JPWO2018181570A1 - Austenitic stainless steel plate and its manufacturing method - Google Patents
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- 229910000963 austenitic stainless steel Inorganic materials 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 238000005096 rolling process Methods 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 51
- 239000010959 steel Substances 0.000 claims description 51
- 238000010438 heat treatment Methods 0.000 claims description 48
- 238000005098 hot rolling Methods 0.000 claims description 39
- 230000009467 reduction Effects 0.000 claims description 22
- 238000006477 desulfuration reaction Methods 0.000 claims description 5
- 230000023556 desulfurization Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 229910052735 hafnium Inorganic materials 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 229910052715 tantalum Inorganic materials 0.000 abstract description 2
- 229910052720 vanadium Inorganic materials 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 238000001953 recrystallisation Methods 0.000 description 30
- 238000005336 cracking Methods 0.000 description 27
- 238000003466 welding Methods 0.000 description 26
- 238000012360 testing method Methods 0.000 description 21
- 239000002253 acid Substances 0.000 description 16
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- 239000000463 material Substances 0.000 description 13
- 239000002244 precipitate Substances 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 229910001566 austenite Inorganic materials 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 229910052761 rare earth metal Inorganic materials 0.000 description 9
- 230000035882 stress Effects 0.000 description 8
- 239000006104 solid solution Substances 0.000 description 6
- 150000001247 metal acetylides Chemical class 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
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- 230000006872 improvement Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
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- 238000005530 etching Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 230000007246 mechanism Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
Abstract
化学組成が、質量%で、Ｃ:0.04%未満、Si:1.5%以下、Mn:2.0%以下、Ｐ:0.04%以下、Ｓ:0.03%以下、Ｎ:0.02〜0.35%、Ｏ:0.03%以下、Nb:0.05〜0.5%、Cr:15.0〜25.0%、Ni:6.0〜30.0%、Al:0〜0.05%、Ti:0〜0.4%、Ｖ:0〜0.4%、Ta:0〜0.2%、Hf:0〜0.2%、Zr:0〜0.2%、Cu:0〜3.0%、Mo:0〜5.0%、Ｗ:0〜5.0%、Co:0〜1.0%、Ｂ:0〜0.012%、Ca:0〜0.02%、Mg:0〜0.02%、および、REM:0〜0.1%、を含有し、残部:Feおよび不純物であり、圧延方向に垂直な断面において、最大結晶粒径が0.3ｍｍ未満である、板厚6.0ｍｍ以上のオーステナイト系ステンレス厚鋼板。Chemical composition, by mass%, C: less than 0.04%, Si: 1.5% or less, Mn: 2.0% or less, P: 0.04% or less, S: 0.03% or less, N: 0.02 to 0.35%, O: 0.03% or less , Nb: 0.05 to 0.5%, Cr: 15.0 to 25.0%, Ni: 6.0 to 30.0%, Al: 0 to 0.05%, Ti: 0 to 0.4%, V: 0 to 0.4%, Ta: 0 to 0.2%, Hf: 0-0.2%, Zr: 0-0.2%, Cu: 0-3.0%, Mo: 0-5.0%, W: 0-5.0%, Co: 0-1.0%, B: 0-0.012%, Ca : 0 to 0.02%, Mg: 0 to 0.02%, and REM: 0 to 0.1%, with the balance being Fe and impurities, and having a maximum crystal grain size of less than 0.3 mm in a cross section perpendicular to the rolling direction. Austenitic stainless steel plate with a thickness of 6.0 mm or more.
Description
本発明は、オーステナイト系ステンレス厚鋼板およびその製造方法に関するものである。 The present invention relates to an austenitic stainless steel plate and a method for producing the same.
石油精製プラントでは、近年の硫黄排出規制の強化に伴い、水素化脱硫装置、または、水素化分解装置の導入が進められている。水素化脱硫装置は、重油に水素を吹き込んで硫黄分を除去する装置である。また、水素化分解装置は、水素化脱硫装置と同様に、重油に水素を吹き込んで硫黄分を除去するとともに、重油を分解し軽質油を製造する装置である。これらの装置は、高温高圧下で稼働するため、その使用材料に、オーステナイト系ステンレス鋼が多く使用されている。 In a petroleum refining plant, introduction of a hydrodesulfurization device or a hydrocracking device has been promoted in accordance with recent tightening of sulfur emission regulations. The hydrodesulfurization device is a device that blows hydrogen into heavy oil to remove sulfur components. In addition, the hydrocracking device is a device that, similar to the hydrodesulfurization device, blows hydrogen into heavy oil to remove sulfur components, and also cracks heavy oil to produce light oil. Since these devices operate under high temperature and high pressure, austenitic stainless steel is often used as a material for the devices.
前述した装置に使用される材料における大きな課題の一つとして、反応生成物であるポリチオン酸（Ｈ２ＳｘＯ６）による「応力腐食割れ」（以下、ＳＣＣ（Ｓｔｒｅｓｓ Ｃｏｒｒｏｓｉｏｎ Ｃｒａｃｋｉｎｇ）と表記する。）の改善がある。ＳＣＣが発生する機構は、以下のメカニズムが一般的に知られている。具体的には、溶接時の入熱、または高温長時間運転時の加熱によって、ステンレス鋼の結晶粒界にＣｒ炭化物が析出し、その近傍でＣｒが欠乏するＣｒ欠乏層が形成され、Ｃｒ欠乏層において割れが伝播していくというものである。One of the major problems in the materials used in the above-described apparatus is “stress corrosion cracking” (hereinafter, referred to as SCC (Stress Corrosion Cracking)) by polythionic acid (H 2 S x O 6 ) as a reaction product. ) There is an improvement. The following mechanism is generally known as a mechanism for generating SCC. Specifically, Cr carbide precipitates at the grain boundaries of stainless steel due to heat input during welding or heating during long-time operation at high temperature, and a Cr-deficient layer in which Cr is depleted is formed in the vicinity thereof, and Cr-deficient layers are formed. Cracks propagate in the layer.
したがって、前述したＳＣＣの抑制対策としては、Ｃｒ炭化物の析出を極力抑制しうる元素が含有された素材を使用することが有効である。例えば、Ｔｉ、または、Ｎｂのような、Ｃｒと比較し炭化物を形成しやすいＣ固定化元素を含有させた、所謂安定型オーステナイト系ステンレス鋼を素材として使用することが適当である。具体的には、Ｔｉを含有するＳＵＳ３２１、Ｎｂを含有するＳＵＳ３４７といった鋼種である（ＪＩＳ規格に準拠する）。 Therefore, as a measure for suppressing the SCC described above, it is effective to use a material containing an element capable of suppressing the precipitation of Cr carbide as much as possible. For example, it is appropriate to use, as a material, a so-called stable austenitic stainless steel containing a C-fixing element, such as Ti or Nb, which easily forms carbide compared to Cr. Specifically, it is a steel type such as SUS321 containing Ti and SUS347 containing Nb (based on JIS standards).
しかしながら、上述の安定型オーステナイト系ステンレス鋼であっても、溶接の際に、入熱の影響を受ける溶接熱影響部（以下、ＨＡＺ（Ｈｅａｔ Ａｆｆｅｃｔｅｄ Ｚｏｎｅ）と表記する。）で、比較的軽度のＣｒ欠乏層を生じる。そして、ポリチオン酸によるＳＣＣの場合、上述した比較的軽度なＣｒ欠乏層であっても割れを生じうる。 However, even the above-mentioned stable austenitic stainless steel is relatively mild in a welding heat affected zone (hereinafter, referred to as HAZ (Heat Affected Zone)) affected by heat input during welding. A Cr-deficient layer is generated. In the case of SCC using polythionic acid, cracks can occur even in the above-described relatively light Cr-deficient layer.
この課題に対して、例えば特許文献１では、Ｃを０．０３％以下に低減し、Ｎを０．０８〜０．４０％、Ｎｂを０．０５〜０．３０％添加し、Ｎｂ／Ｃ≧４、Ｎ／Ｃ≧５とすることにより、耐粒界腐食性、耐粒界ＳＣＣ性を向上させたステンレス鋼が開示されている。 To solve this problem, for example, in Patent Document 1, C is reduced to 0.03% or less, N is added to 0.08 to 0.40%, Nb is added to 0.05 to 0.30%, and Nb / C is added. A stainless steel in which the grain boundary corrosion resistance and the grain boundary SCC resistance are improved by setting ≧ 4 and N / C ≧ 5 is disclosed.
また、非特許文献１では、Ｃを０．０２％以下に低減した上で、０．１％未満の適正なＮを含有させ、さらに、Ｃ固定化元素としては適正な量のＮｂとして、０．２〜０．５％かつＮｂ／Ｃ≧１５を添加したＳＵＳ３４７系のオーステナイト系ステンレス鋼が開示されている。このオーステナイト系ステンレス鋼は、高温強度を確保しつつも、良好な耐ポリチオン酸ＳＣＣ性を有している。 Further, in Non-Patent Document 1, after reducing C to 0.02% or less, an appropriate N of less than 0.1% is contained, and an appropriate amount of Nb as a C-fixing element is 0%. A SUS347-based austenitic stainless steel containing 0.2 to 0.5% and adding Nb / C ≧ 15 is disclosed. This austenitic stainless steel has good polythionic acid SCC resistance while ensuring high-temperature strength.
特許文献２では、Ｃの含有量を低減した上で、適正なＮを含有させ、さらに、Ｃ固定化元素を含有させたオーステナイト系ステンレス鋼が開示されている。このオーステナイト系ステンレス鋼は、耐ポリチオン酸ＳＣＣ性を確保しつつ、ＰおよびＳといった特定の不純物元素を所定以下に低減することで、溶接割れである、ＨＡＺの耐液化割れ性、および長時間時効後の耐脆化割れ性に優れていることを特徴としている。 Patent Document 2 discloses an austenitic stainless steel containing an appropriate amount of N after reducing the content of C and further containing a C-fixing element. This austenitic stainless steel reduces the number of specific impurity elements such as P and S to a predetermined level or less while maintaining the polythionic acid SCC resistance, thereby achieving the liquefaction crack resistance of HAZ, which is a weld crack, and the long-term aging. It is characterized by having excellent resistance to subsequent embrittlement cracking.
