JP5928394B2 - Steel structure for hydrogen excellent in hydrogen embrittlement resistance in high-pressure hydrogen gas, hydrogen pressure accumulator, and method for producing hydrogen line pipe - Google Patents
Steel structure for hydrogen excellent in hydrogen embrittlement resistance in high-pressure hydrogen gas, hydrogen pressure accumulator, and method for producing hydrogen line pipe Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 171
- 239000001257 hydrogen Substances 0.000 title claims description 155
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 155
- 229910000831 Steel Inorganic materials 0.000 title claims description 137
- 239000010959 steel Substances 0.000 title claims description 137
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 238000001816 cooling Methods 0.000 claims description 54
- 230000009466 transformation Effects 0.000 claims description 53
- 229910000734 martensite Inorganic materials 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 32
- 238000010791 quenching Methods 0.000 claims description 26
- 238000005496 tempering Methods 0.000 claims description 26
- 230000000171 quenching effect Effects 0.000 claims description 25
- 229910001563 bainite Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 238000005098 hot rolling Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 description 34
- 238000010438 heat treatment Methods 0.000 description 17
- 229910001566 austenite Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910000851 Alloy steel Inorganic materials 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000003303 reheating Methods 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 2
- 229910001567 cementite Inorganic materials 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 1
- -1 as it is Substances 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Description
本発明は、高圧水素環境中で優れた耐水素脆化特性を有する水素用蓄圧器や水素用ラインパイプ等の水素用鋼構造物、ならびにこれら水素用蓄圧器および水素用ラインパイプの製造方法に関する。 TECHNICAL FIELD The present invention relates to a steel structure for hydrogen, such as a hydrogen pressure accumulator and a hydrogen line pipe having excellent hydrogen embrittlement resistance in a high-pressure hydrogen environment, and a method for producing these hydrogen pressure accumulator and hydrogen line pipe. .
近年、クリーンなエネルギー源として、また、エネルギーの多様化の観点から、世界的に水素が大きく注目されている。特に、高圧水素ガスを燃料源とする燃料電池自動車に対する期待は大きく、燃料電池自動車の開発に関連した研究が世界的に広く進められており、一部では、すでに実用化試験まで行われている。 In recent years, hydrogen has attracted a great deal of attention worldwide as a clean energy source and from the viewpoint of energy diversification. In particular, there are high expectations for fuel cell vehicles that use high-pressure hydrogen gas as the fuel source, and research related to the development of fuel cell vehicles has been widely promoted worldwide, and some have already been put into practical use. .
燃料電池車はガソリンの代わりに水素をタンクに積んで走行するため、燃料電池自動車の普及のためには、ガソリンスタンドに代わって燃料補給を行う水素ステーションが必要となる。水素ステーションでは水素を高圧で貯蔵する水素用容器である水素用蓄圧器から車載の水素燃料タンクへ水素を充填する。車載の水素タンクへの充填最高圧力は、現状では３５ＭＰａであるが、航続距離をガソリン車並とするために、充填最高圧力を７０ＭＰａとすることが期待されており、このような高圧水素環境下で、水素を安全に貯蔵、供給することが要求される。そのため水素ステーションの水素用蓄圧器の圧力も現状では４０ＭＰａが要求されているが、さらに充填最高圧力を７０ＭＰａに上昇する場合、水素ステーションの水素用蓄圧器の圧力は８０ＭＰａが要求されることとなり、水素ステーションの水素用蓄圧器は８０ＭＰａの環境にさらされることになる。 Since a fuel cell vehicle travels with hydrogen stored in a tank instead of gasoline, a hydrogen station for refueling is required instead of a gas station in order to spread the fuel cell vehicle. In the hydrogen station, hydrogen is filled from a hydrogen pressure accumulator, which is a hydrogen container for storing hydrogen at a high pressure, into an on-vehicle hydrogen fuel tank. The maximum filling pressure in an on-vehicle hydrogen tank is currently 35 MPa, but it is expected that the maximum filling pressure is 70 MPa in order to make the cruising range comparable to that of a gasoline vehicle. Therefore, it is required to store and supply hydrogen safely. Therefore, although the pressure of the hydrogen pressure accumulator at the hydrogen station is currently required to be 40 MPa, when the maximum filling pressure is further increased to 70 MPa, the pressure of the hydrogen pressure accumulator at the hydrogen station is required to be 80 MPa, The hydrogen accumulator at the hydrogen station will be exposed to an 80 MPa environment.
一方、低合金鋼に水素が侵入すると脆化することが知られている。水素圧が１５ＭＰａ程度までであれば、十分な肉厚を有する低合金鋼が用いられているが、それ以上の圧力では使用中に水素脆性破壊する危険性が高まるため、低合金鋼は使用されず、低合金鋼よりも水素脆化し難いＳＵＳ３１６Ｌ鋼等のオーステナイト系ステンレス鋼等が用いられている。 On the other hand, it is known that embrittlement occurs when hydrogen enters low alloy steel. If the hydrogen pressure is up to about 15 MPa, a low alloy steel having a sufficient thickness is used, but at higher pressures, the risk of hydrogen embrittlement failure during use increases, so low alloy steel is used. In addition, austenitic stainless steel such as SUS316L steel, which is less susceptible to hydrogen embrittlement than low alloy steel, is used.
しかし、ＳＵＳ３１６Ｌ鋼等は鋼材のコストが高いことに加えて、強度が低いため、８０ＭＰａの水素圧に耐えうるように設計するためには、非常に肉厚が厚くなり、水素用蓄圧器そのものの価格も非常に高価となる。そのため、より低コストで８０ＭＰａの圧力に耐えうる水素ステーション用の水素用蓄圧器を開発することが要望されている。 However, since SUS316L steel has a low strength in addition to the high cost of the steel material, in order to design it to withstand the hydrogen pressure of 80 MPa, the wall thickness becomes very thick, and the hydrogen pressure accumulator itself The price is also very expensive. Therefore, it is desired to develop a hydrogen accumulator for a hydrogen station that can withstand a pressure of 80 MPa at a lower cost.
上記問題点を解決し、低合金鋼を高圧水素蓄圧器に適用するための技術が種々検討されている。特許文献１では、鋼中水素のトラップサイトとして、ＭｎＳやＣａ系介在物、またはＶＣを活用して非拡散性水素とし、拡散性水素による脆化を抑制する高圧水素環境用鋼が提案されている。特許文献２、３では、Ｃｒ−Ｍｏ鋼の調質処理において比較的高い温度で焼戻し処理をすることで引張強度を９００〜９５０ＭＰａの極めて狭い範囲に制御した、耐高圧水素環境脆化特性に優れた低合金高強度鋼が提案されている。特許文献４では、Ｖ−Ｍｏ系炭化物を活用し、焼戻し温度を高めることで耐水素環境脆化特性を向上した、高圧水素環境用低合金鋼が提案され、特許文献５では、ＭｏとＶを多量に添加し、鋼板製造時に焼準処理の後に長時間の応力除去焼鈍を施すことで、（Ｍｏ，Ｖ）Ｃを多量に析出させた耐水素性に優れた高圧水素ガス貯蔵容器用鋼が提案されている。特許文献６では、セメンタイトの微細化により水素侵入量を低減し母材靭性を向上させることにより水素脆化を抑制する技術が、特許文献７では、粗大セメンタイトおよび島状マルテンサイト（ＭＡ）の生成を抑制することにより、水素侵入と延性低下を抑制することにより水素脆化を抑制する技術が提案されている。なお、通常の低合金鋼についての疲労き裂進展特性については、非特許文献１、２等に記載されている。 Various techniques for solving the above problems and applying low alloy steel to a high pressure hydrogen accumulator have been studied. Patent Document 1 proposes a steel for high pressure hydrogen environment that uses MnS, Ca-based inclusions, or VC as non-diffusible hydrogen as a hydrogen trap site in steel and suppresses embrittlement due to diffusible hydrogen. Yes. In Patent Documents 2 and 3, the tensile strength is controlled to an extremely narrow range of 900 to 950 MPa by tempering at a relatively high temperature in the tempering treatment of Cr—Mo steel, and it has excellent high-pressure hydrogen environment embrittlement resistance. Low alloy high strength steels have been proposed. Patent Document 4 proposes a low-alloy steel for high-pressure hydrogen environment in which V-Mo-based carbides are utilized and the tempering temperature is increased to improve hydrogen embrittlement resistance, and in Patent Document 5, Mo and V are combined. Proposed steel for high-pressure hydrogen gas storage vessel with excellent hydrogen resistance by adding a large amount and applying stress-relief annealing for a long time after the normalizing treatment during steel plate production. Has been. In Patent Document 6, a technique for suppressing hydrogen embrittlement by reducing the amount of hydrogen intrusion and improving the base material toughness by refining cementite, and Patent Document 7 generates coarse cementite and island martensite (MA). A technique for suppressing hydrogen embrittlement by suppressing hydrogen intrusion and ductility reduction has been proposed. Note that the fatigue crack growth characteristics of ordinary low alloy steels are described in Non-Patent Documents 1 and 2, etc.
