WO2016147594A1 - 複合容器蓄圧器ライナー用鋼材、複合容器蓄圧器ライナー用鋼管、および複合容器蓄圧器ライナー用鋼管の製造方法 - Google Patents
複合容器蓄圧器ライナー用鋼材、複合容器蓄圧器ライナー用鋼管、および複合容器蓄圧器ライナー用鋼管の製造方法 Download PDFInfo
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- WO2016147594A1 WO2016147594A1 PCT/JP2016/001227 JP2016001227W WO2016147594A1 WO 2016147594 A1 WO2016147594 A1 WO 2016147594A1 JP 2016001227 W JP2016001227 W JP 2016001227W WO 2016147594 A1 WO2016147594 A1 WO 2016147594A1
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- WO
- WIPO (PCT)
- Prior art keywords
- steel
- liner
- composite container
- steel material
- pressure accumulator
- Prior art date
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 168
- 239000010959 steel Substances 0.000 title claims abstract description 168
- 239000000463 material Substances 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title description 16
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 229910001563 bainite Inorganic materials 0.000 claims abstract description 28
- 229910001566 austenite Inorganic materials 0.000 claims abstract description 26
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 25
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000005096 rolling process Methods 0.000 claims description 22
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 description 23
- 229910052751 metal Inorganic materials 0.000 description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 15
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 8
- 238000010791 quenching Methods 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000005496 tempering Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 238000009628 steelmaking Methods 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009661 fatigue test Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 229910001562 pearlite Inorganic materials 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 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
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical class OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
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- C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
- C21D9/085—Cooling or quenching
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- Y10T428/12—All metal or with adjacent metals
- Y10T428/12292—Workpiece with longitudinal passageway or stopweld material [e.g., for tubular stock, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12951—Fe-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12951—Fe-base component
- Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12951—Fe-base component
- Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]
- Y10T428/12979—Containing more than 10% nonferrous elements [e.g., high alloy, stainless]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
Definitions
- the present invention relates to a steel material for a composite container pressure accumulator liner used for producing a liner for a composite container pressure accumulator that contains high-pressure hydrogen. Moreover, this invention relates to the manufacturing method of the steel pipe for composite container accumulator liners which consists of the said steel material for composite container accumulator liners, and the said steel pipe for composite container accumulator liners.
- a fuel cell vehicle using hydrogen as a fuel does not emit carbon dioxide (CO 2 ) and is excellent in energy efficiency. Therefore, it is expected as a vehicle that can solve the CO 2 emission problem and the energy problem.
- CO 2 carbon dioxide
- the entire pressure accumulator is made of metal (Type I), and the composite container accumulator (Type II, III) in which the outer circumference of the metal liner is covered with carbon fiber reinforced plastic (CFRP). And have been proposed.
- CFRP carbon fiber reinforced plastic
- Patent Document 1 proposes a composite container pressure accumulator that improves the fatigue crack growth rate in a high-pressure hydrogen environment by coating the outer periphery of a Cr—Mo steel liner with CFRP.
- a pressure accumulator made of only metal it is necessary to make it thick in order to obtain a strength that can withstand the pressure of hydrogen, but in a composite container pressure accumulator as described in Patent Document 1, a steel liner and Since the load is shared by CFRP, the liner can be made thinner than a pressure accumulator made of only metal, so that weight reduction and cost reduction are possible.
- the load sharing of the liner can be increased in the composite container pressure accumulator, the amount of expensive carbon fiber used can be reduced, so that the cost can be further reduced. Therefore, it is required to improve the characteristics of the steel material used for the liner of the composite container pressure accumulator.
- Patent Document 2 For improving the characteristics of steel materials used in pressure accumulators, for example, techniques described in Patent Documents 2 to 5 have been proposed.
- the hydrogen embrittlement resistance is improved by controlling the component composition and structure of steel and precipitates.
- the toughness of the steel is improved by controlling the aspect ratio of the cementite precipitated while the steel structure is mainly composed of bainite.
- the hydrogen embrittlement resistance is improved by controlling the component composition, and a high drawing value in high-pressure hydrogen is realized.
- the composition of the steel is set within a predetermined range, the formation of carbides is controlled, the hydrogen embrittlement resistance is improved, and a high drawing value in high-pressure hydrogen is realized. .
- Patent Documents 1 to 5 Although there is a certain improvement in the hydrogen embrittlement resistance and strength of the steel material, no study has been made to improve the fatigue limit.
- the accumulator for a hydrogen station is generally used for a long period of 10 years or more. In the meantime, filling and releasing of hydrogen gas are repeated, and the number of repetitions is assumed to be 100,000 times or more. Therefore, the steel material used for the liner of the pressure accumulator is required to have a high fatigue limit (fatigue strength) that does not break even after 100,000 times of fatigue deformation in hydrogen gas. Further, since the steel materials proposed in Patent Documents 2 to 5 are all for use in a pressure accumulator made of only steel materials, they are not assumed to be used as a liner material for a composite container pressure accumulator.
- the present invention is for solving the above problems, and when used as a material for producing a composite container pressure accumulator liner, a liner having sufficient strength and a high fatigue limit can be obtained, and is inexpensive. It aims at providing the steel material for composite container pressure accumulator liners which can manufacture a composite container pressure accumulator. Moreover, this invention aims at providing the manufacturing method of the steel pipe for composite container pressure accumulator liners which consists of the steel material for said composite container pressure accumulator liner, and the steel pipe for composite container pressure accumulator liners.
- a composite container pressure accumulator using a steel liner is manufactured by forming a steel pipe into a liner shape and then coating CFRP on the outer periphery thereof. At that time, in order to ensure the strength and toughness of the liner, the processed liner is quenched and tempered. (2) Therefore, in order to improve the fatigue limit of the liner finally obtained, a steel material capable of obtaining an excellent fatigue limit after quenching and tempering (hereinafter sometimes referred to as “heat treatment”) is used as a material. There is a need.
