WO2023105852A1 - Stainless steel having excellent cold forgeability, hydrogen embrittlement resistance properties or corrosion resistance and non-magnetism - Google Patents
Stainless steel having excellent cold forgeability, hydrogen embrittlement resistance properties or corrosion resistance and non-magnetism Download PDFInfo
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- WO2023105852A1 WO2023105852A1 PCT/JP2022/029784 JP2022029784W WO2023105852A1 WO 2023105852 A1 WO2023105852 A1 WO 2023105852A1 JP 2022029784 W JP2022029784 W JP 2022029784W WO 2023105852 A1 WO2023105852 A1 WO 2023105852A1
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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
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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
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
Definitions
- the present invention relates to stainless steel, and particularly to stainless steel that can satisfy both cold forgeability and resistance to hydrogen embrittlement after cold working.
- the present invention also relates to stainless steel, and more particularly to stainless steel that can satisfy all of cold forgeability, machinability, and resistance to hydrogen embrittlement after cold working.
- the present invention further relates to stainless steel, and more particularly to non-magnetic stainless steel that is excellent in corrosion resistance and cold forgeability.
- Fuel cell vehicles and hydrogen stations that handle hydrogen fuel use many metal parts that come into contact with hydrogen in a high-pressure gas state. Metal parts that come into contact with high-pressure hydrogen gas are prone to hydrogen embrittlement due to penetration of hydrogen into the metal. Therefore, in a high-pressure hydrogen environment, it is required to have mechanical strength and corrosion resistance as well as hydrogen embrittlement resistance.
- austenitic stainless steels such as SUS316 and SUS316L are generally used as stainless steels used for parts that come into contact with high-pressure hydrogen gas.
- SUS316 and SUS316L contain Mo.
- Patent Document 1 discloses austenitic stainless steel for high-pressure hydrogen that is excellent in mechanical strength and corrosion resistance, has low hydrogen embrittlement susceptibility even at a low temperature of -40 ° C., and is inexpensive in a composition system that does not contain Mo. is disclosed.
- hydrogen embrittlement susceptibility is evaluated by SSRT (Slow Strain Rate Test) for test pieces that have been cold drawn at a cold working rate of 0 to 25%.
- Patent Document 2 discloses a water-resistant steel made of austenitic stainless steel having a predetermined composition, subjected to a predetermined cold working, and having a face-centered cubic (fcc) lattice crystal structure after the working.
- a stainless steel wire for elemental springs is disclosed.
- cold wire drawing was performed with a final working ratio of 0 to 75%, and the test pieces were charged with hydrogen and then evaluated for bending stress and tensile stress.
- Non-Patent Document 1 presents Md30 as an evaluation index for the austenite stability of austenitic stainless steel.
- Md30 is the temperature (° C.) at which the structure transforms into 50% martensite phase when a tensile true strain of 0.30 is applied to an austenite single phase sample. The higher the value, the more unstable the material.
- Non-Patent Document 1 presents the formula for Md30 as a function of component composition.
- Patent Document 3 C: 0.15 to 0.80%, Ni: 8.0 to 20.0%, Cr: 8.0 to 18.0%, Mo: 0.05 to 0.50%, A steel having a predetermined composition containing V: 0.50 to 3.00% and Al: 0.001 to 1.000%, and is a modified formula (3) of the Md30 formula described in Non-Patent Document 1 is -100 or less, and 50 or more V (C, N) precipitates of 50 nm or less are present dispersedly in 3.5 ⁇ 10 -2 ⁇ m 2 .
- a high hardness non-magnetic steel is disclosed that combines hydrogen embrittlement resistance, mechanical properties and corrosion resistance.
- Patent Document 4 discloses tilt rolling.
- three work rolls are twisted in the same direction around the material to be rolled and arranged on the roll axes tilted.
- Each work roll revolves around the material to be rolled while rotating.
- the material to be rolled is spirally rolled while moving forward.
- austenitic stainless steels such as SUS316 and SUS316L are generally used as stainless steels used for non-magnetic parts.
- C 0.15 to 0.80%
- Ni 8.0 to 20.0%
- Cr 8.0 to 18.0%
- Mo 0.05 0.50%
- V 0.50 to 3.00%
- Al 0.001 to 1.000%.
- the value of the modified formula (3) is set to ⁇ 100 or less, and 50 or more V(C, N) precipitates of 50 nm or less are dispersed in 3.5 ⁇ 10 ⁇ 2 ⁇ m 2 .
- a high-hardness non-magnetic steel that is inexpensive and has excellent hydrogen embrittlement resistance, mechanical properties and corrosion resistance is disclosed.
- the first object of the present invention is to provide a stainless steel that can lower tensile strength, improve cold forgeability, and further improve hydrogen embrittlement resistance after cold working.
- the second object of the present invention is to provide a stainless steel that can lower tensile strength, improve cold forgeability, improve machinability, and further improve hydrogen embrittlement resistance after cold working. aim.
- non-magnetic steel with excellent mechanical strength is realized.
- it has been found that it is difficult to simultaneously satisfy corrosion resistance, cold forgeability, and non-magnetism after cold working in these conventionally known steels.
- the corrosion resistance deteriorates due to sensitization due to the high C content.
- the strength of the material before cold forging is high, the tool life is short and the forging load for large steel bars increases. Therefore, it was found that the cold forgeability deteriorated due to these factors.
- the processing limit (cracking) of the material occurs in conventional steel in high-strain processing such as cold forging.
- a third object of the present invention is to provide a stainless steel that can improve corrosion resistance, lower tensile strength, improve cold forgeability, and further improve non-magnetic properties after cold working.
- the gist of the present invention is as follows.
- a value represented by the following formula (a) is ⁇ 100 or less, A stainless steel having an average microstrain of 0.0040 or less from the surface layer to D/4 of the steel material.
- a value 551-462 (C+N)-9.2Si-8.1Mn-29(Ni+Cu)-13.7Cr-18.5Mo (a)
- the symbol of an element in the formula (a) means the content (% by mass) of the element in the steel.
- D is the diameter or thickness of the steel material
- the micro strain means the lattice strain calculated from the half width obtained by X-ray diffraction.
- the chemical composition is further, in mass %, As group A, Ti: 0.01 to 2.00%, Nb: 0.01 to 2.00%, Sn: 0.0001 to 2.5%, V: 0.001 to 2.0%, W: 0.05-3.0%, Ga: 0.0004-0.05%, Co: 0.05-2.5%, Sb: 0.01-2.5%, and Ta: 0.01-2 one or more selected from .5%, Group B selected from Ca: 0.0002 to 0.05%, Mg: 0.0002 to 0.012%, Zr: 0.0002 to 0.012%, and REM: 0.0002 to 0.05% one or more As group C, Pb: 0.0001 to 0.30%, Se: 0.0001 to 0.80%, Te: 0.0001 to 0.30%, Bi: 0.0001 to 0.50%, S: 0.0001 to 0.50%, P: one or more selected from 0.0001 to 0.30%, The stainless steel according to [1], containing one or more of Groups A to C of
- the A value represented by the following formula (a) is ⁇ 100 or less, A stainless steel characterized by having an amount of precipitated B as borides of 0.0001% or more and an aspect ratio of sulfides of 50 or less.