特に高圧水素環境下で使用する水素用蓄圧器では、繰り返し水素の充填を行うことにより、容器に繰返し応力がかかるため、長期間の使用寿命を確保することが難しかった。使用寿命を長期間化する上では、疲労き裂進展速度を低減することが重要である。しかしながら、上記したような従来技術では、疲労き裂進展速度を十分に低下させることはできなかった。 In particular, in a hydrogen pressure accumulator used in a high-pressure hydrogen environment, it is difficult to secure a long-term service life because repeated stress is applied to the container by repeatedly filling with hydrogen. In order to extend the service life, it is important to reduce the fatigue crack growth rate. However, the conventional techniques as described above cannot sufficiently reduce the fatigue crack growth rate.
また、水素用パイプラインで使用される水素用ラインパイプ等、現状では必ずしも水素用蓄圧器ほどの高圧水素環境下にはない水素用鋼構造物についても、水素用蓄圧器と同程度の安全性を確保できることが望ましい。 In addition, hydrogen steel pipes used in hydrogen pipelines and other steel structures that are not always in a high-pressure hydrogen environment as high as hydrogen accumulators are as safe as hydrogen accumulators. It is desirable to be able to ensure.
本発明は、上記の現状に鑑み開発されたもので、従来鋼より高圧水素環境中での疲労き裂進展速度を低下させた、優れた耐水素脆化特性を有する水素用蓄圧器や水素用ラインパイプ等の水素用鋼構造物を提供することを目的とする。 The present invention has been developed in view of the above-mentioned present situation, and has a hydrogen accumulator and hydrogen-resistant hydrogen having excellent hydrogen embrittlement resistance, which has a lower fatigue crack growth rate in a high-pressure hydrogen environment than conventional steels. It aims at providing the steel structure for hydrogen, such as a line pipe.
本発明者らは、上記の観点で様々な組織形態を有する水素用鋼構造物の高圧水素ガス中における耐水素脆化特性を慎重に調べた結果、鋼組織を所定量のマルテンサイトを有し残部を実質的にベイナイトとする、すなわち鋼組織を実質的にベイナイトおよびマルテンサイトの二相組織とすることによって、単相組織の従来材よりも高圧水素ガス中での耐水素脆化特性を向上でき、耐水素脆化特性に優れた水素用蓄圧器や水素用ラインパイプ等の水素用鋼構造物を得ることができることを見出した。 As a result of careful examination of hydrogen embrittlement resistance in high-pressure hydrogen gas of a steel structure for hydrogen having various structure forms from the above viewpoint, the present inventors have found that the steel structure has a predetermined amount of martensite. Improves hydrogen embrittlement resistance in high-pressure hydrogen gas than conventional materials with a single-phase structure by making the balance substantially bainite, that is, making the steel structure substantially a two-phase structure of bainite and martensite. It has been found that hydrogen steel structures such as hydrogen pressure accumulators and hydrogen line pipes having excellent hydrogen embrittlement resistance can be obtained.
本発明は、かかる新たな知見に基づき、更に検討を加えてなされたものであって、以下を要旨構成とする。 The present invention has been made on the basis of such new findings and has been further studied.
［１］マルテンサイトの面積率が１０〜９５％であり、残部が実質的にベイナイトからなる鋼組織を有する高圧水素ガス中の耐水素脆化特性に優れた水素用鋼構造物。 [1] A steel structure for hydrogen having excellent martensitic area resistance in high-pressure hydrogen gas in a high-pressure hydrogen gas having a steel structure in which the area ratio of martensite is 10 to 95% and the balance is substantially composed of bainite.
［２］質量％で、Ｃ：０．１０〜０．５０％、Ｓｉ：０．０５〜０．５％、Ｍｎ：０．５〜２．０％、Ａｌ：０．０１〜０．１０％、Ｎ：０．０００５〜０．００８％、Ｐ：０．０５％以下、Ｓ：０．０１％以下、Ｏ：０．０１％以下を含有し、残部がＦｅおよび不可避的不純物からなる鋼組成を有することを特徴とする、前記［１］に記載の水素用鋼構造物。 [2] By mass%, C: 0.10 to 0.50%, Si: 0.05 to 0.5%, Mn: 0.5 to 2.0%, Al: 0.01 to 0.10% , N: 0.0005 to 0.008%, P: 0.05% or less, S: 0.01% or less, O: 0.01% or less, with the balance being Fe and inevitable impurities The steel structure for hydrogen according to the above [1], comprising:
［３］さらに、質量％で、Ｃｕ：０．０５〜１．０％、Ｎｉ：０．０５〜２．０％、Ｃｒ：０．１〜２．５％、Ｍｏ：０．０５〜２．０％、Ｎｂ：０．００５〜０．１％、Ｖ：０．００５〜０．２％、Ｔｉ：０．００５〜０．１％、Ｗ：０．０５〜２．０％、Ｂ：０．０００５〜０．００５％の一種または二種以上を含有する鋼組成を有することを特徴とする、前記［２］に記載の水素用鋼構造物。 [3] Further, in terms of mass%, Cu: 0.05 to 1.0%, Ni: 0.05 to 2.0%, Cr: 0.1 to 2.5%, Mo: 0.05 to 2.%. 0%, Nb: 0.005-0.1%, V: 0.005-0.2%, Ti: 0.005-0.1%, W: 0.05-2.0%, B: 0 The steel structure for hydrogen according to [2] above, which has a steel composition containing one or more of 0.0005 to 0.005%.
［４］さらに、質量％で、Ｎｄ：０．００５〜１．０％、Ｃａ：０．０００５〜０．００５％、Ｍｇ：０．０００５〜０．００５％、ＲＥＭ：０．０００５〜０．００５％の一種または二種以上を含有する鋼組成を有することを特徴とする、前記［２］または［３］に記載の水素用鋼構造物。 [4] Further, in terms of mass%, Nd: 0.005-1.0%, Ca: 0.0005-0.005%, Mg: 0.0005-0.005%, REM: 0.0005-0. The steel structure for hydrogen according to the above [2] or [3], which has a steel composition containing one or more of 005%.
［５］前記水素用鋼構造物が、水素用蓄圧器あるいは水素用ラインパイプである、前記［１］ないし［４］のいずれか一つに記載の水素用鋼構造物。 [5] The hydrogen steel structure according to any one of [1] to [4], wherein the hydrogen steel structure is a hydrogen pressure accumulator or a hydrogen line pipe.
［６］前記［５］に記載する水素用ラインパイプの製造方法であって、前記［２］〜［４］のいずれかに記載の鋼組成を有する鋼素材を、Ａｃ３変態点以上に加熱し、熱間圧延後、引続きＡｒ３変態点以上から冷却速度１〜２００℃／ｓで６００℃以下の温度まで冷却することを特徴とする、高圧水素ガス中の耐水素脆化特性に優れた水素用ラインパイプの製造方法。 [6] The method for producing a hydrogen line pipe according to [5], wherein the steel material having the steel composition according to any one of [2] to [4] is heated to an Ac 3 transformation point or higher. And after hot rolling, it was excellent in hydrogen embrittlement resistance in high-pressure hydrogen gas, characterized in that it was continuously cooled from the Ar 3 transformation point or higher to a temperature of 600 ° C. or lower at a cooling rate of 1 to 200 ° C./s. Manufacturing method of hydrogen line pipe.
［７］前記［５］に記載する水素用ラインパイプの製造方法であって、前記［２］〜［４］のいずれかに記載の鋼組成を有する鋼素材を、Ａｃ３変態点以上に加熱し、熱間圧延後、引続きＡｒ３変態点以上から冷却速度１〜２００℃／ｓで２５０℃以下の温度まで焼入れ、引続きＡｃ１変態点以下の温度で焼戻すことを特徴とする、高圧水素ガス中の耐水素脆化特性に優れた水素用ラインパイプの製造方法。 [7] The method for producing a hydrogen line pipe according to [5], wherein the steel material having the steel composition according to any one of [2] to [4] is heated to an Ac 3 transformation point or higher. Then, after hot rolling, the high pressure hydrogen is characterized in that it is continuously quenched from the Ar 3 transformation point or higher to a temperature of 250 ° C. or lower at a cooling rate of 1 to 200 ° C./s, and subsequently tempered at a temperature below the Ac 1 transformation point. A method for producing a hydrogen line pipe with excellent hydrogen embrittlement resistance in gas.
