress relaxation cracking resistance increases. Furthermore, fine precipitates with an equivalent circle diameter of 0.5 to 2.0 ⁇ m exhibit a precipitation-strengthening function during use in a high-temperature environment, increasing the creep strength of the austenitic stainless alloy material.
  • the preferable lower limit of the number density ND of fine precipitates is 5200 pieces/mm 2 , more preferably 5500 pieces/mm 2 , even more preferably 6000 pieces/mm 2 , and still more preferably 6200 pieces/mm 2 be.
  • the number density ND of fine precipitates can be determined by the following method.
  • a test piece is taken from an austenitic stainless steel alloy material. If the austenitic stainless steel alloy material is an alloy tube, collect a test piece including the thick center part. Among the surfaces of the test pieces, the surface that is a cross section perpendicular to the tube axis direction of the alloy tube and that includes the central part of the wall thickness is used as the observation surface, and the central part of the wall thickness is used as the observation field of view.
  • the austenitic stainless steel alloy material is an alloy plate
  • the surface that is a cross section perpendicular to the rolling direction of the alloy plate and includes the central part of the plate thickness is used as the observation surface, and the central part of the plate thickness is used as the observation field of view.
  • the observation surface After mirror-polishing the observation surface, use an optical microscope to obtain a microstructure photograph of the observation field in the mirror-polished observation surface at a magnification of 500 times.
  • the area of the observation field is 140 ⁇ m ⁇ 160 ⁇ m.
  • the equivalent circle diameter of the particles in the observation field is determined.
  • the equivalent circle diameter means the diameter of a circle having the same area as the particle area.
  • the equivalent circle diameter can be determined by well-known image processing. Particles during visual field observation can be easily identified by contrast. Particles with an equivalent circle diameter of 0.5 to 2.0 ⁇ m are recognized as precipitates (fine precipitates).
  • the number density (number/mm 2 ) of fine precipitates is determined based on the number of all fine precipitates in the observation field and the area of the observation field. Note that the fine precipitates are, for example, one or more of Ti precipitates containing Ti, Nb precipitates containing Nb, and V precipitates containing V.
  • the austenitic stainless steel alloy material of this embodiment satisfies Feature 1 and Feature 2.
  • the austenitic stainless alloy material of this embodiment can have both excellent creep strength and excellent stress relaxation cracking resistance.
  • microstructure of austenitic stainless steel alloy material The microstructure of the alloy material of this embodiment consists of austenite.
  • the shape of the austenitic stainless alloy material of this embodiment is not particularly limited.
  • the austenitic stainless steel alloy material may be an alloy tube or an alloy plate.
  • the austenitic stainless steel alloy material may be a bar material.
  • the austenitic stainless alloy material of this embodiment is an alloy tube.
  • the manufacturing method described below is an example of the manufacturing method of the austenitic stainless alloy material of this embodiment. Therefore, the austenitic stainless steel alloy material of this embodiment may be manufactured by a manufacturing method other than the manufacturing method described below. However, the manufacturing method described below is a preferable example of the manufacturing method of the austenitic stainless alloy material of this embodiment.
  • the method for manufacturing an alloy material of this embodiment includes the following steps.
  • Step 1) Preparation step (Step 2) Hot working step (Step 3) High temperature holding step (Step 4) Cold working step (Step 5) Precipitation heat treatment step
  • the holding temperature in the high temperature holding step is defined as T1 (°C)
  • the holding time at the holding temperature T1 is defined as t1 (minutes)
  • the heat treatment temperature in the precipitation heat treatment step is T2 (°C).
  • a material having a chemical composition that satisfies the above feature 1 is prepared.
  • Materials may be supplied or manufactured by a third party.
  • the material may be an ingot, a slab, a bloom, or a billet.
  • a molten alloy having a chemical composition that satisfies feature 1 above is produced.
  • an ingot is produced by an ingot-forming method.
  • a slab, bloom, or billet may be produced by a continuous casting method.
  • a billet may be manufactured by hot working the manufactured ingot, slab, or bloom.
