WO2020137812A1 - 高圧水素ガス環境用鋼材および高圧水素ガス環境用鋼構造物ならびに高圧水素ガス環境用鋼材の製造方法 - Google Patents
高圧水素ガス環境用鋼材および高圧水素ガス環境用鋼構造物ならびに高圧水素ガス環境用鋼材の製造方法 Download PDFInfo
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- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Definitions
- the present invention relates to a steel material and a steel structure suitable for a high-pressure hydrogen gas environment, and a method for manufacturing a steel material for a high-pressure hydrogen gas environment, and particularly to improvement of hydrogen embrittlement resistance of a steel material under a high-pressure hydrogen gas environment.
- Fuel cell vehicles run by filling hydrogen into a tank instead of conventional gasoline. Therefore, a hydrogen station for refueling is needed instead of the gas station. In order to popularize fuel cell vehicles, it is important to construct many hydrogen stations for refueling in general urban areas.
- the transport pressure is 10 MPa class
- the line pipe is exposed to 10 MPa class hydrogen gas pressure.
- the hydrogen storage steel structures for storing and supplying high-pressure hydrogen gas, and steel structures for hydrogen, such as line pipes used for mass transportation of hydrogen gas, are used while being exposed to the high-pressure hydrogen gas environment. To be done.
- low-alloy steel materials which have the advantages of low price and high strength, can be considered first.
- the low alloy steel material has a problem that it easily becomes so-called “hydrogen embrittlement”, which is brittle when hydrogen enters.
- austenitic stainless steels such as SUS316L, which are less susceptible to hydrogen embrittlement than low-alloy steels, have been used for steel structures used in high-pressure hydrogen gas environments.
- austenitic stainless steels such as SUS316L have high steel costs and low strength, so if they are designed to withstand high hydrogen pressure, the wall thickness becomes thicker and the price of the hydrogen structure itself increases. It becomes expensive. Therefore, there has been a strong demand for a low alloy steel material for a steel structure for hydrogen, which has a lower cost and can withstand a high-pressure hydrogen gas environment.
- Patent Document 1 proposes high-pressure hydrogen environment steel.
- the high-pressure hydrogen environment steel described in Patent Document 1 is a steel used in a high-pressure hydrogen environment, and in mass%, C: 0.03 to 0.18%, Si: 0.1 to 0.5%, Mn: 0.2 to 1.8. %, P: 0.025% or less, S: 0.002-0.02%, sol.Al: 0.01-0.10%, Ca: 0.001-0.10%, or V: 0.03-0.3%, including Ca/S: less than 1.5 or 11
- the above is a steel having a chemical composition consisting of the balance Fe and impurities.
- MnS and Ca-based composite inclusions are formed as trap sites for diffusible hydrogen, and VC is further formed, and diffusible hydrogen is used as non-diffusible hydrogen to adjust the diffusible hydrogen concentration ratio. It is said that the amount of the hydrogen is reduced and the brittleness due to diffusible hydrogen is suppressed.
- Patent Document 2 proposes a low-alloy high-strength steel excellent in high-pressure hydrogen environment embrittlement resistance.
- the low alloy high strength steel described in Patent Document 2 is C: 0.10 to 0.20%, Si: 0.10 to 0.40%, Mn: 0.50 to 1.20%, P: 0.005% or less, S: 0.005% or less in mass%.
- Cr 0.20 to 0.80%, Cu: 0.10 to 0.50%, Mo: 0.10 to 1.00%, V: 0.01 to 0.10%, B: 0.0005 to 0.005%, N: 0.01% or less, balance Fe and inevitable It is a high-strength steel with a composition of impurities.
- tempering is performed at a relatively high temperature of 600 to 640°C, and tensile strength: 900 to 950 MPa. It is said that it is preferable to adjust to an extremely narrow range. It is said that this will result in a low alloy, high strength steel that exhibits excellent elongation and drawing characteristics even in a hydrogen atmosphere of 45 MPa and is excellent in high-pressure hydrogen environment embrittlement resistance.
- Patent Document 3 proposes a low-alloy high-strength steel excellent in high-pressure hydrogen environment embrittlement resistance.
- the low-alloy high-strength steel described in Patent Document 3 is, in mass%, C: 0.10 to 0.20%, Si: 0.10 to 0.40%, Mn: 0.50 to 1.20%, P: 0.005% or less, S: 0.002% or less.
- Ni 0.75 to 1.75%
- Cr 0.20 to 0.80%
- Cu 0.10 to 0.50%
- Mo 0.10 to 1.00%
- V 0.01 to 0.10%
- B 0.0005 to 0.005%
- N 0.01% or less
- it is a Cr-Mo high strength low alloy steel containing Nb: 0.01 to 0.10% and Ti: 0.005 to 0.050%, one or two, and the balance being Fe and inevitable impurities.
- Patent Document 4 proposes a low alloy steel for high-pressure hydrogen gas environment.
- the low alloy steel described in Patent Document 4 is C: 0.15 to 0.60%, Si: 0.05 to 0.5%, Mn: 0.05 to 3.0%, P: 0.025% or less, S: 0.010% or less, Al in mass%. : 0.005-0.10%, Mo: 0.5-3.0%, V: 0.05-0.30%, O (oxygen): 0.01% or less, N: 0.03% or less, and the composition consisting of the balance Fe and impurities, and Tensile strength: Low alloy steel for high pressure hydrogen gas environment with 900MPa or more.
- B 0.0003 to 0.003% may be contained.
- N 0.010% or less.
- Patent Document 5 proposes a steel for a high-pressure hydrogen gas storage container having excellent hydrogen resistance.
- MC-based carbide (Mo, V) C is obtained by subjecting a steel having the above-described composition to stress-relief annealing for a long time after normalizing treatment during steel sheet production. It is said that the particles are finely and densely dispersed and precipitated to improve hydrogen resistance such as hydrogen embrittlement resistance of steel.
- Patent Document 6 proposes a steel material for high-pressure hydrogen storage.
- the steel material described in Patent Document 6 is, by mass%, C: 0.05 to 0.12%, Si: 0.01 to 0.50%, Mn: more than 0.6 to 1.8%, P: 0.02% or less, S: 0.003% or less, Al: It contains 0.01 to 0.08%, the balance is Fe and unavoidable impurities, and the bainite is mainly composed of an area fraction of 90% or more and the average grain size is 50 nm or less and the cementite with an average aspect ratio of 3 or less is contained in bainite. Steel material that is dispersed and precipitated. According to the technique described in Patent Document 6, by dispersing fine cementite having a small aspect ratio, it is possible to reduce the amount of hydrogen penetration from the high-pressure hydrogen atmosphere, further improve the base material toughness, and Brittleness is said to be suppressed.
- Patent Document 7 proposes a high-strength steel material for a high-pressure hydrogen storage container.
- the high-strength steel material described in Patent Document 7 is, by mass%, C: 0.05 to 0.15%, Si: 0.01 to 0.50%, Mn: more than 0.6 to 2.5%, P: 0.02% or less, S: 0.003% or less, Al: 0.01-0.08%, Pcm 0.19 or more, balance Fe and unavoidable impurities, lower bainite with area fraction 70% or more and island martensite with area fraction 3% or less It is a high-strength steel material having a tensile strength of 780 Mpa or more.
- Patent Document 8 describes a steel material having excellent fatigue crack growth resistance in a high-pressure hydrogen environment.