［８］前記［５］に記載する水素用蓄圧器の製造方法であって、前記［２］〜［４］のいずれかに記載の鋼組成を有する鋼材を所定の形状に成形後、Ａｃ３変態点以上に加熱し、引続きＡｒ３変態点以上から冷却速度０．５〜１００℃／ｓで２５０℃以下の温度まで焼入れ、引続きＡｃ１変態点以下の温度で焼戻すことを特徴とする、高圧水素ガス中の耐水素脆化特性に優れた水素用蓄圧器の製造方法。 [8] A method for manufacturing a hydrogen pressure accumulator according to [5], wherein a steel material having the steel composition according to any one of [2] to [4] is formed into a predetermined shape, and then Ac 3 Heating above the transformation point, and subsequently quenching from the Ar 3 transformation point or more to a temperature of 250 ° C. or less at a cooling rate of 0.5 to 100 ° C./s, and subsequently tempering at a temperature below the Ac 1 transformation point, A method for producing a hydrogen pressure accumulator excellent in hydrogen embrittlement resistance in high-pressure hydrogen gas.
本発明によれば、従来よりも高圧水素ガス中の耐水素脆化特性が極めて優れる水素用蓄圧器や水素用ラインパイプ等の水素用鋼構造物を得ることができ、産業上極めて有用である。 According to the present invention, it is possible to obtain a steel structure for hydrogen, such as a hydrogen accumulator or a hydrogen line pipe, which is extremely superior in hydrogen embrittlement resistance in high-pressure hydrogen gas, and is extremely useful industrially. .
以下、本発明を具体的に説明する。
本発明の水素用鋼構造物の鋼組織は、マルテンサイトの面積率が１０〜９５％であり、残部が実質的にベイナイトからなる。
Hereinafter, the present invention will be specifically described.
The steel structure of the steel structure for hydrogen according to the present invention has a martensite area ratio of 10 to 95%, and the balance substantially consists of bainite.
本発明の水素用鋼構造物の鋼組織は、軟質なベイナイトと硬質のマルテンサイトが分散しており、それらの界面近傍で疲労き裂が停滞し、迂回、分岐する効果のため、疲労き裂の進展速度が低下し、優れた耐水素脆化特性を有する。 The steel structure of the steel structure for hydrogen of the present invention has a structure in which soft bainite and hard martensite are dispersed, and the fatigue crack is stagnated near the interface between them, and the effect of diverting and branching The rate of progress of the material decreases, and it has excellent hydrogen embrittlement resistance.
このような効果は、組織全体に対する面積率で、マルテンサイト組織の面積率を１０〜９５％とし、残部を基本的にベイナイトとすること、すなわち主としてマルテンサイトおよびベイナイトの二相組織とすることで、明らかな効果が認められるため、本発明では、上記水素用鋼構造物の鋼組織を、マルテンサイト組織の面積率を１０〜９５％とし、残部を実質的にベイナイト組織とする。好ましくはマルテンサイトの面積率は２０〜９５％、より好ましくは２５〜９５％である。ここで、ベイナイト組織とマルテンサイト組織の面積率がほぼ同じ場合、すなわちベイナイト組織とマルテンサイト組織の合計の面積率に対するマルテンサイト組織の面積率の割合である、マルテンサイト面積率比［マルテンサイト面積率比：（マルテンサイト組織の面積率）／（（ベイナイト組織の面積率）＋（マルテンサイト組織の面積率））］が、０．３〜０．７の場合に、最も疲労き裂進展速度が低下する。このため、マルテンサイト面積率比は０．３〜０．７とすることが好ましい。より好ましくは、マルテンサイト面積率比は０．４〜０．６である。なお、マルテンサイト組織以外の残部は、実質的にはベイナイトとするが、フェライトやパーライト等、マルテンサイトおよびベイナイト以外の組織を合計の面積率で２％以下であれば、本発明の効果に影響はないため、含有しても良い。すなわち、マルテンサイトとベイナイトの合計の面積率が９８％以上であれば、その他の組織を含有しても良い。 Such an effect is an area ratio with respect to the whole structure. The area ratio of the martensite structure is 10 to 95%, and the remainder is basically bainite, that is, mainly a two-phase structure of martensite and bainite. Since an obvious effect is recognized, in the present invention, the steel structure of the hydrogen steel structure has an area ratio of the martensite structure of 10 to 95%, and the balance is substantially a bainite structure. Preferably, the area ratio of martensite is 20 to 95%, more preferably 25 to 95%. Here, when the area ratios of the bainite structure and the martensite structure are substantially the same, that is, the ratio of the area ratio of the martensite structure to the total area ratio of the bainite structure and the martensite structure, the martensite area ratio ratio [martensite area Ratio: (martensite structure area ratio) / ((bainite structure area ratio) + (martensite structure area ratio))] is 0.3 to 0.7, the most fatigue crack growth rate Decreases. For this reason, the martensite area ratio is preferably 0.3 to 0.7. More preferably, the martensite area ratio is 0.4 to 0.6. The remainder other than the martensite structure is substantially bainite. However, if the total area ratio of the structure other than martensite and bainite, such as ferrite and pearlite, is 2% or less, the effect of the present invention is affected. Therefore, it may be contained. That is, other structures may be included as long as the total area ratio of martensite and bainite is 98% or more.
組織分率の測定は、例えばナイタールエッチングによって、ミクロ組織を現出させ、光学顕微鏡またはＳＥＭ（Ｓｃａｎｎｉｎｇ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ）を用いて組織写真を撮影し、それぞれの組織を識別して、面積率を求めればよい。 For the measurement of the tissue fraction, the microstructure is revealed by, for example, nital etching, and a structure photograph is taken using an optical microscope or SEM (Scanning Electron Microscope), and each tissue is identified to obtain the area ratio. That's fine.
なお、高圧水素ガス中の耐水素脆化特性に優れた水素用鋼構造物とは、後述するような応力拡大係数範囲ΔＫ＝２５（ＭＰａ・ｍ１／２）の時の疲労き裂進展速度が１．０×１０−６（ｍ／ｃｙｃｌｅ）以下である水素用鋼構造物を意味し、水素用蓄圧器や水素用ラインパイプが例示される。 Note that a steel structure for hydrogen excellent in hydrogen embrittlement resistance in high-pressure hydrogen gas is a fatigue crack growth rate when the stress intensity factor range ΔK = 25 (MPa · m 1/2 ) as described later. Means a steel structure for hydrogen having 1.0 × 10 −6 (m / cycle) or less, and examples thereof include a hydrogen accumulator and a hydrogen line pipe.
また、本発明の水素用鋼構造物である水素用蓄圧器は、前記したように、水素ステーションなどで使用される蓄圧器であり、例えば、タイプ１の鋼材のみを用いるタイプまたは、タイプ２およびタイプ３の鋼材に炭素繊維強化プラスチック（ＣＦＲＰ：Ｃａｒｂｏｎ Ｆｉｂｅｒ Ｒｅｉｎｆｏｒｃｅｄ Ｐｌａｓｔｉｃ）を巻くタイプである。なお、ここでタイプ１、タイプ２、タイプ３とは、圧縮天然ガス自動車燃料容器に関する各規格、ＩＳＯ１１４３９、ＡＮＳＩ／ＮＧＶ、高圧ガス保安法 容器保安規則例示基準別添９などに記載される容器の構造についての区分である。また、貯蔵される水素の圧力としては、３５ＭＰａ程度または７０ＭＰａ程度である。また、本発明の水素用鋼構造物である水素用ラインパイプは、シームレスタイプまたはＵＯＥタイプの鋼管であり、水素の圧力としては、５ＭＰａ以上である。 Further, as described above, the hydrogen pressure accumulator which is the steel structure for hydrogen of the present invention is a pressure accumulator used in a hydrogen station or the like, for example, a type using only a type 1 steel material, or type 2 and This is a type in which a carbon fiber reinforced plastic (CFRP) is wound around a type 3 steel material. Here, type 1, type 2, and type 3 are the standards for compressed natural gas vehicle fuel containers, ISO 11439, ANSI / NGV, High Pressure Gas Safety Act, Container Safety Regulations, Example Standard Attachment 9, etc. It is a division about the structure. Further, the pressure of hydrogen stored is about 35 MPa or about 70 MPa. Moreover, the hydrogen line pipe which is the steel structure for hydrogen of the present invention is a seamless type or UOE type steel pipe, and the hydrogen pressure is 5 MPa or more.