  • an ingot may be hot forged to produce a cylindrical billet, and this billet may be used as the raw material.
  • the temperature of the material immediately before the start of hot forging is not particularly limited, but is, for example, 1100 to 1300°C.
  • the method for cooling the material after hot forging is not particularly limited.
  • Step 2 Hot processing step hot working is performed on the material prepared in the preparation step to produce an intermediate alloy material.
  • the intermediate alloy material may be, for example, an alloy tube, an alloy plate, or an alloy bar.
  • the intermediate alloy material is an alloy tube
  • the following processing is performed in the hot processing step.
  • the heating temperature is not particularly limited, but is, for example, 1100 to 1300°C.
  • the alloy tube may be manufactured by performing piercing rolling using the Mannesmann method.
  • the cylindrical material is heated.
  • the heating temperature is not particularly limited, but is, for example, 1100 to 1300°C.
  • the heated cylindrical material is punched and rolled using a punching machine to form a hollow tube.
  • the hollow tube is further subjected to elongation rolling or sizing rolling using a mandrel mill, reducer, sizing mill, etc. to produce an intermediate alloy material (alloy tube).
  • the hot working step uses, for example, one or more rolling mills equipped with a pair of work rolls.
  • the material such as a slab is heated.
  • the heating temperature is not particularly limited, but is, for example, 1100 to 1300°C.
  • the heated material is hot rolled using a rolling mill to produce an intermediate alloy material (alloy plate).
  • the hot working step uses, for example, a blooming mill and/or a continuous rolling mill in which a plurality of rolling mills are arranged in a row.
  • the material is heated.
  • the heating temperature is not particularly limited, but is, for example, 1100 to 1300°C.
  • the heated material is hot rolled using a blooming mill and/or a continuous rolling mill to produce an intermediate alloy material (alloy bar material).
  • Step 3 High temperature holding step
  • the intermediate alloy material produced in the hot working step is held at a high temperature to sufficiently dissolve precipitates in the intermediate alloy material.
  • the holding temperature T1 (° C.) and the holding time t1 (minutes) at the holding temperature T1 in the high temperature holding step are adjusted to the range shown below.
  • the intermediate alloy material cooled to room temperature in the hot working step may be heated to a holding temperature T1 and held at the holding temperature T1 for a holding time t1. Further, the intermediate alloy material immediately after the hot working step (that is, the intermediate alloy material that has not been cooled to room temperature) may be held at the holding temperature T1 for a holding time t1. After the holding time t1 has elapsed, the intermediate alloy material is rapidly cooled.
  • the rapid cooling may be water cooling or oil cooling.
  • Step 4 Cold working step
  • the intermediate alloy material is pickled and then cold worked.
  • the cold working is, for example, cold drawing.
  • the intermediate alloy material is an alloy plate
  • the cold working is, for example, cold rolling.
  • the area reduction rate in the cold working process is not particularly limited, but is, for example, 10 to 90%.
  • Step 5 Precipitation heat treatment step
  • the intermediate alloy material after the cold working step is heat treated to generate fine precipitates in the intermediate alloy material.
  • the heat treatment temperature T2 (° C.) in the precipitation heat treatment step and the holding time t2 (minutes) at the heat treatment temperature T2 are adjusted within the following ranges.
  • the rapid cooling method may be water cooling or oil cooling.
  • F1 is a conditional expression for sufficiently dissolving precipitates (Nb precipitates, Ti precipitates, V precipitates, etc.) in the intermediate alloy material in the high temperature holding step.
  • the austenitic stainless steel alloy material of this embodiment has a high N content of 0.10 to 0.35%. In such a case where the N content is high, in order to sufficiently dissolve the Ti precipitates, an amount of heat corresponding to the Ti content in the alloy material is required. Similarly, in order to sufficiently dissolve Nb precipitates and V precipitates, an amount of heat corresponding to the Nb content and V content of the alloy material is required.
