WO2020130060A1 - Acier inoxydable à base de cr présentant une excellente résistance à la fragilisation par l'hydrogène - Google Patents

Acier inoxydable à base de cr présentant une excellente résistance à la fragilisation par l'hydrogène Download PDF

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Publication number
WO2020130060A1
WO2020130060A1 PCT/JP2019/049717 JP2019049717W WO2020130060A1 WO 2020130060 A1 WO2020130060 A1 WO 2020130060A1 JP 2019049717 W JP2019049717 W JP 2019049717W WO 2020130060 A1 WO2020130060 A1 WO 2020130060A1
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Prior art keywords
less
stainless steel
embrittlement resistance
hydrogen
hydrogen embrittlement
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PCT/JP2019/049717
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English (en)
Japanese (ja)
Inventor
秦野　正治
佑一 田村
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日鉄ステンレス株式会社
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Priority to JP2020561497A priority Critical patent/JP7121142B2/ja
Priority to EP19899311.5A priority patent/EP3901292A4/fr
Priority to US17/312,693 priority patent/US20220033944A1/en
Priority to CN201980083521.9A priority patent/CN113227414B/zh
Priority to KR1020217018922A priority patent/KR102539588B1/ko
Publication of WO2020130060A1 publication Critical patent/WO2020130060A1/fr

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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Definitions

  • the present invention relates to a Cr-based stainless steel sheet having excellent hydrogen embrittlement resistance, and particularly to a Cr-based stainless steel sheet suitable as a metal material for high-pressure hydrogen gas equipment.
  • the Ni equivalent (Ni+0. It specifies the use of a material (for example, Ni equivalent ⁇ 28.5) in which 65Cr+0.98Mo+1.05Mn+0.35Si+12.6C) is increased.
  • the operating temperature is -45°C or higher and 250°C or lower.
  • Patent Documents 1 and 2 also disclose stainless steels which are intended to improve the economical efficiency by increasing the strength of SUS316L and lowering expensive Mo.
  • Non-Patent Document 1 discloses hydrogen embrittlement characteristics evaluated in a high-pressure hydrogen gas at room temperature for all steel materials including stainless steel.
  • SUS304 which is a typical austenitic stainless steel
  • Cr-based stainless steel are easily hydrogen embrittled. Therefore, generally, it is recommended to use SUS316L or SUS316 even in a high-pressure hydrogen gas having a pressure of about 20 MPa.
  • the Cr-based stainless steel having a body-centered cubic structure also has a problem (low-temperature brittleness) that the toughness is lowered at a low temperature of room temperature or lower as compared with the austenitic stainless steel having a face-centered cubic structure.
  • Patent Document 3 discloses a high-pressure hydrogen gas pressure vessel and a high-pressure hydrogen gas pipe coated with Al or an Al alloy.
  • the coating of austenitic stainless steels and duplex stainless steels containing an austenitic phase is targeted, and the film formation and hydrogen penetration characteristics in steel materials that are susceptible to hydrogen embrittlement, such as Cr-based stainless steels, are not shown.
  • Patent Document 4 a steel material which is apt to be hydrogen embrittled by itself is subjected to hot dip plating using an Al-Si alloy with an added amount of Si of 1 to 5%, thereby forming a hydrogen permeation resistant film.
  • a formed substrate for a hydrogen appliance is disclosed.
  • the base material is carbon steel, low alloy steel, or Cr-based stainless steel to prevent hydrogen embrittlement and also keep manufacturing costs low.
  • the examples are limited to SUS304, SUS630 (15Cr-4Ni-3Cu) and SCM435 (low alloy steel).
  • SCM435 low alloy steel
  • Patent Documents 1 to 4 described above remain only in the austenite-type and two-phase and SUS630 (precipitation hardening type), and the Cr-type stainless steel disclosed in Non-Patent Document 1 is easily hydrogen embrittlement and is high-pressure hydrogen gas. It does not have hydrogen embrittlement resistance for use in applications. Cr-based stainless steel also has a problem of low temperature brittleness.
  • the present invention has been made in view of the above circumstances, has a hydrogen embrittlement resistance for use in high-pressure hydrogen gas, and is suitable as a metal material for high-pressure hydrogen gas equipment, and is excellent in hydrogen embrittlement resistance Cr-based stainless steel.
