WO2004083477A1 - 高圧水素ガス用ステンレス鋼、その鋼からなる容器および機器 - Google Patents
高圧水素ガス用ステンレス鋼、その鋼からなる容器および機器 Download PDFInfo
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- WO2004083477A1 WO2004083477A1 PCT/JP2004/003809 JP2004003809W WO2004083477A1 WO 2004083477 A1 WO2004083477 A1 WO 2004083477A1 JP 2004003809 W JP2004003809 W JP 2004003809W WO 2004083477 A1 WO2004083477 A1 WO 2004083477A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3053—Fe as the principal constituent
- B23K35/308—Fe as the principal constituent with Cr as next major constituent
- B23K35/3086—Fe as the principal constituent with Cr as next major constituent containing Ni or Mn
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
Definitions
- the present invention relates to a stainless steel having excellent mechanical properties (strength and ductility) and corrosion resistance in a high-pressure hydrogen gas environment, and a container for high-pressure hydrogen gas made of the steel, a pipe, and an accessory thereof.
- These containers and the like are mainly structural equipment and components that are exposed to high-pressure hydrogen gas, such as fuel cells for automobiles and hydrogen gas stands, especially cylinders, piping, and valves.
- Typical methods include a method of mounting a hydrogen gas cylinder, a method of obtaining hydrogen by reforming methanol-gasoline with a vehicle-mounted reformer, and a method of mounting a hydrogen storage alloy that has absorbed hydrogen. .
- the hydrogen storage alloy In the method using a hydrogen storage alloy, the hydrogen storage alloy is extremely expensive, and it takes a long time to absorb hydrogen, which is equivalent to fuel filling. There are also technical problems such as performance degradation, and it is thought that it will still take some time before practical use.
- this includes extending the cruising distance, improving the equipment environment such as hydrogen stations necessary for dissemination, and developing technologies for improving the safety of hydrogen.
- High-pressure hydrogen gas equipment for fuel cell vehicles marketed in 2002 includes: Existing austenitic stainless steel whose soundness is widely recognized at present ⁇ J
- IS SUS 316 material is used. This is because the hydrogen embrittlement susceptibility is better than that of other structural steels, such as carbon steel such as JIS STS 480 and SUS 304 stainless steel, under the hydrogen gas up to about 35 MPa. It has excellent workability, weldability, etc., and its utilization technology has been established.
- JP-A-5-65601 and JP-A-7-188863 As a method for strengthening austenitic stainless steel, a so-called solid solution strengthening method in which a large amount of nitrogen (N) is dissolved in a solid solution is known from JP-A-5-65601 and JP-A-7-188863. .
- Japanese Patent Application Laid-Open No. 5-98391 discloses a precipitation strengthening method for depositing carbides and nitrides.
- these conventional strengthening methods inevitably decrease ductility and toughness.
- the anisotropy of toughness increases, and when used in a high-pressure hydrogen gas environment, the same problem as in cold working occurs. Can cause Further, in Japanese Patent Application Laid-Open Nos.
- High-pressure hydrogen containers and pipes and the equipment attached to them are often used by welding.
- the following problems also exist with the welded joint.
- the strength of the weld metal of the joint decreases due to the melt-solidification, and in the weld heat affected zone, the strength of the weld heat cycle decreases.
- a decrease in the strength of the weld heat affected zone can be prevented by performing appropriate heat treatment after welding.
- the weld metal has a coarse solidified structure, the strength cannot be improved by mere post-weld heat treatment. Disclosure of the invention
- the present invention provides a high-strength stainless steel having excellent mechanical properties and corrosion resistance in a high-pressure hydrogen gas environment, and provides a container, piping, and other equipment for high-pressure hydrogen gas manufactured from the stainless steel.
- the purpose is to.
- Another object of the present invention is to provide a container, a pipe, and other equipment for a high-pressure hydrogen gas in which a welded joint is excellent in mechanical properties such as strength and low-temperature paddy properties, and excellent in hydrogen embrittlement resistance. I do.
- the present inventors have studied in detail the relationship between the chemical composition and the metal structure (microstructure) of various materials on the mechanical properties and the erosion properties under a high-pressure hydrogen gas environment. As a result, the following new knowledge was obtained.