- a value 551-462 (C+N)-9.2Si-8.1Mn-29(Ni+Cu)-13.7Cr-18.5Mo (a)
- the symbol of an element in the formula (a) means the content (% by mass) of the element in the steel. Further, when the content of the element in the formula (a) is 0%, the calculation is performed by substituting "0" in the corresponding symbol.
- the chemical composition is further, in mass %, As group A, Ti: 0.01 to 2.00%, Nb: 0.01 to 2.00%, Sn: 0.0001 to 2.5%, V: 0.001 to 2.0%, W: 0.05-3.0%, Ga: 0.0004-0.05%, Co: 0.05-2.5%, Sb: 0.01-2.5%, and Ta: 0.01-2 .5%, one or more selected from As group B, one or more selected from Mg: 0.0002 to 0.012%, Zr: 0.0002 to 0.012%, and REM: 0.0002 to 0.05%, As group C, Pb: 0.0001 to 0.30%, Se: 0.0001 to 0.80%, Te: 0.0001 to 0.30%, Bi: 0.0001 to 0.50%, P: 0.0001 to 0.30%, one or more selected from The stainless steel according to [7], containing one or more of Groups A to C of
- the A value represented by the following formula (a) is ⁇ 100 or less, A stainless steel having a B grain boundary occupancy of 1% or more.
- a value 551-462 (C+N)-9.2Si-8.1Mn-29(Ni+Cu)-13.7Cr-18.5Mo (a)
- the symbol of an element in the formula (a) means the content (% by mass) of the element in the steel. Further, when the content of the element in the formula (a) is 0%, the calculation is performed by substituting "0" in the corresponding symbol.
- the chemical composition is further, in mass %, As group A, Al: 0.001 to 2.0%, Ti: 0.01 to 2.00%, Nb: 0.01 to 2.00%, Sn: 0.0001 to 2.5%, V: 0.001-2.0%, W: 0.05-3.0%, Ga: 0.0004-0.05%, Co: 0.05-2.5%, Sb: 0.01-2.
- the stainless steel of the first invention contains predetermined components, further contains one or both of Al and B, and has a micro strain of 0.0040 or less from the surface layer to D/4 of the steel material. and hydrogen embrittlement resistance after cold working.
- the stainless steel of the second invention contains predetermined components, further contains one or both of Al and Ca, has an amount of B precipitated as borides of 0.0001% or more, and has a sulfide aspect ratio of 50.
- the stainless steel of the third invention contains predetermined components and has a B grain boundary occupancy of 1% or more, so that it can satisfy corrosion resistance, cold forgeability, and non-magnetic properties after cold working. become.
- the stainless steel of the present invention can be applied in either bar shape or plate shape. Above all, it can be used particularly suitably when used as a bar-shaped steel material.
- Steel bars include “steel bars”, “wire rods”, “steel wires”, “deformed wires”, “deformed steel bars” and the like.
- the stainless steel of the present invention is austenitic stainless steel.
- the first invention aims to provide a stainless steel, particularly a bar steel, which can satisfy both cold forgeability and hydrogen embrittlement resistance after cold working.
- the purpose of the second invention is to provide a stainless steel, particularly a bar steel, which can satisfy all of cold forgeability, machinability, and resistance to hydrogen embrittlement after cold working, as described above.
- the third invention aims to provide stainless steel, particularly bar steel, which can satisfy corrosion resistance, cold forgeability, and non-magnetic properties after cold working.
- a test piece of ⁇ 8 ⁇ 12 mm was used, and an end face restraint compression test (processing temperature: RT (room temperature), strain rate: 10 / s) was performed.
- RT room temperature
- strain rate 10 / s
- the maximum compressibility at which cracks do not occur is defined as the limit compressibility, and the goal is to achieve the limit compressibility of 60% or more.
- a sample is prepared by performing solution heat treatment and then cold working at a cold working rate of 80%.
- Two test pieces are prepared under the same processing conditions, one being a hydrogen test piece and the other an air test piece.
- a hydrogen test piece is subjected to a tensile test at a strain rate of 1 ⁇ 10 ⁇ 5 /s in a hydrogen atmosphere, ⁇ 40° C., 70 MPa.
- tensile tests are performed at the same strain rate in atmospheric conditions.
- the strength and reduction of area are evaluated, respectively, and the percentage display of the value obtained by dividing the evaluation result of the hydrogen test piece by the evaluation result of the air test piece is defined as "relative strength" and "relative reduction of area", respectively.
- the goals of the first and second inventions are to achieve a relative strength of 80% or more and a relative reduction of area of 50% or more.
- the machinability is evaluated by the drilling life index VL-1000 (maximum peripheral speed (m/min) that can be drilled to a cumulative hole depth of 1000 mm).
- VL-1000 maximum peripheral speed (m/min) that can be drilled to a cumulative hole depth of 1000 mm.
- a target of the second invention is to achieve VL-1000 of 1 m/min or more.
- a target of the third invention is to achieve a pitting potential of 0.05 V or higher. In the examples, the pitting potential was measured immediately after polishing without the passivation treatment of the comparative material.
- the non-magnetic properties after cold working first, after performing heat treatment at 1100 ° C. for 30 minutes (water cooling) as solution heat treatment, cold working with a cold working rate (area reduction rate) of 80% is performed. A sample is prepared and the relative permeability at 1000 [Oe] is measured.
- the objective of the third invention is to achieve a relative permeability of 1.10 or less.
- Microstrain is lattice strain calculated from the half width obtained by X-ray line profile analysis, and the magnitude of lattice strain is determined by lattice defects and solid solution elements in the steel material. If the micro strain is small, the crystal lattice will not be easily distorted, and the accumulation of strain in high strain processing such as cold forging will be small. In addition, we thought that cold forging of large-diameter bar steel would be possible due to the reduction of the forging load. In addition, it was conceived that by reducing the local strain concentration in the metal structure, it would lead to suppression of fracture during cold forging and suppression of fracture in a hydrogen atmosphere.
- microstrain was measured by X-ray line profile analysis.
- the steel material surface layer to the D/4 position are measured by X-ray diffraction using CuK ⁇ rays, and (111), (200), The half-value widths of (220) and (311) are measured, and the obtained half-value widths are substituted into the following formula (A) of the Direct-Fitting method.
- D is the diameter or thickness of the steel.
- ⁇ K ⁇ + ⁇ (K/ ⁇ ) (A)
- ⁇ is microstrain and ⁇ is a value related to crystallite size.
- K, ⁇ K, and ⁇ are as follows.
- ⁇ is a function of diffraction line indices h, k, and l, and is given below.
- the average microstrain from the surface layer to D/4 of the steel material is more preferably 0.0020 or less, still more preferably 0.0010 or less, and even more preferably 0.0005 or less.
- the vicinity of the steel material surface layer tends to be a fracture starting point in cold forging, but by controlling the micro strain of the steel material surface layer to D/4 to be small, the deformability of the steel material is increased during cold forging. Strain control becomes important.
- the micro strain from the surface layer to D/4 of the steel material is the average value at the position from the surface layer to D/4 of the steel material.
- % means % by mass, including the second and third inventions.
- the stainless steel of the first invention contains one or more selected from Al: 0.001 to 2.0% and B: 0.0001 to 0.05%. This reduces microstrain, improves cold forgeability, and enhances resistance to hydrogen embrittlement. Also, Al is effective as a deoxidizing element. Excessive addition of Al results in the formation of coarse AlN and the like, degrading cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Al content is set to 2.0%, preferably 1.0% or less, more preferably 0.5% or less, further preferably 0.05% or less.