  • An object is to provide a steel plate. At the same time, it is an object to realize compatibility with low temperature brittleness.
  • the present invention adopts the following configurations. [1]% by mass, C: 0.020% or less, Si: 1.00% or less, Mn: 1.00% or less, P: 0.040% or less, S: 0.0030% or less, Cr: 10 0.0 to 18.0%, N: 0.020% or less, Al: 0.10% or less, Nb: 0.5% or less, Ti: 0.5% or less : 0 to 0.3%, B: 0 to 0.005%, Ni: 0 to 1%, Cu: 0 to 1%, Mo: 0 to 1%, Sb: 0.2% or less, V: 0 to 0.5%, W:0 to 0.5%, Zr:0 to 0.5%, Co:0 to 0.5%, Mg:0 to 0.005%, Ca:0 to 0.005%, Ga: 0 to 0.020%, La: 0 to 0.1%, Y: 0 to 0.1%, Hf: 0 to 0.1%, REM: 0 to 0.1%, the balance being Fe and impurities And
  • the element symbol means the content (mass %) of the element.
  • Ni 1% or less
  • Cu 1% or less
  • Mo 1% or less
  • Sb 0.2% or less
  • V 0.5% or less
  • W 0.5% or less
  • Zr 0.5% or less
  • Co 0.5% or less
  • Mg 0.005% or less
  • Ca 0.005% or less
  • Ga 0.020% or less
  • La 0.1% or less
  • group stainless steel plate of this invention characterized by containing 1 type or 2 types or more of 0.1% or less, Hf:0.1% or less, and REM:0.1% or less.
  • the Cr-based stainless steel sheet according to the present invention which is used as a metal material for a high-pressure hydrogen gas device.
  • a Cr-based stainless steel sheet having excellent hydrogen embrittlement resistance and low temperature toughness can be provided.
  • the Cr-based stainless steel sheet of the present invention can be suitably used as a metal material for high-pressure hydrogen gas equipment.
  • the properties required for the metal material of the high-pressure hydrogen gas device include hydrogen embrittlement resistance and low temperature embrittlement resistance.
  • Cr-based stainless steel sheets reduce the amount of hydrogen penetrating into steel materials from high-pressure hydrogen gas due to the crystal structure, as compared with austenitic stainless steel sheets, but those having hydrogen embrittlement resistance suitable for high-pressure hydrogen gas applications can be obtained. Has not been done.
  • hydrogen embrittlement is characterized as a decrease in mechanical properties (strength, elongation, drawing) involved in plastic deformation. Therefore, hydrogen embrittlement is an event in which the destruction of a material progresses due to the interaction between hydrogen that has penetrated into the steel material from high-pressure hydrogen gas and plastic deformation.
  • Non-Patent Document 2 Therefore, in order to realize a Cr-based stainless steel sheet suitable for high-pressure hydrogen gas, it is necessary to reduce the interaction between hydrogen and plastic deformation as much as possible. In particular, since Cr has a large hydrogen trapping ability, the Cr content is suppressed to 18% or less in the present invention. Furthermore, the present inventors have found that it is preferable to control the added amounts of Si, Mn, P, Ti, and Nb within a predetermined range.
  • Sn and B serves as a diffusion barrier at the crystal grain boundaries of hydrogen and reduces the interaction between hydrogen and plastic deformation.
  • impurity elements such as P and S are segregated at the grain boundaries, which facilitates low temperature brittleness. Therefore, the inventors of the present invention pay attention to a small amount of addition of Sn and B, and by containing these elements in a predetermined range, it is expected that the adverse effects of P, S, etc. are suppressed and hydrogen embrittlement resistance and low temperature embrittlement resistance are compatible. I found that.
  • the gist of the present invention made based on the above findings (a) to (c) is as follows.
  • the Cr-based stainless steel sheet of the present embodiment is, in mass %, C: 0.020% or less, Si: 1.00% or less, Mn: 1.00% or less, P: 0.040% or less, S: 0.0.
  • a Cr-based stainless steel sheet excellent in hydrogen embrittlement resistance and low temperature embrittlement resistance characterized in that it contains two kinds, the balance consisting of Fe and impurities, and the texture on the plate surface satisfies the following (i) and (ii): is there.