- the fatigue limit after quenching and tempering is reduced by reducing the average grain size of the prior austenite grains and by making the ratio of martensite and lower bainite occupying the metal structure a certain level or more. Can be improved.
- (4) By controlling the component composition of the steel material and the hot working conditions, it is possible to manufacture a steel material that satisfies the above condition (3).
- the gist configuration of the present invention is as follows. 1. % By mass C: 0.10 to 0.60% Si: 0.01 to 2.0%, Mn: 0.1 to 5.0%, P: 0.0005 to 0.060%, S: 0.0001 to 0.010%, N: 0.0001 to 0.010%, and Al: 0.01 to 0.06%, It has a component composition consisting of the balance Fe and inevitable impurities, A steel material for a composite container pressure accumulator liner, having an average austenite grain size of 20 ⁇ m or less and a total microstructure of martensite and lower bainite of 90% or more.
- the component composition is mass%, Mo: 0.005 to 2.0%, 2.
- the component composition is mass%, 3.
- a steel tube for a composite container pressure accumulator liner comprising the steel material for a composite container pressure accumulator liner according to any one of 1 to 5 above.
- a method of manufacturing a steel pipe for a composite container pressure accumulator liner A heating step of heating the steel material having the component composition according to any one of 1 to 3 to a temperature of 1350 ° C. or less; Rolling and expanding the heated steel material at a tube expansion end temperature of 820 ° C. or more to obtain a steel tube by expanding the tube;
- a method of manufacturing a steel tube for a composite container pressure accumulator liner comprising: a cooling step of cooling the steel tube obtained in the rolling tube expansion step at an average cooling rate at 800 to 350 ° C: 5 ° C / s or more.
- a method of manufacturing a steel pipe for a composite container pressure accumulator liner A heating step of heating the steel material having the component composition described in 4 to a temperature of 1350 ° C. or less; Rolling and expanding the heated steel material at a tube expansion end temperature of 820 ° C. or more to obtain a steel tube by expanding the tube;
- a method for producing a steel tube for a composite container pressure accumulator liner comprising: a cooling step of cooling the steel tube obtained in the rolling tube expansion step at an average cooling rate at 800 to 350 ° C: 3 ° C / s or more.
- a method of manufacturing a steel pipe for a composite container pressure accumulator liner A heating step of heating the steel material having the component composition described in 5 to a temperature of 1350 ° C. or less; Rolling and expanding the heated steel material at a tube expansion end temperature of 820 ° C. or more to obtain a steel tube by expanding the tube;
- a method of manufacturing a steel tube for a composite container pressure accumulator liner comprising: a cooling step of cooling the steel pipe obtained in the rolling tube expansion step under a condition of an average cooling rate at 800 to 350 ° C. of 1 ° C./s or more.
- the present invention when used as a material for producing a composite container pressure accumulator liner, it is possible to provide a steel material for a composite container pressure accumulator liner that can obtain a liner having sufficient strength and a high fatigue limit. it can. Therefore, if a liner is made using the steel material for a composite container pressure accumulator liner according to the present invention, more load can be shared by the liner, so the amount of CFRP used is reduced and the composite container pressure accumulator is made cheaper. Can be provided.
- the steel material has a metal structure in which the average grain size of the prior austenite grains is 20 ⁇ m or less and the total area fraction of martensite and lower bainite is 90% or more.
- the reason for limiting the metal structure of the steel material in the present invention as described above will be described.
- "%" display regarding a metal structure shall mean an area fraction.
- the average austenite grain size is 20 ⁇ m or less
- the average particle diameter of the prior austenite grain in steel materials for liners ie, the steel materials as a raw material for manufacturing a liner, shall be 20 micrometers or less.
- the average particle size of the prior austenite grains is preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less.
- the lower limit of the average grain size of the prior austenite grains is not particularly limited, but is preferably 1 ⁇ m or more.
- the total area fraction of martensite and lower bainite in the metal structure of the steel for liner is 90% or more.
- the total area fraction of martensite and lower bainite is preferably 95% or more.
- the ratio of the area fraction of martensite and lower bainite is not particularly limited, but from the viewpoint of suppressing the coarsening of the prior austenite grains, the area fraction of martensite is made higher than the area fraction of lower bainite. It is preferable.
- the upper limit of the total area fraction of martensite and lower bainite is not particularly limited and may be 100% or less.
- the structure other than martensite and lower bainite is preferably 5% or less in terms of the total area fraction.
- C 0.10 to 0.60%
- the tensile strength of the liner after quenching and tempering is preferably 800 MPa or more.
- the C content of the steel for liner is set to 0.10% or more.
- the C content is set to 0.60% or less.
- the C content is preferably 0.33% or more and 0.45% or less.
- Si 0.01 to 2.0% Si is an element that contributes to improvement in strength and fatigue limit by solid solution strengthening. The above effect can be obtained if the Si content is 0.01% or more. On the other hand, when the Si content exceeds 2.0%, the effect is saturated, the surface properties of the steel material are deteriorated, and the rollability is also lowered. Therefore, the Si content is 0.01% or more and 2.0% or less. In addition, it is preferable that Si content shall be 0.15% or more and 0.5% or less.
- Mn 0.1 to 5.0%
- Mn is an element that has the function of improving the fatigue limit while contributing to the improvement of strength by improving the solid solution strengthening and hardenability. Moreover, Mn suppresses the coarsening of prior austenite grains.
- Mn content shall be 0.1% or more.
- the Mn content is preferably 0.5% or more, and more preferably 0.6% or more.
- the Mn content is 5.0% or less.
- the Mn content is preferably 1.5% or less.