- the reason for the lower limit of B is as described above, and in addition, it has the effect of forming B-based precipitates to improve machinability. Preferably it is 0.0005% or more. Excessive addition of B forms coarse B-based precipitates and the like, deteriorating cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the B content is set to 0.05%, preferably 0.02% or less, and more preferably 0.015% or less. If neither Al nor B is contained, or if the lower limit is exceeded, the microstrain will be outside the range of the present invention, and the tensile strength, critical compressibility, relative tensile strength after cold working, and reduction of area will be poor.
- C (C: 0.0010 to 0.15%) C is made 0.0010% or more in order to suppress the formation of deformation-induced martensite and improve hydrogen embrittlement resistance. Excessive addition of C increases microstrain and deteriorates cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the C content is set to 0.15%, preferably 0.12% or less, more preferably 0.05% or less, still more preferably 0.02% or less. It is preferable to set the upper limit of C to less than 0.15%.
- Si 0.01 to 2.00%
- Si is added as a deoxidizing element to be 0.01% or more. Excessive addition of Si increases microstrain and deteriorates cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Si content is set to 2.0%, preferably 1.2% or less, more preferably 0.6% or less, still more preferably 0.5% or less.
- Mn 0.01 to 10.00%
- Mn is made 0.01% or more in order to suppress the formation of deformation-induced martensite and improve hydrogen embrittlement resistance. Excessive addition of Mn increases microstrain and deteriorates cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Mn content is set to 10.0%, preferably 2.5% or less, more preferably 1.5% or less, still more preferably 1.0% or less.
- Ni 8.00-30.00%
- Ni suppresses the formation of deformation-induced martensite and enhances hydrogen embrittlement resistance.
- the Ni content is made 8.00% or more. It is preferably 10.00% or more, more preferably 13.00% or more, and still more preferably 15.00% or more. Excessive addition of Ni, on the contrary, increases microstrain and deteriorates cold forgeability and resistance to hydrogen embrittlement. Therefore, the upper limit of the Ni content is 30.00%, preferably 25.00% or less.
- Cr 9.0 to 21.0% Cr suppresses the formation of deformation-induced martensite and enhances hydrogen embrittlement resistance. Moreover, in order to improve corrosion resistance, the Cr content is set to 9.0% or more. Preferably it is 10.5% or more. Excessive addition of Cr increases microstrain and degrades cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Cr content is set to 21.0%, preferably 19.5% or less, more preferably 15.0% or less.
- Mo 0.01 to 3.00%
- Mo suppresses the formation of deformation-induced martensite and enhances hydrogen embrittlement resistance.
- the Mo content is set to 0.01% or more in order to reduce microstrain and improve cold forgeability. Excessive addition of Mo, on the contrary, increases microstrain and deteriorates cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Mo content is 3.0%, preferably 2.8% or less, more preferably 2.5% or less, and even more preferably 1.0% or less.
- Cu 0.01 to 5.00%
- Cu suppresses the formation of deformation-induced martensite and enhances hydrogen embrittlement resistance.
- the Cu content is made 0.01% or more. It is preferably 1.00% or more, more preferably 2.00% or more. Excessive addition of Cu conversely increases microstrain, degrades cold forgeability and hydrogen embrittlement resistance, and causes hot shortness. Therefore, the upper limit of the Cu content is set to 5.00%, preferably 3.50% or less.
- N 0.0010 to 0.10%
- N is made 0.0010% or more in order to suppress the formation of deformation-induced martensite and improve hydrogen embrittlement resistance. Excessive addition of N increases microstrain and deteriorates cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the N content is set to 0.10%, preferably 0.08% or less, more preferably 0.05% or less, still more preferably 0.03% or less.
- the stainless steel of the first invention contains the above components, and the balance is Fe and impurities. Furthermore, it may contain one or more selected from the following components.
- Ti 0 to 2.00%
- Ti may be added for fixing C and N which enhance microstrain.
- the upper limit of the Ti content is set to 2.00%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less.
- a preferable lower limit of Ti is 0.03% or more, more preferably 0.05% or more.
- Nb 0 to 2.00%
- Nb may be added for fixing C and N to enhance microstrain.
- the upper limit of the Nb content is set to 2.00%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less.
- a preferable lower limit of Nb is 0.03% or more, more preferably 0.05% or more.
- Sn is an effective element for improving corrosion resistance, it may be contained. However, excessive Sn content saturates the effect, and conversely, there is a possibility that the cold forgeability and the hydrogen embrittlement resistance deteriorate. Therefore, the upper limit of the content of Sn is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.2% or less. In order to exhibit the above effects, the Sn content is preferably 0.0001% or more, more preferably 0.01% or more. More preferably, it is 0.05% or more.
- V (V: 0-2.0%) V may be added for fixing C and N which enhances microstrain.
- the upper limit of the V content is set to 2.0%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less.
- a preferable lower limit of V is 0.001%.
- W is an effective element for improving corrosion resistance, it may be contained. However, if W is contained excessively, the effect is saturated, and the cold forgeability and hydrogen embrittlement resistance may deteriorate. Therefore, when W is contained, the upper limit is set to 3.0%. More preferably, it is 2.0% or less, and still more preferably 1.5% or less. In order to exhibit the above effects, it is preferable to set the W amount to 0.05% or more. More preferably, it is 0.10% or more.
- Ga is an effective element for improving corrosion resistance, so it may be contained. However, if Ga is contained excessively, the effect is saturated, and the cold forgeability and hydrogen embrittlement resistance may deteriorate. Therefore, the upper limit when Ga is contained is set to 0.05%. In order to exhibit the above effect, it is preferable to set the amount of Ga to 0.0004% or more.
- Co (Co: 0-2.5%) Co has the effect of improving the corrosion resistance, so it may be contained. However, if Co is contained excessively, the effect is saturated, and the cold forgeability and hydrogen embrittlement resistance may deteriorate. Therefore, the upper limit of the content of Co is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.8% or less. In order to exhibit the above effects, the Co content is preferably 0.05% or more, more preferably 0.10% or more.
- Sb Since Sb has an effect of improving corrosion resistance, it may be contained. However, if Sb is contained excessively, the effect is saturated, and the cold forgeability and hydrogen embrittlement resistance may deteriorate. Therefore, the upper limit when Sb is contained is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.8% or less. In order to exhibit the above effect, the Sb content is preferably 0.01% or more, more preferably 0.05% or more.
- Ta (Ta: 0-2.5%) Ta may be added for fixing C and N to enhance microstrain.
- the upper limit of the Ta content is set to 2.5%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less.
- a preferable lower limit of Ta is 0.01%.
- Ca 0-0.05% Ca may be contained as needed for deoxidation.
- the upper limit of the Ca content is 0.05%, preferably 0.010% or less, and more preferably 0.005% or less.
- a preferable lower limit of Ca is 0.0002%.
- Mg 0-0.012%
- Mg may be contained as necessary for deoxidation.
- the upper limit of the Mg content is 0.012%, preferably 0.010% or less, and more preferably 0.005% or less.
- a preferred lower limit for Mg is 0.0002%.
- Zr 0 to 0.012% Zr may be contained as necessary for deoxidation.