次に、本発明の水素用鋼構造物の好ましい鋼組成を上記範囲に限定した理由について、説明する。なお、成分組成を示す％は、特に断らない限り、質量％を意味する。 Next, the reason why the preferable steel composition of the steel structure for hydrogen of the present invention is limited to the above range will be described. In addition,% which shows a component composition means the mass% unless there is particular notice.
Ｃ：０．１０〜０．５０％
Ｃは、適度な焼入れ性を確保するために含有するが、０．１０％未満ではその効果が不十分であり、一方、０．５０％を超えると母材および溶接熱影響部の靭性が劣化するとともに、溶接性が著しく劣化する。従って、Ｃ含有量を０．１０〜０．５０％に限定する。
C: 0.10 to 0.50%
C is contained in order to ensure moderate hardenability. However, if it is less than 0.10%, the effect is insufficient. On the other hand, if it exceeds 0.50%, the toughness of the base metal and the weld heat-affected zone deteriorates. In addition, the weldability is significantly deteriorated. Therefore, the C content is limited to 0.10 to 0.50%.
Ｓｉ：０．０５〜０．５％
Ｓｉは、製鋼段階の脱酸材および焼入れ性を確保する元素として含有するが、０．０５％未満ではその効果が不十分であり、一方、０．５％を超えると粒界が脆化し、低温靭性を劣化させる。従って、Ｓｉ含有量を０．０５〜０．５％に限定する。
Si: 0.05-0.5%
Si is contained as a deoxidizing material in the steelmaking stage and an element that ensures hardenability, but if less than 0.05%, the effect is insufficient, while if exceeding 0.5%, the grain boundary becomes brittle, Deteriorates low temperature toughness. Therefore, the Si content is limited to 0.05 to 0.5%.
Ｍｎ：０．５〜２．０％
Ｍｎは、焼入れ性を確保する元素として含有するが、０．５％未満ではその効果が不十分であり、一方、２．０％を超えて含有すると、粒界強度が低下し、低温靭性が劣化する。したがって、Ｍｎ含有量を０．５〜２．０％に限定する。
Mn: 0.5 to 2.0%
Mn is contained as an element for ensuring hardenability. However, if it is less than 0.5%, the effect is insufficient. On the other hand, if it exceeds 2.0%, the grain boundary strength is lowered, and the low temperature toughness is low. to degrade. Therefore, the Mn content is limited to 0.5 to 2.0%.
Ａｌ：０．０１〜０．１０％
Ａｌは、脱酸材として添加されると同時に、Ａｌ系窒化物の微細析出物として加熱時にオーステナイト粒をピンニングし、粒の粗大化を抑制する効果があるが、０．０１％未満の場合にはその効果が十分でなく、一方、０．１０％を超えて含有すると、鋼板の表面疵が発生し易くなる。従って、Ａｌ含有量を０．０１〜０．１０％に限定する。
Al: 0.01-0.10%
Al is added as a deoxidizer and at the same time, pinning austenite grains during heating as Al-based nitride fine precipitates, and has the effect of suppressing grain coarsening, but less than 0.01% The effect is not sufficient. On the other hand, if the content exceeds 0.10%, surface flaws of the steel sheet are likely to occur. Therefore, the Al content is limited to 0.01 to 0.10%.
Ｎ：０．０００５〜０．００８％
Ｎは、Ｎｂ、Ｔｉ、Ａｌなどと窒化物を形成することによって微細析出物を形成し、加熱時にオーステナイト粒をピンニングすることによって、粒の粗大化を抑制し、低温靭性を向上させる効果を有するために添加する。０．０００５％未満の添加では組織の微細化効果が充分にもたらされず、一方、０．００８％を超える添加は固溶Ｎ量が増加するために母材および溶接熱影響部の靭性を損なう。従って、Ｎ含有量を０．０００５〜０．００８％に限定する。
N: 0.0005 to 0.008%
N forms fine precipitates by forming nitrides with Nb, Ti, Al, etc., and pinning austenite grains during heating, thereby suppressing grain coarsening and improving low-temperature toughness Add for. If the addition is less than 0.0005%, the effect of refining the structure is not sufficiently brought about. On the other hand, the addition exceeding 0.008% impairs the toughness of the base metal and the weld heat-affected zone because the amount of solute N increases. Therefore, the N content is limited to 0.0005 to 0.008%.
Ｐ：０．０５％以下
不純物元素であるＰは、結晶粒界に偏析しやすく、０．０５％を超えると隣接結晶粒の接合強度を低下させ、低温靭性を劣化させる。従って、Ｐ含有量を０．０５％以下に限定する。
P: 0.05% or less P, which is an impurity element, is easily segregated at the grain boundaries. Therefore, the P content is limited to 0.05% or less.
Ｓ：０．０１％以下
不純物元素であるＳは、結晶粒界に偏析しやすく、また、非金属介在物であるＭｎＳを生成しやすい。０．０１％を超えると隣接結晶粒の接合強度が低下し、介在物の量が多くなり、低温靭性を劣化させる。従って、Ｓ含有量を０．０１％以下に限定する。
S: 0.01% or less S, which is an impurity element, easily segregates at the crystal grain boundaries and easily generates MnS, which is a non-metallic inclusion. When it exceeds 0.01%, the bonding strength of adjacent crystal grains decreases, the amount of inclusions increases, and the low-temperature toughness deteriorates. Therefore, the S content is limited to 0.01% or less.
Ｏ：０．０１％以下
Ｏは、Ａｌなどと酸化物を形成することによって、材料の加工性に影響を及ぼす。０．０１％を超える含有は介在物が増加し、加工性を損なう。従って、Ｏ含有量を０．０１％以下に限定する。
O: 0.01% or less O affects the workability of the material by forming an oxide with Al or the like. Inclusions exceeding 0.01% increase inclusions and impair processability. Therefore, the O content is limited to 0.01% or less.
本発明では、上記成分組成の残部はＦｅおよび不可避的不純物からなる鋼組成とすることが好ましいが、所望する特性に応じて更に、Ｃｕ：０．０５〜１．０％、Ｎｉ：０．０５〜２．０％、Ｃｒ：０．１〜２．５％、Ｍｏ：０．０５〜２．０％、Ｎｂ：０．００５〜０．１％、Ｖ：０．００５〜０．２％、Ｔｉ：０．００５〜０．１％、Ｗ：０．０５〜２．０％、Ｂ：０．０００５〜０．００５％の一種または二種以上、Ｎｄ：０．００５〜１．０％、Ｃａ：０．０００５〜０．００５％、Ｍｇ：０．０００５〜０．００５％、ＲＥＭ：０．０００５〜０．００５％の一種または二種以上を、個別にあるいは同時に適宜含有させることがより好ましい。 In the present invention, the balance of the above component composition is preferably a steel composition composed of Fe and inevitable impurities. However, depending on the desired characteristics, Cu: 0.05 to 1.0%, Ni: 0.05 -2.0%, Cr: 0.1-2.5%, Mo: 0.05-2.0%, Nb: 0.005-0.1%, V: 0.005-0.2%, Ti: 0.005 to 0.1%, W: 0.05 to 2.0%, B: 0.0005 to 0.005%, one or more, Nd: 0.005 to 1.0%, One or two or more of Ca: 0.0005-0.005%, Mg: 0.0005-0.005%, REM: 0.0005-0.005% may be appropriately contained individually or simultaneously. preferable.
Ｃｕ：０．０５〜１．０％
Ｃｕは、焼入れ性を向上する作用を有している。０．０５％未満ではその効果が充分でなく、一方、１．０％を超えると、鋼片加熱時や溶接時に熱間での割れを生じやすくする。従って、Ｃｕを添加する場合には、その含有量を０．０５〜１．０％に限定する。
Cu: 0.05 to 1.0%
Cu has the effect | action which improves hardenability. If it is less than 0.05%, the effect is not sufficient. On the other hand, if it exceeds 1.0%, hot cracking is likely to occur during heating of the steel slab or welding. Therefore, when adding Cu, the content is limited to 0.05 to 1.0%.
Ｎｉ：０．０５〜２．０％
Ｎｉは、Ｃｕと同様に焼入れ性を向上する作用を有しており、さらに靭性を向上する作用も有する。０．０５％未満ではその効果が充分ではなく、一方、２．０％を超えると、経済性が劣る。従って、Ｎｉを添加する場合には、その含有量を０．０５〜２．０％に限定する。
Ni: 0.05-2.0%
Ni, like Cu, has an effect of improving hardenability, and further has an effect of improving toughness. If it is less than 0.05%, the effect is not sufficient, while if it exceeds 2.0%, the economy is inferior. Therefore, when adding Ni, the content is limited to 0.05 to 2.0%.