  • the Nb content, Ti content, and V content are arranged in the denominator. That is, F1 is adjusted according to the Nb content, Ti content, and V content in the alloy material. As described above, the austenitic stainless alloy material of this embodiment has a high N content. Therefore, among Nb precipitates, Ti precipitates, and V precipitates, Ti, which has a strong bond with N, is the most difficult to dissolve. Therefore, the coefficient of Ti in F1 is large.
  • F1 is 4100 or more, sufficient heat is applied to the intermediate alloy material in the high temperature holding step to melt Nb precipitates, Ti precipitates, and V precipitates in the intermediate alloy material. Therefore, the precipitates present in the intermediate alloy material can be sufficiently dissolved.
  • a preferable lower limit of F1 is 4200, more preferably 4300.
  • F2 (T2+t2) ⁇ (Nb+50Ti+20V).
  • F2 is a conditional expression for setting the number density ND of fine precipitates to 5000 pieces/mm 2 or more. If F2 is 1000 or more, the number density of fine precipitates will be 5000 pieces/mm 2 or more on the premise that formulas (A) and (B) are satisfied.
  • a preferable lower limit of F2 is 1020, more preferably 1100, and still more preferably 1200.
  • an austenitic stainless steel alloy material that satisfies Features 1 and 2 can be produced.
  • the method for manufacturing the austenitic stainless alloy material of this embodiment is not limited to the above-described manufacturing method. Other manufacturing methods may be used as long as an austenitic stainless steel alloy material that satisfies Features 1 and 2 can be produced.
  • the austenitic stainless alloy material of this embodiment will be explained in more detail with reference to Examples.
  • the conditions in the following examples are examples of conditions adopted to confirm the feasibility and effects of the austenitic stainless alloy material of this embodiment. Therefore, the austenitic stainless alloy material of this embodiment is not limited to this one example condition.
  • the produced ingot was hot forged to produce a cylindrical material with a diameter of 180 mm.
  • the heating temperature of the ingot during hot forging was 1100 to 1300°C.
  • a hot working process was performed on the manufactured cylindrical material. Specifically, the material was heated in a heating furnace. The heating temperature in the hot working step was 1100 to 1300°C. Hot extrusion was performed on the heated cylindrical material to produce a blank pipe.
  • Cold working was performed on the raw tube after the high temperature holding process. Specifically, cold drawing was performed on the raw pipe. Note that the area reduction rate during cold working was 20 to 70%.
  • a precipitation heat treatment process was performed on the raw pipe after the cold working process.
  • the heat treatment temperature T2 (° C.) in the precipitation heat treatment step and the holding time t2 (minutes) at the heat treatment temperature T2 were as shown in Table 2.
  • the F1 value is shown in the "F1” column in Table 2.
  • T (Ture) indicates that the holding temperature T1 was greater than or equal to the heat treatment temperature T2
  • F (False) indicates that the holding temperature T1 was less than the heat treatment temperature T2. shows.
  • the F2 value is shown in the "F2" column.
  • an austenitic stainless steel alloy material (alloy tube) was manufactured.
  • a creep test in accordance with JIS Z2271:2010 was conducted using the collected creep rupture test piece. Specifically, a creep rupture test piece was heated to 700°C. Thereafter, a creep rupture test was conducted. The test stress was 80 MPa. In the test, creep rupture time (hours) was determined.
  • the creep strength was evaluated as follows according to the obtained creep rupture time. Evaluation E (Excellent): Creep rupture time is 1500 hours or more Evaluation B (Bad): Creep rupture time is less than 1500 hours In the case of evaluation E, it was determined that excellent creep strength was obtained. The evaluation results are shown in the "Creep strength" column in Table 2.
  • a C-ring type restrained weld crack test piece shown in FIG. 1 was prepared from the center of the wall thickness of the alloy material (alloy tube) of each test number.
  • the situation was As shown in FIG. 1, a gap G of 1.5 mm was formed in the opening.
  • a notch portion was formed at a position 180° from the opening with respect to the central axis of the C-ring type restrained weld crack test piece when viewed in the tube axis direction.
  • the width NW of the notch portion was 0.4 mm
  • the depth NOD was 0.5 mm
  • the radius of curvature R of the bottom portion was 0.2 mm.