ところで、脱硫装置に用いる素材の中で、反応器またはインターナル等に、例えば４５ｍｍといった厚鋼板が用いられる。厚鋼板を製造する場合、鋳片または鋼片（以下、総称して「鋳片」ということがある。）から最終製品までの圧下率が限定されるため、薄鋼板またはシームレス鋼管を製造する際に用いられるような圧下率の高い加工を施すことはできない。その結果、必ずしも再結晶に十分なレベルの加工度を確保できるとは限らない。 By the way, among materials used for a desulfurization device, a thick steel plate of, for example, 45 mm is used for a reactor or an internal. When manufacturing thick steel plates, the reduction rate from the slab or slab (hereinafter sometimes collectively referred to as “slabs”) to the final product is limited, so when manufacturing thin steel plates or seamless steel pipes It is not possible to perform processing with a high draft as used in As a result, it is not always possible to secure a sufficient level of workability for recrystallization.
特許文献１および２、ならびに非特許文献１では、上記のような厚鋼板特有の問題について、十分に検討がなされているとは言えない。 In Patent Literatures 1 and 2, and Non-Patent Literature 1, it cannot be said that the above-described problems specific to thick steel plates have been sufficiently studied.
また、脱硫装置に用いる素材として、これら高耐食オーステナイト系ステンレス鋼を溶接して使用する際には、溶接部に亀裂を生じる溶接割れと呼ばれる現象が発生することがあり、特に高温割れの発生が懸念される。 Also, when welding these highly corrosion-resistant austenitic stainless steels as a material to be used in a desulfurization device, a phenomenon called weld cracking that causes cracks in the weld may occur, and particularly high-temperature cracking occurs. I am concerned.
高温割れには、液化割れ、延性低下割れ等がある。そして、液化割れは、溶接時の入熱により、粒内に析出していたＮｂＣ等の炭化物が固溶し、Ｃ固定化元素もしくはＣ、またはＰ、Ｓ等の粒界偏析傾向の高い元素が粒界に偏析し、融点の低い化合物が形成することに起因する。その結果、２パス目以降の溶接熱サイクルによって、粒界が液化して割れが発生する現象が液化割れである。 Hot cracking includes liquefaction cracking and ductility-reducing cracking. Liquefaction cracks are caused by the heat input during welding, where carbides such as NbC precipitated in the grains form a solid solution, and C-fixing elements or C or elements having a high tendency to segregate at the grain boundaries such as P, S, etc. This is due to segregation at the grain boundaries and formation of a compound having a low melting point. As a result, liquefaction cracking is a phenomenon in which the grain boundaries are liquefied and cracked by the welding heat cycle after the second pass.
一方、延性低下割れは、溶接時の高温ＨＡＺにおいて、溶接熱サイクル中、および高温での使用中にＰ、Ｓ等の粒界脆化元素の偏析が生じることに起因する。この結果、外部応力、または加熱による熱膨張収縮で生じる残留応力が発生した際に、ＮｂＣ等が多量に析出した粒内よりも、脆化した粒界に応力集中が生じる。そして、粒界を起点として割れが発生する。この現象が延性低下割れである。 On the other hand, ductility-reducing cracks are caused by segregation of grain boundary embrittlement elements such as P and S in a high-temperature HAZ during welding, during a welding heat cycle, and during use at a high temperature. As a result, when external stress or residual stress generated by thermal expansion and contraction due to heating occurs, stress concentration occurs in the embrittled grain boundary rather than in the grain where a large amount of NbC or the like is precipitated. Then, cracks occur starting from the grain boundaries. This phenomenon is called ductility reduction cracking.
本発明者らがＨＡＺで発生する割れについて検討を行った結果、割れの形態は、液化割れ、または長時間時効後の脆化割れではなく、前述した延性低下割れであることがわかった。特許文献１および２、ならびに非特許文献１では、延性低下割れについては一切検討がなされていない。 As a result of the present inventors' examination of cracks generated in the HAZ, it was found that the form of the cracks was not the liquefaction crack or the embrittlement crack after long-term aging, but the above-described ductility-lowering crack. In Patent Literatures 1 and 2, and Non-Patent Literature 1, ductility-reducing cracks are not examined at all.
本発明は耐ポリチオン酸ＳＣＣ性に優れ、かつ溶接時の割れを抑制し、良好な耐溶接割れ性を有する、オーステナイト系ステンレス厚鋼板およびその製造方法を提供することを目的とする。 An object of the present invention is to provide an austenitic stainless steel plate excellent in polythionic acid SCC resistance, suppressing cracking during welding, and having good weld cracking resistance, and a method for producing the same.
本発明は上記の課題を解決するためになされたものであり、その要旨は、下記に示すオーステナイト系ステンレス厚鋼板およびその製造方法にある。 The present invention has been made to solve the above problems, and the gist of the present invention resides in the following austenitic stainless steel plate and a method of manufacturing the same.
（１）化学組成が、質量％で、
Ｃ：０．０４％未満、
Ｓｉ：１．５％以下、
Ｍｎ：２．０％以下、
Ｐ：０．０４％以下、
Ｓ：０．０３％以下、
Ｎ：０．０２〜０．３５％、
Ｏ：０．０３％以下、
Ｎｂ：０．０５〜０．５％、
Ｃｒ：１５．０〜２５．０％、
Ｎｉ：６．０〜３０．０％、
Ａｌ：０．０５％以下、
Ｔｉ：０〜０．４％、
Ｖ：０〜０．４％、
Ｔａ：０〜０．２％、
Ｈｆ：０〜０．２％、
Ｚｒ：０〜０．２％、
Ｃｕ：０〜３．０％、
Ｍｏ：０〜５．０％、
Ｗ：０〜５．０％、
Ｃｏ：０〜１．０％、
Ｂ：０〜０．０１２％、
Ｃａ：０〜０．０２％、
Ｍｇ：０〜０．０２％、および、
ＲＥＭ：０〜０．１％、を含有し、
残部：Ｆｅおよび不純物、
であり、圧延方向に垂直な断面において、最大結晶粒径が０．３ｍｍ未満である、板厚６．０ｍｍ以上のオーステナイト系ステンレス厚鋼板。(1) The chemical composition is expressed in mass%
C: less than 0.04%,
Si: 1.5% or less,
Mn: 2.0% or less,
P: 0.04% or less,
S: 0.03% or less,
N: 0.02 to 0.35%,
O: 0.03% or less,
Nb: 0.05-0.5%,
Cr: 15.0 to 25.0%,
Ni: 6.0 to 30.0%,
Al: 0.05% or less,
Ti: 0 to 0.4%,
V: 0 to 0.4%,
Ta: 0 to 0.2%,
Hf: 0 to 0.2%,
Zr: 0 to 0.2%,
Cu: 0 to 3.0%,
Mo: 0 to 5.0%,
W: 0 to 5.0%,
Co: 0 to 1.0%,
B: 0 to 0.012%,
Ca: 0 to 0.02%,
Mg: 0 to 0.02%, and
REM: 0-0.1%,
The balance: Fe and impurities,
An austenitic stainless steel plate having a maximum grain size of less than 0.3 mm in a cross section perpendicular to the rolling direction and having a plate thickness of 6.0 mm or more.
（２）前記鋼板の化学組成が、さらに、質量％で、
Ｔｉ：０．００５〜０．４％、
Ｖ：０．００５〜０．４％、
Ｔａ：０．００３〜０．２％、
Ｈｆ：０．００３〜０．２％、
Ｚｒ：０．００３〜０．２％、
Ｃｕ：０．０２〜３．０％、
Ｍｏ：０．０５〜５．０％、
Ｗ：０．０５〜５．０％、
Ｃｏ：０．０３〜１．０％、
Ｂ：０．０００１〜０．０１２％、
Ｃａ：０．０００１〜０．０２％、
Ｍｇ：０．０００１〜０．０２％、および、
ＲＥＭ：０．００１〜０．１％、
から選択される１種以上を含有する、（１）に記載のオーステナイト系ステンレス厚鋼板。(2) The chemical composition of the steel sheet is further, in mass%,
Ti: 0.005 to 0.4%,
V: 0.005 to 0.4%,
Ta: 0.003 to 0.2%,
Hf: 0.003-0.2%,
Zr: 0.003-0.2%,
Cu: 0.02 to 3.0%,
Mo: 0.05-5.0%,
W: 0.05 to 5.0%,
Co: 0.03 to 1.0%,
B: 0.0001 to 0.012%,
Ca: 0.0001 to 0.02%,
Mg: 0.0001 to 0.02%, and
REM: 0.001-0.1%,
The austenitic stainless steel plate according to (1), containing at least one member selected from the group consisting of:
（３）石油脱硫装置に使用される、（１）または（２）に記載のオーステナイト系ステンレス厚鋼板。 (3) The austenitic stainless steel plate according to (1) or (2), which is used for a petroleum desulfurization device.
（４）前記化学組成を有するオーステナイト系ステンレス厚鋼板を製造する方法であって、
（ａ）（１）または（２）に記載の化学組成を有する鋳片または鋼片を加熱し、圧下率を３０％以上の条件で一次熱間圧延し、鋼板とする工程と、
（ｂ）前記鋼板を１１００〜１２５０℃に加熱し、圧延終了温度を１０５０℃以下、圧下率を３０％以上の条件で、二次熱間圧延し、
当該工程において、加熱後、二次熱間圧延終了までの間に８５０〜１１００℃の温度域で３分以上保持する工程と、
（ｃ）９５０〜１１５０℃温度域で固溶化熱処理を行う工程と
を、順に施す、オーステナイト系ステンレス厚鋼板の製造方法。(4) A method for producing an austenitic stainless steel plate having the chemical composition,
(A) a step of heating a slab or a slab having the chemical composition according to (1) or (2) and subjecting the slab or primary slab to primary hot rolling at a reduction ratio of 30% or more to form a steel sheet;
(B) The steel sheet is heated to 1100 to 1250 ° C, and subjected to secondary hot rolling under the conditions of a rolling end temperature of 1050 ° C or less and a rolling reduction of 30% or more,
In the process, after heating, maintaining the temperature range of 850 to 1100 ° C. for 3 minutes or more until the end of the secondary hot rolling,
(C) performing a solution heat treatment in a temperature range of 950 to 1150 ° C., in that order.