Ｃｒ：０．１〜２．５％
Ｃｒは、焼入れ性を確保する元素として含有するが、０．１％未満ではその効果が不十分であり、一方、２．５％を超えて含有すると溶接性が劣化する。従って、Ｃｒを添加する場合には、その含有量を０．１〜２．５％に限定する。
Cr: 0.1 to 2.5%
Cr is contained as an element for ensuring hardenability. However, if it is less than 0.1%, its effect is insufficient. On the other hand, if it exceeds 2.5%, weldability deteriorates. Therefore, when adding Cr, the content is limited to 0.1 to 2.5%.
Ｍｏ：０．０５〜２．０％
Ｍｏは、焼入れ性を向上する作用を有するが、０．０５％未満ではその効果が不十分であり、一方、２．０％を超える添加は経済性が劣る。従って、Ｍｏを添加する場合には、その含有量を０．０５〜２．０％に限定する。
Mo: 0.05-2.0%
Mo has the effect of improving the hardenability, but if less than 0.05%, the effect is insufficient, while the addition exceeding 2.0% is inferior in economic efficiency. Therefore, when adding Mo, the content is limited to 0.05 to 2.0%.
Ｎｂ：０．００５〜０．１％
Ｎｂは、焼入れ性を向上する作用を有するとともに、Ｎｂ系炭窒化物の微細析出物として加熱時にオーステナイト粒をピンニングし、粒の粗大化を抑制する。含有量が０．００５％未満ではその効果が不十分であり、一方、０．１％を超える添加は溶接熱影響部の靭性を劣化させる。従って、Ｎｂを添加する場合には、その含有量を０．００５〜０．１％に限定する。
Nb: 0.005 to 0.1%
Nb has the effect of improving hardenability, and also pinns austenite grains during heating as fine precipitates of Nb-based carbonitrides, thereby suppressing grain coarsening. If the content is less than 0.005%, the effect is insufficient. On the other hand, addition exceeding 0.1% deteriorates the toughness of the weld heat affected zone. Therefore, when adding Nb, the content is limited to 0.005 to 0.1%.
Ｖ：０．００５〜０．２％
Ｖは、焼入れ性を向上する作用を有すると共に、Ｖ系炭化物の微細析出物として加熱時にオーステナイト粒をピンニングし、粒の粗大化を抑制する。含有量が０．００５％未満ではその効果が不十分であり、一方、０．２％を超える添加は溶接熱影響部の靭性を劣化させる。従って、Ｖを添加する場合には、その含有量を０．００５〜０．２％に限定する。
V: 0.005-0.2%
V has the effect of improving hardenability, and also pinns austenite grains during heating as fine precipitates of V-based carbides, and suppresses coarsening of the grains. If the content is less than 0.005%, the effect is insufficient. On the other hand, addition exceeding 0.2% deteriorates the toughness of the weld heat affected zone. Therefore, when adding V, the content is limited to 0.005 to 0.2%.
Ｔｉ：０．００５〜０．１％
Ｔｉは、焼入れ性を向上する作用を有するとともに、Ｔｉ系炭窒化物の微細析出物として加熱時にオーステナイト粒をピンニングし、粒の成長を抑制する効果がある。含有量が０．００５％未満ではその効果が不十分であり、一方、０．１％を超える添加は溶接熱影響部の靭性を劣化させる。従って、Ｔｉを添加する場合には、その含有量を０．００５〜０．１％に限定する。
Ti: 0.005 to 0.1%
Ti has the effect of improving the hardenability and has the effect of pinning austenite grains during heating as a fine precipitate of Ti-based carbonitride to suppress grain growth. If the content is less than 0.005%, the effect is insufficient. On the other hand, addition exceeding 0.1% deteriorates the toughness of the weld heat affected zone. Therefore, when adding Ti, the content is limited to 0.005 to 0.1%.
Ｗ：０．０５〜２．０％
Ｗは、焼入れ性を向上する作用を有するが、０．０５％未満ではその効果が不十分であり、一方、２．０％を超えると、溶接性が劣化する。従って、Ｗを添加する場合は、その含有量を０．０５〜２．０％に限定する。
W: 0.05-2.0%
W has an effect of improving the hardenability, but if it is less than 0.05%, its effect is insufficient. On the other hand, if it exceeds 2.0%, the weldability deteriorates. Therefore, when adding W, the content is limited to 0.05 to 2.0%.
Ｂ：０．０００５〜０．００５％
Ｂは、焼入れ性を確保する元素として含有するが、０．０００５％未満ではその効果が不十分であり、一方、０．００５％を超えると、靭性を劣化させる。従って、Ｂを添加する場合には、その含有量を０．０００５〜０．００５％に限定する。
B: 0.0005 to 0.005%
B is contained as an element for ensuring hardenability. However, if it is less than 0.0005%, its effect is insufficient. On the other hand, if it exceeds 0.005%, the toughness is deteriorated. Therefore, when adding B, the content is limited to 0.0005 to 0.005%.
Ｎｄ：０．００５〜１．０％
Ｎｄは、Ｓを介在物として取り込み、Ｓの粒界偏析量を低減させ、低温靭性および耐水素脆性を向上させる作用を有している。含有量が０．００５％未満ではその効果が不十分であり、一方、１．０％を超える添加は溶接熱影響部の靭性を劣化させる。従って、Ｎｄを添加する場合には、その含有量を０．００５〜１．０％に限定する。
Nd: 0.005 to 1.0%
Nd has the effect of incorporating S as inclusions, reducing the amount of S grain boundary segregation, and improving low-temperature toughness and hydrogen embrittlement resistance. If the content is less than 0.005%, the effect is insufficient. On the other hand, addition exceeding 1.0% degrades the toughness of the weld heat affected zone. Therefore, when adding Nd, the content is limited to 0.005 to 1.0%.
Ｃａ：０．０００５〜０．００５％
Ｃａは、ＣａＳを形成し、圧延によって展伸しやすい介在物であるＭｎＳの代わりに、圧延により展伸しにくい球状介在物であるＣａＳへと、硫化物系介在物の形態を制御する作用を有する。含有量が０．０００５％未満ではその効果は充分ではなく、一方、０．００５％を超えて含有すると清浄度が低下するため、靭性などの材質が劣化する。したがって、Ｃａを添加する場合には、その含有量を０．０００５〜０．００５％に限定する。
Ca: 0.0005 to 0.005%
Ca forms CaS and acts to control the form of sulfide inclusions to CaS, which is a spherical inclusion that is difficult to expand by rolling, instead of MnS, which is an inclusion that is easy to expand by rolling. Have. If the content is less than 0.0005%, the effect is not sufficient. On the other hand, if the content exceeds 0.005%, the cleanliness is lowered, and thus materials such as toughness deteriorate. Therefore, when adding Ca, the content is limited to 0.0005 to 0.005%.
Ｍｇ：０．０００５〜０．００５％
Ｍｇは、溶銑脱硫材として使用する場合がある。含有量が０．０００５％未満ではその効果は充分ではなく、一方、０．００５％を超える添加は、清浄度の低下を招く。従って、Ｍｇを添加する場合には、その添加量を０．０００５〜０．００５％に限定する。
Mg: 0.0005 to 0.005%
Mg may be used as a hot metal desulfurization material. If the content is less than 0.0005%, the effect is not sufficient. On the other hand, addition exceeding 0.005% causes a decrease in cleanliness. Therefore, when adding Mg, the addition amount is limited to 0.0005 to 0.005%.
ＲＥＭ：０．０００５〜０．００５％
ＲＥＭは、鋼中でＲＥＭ（Ｏ、Ｓ）として硫化物を生成することによって結晶粒界の固溶Ｓ量を低減して耐ＳＲ割れ特性を改善する。含有量が０．０００５％未満ではその効果が充分ではなく、一方、０．００５％を超える添加は、沈殿晶帯にＲＥＭ硫化物が著しく集積し、材質の劣化を招く。従って、ＲＥＭを添加する場合には、その添加量を０．０００５〜０．００５％に限定する。なお、ＲＥＭとはＲａｒｅ Ｅａｒｔｈ Ｍｅｔａｌの略、であり、希土類金属である。
REM: 0.0005 to 0.005%
REM improves the SR cracking resistance by reducing the amount of solid solution S at the grain boundaries by producing sulfide as REM (O, S) in steel. When the content is less than 0.0005%, the effect is not sufficient. On the other hand, when the content exceeds 0.005%, REM sulfide is remarkably accumulated in the precipitation crystal zone, resulting in deterioration of the material. Therefore, when adding REM, the addition amount is limited to 0.0005 to 0.005%. Note that REM is an abbreviation for Rare Earth Metal and is a rare earth metal.