- the steel materials described in Patent Document 8 are C: 0.05 to 0.60%, Si: 0.01 to 2.0%, Mn: 0.3 to 3.0%, P: 0.001 to 0.040%, S: 0.0001 to 0.010%, N in mass%. : 0.0001-0.0060%, Al: 0.01-1.5%, Ti: 0.01-0.20%, Nb: 0.01-0.20%, V: 0.01% or more and less than 0.05%, or 2 or more,
- B 0.0001 to 0.01%
- Mo 0.005 to 2.0%
- Cr 0.005 to 3.0%
- one or more components and 95% or more by volume of tempered martensite.
- the fatigue crack growth rate can be dramatically reduced in a high-pressure hydrogen environment of 80 MPa or more compared with conventional steel, and use of a hydrogen pressure accumulator or the like used in a high-pressure hydrogen environment It is said that the life can be improved and the safety of hydrogen storage containers used in a high-pressure hydrogen environment can be improved.
- Non-Patent Document 1 and Non-Patent Document 2 describe fracture toughness values of low alloy steels.
- the upper bainite containing coarse carbides should be reduced.
- the present invention is suitable for a steel structure used in a high-pressure hydrogen gas environment, such as a hydrogen pressure accumulator, a hydrogen line pipe, etc.
- An object of the present invention is to provide a steel material and a steel structure having excellent brittleness characteristics, and a method for producing a steel material for a high-pressure hydrogen gas environment.
- excellent in hydrogen embrittlement resistance under high-pressure hydrogen gas environment means that at a room temperature (20 ⁇ 10°C) and a pressure of 115 MPa in a hydrogen gas atmosphere, the Japan Pressure Vessel Research Conference Material Research Group
- the fracture toughness value K IH obtained by conducting the fracture toughness test in accordance with the Task Force for Hydrogen Embrittlement TASK Group V (1991) is 40 MPa ⁇ m 1/2 or more.
- steel material here includes thin steel plates, thick steel plates, seamless steel pipes, electric resistance welded steel pipes, shaped steels, steel bars, and the like.
- the present inventor diligently studied various factors affecting the hydrogen embrittlement resistance of carbon-based and low-alloy steels.
- Si and Cu, or even Al in a composite amount of 0.5% or more by mass %, the hydrogen embrittlement resistance of steel materials in a high-pressure hydrogen gas atmosphere is significantly improved. I found it.
- uniformly cooling the steel material it is possible to suppress the local temperature rise due to localization of the transformation heat generation by homogenizing the transformation timing, making it easier to obtain martensite or lower bainite. It was found that the fracture toughness value K IH in gas can be increased.
- the present invention has been completed by further studies based on such findings. That is, the gist of the present invention is as follows. (1)% by mass, C: 0.04 to 0.50%, Si: 0.5 to 2.0%, Mn: 0.5 to 2.0%, P: 0.05% or less, S: 0.010% or less, N: 0.0005 to 0.0080%, Al: 0.010 %-2.0%, O: 0.0100% or less, Cu: 0.5-2.0%, with a composition consisting of balance Fe and unavoidable impurities, tensile strength: 560 MPa or more, in a high-pressure hydrogen gas atmosphere High-pressure hydrogen gas environment steel with fracture toughness value K IH of 40 MPa ⁇ m 1/2 or more.
- a steel material for high pressure hydrogen gas environment wherein the mass% is Al: 0.5 to 2.0% in (1).
- Mass% C 0.04 to 0.50%, Si: 0.5 to 2.0%, Mn: 0.5 to 2.0%, P: 0.05% or less, S: 0.010% or less, N: 0.0005 to 0.0080%, Al: 0.010 % To 2.0%, O: 0.0100% or less, Cu: 0.5 to 2.0%, and a steel material having a composition of balance Fe and unavoidable impurities, heated to the Ac 3 transformation point or higher, and hot rolled.
- a method for producing a steel material for a high-pressure hydrogen gas environment which has a fracture toughness value K IH of at least 560 MPa in a high-pressure hydrogen gas atmosphere of 40 MPa ⁇ m 1/2 or more.
- Mass% C 0.04 to 0.50%, Si: 0.5 to 2.0%, Mn: 0.5 to 2.0%, P: 0.05% or less, S: 0.010% or less, N: 0.0005 to 0.0080%, Al: 0.010 % To 2.0%, O: 0.010% or less, Cu: 0.5 to 2.0%, and a steel material having a composition consisting of the balance Fe and unavoidable impurities, heated to the Ac 3 transformation point or higher, and hot rolled. alms and steel of a predetermined shape and subsequently with (Ar 3 transformation point -50 ° C.) or more cooling rate from the temperature 1 ⁇ 200 °C / s, and cooled to the cooling stop temperature of 250 ° C.
- Ac 1 transformation point A method for producing a steel material for high-pressure hydrogen gas environment that has been subjected to direct quenching and tempering treatment at a temperature and has a tensile strength of 560 MPa or more and a fracture toughness value K IH in a high-pressure hydrogen gas atmosphere of 40 MPa ⁇ m 1/2 or more.
- Tensile strength 560 MPa or more
- fracture toughness value K IH in high-pressure hydrogen gas atmosphere is 40 MPa -Method for producing steel material for high-pressure hydrogen gas environment with m 1/2 or more.
- a steel material having extremely improved hydrogen embrittlement resistance under a high-pressure hydrogen gas environment can be easily and simply manufactured, and the industrially remarkable effect is achieved.
- the hydrogen embrittlement resistance of steel structures such as high-pressure hydrogen gas pressure accumulators and high-pressure hydrogen gas line pipes can be significantly improved, and fatigue resistance characteristics are improved. It also has the effect of greatly contributing to the extension of life.
- the steel material of the present invention has, as a basic composition, in mass%, C: 0.04 to 0.50%, Si: 0.5 to 2.0%, Mn: 0.5 to 2.0%, P: 0.05% or less, S: 0.010% or less, N: 0.0005. .About.0.0080%, Al:0.010% to 2.0%, O:0.0100% or less, Cu:0.5 to 2.0%, and the balance Fe and inevitable impurities.
- Si and Cu, or further Al makes the structure of dislocation generated when the material is deformed in hydrogen gas into a bain, and fracture toughness value K IH in hydrogen gas It has been found that it has the effect of increasing the. This improves the hydrogen embrittlement resistance. Such an effect becomes remarkable when at least both Si and Cu are contained by 0.5% or more, and further when Al is contained by 0.5% or more. Therefore, in the present invention, Si: 0.5 to 2.0%, Cu: 0.5 to 2.0%, or Al: 0.5 to 2.0% is added.
- Si 0.5-2.0% Si, like Cu and Al, is an element that improves the hydrogen embrittlement resistance, and is contained in the present invention in an amount of 0.5% or more.
- Si is limited to the range of 0.5 to 2.0%. In addition, it is preferably 0.75% or more, and preferably 2.00% or less. It is more preferably 1.00% or more.
- Cu 0.5-2.0% Like Si and Al, Cu is an element that improves the hydrogen embrittlement resistance, and is contained in the present invention in an amount of 0.5% or more. On the other hand, a large content of Cu exceeding 2.0% facilitates hot cracking during heating or welding. Therefore, Cu is limited to the range of 0.5 to 2.0%. In addition, it is preferably 0.75% or more, and preferably 2.00% or less. It is more preferably 1.00% or more.
- Al 0.010-2.0%
- Al is an element that contributes to the improvement of hydrogen embrittlement resistance.
- Al which is contained in a relatively small amount, acts as a deoxidizer, forms nitride AlN, suppresses coarsening of crystal grains during heating, and contributes to refinement of the structure.