- P 0.0005 to 0.060%
- P is an element that contributes to improving the strength by solid solution strengthening.
- P is also an element that deteriorates toughness.
- the P content is preferably 0.025% or less, and more preferably 0.015% or less.
- excessive P reduction such that the P content is less than 0.0005% is accompanied by an increase in manufacturing cost in the steelmaking process. Therefore, the P content is 0.0005% or more.
- S 0.0001 to 0.010%
- An increase in the S content causes hot red hot brittleness, which may cause a manufacturing defect.
- S forms inclusion MnS and reduces toughness. These effects are not a problem if the S content is 0.010% or less. Therefore, the S content is set to 0.010% or less.
- the S content is preferably 0.0030% or less.
- excessive reduction such that the S content is less than 0.0001% is accompanied by an increase in desulfurization cost in the steelmaking process. Therefore, the S content is 0.0001% or more.
- the total of the P content and the S content is more preferably 0.02% or less for high toughness stabilization. On the other hand, it is desirable to lower the total of the P content and the S content, but excessive reduction leads to an increase in manufacturing cost, so the total of the P content and the S content is 0.0006% or more.
- N 0.0001 to 0.010%
- the influence of N on the fatigue characteristics of the steel material is small, and the effect of the present invention is not impaired if the N content is 0.010% or less. Therefore, the N content is set to 0.010% or less.
- the N content is preferably 0.004% or less.
- the N content is small. However, excessive reduction increases the cost of steelmaking, so the N content is set to 0.0001% or more.
- Al 0.01 to 0.06%
- Al is an element effective as a deoxidizer in the steel making process.
- the Al content is set to 0.01% or more.
- the Al content is preferably 0.02% or more.
- the Al content is set to 0.06% or less.
- the steel material for a composite container pressure accumulator liner of the present invention is composed of the remaining Fe and unavoidable impurities in addition to the above components. Further, the steel material for a composite container pressure accumulator liner according to the present invention may include any one or both of Mo: 0.005 to 2.0% and Cr: 0.005 to 3.0% in addition to the above elements. Can be further contained.
- Mo 0.005 to 2.0%
- Mo is an element that improves hardenability and contributes to an increase in liner strength and has a function of increasing the ratio of martensite and lower bainite in the metal structure of the steel material. Further, Mo suppresses coarsening of prior austenite grains and contributes to an increase in fatigue strength by solid solution strengthening.
- content is made into 0.005% or more.
- the Mo content is preferably 0.1% or more.
- the Mo content exceeds 2.0%, the effect is saturated and the cost increases, so the Mo content is set to 2.0% or less.
- the Mo content is preferably 1.0% or less, and more preferably 0.5% or less.
- Cr 0.005 to 3.0%
- Cr is an element that improves hardenability and contributes to an increase in liner strength and has a function of increasing the ratio of martensite and lower bainite in the metal structure of the steel material. Cr also suppresses coarsening of prior austenite grains.
- content is made into 0.005% or more.
- the Cr content is preferably 0.5% or more.
- the Cr content exceeds 3.0%, the effect is saturated and the cost increases, so the Cr content is 3.0% or less.
- the Cr content is more preferably 1.5% or less.
- the steel material for a composite container pressure accumulator liner according to the present invention may optionally further contain Ni: 0.005 to 3.0% in addition to the above elements.
- Ni 0.005 to 3.0%
- Ni is an element that improves hardenability, and contributes to an increase in liner strength and has a function of increasing the ratio of martensite and lower bainite in the metal structure of the steel material. Ni also suppresses coarsening of prior austenite grains.
- content is made into 0.005% or more.
- the Ni content is preferably 0.5% or more.
- the Ni content is set to 3.0% or less. In order to reduce costs, the Ni content is preferably set to 2.0% or less.
- the component composition of the said steel material further satisfy
- fills the relationship of following (1) Formula. [Mn] + 1.30 ⁇ [Cr] + 2.67 ⁇ [Mo] + 0.30 ⁇ [Ni] ⁇ 2.30 (1) (However, [M] represents the content (mass%) of the element M, and [M] 0 when the element M is not contained)
- the shape of the steel material for the composite container pressure accumulator liner in the present invention is not particularly limited, and may be any shape such as a steel pipe or a steel plate. From the viewpoint of using the composite container pressure accumulator liner as a material for molding, it is preferably a steel pipe, and more preferably a seamless steel pipe. Moreover, it is good also as a steel plate for using it when manufacturing welded steel pipes, such as a forged steel pipe and an electrical resistance welded steel pipe.
- the thickness is preferably 20 mm or more. If the thickness of the steel pipe is 20 mm or more, the stress distribution of the liner can be increased in the finally obtained composite container accumulator, so the amount of CFRP used can be reduced and the cost of the composite container accumulator can be reduced. It becomes possible. Furthermore, the fatigue limit in high-pressure hydrogen can be further improved by forming a steel pipe having a thickness of 20 mm or more into a liner and then applying a self-tightening treatment to impart residual compressive stress inside the liner.
- the wall thickness of the steel pipe is more preferably 30 mm or more, and further preferably 36 mm or more.
- board thickness shall be 20 mm or more, it is more preferable to set it as 30 mm or more, and it is further more preferable to set it as 36 mm or more.
- the wall thickness is too thick, the stress on the outside of the liner will be too high during pressure accumulation, and it will be necessary to increase the amount of alloy addition in order to make the structure the desired structure, which will increase the cost.
- it is 60 mm or less.
- the manufacturing method of the steel material for composite container pressure accumulator liners of this invention is demonstrated.
- the manufacturing method will be described by taking as an example the case where the steel material is a seamless steel pipe, but it is possible to manufacture steel materials of other shapes by performing the treatment so as to have a similar thermal history. Needless to say.