本発明の水素用鋼構造物は、上記鋼組織を有するものであり、好ましくは、上記の成分組成を有するものとすればよく、その製造方法は、特に限定されるものではない。以下に、本発明の水素用鋼構造物である水素用ラインパイプ、水素用蓄圧器を例示して、本発明の水素用鋼構造物の好ましい製造方法について説明する。なお、本発明の水素用鋼構造物は、上記鋼組織を有し、好ましくは上記の成分組成を有する高圧水素ガス中の耐疲労き裂進展特性に優れる薄板、厚板、パイプ、形鋼および棒鋼など種々の鋼材をそのまま使用する水素用鋼構造物、あるいは所定形状に成形した水素用鋼構造物としてもよい。 The steel structure for hydrogen of the present invention has the above steel structure, and preferably has the above component composition, and the production method is not particularly limited. Below, the hydrogen steel pipe and hydrogen pressure accumulator which are the steel structures for hydrogen of this invention are illustrated, and the preferable manufacturing method of the steel structure for hydrogen of this invention is demonstrated. The steel structure for hydrogen of the present invention has a steel structure, preferably a thin plate, a thick plate, a pipe, a shape steel, and excellent fatigue crack growth resistance in high-pressure hydrogen gas having the above component composition, and It is good also as a steel structure for hydrogen which uses various steel materials, such as bar steel, as it is, or a steel structure for hydrogen formed in a predetermined shape.
また、製造条件における温度規定は鋼材中心部のものとし、薄板、厚板、パイプ、形鋼は板厚中心、棒鋼では径方向の中心とする。但し、中心部近傍はほぼ同様の温度履歴となるので、中心そのものに限定するものではない。 In addition, the temperature regulation in the manufacturing conditions is the center of the steel material, and the thin plate, thick plate, pipe, and shape steel are the center of the plate thickness, and the steel bar is the center of the radial direction. However, the vicinity of the center portion has substantially the same temperature history, and is not limited to the center itself.
本発明の水素用鋼構造物である水素用ラインパイプは、例えば鋼素材を熱間圧延して加速冷却する、あるいは直接焼入れ焼戻しすることにより製造することができる。 The hydrogen line pipe that is the steel structure for hydrogen of the present invention can be produced, for example, by hot rolling and accelerated cooling of a steel material, or by direct quenching and tempering.
鋼素材
本発明の水素用ラインパイプの製造に用いる鋼素材は、上記成分組成に調整された溶鋼から鋳造する。ここで、特に鋳造条件を限定する必要はなく、いかなる鋳造条件で製造された鋼素材としてもよい。溶鋼から鋳片を製造する方法や、鋳片を圧延して鋼片を製造する方法は特に規定しない。転炉法・電気炉法等で溶製された鋼や、連続鋳造・造塊法等で製造された鋼スラブが利用できる。
Steel material The steel material used for the production of the hydrogen line pipe of the present invention is cast from molten steel adjusted to the above composition. Here, it is not necessary to limit the casting conditions in particular, and a steel material manufactured under any casting conditions may be used. A method for producing a slab from molten steel and a method for producing a slab by rolling the slab are not particularly specified. Steel melted by a converter method, an electric furnace method, etc., or a steel slab produced by a continuous casting / ingot-making method can be used.
加速冷却による製造
上記鋼素材を、Ａｃ３変態点以上に加熱し、熱間圧延によって所定の板厚とし、引続きＡｒ３変態点以上から、水冷などにより冷却速度を１〜２００℃／ｓとして６００℃以下の温度まで加速冷却する。加熱温度がＡｃ３変態点未満では、一部未変態オーステナイトが残存するため、熱間圧延および加速冷却後に所望の鋼組織を得ることができない。このため、熱間圧延前の加熱温度はＡｃ３変態点以上とする。また、熱間圧延後の冷却の開始温度がＡｒ３変態点未満であるとオーステナイトの一部の変態が冷却開始前に生じてしまうため、加速冷却後に所望の鋼組織を得ることができない。このため熱間圧延後、Ａｒ３変態点以上から冷却を開始する。Ａｒ３変態点以上からの冷却速度は、所望の組織を得るため、１〜２００℃／ｓとする。なお、該冷却速度は、板厚中心での平均冷却速度である。冷却手段は特に限定する必要はなく、水冷等により行えばよい。また、該冷却を６００℃超えの温度で停止すると、所望の変態が完了しないため、所望の鋼組織を得ることができない。このため、６００℃以下の温度まで加速冷却する。
Production by Accelerated Cooling The steel material is heated to the Ac 3 transformation point or higher, hot rolled to a predetermined plate thickness, and continuously from the Ar 3 transformation point to 600 ° C./s with a cooling rate of 1 to 200 ° C./s. Accelerate cooling to below ℃. When the heating temperature is less than the Ac 3 transformation point, a part of untransformed austenite remains, so that a desired steel structure cannot be obtained after hot rolling and accelerated cooling. Therefore, the heating temperature before hot rolling is set to Ac 3 transformation point or more. Further, if the start temperature of cooling after hot rolling is less than the Ar 3 transformation point, some transformation of austenite occurs before the start of cooling, so that a desired steel structure cannot be obtained after accelerated cooling. For this reason, after hot rolling, cooling is started from the Ar 3 transformation point or higher. The cooling rate from the Ar 3 transformation point or higher is set to 1 to 200 ° C./s in order to obtain a desired structure. The cooling rate is an average cooling rate at the center of the plate thickness. The cooling means is not particularly limited and may be performed by water cooling or the like. Further, when the cooling is stopped at a temperature exceeding 600 ° C., the desired transformation is not completed, so that a desired steel structure cannot be obtained. For this reason, accelerated cooling is performed to a temperature of 600 ° C. or lower.
直接焼入れ焼戻し
上記鋼素材を、Ａｃ３変態点以上に加熱し、熱間圧延後、引続きＡｒ３変態点以上から冷却速度１〜２００℃／ｓで２５０℃以下の温度まで焼入れ、引続きＡｃ１変態点以下の温度で焼戻す。加熱温度がＡｃ３変態点未満では、一部未変態オーステナイトが残存するため、熱間圧延および焼入れ、焼戻し後に所望の鋼組織を得ることができない。このため、熱間圧延前の加熱温度はＡｃ３変態点以上とする。また、熱間圧延後の焼入れの開始温度がＡｒ３変態点未満であるとオーステナイトの一部の変態が焼入れ前に生じてしまうため、焼入れ、焼戻し後に所望の鋼組織を得ることができない。このため熱間圧延後、Ａｒ３変態点以上から冷却を開始し、焼入れを行う。Ａｒ３変態点以上から焼入れる際の冷却速度は、所望の組織を得るため、１〜２００℃／ｓとする。なお、該冷却速度は、板厚中心での平均冷却速度である。冷却手段は特に限定する必要はなく、水冷等により行えばよい。また、該焼入れを２５０℃超えの温度で停止すると、所望の変態が完了しないため、焼戻し後に所望の鋼組織を得ることができない。このため、２５０℃以下の温度まで焼入れることとする。焼入れ後は、引き続きＡｃ１変態点以下の温度で焼戻す。焼戻し温度がＡｃ１変態点を超えると、一部オーステナイトに変態するため、焼戻し後に所望の鋼組織を得ることができない。
Direct quenching and tempering The above steel material is heated to the Ac 3 transformation point or higher, and after hot rolling, is subsequently quenched from the Ar 3 transformation point to a temperature of 250 ° C. or less at a cooling rate of 1 to 200 ° C./s, and subsequently the Ac 1 transformation. Temper at a temperature below the point. When the heating temperature is less than the Ac 3 transformation point, a part of untransformed austenite remains, and thus a desired steel structure cannot be obtained after hot rolling, quenching, and tempering. Therefore, the heating temperature before hot rolling is set to Ac 3 transformation point or more. Further, if the start temperature of quenching after hot rolling is less than the Ar 3 transformation point, a part of austenite transformation occurs before quenching, and thus a desired steel structure cannot be obtained after quenching and tempering. For this reason, after hot rolling, cooling is started from the Ar 3 transformation point or higher, and quenching is performed. The cooling rate at the time of quenching from the Ar 3 transformation point or higher is set to 1 to 200 ° C./s in order to obtain a desired structure. The cooling rate is an average cooling rate at the center of the plate thickness. The cooling means is not particularly limited and may be performed by water cooling or the like. Further, when the quenching is stopped at a temperature exceeding 250 ° C., the desired transformation is not completed, so that a desired steel structure cannot be obtained after tempering. For this reason, it shall temper to the temperature of 250 degrees C or less. After quenching, tempering is continued at a temperature below the Ac 1 transformation point. When the tempering temperature exceeds the Ac 1 transformation point, a part of the steel is transformed into austenite, so that a desired steel structure cannot be obtained after tempering.