- Cr nitrides such as CrN and Cr 2 N are formed. If these nitrides are finely dispersed, they contribute to high strength. However, coarse nitrides not only degrade ductility and toughness, but also increase hydrogen embrittlement susceptibility.
- Cr nitrides such as CrN and Cr 2 N have a hexagonal crystal structure and poor compatibility with the austenite matrix. Therefore, they easily aggregate and coarsen.
- V is further added to steel in which the types and contents of constituent elements such as Ni and Cr are adjusted, V will also be contained in the Cr nitride. Even if such a Cr nitride remains hexagonal, the consistency with the austenite matrix is improved and it becomes difficult to coarsen.
- V is contained in steel, Cr nitride will be finely dispersed even if it is hexagonal, and if a part of it becomes cubic, fine dispersion will be more reliable. Become.
- the present invention has been completed based on the above findings, and its gist is as follows (1) Stainless steel and containers (2) and (3).
- % for the alloy component content means “% by mass”.
- the stainless steel may include at least one element selected from at least one of the following first to third groups.
- Group 1 element Mo: 0.3 to 3.0%, W: 0.3 to 6.0%, Nb: 0.001 to 0.20%, and Ta: 0.001 to 0.40% .
- Second group elements B: 0.0001 to 0.020%, Cu: 0.3 to 5.0%, and Co: 0.3 to 10.0%.
- Group 3 elements Mg: 0.0001-0.0050%, Ca: 0.0001-0.0050%, La: 0.0001-0.20%, Ce: 0.0001-0.20%, Y : 0.0001 to 0.40%, Sm: 0.0001 to 0.40%, Pr: 0.0001 to 0.40% and id: 0.0001 to 0.50%.
- the stainless steel preferably has the following microstructures (a) to (d). (a) the average grain size of austenite is 20 jum or less,
- the above-mentioned fine nitride of 0.1 m or less contains V in an amount of 10% by mass or more,
- containers are storage containers such as cylinders and tanks, and pipes are between these containers.
- it is a pipe that connects the container to other equipment, and the accessory equipment is one that is attached to the container or piping such as a valve.
- the weld metal of the weld joint is C: 0.04% or less, Si: 1.0% or less, Mn: 7 to 30%, Cr: 15 to 22 %, Ni: 4 to 20%, V: 0.05 to 0%, Mo: 0 to 3.0%, N: 0.20 to 0.50%, A1: 0.10% or less, Ti, Nb , Zr and Hf are each 0-0.01%, and the balance consists of Fe and impurities, P in the impurities is not more than 0.003%, S is not more than 0.005%, and the following (2) Containers and pipes for high-pressure hydrogen gas and their accessories, which satisfy the formula.
- the element symbols in the above formulas (3) and (4) are the contents (% by mass) of each element.
- the above weld metal may contain W and Ta in the first group described above, and at least one element selected from the elements of the second group and the elements of the third group. .
- FIG. 1 is an optical micrograph of the steel of the present invention.
- FIG. 2 is an electron micrograph showing a dispersion state of fine nitrides precipitated in the austenite matrix of the steel of the present invention.
- FIG. 3 is an X-ray spectrum diagram showing the fine nitride of 0.1 m or less of the steel of the present invention and its chemical composition (composition is the ratio of metal / metal components).
- FIG. 4 is a graph showing the relationship between the N content of the steel of the present invention, the conventional steel, and the comparative steel and the tensile strength (TS).
- FIG. 5 is a diagram showing the relationship between the N content of the steel of the present invention, the conventional steel, and the comparative steel and ductility (elongation).
- Figure 6 shows the N content and toughness (Charby absorption) of the steel of the present invention, the conventional steel, and the comparative steel.
- FIG. 6 shows the N content and toughness (Charby absorption) of the steel of the present invention, the conventional steel, and the comparative steel.
- FIG. 7 is a graph showing the relationship between Pmcn (2.5Cr + 3.4Mn-300N) of the steel of the present invention, conventional steel and comparative steel, and tensile strength (TS).
- FIG. 8 is a graph showing the relationship between the Pmcn (2.5 Cr + 3.4 Mn to 300 N) of the steel of the present invention, the conventional steel, and the comparative steel and ductility (elongation).
- FIG. 9 shows the relationship between the tensile strength and the ductility (elongation) of the steel of the present invention and the comparative steel.