（５）前記化学組成を有するオーステナイト系ステンレス厚鋼板を製造する方法であって、
（Ａ）（１）または（２）に記載の化学組成を有する鋳片または鋼片を加熱し、圧下率を３０％以上の条件で一次熱間圧延し、鋼板とする工程と、
（Ｂ）前記鋼板を１１００〜１２５０℃で中間熱処理する工程と、
（Ｃ）前記鋼板を９５０〜１１００℃に加熱し、圧延終了温度を１０５０℃以下、圧下率を３０％以上の条件で、二次熱間圧延する工程と、
（Ｄ）９５０〜１１５０℃温度域で固溶化熱処理を行う工程と
を、順に施す、オーステナイト系ステンレス厚鋼板の製造方法。(5) A method for producing an austenitic stainless steel plate having the chemical composition,
(A) a step of heating a slab or a slab having the chemical composition according to (1) or (2) and subjecting the slab or primary slab to primary hot rolling at a reduction ratio of 30% or more to form a steel sheet;
(B) an intermediate heat treatment of the steel sheet at 1100 to 1250 ° C;
(C) a step of heating the steel sheet to 950 to 1100 ° C., and performing secondary hot rolling under the conditions of a rolling end temperature of 1050 ° C. or less and a rolling reduction of 30% or more;
(D) a step of performing solution heat treatment in a temperature range of 950 to 1150 ° C., in that order.
本発明によれば、耐ポリチオン酸ＳＣＣ性に優れ、かつ溶接時の割れを抑制し、良好な耐溶接割れ性を有する、オーステナイト系ステンレス厚鋼板を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the austenitic stainless steel thick plate which is excellent in polythionic-acid SCC resistance, suppresses the crack at the time of welding, and has favorable welding crack resistance can be provided.
本発明者らは、耐ポリチオン酸ＳＣＣ性の確保と溶接時の延性低下割れの抑制を両立しうるオーステナイト系ステンレス厚鋼板を得るために、以下の検討を行なった。具体的には、延性低下割れを生じた厚鋼板溶接材と、延性低下割れを生じなかった厚鋼板溶接材について、割れ発生部の金属組織、およびその製造条件について、検討を行ない、以下の知見（ａ）〜（ｃ）を得た。 The present inventors have conducted the following studies in order to obtain an austenitic stainless steel plate capable of ensuring both polythionic acid SCC resistance and suppression of ductility reduction cracking during welding. Specifically, for the thick steel plate welded material with reduced ductility cracking and the thick steel plate welded material without ductility reduced cracking, the metallographic structure of the cracked portion and the manufacturing conditions were studied, and the following findings were obtained. (A) to (c) were obtained.
（ａ）割れが生じているのは、粗大な結晶粒の粒界である。これは、結晶粒が微細である場合、粒界に掛かる応力が分散され、粒界破壊に至らないのに対し、結晶粒が粗大である場合、応力が粗大な粒の粒界に集中し、粒界破壊に至るためであると考えられる。 (A) The occurrence of cracks is at the grain boundaries of coarse crystal grains. This is because, when the crystal grains are fine, the stress applied to the grain boundaries is dispersed and does not lead to grain boundary destruction, whereas when the crystal grains are coarse, the stress concentrates on the grain boundaries of the coarse grains, It is thought to be due to grain boundary destruction.
（ｂ）溶接割れ部を多数観察した結果、最大結晶粒径が０．３ｍｍ未満であれば、割れが生じない。 (B) As a result of observing a large number of weld cracks, if the maximum crystal grain size is less than 0.3 mm, no crack occurs.
（ｃ）最大結晶粒径が０．３ｍｍ未満を満足する厚鋼板を得るための適切な製造条件を調べる必要がある。本発明者は、化学組成および製造条件が異なる種々の厚鋼板を作製し、得られた厚鋼板の組織観察を行うことで、後述する適切な製造条件を知見した。 (C) It is necessary to examine appropriate manufacturing conditions for obtaining a thick steel plate having a maximum crystal grain size of less than 0.3 mm. The present inventor has made various thick steel plates having different chemical compositions and manufacturing conditions, and has observed the microstructure of the obtained thick steel plates to find appropriate manufacturing conditions described later.
粗大粒は、加工熱処理による再結晶が完了せず、鋳造ままの粗大粒組織が一部残存している場合に生じるものである。粗大粒の最大粒径を抑制するためには、再結晶をできる限り促進させることが必要となる。その場合、加工ひずみをより多く蓄積する、または固溶化熱処理を高温長時間化するなどの一般的な促進策を適用することが考えられる。 Coarse grains occur when recrystallization by thermomechanical treatment is not completed and a part of the as-cast coarse grain structure remains. In order to suppress the maximum grain size of the coarse grains, it is necessary to promote recrystallization as much as possible. In that case, it is conceivable to apply a general promotion measure such as accumulating more processing strain or prolonging the solution heat treatment at a high temperature for a long time.
ところで、Ｃ固定化元素としてＮｂを含有したＳＵＳ３４７系の場合、熱間加工による再結晶が、Ｎｂを含有していない非含有材より大きく遅延する場合がある。例えば非特許文献２では、加工−保持温度が１０５０℃以下の場合に、再結晶が途中で停止する現象がある。その理由として、上述の温度では、Ｎｂ析出物の析出が再結晶に先行し、再結晶を抑止するためと考えられている。 Incidentally, in the case of the SUS347 system containing Nb as a C-fixing element, recrystallization by hot working may be delayed more than a non-containing material not containing Nb. For example, in Non-patent Document 2, there is a phenomenon that recrystallization stops halfway when the processing-holding temperature is 1050 ° C. or lower. It is considered that the reason for this is that at the above-mentioned temperature, precipitation of Nb precipitates precedes recrystallization and suppresses recrystallization.
当該課題に対しては、十分な加工ひずみと熱処理を行うことができれば再結晶を完了できるが、本発明のような厚鋼板を製造する場合、鋳片から最終製品までの圧下率が限定され、必ずしも再結晶に必要なレベルの加工度を確保できるとは限らない。さらに、固溶化熱処理の温度については、Ｎｂ含有鋼の場合、高温熱処理を行うとＮｂ炭化物が固溶したまま製品となり、高温使用時にこれがＮｂ炭化物として微細析出することで、長時間時効後の脆化割れの原因となることから上限を設けざるを得ない。加えて、時効時間の長時間化については著しく作業性および経済性を阻害するにもかかわらず、効果はあまり大きくはない。 For this problem, recrystallization can be completed if sufficient processing strain and heat treatment can be performed, but when manufacturing a thick steel plate as in the present invention, the rolling reduction from the slab to the final product is limited, It is not always possible to secure a required level of workability for recrystallization. Furthermore, regarding the temperature of solution heat treatment, in the case of Nb-containing steel, when high-temperature heat treatment is performed, the product remains as a solid solution of Nb carbide, and when used at high temperature, this precipitates finely as Nb carbide, so that it becomes brittle after aging for a long time. An upper limit must be set because it causes cracking. In addition, the effect of increasing the aging time is not so large, although the workability and economy are significantly impaired.
そこで、発明者らは、上記制約下で、オーステナイト系ステンレス鋼の再結晶を促進する製造条件について詳細に検討した結果、以下に示す（ｉ）、および（ｉｉ）に記載の製造方法が有効であることを知見した。 Then, the present inventors have studied in detail the manufacturing conditions for promoting the recrystallization of austenitic stainless steel under the above-described restrictions, and as a result, the manufacturing methods described in (i) and (ii) below are effective. I found that there was.
（ｉ）熱間圧延を分割して２段階とし、１段階目の熱間圧延後に高温熱処理を行う。
前述したように、再結晶を促進するために最終の固溶化熱処理を高温化することはできない。そのような制約をクリアするため、熱間圧延を分割して２段階とし、１段階目の熱間圧延後に高温熱処理を行い鋳片の粗大結晶を再結晶させる。この場合、２段階目の加工熱処理では、初期粒径が小さくなるため、比較的低温の熱処理でも再結晶は進行する。(I) The hot rolling is divided into two stages, and a high-temperature heat treatment is performed after the first stage hot rolling.
As mentioned above, it is not possible to raise the temperature of the final solution heat treatment to promote recrystallization. In order to clear such a restriction, hot rolling is divided into two stages, and high-temperature heat treatment is performed after the first stage of hot rolling to recrystallize coarse crystals of a slab. In this case, in the second-stage processing heat treatment, the recrystallization proceeds even at a relatively low temperature heat treatment because the initial grain size becomes small.
（ｉｉ）２段階目の熱間圧延時に、Ｎｂ析出物の析出を概ね完了させる。
高温加熱で固溶したＮｂが熱処理時に析出すると、再結晶が遅延する。これを回避するためには、熱処理により再結晶を行う前の２段階目の熱間圧延時において、Ｎｂ析出物が十分に析出するよう温度および時間の条件を適切に制御することで、Ｎｂ析出物の析出を概ね完了させることが肝要である。(Ii) The precipitation of Nb precipitates is substantially completed during the second stage of hot rolling.
When Nb dissolved as a solid solution by heating at a high temperature precipitates during heat treatment, recrystallization is delayed. In order to avoid this, at the time of the second stage of hot rolling before recrystallization by heat treatment, the conditions of temperature and time are appropriately controlled so that Nb precipitates are sufficiently precipitated. It is important to substantially complete the precipitation of the material.
本発明は、上記知見に基づいてなされたものである。以下、本発明の各要件について説明する。 The present invention has been made based on the above findings. Hereinafter, each requirement of the present invention will be described.
１．化学組成
各元素の限定理由は下記のとおりである。なお、以下の説明において含有量についての「％」は、「質量％」を意味する。1. Chemical composition Reasons for limiting each element are as follows. In the following description, “%” for the content means “% by mass”.
Ｃ：０．０４％未満
Ｃは、過剰に含有させるとＣｒ炭化物の析出を促進し、耐粒界腐食性および耐ポリチオン酸ＳＣＣ性が低下するため、極力低減することが望ましい。そのため、Ｃ含有量は、０．０４％未満とする。Ｃ含有量は０．０３％以下であるのが好ましく、０．０２％以下であるのがより好ましい。一方で、過度の低減は、精錬コストの上昇に繋がるため、Ｃ含有量は０．００５％以上であるのが好ましい。C: less than 0.04% If C is contained excessively, the precipitation of Cr carbide is promoted, and the intergranular corrosion resistance and the polythionic acid SCC resistance are reduced. Therefore, it is desirable to reduce C as much as possible. Therefore, the C content is less than 0.04%. The C content is preferably 0.03% or less, more preferably 0.02% or less. On the other hand, an excessive reduction leads to an increase in refining costs, so that the C content is preferably 0.005% or more.