- the upper limit of the Zr content is 0.012%, preferably 0.010% or less, and more preferably 0.005% or less.
- a preferable lower limit of Zr is 0.0002%.
- REM 0-0.05%) REM may optionally be included for deacidification.
- the upper limit of the REM content is 0.05%, preferably 0.010% or less, and more preferably 0.005% or less.
- a preferred lower limit for REM is 0.0002%.
- Pb 0 to 0.30%)
- Pb is an element that enhances machinability and may be contained as necessary.
- the upper limit of the Pb content is set to 0.30%, preferably 0.10% or less, and more preferably 0.05% or less.
- a preferable lower limit of Pb is 0.0001%.
- Se is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of Se deteriorates cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Se content is 0.80%, preferably 0.1% or less, and more preferably 0.05% or less. A preferred lower limit for Se is 0.0001%.
- Te 0 to 0.30% Te is an element that enhances machinability and may be contained as necessary. On the other hand, if Te is added excessively, cold forgeability and hydrogen embrittlement resistance deteriorate. Therefore, the upper limit of the Te content is set to 0.30%, preferably 0.1% or less, and more preferably 0.05% or less. A preferable lower limit of Te is 0.0001%.
- Bi (Bi: 0 to 0.50%) Bi is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of Bi degrades cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Bi content is 0.50%, preferably 0.1% or less, and more preferably 0.05% or less. A preferable lower limit of Bi is 0.0001%.
- S is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of S degrades cold forgeability and resistance to hydrogen embrittlement. Therefore, the upper limit of the S content is 0.50%, preferably 0.1% or less, and more preferably 0.05% or less. A preferred lower limit for S is 0.0001%. Incidentally, S is usually contained in steel as an impurity mixed from steelmaking raw materials.
- P 0-0.30%)
- the upper limit of the P content is 0.30%, preferably 0.1% or less, and more preferably 0.05% or less.
- a preferred lower limit for P is 0.0001%.
- ⁇ Second invention> ⁇ Amount of precipitated B as borides on the steel material of the second invention>>
- the inventors of the present invention have found that as a means of satisfying all of the cold forgeability, machinability, and resistance to hydrogen embrittlement after cold working in stainless steel materials, the amount of B precipitated as borides in steel materials is controlled. was conceived. With regard to cold forgeability, the formation of borides reduces solute elements (such as N) and softens the steel. In addition, since borides are finely precipitated, they are less likely to initiate cracks, which also improves the cold forgeability. Regarding machinability, the lubricating action of borides prolongs the tool life during cutting.
- the formation of borides softens the material and increases the mobility of dislocations.
- the borides contribute as trap sites for hydrogen, thereby improving the resistance to hydrogen embrittlement.
- the amount of B precipitated as borides in the steel can be evaluated by subjecting the steel to electrolytic extraction residue, extracting the borides, and measuring the amount of B (Bpre) in the borides.
- the aspect ratio means a value calculated as L/W from the length (L) of the sulfide in the rolling direction and the length (W) of the sulfide in the direction perpendicular to the rolling direction.
- the aspect ratio of sulfide in the L cross section of the steel material (the cross section including the center line of the steel material), the surface layer, the central part, and the 1/4 depth position part existing between the surface layer and the central part
- one or more fields of view are measured in a field of view of 200 times, and the average value of the aspect ratio L/W of the sulfides in the same field of view is calculated from an optical microscope.
- % means % by mass.
- B is necessary in order to secure the amount of precipitated B as the boride.
- the B content is more preferably 0.0005% or more. More preferably, it is 0.0020% or more.
- the upper limit is set to 0.05%.
- the B content is more preferably 0.02% or less. It is more preferably 0.015% or less.
- S is an element that forms sulfides in steel and improves machinability, and is contained in an amount of 0.0001% or more.
- the upper limit is made 0.50%, preferably 0.1% or less, more preferably 0.5%. 05% or less.
- S is usually contained in steel as an impurity mixed from steelmaking raw materials.
- the stainless steel of the second invention contains one or more selected from Al: 0.001 to 2.0% and Ca: 0.0001 to 0.05%.
- an Al- or Ca-based oxide is formed, and together with the above-mentioned content of S and the provisions of the production method described later, it becomes the nucleus of sulfide and fine sulfidation.
- the aspect ratio of the sulfide after rolling can be 50 or less. Excessive addition of Al forms coarse AlN and the like, deteriorating cold forgeability, machinability, and resistance to hydrogen embrittlement.
- the upper limit of the Al content is set to 2.0%, preferably 1.0% or less, more preferably 0.5% or less, further preferably 0.05% or less.
- the upper limit of Ca content is set to 0.05%.
- Ca is preferably 0.010% or less, more preferably 0.005% or less. If neither Al nor Ca is contained, or if the lower limit is exceeded, the aspect ratio of the sulfide will be outside the range of the present invention, and the tensile strength, critical compressibility, machinability, relative tensile strength after cold working, and drawing will be poor. becomes.
- C (C: 0.0010 to 0.15%) C is made 0.0010% or more in order to suppress the formation of deformation-induced martensite and improve hydrogen embrittlement resistance. Excessive addition of C degrades cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the C content is set to 0.15%, preferably 0.12% or less, more preferably 0.05% or less, still more preferably 0.02% or less. It is preferable to set the upper limit of C to less than 0.15%.
- Si 0.01 to 2.00%
- Si is added as a deoxidizing element to be 0.01% or more.
- the upper limit of the Si content is set to 2.0%, preferably 1.2% or less, more preferably 0.6% or less, still more preferably 0.5% or less.
- Mn 0.01 to 10.00%
- Mn is made 0.01% or more in order to suppress the formation of deformation-induced martensite and improve hydrogen embrittlement resistance. Excessive addition of Mn deteriorates cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the Mn content is set to 10.0%, preferably 2.5% or less, more preferably 1.5% or less, still more preferably 1.0% or less.
- Ni 8.00-30.00%
- Ni suppresses the formation of deformation-induced martensite and enhances hydrogen embrittlement resistance.
- the Ni content is set to 8.00% or more. It is preferably 10.00% or more, more preferably 13.00% or more, and still more preferably 15.00% or more. If Ni is added excessively, cold forgeability, machinability and resistance to hydrogen embrittlement deteriorate. Therefore, the upper limit of the Ni content is 30.00%, preferably 25.00% or less.
- Cr 9.0 to 21.0% Cr suppresses the formation of deformation-induced martensite and enhances hydrogen embrittlement resistance. Moreover, in order to improve corrosion resistance, the Cr content is set to 9.0% or more. Preferably it is 10.5% or more. Excessive addition of Cr deteriorates cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the Cr content is set to 21.0%, preferably 19.5% or less, more preferably 15.0% or less.
- Mo 0.01 to 3.00%
- Mo suppresses the formation of deformation-induced martensite and enhances hydrogen embrittlement resistance.
- the Mo content is set to 0.01% or more in order to improve cold forgeability. Excessive addition of Mo deteriorates cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the Mo content is 3.0%, preferably 2.8% or less, more preferably 2.5% or less, and even more preferably 1.0% or less.
- Cu 0.01 to 5.00%
- Cu suppresses the formation of deformation-induced martensite and enhances hydrogen embrittlement resistance.