- FIG. 10 is a graph showing the relationship between “1 (average particle size) ° ⁇ 5 ” and the proof stress of the steel of the present invention and the conventional steel.
- FIG. 11 is a graph showing the relationship between “1 (average particle size) ° ⁇ 5 ” and elongation of the steel of the present invention and the conventional steel.
- FIG. 12 is a graph showing the relationship between the amount (volume%) of fine nitrides of 0.1 / im or less and the strength of the steel of the present invention.
- FIG. 13 is a diagram showing the relationship between the V concentration in fine nitrides (methanol composition in nitrides: mass%) of 0.1 l / xm or less and the strength of the steel of the present invention.
- FIG. 14 is a diagram showing the relationship between the crystal structure of the nitride of the steel of the present invention and toughness.
- Si is known as an element that is effective in improving corrosion resistance in certain environments, but when it is contained in large amounts, it forms intermetallic compounds with Ni, Cr, etc., or intermetallic compounds such as sigma phase. May be promoted to significantly reduce hot workability. Therefore, the content of Si is set to 1.0% or less. More preferably, it is 0.5% or less. The smaller the amount of Si, the better, but it is preferably 0.001% or more in consideration of the refining cost.
- Mn is an inexpensive austenite stabilizing element.
- a proper combination with Cr, Ni, N and the like contributes to high strength and improvement in ductility and toughness. Therefore, Mn is contained in an amount of 7% or more. However, if it exceeds 30%, the hot workability and the weather resistance may decrease. Therefore, the appropriate content is 7 to 30%. The more desirable content of Mn is 7 to 17%.
- Cr is an essential component as an element that improves corrosion resistance in a high-pressure hydrogen gas environment. Its content is required to be not less than 15%, CrN reduce the ductility and toughness if the content is excessive, a large amount is nitride or M 2 3 C e-type carbides, such as Cr 2 N generated Becomes responsive. Therefore, the proper content of Cr is 15 to 22%.
- Ni is added as an austenite stabilizing element, but in the steel of the present invention, an appropriate combination of Cr, Mn, and N contributes to high strength, ductility, and improvement in toughness. Therefore, the Ni content is set to 5% or more, but if it exceeds 20%, the effect is small and the material cost rises. Therefore, the proper content is 5 to 20%.
- V 0.001 to 1.0%
- V improves the consistency with the matrix of hexagonal Cr nitride and prevents its coarsening, and promotes the formation of cubic nitride, It also partially dissolves in Cr N and Cr 2 N to suppress its coarsening, and greatly contributes to higher strength, improved ductility and toughness, and improved hydrogen embrittlement resistance.
- 0.001% or more is required.
- the V content is desirably 0.05 to 1.0%, and most desirably 0.1 to 1.0%, to increase the amount of cubic nitride.
- N is the most important solid solution strengthening element and contributes to high strength within the proper content range of Mn, Cr, Ni, C, etc., and also suppresses the formation of intermetallic compounds such as sigma phase, and toughness. It also contributes to the improvement of For that purpose, the content of 0.20% or more is necessary. Shikakashi, exceeds 50% 0., CrN, because formation of coarse hexagonal nitrides such as Cr 2 N is unavoidable, appropriate content is from 0.20 to 0.50% . However, in the steel of the present invention, when the balance of Mn, Cr and N satisfies the following expression (1), high strength and high ductility can be most compatible.
- the element symbols in the formula (1) mean the respective contents (% by mass).
- the coefficients of Cr and Mn in the above equation (1) are values determined from the contribution ratio of Cr and Mn to the solid solubility limit of N and the tendency to form a sigma phase.
- A1 0.10% or less
- A1 is an important element as a deoxidizer, but a large amount exceeding 0.10% promotes the formation of intermetallic compounds such as sigma phase. Therefore, it is not desirable for the balance of strength and toughness intended by the present invention. In order to ensure the deoxidizing effect, the content of 0.001% or more is desirable.
- One of the stainless steels of the present invention has the above components and the balance of Fe and impurities. The regulation of the specific element in the impurity will be described later.
- Another one of the stainless steels of the present invention further contains at least one element selected from at least one of the first to third groups described below. Elements belonging to the first group are Mo, W, Nb and Ta. These have the common effect of promoting the formation and stabilization of cubic nitride. The reasons for limiting each content are as follows.