- the final finish rolling temperature is rolled at 820 ° C. or higher, and then the average cooling rate at 800 to 350 ° C. is cooled at a temperature of 5 ° C./s or higher. Obtainable.
- the steel tube for a composite container pressure accumulator liner of the present invention can be produced by sequentially performing the following steps (1) to (3).
- a heating process for heating a steel material (2) A rolling tube expanding step for rolling and expanding the heated steel material to obtain a steel tube, and (3) a cooling step for cooling the steel tube obtained in the rolling tube expanding step.
- a heating process for heating a steel material (2) A rolling tube expanding step for rolling and expanding the heated steel material to obtain a steel tube, and (3) a cooling step for cooling the steel tube obtained in the rolling tube expanding step.
- each step will be described.
- the temperature in description of the following heating processes, rolling tube expansion processes, and cooling processes means the temperature in the surface of a steel raw material or a steel pipe unless there is particular notice.
- the heating temperature in the heating step exceeds 1350 ° C., the average particle size of the prior austenite grains cannot be made 20 ⁇ m or less, so the heating temperature is made 1350 ° C. or less.
- the lower the heating temperature the better.
- the heating temperature is preferably 950 ° C. or higher.
- the steel material heated in the heating step is rolled and expanded to obtain a steel pipe shape.
- hot rolling including piercing and rolling of a normal Mannesmann-plug mill system or Mannesmann-Mandrel mill system can be used.
- the tube expansion end temperature is set to 820 ° C. or higher.
- the upper limit of the tube expansion end temperature is not particularly limited, but if the temperature is too high, the metal structure tends to be non-uniform, and therefore the tube expansion end temperature is preferably set to 1200 ° C. or lower.
- a desired structure can be obtained by setting the average cooling rate at 800 to 350 ° C. to 3 ° C./s or more.
- a desired structure can be obtained by setting the average cooling rate at 800 to 350 ° C. to 1 ° C./s or more.
- the cooling method is not particularly limited, and any method such as water cooling, oil cooling, air cooling or the like can be used alone or in combination, but oil cooling is preferable in terms of both high-speed cooling and prevention of burning cracks.
- a billet having a component composition shown in Table 1 having a diameter of 330 mm was prepared, and the billet was rolled and expanded to an outer diameter of 370 mm to obtain a steel pipe.
- the manufacturing conditions are shown in Table 2.
- the metal structure was evaluated for each of the obtained steel pipes. The evaluation method is as follows.
- the prior austenite ( ⁇ ) grain size is determined by etching the cross-section of the specimen taken from the center of the longitudinal direction of the steel pipe at a thickness of 1/4 with a saturated picric acid aqueous solution. Grain boundaries were revealed and determined by a cutting method from observation photographs taken using an optical microscope.
- the metal structure of steel pipes was evaluated as follows. The cross section of the test piece taken from the central part in the longitudinal direction of the steel pipe and the thickness 1 ⁇ 4 was etched using a 3 vol% nital solution. Thereafter, the cross section was observed with a scanning electron microscope (SEM) at an appropriate magnification of 1000 to 5000 times, and the obtained image was analyzed to evaluate the tissue type and area fraction. Residual austenite was measured by X-ray diffraction measurement.
- SEM scanning electron microscope
- the liner was manufactured by sequentially performing the following steps (a) to (c).
- (B) The obtained liner is heated to 850 ° C., held at the temperature for 120 minutes, and then immersed in oil for quenching; and (c) the quenched liner is baked at 650 ° C. for 180 minutes. Tempering process to return.
- the temperature in the above steps (b) and (c) is the temperature at the center of the thickness in the center in the longitudinal direction of the liner, and was measured by embedding a thermocouple in the liner.
- the average particle size and structure of the prior austenite grains are measured within 5 mm from the inner surface to the thickness direction of the test piece collected from the center part in the longitudinal direction of the liner and the surface on the inner surface side.
- evaluation about other items was performed by the following method. Unless otherwise specified, the evaluation and measurement related to the liner were all performed by collecting test pieces from the central portion in the longitudinal direction and the inner surface portion of the liner. The measurement results are as shown in Table 2.
- the average block length in a martensite and a lower bainite structure was determined based on the electron backscattering pattern (EBSP) measurement.
- EBSP measurement was performed in a region of three or more prior austenite grains, the block was specified, and the average length in the longitudinal direction was obtained. At that time, the length was the maximum length in the direction parallel to the (110) plane in each block, and the average was the arithmetic average.
- the block referred to in the present invention is defined as a region that is surrounded by a large-angle grain boundary and does not include a boundary having an orientation difference of 8 ° or more.
- the fatigue limit was measured by a fatigue test in high-pressure hydrogen. Using a test piece with a diameter of 7 mm taken from the liner, a fatigue test was performed in 90 MPa high-pressure hydrogen under the condition of a stress ratio of ⁇ 1. The limit.
- a Charpy impact test was conducted according to JIS Z 2242, and Charpy absorbed energy at -30 ° C was measured.
- the test piece was collected in parallel with the rolling direction of the material and provided with a V-notch. The test was performed on three test pieces, and the average value was defined as Charpy absorbed energy.
- the liners (invention examples) manufactured using a steel pipe whose component composition and metal structure satisfy the conditions of the present invention are all sufficient tensile strength of 800 MPa or more and excellent of 350 MPa or more. It has a fatigue limit, a relative fatigue strength index (fatigue limit / tensile strength) of 0.47 or more, and a Charpy absorbed energy of ⁇ 30 ° C. of 54 J or more. Indicated. On the other hand, No. 1 in which at least one of the steel component composition and the metal structure does not satisfy the conditions of the present invention.