Ｓｉ：１．５％以下
Ｓｉは、脱酸剤として含有させる元素である。しかし、過剰に含有させると液化割れ感受性を増大させるとともに、オーステナイト相の安定性を低下させる。そのため、Ｓｉ含有量は、１．５％以下とする。Ｓｉ含有量は、１．０％以下であるのが好ましく、０．７５％以下であるのがより好ましい。一方、脱酸の効果を得るためには、Ｓｉ含有量は、０．０２％以上であるのが好ましく、０．１％以上であるのがより好ましく、０．２％以上であるのがさらに好ましい。Si: 1.5% or less Si is an element contained as a deoxidizing agent. However, when it is contained excessively, liquefaction cracking sensitivity is increased and stability of the austenite phase is reduced. Therefore, the Si content is set to 1.5% or less. The Si content is preferably at most 1.0%, more preferably at most 0.75%. On the other hand, in order to obtain the effect of deoxidation, the Si content is preferably at least 0.02%, more preferably at least 0.1%, further preferably at least 0.2%. preferable.
Ｍｎ：２．０％以下
Ｍｎは、オーステナイト相を安定化させるとともに、Ｓによる熱間加工性劣化の低減に有効な元素である。しかし、Ｍｎを過剰に含有させると、靭性および耐食性等の劣化を引き起こす。そのため、Ｍｎ含有量は２．０％以下とする。Ｍｎ含有量は、１．８％以下であるのが好ましく、１．６％以下であるのがより好ましい。一方で、上記効果を得るためには、Ｍｎ含有量は０．５％以上であるのが好ましい。Mn: 2.0% or less Mn is an element that stabilizes the austenite phase and is effective in reducing the deterioration of hot workability due to S. However, when Mn is excessively contained, deterioration of toughness, corrosion resistance and the like is caused. Therefore, the Mn content is set to 2.0% or less. The Mn content is preferably 1.8% or less, more preferably 1.6% or less. On the other hand, in order to obtain the above effects, the Mn content is preferably 0.5% or more.
Ｐ：０．０４％以下
Ｐは、原料等から不可避的に混入する不純物である。Ｐは溶接熱サイクル中およびその後の高温での使用中に溶接部の粗大粒（粗粒ＨＡＺ）の粒界に偏析し、溶接後の液化割れだけでなく延性低下割れの原因にもなるため、低減することが好ましい。そのため、Ｐ含有量は０．０４％以下とする。Ｐ含有量は０．０３％以下であるのが好ましい。P: 0.04% or less P is an impurity unavoidably mixed from the raw material or the like. P segregates at the grain boundaries of the coarse grains (coarse grain HAZ) of the weld during the welding heat cycle and during use at a high temperature thereafter, which causes not only liquefaction cracking after welding but also ductility degradation cracking, It is preferable to reduce it. Therefore, the P content is set to 0.04% or less. The P content is preferably 0.03% or less.
Ｓ：０．０３％以下
Ｓは、原料等から不可避的に混入する不純物である。ＳもＰと同様に、粒界に偏析し、粗粒ＨＡＺ部における溶接後の液化割れ、および延性低下割れの原因となる。そのため、Ｓ含有量は０．０３％以下とする。Ｓ含有量は、０．０１５％以下であるのが好ましく、０．００５％以下であるのがより好ましく、０．００１％以下であるのがさらに好ましい。S: 0.03% or less S is an impurity unavoidably mixed from a raw material or the like. S also segregates at the grain boundary similarly to P, and causes liquefaction cracks and reduced ductility cracks after welding in coarse HAZ portions. Therefore, the S content is set to 0.03% or less. The S content is preferably 0.015% or less, more preferably 0.005% or less, and even more preferably 0.001% or less.
Ｎ：０．０２〜０．３５％
Ｎは、オーステナイト相を安定化させ、オーステナイト相に固溶するとともに、粒内に微細な窒化物として析出し、クリープ強度を向上させるのに有効な元素である。そのため、Ｎ含有量は、０．０２％以上とする。しかし、Ｎを過剰に含有させると、Ｃｒ窒化物が粒界に析出し、ＨＡＺでの耐ポリチオン酸ＳＣＣ性が低下する。そのため、Ｎ含有量は、０．３５％以下とする。Ｎ含有量は、０．０４％以上が好ましく、０．０６％以上がより好ましい。また、Ｎ含有量は、０．３％以下であるのが好ましく、０．２％以下であるのがより好ましく、０．１％以下であるのがさらに好ましい。N: 0.02 to 0.35%
N is an element that stabilizes the austenite phase, dissolves in the austenite phase, precipitates as fine nitrides in the grains, and is effective in improving creep strength. Therefore, the N content is set to 0.02% or more. However, when N is excessively contained, Cr nitride precipitates at the grain boundary, and the SCC resistance of polythionic acid in HAZ decreases. Therefore, the N content is set to 0.35% or less. The N content is preferably at least 0.04%, more preferably at least 0.06%. Further, the N content is preferably 0.3% or less, more preferably 0.2% or less, and still more preferably 0.1% or less.
Ｏ：０．０３％以下
Ｏは、不可避的に混入する不純物である。非金属介在物の代表である酸化物を構成する元素であり、過剰な含有は靭性を阻害する。また粗大なクラスター状酸化物が生成すると表面疵の原因となる。そのため、Ｏ含有量は０．０３％以下とする。Ｏ含有量は０．０１％以下であるのが好ましく、０．００７％以下であるのがより好ましく、０．００５％以下であるのがさらに好ましい。O: 0.03% or less O is an impurity unavoidably mixed. It is an element constituting an oxide that is representative of non-metallic inclusions, and an excessive content inhibits toughness. Also, the formation of coarse cluster oxides causes surface flaws. Therefore, the O content is set to 0.03% or less. The O content is preferably 0.01% or less, more preferably 0.007% or less, and even more preferably 0.005% or less.
Ｎｂ：０．０５〜０．５％
Ｎｂは、Ｃ固定化元素として含有される。具体的には、鋼中のＣと結合して炭化物を析出させることによって、粒界へのＣｒ炭化物析出が抑制され、耐粒界腐食性および耐ポリチオン酸ＳＣＣ性を高める効果を有する。また、粒内に析出した微細なＮｂ炭化物は、クリープ強度の向上にも寄与する。そのため、Ｎｂ含有量は０．０５％以上とする。Nb: 0.05-0.5%
Nb is contained as a C-fixing element. More specifically, by combining with C in steel to precipitate carbides, precipitation of Cr carbides at grain boundaries is suppressed, and this has the effect of increasing intergranular corrosion resistance and polythionic acid SCC resistance. Further, fine Nb carbide precipitated in the grains also contributes to improvement in creep strength. Therefore, the Nb content is set to 0.05% or more.
しかしながら、Ｎｂを過剰に含有させた場合、炭化物が粒内に過剰に析出してしまい、粒内の変形を妨げてしまう。そして、粒内の変形が妨げられた結果、不純物元素が偏析した粒界に応力集中を生じ、ＨＡＺ部の高温割れを助長する。また、鋳片加熱時に固溶したＮｂの再析出により、再結晶が妨げられる。そのため、Ｎｂ含有量は０．５％以下とする。 However, when Nb is excessively contained, carbides are excessively precipitated in the grains, which hinders deformation in the grains. Then, as a result of the inhibition of intragranular deformation, stress concentration occurs at the grain boundary where the impurity element has segregated, which promotes hot cracking of the HAZ. In addition, recrystallization of Nb dissolved in slab during heating prevents recrystallization. Therefore, the Nb content is set to 0.5% or less.
Ｎｂ含有量は、０．１０％以上であるのが好ましく、０．２０％以上であるのがより好ましい。また、Ｎｂ含有量は、０．４％以下であるのが好ましく、０．３５％以下であるのがさらに好ましい。加えて、Ｃとの関係でＮｂ／Ｃ≧１０であることが好ましく、Ｎｂ／Ｃ≧１５であるのがより好ましい。
但し、上記式中の元素記号は、鋼中に含まれる各元素の含有量（質量％）を表す。The Nb content is preferably at least 0.10%, more preferably at least 0.20%. Further, the Nb content is preferably at most 0.4%, more preferably at most 0.35%. In addition, it is preferable that Nb / C ≧ 10 in relation to C, and it is more preferable that Nb / C ≧ 15.
However, the symbol of the element in the above formula indicates the content (% by mass) of each element contained in the steel.
Ｃｒ：１５．０〜２５．０％
Ｃｒは、高温での耐酸化性および耐食性を確保するために必要な元素である。そのため、Ｃｒ含有量は、１５．０％以上とする。しかしながら、多量に含有させると、高温でのオーステナイト相の安定性を低下させ、クリープ強度の低下を引き起こす。そのため、Ｃｒ含有量は２５．０％以下とする。Ｃｒ含有量は、１６．０％以上であるのが好ましく、１７．０％以下であるのがより好ましい。Cr: 15.0 to 25.0%
Cr is an element necessary for securing oxidation resistance and corrosion resistance at high temperatures. Therefore, the Cr content is set to 15.0% or more. However, when it is contained in a large amount, the stability of the austenite phase at a high temperature is reduced, and the creep strength is reduced. Therefore, the Cr content is set to 25.0% or less. The Cr content is preferably at least 16.0%, more preferably at most 17.0%.
Ｎｉ：６．０〜３０．０％
Ｎｉは、オーステナイト相を安定化させる元素であり、長時間使用後のクリープ強度を維持するために必須な元素である。また、耐酸性および耐塩化物ＳＣＣ性を向上させる元素でもある。そのため、Ｎｉ含有量は、６．０％以上とする。しかしながら、Ｎｉは、高価な元素であるため、含有量が多いとコストが上昇する。そのため、Ｎｉ含有量は３０．０％以下とする。Ｎｉ含有量は７．０％以上であるのが好ましく、９．０％以上であるのがより好ましい。また、Ｎｉ含有量は、１３．０％以下であるのが好ましい。Ni: 6.0 to 30.0%
Ni is an element that stabilizes the austenite phase and is an essential element for maintaining the creep strength after long-term use. It is also an element that improves acid resistance and chloride SCC resistance. Therefore, the Ni content is set to 6.0% or more. However, Ni is an expensive element, so that a high content increases the cost. Therefore, the Ni content is set to 30.0% or less. The Ni content is preferably at least 7.0%, more preferably at least 9.0%. Further, the Ni content is preferably 13.0% or less.