- Al is set to 0.010% or more in the present invention.
- Al is preferably 0.5% or more and 2.0% or less. It is more preferably 0.75% or more, and further preferably 1.00% or more.
- C 0.04 to 0.50%
- C is an element that contributes to the increase of strength and improves hardenability, and it is necessary to contain 0.04% or more in order to secure desired strength and hardenability.
- the content exceeds 0.50%, the weldability is significantly lowered and the toughness of the base material and the weld heat affected zone is lowered. Therefore, C is limited to the range of 0.04 to 0.50%. In addition, it is preferably 0.10% or more, and preferably 0.45% or less.
- Mn 0.5-2.0%
- Mn is an element that contributes to the increase in strength through the improvement of hardenability. In order to obtain such an effect, it is necessary to contain 0.5% or more, but if it exceeds 2.0%, the grain boundary strength is lowered and the low temperature toughness is lowered. Therefore, Mn is limited to the range of 0.5 to 2.0%. In addition, it is preferably 0.8% or more, and preferably 1.5% or less.
- P 0.05% or less P tends to segregate in the crystal grain boundaries and the like, and reduces the bonding strength of the crystal grains and the toughness. Therefore, it is desirable to reduce P as much as possible, but up to 0.05% is acceptable. Therefore, P was limited to 0.05% or less.
- S 0.010% or less S is likely to segregate at the crystal grain boundaries and easily form MnS which is a non-metallic inclusion, resulting in a decrease in ductility and toughness. Therefore, it is desirable to reduce S as much as possible, but up to 0.010% is acceptable. Therefore, S is limited to 0.010% or less.
- N 0.0005 to 0.0080% N combines with a nitride forming element such as Nb, Ti and Al to form a nitride, pinning austenite grains during heating, suppressing coarsening of crystal grains, and having an effect of refining the structure.
- a nitride forming element such as Nb, Ti and Al
- the content of 0.0005% or more is required.
- the content exceeds 0.0080% the amount of solute N increases, and the toughness of the base material and the weld heat affected zone is reduced. Therefore, N is limited to the range of 0.0005 to 0.0080%. In addition, it is preferably 0.0020% or more, and preferably 0.0050% or less.
- O 0.0100% or less
- O (oxygen) forms oxides such as alumina, increases the amount of non-metallic inclusions, and leads to deterioration of workability such as deterioration of ductility, so it is desirable to reduce as much as possible. Up to% is acceptable. Therefore, O (oxygen) is limited to 0.0100% or less. The content is preferably 0.0050% or less.
- the above-mentioned components are the basic composition.
- Ni, Cr, Mo, W, Nb, V, Ti, and B are elements that contribute to the improvement of hardenability, and one element or two or more elements can be contained as necessary.
- Ni 0.05-2.00%
- Ni is an element that not only improves hardenability but also has an effect of improving toughness. In order to obtain such effects, the content of 0.05% or more is required. On the other hand, if the content exceeds 2.00%, the material cost increases and the economic efficiency decreases. Therefore, when Ni is contained, it is preferable to limit Ni to the range of 0.05 to 2.00%. In addition, it is more preferably 0.50% or more, and further preferably 1.50% or less.
- Cr 0.10-2.50% Cr is an element that contributes to ensuring strength through improvement of hardenability, and in order to obtain such an effect, the content of Cr is required to be 0.10% or more. On the other hand, if it is contained in a large amount exceeding 2.50%, the weldability is deteriorated. For this reason, it is preferable to limit the content of Cr to the range of 0.10 to 2.50%. In addition, it is more preferably 0.50% or more, and further preferably 1.50% or less.
- Mo 0.05-2.00%
- Mo is an element that contributes to ensuring the strength through the improvement of the hardenability, and in order to obtain such an effect, the content of 0.05% or more is required.
- Mo is preferably limited to the range of 0.05 to 2.00%.
- the content is more preferably 0.20% or more, and even more preferably 1.50% or less.
- W 0.05-2.00%
- W is an element that contributes to ensuring the strength through the improvement of the hardenability, and in order to obtain such an effect, the content of 0.05% or more is required.
- W is preferably limited to 0.05 to 2.00%.
- the content is more preferably 0.20% or more, and even more preferably 1.50% or less.
- Nb 0.005-0.100%
- Nb is an element that has the effect of suppressing the coarsening of crystal grains by finely precipitating carbonitrides during heating and pinning austenite grains in addition to improving the hardenability. Such an effect is recognized when the content is 0.005% or more. On the other hand, if the content exceeds 0.100%, the toughness of the weld heat affected zone is reduced. Therefore, when it is contained, Nb is preferably limited to the range of 0.005 to 0.100%. The content is more preferably 0.010% or more, and further preferably 0.050% or less.
- V 0.005-0.200%
- V is an element which has the effect of suppressing the coarsening of crystal grains by further precipitating carbonitrides during heating and pinning austenite grains in addition to improving the hardenability. Such an effect is recognized when the content is 0.005% or more. On the other hand, if the content exceeds 0.200%, the toughness of the weld heat affected zone is reduced. Therefore, when it is contained, V is preferably limited to the range of 0.005 to 0.200%. The content is more preferably 0.010% or more, and further preferably 0.150% or less.
- Ti 0.005-0.100%
- Ti is an element that not only improves hardenability, but also finely precipitates carbonitrides during heating, pinning austenite grains and suppressing coarsening of crystal grains. Such an effect is recognized when the content is 0.005% or more. On the other hand, if the content exceeds 0.100%, the toughness of the weld heat affected zone is reduced. Therefore, when it is contained, Ti is preferably limited to the range of 0.005 to 0.100%. The content is more preferably 0.010% or more, and further preferably 0.050% or less.
- B 0.0005 to 0.0050%
- B is an element that contributes to the improvement of hardenability when contained in a trace amount. In order to obtain such effects, the content of 0.0005% or more is required. On the other hand, if the content exceeds 0.0050%, the toughness decreases. Therefore, when B is contained, it is preferable to limit B to the range of 0.0005 to 0.0050%. In addition, it is more preferably 0.0010% or more, and further preferably 0.0020% or less.
- Nd, Ca, Mg, REM are all elements that contribute to the improvement of ductility, toughness, and further hydrogen embrittlement resistance through the morphology control of inclusions, and are selected as necessary, You may contain 1 type(s) or 2 or more types.
- Nd 0.005 ⁇ 1.000%
- Nd is an element that forms a sulfide-based inclusion by combining with S, reduces the amount of segregation of S at grain boundaries, and contributes to the improvement of toughness and hydrogen embrittlement resistance. In order to obtain such effects, the content of 0.005% or more is required. On the other hand, if the content exceeds 1.000%, the toughness of the weld heat affected zone is reduced. Therefore, when it is contained, Nd is preferably limited to the range of 0.005 to 1.000%. In addition, it is more preferably 0.010% or more, and further preferably 0.500% or less.
- Ca 0.0005 to 0.0050%
- Ca has a strong affinity with S and replaces MnS, which is a sulfide-based inclusion that is easily expanded by rolling, and forms CaS, which is a spherical sulfide-based inclusion that is difficult to expand by rolling, and forms a sulfide. It is an element that contributes to the morphology control of system inclusions and has the effect of improving ductility and toughness. In order to obtain such effects, the content of 0.0005% or more is required. On the other hand, if the content exceeds 0.0050%, the cleanliness decreases, and the ductility, toughness, etc. decrease. Therefore, when Ca is contained, it is preferable to limit Ca to the range of 0.0005 to 0.0050%. In addition, it is more preferably 0.0010% or more, and further preferably 0.0020% or less.