- a composite container pressure accumulator liner is produced using the steel material for a liner and steel pipe of the present invention, a liner having sufficient strength and a high fatigue limit can be obtained. If a composite container pressure accumulator is manufactured using such a liner, more load can be shared by the liner, so the amount of CFRP used can be reduced and the composite container pressure accumulator can be provided at a lower cost. it can.
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Abstract
Description
また、本発明は、上記複合容器蓄圧器ライナー用鋼材からなる複合容器蓄圧器ライナー用鋼管と、前記複合容器蓄圧器ライナー用鋼管の製造方法に関するものである。
(1)鋼製ライナーを用いる複合容器蓄圧器は、鋼管を成形してライナー形状とした後、その外周にCFRPを被覆して製造される。その際、ライナーの強度とじん性を確保するために、加工後のライナーに対して、焼入れと焼戻しが行われる。
(2)したがって、最終的に得られるライナーの疲労限を向上させるためには、焼入れ焼戻し(以下、「熱処理」という場合がある)後において優れた疲労限を得ることができる鋼材を素材として用いる必要がある。
(3)所定の成分組成を有する鋼材において、旧オーステナイト粒の平均粒径を小さくするとともに、金属組織に占めるマルテンサイトおよび下部ベイナイトの割合を一定以上とすることにより、焼入れ焼戻し後における疲労限を向上させることができる。
(4)鋼素材の成分組成と熱間加工条件とを制御することにより、上記(3)の条件を満たす鋼材を製造することができる。
1.質量%で、
C :0.10~0.60%、
Si:0.01~2.0%、
Mn:0.1~5.0%、
P :0.0005~0.060%、
S :0.0001~0.010%、
N :0.0001~0.010%、および
Al:0.01~0.06%を含有し、
残部Feおよび不可避不純物からなる成分組成を有し、
旧オーステナイト粒の平均粒径が20μm以下、かつ、マルテンサイトおよび下部ベイナイトの面積分率の合計が90%以上である金属組織を有する、複合容器蓄圧器ライナー用鋼材。
Mo:0.005~2.0%、
Cr:0.005~3.0%の、いずれか一方または両方をさらに含有する、前記1に記載の複合容器蓄圧器ライナー用鋼材。
Ni:0.005~3.0%をさらに含有する、前記2に記載の複合容器蓄圧器ライナー用鋼材。
記
[Mn]+1.30×[Cr]+2.67×[Mo]+0.30×[Ni]≧2.30 …… (1)
(ただし、[M]は元素Mの含有量(質量%)を表し、元素Mを含有しない場合には[M]=0とする)
記
[Mn]+1.30×[Cr]+2.67×[Mo]+0.30×[Ni]≧3.00 …… (2)
(ただし、[M]は元素Mの含有量(質量%)を表し、元素Mを含有しない場合には[M]=0とする)
前記1~3のいずれか一つに記載の成分組成を有する鋼素材を1350℃以下の温度に加熱する加熱工程と、
加熱された前記鋼素材を、拡管終了温度:820℃以上の条件で圧延、拡管して鋼管を得る圧延拡管工程と、
前記圧延拡管工程で得られた鋼管を、800~350℃における平均冷却速度:5℃/s以上の条件で冷却する冷却工程とを有する、複合容器蓄圧器ライナー用鋼管の製造方法。
前記4に記載の成分組成を有する鋼素材を1350℃以下の温度に加熱する加熱工程と、
加熱された前記鋼素材を、拡管終了温度:820℃以上の条件で圧延、拡管して鋼管を得る圧延拡管工程と、
前記圧延拡管工程で得られた鋼管を、800~350℃における平均冷却速度:3℃/s以上の条件で冷却する冷却工程とを有する、複合容器蓄圧器ライナー用鋼管の製造方法。
前記5に記載の成分組成を有する鋼素材を1350℃以下の温度に加熱する加熱工程と、
加熱された前記鋼素材を、拡管終了温度:820℃以上の条件で圧延、拡管して鋼管を得る圧延拡管工程と、
前記圧延拡管工程で得られた鋼管を、800~350℃における平均冷却速度:1℃/s以上の条件で冷却する冷却工程とを有する、複合容器蓄圧器ライナー用鋼管の製造方法。
本発明においては、鋼材が、旧オーステナイト粒の平均粒径が20μm以下、かつ、マルテンサイトおよび下部ベイナイトの面積分率の合計が90%以上である金属組織を有することが重要である。以下、本発明における鋼材の金属組織を上記のように限定する理由を説明する。なお、金属組織に関する「%」表示は、特に断らない限り面積分率を意味するものとする。
・旧オーステナイト粒の平均粒径が20μm以下
複合容器蓄圧器ライナー用鋼材の旧オーステナイト粒径が小さいほど、該鋼材を成形してライナーを作製し、焼入れ焼戻し(熱処理)を行った後の旧オーステナイト粒径が小さくなる。そして、ライナーの旧オーステナイト粒径が小さいほど、高圧水素中でのライナーの疲労限が高くなる。前記効果を得るために、本発明においては、ライナー用鋼材、すなわち、ライナーを製造するための素材としての鋼材における旧オーステナイト粒の平均粒径を20μm以下とする。旧オーステナイト粒の平均粒径は、10μm以下とすることが好ましく、5μm以下とすることがより好ましい。一方、旧オーステナイト粒の平均粒径の下限は特に限定されないが、1μm以上とすることが好ましい。