  • the Cr-based stainless steel sheet of the present embodiment is further mass %, Ni: 1% or less, Cu: 1% or less, Mo: 1% or less, Sb: 0.2% or less, V: 0.5% or less. , W: 0.5% or less, Zr: 0.5% or less, Co: 0.5% or less, Mg: 0.005% or less, Ca: 0.005% or less, Ga: 0.020% or less, La : 0.1% or less, Y: 0.1% or less, Hf: 0.1% or less, REM: 0.1% or less, or two or more thereof may be contained.
  • the Cr-based stainless steel sheet of the present embodiment is preferably used as a metal material for high-pressure hydrogen gas equipment.
  • C 0.020% or less C increases the work hardening of steel due to solid solution and precipitation of carbides to deteriorate hydrogen embrittlement resistance, and further lowers toughness to deteriorate low temperature embrittlement resistance. Is as small as possible, and the upper limit is made 0.020% or less. However, in order to reduce the amount of C, the refining process becomes complicated and the cost increases. Therefore, the C content is preferably 0.001% or more. Considering the refining cost, the preferable range is 0.003 to 0.015%, and the more preferable range is 0.003 to 0.010%.
  • Si 1.00% or less Si is effective as a deoxidizing element, but when contained in excess, it causes solid solution strengthening and work hardening to increase, leading to a reduction in hydrogen embrittlement resistance and low temperature embrittlement resistance. It should be 0.000% or less.
  • the lower limit is preferably 0.01% or more in order to secure deoxidizing ability.
  • the preferable range is 0.05 to 0.50% in view of manufacturability and characteristics, and may be 0.05 to 0.30%.
  • Mn 1.00% or less
  • Mn is an element effective as a deoxidizing element, and is also an element effective for fixing S to improve toughness and to obtain low temperature brittleness resistance.
  • the upper limit is made 1.00% or less.
  • the lower limit is preferably 0.01% or more.
  • the preferable range is 0.05 to 0.50%, and may be 0.05 to 0.30%.
  • P 0.040% or less P is an element that segregates at grain boundaries to reduce low temperature embrittlement resistance, and the lower the content, the better. Therefore, the upper limit is 0.040%. However, excessive reduction leads to an increase in refining cost, so the lower limit is preferably made 0.005% or more. A more preferable range is 0.010 to 0.030%, and may be 0.010 to 0.020% in consideration of manufacturing cost and characteristics.
  • S 0.0030% or less Since S forms grain boundary segregation and sulfides in steel to deteriorate low temperature embrittlement resistance, the smaller the content, the better.
  • the upper limit is 0.0030%. However, excessive reduction leads to an increase in raw materials and refining costs, so the lower limit is preferably made 0.0001% or more.
  • a more preferable range is 0.0002 to 0.0015%, and may be 0.0002 to 0.0008% in consideration of manufacturing cost and characteristics.
  • Cr 10.0-18.0%
  • Cr is a basic element of the Cr-based stainless steel of the present embodiment, and is an essential element for maintaining hydrogen embrittlement resistance and low temperature embrittlement resistance in addition to the corrosion resistance of the steel.
  • the lower limit is made 10.0% or more in order to obtain the above-mentioned characteristics for use in high-pressure hydrogen gas of this embodiment.
  • the upper limit is 18.0% or less from the viewpoint of achieving both hydrogen embrittlement resistance and low temperature embrittlement resistance.
  • Cr which has a high hydrogen trapping capacity, exceeds 18.0%, the amount of hydrogen penetrating into the steel from the high-pressure hydrogen gas environment increases, the hydrogen embrittlement resistance deteriorates, and the texture deviates from the preferred range of the present invention. is there.
  • a more preferable range of Cr may be 11.0 to less than 17.0%, or 12.0 to 15.0%.
  • N 0.020% or less
  • N increases work hardening of steel due to solid solution and precipitation of carbides to deteriorate hydrogen embrittlement resistance, and further reduces toughness to deteriorate low temperature embrittlement resistance. Therefore, the smaller the content, the better, and the upper limit is made 0.020% or less.
  • the N content is preferably 0.001% or more.
  • a preferable range is 0.005 to 0.015% in consideration of characteristics and manufacturing cost.
  • Al 0.10% or less
  • Al is an extremely effective element as a deoxidizing element.