- Mg 0.0005 to 0.0050% Similar to Ca, Mg has a strong affinity with S, forms sulfide inclusions, and improves ductility and toughness. In order to obtain such effects, the content of 0.0005% or more is required. On the other hand, if the content exceeds 0.0050%, the cleanliness decreases. Therefore, when containing Mg, it is preferable to limit the Mg content to the range of 0.0005 to 0.0050%. In addition, it is more preferably 0.0010% or more, and further preferably 0.0020% or less.
- REM 0.0005 to 0.0050% REM is an element that forms sulfide-based inclusions such as REM(O,S), reduces the amount of solute S in crystal grain boundaries, and contributes to the improvement of SR crack resistance. In order to obtain such effects, it is necessary to contain 0.0005% or more of REM. On the other hand, if the content exceeds 0.0050%, a large amount of REM sulfides are accumulated in the precipitated crystal zone during casting, resulting in deterioration of the material such as ductility and toughness. Therefore, when it is contained, REM is preferably limited to the range of 0.0005 to 0.0050%. In addition, it is more preferably 0.0010% or more, and further preferably 0.0020% or less. It should be noted that “REM” here is an abbreviation for Rare Earth Metal (rare earth element).
- the balance other than the above components consists of Fe and inevitable impurities.
- the high-pressure hydrogen gas environment steel material of the present invention is a steel material having the composition described above, and a structure comprising a combination of ferrite and pearlite, or lower bainite, martensite, tempered lower bainite, tempered martensite, or a combination thereof. ..
- the steel material for high-pressure hydrogen gas environment of the present invention has the above-mentioned composition and the above-mentioned structure, and has a tensile strength: high strength of 560 MPa or more, and a fracture toughness value K in a high-pressure hydrogen gas atmosphere.
- IH A steel material with a hydrogen embrittlement resistance of 40 MPa ⁇ m 1/2 or more.
- molten steel having the composition described above is melted in a conventional melting furnace such as a converter or an electric furnace, and a cast piece such as a slab having a predetermined shape by a continuous casting method, or a cast piece (a steel ingot) by an ingot making method or the like. ) Is hot-rolled to form a slab or other shaped piece of steel into a steel material.
- a conventional melting furnace such as a converter or an electric furnace
- a cast piece such as a slab having a predetermined shape by a continuous casting method, or a cast piece (a steel ingot) by an ingot making method or the like.
- the steel material obtained is then placed in a heating furnace.
- the heating temperature is the Ac 3 transformation point or higher. If the heating temperature is lower than the Ac 3 transformation point, the deformation resistance of the material to be rolled becomes high and the load on the rolling apparatus becomes large, and a part of the untransformed structure remains. It cannot be secured.
- the heating temperature is preferably 1100 to 1300°C. If the heating temperature is less than 1100°C, the deformation resistance is high and the load on the rolling mill becomes too large. On the other hand, if the heating temperature exceeds 1300°C, the crystal grains become coarse and the toughness decreases.
- the steel material heated to the prescribed temperature is then hot-rolled to obtain the steel material with prescribed dimensions and shape.
- the “steel material” here includes thin plates, thick plates, steel pipes, shaped steels, steel bars, and the like.
- the "hot rolling” referred to here may be a steel material having a predetermined size and shape, and the rolling conditions are not particularly limited. When the steel material is a seamless steel pipe, the hot rolling includes rolling including piercing rolling.
- the steel material rolled into the specified size and shape is allowed to cool to room temperature as it is, and after cooling, reheated and tempered by reheating and quenching and tempering treatment, or hot rolling followed by accelerated cooling treatment. Alternatively, it is preferable that direct quenching and tempering treatment is performed subsequent to hot rolling.
- the temperature is specified in the manufacturing conditions at the center of the steel material.
- the steel material is a thin plate, a thick plate, a steel pipe, or a shaped steel, it is the center of the plate thickness (wall thickness), and the bar steel is the center of the radial direction.
- the regulation of the temperature is not limited to the center itself.
- the steel material rolled into the prescribed size and shape is not cooled to room temperature and continues to be cooled at a cooling start temperature of (Ar 3 transformation point ⁇ 50° C.) or higher at a cooling rate of 1 to 200° C./s and a cooling stop temperature: Accelerated cooling is performed to cool to a cooling stop temperature of 600°C or less.
- the cooling start temperature is lower than (Ar 3 transformation point ⁇ 50° C.)
- the transformation amount of austenite increases before the cooling starts, and desired properties cannot be ensured after accelerated cooling. Therefore, the cooling start temperature is limited to a temperature higher than (Ar 3 transformation point ⁇ 50° C.).
- the cooling rate of the accelerated cooling is less than 1° C./s, the cooling is too slow and desired characteristics cannot be secured.
- the usual cooling method does not exceed 200°C/s. Therefore, the cooling rate of the accelerated cooling process is limited to the range of 1 to 200°C/s.
- the cooling rate is an average cooling rate at the center of the plate thickness (wall thickness).
- the cooling means is not particularly limited, and water cooling or the like is preferable.
- the cooling stop temperature of accelerated cooling is higher than 600° C., the desired transformation cannot be completed, so that the desired characteristics cannot be secured. Therefore, the cooling stop temperature for accelerated cooling is limited to 600°C or lower.
- the above steel material is heated to the Ac 3 transformation point or higher and hot-rolled into a steel material having a predetermined size and shape, and then continuously (Ar 3 transformation point ⁇ 50° C.) or higher temperature in the range of 1 to 200° C./s.
- a quenching process of cooling to a cooling stop temperature of 250° C. or less at a cooling rate and a tempering process of subsequently tempering at a tempering temperature of an Ac 1 transformation point or less are performed.
- the heating temperature of the steel material is less than the Ac 3 transformation point, a part of the untransformed structure remains, so that the desired steel structure cannot be obtained after hot rolling, quenching and tempering.
- the heating temperature before hot rolling is set to the Ac 3 transformation point or higher. If the quenching start temperature after hot rolling is lower than (Ar 3 transformation point ⁇ 50° C.), the transformation amount of austenite before quenching is large and the desired steel structure cannot be obtained after quenching and tempering. Therefore, after hot rolling, quenching is performed by starting cooling from (Ar 3 transformation point ⁇ 50° C.) or higher.
- the cooling rate when quenching from (Ar 3 transformation point ⁇ 50° C.) or higher is 1 to 200° C./s in order to obtain a desired structure.
- the cooling rate is an average cooling rate at the plate thickness center.
- the cooling means is not particularly limited and may be water cooling or the like.
- the quenching process is a quenching that cools to a temperature of 250° C. or less. After quenching, continue to temper at a temperature below the Ac 1 transformation point. If the tempering temperature exceeds the Ac 1 transformation point, a portion of the material is transformed into austenite, so that the desired characteristics cannot be obtained after tempering.
- the steel material which has been rolled to a predetermined size and once cooled to room temperature, is then heated at a quenching heating temperature of the Ac 3 transformation point or higher, and then from the quenching start temperature of (Ar 3 transformation point ⁇ 50° C.) or higher. Then, a quenching treatment of cooling at a cooling rate of 0.5 to 100° C./s to a temperature of 250° C. or less is performed, and then a reheating quenching and tempering process of performing tempering at a temperature of an Ac 1 transformation point or less is performed.