ライナー用鋼材の金属組織に占めるマルテンサイトおよび下部ベイナイトの合計が90%未満であると、ライナー成形後の熱処理の際に、粗大な旧オーステナイト粒が発生する。そのため、本発明においては、ライナー用鋼材の金属組織に占めるマルテンサイトおよび下部ベイナイトの面積分率の合計を90%以上とする。マルテンサイトおよび下部ベイナイトの面積分率の合計は、95%以上とすることが好ましい。なお、マルテンサイトと下部ベイナイトの面積分率の比率は特に限定されないが、旧オーステナイト粒の粗大化を抑制するという観点からは、マルテンサイトの面積分率を下部ベイナイトの面積分率よりも高くすることが好ましい。一方、マルテンサイトおよび下部ベイナイトの面積分率の合計の上限については特に限定されず、100%以下であればよい。
本発明においては、さらに、複合容器蓄圧器ライナー用鋼材が所定の成分組成を有することが重要である。そこで、次に、本発明において鋼材の成分組成を限定する理由を説明する。なお、成分に関する「%」表示は、特に断らない限り「質量%」を意味するものとする。
Cは、ライナーの強度を上昇させるために必要な元素である。焼入れ焼戻しを行った後のライナーの引張強さは800MPa以上であることが好ましく、そのような強度を得るために、ライナー用鋼材のC含有量を0.10%以上とする。一方、C含有量が0.60%を超えると、焼入れの際に焼き割れが生じることがあるため、C含有量を0.60%以下とする。C含有量は、0.33%以上0.45%以下とすることが好ましい。
Siは、固溶強化により強度向上および疲労限の向上に寄与する元素である。Si含有量が0.01%以上であれば前記効果が得られる。一方、Si含有量が2.0%を超えると効果が飽和し、さらに鋼材の表面性状が劣化するとともに、圧延性も低下する。よって、Si含有量は0.01%以上2.0%以下とする。なお、Si含有量は0.15%以上0.5%以下とすることが好ましい。
Mnは、固溶強化および焼き入れ性の向上により強度向上に寄与するとともに、疲労限を向上させる機能を有する元素である。また、Mnは旧オーステナイト粒の粗大化を抑制する。前記効果を得るために、Mn含有量を0.1%以上とする。Mn含有量は0.5%以上とすることが好ましく、0.6%以上とすることがより好ましい。一方、Mn含有量が5.0%を超えると効果が飽和し、さらに圧延や成形が困難となる。また、ライナー成形後の熱処理の後にオーステナイトが残留し、疲労特性が劣化する。よって、Mn含有量は5.0%以下とする。Mn含有量は1.5%以下とすることが好ましい。
Pは、固溶強化によって強度向上に寄与する元素であるが、その反面、じん性を劣化させる元素でもある。P含有量が0.060%を超えるとじん性の劣化が顕著となるため、P含有量は0.060%以下とする。P含有量は0.025%以下とすることが好ましく、0.015%以下とすることがより好ましい。一方、P含有量を0.0005%未満とするような過度のP低減は製鋼工程における製造コストの増加を伴う。よって、P含有量は0.0005%以上とする。
S含有量の増加は熱間赤熱脆性の原因となり、製造上の不具合を生じる場合がある。また、Sは介在物MnSを形成し、じん性を低下させる。これらの影響は、S含有量が0.010%以下であれば問題とならない。よって、S含有量は0.010%以下とする。S含有量は0.0030%以下とすることが好ましい。一方、S含有量を0.0001%未満とするような過度の低減は製鋼工程における脱硫コストの増加を伴う。よって、S含有量は0.0001%以上とする。
なお、P含有量とS含有量の合計は、じん性の高位安定化のため、0.02%以下とすることがより好ましい。一方、P含有量とS含有量の合計は低くすることが望ましいが、過度の低減は製造コストの増加を招くため、P含有量とS含有量の合計は0.0006%以上とする。
鋼材の疲労特性に及ぼすNの影響は小さく、N含有量が0.010%以下であれば本発明の効果を損なわない。よって、N含有量は0.010%以下とする。N含有量は0.004%以下とすることが好ましい。一方、じん性向上の観点からは、N含有量が少ないことが望ましいが、過度の低減は製鋼上のコストを増大させるので、N含有量は0.0001%以上とする。
Alは、製鋼工程において脱酸剤として有効な元素である。その効果を得るため、Al含有量は0.01%以上とする。Al含有量は0.02%以上とすることが好ましい。一方、Al含有量が0.06%を超えると効果が飽和するため、Al含有量は0.06%以下とする。
Moは焼き入れ性を向上させる元素であり、ライナーの強度上昇に寄与するとともに、鋼材の金属組織におけるマルテンサイトおよび下部ベイナイトの比率を増加させる機能を有している。また、Moは、旧オーステナイト粒の粗大化を抑制するとともに、固溶強化によって疲労強度の上昇に寄与する。前記効果を得るために、Moを添加する場合には、含有量を0.005%以上とする。Mo含有量は0.1%以上とすることが好ましい。一方、Mo含有量が2.0%を越えると、効果が飽和し、コストアップの要因となるため、Mo含有量は2.0%以下とする。Mo含有量は1.0%以下とすることが好ましく、0.5%以下とすることがより好ましい。
Crは焼き入れ性を向上させる元素であり、ライナーの強度上昇に寄与するとともに、鋼材の金属組織におけるマルテンサイトおよび下部ベイナイトの比率を増加させる機能を有している。また、Crは旧オーステナイト粒の粗大化を抑制する。前記効果を得るために、Crを添加する場合には、含有量を0.005%以上とする。Cr含有量は0.5%以上とすることが好ましい。一方、Cr含有量が3.0%を越えると効果が飽和し、コストアップの要因となるため、Cr含有量は3.0%以下とする。Cr含有量は1.5%以下とすることがより好ましい。