- Mo and W have a function of stabilizing the cubic nitride and are also a solution strengthening element, so one or both of them are added as necessary. Each has its effect at 0.3% or more. However, if added excessively, austenite becomes unstable, so when these are added, the contents are preferably 0.3 to 3.0% and 0.3 to 6.0%, respectively.
- Nb 0.001 to 0.20%
- Ta 0.001 to 0.40%
- Nb and Ta also form a cubic nitride like V, one or both of them are added as necessary. The effect becomes significant at 0.001% or more. However, if added excessively, austenite becomes unstable, so when these are added, they should be kept at 0.20% or less and 0.40% or less, respectively.
- Elements belonging to the second group are B, Cu and Co. These contribute to the improvement of the strength of the steel of the present invention.
- the reasons for limiting the respective contents are as follows.
- the upper limit is set to 0.020%.
- Cu and Co are austenite stabilizing elements.
- Mn, Mn, Mn, and Co are austenite stabilizing elements.
- Ni, Cr and C contributes to higher strength, one or both of them can be contained in an amount of 0.3% or more as necessary.
- the upper limit of the content is set to 5.0% and 10.0%, respectively, based on the balance between effects and material costs.
- Belonging to the third group are Mg, Ca, La, Ce, Y, Sm, Pr and TSid.
- the effects and the reasons for limiting the contents are as follows.
- La, Ce, Y, Sm, Pr and Nd have the function of preventing solidification cracking during production and the effect of hydrogen embrittlement after long-term use within the composition range of the steel of the present invention.
- the upper limit is 0.050% for Mg and Ca respectively, 0.20% for La and Ce, respectively, and Y and Sm. 0.40% for Nd and 0.50% for Nd.
- P and S are elements that adversely affect the toughness of steel. Therefore, it is better to be as small as possible. However, if the content is not more than 0.003% and 0.005%, respectively, no remarkable deterioration in the properties of the steel of the present invention is recognized.
- Ti, Zr and 3 ⁇ 4f form cubic nitrides like V, but they form nitrides from a high temperature region prior to V, and thus inhibit the formation of V-based nitrides.
- nitrides of Ti, Zr and Hf have poor coherence with the austenite matrix, so that they themselves tend to agglomerate and coarse, and have little effect on improving strength. Therefore, in the steel of the present invention, these contents are each limited to 0.01% or less.
- Equation (1) The content of Cr, Mn, and N needs to satisfy the above equation (Equation (1)) when the equation (1) is satisfied, as shown in FIGS. This is because when O, the tensile strength of the steel is high and the elongation is large.
- the figure The Pmcn on the horizontal axis in Fig. 7 and Fig. 8 is "2.5Cr + 3.4Mn-300N".
- the stainless steel of the present invention is used as it is as hot worked or after being subjected to one or more heat treatments at 700 to 1200 ° C. Heating temperature of hot working and cooling conditions after working First, the following desirable microstructure can be obtained even with hot working. After hot working or after various workings after hot working, the above heat treatment will give more ⁇ ! Indeed, the following desirable organizational state is obtained.
- the stainless steel of the present invention preferably has the following microstructure.
- the average particle size means an average value of crystal grain sizes obtained by a particle size measuring method defined in JIS G 0551.
- the above matching is the matching between the crystal structure of Cr nitride and austenite due to the difference between the lattice constant and the lattice constant.
- the matching is best. Therefore, in the steel of the present invention, when nitrides are used, fine particles of 0.1 / im or less are dispersed and precipitated in 0.005% by volume or more ( ⁇ is desirable).
- the size of the nitride is obtained by converting the shape of the cut surface of the nitride into an equivalent circle. Evaluate by the maximum diameter of the case.
- Fine nitride of 0.1 l / xm or less contains V in an amount of 10% by mass or more:
- the nitride When the crystal structure of the Cr nitride is the same as the face-centered cubic crystal of the austenite matrix, the nitride is co-precipitated with the austenite matrix, making it more difficult to agglomerate and coarsen. Therefore, it is desirable that at least a part of the Cr nitride has a face-centered cubic crystal structure.
- the austenitic stainless steel of the present invention has high strength but also excellent ductility and toughness.
- hydrogen embrittlement susceptibility is low even in a high-pressure hydrogen environment. Therefore, this steel is extremely useful as a material for high-pressure hydrogen vessels, pipes and their accessories.