- the quenching treatment for example, water or oil was used as a cooling medium, and the cooling medium was sprayed or heated so that the cooling rate was 0.5 to 100° C./s to the steel material heated to high temperature, which is the material to be cooled. It is preferable to immerse the steel material in a bath containing a refrigerant. From the viewpoint of uniform cooling, it is preferable that a steel material having a predetermined size and shape is cooled while being sprayed with a jet jet of the refrigerant while rotating in a bath containing the refrigerant. Further, the tempering treatment may be carried out by allowing the steel material heated in a tempering heating furnace or the like to cool in the air or in a protective atmosphere.
- the quenching heating temperature is set to the Ac 3 transformation point or higher. If the quenching start temperature is lower than (Ar 3 transformation point ⁇ 50° C.), austenite starts transformation before quenching, so that desired characteristics cannot be obtained after quenching and tempering. Therefore, the quenching start temperature is limited to a temperature of (Ar 3 transformation point ⁇ 50° C.) or higher. Further, the quenching cooling rate is limited to 0.5 to 100° C./s in order to obtain desired characteristics and prevent quench cracking.
- the quenching stop temperature is higher than 250° C.
- the desired transformation (martensite transformation or bainite transformation) is not completed, so that the desired characteristics cannot be ensured after the tempering treatment. Therefore, the quenching stop temperature is limited to 250°C or lower.
- the steel material is subsequently heated to a tempering temperature not higher than the Ac 1 transformation point and tempered by tempering. If the tempering temperature exceeds the Ac 1 transformation point, a part of the material is transformed into austenite, so that it becomes impossible to secure desired characteristics after the tempering treatment.
- the Ac 3 transformation point (°C), the Ar 3 transformation point (°C) and the Ac 1 transformation point (°C) described above are calculated by using the following equations.
- the steel material manufactured by the above manufacturing method and having excellent hydrogen permeation resistance is suitable for a steel structure for hydrogen used in a high-pressure hydrogen gas environment.
- Examples of the "hydrogen steel structure" herein include a pressure accumulator (hydrogen accumulator) used in a hydrogen station and the like, a line pipe for hydrogen gas transportation (hydrogen line pipe), and the like.
- type 1 using only steel material type 2 and type 3 in which carbon fiber reinforced plastic (CFRP: Carbon Fiber Reinforced Plastic) is wound around steel material are known.
- CFRP Carbon Fiber Reinforced Plastic
- These types are, for example, the classification of compressed natural gas automobile fuel containers, ISO 11439, ANSI/NGV, and the structure of the containers described in the High Pressure Gas Safety Act, Container Safety Regulations, Example Standards, Appendix 9, etc. ..
- the pressure accumulator is preferably manufactured, for example, by shaping a steel material having the above-described composition into a predetermined shape and then subjecting it to reheating, quenching and tempering.
- the design pressure of hydrogen stored in the pressure accumulator is about 35 MPa or about 70 MPa.
- a line pipe for hydrogen transportation a seamless steel pipe, an electric resistance welded steel pipe, or a UOE type steel pipe is suitable.
- the line pipe may be a line pipe (steel pipe) using the steel material having the above composition as it is, or a steel material having the above composition may be subjected to the above-described accelerated cooling treatment and direct quenching treatment to obtain a steel pipe. It is preferable.
- the design pressure of hydrogen used is about 10 MPa.
- ____ Molten steel with the composition shown in Table 1 was melted in a converter and continuously cast into slabs (slab: wall thickness 250 mm). The obtained slab was heated and hot-rolled to form a thick steel plate (thickness: 38 mm), which was once cooled to room temperature, and then subjected to reheating quenching and tempering treatment under the conditions shown in Table 2 (steel plate No. 1 to No. 16, No. 21 to No. 23). The quenching treatment was water cooling or oil cooling.
- the obtained slab was heated under the conditions shown in Table 2 and hot-rolled into a thick steel plate having a predetermined plate thickness (38 mm), and subsequently, accelerated cooling treatment was performed under the conditions shown in Table 2. (Steel plate No. 17, No. 18).
- the obtained slab was heated under the conditions shown in Table 2 and hot-rolled into a thick steel plate having a predetermined plate thickness (38 mm), followed by direct quenching under the conditions shown in Table 2, and then Direct quenching and tempering was performed at the tempering temperatures shown in Table 2 (steel sheets No. 19 and No. 20).
- the temperature of the steel plate was measured with a thermocouple inserted in the center of the plate thickness.
- the reheating quenching and tempering process simulates the production of a hydrogen pressure accumulator, and the accelerated cooling process and the direct quenching process both simulate the production of a hydrogen line pipe (steel pipe).
- the obtained steel sheet was subjected to a tensile test, a fracture toughness test, and further a structure observation.
- the test method was as follows. (1) Tensile properties Based on JIS Z 2201 (1980), full-thickness tensile test pieces with the rolling direction as the longitudinal direction (tensile direction) were collected from the obtained thick steel plate and conformed to JIS Z 2241. Then, a tensile test was performed to measure the tensile strength. (2) Fracture toughness test A CT test piece (sheet width: 50.8 mm) was taken from each of the obtained steel sheets so that the load direction was parallel to the rolling direction, and hydrogen embrittlement was made by the Japan Pressure Vessel Research Council Material Subcommittee.
- a fracture toughness test was carried out in a high-pressure hydrogen gas atmosphere to determine the fracture toughness value K IH according to the Special Committee TASK Group V (1991). The test was carried out in a high-pressure hydrogen gas atmosphere of 115 MPa at room temperature (20 ⁇ 10° C.) at a constant displacement rate of 2.5 ⁇ m/min.
- the fracture toughness test based on the rules of ASTM E399 or ASTM E1820 was also carried out to obtain the fracture toughness value K IH .
- the fracture toughness value K IH obtained by the fracture toughness test carried out in accordance with (1 year) was almost the same as the error within 5%, and therefore is not particularly described in Table 2.
- (3) Microstructure observation A test piece for microstructure observation was taken from the center of the thickness of the obtained steel sheet, polished, corroded (nital solution), and observed with an optical microscope (magnification: 200 times) to identify the microstructure. The tissue fraction was calculated by image analysis.
- the fracture toughness value K IH in a high-pressure hydrogen gas atmosphere of 115 MPa is 40 MPa ⁇ m 1/2 or more, and it can be said that the hydrogen embrittlement resistance is excellent.
- the fracture toughness value K IH in a high-pressure hydrogen gas atmosphere is less than 40 MPa ⁇ m 1/2, and the hydrogen embrittlement resistance is deteriorated.
- Each of the examples of the present invention had high strength of tensile strength: 560 MPa or more.