  • the upper limit is set to 0.10% or less.
  • the lower limit is preferably 0.005% or more in consideration of the deoxidizing effect. Considering the characteristics and manufacturability, the preferable range is 0.01 to 0.07%, and may be 0.01 to 0.05%.
  • Nb 0.5% or less
  • Ti 0.5% or less 1 type or 2 types
  • Nb and Ti segregate at grain boundaries to suppress grain boundary segregation of P and S and improve low temperature brittleness resistance. There is an action to try.
  • Nb and Ti can be expected to improve hydrogen embrittlement resistance by suppressing work hardening of steel due to the action as a stabilizing element that fixes C, N, P, and S. Both Nb and Ti exhibit these two effects, and are effective elements for improving the hydrogen embrittlement resistance and the low temperature embrittlement resistance, which are the goals of the present invention.
  • the content is preferably 0.01% or more so that the respective effects are exhibited.
  • the upper limits are set to 0.5% or less, respectively.
  • the preferable range is 0.05 to 0.5% with respect to the total of one or two of Nb and Ti in consideration of the effect of improving the characteristics and alloy cost.
  • a more preferable range is 0.08 to 0.4% for one kind or the sum of two kinds, and it may be 0.1 to 0.3%.
  • Sn and B are contained in the following content ranges.
  • Sn is an element effective for improving the hydrogen embrittlement resistance and the low temperature embrittlement resistance which are the targets of the present invention.
  • Sn which is a grain boundary segregation element, serves as a diffusion barrier at hydrogen crystal grain boundaries and reduces the interaction between hydrogen and plastic deformation. It also suppresses the segregation of P and S at the crystal grain boundaries and alleviates the adverse effects of low temperature embrittlement resistance.
  • Sn in a predetermined range, both hydrogen embrittlement resistance and low temperature embrittlement resistance are expected to be compatible. Therefore, in the present invention, it is preferable to contain Sn in the range of 0.001 to 0.5%.
  • B 0.005% or less
  • B is a grain boundary segregation element and is an element that improves hydrogen embrittlement resistance and low temperature embrittlement resistance like Sn, and it is effective to contain Cr in the Cr-based stainless steel of the present embodiment. is there.
  • the content in order to improve the hydrogen embrittlement resistance, the content is preferably 0.0003% or more.
  • the upper limit is made 0.005% or less. It is preferably 0.0005 to 0.002%, and may be 0.001 to 0.002%.
  • Si, Mn, P, Nb, and Ti each satisfy the following formula (1) in order to improve the hydrogen embrittlement resistance and the low temperature embrittlement resistance, which are the targets of the present invention, in addition to the content ranges described above. It is preferable. Si+0.5Mn+10P+5Nb+2Ti ⁇ 2.00... Formula (1)
  • the element symbol means the content (mass %) of the element.
  • the formula (1) is less than 2.00, and the lower limit is 0.05 from the viewpoint of properties and manufacturability.
  • a preferred range is 0.35 to 1.80, and a more preferred range is 0.50 to 1.50.
  • Ni, Cu and Mo are effective elements for improving corrosion resistance and Ni and Cu for improving low temperature toughness.
  • each of Ni, Cu, and Mo may be contained in the range of 0.05% or more. Excessive content increases the solid solution strengthening and work hardening of stainless steel, leading to a decrease in hydrogen embrittlement resistance, so the upper limit is made 1% or less.
  • a more preferable range is 0.1% or more and 0.8% or less, and a still more preferable range is 0.2% or more and 0.5% or less.
  • Mg forms Mg oxide together with Al in molten steel and acts as a deoxidizing agent, and also acts as a crystallization nucleus of TiN.
  • TiN serves as a solidification nucleus of the ferrite phase in the solidification process, and promotes crystallization of TiN, so that the ferrite phase can be finely generated during solidification.
  • the content is preferably 0.0001% or more for exhibiting these effects.
  • Mg exceeds 0.005%, manufacturability and corrosion resistance deteriorate, so the upper limit is made 0.005% or less. It is preferably 0.0003 to 0.002%, and more preferably 0.0003 to 0.001%.