- the Cu content is made 0.01% or more. It is preferably 1.00% or more, more preferably 2.00% or more. Excessive addition of Cu deteriorates cold forgeability, machinability and resistance to hydrogen embrittlement, and causes hot shortness. Therefore, the upper limit of the Cu content is set to 5.00%, preferably 3.50% or less.
- N 0.0010 to 0.10%
- N is made 0.0010% or more in order to suppress the formation of deformation-induced martensite and improve hydrogen embrittlement resistance. Excessive addition of N degrades cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the N content is set to 0.10%, preferably 0.08% or less, more preferably 0.05% or less, still more preferably 0.03% or less.
- the stainless steel of the second invention contains the above components, and the balance is Fe and impurities. Furthermore, it may contain one or more selected from the following components.
- Ti 0 to 2.00%
- Ti may be added for fixing C and N which enhance microstrain.
- the upper limit of the Ti content is set to 2.00%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less.
- a preferable lower limit of Ti is 0.01% or more, more preferably 0.05% or more.
- Nb 0 to 2.00%
- Nb may be added for fixing C and N.
- the upper limit of the Nb content is set to 2.00%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less.
- a preferable lower limit of Nb is 0.01% or more, more preferably 0.05% or more.
- Sn is an effective element for improving corrosion resistance, it may be contained. However, if Sn is contained excessively, the effect is saturated, and cold forgeability, machinability, and resistance to hydrogen embrittlement may deteriorate. Therefore, the upper limit of the content of Sn is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.2% or less. In order to exhibit the above effects, the Sn content is preferably 0.0001% or more, more preferably 0.01% or more. More preferably, it is 0.05% or more.
- V (V: 0-2.0%) V may be added for fixing C and N.
- the upper limit of the V content is 2.0%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less.
- a preferable lower limit of V is 0.001%.
- W is an effective element for improving corrosion resistance, it may be contained. However, if W is contained excessively, the effect is saturated, and cold forgeability, machinability, and resistance to hydrogen embrittlement may deteriorate. Therefore, when W is contained, the upper limit is set to 3.0%. More preferably, it is 2.0% or less, and still more preferably 1.5% or less. In order to exhibit the above effects, it is preferable to set the W amount to 0.05% or more. More preferably, it is 0.10% or more.
- Ga is an effective element for improving corrosion resistance, so it may be contained. However, if Ga is contained excessively, the effect is saturated, and the cold forgeability, machinability, and resistance to hydrogen embrittlement may deteriorate. Therefore, the upper limit when Ga is contained is set to 0.05%. In order to exhibit the above effect, it is preferable to set the amount of Ga to 0.0004% or more.
- Co (Co: 0-2.5%) Co has the effect of improving the corrosion resistance, so it may be contained. However, if Co is contained excessively, the effect is saturated, and cold forgeability, machinability, and resistance to hydrogen embrittlement may deteriorate. Therefore, the upper limit of the content of Co is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.8% or less. In order to exhibit the above effects, the Co content is preferably 0.05% or more, more preferably 0.10% or more.
- Sb Since Sb has an effect of improving corrosion resistance, it may be contained. However, if Sb is contained excessively, the effect is saturated, and cold forgeability, machinability, and resistance to hydrogen embrittlement may deteriorate. Therefore, the upper limit when Sb is contained is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.8% or less. In order to exhibit the above effect, the Sb content is preferably 0.01% or more, more preferably 0.05% or more.
- Ta (Ta: 0-2.5%) Ta may be added for fixing C and N.
- the upper limit of the Ta content is set to 2.5%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less.
- a preferable lower limit of Ta is 0.01%.
- Mg 0-0.012%
- Mg may be contained as necessary for deoxidation.
- the upper limit of the Mg content is 0.012%, preferably 0.010% or less, and more preferably 0.005% or less.
- a preferred lower limit for Mg is 0.0002%.
- Zr 0 to 0.012% Zr may be contained as necessary for deoxidation.
- the upper limit of the Zr content is 0.012%, preferably 0.010% or less, and more preferably 0.005% or less.
- a preferable lower limit of Zr is 0.0002%.
- REM 0-0.05%) REM may optionally be included for deacidification.
- the upper limit of the REM content is 0.05%, preferably 0.010% or less, and more preferably 0.005% or less.
- a preferred lower limit for REM is 0.0002%.
- Pb 0 to 0.30%)
- Pb is an element that enhances machinability and may be contained as necessary.
- the upper limit of the Pb content is set to 0.30%, preferably 0.10% or less, and more preferably 0.05% or less.
- a preferable lower limit of Pb is 0.0001%.
- Se is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of Se deteriorates cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the Se content is 0.80%, preferably 0.1% or less, and more preferably 0.05% or less. A preferred lower limit for Se is 0.0001%.
- Te 0 to 0.30% Te is an element that enhances machinability and may be contained as necessary. On the other hand, if Te is added excessively, cold forgeability, machinability and resistance to hydrogen embrittlement deteriorate. Therefore, the upper limit of the Te content is set to 0.30%, preferably 0.1% or less, and more preferably 0.05% or less. A preferable lower limit of Te is 0.0001%.
- Bi is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of Bi degrades cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the Bi content is 0.50%, preferably 0.1% or less, and more preferably 0.05% or less. A preferable lower limit of Bi is 0.0001%.
- P 0-0.30%)
- P is an element that enhances machinability and may be contained as necessary.
- the upper limit of the P content is 0.30%, preferably 0.1% or less, and more preferably 0.05% or less.
- a preferred lower limit for P is 0.0001%.
- the present inventors came up with the idea of controlling the B grain boundary occupancy of stainless steel, particularly bar steel, as a means of satisfying corrosion resistance, cold forgeability, and non-magnetic properties after cold working.
- the B grain boundary occupation ratio (%) is the ratio (B/A ⁇ 100) occupied by the grain boundaries (B) in which a finite amount of B exists with respect to all the grain boundaries (A).
- passivation is promoted in the Cr-deficient region due to grain boundary Cr-based precipitates, improving corrosion resistance, facilitating plastic deformation at grain boundaries, and improving cold forgeability. It was conceived that the local deformation in the field is suppressed, suppressing the formation of deformation-induced ⁇ '-martensite in the magnetic phase, and maintaining the non-magnetism.
- the evaluation of the B grain boundary occupation rate was measured by EPMA analysis.
- the total length (A) of the grain boundary in an arbitrary field of view is measured.
- a grain boundary having a higher B concentration than the parent phase was defined as a B grain boundary occupancy
- the B grain boundary occupancy length (B) was calculated
- the B grain boundary occupancy was calculated from the above formula.
- the average B grain boundary occupation rate is more preferably 5% or more, more preferably 15% or more, and even more preferably 20% or more.
- % means % by mass.
- C (C: 0.0010 to 0.15%) C is made 0.0010% or more in order to suppress the formation of deformation-induced martensite and improve non-magnetic properties. Excessive addition of C lowers the B grain boundary occupancy and deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the C content is set to 0.15%, preferably 0.12% or less, more preferably 0.05% or less, still more preferably 0.02% or less. It is preferable to set the upper limit of C to less than 0.15%.
- Si 0.01 to 2.00%
- Si is added as a deoxidizing element to be 0.01% or more. Excessive addition of Si lowers the B grain boundary occupancy and deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Si content is set to 2.0%, preferably 1.2% or less, more preferably 0.6% or less, still more preferably 0.5% or less.