- the high-pressure hydrogen gas means a hydrogen gas having a pressure of 50 MPa or more, particularly a pressure of 70 MPa or more.
- the container and the like of the present invention are a container for high-pressure hydrogen gas made of the above stainless steel, a pipe, and an accessory thereof.
- the weld metal preferably has the chemical composition described above. The components of the weld metal that characterize welded joints are described below.
- C is preferably as low as less than 0.04%. More preferred is 0.03% or less, and most preferred is 0.02% or less.
- Si is an element required as a deoxidizing element, but since the weld metal generates an intermetallic compound and deteriorates toughness, the content is preferably as low as 1.0% or less. Desirable Si content is 0.5% or less, more preferably 0.2% or less. The lower limit may be the amount of impurities.
- Mn is effective as an element that increases the solubility of N and suppresses the release of N during welding. To obtain the effect, it should be 7% or more.
- the upper limit is 30%. A more desirable upper limit is 25%.
- Cr is an element necessary for improving corrosion resistance in a high-pressure gas environment. To obtain this effect, the content of weld metal must be 15% or more. However, if Cr is excessive, mechanical properties such as toughness and workability are impaired, so the upper limit is 22%.
- M is an element necessary for stabilizing the austenite phase of the weld metal, and at least 4% is required to achieve its effect. However, from the viewpoint of the effect, 20% is sufficient, and the inclusion of more than 20% is not preferable because it increases the price of the welding material.
- V 0.05 to 1.0%
- V has the following effects in the weld metal in a state where Nieq and Creq satisfy the above equation (2). That is, within the range satisfying the expression (2), when the solidification mode of the weld metal becomes the primary ⁇ ferrite phase, and from the middle of the solidification to the austenite phase due to the eutectic reaction, V concentrates in the remaining liquid phase. Primary crystals V no longer segregates between the tree branches. As a result, V efficiently combines with N during the solidification process to form fine VN. This makes it possible to suppress degradation of toughness. The effect is remarkable at 0.05% or more, but even if it exceeds 1.0%, the effect saturates and only the cost disadvantage becomes remarkable.
- Mo is an element effective in improving the strength and corrosion resistance of the weld metal, and is added as necessary. If added excessively, it segregates and causes a decrease in ductility. Therefore, when added, the upper limit is set to 3.0%. If added, the content is desirably adjusted to 1.0% or more.
- N is necessary to secure the strength of the weld metal. N forms a solid solution in the weld metal and contributes to strengthening, and also combines with V to form fine nitrides and contribute to precipitation strengthening. Below 0.20%, these effects are small. On the other hand, excessive addition of N causes welding defects such as blow holes, so the upper limit of the content is set to 0.50%.
- A1 0.10% or less
- A1 is an effective element as a deoxidizing element, but forms a nitride in combination with N to reduce the effect of N addition. Therefore, the content of A1 is preferably suppressed to 0.10% or less.
- the desirable content is 0.05% or less, and more desirably 0.02% or less. In order to ensure the deoxidizing effect, the content is preferably 0.005% or more.
- P is an undesirable impurity that degrades the toughness of the weld metal. 0.030% or less It is better to have as little as possible.
- Equation (2) is the following equation.
- Creq Cr + Mo + l. 5 X Si
- the low-temperature toughness and hydrogen embrittlement resistance of the weld metal can be improved by setting 1 ll ⁇ Nieq-1. l X Creq. If this condition is satisfied, excellent susceptibility to hydrogen cracking at room temperature after solidification cooling of the weld metal is reduced, and excellent low-temperature toughness can be ensured by suppressing the amount of ⁇ -flight that is brittle at low temperatures.
- the above weld metal may contain W and Ta in the first group described above, and at least one element selected from the elements of the second group and the third group. ,.
- the effects of these elements and the reasons for limiting the contents are the same as in the stainless steel of the present invention.
- the composition of the weld metal obtained as a result of mixing and melting the base material and the weld material satisfies the requirements described above.
- the base metal dilution ratio defined as the combination is determined by the welding method, and is about 5 to 30% for TIG and TV1IG welding and about 40 to 60% for submerged arc welding. Therefore, when the composition of the base metal is determined, the composition of the welding material can be selected by calculating so that the weld metal composition falls within the above-mentioned range within the range of the assumed base metal dilution ratio.