本発明の水素用鋼構造物である水素用蓄圧器は、例えば所定の成分組成を有する鋼材を所定形状、すなわち所望する水素用蓄圧器の形状に成形後、再加熱焼入れ焼戻しすることにより製造することができる。 The hydrogen pressure accumulator which is the steel structure for hydrogen of the present invention is produced by, for example, forming a steel material having a predetermined component composition into a predetermined shape, that is, a desired hydrogen pressure accumulator shape, and then reheating and tempering. be able to.
再加熱焼入れ焼戻し
上記の成分組成を有する鋼材を、所定形状に成形後、Ａｃ３変態点以上に加熱し、引続きＡｒ３変態点以上から冷却速度０．５〜１００℃／ｓで２５０℃以下の温度まで焼入れ、引続きＡｃ１変態点以下の温度で焼戻す。ここで、Ａｃ３変態点以上に加熱する鋼材は、上記した成分組成を有するものであれば良く、鋼組織は特に規定する必要はない。所定形状に成形後の加熱温度がＡｃ３変態点未満では、一部未変態オーステナイトが残存するため、熱間圧延および焼入れ、焼戻し後に所望の鋼組織を得ることができない。このため、加熱温度はＡｃ３変態点以上とする。また、加熱後の焼入れの開始温度がＡｒ３変態点未満であるとオーステナイトの一部の変態が冷却前に生じてしまうため、焼入れ、焼戻し後に所望の鋼組織を得ることができない。このため前記加熱後に、Ａｒ３変態点以上から冷却を開始し、焼入れを行う。Ａｒ３変態点以上から焼入れる際の冷却速度は、所望の組織を得るとともに、焼割れを防止するため、０．５〜１００℃／ｓとする。なお、該冷却速度は、板厚（蓄圧器の壁厚）中心での平均冷却速度である。冷却手段は特に限定する必要はなく、油冷や水冷等により行えばよい。また、該焼入れ、すなわち該冷却を２５０℃超えの温度で停止すると、所望の変態が完了しないため、焼戻し後に所望の鋼組織を得ることができない。このため、２５０℃以下の温度まで焼入れることとする。焼入れ後は、引き続きＡｃ１変態点以下の温度で焼戻す。焼戻し温度がＡｃ１変態点を超えると、一部オーステナイトに変態するため、焼戻し後に所望の鋼組織を得ることができない。
Reheating, quenching, and tempering After forming the steel material having the above-described composition into a predetermined shape, the steel material is heated to the Ac 3 transformation point or higher, and continuously from the Ar 3 transformation point to the cooling rate of 0.5 to 100 ° C./s at 250 ° C. or lower. Quenching to temperature, followed by tempering at a temperature below the Ac 1 transformation point. Here, the steel material to be heated to the Ac 3 transformation point or higher is only required to have the above-described component composition, and the steel structure is not particularly required to be defined. If the heating temperature after forming into a predetermined shape is less than the Ac 3 transformation point, a part of untransformed austenite remains, and thus a desired steel structure cannot be obtained after hot rolling, quenching, and tempering. Therefore, the heating temperature is set to Ac 3 transformation point or more. Further, if the quenching start temperature after heating is less than the Ar 3 transformation point, a partial transformation of austenite occurs before cooling, so that a desired steel structure cannot be obtained after quenching and tempering. For this reason, after the heating, cooling is started from the Ar 3 transformation point or higher, and quenching is performed. The cooling rate at the time of quenching from the Ar 3 transformation point or higher is set to 0.5 to 100 ° C./s in order to obtain a desired structure and prevent quench cracking. The cooling rate is an average cooling rate at the center of the plate thickness (wall thickness of the accumulator). The cooling means is not particularly limited and may be performed by oil cooling or water cooling. Further, when the quenching, that is, the cooling is stopped at a temperature exceeding 250 ° C., the desired transformation is not completed, and thus a desired steel structure cannot be obtained after tempering. For this reason, it shall temper to the temperature of 250 degrees C or less. After quenching, tempering is continued at a temperature below the Ac 1 transformation point. When the tempering temperature exceeds the Ac 1 transformation point, a part of the steel is transformed into austenite, so that a desired steel structure cannot be obtained after tempering.
なお、本発明では、Ａｃ３変態点（℃）、Ａｒ３変態点（℃）およびＡｃ１変態点（℃）の求め方については特に規定しないが、例えばＡｃ３＝８５４−１８０Ｃ＋４４Ｓｉ−１４Ｍｎ−１７．８Ｎｉ−１．７Ｃｒ、Ａｒ３＝９１０−３１０Ｃ−８０Ｍｎ−２０Ｃｕ−１５Ｃｒ−５５Ｎｉ−８０Ｍｏ、Ａｃ１＝７２３−１４Ｍｎ＋２２Ｓｉ−１４．４Ｎｉ＋２３．３Ｃｒとして求めることができる。なお、上記式中において各元素記号は各元素の鋼中含有量（質量％）である。 In the present invention, the method for obtaining the Ac 3 transformation point (° C.), the Ar 3 transformation point (° C.), and the Ac 1 transformation point (° C.) is not particularly specified. For example, Ac 3 = 854-180C + 44Si-14Mn-17 .8Ni-1.7Cr, Ar 3 = 910-310C -80Mn-20Cu-15Cr-55Ni-80Mo, can be obtained as Ac 1 = 723-14Mn + 22Si-14.4Ni + 23.3Cr. In the above formula, each element symbol is the content (% by mass) of each element in steel.
以上の条件によって、所望の量のマルテンサイトを有し残部を実質的にベイナイトとする鋼組織を有する水素用鋼構造物である水素用ラインパイプあるいは水素用蓄圧器が得られる。 Under the above conditions, a hydrogen line pipe or a hydrogen pressure accumulator which is a steel structure for hydrogen having a steel structure having a desired amount of martensite and the remainder substantially bainite is obtained.
以下、本発明の効果を検証した実施例について、説明する。なお、以下の実施例においては、水素用ラインパイプおよび水素用蓄圧器の製造方法および特性評価を、鋼板の製造方法および特性評価でシミュレイトした。具体的には、製造方法が加速冷却あるいは直接焼入れ焼戻しの場合は、水素用ラインパイプをシミュレイトした場合であり、再加熱焼入れ焼戻しの場合は水素用蓄圧器をシミュレイトした場合である。 Examples in which the effects of the present invention are verified will be described below. In the following examples, the manufacturing method and characteristic evaluation of the hydrogen line pipe and the hydrogen pressure accumulator were simulated by the steel sheet manufacturing method and characteristic evaluation. Specifically, when the production method is accelerated cooling or direct quenching and tempering, the hydrogen line pipe is simulated, and when reheating and quenching and tempering, the hydrogen pressure accumulator is simulated.
表１に示す化学成分の鋼Ａ〜Ｈを溶製してスラブに鋳造し、表２に示す加熱温度に加熱後、熱間圧延して、表２に示す条件で水冷により加速冷却して（鋼板Ｎｏ．１、４）あるいは直接焼入れ焼戻して（鋼板Ｎｏ．２、５）鋼板を製造した。また、スラブに鋳造後、一旦鋼板とし、該鋼板を表２に示す条件にて水冷あるいは油冷により焼入れを行う再加熱焼入れ焼戻しをして（鋼板Ｎｏ．３、６〜１５）鋼板を製造した。なお、鋼板の温度測定は、板厚中心部に挿入した熱電対によって実施した。また、表２に示す水冷の際の冷却速度は１０〜５０℃／ｓ、油冷の際の冷却速度は１℃／ｓ〜５０℃／ｓの範囲内であった。 Steels A to H having chemical components shown in Table 1 are melted and cast into slabs, heated to the heating temperatures shown in Table 2, hot-rolled, and accelerated and cooled by water cooling under the conditions shown in Table 2 ( Steel plates No. 1 and 4) or directly quenched and tempered (steel plates No. 2 and 5) were produced. Moreover, after casting into a slab, it was once made into a steel plate, and the steel plate was subjected to reheating quenching and tempering by quenching by water cooling or oil cooling under the conditions shown in Table 2 (steel plates No. 3, 6 to 15) to produce steel plates. . In addition, the temperature measurement of the steel plate was implemented with the thermocouple inserted in plate thickness center part. Moreover, the cooling rate at the time of water cooling shown in Table 2 was in the range of 10 to 50 ° C./s, and the cooling rate at the time of oil cooling was in the range of 1 ° C./s to 50 ° C./s.