Ａｌ：０．０５％以下
Ａｌは、鋼の脱酸のために用いられる元素であり、鋼中の酸素を低減するためにＳｉと併せて含有させる。しかしながら、ＡｌはＮとの親和力が比較的大きな元素であり、過剰に含有させるとＡｌＮを生じて母材の靭性を劣化させる。その程度はＮ含有量にも依存するが、Ａｌが０．０５％を超えると靭性低下が著しくなるため、Ａｌ含有量は、０．０５％以下とする。一方で、上記効果を得るためには、０．００３％以上であるのが好ましい。Al: 0.05% or less Al is an element used for deoxidation of steel, and is contained together with Si to reduce oxygen in steel. However, Al is an element having a relatively large affinity for N, and when contained in excess, AlN is generated to deteriorate the toughness of the base material. Although the degree depends on the N content, if the Al content exceeds 0.05%, the toughness is significantly reduced. Therefore, the Al content is set to 0.05% or less. On the other hand, in order to obtain the above effects, the content is preferably 0.003% or more.
Ｔｉ：０〜０．４％
Ｖ：０〜０．４％
Ｔａ：０〜０．２％
Ｈｆ：０〜０．２％
Ｚｒ：０〜０．２％
Ｔｉ、Ｖ、Ｔａ、ＨｆおよびＺｒは、Ｃ固定化元素として重要であり、鋼中のＣと結合した炭化物が粒内に析出することによって、粒界へのＣｒ窒化物析出が抑制され、耐食性を高める効果を有する。また、粒内に析出した微細な炭化物は、クリープ強度の向上にも寄与する。そのため、この効果を得るために、これらの元素から選択される１種以上を、必要に応じて含有させても良い。Ti: 0 to 0.4%
V: 0 to 0.4%
Ta: 0 to 0.2%
Hf: 0 to 0.2%
Zr: 0 to 0.2%
Ti, V, Ta, Hf, and Zr are important as C-fixing elements. Carbide bonded to C in steel precipitates in the grains, thereby suppressing precipitation of Cr nitride at the grain boundaries and improving corrosion resistance. Has the effect of increasing Further, fine carbides precipitated in the grains also contribute to improvement in creep strength. Therefore, in order to obtain this effect, one or more elements selected from these elements may be contained as necessary.
しかしながら、これらの元素を過剰に含有させた場合、炭窒化物の過剰な析出により靭性を阻害する。したがって、Ｔｉ含有量は、０．４％以下とする。また、Ｖ含有量は、０．４％以下とする。Ｔａ含有量は、０．２％以下とする。Ｈｆ含有量は、０．２％以下とする。Ｚｒ含有量は、０．２％以下とする。一方で、上記の効果を得るためには、Ｔｉ含有量は、０．００５％以上であるのが好ましい。また、Ｖ含有量は、０．００５％以上であるのが好ましい。Ｔａ含有量は、０．００３％以上であるのが好ましい。Ｈｆ含有量は、０．００３％以上であるのが好ましい。Ｚｒ含有量は、０．００３％以上であるのが好ましい。 However, when these elements are excessively contained, the toughness is hindered by excessive precipitation of carbonitride. Therefore, the Ti content is set to 0.4% or less. Further, the V content is set to 0.4% or less. The Ta content is set to 0.2% or less. The Hf content is set to 0.2% or less. The Zr content is set to 0.2% or less. On the other hand, in order to obtain the above effects, the Ti content is preferably 0.005% or more. Further, the V content is preferably 0.005% or more. The Ta content is preferably 0.003% or more. The Hf content is preferably 0.003% or more. The Zr content is preferably at least 0.003%.
Ｃｕ、Ｍｏ、ＷおよびＣｏは高温強度を高める作用を有している。そのため、この効果を得るために、上記の元素を必要に応じて、１種以上含有させても良い。 Cu, Mo, W and Co have an effect of increasing the high-temperature strength. Therefore, in order to obtain this effect, one or more of the above-mentioned elements may be contained as necessary.
Ｃｕ：０〜３．０％
Ｃｕは、高温で微細に析出して高温強度を向上させることに有効である上に、オーステナイト相を安定化させる作用を有するので、必要に応じて含有させる。しかし、Ｃｕを過度に含有させた場合、熱間加工時、および溶接時に液相Ｃｕが粒界に析出し、熱間加工性、または耐液化割れ性を著しく低下させる。そのため、Ｃｕ含有量を３．０％以下とする。Ｃｕ含有量は２．０％以下であるのが好ましい。一方で、上記の効果を得るためには、Ｃｕ含有量は０．０２％以上であるのが好ましく、０．５％以上であるのが好ましい。Cu: 0 to 3.0%
Cu is effective in improving the high-temperature strength by precipitating finely at a high temperature, and has an effect of stabilizing an austenite phase. Therefore, Cu is contained as necessary. However, when Cu is excessively contained, liquid phase Cu precipitates at the grain boundary during hot working and welding, and the hot workability or liquefaction cracking resistance is significantly reduced. Therefore, the Cu content is set to 3.0% or less. The Cu content is preferably 2.0% or less. On the other hand, in order to obtain the above effects, the Cu content is preferably 0.02% or more, and more preferably 0.5% or more.
Ｍｏ：０〜５．０％
Ｗ：０〜５．０％
ＭｏおよびＷは、マトリックスに固溶して高温強度を向上させる効果を有し、特に高温でのクリープ強度の向上に有効な元素であるので、必要に応じて含有させる。しかし、両元素とも含有量が高い場合、オーステナイト相の安定性を低下させ、クリープ強度を低下させる。加えて、粗粒ＨＡＺでの延性低下割れ感受性が高くなる。Mo: 0 to 5.0%
W: 0 to 5.0%
Mo and W have the effect of improving the high-temperature strength by forming a solid solution in the matrix, and are particularly effective elements for improving the creep strength at high temperatures. However, when the content of both elements is high, the stability of the austenite phase is reduced, and the creep strength is reduced. In addition, the ductility reduction crack susceptibility of the coarse-grained HAZ increases.
そのため、ＭｏおよびＷの含有量は、それぞれ、Ｍｏ：５．０％以下、Ｗ：５．０％以下とする。また、Ｍｏ含有量は、１．５％以下であるのが好ましく、Ｗ含有量は、３．０％以下であるのが好ましい。一方で、上記効果を得るためには、Ｍｏ：０．０５％以上、Ｗ：０．０５％以上から選択される１種以上を含有させるのが好ましい。 Therefore, the contents of Mo and W are set to 5.0% or less for Mo and 5.0% or less for W, respectively. Further, the Mo content is preferably 1.5% or less, and the W content is preferably 3.0% or less. On the other hand, in order to obtain the above effects, it is preferable to contain at least one selected from Mo: 0.05% or more and W: 0.05% or more.
Ｃｏ：０〜１．０％
Ｃｏは、オーステナイト相の安定性を高めて、高温強度を向上させる元素であるので、必要に応じて含有させる。しかし、Ｃｏは非常に高価な元素であるため、多量に含有させるとコスト上昇を招く。そのため、Ｃｏ含有量は１．０％以下とする。Ｃｏ含有量は、０．８％以下であるのが好ましい。一方で、上記効果を得るためには、Ｃｏ含有量は０．０３％以上であるのが好ましい。Co: 0 to 1.0%
Co is an element that enhances the stability of the austenite phase and improves the high-temperature strength, and is therefore included as necessary. However, since Co is a very expensive element, if it is contained in a large amount, the cost will increase. Therefore, the Co content is set to 1.0% or less. The Co content is preferably 0.8% or less. On the other hand, in order to obtain the above effect, the Co content is preferably 0.03% or more.
Ｂ：０〜０．０１２％
Ｃａ：０〜０．０２％
Ｍｇ：０〜０．０２％
ＲＥＭ：０〜０．１％
Ｂ、Ｃａ、ＭｇおよびＲＥＭは熱間加工性を向上させる元素であるので、必要に応じて含有させる。しかしながら、これら元素を過剰に含有させた場合、逆に熱間加工性、および靭性の低下を引き起こす。そのため、これら元素の含有量はそれぞれ、Ｂ：０．０１２％以下、Ｃａ：０．０２％以下、Ｍｇ：０．０２％以下、およびＲＥＭ：０．１％以下とする。B: 0 to 0.012%
Ca: 0 to 0.02%
Mg: 0 to 0.02%
REM: 0-0.1%
Since B, Ca, Mg and REM are elements that improve hot workability, they are included as necessary. However, when these elements are excessively contained, hot workability and toughness are reduced. Therefore, the contents of these elements are set to B: 0.012% or less, Ca: 0.02% or less, Mg: 0.02% or less, and REM: 0.1% or less, respectively.
また、Ｂ含有量は、０．００５％以下、Ｃａ含有量は、０．０１％以下、Ｍｇ含有量は、０．０１％以下、ＲＥＭ含有量は、０．０５％以下であるのが好ましい。上記効果を得るために、Ｂ：０．０００１％以上、Ｃａ：０．０００１％以上、Ｍｇ：０．０００１％以上、およびＲＥＭ：０．００１％以上、から選択される１種以上を含有させるのが好ましい。 Further, it is preferable that the B content is 0.005% or less, the Ca content is 0.01% or less, the Mg content is 0.01% or less, and the REM content is 0.05% or less. . In order to obtain the above effects, one or more selected from B: 0.0001% or more, Ca: 0.0001% or more, Mg: 0.0001% or more, and REM: 0.001% or more are contained. Is preferred.
ＲＥＭは、Ｓｃ、Ｙおよびランタノイドの合計１７元素の総称であり、ＲＥＭの含有量は上記元素の合計量を意味する。 REM is a general term for a total of 17 elements of Sc, Y and lanthanoid, and the content of REM means the total amount of the above elements.
本発明の鋼板において残部はＦｅおよび不純物である。ここで「不純物」とは、鋼を工業的に製造する際に、鉱石、スクラップ等の原料、製造工程の種々の要因によって混入する成分であって、本発明に悪影響を与えない範囲で許容されるものを意味する。 The balance in the steel sheet of the present invention is Fe and impurities. Here, the "impurities" are components that are mixed due to various factors in the ore, scrap and other raw materials, and the manufacturing process when steel is industrially manufactured, and are acceptable as long as they do not adversely affect the present invention. Means something.
２．金属組織
本発明では、溶接時の延性低下割れを回避しうる金属組織の要件を、圧延方向に垂直な断面における最大結晶粒径が０．３ｍｍ未満と規定する。０．３ｍｍ以上の粗大粒が無い場合には、粗大粒の粒界への応力集中が少なく、割れを抑制することができる。更に、最大結晶粒径が０．１５ｍｍ未満であるのが好ましい。2. Metallographic structure In the present invention, the requirement of the metallographic structure capable of avoiding the ductility-reducing crack during welding specifies that the maximum crystal grain size in a cross section perpendicular to the rolling direction is less than 0.3 mm. When there is no coarse grain of 0.3 mm or more, stress concentration on the grain boundary of the coarse grain is small, and cracking can be suppressed. Further, the maximum crystal grain size is preferably less than 0.15 mm.