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Abstract
Description
(1)質量%で、C:0.04~0.50%、Si:0.5~2.0%、Mn:0.5~2.0%、P:0.05%以下、S:0.010%以下、N:0.0005~0.0080%、Al:0.010%~2.0%、O:0.0100%以下、Cu:0.5~2.0%、を含有し、残部Feおよび不可避的不純物からなる組成を有し、引張強さ:560MPa以上を有し、高圧水素ガス雰囲気中の破壊靭性値KIHが40MPa・m1/2以上である高圧水素ガス環境用鋼材。
(2)(1)において、質量%で、Al:0.5~2.0%である高圧水素ガス環境用鋼材。
(3)(1)または(2)において、前記組成に加えてさらに、質量%で、Ni:0.05~2.00%、Cr:0.10~2.50%、Mo:0.05~2.00%、W:0.05~2.00%、Nb:0.005~0.100%、V:0.005~0.200%、Ti:0.005~0.100%、B:0.0005~0.0050%のうちから選ばれた1種または2種以上を含有する高圧水素ガス環境用鋼材。
(4)(1)ないし(3)のいずれかにおいて、前記組成に加えてさらに、質量%で、Nd:0.005~1.000%、Ca:0.0005~0.0050%、Mg:0.0005~0.0050%、REM:0.0005~0.0050%のうちから選ばれた1種または2種以上を含有する高圧水素ガス環境用鋼材。
(5)(1)ないし(4)のいずれかに記載の高圧水素ガス環境用鋼材製である高圧水素ガス環境用鋼構造物。
(6)(5)において、前記鋼構造物が蓄圧器またはラインパイプである高圧水素ガス環境用鋼構造物。
(7)質量%で、C:0.04~0.50%、Si:0.5~2.0%、Mn:0.5~2.0%、P:0.05%以下、S:0.010%以下、N:0.0005~0.0080%、Al:0.010%~2.0%、O:0.0100%以下、Cu:0.5~2.0%、を含有し、残部Feおよび不可避的不純物からなる組成を有する鋼素材を、Ac3変態点以上に加熱し、熱間圧延を施して所定形状の鋼材とし、引続き(Ar3変態点-50℃)以上の温度から冷却速度:1~200℃/sで、600℃以下の冷却停止温度まで冷却する加速冷却処理を施し、引張強さ:560MPa以上で、高圧水素ガス雰囲気中の破壊靭性値KIHが40MPa・m1/2以上である高圧水素ガス環境用鋼材の製造方法。
(8)質量%で、C:0.04~0.50%、Si:0.5~2.0%、Mn:0.5~2.0%、P:0.05%以下、S:0.010%以下、N:0.0005~0.0080%、Al:0.010%~2.0%、O:0.010%以下、Cu:0.5~2.0%、を含有し、残部Feおよび不可避的不純物からなる組成を有する鋼素材を、Ac3変態点以上に加熱して、熱間圧延を施し所定形状の鋼材とし、引続き(Ar3変態点-50℃)以上の温度から冷却速度1~200℃/sで、250℃以下の冷却停止温度まで冷却し、さらにAc1変態点以下の温度で焼戻しする直接焼入れ焼戻し処理を施し、引張強さ:560MPa以上で、高圧水素ガス雰囲気中の破壊靭性値KIHが40MPa・m1/2以上である高圧水素ガス環境用鋼材の製造方法。
(9)質量%で、C:0.04~0.50%、Si:0.5~2.0%、Mn:0.5~2.0%、P:0.05%以下、S:0.010%以下、N:0.0005~0.0080%、Al:0.010%~2.0%、O:0.0100%以下、Cu:0.5~2.0%、を含有し、残部Feおよび不可避的不純物からなる組成を有し、所定形状に成形した鋼材を、Ac3変態点以上に加熱したのち、水焼入れまたは油焼入れし、さらにAc1変態点以下の温度で焼戻しする再加熱焼入れ焼戻し処理を施し、引張強さ:560MPa以上で、高圧水素ガス雰囲気中の破壊靭性値KIHが40MPa・m1/2以上である高圧水素ガス環境用鋼材の製造方法。
(10)(7)ないし(9)のいずれかにおいて、質量%で、Al:0.5~2.0%である高圧水素ガス環境用鋼材の製造方法。
(11)(7)ないし(10)のいずれかにおいて、前記組成に加えてさらに、質量%で、Ni:0.05~2.00%、Cr:0.10~2.50%、Mo:0.05~2.00%、W:0.05~2.00%、Nb:0.005~0.100%、V:0.005~0.200%、Ti:0.005~0.100%、B:0.0005~0.0050%のうちから選ばれた1種または2種以上を含有する高圧水素ガス環境用鋼材の製造方法。
(12)(7)ないし(11)のいずれかにおいて、前記組成に加えてさらに、質量%で、Nd:0.005~1.000%、Ca:0.0005~0.0050%、Mg:0.0005~0.0050%、REM:0.0005~0.0050%のうちから選ばれた1種または2種以上を含有する高圧水素ガス環境用鋼材の製造方法。
Siは、Cu、Alと同様に、耐水素脆化特性を向上させる元素であり、本発明では0.5%以上含有させる。一方、2.0%を超えるSiの多量含有は、結晶粒界を脆化させ、靭性の低下を招く。このため、Siは0.5~2.0%の範囲に限定した。なお、好ましくは0.75%以上であり、好ましくは2.00%以下である。より好ましくは1.00%以上である。
Cuは、Si、Alと同様に、耐水素脆化特性を向上させる元素であり、本発明では0.5%以上含有させる。一方、2.0%を超えるCuの多量含有は、加熱時や溶接時に、熱間での割れを発生させ易くする。このため、Cuは0.5~2.0%の範囲に限定した。なお、好ましくは0.75%以上であり、好ましくは2.00%以下である。より好ましくは1.00%以上である。
Alは、Si、Cuと同様に、耐水素脆化特性の向上に寄与する元素である。Alは、比較的少量の含有で、脱酸剤として作用するとともに、窒化物AlNを形成し、加熱時の結晶粒の粗大化を抑制し、組織の微細化に寄与する。このような効果を得るために、本発明では、Alを0.010%以上とする。一方、2.0%を超えるAlの多量含有は、鋼材の表面疵が発生しやすくなる。なお、耐水素脆化特性の顕著な向上のためには、Alは0.5%以上であることが好ましく、2.0%以下とすることが好ましい。より好ましくは0.75%以上であり、さらに好ましくは1.00%以上である。
Cは、強度増加に寄与するとともに、焼入れ性を向上させる元素であり、所望の強度、焼入れ性を確保するために、0.04%以上含有する必要がある。一方、0.50%を超える含有は、溶接性が著しく低下するとともに、母材および溶接熱影響部の靭性低下を招く。このため、Cは0.04~0.50%の範囲に限定した。なお、好ましくは0.10%以上であり、好ましくは0.45%以下である。
Mnは、焼入れ性向上を介して強度増加に寄与する元素である。このような効果を得るためには、0.5%以上含有する必要があるが、2.0%を超えて含有すると、粒界強度が低下し、低温靭性が低下する。このため、Mnは0.5~2.0%の範囲に限定した。なお、好ましくは0.8%以上であり、好ましくは1.5%以下である。
Pは、結晶粒界等に偏析しやすく、結晶粒の接合強度を低下させ、靭性を低下させる。このため、Pはできるだけ低減することが望ましいが、0.05%までは許容できる。このようなことから、Pは0.05%以下に限定した。
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を生成しやすく、延性、靭性の低下を招く。このため、Sはできるだけ低減することが望ましいが、0.010%までは許容できる。このようなことから、Sは0.010%以下に限定した。