  • Ca and Ga are elements that improve the cleanliness of steel, and are contained as necessary to suppress an increase in work hardening and increase hydrogen embrittlement resistance. .. When they are contained, the content is preferably 0.0003% or more in order to exhibit these effects. However, since excessive content leads to deterioration in manufacturability and corrosion resistance, the upper limits are set to 0.005% or less for Ca and 0.020% or less for Ga. Preferably, Ca is 0.0003 to 0.0030% and Ga is 0.0030 to 0.015%.
  • La, Y, Hf, and REM improve the cleanliness of steel similarly to Ca and Ga. It is an element and may be contained if necessary in order to suppress an increase in work hardening and enhance hydrogen embrittlement resistance. When they are contained, they are preferably contained in an amount of 0.001% or more in order to exhibit the effect. However, excessive contents lead to an increase in alloy cost and deterioration in manufacturability, so the upper limits are made 0.1% or less. It is preferably 0.001 to 0.05%, and more preferably 0.001 to 0.03%.
  • REM rare earth element
  • Sc scandium
  • Y yttrium
  • Lu lutetium
  • the impurities contained in the balance are those that are mixed in from the ore as a raw material, scrap, or the manufacturing environment when steel is industrially manufactured, and are allowed within the limit of solving the problem of the present invention. Means what is done. If necessary, Ta: 0.1% or less, Bi: 0.01% or less, Zn: 0.05%, H: 0.0005% or less may be contained.
  • the Cr-based stainless steel of the present embodiment contains ferrite crystal grains, and may contain martensite crystal grains.
  • the texture on the plate surface satisfies the following (i) and (ii).
  • the area ratio of crystal grains ( ⁇ 211 ⁇ 10° oriented grains) in which the angle difference between the normal direction of the steel sheet surface and the ⁇ 211 ⁇ plane orientation on the plate surface is within 10° is less than 30%
  • ⁇ 211 ⁇ 10° oriented grains defined in (i) both the length in the rolling direction and the length in the strip width direction are less than 0.15 mm on average, where ⁇ 211 ⁇ plane orientation is ⁇ 211 ⁇ . It means the direction normal to the surface.
  • the ⁇ 211 ⁇ orientation is called ⁇ -fiber and is a rolling texture that accumulates in cold rolling.
  • the area ratio of ⁇ 211 ⁇ 10° oriented grains is set to less than 30%, and the presence ratio of ⁇ 111 ⁇ orientation, which is a recrystallization texture, on the plate surface can be contributed to the improvement of hydrogen embrittlement resistance.
  • the area ratio of ⁇ 211 ⁇ 10° oriented grains is preferably in the range of 5 to 20%, more preferably in the range of 3 to 15%.
  • the average grain size of ⁇ 211 ⁇ 10° grains on the plate surface is less than 0.15 mm in both rolling direction and plate width direction (rolling vertical direction).
  • the preferable size of the ⁇ 211 ⁇ 10° oriented grains is less than 0.10 mm, more preferably less than 0.07 mm.
  • the “plate surface” is a region up to t/8 of the plate thickness t of the steel plate, and a region from the surface of the steel plate to a thickness of 1/8 t in the surface direction on both sides of the steel plate.
  • the ⁇ 211 ⁇ 10° oriented grains mean, on the plate surface, crystal grains having a crystal orientation in which an angle difference between the normal line direction of the steel sheet surface and the ⁇ 211 ⁇ plane orientation is within 10°.
  • EBSD electron beam backscattering diffraction method
  • the above-mentioned texture can be analyzed using electron beam backscattering diffraction method (hereinafter referred to as EBSD).
  • EBSD is to measure and analyze the crystal orientation of each crystal grain in a micro region of the sample surface at high speed.
  • the crystal orientation group that contributes to hydrogen embrittlement resistance is displayed by displaying a crystal orientation map divided into ⁇ 211 ⁇ 10° oriented grains and other regions on the plate surface, and the area ratio and grain of the ⁇ 211 ⁇ 10° oriented grains are displayed. You can quantify the size.
  • EBSD is measured at a magnification of 100 in a measurement region of a plate width direction of 850 ⁇ m and a rolling direction of 2250 ⁇ m, and parallel to the steel plate surface.
  • the crystal orientation map of crystal grains that is, ⁇ 211 ⁇ 10° orientation grains
  • the size can be quantified. If the range from the steel plate surface to t/8 of the steel plate thickness t is used as the inspection surface, the texture of the plate surface can be evaluated with good reproducibility.