- Mn 0.01 to 10.00%
- Mn is made 0.01% or more in order to suppress the formation of deformation-induced martensite and improve non-magnetic properties. Excessive addition of Mn lowers the B grain boundary occupancy and deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Mn content is set to 10.0%, preferably 2.5% or less, more preferably 1.5% or less, still more preferably 1.0% or less.
- Ni 8.00-30.00%
- Ni suppresses the formation of deformation-induced martensite and enhances non-magnetic properties.
- the Ni content is set to 8.00% or more. It is preferably 10.00% or more, more preferably 13.00% or more, and still more preferably 15.00% or more. Excessive addition of Ni lowers the B grain boundary occupancy and deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Ni content is 30.00%, preferably 25.00% or less.
- Cr 9.0 to 21.0% Cr suppresses the formation of deformation-induced martensite and enhances non-magnetic properties. Moreover, in order to improve corrosion resistance, the Cr content is set to 9.0% or more. Preferably it is 10.5% or more. Excessive addition of Cr lowers the B grain boundary occupancy and deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Cr content is set to 21.0%, preferably 19.5% or less, more preferably 15.0% or less.
- Mo 0.01 to 3.00%
- Mo suppresses the formation of deformation-induced martensite and enhances non-magnetic properties.
- the Mo content is set to 0.01% or more in order to improve cold forgeability. Excessive addition of Mo lowers the B grain boundary occupancy and deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Mo content is 3.0%, preferably 2.8% or less, more preferably 2.5% or less, and even more preferably 1.0% or less.
- Cu 0.01 to 5.00%
- Cu suppresses the formation of deformation-induced martensite and enhances non-magnetic properties.
- the Cu content is made 0.01% or more. It is preferably 1.00% or more, more preferably 2.00% or more. Excessive addition of Cu lowers the B grain boundary occupancy, degrades corrosion resistance, cold forgeability, and non-magnetic properties, and causes hot shortness. Therefore, the upper limit of the Cu content is set to 5.00%, preferably 3.50% or less.
- N 0.0010 to 0.10%
- N is made 0.0010% or more in order to suppress the formation of deformation-induced martensite and improve non-magnetic properties. Excessive addition of N lowers the B grain boundary occupancy and deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the N content is set to 0.10%, preferably 0.08% or less, more preferably 0.05% or less, still more preferably 0.03% or less.
- B is the main element that increases the B grain boundary occupation ratio, and is made 0.0001% or more in order to improve corrosion resistance, cold forgeability, and non-magnetic properties. Preferably it is 0.0005% or more. Excessive addition of B causes the formation of coarse B-based precipitates and conversely deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the B content is set to 0.05%, preferably 0.02% or less, and more preferably 0.015% or less.
- the stainless steel of the third invention contains the above components, and the balance is Fe and impurities. Furthermore, it may contain one or more selected from the following components.
- Al 0-2.0%
- Al may be added for fixing N which lowers the B grain boundary occupancy.
- the upper limit of the Al content is set to 2.0%, preferably 1.0% or less, more preferably 0.5% or less, further preferably 0.05% or less.
- a preferable lower limit of Al is 0.001% or more.
- Ti 0 to 2.00%
- Ti may be added for fixing C and N which lowers the B grain boundary occupancy.
- the upper limit of the Ti content is set to 2.00%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less.
- a preferable lower limit of Ti is 0.01% or more, more preferably 0.05% or more.
- Nb 0 to 2.00%
- Nb may be added for fixing C and N which lowers the B grain boundary occupancy.
- the upper limit of the Nb content is set to 2.00%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less.
- a preferable lower limit of Nb is 0.01% or more, more preferably 0.05% or more.
- Sn is an effective element for improving corrosion resistance, it may be contained. However, excessive Sn content saturates the effect, and conversely, the corrosion resistance, cold forgeability, and non-magnetic properties may deteriorate. Therefore, the upper limit of the content of Sn is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.2% or less. In order to exhibit the above effects, the Sn content is preferably 0.0001% or more, more preferably 0.01% or more. More preferably, it is 0.05% or more.
- V (V: 0-2.0%) V may be added for fixing C and N which lower the B grain boundary occupation rate.
- the upper limit of the V content is set to 2.0%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less.
- a preferable lower limit of V is 0.001%.
- W is an effective element for improving corrosion resistance, it may be contained. However, if W is contained excessively, the effect is saturated, and the corrosion resistance, cold forgeability, and non-magnetic properties may deteriorate. Therefore, when W is contained, the upper limit is set to 3.0%. More preferably, it is 2.0% or less, and still more preferably 1.5% or less. In order to exhibit the above effects, it is preferable to set the W amount to 0.05% or more. More preferably, it is 0.10% or more.
- Ga is an effective element for improving corrosion resistance, so it may be contained. However, if Ga is contained excessively, the effect is saturated, and the corrosion resistance, cold forgeability, and non-magnetic properties may deteriorate. Therefore, the upper limit when Ga is contained is set to 0.05%. In order to exhibit the above effect, it is preferable to set the amount of Ga to 0.0004% or more.
- Co (Co: 0-2.5%) Co has the effect of improving the corrosion resistance, so it may be contained. However, if Co is contained excessively, the effect is saturated, and the corrosion resistance, cold forgeability, and non-magnetic properties may deteriorate. Therefore, the upper limit of the content of Co is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.8% or less. In order to exhibit the above effects, the Co content is preferably 0.05% or more, more preferably 0.10% or more.
- Sb Since Sb has an effect of improving corrosion resistance, it may be contained. However, if Sb is contained excessively, the effect is saturated, and the corrosion resistance, cold forgeability, and non-magnetic properties may deteriorate. Therefore, the upper limit when Sb is contained is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.8% or less. In order to exhibit the above effect, the Sb content is preferably 0.01% or more, more preferably 0.05% or more.
- Ta (Ta: 0-2.5%) Ta may be added for fixing C and N which lowers the B grain boundary occupancy.
- the upper limit of the Ta content is set to 2.5%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less.
- a preferable lower limit of Ta is 0.01%.
- Ca 0-0.05% Ca may be contained as needed for deoxidation.
- the upper limit of the Ca content is 0.05%, preferably 0.010% or less, and more preferably 0.005% or less.
- a preferable lower limit of Ca is 0.0002%.
- Mg 0-0.012%
- Mg may be contained as necessary for deoxidation.
- the upper limit of the Mg content is 0.012%, preferably 0.010% or less, and more preferably 0.005% or less.
- a preferred lower limit for Mg is 0.0002%.
- Zr 0 to 0.012% Zr may be contained as necessary for deoxidation.
- the upper limit of the Zr content is 0.012%, preferably 0.010% or less, and more preferably 0.005% or less.
- a preferable lower limit of Zr is 0.0002%.
- REM 0-0.05%) REM may optionally be included for deacidification.
- the upper limit of the REM content is 0.05%, preferably 0.010% or less, and more preferably 0.005% or less.
- a preferred lower limit for REM is 0.0002%.
- Pb 0 to 0.30%)
- Pb is an element that enhances machinability and may be contained as necessary.
- the upper limit of the Pb content is set to 0.30%, preferably 0.10% or less, and more preferably 0.05% or less.
- a preferable lower limit of Pb is 0.0001%.
- Se is an element that enhances machinability and may be contained as necessary.
- the upper limit of the Se content is 0.80%, preferably 0.1% or less, and more preferably 0.05% or less.