- high-strength welded joints with a tensile strength of 800 MPa or more can be obtained by performing aging heat treatment at 550 to 700 ° C for about 30 to 100 hours.
- Tables 1 and 2 show the chemical compositions (% by mass) of the conventional steel and the comparative steel, as well as the austenitic stainless steel of the present invention.
- the steels with the compositions shown in Tables 1 and 2 were melted using a 150 kg vacuum induction melting furnace, ingoted, then soaked at 1200 ° C for 4 hours, and then hot-forged at 1000 ° C or more.
- the plate was 25 mm thick and 100 mm wide. After that, it was heated and maintained at 1000 ° C for 1 hour, and then subjected to a solution treatment in which it was cooled with water to obtain a test material.
- FIG. 1 is an optical micrograph of the steel of the present invention (No. 1 in Table 1).
- FIG. 2 is an electron micrograph showing the dispersion state of the fine nitride precipitated in the austenite matrix of the steel of the present invention (No. 7 in Table 1).
- Fig. 3 is an X-ray spectrum diagram showing the fine nitride of 0.1 / im or less and the chemical composition (composition is the ratio of the metal component) of the steel of the present invention (No. 7 in Table 1). .
- Each of the steels of the present invention has an austenitic single phase structure as shown in FIG.
- the structure was such that nitrides (black dots in the figure) were dispersed and precipitated in the austenite matrix. Then, as shown in Fig. 3, 10 mass% of the nitride in the metal composition % Or more was V.
- rPmcnJ means the calculated value of ⁇ 2.5 ⁇ + 3.4 ⁇ ⁇ —300 ⁇ ”.
- Hydrogen embrittlement susceptibility means the calculated value of “(tensile elongation under hydrogen gas environment)” (tensile elongation in air).
- “Hydrogen embrittlement susceptibility” means the calculated value of "(Tension elongation in the atmosphere under hydrogen gas I) / (Elongation in the atmosphere)".
- the steels of the present invention Nos. 1 to 20 have a TS (tensile strength) force of 3 ⁇ 400 MPa or more, a YS (proof stress) of 400 MPa or more, and an elongation of 30% or more at room temperature.
- toughness V E .: Impact Energy
- the hydrogen embrittlement susceptibility evaluated by the ratio of the ductility in a tensile test in a hydrogen gas environment to the ductility in the atmosphere is extremely low.
- the content of at least one component or the value of Pmcn is out of the range specified in the present invention. These are not good in any of strength, ductility, toughness, and hydrogen embrittlement resistance compared with the steel of the present invention.
- Figures 10 and 11 show the results of using the No. 1 steel of the present invention and No. A of the conventional steel, and changing the solution treatment temperature after hot working from 950 ° C to 1100 ° C. It compares the relationship between the austenite grain size and the power and ductility (elongation).
- the resistance to power is improved with the refinement of the grain, and the ductility does not decrease so much.
- the particle diameter is 20 x m or less, a high strength of 50 MPa or more is obtained.
- conventional steels although the strength is increased by grain refinement, the ductility is significantly reduced.
- Fig. 12 to Fig. 14 show that the steel of No. 6 of the present invention was heated at 1100 ° C for 1 hour, then subjected to a solution treatment of water cooling, and then at a temperature of 700 to 1000 ° C. After the heat treatment for 3 hours, the crystal structure of the deposited nitride, the amount (volume%) of fine nitrides of 0.1 jum or less and the V concentration (metal composition in nitride; mass%) were measured. Furthermore, the results of a comparison between strength (tensile strength: TS) and toughness (absorbed energy: vE) are shown.
- TS tensile strength
- vE toughness
- the strength and toughness can be improved by using the structure specified in the present invention. This can be further improved.
- a plate with a thickness of 25mm, width of 100mm and length of 200mm is provided with a 20 ° V-groove on one side, butted with a plate of the same composition, and the welding materials shown in Table 5 are combined with the base material as shown in Tables 6 and 7 Then, a welded joint was produced by multi-layer welding within the groove by TIG welding.
- the welding conditions were a welding current of 130 A, a welding voltage of 12 V, and a welding speed of IScmZmin.