  • Hydrogen embrittlement resistance is evaluated by the tensile strength and elongation at break in the low strain rate tensile test described above, and the value in high-pressure hydrogen gas is less likely to decrease in comparison with the tensile strength and elongation at break in air or inert gas.
  • the value obtained by dividing the tensile strength in the high-pressure hydrogen gas by the tensile strength in the atmosphere or the inert gas is referred to as "relative tensile strength”.
  • the value obtained by dividing the elongation at break in high-pressure hydrogen gas by the elongation at break in air or an inert gas is called “relative elongation”.
  • the Cr-based stainless steel sheet of this embodiment preferably has a relative tensile strength of 0.98 or more and a relative elongation of 0.75 or more. More preferable ranges are a relative tensile strength of 0.98 to 1.05 and a relative elongation of 0.85 to 1.05.
  • the low temperature brittleness shall be evaluated by the Charpy impact test according to JIS Z 2242, and the absorbed energy shall be measured using, for example, a 2 mm thick test piece with a V notch.
  • the low temperature brittleness resistance is evaluated by the energy transition temperature according to JIS D, and the lower the energy transition temperature, the better.
  • the energy transition temperature is a temperature corresponding to 1/2 of the absorbed energy at the temperature at which the fracture surface ratio due to ductile fracture is 100%.
  • the Cr-based stainless steel sheet of the present embodiment preferably has an energy transition temperature of ⁇ 10° C. or lower in consideration of the use in outdoor or on-vehicle hydrogen equipment. More preferably, it is -40°C or lower in consideration of use in cold regions.
  • the steel having the above-described chemical composition it is annealed after hot rolling at 900° C. or less, then cold rolling at a reduction rate of 40% or more, and finish annealing at a temperature of more than 900° C. ..
  • the heat treatment after hot rolling is 900° C. or lower, more preferably 700 to 900° C., in order to suppress the growth of ⁇ 211 ⁇ oriented grains generated in the hot rolling stage.
  • Cold rolling may be carried out by a reversible 20-high Sendzimir rolling machine, a 6-high rolling mill or a 12-high rolling mill, or a tandem rolling mill that continuously rolls multiple passes.
  • the work roll diameter is preferably large. Therefore, the work roll diameter is preferably 200 mm or more.
  • Such large-diameter roll rolling is preferably carried out at the time of primary cold rolling (initial cold rolling when cold rolling is repeated a plurality of times). As a result, the ⁇ 111 ⁇ oriented grains that are recrystallized textures develop and the area ratio of the ⁇ 211 ⁇ 10° oriented grains that are the rolling textures is reduced, which is effective in forming the target texture of the present invention. Is.
  • Cold rolling is preferably carried out at a reduction rate of 40% or more. If the cold rolling ratio is less than 40%, the area ratio and size of the ⁇ 211 ⁇ 10° oriented grains in the recrystallized texture tend to increase, and the hydrogen embrittlement resistance may decrease. From the viewpoint of hydrogen embrittlement resistance and manufacturability, the preferable range of the rolling reduction is 40 to 90%, and the more preferable range is 50 to 80%.
  • finish annealing after cold rolling it is preferable to perform heat treatment at over 900°C in order to develop ⁇ 111 ⁇ oriented grains and reduce the area ratio and size of ⁇ 211 ⁇ oriented grains. Since the excessive temperature rise increases the size of ⁇ 211 ⁇ 10° oriented grains due to the grain growth, the upper limit of the finish annealing temperature is preferably 1050°C. Further, the atmosphere at the time of finish annealing is not particularly specified, but the atmosphere, the LNG fuel atmosphere, and the BA atmosphere are preferable.
  • the soaking time for heat treatment is preferably 10 seconds to 10 minutes.
  • a soaking time of 10 seconds or more is preferable because the material for cold rolling can be softened. Further, if the soaking time is 10 minutes or less, the growth of ⁇ 211 ⁇ 10° oriented grains can be suppressed, the size of the crystal grains can be suppressed small, and a texture effective for hydrogen embrittlement resistance can be secured. ..