- a preferred lower limit for Se is 0.0001%.
- Te 0 to 0.30% Te is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of Te deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Te content is set to 0.30%, preferably 0.1% or less, and more preferably 0.05% or less. A preferable lower limit of Te is 0.0001%.
- Bi (Bi: 0 to 0.50%) Bi is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of Bi degrades corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Bi content is 0.50%, preferably 0.1% or less, and more preferably 0.05% or less. A preferable lower limit of Bi is 0.0001%.
- S is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of S degrades corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the S content is 0.50%, preferably 0.1% or less, and more preferably 0.05% or less. A preferred lower limit for S is 0.0001%. Incidentally, S is usually contained in steel as an impurity mixed from steelmaking raw materials.
- P 0-0.30%)
- P is an element that enhances machinability and may be contained as necessary.
- the upper limit of the P content is 0.30%, preferably 0.1% or less, and more preferably 0.05% or less.
- a preferred lower limit for P is 0.0001%.
- the A value represented by the above formula (a) is -100 or less.
- the formation of strain-induced martensite is suppressed, and work hardening is reduced, which softens the steel and suppresses the occurrence of cracks, thereby improving the cold forgeability.
- the first invention can obtain the effects of reducing microstrain and improving hydrogen embrittlement resistance.
- softening reduces cutting resistance and improves machinability.
- the resistance to hydrogen embrittlement since deformation-induced martensite at the starting point of fracture is reduced, the resistance to hydrogen embrittlement is improved.
- the third invention can obtain the effect of improving the non-magnetic properties.
- the stainless steel of the present invention particularly the bar steel, has the above-mentioned chemical composition, and the first invention has a micro strain of D/4 from the surface layer of the steel material.
- the third invention can realize the following qualities as a result of having the B grain boundary occupancy of the steel material.
- ⁇ Common to the first to third inventions> It can be stainless steel with a tensile strength of 700 MPa or less.
- ⁇ Common to the first to third inventions> A stainless steel having a critical compressibility of 60% or more can be used.
- the above-described method is used for all of the shape of the test piece, the contents of the compression test, and the definition of the critical compressibility.
- ⁇ Common to the first and second inventions> A stainless steel having a relative tensile strength of 80% or more in high-pressure hydrogen after cold working can be used.
- a stainless steel having a relative reduction in area of 50% or more in high-pressure hydrogen after cold working can be used.
- the cold working rate (area reduction rate) of the cold working is 80%.
- a tensile test is performed at a strain rate of 1 ⁇ 10 ⁇ 5 /s in a hydrogen atmosphere at ⁇ 40° C. and 70 MPa.
- the % display of the value obtained by dividing the tensile strength and reduction of area in the hydrogen atmosphere obtained in this way by the tensile strength and reduction of area evaluated at the same strain rate in the air atmosphere is the relative tensile strength in high pressure hydrogen, and the value in high pressure hydrogen. is the relative aperture of
- Stainless steel having a drilling life index VL-1000 of 1 m/min or more can be used.
- Stainless steel having a pitting potential of 0.05 V or higher can be used.
- Stainless steel having a relative magnetic permeability of 1.10 or less after cold working can be used.
- the cold working rate (area reduction rate) of the cold working is 80%.
- a set temperature is provided in the induction heating device that heats the rolled steel material. After specifying this set temperature to be 1000 to 1400° C., the time for passing the material to be rolled through the induction heating device is set within the range of 10 to 300 seconds. It is more preferable that the set temperature is in the range of 1000 to 1300° C. and the passing time is in the range of 10 to 200 seconds.
- the set temperature is more preferably 1050 to 1300°C, more preferably 1100 to 1300°C.
- the passage time is more preferably 20 to 200 seconds, more preferably 20 to 150 seconds.
- the set temperature of the induction heating device is less than 1000 ° C.
- the strain on the steel material accumulates during hot rolling, and in addition to the large micro strain of the steel material surface layer to D / 4, coarse undissolved precipitates are formed. It remains and deteriorates cold forgeability and hydrogen embrittlement resistance.
- the temperature exceeds 1400°C the undissolved precipitates are dissolved, and the increase in the dissolved elements increases the micro strain of the steel material.
- high-temperature heating causes a reduction in yield due to oxidation of the steel material, or creep deformation of the steel material during rolling, resulting in poor rolling.
- the steel material temperature does not uniformly reach the set temperature in the steel material surface layer to D/4, and the strain in the steel material accumulates during hot rolling.
- coarse undissolved precipitates remain, resulting in deterioration of cold forgeability and hydrogen embrittlement resistance.
- the induction heating device passing time exceeds 300 seconds, the steel material temperature in the steel material surface layer to D/4 is locally overheated non-uniformly with respect to the set temperature, and the undissolved precipitates dissolve into solid solution. An increase in the number of elements increases the micro strain of the steel.
- the set temperature of the induction heating device specifically means the output temperature in the induction heating device through which the steel material passes.
- tilt rolling After heating the rolled material in this way, tilt rolling is performed.
- tilt rolling for example, as disclosed in Patent Document 4, three work rolls are arranged on roll axes that are tilted in the same direction around the material to be rolled, and each work roll rotates the material to be rolled. It revolves around itself while rotating. As a result, the material to be rolled is spirally rolled while moving forward.
- the temperature distribution is such that the steel material temperature from the steel material surface layer to the D/4 position uniformly coincides with the set temperature.
- the micro strain of the steel material surface layer to D/4 can be reduced to 0.0040 or less by the mechanism of reducing the strain accumulation by recrystallization in the steel material surface layer to D/4.
- the above process eliminates coarse undissolved precipitates and refines the precipitates, which also contributes to the enhancement of cold forgeability and hydrogen embrittlement resistance.
- the shape of the steel material may be adjusted by peeling or drawing of the steel material.
- hot working is performed using tilt rolling as described above.
- hot working is not limited to tilt rolling, and any method that follows a similar heat working history may be used.
- blooming rolling breakdown
- ⁇ Second invention> In producing the stainless steel of the second invention, particularly the bar steel, it is preferable to employ tilt rolling as the hot working method and use induction heating to heat the raw material before tilt rolling.
- a set temperature is provided in an induction heating device that heats a rolled steel material. After specifying this set temperature to be 1000 to 1400° C., the speed at which the material to be rolled passes through the induction heating device is set within the range of 0.003 to 4.0 m/s. It is more preferable that the set temperature is in the range of 1000 to 1300° C. and the feed speed is in the range of 0.005 to 2.0 m/s.
- the set temperature is more preferably 1050 to 1300°C, more preferably 1100 to 1300°C.
- the threading speed is more preferably 0.01 to 2.0 m/s, more preferably 0.1 to 1.0 m/s.
- the set temperature of the induction heating device and the feeding speed By setting the set temperature of the induction heating device and the feeding speed within the above ranges, coupled with containing B in the steel, it is possible to make the amount of precipitated B as borides in the steel 0.0001% or more. can.
- the aspect ratio of the sulfides is reduced to 50 or less, coupled with the inclusion of S in the steel and the inclusion of one or more types of Al and Ca. can be
- the set temperature of the induction heating device is less than 1000°C, the amount of precipitated B decreases, the aspect ratio of sulfides increases, and coarse undissolved precipitates remain, resulting in poor cold forgeability and machinability. Hydrogen embrittlement resistance deteriorates. If the temperature exceeds 1400° C., cold forgeability, machinability, and resistance to hydrogen embrittlement deteriorate due to a decrease in the amount of precipitated B and an increase in aspect ratio due to elongation of sulfides. In addition, high-temperature heating causes a decrease in yield due to oxidation of the steel material, or creep deformation of the steel material during rolling, resulting in poor rolling.