Niは、焼き入れ性を向上させる元素であり、ライナーの強度上昇に寄与するとともに、鋼材の金属組織におけるマルテンサイトおよび下部ベイナイトの比率を増加させる機能を有している。また、Niは、旧オーステナイト粒の粗大化を抑制する。前記効果を得るために、Niを添加する場合には、含有量を0.005%以上とする。Ni含有量は0.5%以上とすることが好ましい。一方、Ni含有量が3.0%を越えると効果が飽和し、コストアップの要因となるため、Ni含有量は3.0%以下とする。コスト抑制のためには、Ni含有量を2.0%以下とすることが好ましい。
[Mn]+1.30×[Cr]+2.67×[Mo]+0.30×[Ni]≧2.30 …… (1)
(ただし、[M]は元素Mの含有量(質量%)を表し、元素Mを含有しない場合には[M]=0とする)
鋼材の成分組成を、(1)式の関係を満足するものとすることにより、鋼の焼入れ性が向上し、より容易にマルテンサイトおよび下部ベイナイトを得ることが可能となる。
[Mn]+1.30×[Cr]+2.67×[Mo]+0.30×[Ni]≧3.00 …… (2)
(ただし、[M]は元素Mの含有量(質量%)を表し、元素Mを含有しない場合には[M]=0とする)
マルテンサイトおよび下部ベイナイトを得るための具体的な製造条件については後述する。
本発明における複合容器蓄圧器ライナー用鋼材の形状は特に限定されることなく、鋼管、鋼板など、任意の形状とすることができる。該複合容器蓄圧器ライナーを成形するための素材として使用するという観点からは、鋼管とすることが好ましく、継目無鋼管とすることがより好ましい。また、鍛接鋼管、電気抵抗溶接鋼管などの溶接鋼管を製造する際に用いるための鋼板としてもよい。
本発明の複合容器蓄圧器ライナー用鋼材を鋼管形状とする場合、肉厚を20mm以上とすることが好ましい。鋼管の肉厚が20mm以上であれば、最終的に得られる複合容器蓄圧器においてライナーの応力分担を大きくすることができるため、CFRPの使用量を低減し、複合容器蓄圧器の低コスト化が可能となる。さらに、肉厚20mm以上の鋼管を成形してライナーとした後、自緊処理を施してライナー内部に残留圧縮応力を付与することにより、高圧水素中における疲労限をさらに向上させることができる。なお、鋼管の肉厚は30mm以上とすることがより好ましく、36mm以上とすることがさらに好ましい。また、本発明の複合容器蓄圧器ライナー用鋼材を鋼板形状とする場合にも、板厚を20mm以上とすることが好ましく、30mm以上とすることがより好ましく、36mm以上とすることがさらに好ましい。一方、肉厚は厚すぎると蓄圧時にライナー外側の応力が高くなりすぎ、また組織を所望の組織とするためにより合金添加量を増加させる必要がでてコストアップの要因となるため、80mm以下とすることが好ましく、さらに好ましくは60mm以下である。
次に、本発明の複合容器蓄圧器ライナー用鋼材の製造方法について説明する。以下の説明においては、前記鋼材が継目無鋼管である場合を例として製造方法を説明するが、同様の熱履歴となるように処理を行うことにより、他の形状の鋼材を製造可能であることはいうまでもない。例えば、鋼板の場合には、最終仕上げ圧延温度:820℃以上の条件で圧延し、引き続き、800~350℃における平均冷却速度:5℃/s以上の条件で冷却することにより、同様の特性を得ることができる。
(1)鋼素材を加熱する加熱工程、
(2)加熱された前記鋼素材を圧延、拡管して鋼管を得る圧延拡管工程、および
(3)前記圧延拡管工程で得られた鋼管を冷却する冷却工程。
以下、各工程について説明する。なお、以下の加熱工程、圧延拡管工程、冷却工程の説明における温度は、特に断らない限り、鋼素材または鋼管の表面における温度を意味する。
熱間圧延を行うために、上記した成分組成を有する鋼素材を加熱する。前記鋼素材としては、特に限定されないが、例えば、通常の連続鋳造法で得られるビレット等を使用することができる。
次に、上記加熱工程で加熱された鋼素材を圧延、拡管して鋼管形状とする。前記圧延には、通常のマンネスマン-プラグミル方式またはマンネスマン-マンドレルミル方式の、穿孔圧延を含む熱間圧延を用いることができる。この際、拡管終了温度が820℃未満であると、マルテンサイトおよび下部ベイナイトの面積分率の合計を90%以上にすることが困難となる。そのため、拡管終了温度は820℃以上とする。一方、拡管終了温度の上限は特に限定されないが、温度が高すぎると金属組織が不均一となりやすいため、拡管終了温度を1200℃以下とすることが好ましい。
前記圧延拡管工程で得られた鋼管は、次いで、室温まで冷却されるが、その際、所望の金属組織を得るために、冷却速度を制御する必要がある。鋼管の長手方向中央部における温度:800℃~350℃における平均冷却速度が5℃/s未満であると、フェライト、上部ベイナイト、パーライト等、マルテンサイトおよび下部ベイナイト以外の組織が生成し、最終製品であるライナーの疲労特性を劣化させる。そのため、本発明の一実施形態においては、800~350℃における平均冷却速度を5℃/s以上とする。ただし、上述したように、鋼の成分組成が(1)式の関係を満足する場合には、800~350℃における平均冷却速度を3℃/s以上とすれば所望の組織を得ることができる。さらに、鋼の成分組成が(2)式の関係を満足する場合には、800~350℃における平均冷却速度を1℃/s以上とすれば所望の組織を得ることができる。冷却方法は特に限定されず、水冷、油冷、空冷等、任意の方法を単独または組み合わせて用いることができるが、高速冷却と焼き割れ防止の両立の点では、油冷が好ましい。