  • the hot rolled steel sheet was annealed after hot rolling in the range of 700 to 900° C., pickled and then cold rolled in the range of sheet thickness of 1.5 to 2.5 mm to obtain a cold rolled steel sheet.
  • Cold rolling conditions are shown in Table 2.
  • Cold rolling was carried out on a Sendzimir rolling machine and a tandem rolling machine with different work roll diameters. The former is a small diameter roll (60 mm) (indicated as “S” in Table 2) and the latter is a large diameter roll (200 mm) (in Table 2). "L” is used).
  • the cold rolled steel sheet was subjected to finish annealing at 920 to 1020° C. and pickling to produce a Cr-based stainless steel sheet.
  • the organization was analyzed using EBSD.
  • the crystal orientation group contributing to the hydrogen embrittlement resistance was numerically displayed by displaying a crystal orientation map divided into ⁇ 211 ⁇ 10° oriented grains and other regions on the plate surface. That is, EBSD was measured at a magnification of 100 in a measurement region of 850 ⁇ m in the width direction and 2250 ⁇ m in the rolling direction on a plane parallel to the steel plate surface within a range of t/8 of the thickness t of the steel plate from the steel plate surface, and parallel to the steel plate surface.
  • a crystal orientation map of crystal grains that is, ⁇ 211 ⁇ 10° orientation grains in which the angle difference between the normal direction of the plane and the ⁇ 211 ⁇ plane orientation is within 10° is displayed, and the grain boundaries are also displayed.
  • the area ratio of the crystal grains and the average particle diameter were measured.
  • the notation in the “size” column of ⁇ 211 ⁇ 10° oriented grains in Table 2 means “rolling direction/plate width direction”. Further, for some of the comparative examples, the measurement results at the plate thickness center (t/2) are also shown for reference. The site where the crystal orientation differs by 15° or more was defined as a crystal grain boundary.
  • the obtained Cr-based stainless steel sheet was evaluated for hydrogen embrittlement and low temperature embrittlement.
  • a commercially available 2 mm thick SUS316L steel plate (17.5%Cr-12%Ni-2%Mo) and SUS316 steel plate (17.5%Cr-10%Ni-2%Mo) were used for evaluation. I was there.
  • the hydrogen embrittlement was evaluated by the following procedure.
  • a tensile test piece having a width of 4 mm and a length of 20 mm in the parallel portion was prepared, and immediately before the tensile test in high-pressure hydrogen gas, the surface was polished with dry type #600 emery paper and then degreased and washed with an organic solvent.
  • the tensile test in high-pressure hydrogen gas was carried out at a hydrogen gas pressure of 20 MPa or 45 MPa, a test temperature of ⁇ 40° C., and a strain rate of 10 ⁇ 5 /s, as shown in Table 1.
  • the comparative tensile test was carried out in 0.1 MPa nitrogen at -40°C.
  • the tensile strength in high-pressure hydrogen gas is divided by the tensile strength in 0.1 MPa nitrogen to obtain the relative tensile strength
  • the breaking elongation in high-pressure hydrogen gas is divided by the breaking elongation in 0.1 MPa nitrogen to obtain the relative elongation.
  • the hydrogen embrittlement resistance was evaluated using relative tensile strength and relative elongation as evaluation indexes. The evaluation criteria are as follows. A and B were passed. A: The relative tensile strength is 0.98 or more and the relative elongation is 0.85 or more. B: Other than the above, the relative tensile strength is 0.98 or more and the relative elongation is 0.75 or more.
  • X Either or both of the relative tensile strength of less than 0.98 and the relative elongation of less than 0.75.
  • the hydrogen gas pressure is 45 MPa and the test temperature is ⁇ 40° C.
  • the relative elongation of the SUS316L steel sheet is less than 0.75
  • the evaluation is X.
  • the hydrogen gas pressure is 20 MPa and the test temperature is ⁇ 40° C.
  • the relative elongation of the SUS316 steel sheet is less than 0.75, and the evaluation is X.
  • the evaluation of the low temperature brittleness was performed by the Charpy impact test according to JIS Z2242.
  • the test piece had a V-notch shape of 1.5 to 2.5 mm thickness ⁇ 10 mm width ⁇ 55 mm length, and the test temperature was in the range of ⁇ 100° C. to room temperature (20° C.).