なお、最大結晶粒径は、圧延方向に垂直な断面を樹脂に埋め込み研磨してエッチングした後、複数の観測視野の観測領域の合計が１ｍｍ２以上となるように観測領域を選択し、その観察視野で観察した各々の粒の最大結晶粒径を記録していき、その中の最大の値として求める。The maximum crystal grain size is determined by embedding a cross section perpendicular to the rolling direction in a resin, polishing and etching, and then selecting an observation area such that the sum of observation areas in a plurality of observation fields is 1 mm 2 or more. The maximum crystal grain size of each grain observed in the visual field is recorded, and the maximum grain size is determined.
３．板厚
本発明における延性低下割れの課題は、素材厚との関係で大きな圧下率を確保し難い板厚６．０ｍｍ以上の厚鋼板の場合に生じる。したがって、本発明においては、板厚６．０ｍｍ以上の厚鋼板を対象とする。板厚は１０．０ｍｍ以上であるのが好ましく、２１．０ｍｍ以上であるのがより好ましい。板厚は、２６．０ｍｍ以上であるのがさらに好ましく、３５．０ｍｍ以上であるのが一層好ましい。上限に関し、特に規定は設けないが、８０．０ｍｍ以下が好ましい。3. The problem of ductility reduction cracking in the present invention occurs in the case of a thick steel plate having a thickness of 6.0 mm or more in which it is difficult to secure a large rolling reduction in relation to the material thickness. Therefore, the present invention is directed to a thick steel plate having a thickness of 6.0 mm or more. The plate thickness is preferably 10.0 mm or more, and more preferably 21.0 mm or more. The plate thickness is more preferably at least 26.0 mm, even more preferably at least 35.0 mm. The upper limit is not particularly defined, but is preferably 80.0 mm or less.
４．製造方法
以上の観点から、以下に示す２通りの工程で圧延を行うことによって、本発明の厚鋼板において再結晶を促進させることができる。以下各工程について説明する。4. Manufacturing Method From the above viewpoint, recrystallization can be promoted in the thick steel plate of the present invention by performing rolling in the following two steps. Hereinafter, each step will be described.
４−１．下記（ａ）〜（ｃ）の工程による製造方法
（ａ）一次熱間圧延工程
本発明に係るオーステナイト系ステンレス鋼板は、粗大な粒組織の再結晶を促進するため、熱間圧延を２回に分けて行う。１段階目の熱間圧延の鋳片または鋼片の加熱温度は、加熱によるＮｂの固溶を抑制し、低温圧延によってひずみをより蓄積させるために、比較的低温が好ましい。しかしながら、温度が低すぎると加工時に熱間加工割れを生じる可能性が出てくるため、１０００〜１２００℃で実施するのが好ましく、１０５０〜１１５０℃であるのがより好ましい。つまり、一次熱間圧延の圧延終了温度は、１２００℃以下であるのが好ましい。また、圧下率は、再結晶を促進させるために３０％以上とする。4-1. (A) Primary Hot Rolling Step The austenitic stainless steel sheet according to the present invention is subjected to hot rolling twice in order to promote recrystallization of a coarse grain structure. Perform separately. The heating temperature of the slab or slab in the first stage of hot rolling is preferably relatively low in order to suppress solid solution of Nb by heating and to accumulate strain by low-temperature rolling. However, if the temperature is too low, there is a possibility that hot working cracks may occur at the time of working. Therefore, the working is preferably performed at 1000 to 1200 ° C, and more preferably at 1050 to 1150 ° C. That is, the rolling end temperature of the primary hot rolling is preferably 1200 ° C. or less. The rolling reduction is 30% or more to promote recrystallization.
（ｂ）二次熱間圧延工程
前述の通り、再結晶を促進させるために、本工程において、１１００〜１２５０℃の温度域まで鋼板を加熱する。そのため、加熱温度は、１１００℃以上とする。一方、加熱温度が１２５０℃超では強度が低下し、自重による曲がり等の原因となるため、１２５０℃以下とする。(B) Secondary hot rolling step As described above, in order to promote recrystallization, the steel sheet is heated to a temperature range of 1100 to 1250 ° C in this step. Therefore, the heating temperature is set to 1100 ° C. or higher. On the other hand, if the heating temperature is higher than 1250 ° C., the strength is reduced, causing bending or the like due to its own weight.
熱間圧延は低温で行うほど、ひずみ蓄積量が増大し、再結晶が促進される。そのため、圧延終了温度を１０５０℃以下とし、１０００℃以下であるのが好ましい。二次熱間圧延温度は、８５０〜１１５０℃で実施するのが好ましく、９００〜１０５０℃で実施するのがより好ましい。 As hot rolling is performed at a lower temperature, the amount of strain accumulation increases, and recrystallization is promoted. Therefore, the rolling end temperature is set to 1050 ° C or lower, and preferably 1000 ° C or lower. The secondary hot rolling temperature is preferably performed at 850 to 1150 ° C, and more preferably at 900 to 1050 ° C.
さらに、圧延時の加工度が低すぎる場合、ひずみ蓄積量が少なく、再結晶が生じにくい。そのため、二次熱間圧延における圧下率は、３０％以上とする。二次熱間圧延における圧下率は、４０％以上であるのが好ましい。 Further, when the working ratio at the time of rolling is too low, the amount of accumulated strain is small, and recrystallization hardly occurs. Therefore, the rolling reduction in the secondary hot rolling is set to 30% or more. The rolling reduction in the secondary hot rolling is preferably 40% or more.
なお、二次熱間圧延工程においては、加熱後、圧延終了までの間に８５０〜１１００℃の温度域で３分以上保持する。前述したように、最終熱処理で再結晶を完了させるためには、熱処理前にＮｂ析出物の析出を概ね完了させることが肝要である。そこで、８５０℃以上かつ析出温度以下の１１００℃以下で、３分以上保持することによってＮｂ析出物析出を行わせる。 In the secondary hot rolling step, after the heating, the temperature is maintained in a temperature range of 850 to 1100 ° C. for 3 minutes or more until the end of the rolling. As described above, in order to complete recrystallization in the final heat treatment, it is important to substantially complete the precipitation of Nb precipitates before the heat treatment. Therefore, Nb precipitates are deposited by holding at 850 ° C. or higher and 1100 ° C. or lower which is lower than the deposition temperature for 3 minutes or longer.
当該製造条件では加工を加えているため、析出に要する時間が短縮されており、３分でもかなりの析出が見込める。なお、保持温度が低温すぎる場合は、拡散が進まず析出を生じにくくなる。このため、保持温度を８５０℃以上とする。 Since processing is performed under the manufacturing conditions, the time required for precipitation is reduced, and considerable precipitation can be expected even in 3 minutes. If the holding temperature is too low, diffusion does not proceed and precipitation hardly occurs. For this reason, the holding temperature is set to 850 ° C. or higher.
（ｃ）固溶化熱処理工程
Ｎｂの再固溶を防止しかつ再結晶を促進するために、固溶化熱処理の温度は９５０〜１１５０℃とする。(C) Solution heat treatment step In order to prevent re-solution of Nb and promote recrystallization, the temperature of the solution heat treatment is 950 to 1150 ° C.
４−２．下記（Ａ）〜（Ｄ）の工程による製造方法
（Ａ）一次熱間圧延工程
上述の方法と同様に、１段階目の熱間圧延の鋳片加熱温度は、加熱によるＮｂの固溶を抑制し、低温圧延によってひずみをより蓄積させるために、比較的低温が好ましい。しかしながら、温度が低すぎると加工時に熱間加工割れを生じる可能性が出てくるため、１０００〜１２００℃で実施するのが好ましく、１０５０〜１１５０℃であるのがより好ましい。つまり、一次熱間圧延の圧延終了温度は、１２００℃以下であるのが好ましい。また、圧下率は、再結晶を促進させるために３０％以上とする。4-2. (A) Primary Hot Rolling Step As in the above-described method, the slab heating temperature of the first-stage hot rolling suppresses solid solution of Nb by heating. However, in order to further accumulate strain by low-temperature rolling, a relatively low temperature is preferable. However, if the temperature is too low, there is a possibility that hot working cracks may occur at the time of working. Therefore, the working is preferably performed at 1000 to 1200 ° C, and more preferably at 1050 to 1150 ° C. That is, the rolling end temperature of the primary hot rolling is preferably 1200 ° C. or less. The rolling reduction is 30% or more to promote recrystallization.
（Ｂ）中間熱処理工程
前述の通り、再結晶を促進させるために、一次熱間圧延後で、かつ後述する二次熱間圧延前に、鋼板を１１００〜１２５０℃に加熱する。本発明においては、一次熱間圧延後、二次熱間圧延前における上記の加熱を中間熱処理と記載する。(B) Intermediate heat treatment step As described above, in order to promote recrystallization, the steel sheet is heated to 1100 to 1250 ° C after the primary hot rolling and before the secondary hot rolling described below. In the present invention, the above-mentioned heating after the primary hot rolling and before the secondary hot rolling is described as an intermediate heat treatment.
（Ｃ）二次熱間圧延工程
Ｎｂ析出物の析出を促進するために、本工程において、９５０〜１１００℃の温度域まで鋼板を加熱したうえで熱間圧延を行う。(C) Secondary Hot Rolling Step In order to promote the precipitation of Nb precipitates, in this step, the steel sheet is heated to a temperature range of 950 to 1100 ° C. and then hot-rolled.
熱間圧延は低温で行うほど、ひずみ蓄積量が増大し、再結晶が促進される。そのため、圧延終了温度を１０５０℃以下とし、１０００℃以下であるのが好ましい。二次熱間圧延温度は、８５０〜１１００℃で実施するのが好ましく、９００〜１０５０℃で実施するのがより好ましい。 As hot rolling is performed at a lower temperature, the amount of strain accumulation increases, and recrystallization is promoted. Therefore, the rolling end temperature is set to 1050 ° C or lower, and preferably 1000 ° C or lower. The secondary hot rolling temperature is preferably performed at 850 to 1100 ° C, and more preferably at 900 to 1050 ° C.