旧オーステナイト(γ)粒径は、鋼管の長手方向中央部、肉厚1/4の位置から採取した試験片の断面を飽和ピクリン酸水溶液によりエッチングして旧オーステナイト結晶粒界を現出させ、光学顕微鏡を用いて撮影した観察写真から切断法により求めた。
鋼管における金属組織は以下のようにして評価した。鋼管の長手方向中央部、肉厚1/4から採取した試験片の断面を、3vol%ナイタール溶液を用いてエッチングした。その後、前記断面を1000~5000倍間の適正な倍率で走査型電子顕微鏡(SEM)を用いて観察し、得られた画像を解析して組織の種類、および面積分率を評価した。また、残留オーステナイトはX線回折測定により測定した。
(a)鋼管を成形、加工してライナー形状とする成形工程、
(b)得られたライナーを850℃に加熱し、該温度で120分間保持した後、焼入れ用の油に浸漬する油焼入れ工程、および
(c)焼入れ後のライナーを、650℃で180分間焼き戻す焼戻し工程。
なお、上記(b)および(c)の工程における温度は、ライナー長手方向中央部における、肉厚中心部における温度であり、ライナーに熱電対を埋め込んで測定した。
マルテンサイトおよび下部ベイナイト組織における平均ブロック長さは、電子後方散乱パターン(Electron BackScattering Pattern:EBSP)測定に基づいて決定した。旧オーステナイト粒3個以上の領域においてEBSP測定を行い、ブロックを特定して、その長手方向の長さの平均値を求めた。その際、前記長さは、各ブロックにおける(110)面に平行な方向の最大長さとし、前記平均は、算術平均とした。なお、本発明で呼称するブロックとは、大角粒界で囲われ、かつ方位差8°以上の境界をその内部に含まない領域と定義する。
得られたライナーから、JIS Z 2201に準じて直径7mmの丸棒試験片を採取し、引張強さを測定した。
疲労限は、高圧水素中における疲労試験により測定した。ライナーより採取した評価部直径7mmの試験片を用いて、応力比:-1の条件で、90MPaの高圧水素中で疲労試験を行い、繰り返し数20万回で試験片が破断しない限界応力を疲労限とした。
シャルピー衝撃試験をJIS Z 2242に準じて実施し、-30℃でのシャルピー吸収エネルギーを測定した。試験片は素材の圧延方向に平行に採取し、Vノッチを付与した。試験は3本の試験片について行い、その平均値をシャルピー吸収エネルギーと定義した。
Claims (10)
- 質量%で、
C :0.10~0.60%、
Si:0.01~2.0%、
Mn:0.1~5.0%、
P :0.0005~0.060%、
S :0.0001~0.010%、
N :0.0001~0.010%、および
Al:0.01~0.06%を含有し、
残部Feおよび不可避不純物からなる成分組成を有し、
旧オーステナイト粒の平均粒径が20μm以下、かつ、マルテンサイトおよび下部ベイナイトの面積分率の合計が90%以上である金属組織を有する、複合容器蓄圧器ライナー用鋼材。 - 前記成分組成が、質量%で、
Mo:0.005~2.0%、
Cr:0.005~3.0%の、いずれか一方または両方をさらに含有する、請求項1に記載の複合容器蓄圧器ライナー用鋼材。 - 前記成分組成が、質量%で、
Ni:0.005~3.0%をさらに含有する、請求項2に記載の複合容器蓄圧器ライナー用鋼材。 - 前記成分組成が、さらに下記(1)式の関係を満足する、請求項1~3のいずれか一項に記載の複合容器蓄圧器ライナー用鋼材。
記
[Mn]+1.30×[Cr]+2.67×[Mo]+0.30×[Ni]≧2.30 …… (1)
(ただし、[M]は元素Mの含有量(質量%)を表し、元素Mを含有しない場合には[M]=0とする) - 前記成分組成が、さらに下記(2)式の関係を満足する、請求項1~3のいずれか一項に記載の複合容器蓄圧器ライナー用鋼材。
記
[Mn]+1.30×[Cr]+2.67×[Mo]+0.30×[Ni]≧3.00 …… (2)
(ただし、[M]は元素Mの含有量(質量%)を表し、元素Mを含有しない場合には[M]=0とする) - 請求項1~5のいずれか一項に記載の複合容器蓄圧器ライナー用鋼材からなる複合容器蓄圧器ライナー用鋼管。
- 肉厚が20mm以上である、請求項6に記載の複合容器蓄圧器ライナー用鋼管。
- 複合容器蓄圧器ライナー用鋼管の製造方法であって、
請求項1~3のいずれか一項に記載の成分組成を有する鋼素材を1350℃以下の温度に加熱する加熱工程と、
加熱された前記鋼素材を、拡管終了温度:820℃以上の条件で圧延、拡管して鋼管を得る圧延拡管工程と、
前記圧延拡管工程で得られた鋼管を、800~350℃における平均冷却速度:5℃/s以上の条件で冷却する冷却工程とを有する、複合容器蓄圧器ライナー用鋼管の製造方法。 - 複合容器蓄圧器ライナー用鋼管の製造方法であって、
請求項4に記載の成分組成を有する鋼素材を1350℃以下の温度に加熱する加熱工程と、
加熱された前記鋼素材を、拡管終了温度:820℃以上の条件で圧延、拡管して鋼管を得る圧延拡管工程と、
前記圧延拡管工程で得られた鋼管を、800~350℃における平均冷却速度:3℃/s以上の条件で冷却する冷却工程とを有する、複合容器蓄圧器ライナー用鋼管の製造方法。 - 複合容器蓄圧器ライナー用鋼管の製造方法であって、
請求項5に記載の成分組成を有する鋼素材を1350℃以下の温度に加熱する加熱工程と、
加熱された前記鋼素材を、拡管終了温度:820℃以上の条件で圧延、拡管して鋼管を得る圧延拡管工程と、
前記圧延拡管工程で得られた鋼管を、800~350℃における平均冷却速度:1℃/s以上の条件で冷却する冷却工程とを有する、複合容器蓄圧器ライナー用鋼管の製造方法。
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