Nは、Nb、Ti、Al等の窒化物形成元素と結合し、窒化物を形成し、加熱時にオーステナイト粒をピンニングし、結晶粒の粗大化を抑制し、組織を微細化する効果を有する。このような組織微細化効果を得るためには、0.0005%以上の含有を必要とする。一方、0.0080%を超える含有は、固溶N量が増加し、母材、溶接熱影響部の靭性低下を招く。このため、Nは0.0005~0.0080%の範囲に限定した。なお、好ましくは0.0020%以上であり、好ましくは0.0050%以下である。
O(酸素)は、アルミナ等の酸化物を形成し、非金属介在物量を増加させ、延性の低下など、加工性の低下を招くため、できるだけ低減することが望ましいが、0.0100%までは許容できる。このため、O(酸素)は0.0100%以下に限定した。なお、好ましくは0.0050%以下である。
Niは、焼入れ性の向上に加えてさらに、靭性をも向上させる作用も有する元素である。このような効果を得るためには、0.05%以上の含有を必要とする。一方、2.00%を超える含有は、材料コストを上昇させ、経済性が低下する。このため、含有する場合には、Niは0.05~2.00%の範囲に限定することが好ましい。なお、より好ましくは0.50%以上であり、より好ましくは1.50%以下である。
Crは、焼入れ性の向上を介して、強度確保に寄与する元素であり、このような効果を得るためには、0.10%以上の含有を必要とする。一方、2.50%を超えて多量に含有すると、溶接性が低下する。このため、含有するには、Crは0.10~2.50%の範囲に限定することが好ましい。なお、より好ましくは0.50%以上であり、より好ましくは1.50%以下である。
Moは、焼入れ性の向上を介して、強度確保に寄与する元素であり、このような効果を得るためには、0.05%以上の含有を必要とする。一方、2.00%を超えて多量に含有すると、材料コストの高騰を招き、経済性が低下する。このため、含有する場合には、Moは0.05~2.00%の範囲に限定することが好ましい。なお、より好ましくは0.20%以上であり、より好ましくは1.50%以下である。
Wは、焼入れ性の向上を介して、強度確保に寄与する元素であり、このような効果を得るためには、0.05%以上の含有を必要とする。一方、2.00%を超えて多量に含有すると、溶接性が低下する。このため、含有する場合には、Wは0.05~2.00%に限定することが好ましい。なお、より好ましくは0.20%以上であり、より好ましくは1.50%以下である。
Nbは、焼入れ性の向上に加えてさらに、加熱時に炭窒化物を微細析出させ、オーステナイト粒をピンニングして、結晶粒の粗大化を抑制する作用を有する元素である。このような効果は0.005%以上の含有で認められる。一方、0.100%を超える含有は、溶接熱影響部の靭性を低下させる。このため、含有する場合には、Nbは0.005~0.100%の範囲に限定することが好ましい。なお、より好ましくは0.010%以上であり、より好ましくは0.050%以下である。
Vは、焼入れ性の向上に加えてさらに、加熱時に炭窒化物を微細析出させ、オーステナイト粒をピンニングして、結晶粒の粗大化を抑制する作用を有する元素である。このような効果は0.005%以上の含有で認められる。一方、0.200%を超える含有は、溶接熱影響部の靭性を低下させる。このため、含有する場合には、Vは0.005~0.200%の範囲に限定することが好ましい。なお、より好ましくは0.010%以上であり、より好ましくは0.150%以下である。
Tiは、焼入れ性の向上に加えてさらに、加熱時に炭窒化物を微細析出させ、オーステナイト粒をピンニングして、結晶粒の粗大化を抑制する作用を有する元素である。このような効果は0.005%以上の含有で認められる。一方、0.100%を超える含有は、溶接熱影響部の靭性を低下させる。このため、含有する場合には、Tiは0.005~0.100%の範囲に限定することが好ましい。なお、より好ましくは0.010%以上であり、より好ましくは0.050%以下である。
Bは、微量の含有で焼入れ性の向上に寄与する元素である。このような効果を得るためには、0.0005%以上の含有を必要とする。一方、0.0050%を超えて含有すると、靭性が低下する。このため、含有する場合には、Bは0.0005~0.0050%の範囲に限定することがこのましい。なお、より好ましくは0.0010%以上であり、より好ましくは0.0020%以下である。
Ndは、Sと結合し硫化物系介在物を形成し、Sの粒界偏析量を低減して、靭性および耐水素脆性の向上に寄与する元素である。このような効果を得るためには、0.005%以上の含有を必要とする。一方、1.000%を超える含有は、溶接熱影響部の靭性を低下させる。このため、含有する場合には、Ndは0.005~1.000%の範囲に限定することが好ましい。なお、より好ましくは0.010%以上であり、より好ましくは0.500%以下である。
Caは、Sとの親和力が強く、圧延によって展伸しやすい硫化物系介在物であるMnSに代えて、圧延により展伸しにくい球状の硫化物系介在物であるCaSを形成し、硫化物系介在物の形態制御に寄与する元素であり、延性、靭性を向上させる作用を有する。このような効果を得るためには、0.0005%以上の含有を必要とする。一方、0.0050%を超えて含有すると、清浄度が低下し、延性、靭性等が低下する。このため、含有する場合には、Caは0.0005~0.0050%の範囲に限定することが好ましい。なお、より好ましくは0.0010%以上であり、より好ましくは0.0020%以下である。
Mgは、Caと同様に、Sとの親和力が強く、硫化物系介在物を形成し、延性、靭性を向上させる。このような効果を得るためには、0.0005%以上の含有を必要とする。一方、0.0050%を超えて含有すると、清浄度の低下を招く。このため、含有する場合には、Mgは0.0005~0.0050%の範囲に限定することが好ましい。なお、より好ましくは0.0010%以上であり、より好ましくは0.0020%以下である。
REMは、REM(O,S)等の硫化物系介在物を形成し、結晶粒界の固溶S量を低減して、耐SR割れ性の改善に寄与する元素である。このような効果を得るためには、REMは0.0005%以上含有する必要がある。一方、0.0050%を超える含有は、鋳造時に沈殿晶帯にREM系硫化物が多量に集積し、延性、靭性等材質の低下を招く。このため、含有する場合には、REMは0.0005~0.0050%の範囲に限定することが好ましい。なお、より好ましくは0.0010%以上であり、より好ましくは0.0020%以下である。なお、ここでいう「REM」は、Rare Earth Metal(希土類元素)の略である。
(加速冷却処理)
所定寸法形状に圧延された鋼材は、室温に冷却されることなく、引続き、(Ar3変態点-50℃)以上の冷却開始温度から、冷却速度:1~200℃/sで冷却停止温度:600℃以下の冷却停止温度まで冷却する加速冷却処理を施される。冷却開始温度が(Ar3変態点-50℃)未満では、冷却開始前にオーステナイトの変態量が多くなり、加速冷却後に所望の特性を確保できなくなる。このため、冷却開始温度は(Ar3変態点-50℃)以上の温度に限定した。また、加速冷却の冷却速度が1℃/s未満では冷却が遅すぎ、所望の特性を確保できない。一方、通常の冷却方法では、200℃/sを超えることはない。このため、加速冷却処理の冷却速度は1~200℃/sの範囲に限定した。なお、冷却速度は、板厚(肉厚)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、水冷等とすることが好ましい。また、加速冷却の冷却停止温度が600℃超えの高温では、所望の変態が完了しないため、所望の特性を確保できない。このため、加速冷却の冷却停止温度は600℃以下の温度に限定した。
(直接焼入れ焼戻し処理)