  • the tanned C-ring type restrained weld crack test piece was heat treated at 650° C. for 500 hours. After the heat treatment, the number of cracks occurring at the notch bottom of the C-ring restraint weld crack test piece was counted. Specifically, crack observation test pieces including the notch bottom of the C-ring type restrained weld crack test piece and a cross section perpendicular to the pipe axis direction of the C-ring type restrained weld crack test piece were collected at three locations in the pipe axis direction. did. The surface corresponding to the above-mentioned cross section of each crack observation test piece was taken as the observation surface. After the observation surface was mirror polished, it was etched with a 10% oxalic acid aqueous solution.
  • the stress relaxation cracking resistance was evaluated according to the obtained cracking incidence as follows. Evaluation E: The cracking incidence is 30% or less. Evaluation B: The cracking incidence is more than 30%. In the case of evaluation E, it was determined that excellent stress relaxation cracking resistance was obtained. The evaluation results are shown in Table 2.
  • test numbers 13 and 14 F1 was too low and did not satisfy formula (A). Therefore, in the austenitic stainless steel alloy materials having these test numbers, the number density ND of fine precipitates was less than 5000 pieces/mm 2 . As a result, sufficient stress relaxation cracking resistance could not be obtained.
  • test numbers 18 and 19 F2 was too low and did not satisfy formula (C). Therefore, in the austenitic stainless steel alloy materials having these test numbers, the number density ND of fine precipitates was less than 5000 pieces/mm 2 . As a result, sufficient creep strength could not be obtained. Furthermore, sufficient stress relaxation cracking resistance could not be obtained.

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Abstract

La présente invention concerne un matériau d'alliage inoxydable austénitique qui présente une excellente résistance au fluage et une excellente résistance à la fissuration de relaxation des contraintes. Un matériau d'alliage inoxydable austénitique selon la présente invention contient, en % en masse, 0,03 % à 0,12 % de C, 0,05 % à 2,00 % de Si, 0,05 % à 3,00 % de Mn, 0,03 % ou moins de P, 0,010 % ou moins de S, pas moins de 18,0 % mais moins de 25,0 % de Ni, pas moins de 22,0 % mais moins de 30,0 % de Cr, 0,04 % à 0,80 % de Co, 0,002 % à 0,010 % de Ti, 0,1 % à 1,0 % de Nb, 0,01 % à 1,00 % de V, pas moins de 0,001 % mais moins de 0,030 % d'Al et 0,10 % à 0,35 % de N, tout en ayant une densité en nombre de précipités ayant un diamètre de cercle équivalent de 0,5 µm à 2,0 µm de 5000 par mm2 ou plus.
PCT/JP2023/020959 2022-06-07 2023-06-06 Matériau d'alliage inoxydable austénitique WO2023238851A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020164919A (ja) * 2019-03-29 2020-10-08 日本製鉄株式会社 オーステナイト系耐熱鋼
JP2021021093A (ja) * 2019-07-25 2021-02-18 日本製鉄株式会社 オーステナイト系ステンレス鋼材
WO2021141107A1 (fr) * 2020-01-10 2021-07-15 日本製鉄株式会社 Matériau d'acier inoxydable austénitique
US20210348248A1 (en) * 2018-11-13 2021-11-11 Korea Advanced Institute Of Science And Technology Austenitic stainless steel containing niobium and manufacturing method of the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210348248A1 (en) * 2018-11-13 2021-11-11 Korea Advanced Institute Of Science And Technology Austenitic stainless steel containing niobium and manufacturing method of the same
JP2020164919A (ja) * 2019-03-29 2020-10-08 日本製鉄株式会社 オーステナイト系耐熱鋼
JP2021021093A (ja) * 2019-07-25 2021-02-18 日本製鉄株式会社 オーステナイト系ステンレス鋼材
WO2021141107A1 (fr) * 2020-01-10 2021-07-15 日本製鉄株式会社 Matériau d'acier inoxydable austénitique

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