表２に得られた鋼板のマルテンサイト面積率、引張強さ、９０ＭＰａ高圧水素ガス中における応力拡大係数範囲＝２５ＭＰａ・ｍ１／２時の疲労き裂進展速度（ｍ／ｃｙｃｌｅ）を示す。材料試験および材料特性の評価法は次のとおりである。なお、表２に示す各鋼板のマルテンサイト以外の組織は主としてベイナイトであり、マルテンサイトおよびベイナイト以外の組織の合計の面積率は２％以下であった。また、疲労き裂進展速度は、１．０×１０−６（ｍ／ｃｙｃｌｅ）以下を目標とし、この目標を満足する場合、耐水素脆化特性に優れるとした。 Table 2 shows the martensite area ratio, tensile strength, and fatigue crack growth rate (m / cycle) when the stress intensity factor range in high-pressure 90 MPa hydrogen gas is 25 MPa · m 1/2 . The material test and the evaluation method of material properties are as follows. In addition, the structures other than martensite of each steel sheet shown in Table 2 were mainly bainite, and the total area ratio of the structures other than martensite and bainite was 2% or less. Further, the fatigue crack growth rate is set to 1.0 × 10 −6 (m / cycle) or less, and when this target is satisfied, the hydrogen embrittlement resistance is excellent.
（１）鋼板の組織
３％ナイタールエッチングによって、ミクロ組織を現出させ、圧延方向に平行な断面の２００〜４００倍間の適切な倍率で板厚１／４位置の光学顕微鏡写真を撮影し、それぞれの組織を目視で識別して、画像解析により面積率を求めた。
(1) Microstructure of steel sheet by 3% nital etching, and an optical micrograph at a thickness of 1/4 is taken at an appropriate magnification between 200 and 400 times the cross section parallel to the rolling direction. Each tissue was visually identified, and the area ratio was determined by image analysis.
（２）引張特性
ＪＩＳＺ２２０１（１９８０）に準拠する圧延方向を長手方向（引張方向）とする全厚引張試験片を用い、ＪＩＳＺ ２２４１に準拠して引張試験を行い評価した。
(2) Tensile properties A full thickness tensile test piece having a rolling direction based on JISZ2201 (1980) as a longitudinal direction (tensile direction) was used, and a tensile test was performed based on JISZ 2241 for evaluation.
（３）疲労き裂進展試験
疲労き裂伝播特性の調査は、各鋼板から、荷重負荷方向が圧延方向と平行になるようＡＳＴＭ Ｅ ６４７に準拠したＣＴ試験片を採取し、クリップゲージを用いて、コンプライアンス法で疲労き裂の長さを測定して、９０ＭＰａ高圧水素ガス中における疲労き裂伝播速度を求めた。なお試験片は、板厚が１０ｍｍ以下の場合は表面から０．５ｍｍずつ研削して各々２ｍｍ、５ｍｍ、８ｍｍ、９ｍｍとし、これら以外の板厚の場合はｔ／２（ｔ：板厚）の位置から１０ｍｍ厚さの試験片を採取し、また、き裂進展部には表裏ともに鏡面研磨を施した。この際、パリス則が成り立つ安定成長領域として、応力拡大係数範囲ΔＫ＝２５（ＭＰａ・ｍ１／２）での疲労き裂進展速度（ｍ／ｃｙｃｌｅ）を代表値として評価した。また、疲労き裂進展速度の目標は、１．０×１０−６（ｍ／ｃｙｃｌｅ）以下とした。
(3) Fatigue crack growth test Fatigue crack propagation characteristics were investigated by collecting CT specimens according to ASTM E 647 from each steel plate so that the load direction is parallel to the rolling direction, and using a clip gauge. The fatigue crack propagation rate in 90 MPa high-pressure hydrogen gas was determined by measuring the length of the fatigue crack by the compliance method. When the plate thickness is 10 mm or less, the test piece is ground by 0.5 mm from the surface to 2 mm, 5 mm, 8 mm, and 9 mm, respectively. For other plate thicknesses, t / 2 (t: plate thickness) A specimen having a thickness of 10 mm was taken from the position, and the front and back surfaces were mirror-polished on the crack propagation part. At this time, the fatigue crack growth rate (m / cycle) in the stress intensity factor range ΔK = 25 (MPa · m 1/2 ) was evaluated as a representative value as a stable growth region where the Paris law is established. The target of the fatigue crack growth rate was 1.0 × 10 −6 (m / cycle) or less.
表２に示した鋼板Ｎｏ．１〜６、８、１１、１４は、化学成分および製造条件いずれの条件も本発明を満足し、主としてベイナイトおよびマルテンサイトの二相組織を呈し、マルテンサイト面積率は本発明の範囲を満足し、疲労き裂進展速度は１．０×１０−６（ｍ／ｃｙｃｌｅ）以下であり、高圧水素ガス中の耐水素脆化特性に優れていることが判る。 Steel plate No. shown in Table 2 1 to 6, 8, 11, and 14 satisfy the present invention in any of the chemical components and the production conditions, mainly exhibit a two-phase structure of bainite and martensite, and the martensite area ratio satisfies the scope of the present invention. The fatigue crack growth rate is 1.0 × 10 −6 (m / cycle) or less, which indicates that the hydrogen embrittlement resistance in high-pressure hydrogen gas is excellent.
一方、鋼板Ｎｏ．７は、加熱温度が、本発明範囲の下限（Ａｃ３）より低く、マルテンサイト面積率および疲労き裂進展速度のいずれも目標値に達していない。鋼板Ｎｏ．９、１２は、冷却開始温度（水冷または油冷の開始温度）が、本発明範囲の下限（Ａｒ３）より低く、本発明範囲から外れており、マルテンサイト面積率および疲労き裂進展速度のいずれも目標値に達していない。鋼板Ｎｏ．１０、１３は、冷却停止温度（水冷または油冷の停止温度）が、本発明範囲の上限（２５０℃）より高く、本発明範囲から外れており、マルテンサイト面積率および疲労き裂進展速度のいずれも目標値に達していない。鋼板Ｎｏ．１５は、焼戻し温度が、本発明範囲の上限（Ａｃ１）より高く、本発明範囲から外れており、マルテンサイト面積率および疲労き裂進展速度のいずれも目標値に達していない。なお、これら比較例として提示した鋼板Ｎｏ．７、９、１０、１２、１３、１５に関しても、主としてベイナイトおよびマルテンサイトの二相組織を呈していた。 On the other hand, steel plate No. In No. 7, the heating temperature is lower than the lower limit (Ac 3 ) of the present invention range, and neither the martensite area ratio nor the fatigue crack growth rate has reached the target value. Steel plate No. Nos. 9 and 12 have a cooling start temperature (starting temperature of water cooling or oil cooling) lower than the lower limit (Ar 3 ) of the scope of the present invention and out of the scope of the present invention, and the martensite area ratio and fatigue crack growth rate None of them reached the target value. Steel plate No. 10 and 13, the cooling stop temperature (water cooling or oil cooling stop temperature) is higher than the upper limit (250 ° C.) of the present invention range and deviates from the present invention range, and the martensite area ratio and fatigue crack growth rate None of them reached the target value. Steel plate No. No. 15 has a tempering temperature that is higher than the upper limit (Ac 1 ) of the present invention range and is outside the present invention range, and neither the martensite area ratio nor the fatigue crack growth rate has reached the target value. In addition, steel plate No. shown as these comparative examples. 7, 9, 10, 12, 13, and 15 also exhibited a two-phase structure mainly of bainite and martensite.
上記結果から明らかなように、本発明例は、疲労き裂進展速度は１．０×１０−６（ｍ／ｃｙｃｌｅ）以下であり、水素脆化特性に優れるものであり、耐水素脆化特性に優れる水素用蓄圧器や水素用ラインパイプ等の水素用鋼構造物を得られることがわかる。 As is clear from the above results, in the examples of the present invention, the fatigue crack growth rate is 1.0 × 10 −6 (m / cycle) or less, and the hydrogen embrittlement characteristics are excellent. It can be seen that a steel structure for hydrogen such as a hydrogen pressure accumulator or a hydrogen line pipe can be obtained.
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