さらに、圧延時の加工度が低すぎる場合、ひずみ蓄積量が少なく、再結晶が生じにくい。そのため、二次熱間圧延における圧下率は、３０％以上とする。二次熱間圧延における圧下率は、４０％以上であるのが好ましい。 Further, when the working ratio at the time of rolling is too low, the amount of accumulated strain is small, and recrystallization hardly occurs. Therefore, the rolling reduction in the secondary hot rolling is set to 30% or more. The rolling reduction in the secondary hot rolling is preferably 40% or more.
（Ｄ）固溶化熱処理工程
Ｎｂの再固溶を防止しかつ再結晶を促進するために、固溶化熱処理の温度は９５０℃〜１１５０℃とする。(D) Solution heat treatment step In order to prevent re-solution of Nb and promote recrystallization, the temperature of the solution heat treatment is 950 ° C to 1150 ° C.
以下、実施例によって本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.
表１に示す化学組成を有するオーステナイト系ステンレス鋼を電気炉にて溶製し、厚さ１５０ｍｍの連続鋳造鋳片を得た。
熱間圧延は二回に分けて行い、一次熱間圧延は、１１００℃で加熱後、圧延終了温度９５０℃の条件にて実施し、厚さ９０ｍｍの一次熱間圧延鋼板を得た。圧下率は４０％とした。その後、二次熱間圧延は、１２００℃で１時間加熱後、圧延終了温度９５０℃の条件にて実施し、厚さ４５ｍｍの熱間圧延鋼板を得た。圧下率は５０％とした。１１００℃〜８００℃までの保持時間は５．３分となるようにし、直後に水冷を行った。固溶化熱処理は、１１００℃の温度で５分間均熱後、水冷を行った。 The hot rolling was performed twice, and the primary hot rolling was performed at a temperature of 1100 ° C. and then at a rolling end temperature of 950 ° C. to obtain a primary hot-rolled steel sheet having a thickness of 90 mm. The rolling reduction was 40%. Thereafter, the secondary hot rolling was performed at 1200 ° C. for 1 hour and then performed at a rolling end temperature of 950 ° C. to obtain a hot-rolled steel sheet having a thickness of 45 mm. The rolling reduction was 50%. The holding time from 1100 ° C. to 800 ° C. was set to 5.3 minutes, and water cooling was performed immediately thereafter. The solution heat treatment was performed by soaking at a temperature of 1100 ° C. for 5 minutes and then cooling with water.
得られた鋼板について、最大結晶粒径の評価を行った。最大結晶粒径は、鋼板の圧延方向に直角な断面を、凹凸を除去した後樹脂に埋め込み鏡面研磨したものに、王水浸漬エッチングを行った後、合計観測域の面積が１．２３ｍｍ２になるまでランダムに観察を行い、粒の最大結晶粒径を求めた。About the obtained steel plate, the maximum crystal grain size was evaluated. Maximum crystal grain size, a cross section perpendicular to the rolling direction of the steel sheet, to that mirror polishing embedded in the resin after removal of the irregularities, after the aqua regia immersion etching, the area of the total observation area within 1.23 mm 2 Observation was carried out randomly until the maximum was obtained.
延性低下割れ感受性は、ロンジバレストレイン試験による総割れ長さにより評価した。この試験は溶接を行っている最中に曲げを行ってひずみを付加し、その際にＨＡＺ部に生じた割れの長さを測定するもので、溶接方向と平行にひずみをかけるロンジバレストレイン試験は、ＨＡＺ部における溶接高温割れ性評価法として広く用いられているものである。 The ductility-reduced cracking susceptibility was evaluated by the total crack length by the Longie Varestraint test. In this test, bending is applied during welding to add strain, and the length of the cracks generated in the HAZ at that time is measured. Is widely used as a method for evaluating hot cracking resistance in a HAZ portion.
具体的には、まず上記により製造した固溶化熱処理後の鋼板（板厚方向３枚取り）から、厚さ１２ｍｍ、幅５０ｍｍ、長さ３００ｍｍの試験片を採取し、曲げブロック上に片持ばり式に固定し、試験片の長手方向にＧＴＡＷ（Ｇａｓ Ｔｕｎｇｓｔｅｎ Ａｒｃ Ｗｅｌｄｉｎｇ）によりビードオンプレート溶接を行った。 Specifically, first, a test piece having a thickness of 12 mm, a width of 50 mm, and a length of 300 mm is sampled from the solution-treated heat-treated steel sheet (three pieces in the thickness direction) manufactured as described above, and is cantilevered on a bending block. The test piece was fixed, and bead-on-plate welding was performed by GTAW (Gas Tungsten Arc Welding) in the longitudinal direction of the test piece.
その後、溶融池が試験片長手方向の中央部に達した時に、試験片の片側を曲げブロックの曲率に沿って試験片を変形させ、溶接ビードとＨＡＺ表面に割れを発生させた。その後、ＨＡＺにて発生した割れの長さを測定し、総割れ長さを求めた。なお、溶接条件は溶接電流２００Ａ、溶接電圧１６Ｖ、溶接速度１５ｃｍ／分、負荷歪２％とした。ＨＡＺ表面に割れ長さが１．５ｍｍ以下の場合に、ＨＡＺ割れ感受性が低く、耐高温割れ性に優れると判断し、これを目標とした。 Thereafter, when the molten pool reached the center in the longitudinal direction of the test piece, one side of the test piece was bent to deform the test piece along the curvature of the block, and cracks were generated on the weld bead and the HAZ surface. Thereafter, the length of the crack generated in the HAZ was measured, and the total crack length was determined. The welding conditions were a welding current of 200 A, a welding voltage of 16 V, a welding speed of 15 cm / min, and a load strain of 2%. When the crack length on the HAZ surface was 1.5 mm or less, it was determined that the HAZ crack susceptibility was low and the hot crack resistance was excellent, and this was targeted.
次に、耐ポリオチオン酸ＳＣＣ性の確認のため、上記溶接材を７００℃で１０００時間の鋭敏化熱処理を行った後、Ｗａｃｋｅｎｒｏｄｅｒ溶液（蒸留水中にＳＯ２ガスを吹き込んで作製したＨ２Ｓ０３飽和水溶液に多量のＨ２Ｓガスを吹き込んだ溶液）中での浸漬試験を行った。評価は溶接線を中央にした厚さ２ｍｍ、幅１０ｍｍ、長さ７５ｍｍの短冊状のものを半径５ｍｍで拘束したＵベンド試験片を用い、Ｗａｃｋｅｎｒｏｄｅｒ溶液に室温で４８時間浸漬し、割れ発生の有無を光学顕微鏡にて観察し、割れが発生しなかったものを耐ポリチオン酸ＳＣＣ性に優れると判断した。Next, in order to confirm the SCC resistance of the polythiothioic acid, the above-mentioned welding material was subjected to a sensitizing heat treatment at 700 ° C. for 1000 hours, and then a Wackenroder solution (H 2 SO 3 saturation produced by blowing SO 2 gas into distilled water). (A solution in which a large amount of H 2 S gas was blown into an aqueous solution). Evaluation was performed using a U-bend test piece in which a strip having a thickness of 2 mm, a width of 10 mm, and a length of 75 mm centered on the welding line and constrained at a radius of 5 mm was immersed in a Wackenroder solution for 48 hours at room temperature to check for cracks. Was observed with an optical microscope, and those having no cracks were judged to be excellent in polythionic acid SCC resistance.
上記測定結果を表２に併せて示す。なお、表２の「耐ポリチオン酸ＳＣＣ性に関する評価データ」欄のうち、「○」は４８時間の浸漬にて割れの発生しなかったもの、「×」は４８時間の浸漬にて割れの発生が認められたものを意味する。 The measurement results are shown in Table 2. In the column of "Evaluation data on polythionic acid SCC resistance" in Table 2, "O" indicates that no crack was generated after immersion for 48 hours, and "X" indicates that crack was generated after immersion for 48 hours. Means that it was recognized.
試験Ｎｏ．１〜１０は本発明の規定を満足する本発明例に係る鋼である。表２から分かるように、本発明例の鋼板は最大結晶粒径が０．３ｍｍ未満であり、ＨＡＺ総割れ長さも１．５ｍｍ以下であることから、良好な耐ＨＡＺ割れ性を示し、優れた耐高温割れ性を有する。 Test No. Steels 1 to 10 according to the present invention satisfy the requirements of the present invention. As can be seen from Table 2, the steel sheet of the present invention has a maximum crystal grain size of less than 0.3 mm and a total HAZ crack length of 1.5 mm or less. Has high temperature cracking resistance.
一方で、本発明の成分範囲を満たさない試験Ｎｏ．１１〜１８の鋼は、以下に示す理由で特性を満足しなかった。Ｎｂの含有量が本発明の規定以上である、試験Ｎｏ．１８は再結晶が促進されず、大きな結晶粒が残存した。それぞれＳｉ、またはＰの含有量が本発明の規定以上である、試験Ｎｏ．１２、および１７は、ＨＡＺ総割れ長さが、１．５ｍｍ超となり、耐高温割れ性が不良であり、高温割れを生じた。それぞれＣ、またはＮが、本発明の規定以上に含有されている試験Ｎｏ．１１、および１６は、耐ポリチオンＳＣＣ性に劣る。Ｍｎの含有量が本発明の規定以上である、試験Ｎｏ．１３は耐食性が劣る。それぞれＮｉまたはＣｒの含有量が本発明の規定を満足しない試験Ｎｏ．１４、および１５は、クリープ強度に劣る。 On the other hand, Test No. which does not satisfy the component range of the present invention. The steels of Nos. 11 to 18 did not satisfy the properties for the following reasons. Test No. 1 in which the content of Nb is equal to or higher than the content of the present invention. In No. 18, recrystallization was not promoted and large crystal grains remained. Test Nos., In which the content of Si or P is equal to or more than the content of the present invention, respectively. In Nos. 12 and 17, the HAZ total crack length exceeded 1.5 mm, the hot crack resistance was poor, and hot cracks occurred. Test No. 1 in which C or N is contained in excess of the definition of the present invention, respectively. 11 and 16 are inferior in polythione SCC resistance. Test No. 1 in which the content of Mn is equal to or higher than the content of the present invention. No. 13 is inferior in corrosion resistance. Test Nos. In which the content of Ni or Cr did not satisfy the requirements of the present invention, respectively. 14 and 15 have inferior creep strength.