上記鋼素材を、Ac3変態点以上に加熱し、所定寸法形状の鋼材に熱間圧延されたのち、引続き(Ar3変態点-50℃)以上の温度から1~200℃/sの範囲の冷却速度で250℃以下の冷却停止温度まで冷却する焼入れ処理と、引続きAc1変態点以下の焼戻し温度で焼戻しする焼戻し処理を施される。鋼素材の加熱温度がAc3変態点未満では、一部未変態組織が残存するため、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-50℃)未満であると、焼入れ前のオーステナイトの変態量が多く、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-50℃)以上から冷却を開始し、焼入れを行う。(Ar3変態点-50℃)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、焼入れの冷却速度が1℃/s未満では冷却が遅すぎ、所望の特性を確保できない。一方、通常の冷却方法では、200℃/sを超えることはない。また、該焼入れを250℃超えの温度で停止すると、所望のマルテンサイト変態、ベイナイト変態が完了しないため、焼戻し後に所望の特性を得ることができない。このため、焼入れ処理は、250℃以下の温度まで冷却する焼入れとすることとする。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、焼戻し後に所望の特性を得ることができなくなる。
(再加熱焼入れ焼戻し処理)
所定寸法形状に圧延され、一旦、室温まで冷却された鋼材は、ついで、Ac3変態点以上の焼入れ加熱温度で加熱されたのち、引続き(Ar3変態点-50℃)以上の焼入れ開始温度から、冷却速度:0.5~100℃/sで250℃以下の温度まで冷却する焼入れ処理を施され、ついで、Ac1変態点以下の温度で焼戻しする、再加熱焼入れ焼戻し処理を施す。
Ar3(℃)=910-310C-80Mn-20Cu-15Cr-55Ni-80Mo、
Ac1(℃)=723-14Mn+22Si-14.4Ni+23.3Cr
ここで、各元素記号は、各元素の鋼中含有量(質量%)である。
(1)引張特性
得られた厚鋼板から、JIS Z 2201(1980)に準拠して、圧延方向を長手方向(引張方向)とする全厚引張試験片を採取し、JIS Z 2241の規定に準拠して引張試験を行い、引張強さを測定した。
(2)破壊靱性試験
得られた各鋼板から、荷重負荷方向が圧延方向と平行になるように、CT試験片(板幅:50.8mm)を採取し、日本圧力容器研究会議材料部会水素脆化専門委員会TASKGroup V編(1991年)に準拠して、高圧水素ガス雰囲気中で破壊靭性試験を実施し、破壊靭性値KIHを求めた。なお、試験は、室温(20±10℃)、115MPaの高圧水素ガス雰囲気中で、2.5μm/minの一定変位速度で実施した。
(3)組織観察
得られた鋼板の板厚中央部から、組織観察用試験片を採取し、研磨し腐蝕(ナイタール液)し、光学顕微鏡(倍率:200倍)で観察し、組織の同定と、画像解析により組織分率を算出した。
Claims (12)
- 質量%で、
C :0.04~0.50%、 Si:0.5~2.0%、
Mn:0.5~2.0%、 P :0.05%以下、
S :0.010%以下、 N :0.0005~0.0080%、
Al:0.010%~2.0%、 O :0.0100%以下、
Cu:0.5~2.0%、
を含有し、残部Feおよび不可避的不純物からなる組成を有し、
引張強さ:560MPa以上を有し、高圧水素ガス雰囲気中の破壊靭性値KIHが40MPa・m1/2以上である高圧水素ガス環境用鋼材。 - 質量%で、Al:0.5~2.0%である請求項1に記載の高圧水素ガス環境用鋼材。
- 前記組成に加えてさらに、質量%で、Ni:0.05~2.00%、Cr:0.10~2.50%、Mo:0.05~2.00%、W:0.05~2.00%、Nb:0.005~0.100%、V:0.005~0.200%、Ti:0.005~0.100%、B:0.0005~0.0050%のうちから選ばれた1種または2種以上を含有する請求項1または2に記載の高圧水素ガス環境用鋼材。
- 前記組成に加えてさらに、質量%で、Nd:0.005~1.000%、Ca:0.0005~0.0050%、Mg:0.0005~0.0050%、REM:0.0005~0.0050%のうちから選ばれた1種または2種以上を含有する請求項1ないし3のいずれかに記載の高圧水素ガス環境用鋼材。
- 請求項1ないし4のいずれかに記載の高圧水素ガス環境用鋼材製である高圧水素ガス環境用鋼構造物。
- 前記鋼構造物が蓄圧器またはラインパイプである請求項5に記載の高圧水素ガス環境用鋼構造物。
- 質量%で、
C :0.04~0.50%、 Si:0.5~2.0%、
Mn:0.5~2.0%、 P :0.05%以下、
S :0.010%以下、 N :0.0005~0.0080%、
Al:0.010%~2.0%、 O :0.0100%以下、
Cu:0.5~2.0%、を含有し、
残部Feおよび不可避的不純物からなる組成を有する鋼素材を、Ac3変態点以上に加熱し、熱間圧延を施して所定形状の鋼材とし、引続き(Ar3変態点-50℃)以上の温度から冷却速度:1~200℃/sで、600℃以下の冷却停止温度まで冷却する加速冷却処理を施し、引張強さ:560MPa以上で、高圧水素ガス雰囲気中の破壊靭性値KIHが40MPa・m1/2以上である高圧水素ガス環境用鋼材の製造方法。 - 質量%で、
C :0.04~0.50%、 Si:0.5~2.0%、
Mn:0.5~2.0%、 P :0.05%以下、
S :0.010%以下、 N :0.0005~0.0080%、
Al:0.010%~2.0%、 O :0.0100%以下、
Cu:0.5~2.0%、を含有し、
残部Feおよび不可避的不純物からなる組成を有する鋼素材を、Ac3変態点以上に加熱して、熱間圧延を施し所定形状の鋼材とし、引続き(Ar3変態点-50℃)以上の温度から冷却速度1~200℃/sで、250℃以下の冷却停止温度まで冷却し、さらにAc1変態点以下の温度で焼戻しする直接焼入れ焼戻し処理を施し、引張強さ:560MPa以上で、高圧水素ガス雰囲気中の破壊靭性値KIHが40MPa・m1/2以上である高圧水素ガス環境用鋼材の製造方法。 - 質量%で、
C :0.04~0.50%、 Si:0.5~2.0%、
Mn:0.5~2.0%、 P :0.05%以下、
S :0.010%以下、 N :0.0005~0.0080%、
Al:0.010%~2.0%、 O :0.0100%以下、
Cu:0.5~2.0%、を含有し、
残部Feおよび不可避的不純物からなる組成を有し、所定形状に成形した鋼材を、Ac3変態点以上に加熱したのち、水焼入れまたは油焼入れし、さらにAc1変態点以下の温度で焼戻しする再加熱焼入れ焼戻し処理を施し、引張強さ:560MPa以上で、高圧水素ガス雰囲気中の破壊靭性値KIHが40MPa・m1/2以上である高圧水素ガス環境用鋼材の製造方法。 - 質量%で、Al:0.5~2.0%である請求項7ないし9のいずれかに記載の高圧水素ガス環境用鋼材の製造方法。
- 前記組成に加えてさらに、質量%で、Ni:0.05~2.00%、Cr:0.10~2.50%、Mo:0.05~2.00%、W:0.05~2.00%、Nb:0.005~0.100%、V:0.005~0.200%、Ti:0.005~0.100%、B:0.0005~0.0050%のうちから選ばれた1種または2種以上を含有する請求項7ないし10のいずれかに記載の高圧水素ガス環境用鋼材の製造方法。
- 前記組成に加えてさらに、質量%で、Nd:0.005~1.000%、Ca:0.0005~0.0050%、Mg:0.0005~0.0050%、REM:0.0005~0.0050%のうちから選ばれた1種または2種以上を含有する請求項7ないし11のいずれかに記載の高圧水素ガス環境用鋼材の製造方法。
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