  • the low temperature brittleness resistance was used as an evaluation index by obtaining the energy transition temperature from the absorbed energy measured by the Charpy test.
  • the evaluation criteria are as follows. A and B were passed. A: Energy transition temperature of ⁇ 40° C. or lower is satisfied. B: Energy transition temperature of more than ⁇ 40° C. and below ⁇ 10° C. is satisfied. X: Energy transition temperature is higher than ⁇ 10° C.
  • No. Nos. 1 to 11 were all Cr-based stainless steel sheets having the chemical composition and texture within the scope of the present invention, and had good hydrogen embrittlement resistance and low temperature embrittlement resistance.
  • No. 1 with the range of preferable components and textures.
  • 5, 6, 9, and 10 had a hydrogen embrittlement resistance index of "B" or "A” at a hydrogen gas pressure of 45 MPa, and the hydrogen embrittlement resistance was higher than that of SUS316L.
  • No. Nos. 6, 8 and 10 are obtained by reducing the ⁇ 211 ⁇ 10° oriented grains using a large-diameter roll and have the same chemical composition as No. The hydrogen embrittlement resistance was further improved as compared with 5, 7, and 9.
  • No. Nos. 12 to 20 are Cr-based stainless steel sheets that do not have chemical components within the scope of the present invention, cannot form a texture within the scope of the present invention, and either or both of hydrogen embrittlement resistance and low temperature embrittlement resistance are inferior. became.
  • the hydrogen embrittlement resistance of the Cr-based stainless steel sheet was higher than that of SUS316 in the market by having the components and the texture within the scope of the present invention. Further, it has been found that the hydrogen embrittlement resistance surpassing that of SUS316L can be obtained by controlling the texture to have a preferable texture by using a large diameter roll having a preferable component.

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Abstract

L'invention concerne un acier inoxydable à base de Cr présentant une excellente résistance à la fragilisation par l'hydrogène, l'acier inoxydable à base de Cr étant caractérisé en ce qu'il comprend un ou deux types d'acier inoxydable ayant, en % en masse : 0 020 % ou moins de C ; 1,00 % ou moins de Si ; 1,00 % ou moins de Mn ; 0,04 % ou moins de P ; 0,0030 % ou moins de S ; 10,0 à 18,0 % de Cr ; 0,0020 % ou moins de N ; 0,10 % ou moins d'Al ; 0,5 % ou moins de Nb ; et 0,5 % ou moins de Ti, une structure d'agrégat sur une surface de feuille satisfaisant les suivantes (i) et (ii) : (i) sur la surface de la feuille, la proportion surfacique de grains cristallins (grains orientés {211}±10°), dans laquelle une différence d'angle entre la direction normale d'une surface de feuille d'acier et l'orientation de face {211} est inférieure à 10°, est inférieure à 30 % ; et (ii) dans les grains orientés {211}±10° , à la fois la longueur dans la direction de laminage et la longueur dans la direction de la largeur de la feuille sont inférieures à 0,15 mm en moyenne.
PCT/JP2019/049717 2018-12-21 2019-12-18 Acier inoxydable à base de cr présentant une excellente résistance à la fragilisation par l'hydrogène WO2020130060A1 (fr)

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EP19899311.5A EP3901292A4 (fr) 2018-12-21 2019-12-18 Acier inoxydable à base de cr présentant une excellente résistance à la fragilisation par l'hydrogène
US17/312,693 US20220033944A1 (en) 2018-12-21 2019-12-18 Cr-based stainless steel having excellent hydrogen embrittlement resistance
CN201980083521.9A CN113227414B (zh) 2018-12-21 2019-12-18 耐氢脆性优异的Cr系不锈钢板
KR1020217018922A KR102539588B1 (ko) 2018-12-21 2019-12-18 내수소 취성이 우수한 Cr계 스테인리스 강판

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JP2020100866A (ja) * 2018-12-21 2020-07-02 日鉄ステンレス株式会社 耐水素脆性と耐低温脆性に優れたＣｒ系ステンレス鋼

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CN114107630B (zh) * 2021-11-19 2022-08-19 北京科技大学 提高马氏体不锈钢抗氢脆性的热处理方法、不锈钢及应用

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CN113227414B (zh) 2023-08-11
US20220033944A1 (en) 2022-02-03
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