- an outer diameter of 6 mm has a parallel portion length of 30mm, the tensile test piece having a weld metal in the center of the parallel portion, and the outer diameter 2. 5 4 mm, the parallel portion length of 30mm
- Tensile test specimens in a hydrogen gas environment with a weld metal in the center of the parallel part were taken in the direction perpendicular to the welding line.
- a 10 x 10 x 55 mm Charpy impact test specimen with a 2 mm deep V notch in the center of the weld metal was sampled in a direction perpendicular to the weld line.
- a tensile test was performed at room temperature and a Charpy impact test was performed at -60 ° C to evaluate the strength and toughness of the welded joint.
- the tensile test in a hydrogen gas environment was carried out at a strain rate of 10-4 in a high-pressure hydrogen gas environment of 75MPa Te to room temperature.
- the tensile strength was 800 MPa
- the toughness was Charpy absorbed energy of at least 20 J
- the hydrogen embrittlement resistance was 0.8 when the tensile elongation ratio in a tensile test under a hydrogen gas environment and 0.8 in the atmosphere.
- Table 7 shows the above as good (marked with “ ⁇ ”).
- the tensile strength, toughness and Charpy absorbed energy of all the joints A1 to A4 in which the weld metal satisfies the requirements of the present invention exceed the above criteria.
- the hydrogen embrittlement resistance the ratio of the elongation at break in a tensile test in a hydrogen gas environment to that in the air was 0.8 or more. That is, these joints show excellent toughness and hydrogen embrittlement resistance while having high strength.
- the austenitic stainless steel of the present invention is a steel having excellent mechanical properties and corrosion resistance (hydrogen cracking resistance). This steel is extremely useful as equipment and components for containers and equipment that handle high-pressure hydrogen gas, mainly cylinders for fuel cell vehicles and hydrogen storage containers for hydrogen gas stands.
- the weld metal is of high strength having excellent low-temperature toughness and hydrogen embrittlement resistance. And so on.
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020047018651A KR100617465B1 (ko) | 2003-03-20 | 2004-03-19 | 고압 수소 가스용 스테인레스강, 그 강으로 이루어지는 용기 및 기기 |
CA2502207A CA2502207C (en) | 2003-03-20 | 2004-03-19 | High-strength stainless steel, container and hardware made of such steel |
EP04722083A EP1605073B1 (en) | 2003-03-20 | 2004-03-19 | Use of an austenitic stainless steel |
JP2005503770A JP4264754B2 (ja) | 2003-03-20 | 2004-03-19 | 高圧水素ガス用ステンレス鋼、その鋼からなる容器および機器 |
US11/108,098 US7749431B2 (en) | 2003-03-20 | 2005-04-18 | Stainless steel for high-pressure hydrogen gas |
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JP2003-078967 | 2003-03-20 | ||
JP2003078967 | 2003-03-20 | ||
JP2003165623 | 2003-06-10 | ||
JP2003-165623 | 2003-06-10 |
Related Child Applications (1)
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US11/108,098 Continuation US7749431B2 (en) | 2003-03-20 | 2005-04-18 | Stainless steel for high-pressure hydrogen gas |
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WO2004083477A1 true WO2004083477A1 (ja) | 2004-09-30 |
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PCT/JP2004/003809 WO2004083477A1 (ja) | 2003-03-20 | 2004-03-19 | 高圧水素ガス用ステンレス鋼、その鋼からなる容器および機器 |
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US (1) | US7749431B2 (ja) |
EP (1) | EP1605073B1 (ja) |
JP (1) | JP4264754B2 (ja) |
KR (1) | KR100617465B1 (ja) |
CA (1) | CA2502207C (ja) |
WO (1) | WO2004083477A1 (ja) |
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JPWO2004083477A1 (ja) | 2006-06-22 |
US7749431B2 (en) | 2010-07-06 |
EP1605073A1 (en) | 2005-12-14 |
KR100617465B1 (ko) | 2006-09-01 |
JP4264754B2 (ja) | 2009-05-20 |
US20050178477A1 (en) | 2005-08-18 |
EP1605073A4 (en) | 2007-11-14 |
EP1605073B1 (en) | 2011-09-14 |
CA2502207A1 (en) | 2004-09-30 |
KR20040111648A (ko) | 2004-12-31 |
CA2502207C (en) | 2010-12-07 |
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