表３に、表１中のＡ〜Ｆの成分を有する鋼について、種々の製造条件にて鋼板を作製し、最大結晶粒径およびＨＡＺ割れ感受性を評価した結果を示す。 Table 3 shows the results of evaluating steel sheets having the components A to F in Table 1 under various manufacturing conditions and evaluating the maximum crystal grain size and the HAZ crack susceptibility.
本発明の製造条件を満足する試験Ｎｏ．１９〜２４の発明例は、最大結晶粒径が０．３ｍｍ未満であり、ＨＡＺ総割れ長さも１．５ｍｍ以下であることから、良好な耐ＨＡＺ割れ性を示した。 Test No. 3 satisfying the production conditions of the present invention. The invention examples 19 to 24 exhibited good HAZ crack resistance because the maximum crystal grain size was less than 0.3 mm and the total HAZ crack length was 1.5 mm or less.
一方で、本発明の製造条件を満足しない試験Ｎｏ．２５〜３３の鋼は、以下に示す理由で要求される特性を満足しなかった。
まず、試験Ｎｏ．３３は、二回圧延を実施しないことで非常に粗大な未再結晶粒が残存し、試験Ｎｏ．２５、および２７〜３１は、本発明の規定する製造条件を実施しないことで粗大な未再結晶粒が残存しており、ＨＡＺ総割れ長さも１．５ｍｍ超となり、耐ＨＡＺ割れ感受性が低下していた。試験Ｎｏ．２６とＮｏ．３２は、本発明の規定する製造条件を満足せず、熱延疵が発生した。On the other hand, Test No. which does not satisfy the manufacturing conditions of the present invention. Steels Nos. 25 to 33 did not satisfy the required properties for the following reasons.
First, test no. In Test No. 33, very coarse unrecrystallized grains remained due to not performing rolling twice. Nos. 25 and 27 to 31 have coarse unrecrystallized grains remaining by not performing the production conditions specified in the present invention, the total HAZ crack length also exceeds 1.5 mm, and the HAZ cracking susceptibility decreases. I was Test No. 26 and no. No. 32 did not satisfy the production conditions specified in the present invention, and hot rolling defects occurred.
本発明によれば、板厚６．０ｍｍ以上の厚鋼板であっても、耐ポリチオン酸ＳＣＣ性と耐溶接割れ性とに優れたオーステナイト系ステンレス鋼板を得ることができる。本発明によれば、耐ポリチオン酸ＳＣＣ性が要求される石油脱硫装置のうち、加熱炉管といった鋼管および薄鋼板だけでなく、反応器またはインターナル等、厚鋼板での製造が必要な装置または設備にも使用するオーステナイト系ステンレス鋼板を提供することができる。
According to the present invention, it is possible to obtain an austenitic stainless steel sheet having excellent polythionic acid SCC resistance and weld crack resistance even with a thick steel sheet having a thickness of 6.0 mm or more. According to the present invention, among petroleum desulfurization apparatuses that require polythionic acid SCC resistance, not only steel pipes and thin steel sheets such as heating furnace tubes, but also equipment that requires the production of thick steel sheets, such as reactors or internals, or An austenitic stainless steel sheet used for equipment can be provided.
Claims (5)
Ｃ：０．０４％未満、
Ｓｉ：１．５％以下、
Ｍｎ：２．０％以下、
Ｐ：０．０４％以下、
Ｓ：０．０３％以下、
Ｎ：０．０２〜０．３５％、
Ｏ：０．０３％以下、
Ｎｂ：０．０５〜０．５％、
Ｃｒ：１５．０〜２５．０％、
Ｎｉ：６．０〜３０．０％、
Ａｌ：０．０５％以下、
Ｔｉ：０〜０．４％、
Ｖ：０〜０．４％、
Ｔａ：０〜０．２％、
Ｈｆ：０〜０．２％、
Ｚｒ：０〜０．２％、
Ｃｕ：０〜３．０％、
Ｍｏ：０〜５．０％、
Ｗ：０〜５．０％、
Ｃｏ：０〜１．０％、
Ｂ：０〜０．０１２％、
Ｃａ：０〜０．０２％、
Ｍｇ：０〜０．０２％、および、
ＲＥＭ：０〜０．１％、を含有し、
残部：Ｆｅおよび不純物、
であり、圧延方向に垂直な断面において、最大結晶粒径が０．３ｍｍ未満である、板厚６．０ｍｍ以上のオーステナイト系ステンレス厚鋼板。Chemical composition in mass%
C: less than 0.04%,
Si: 1.5% or less,
Mn: 2.0% or less,
P: 0.04% or less,
S: 0.03% or less,
N: 0.02 to 0.35%,
O: 0.03% or less,
Nb: 0.05-0.5%,
Cr: 15.0 to 25.0%,
Ni: 6.0 to 30.0%,
Al: 0.05% or less,
Ti: 0 to 0.4%,
V: 0 to 0.4%,
Ta: 0 to 0.2%,
Hf: 0 to 0.2%,
Zr: 0 to 0.2%,
Cu: 0 to 3.0%,
Mo: 0 to 5.0%,
W: 0 to 5.0%,
Co: 0 to 1.0%,
B: 0 to 0.012%,
Ca: 0 to 0.02%,
Mg: 0 to 0.02%, and
REM: 0-0.1%,
The balance: Fe and impurities,
An austenitic stainless steel plate having a maximum grain size of less than 0.3 mm in a cross section perpendicular to the rolling direction and having a plate thickness of 6.0 mm or more.
Ｔｉ：０．００５〜０．４％、
Ｖ：０．００５〜０．４％、
Ｔａ：０．００３〜０．２％、
Ｈｆ：０．００３〜０．２％、
Ｚｒ：０．００３〜０．２％、
Ｃｕ：０．０２〜３．０％、
Ｍｏ：０．０５〜５．０％、
Ｗ：０．０５〜５．０％、
Ｃｏ：０．０３〜１．０％、
Ｂ：０．０００１〜０．０１２％、
Ｃａ：０．０００１〜０．０２％、
Ｍｇ：０．０００１〜０．０２％、および、
ＲＥＭ：０．００１〜０．１％、
から選択される１種以上を含有する、請求項１に記載のオーステナイト系ステンレス厚鋼板。The chemical composition of the steel sheet is further, in mass%,
Ti: 0.005 to 0.4%,
V: 0.005 to 0.4%,
Ta: 0.003 to 0.2%,
Hf: 0.003-0.2%,
Zr: 0.003-0.2%,
Cu: 0.02 to 3.0%,
Mo: 0.05-5.0%,
W: 0.05 to 5.0%,
Co: 0.03 to 1.0%,
B: 0.0001 to 0.012%,
Ca: 0.0001 to 0.02%,
Mg: 0.0001 to 0.02%, and
REM: 0.001-0.1%,
The austenitic stainless steel plate according to claim 1, comprising at least one member selected from the group consisting of:
（ａ）請求項１または２に記載の化学組成を有する鋳片または鋼片を加熱し、圧下率を３０％以上の条件で一次熱間圧延し、鋼板とする工程と、
（ｂ）前記鋼板を１１００〜１２５０℃に加熱し、圧延終了温度を１０５０℃以下、圧下率を３０％以上の条件で、二次熱間圧延し、
当該工程において、加熱後、二次熱間圧延終了までの間に８５０〜１１００℃の温度域で３分以上保持する工程と、
（ｃ）９５０〜１１５０℃温度域で固溶化熱処理を行う工程と
を、順に施す、オーステナイト系ステンレス厚鋼板の製造方法。A method for producing an austenitic stainless steel plate having the chemical composition,
(A) heating a slab or a slab having the chemical composition according to claim 1 or 2 and subjecting the slab or primary slab to primary hot rolling under a condition of a draft of 30% or more to form a steel sheet;
(B) The steel sheet is heated to 1100 to 1250 ° C, and subjected to secondary hot rolling under the conditions of a rolling end temperature of 1050 ° C or less and a rolling reduction of 30% or more,
In the process, after heating, maintaining the temperature range of 850 to 1100 ° C. for 3 minutes or more until the end of the secondary hot rolling,
(C) performing a solution heat treatment in a temperature range of 950 to 1150 ° C., in that order.
（Ａ）請求項１または２に記載の化学組成を有する鋳片または鋼片を加熱し、圧下率を３０％以上の条件で一次熱間圧延し、鋼板とする工程と、
（Ｂ）前記鋼板を１１００〜１２５０℃で中間熱処理する工程と、
（Ｃ）前記鋼板を９５０〜１１００℃に加熱し、圧延終了温度を１０５０℃以下、圧下率を３０％以上の条件で、二次熱間圧延する工程と、
（Ｄ）９５０〜１１５０℃温度域で固溶化熱処理を行う工程と
を、順に施す、オーステナイト系ステンレス厚鋼板の製造方法。
A method for producing an austenitic stainless steel plate having the chemical composition,
(A) a step of heating a slab or a slab having the chemical composition according to claim 1 or 2 and subjecting the slab or primary slab to primary hot rolling under a condition of a draft of 30% or more to form a steel sheet;
(B) an intermediate heat treatment of the steel sheet at 1100 to 1250 ° C;
(C) a step of heating the steel sheet to 950 to 1100 ° C., and performing secondary hot rolling under the conditions of a rolling end temperature of 1050 ° C. or less and a rolling reduction of 30% or more;
(D) a step of performing solution heat treatment in a temperature range of 950 to 1150 ° C., in that order.
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| CN110484836B (en) * | 2019-09-24 | 2021-01-05 | 南京佑天金属科技有限公司 | Hafnium zirconium titanium molybdenum reinforced austenitic stainless steel and preparation method thereof |
| KR20220124238A (en) * | 2020-01-10 | 2022-09-13 | 닛폰세이테츠 가부시키가이샤 | austenitic stainless steel |
| WO2021215203A1 (en) * | 2020-04-20 | 2021-10-28 | 日鉄ステンレス株式会社 | Austenitic stainless steel and spring |
| CN112853231A (en) * | 2020-08-18 | 2021-05-28 | 浙江增诚钢管有限公司 | Stainless steel seamless steel tube for high-pressure boiler and manufacturing method thereof |
| CN114457223B (en) * | 2020-11-09 | 2024-05-17 | 中国科学院金属研究所 | Thermal deformation processing technology of austenitic stainless steel |
| WO2023166926A1 (en) * | 2022-03-01 | 2023-09-07 | 日鉄ステンレス株式会社 | HIGH-Ni ALLOY THICK STEEL SHEET HAVING EXCELLENT WELD HIGH-TEMPERATURE CRACKING RESISTANCE, AND METHOD FOR PRODUCING SAME |
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