- the speed of passing through the induction heating device of the rolled material is less than 0.003 m / s, the amount of precipitated B decreases and the sulfide is elongated, which causes the sulfide to have a high aspect ratio and cold forgeability. , the machinability and hydrogen embrittlement resistance deteriorate. If the induction heating device passing speed exceeds 4.0 m / s, the amount of precipitated B decreases, the aspect ratio of sulfide increases, and coarse undissolved precipitates remain, so cold forgeability and machinability properties and hydrogen embrittlement resistance deteriorate.
- the set temperature of the induction heating device specifically means the output temperature in the induction heating device through which the steel material passes.
- tilt rolling After heating the rolled material in this way, tilt rolling is performed.
- tilt rolling for example, as disclosed in Patent Document 4, three work rolls are arranged on roll axes that are tilted in the same direction around the material to be rolled, and each work roll rotates the material to be rolled. It revolves around itself while rotating. As a result, the material to be rolled is spirally rolled while moving forward.
- the temperature distribution is such that the steel material temperature from the steel material surface layer to the D/4 position uniformly coincides with the set temperature. This reduces the amount of precipitated B and suppresses elongation of sulfides, thereby improving cold forgeability, machinability, and resistance to hydrogen embrittlement.
- the above process eliminates coarse undissolved precipitates and refines the precipitates, which also contributes to the enhancement of cold forgeability, machinability, and hydrogen embrittlement resistance.
- the shape of the steel material may be adjusted by peeling or drawing of the steel material.
- hot working is performed using tilt rolling as described above.
- hot working is not limited to tilt rolling, and any method that follows a similar heat working history may be used.
- blooming rolling breakdown
- ⁇ Third invention> In the production of the stainless steel of the third invention, particularly the steel bar, it is preferable to subject the raw material to heating, hot rolling (tilt rolling, BD, bar rolling, etc.), heat treatment, pickling, etc. In particular, rough rolling is preferred. It is preferable to control the entry-side temperature and the average time between rough rolling stands and perform the passivation treatment.
- the average time between the rough rolling stands of the rolled material is set within the range of 0.01 to 30 seconds. More preferably, the rough rolling entrance temperature is in the range of 1000 to 1300° C., and the average time between rough rolling stands is in the range of 0.03 to 10 seconds.
- the entry temperature for rough rolling is more preferably 1050 to 1300°C, more preferably 1100 to 1300°C.
- the average time between rough rolling stands is more preferably 0.05 to 5 seconds, more preferably 0.1 to 2 seconds.
- the rough rolling inlet temperature is less than 1000°C
- the strain on the steel material accumulates during hot rolling, B-based precipitates are formed in the grains, and the B grain boundary occupancy decreases, so corrosion resistance and cold rolling are improved. Forgeability and non-magnetic properties deteriorate.
- the entry temperature of rough rolling exceeds 1400° C.
- B present at grain boundaries diffuses into grains and forms intragranular B precipitates during rolling, reducing the B grain boundary occupancy.
- high-temperature heating causes a decrease in yield due to oxidation of the steel material, or creep deformation of the steel material during rolling, resulting in poor rolling.
- the average time between rough rolling stands is less than 0.01 seconds, the strain on the steel material accumulates during hot rolling, B-based precipitates are formed in grains, and the B grain boundary occupancy decreases. Therefore, corrosion resistance, cold forgeability, and non-magnetic properties deteriorate.
- the average time between rough rolling stands exceeds 30 seconds, B present at grain boundaries diffuses into grains and forms intragranular B precipitates during rolling, reducing the B grain boundary occupancy.
- high-temperature heating causes a decrease in yield due to oxidation of the steel material, or creep deformation of the steel material during rolling, resulting in poor rolling.
- the passivation treatment is a treatment of immersing the material in a solution such as nitric acid, and may be a single treatment or an acid treatment. This is effective in the treatment of stainless steel (especially bar steel), and also in the treatment of products obtained by secondary processing (drawing, forging, cutting, etc.) of the bar steel.
- Example 1-1 When the steel was smelted, assuming AOD smelting, which is a low-cost stainless steel smelting process, the steel was melted in a 100 kg vacuum melting furnace and cast into a slab with a diameter of 180 mm. Thereafter, stainless steel rods having a diameter of 20.0 mm and chemical compositions shown in Tables 1 to 3 were manufactured under the following manufacturing conditions. In Tables 1 to 6, items outside the scope of the present invention and items outside the preferred manufacturing conditions of the present invention are underlined.
- the cast slab is heated in a heating furnace at 1130 ° C., then induction heating is used to heat the rolling material before tilt rolling, the set temperature of the induction heating device is 1210 ° C., and the induction heating device passing time is 110 s.
- tilt rolling, in-line heat treatment, bar and wire rolling, offline heat treatment at 1100° C. for 30 minutes (water cooling) and pickling a bar steel with a diameter of 20.0 mm was produced.
- the methods described above were used for measuring the micro strain of bar steel, measuring the critical compressibility, and evaluating the relative tensile strength and relative reduction of area after cold working.
- AA is 0.0005 or less, A is more than 0.0005 and 0.0020 or less, B is more than 0.0020 and 0.0040 or less, and C is more than 0.0040.
- AA is 500 MPa or less, A is more than 500 MPa and 620 MPa or less, B is more than 620 MPa and 700 MPa or less, and C is more than 700 MPa.
- AA is 80% or more, A is 70% or more and less than 80%, B is 60% or more and less than 70%, and C is less than 60%.
- AA indicates 95% or more
- A indicates 90% or more and less than 95%
- B indicates 80% or more and less than 90%
- C indicates less than 80%.
- AA indicates 70% or more
- A indicates 60% or more and less than 70%
- B indicates 50% or more and less than 60%
- C indicates less than 50%. Evaluation results are shown in Tables 4 and 5.
- the steel bars have the chemical composition and microstrain specified in the first invention, and all of the tensile strength, critical compressibility, relative tensile strength and reduction of area after cold working. , AA, A, or B, and was good.
- Comparative Example No. For 40 to 54, one of the components is outside the first invention range, and the microstrain is outside the first invention range, resulting in tensile strength, critical compressibility, relative tensile strength after cold working, and Aperture was C in both cases.
- Example 1-2 Using steel type P in Table 1 as the chemical composition, induction heating conditions before tilt rolling were set to the conditions shown in Table 6, and other manufacturing conditions were the same as in Example 1-1 above, to produce bar steels.
- invention example No. 55 to 64 have the manufacturing method under the preferred conditions of the first invention, have the composition and microstrain specified in the first invention, and have tensile strength, critical compressibility, and relative tensile strength after cold working. All of AA, A, and B were good in both of AA, A, and B.
- Comparative Example No. For 65 to 70, one of the manufacturing conditions is outside the preferred range of the first invention, and the microstrain is outside the range of the first invention, resulting in tensile strength, critical compressibility, relative after cold working Both tensile strength and area of drawing were C.
- the cast slab is heated at 1130 ° C. in a heating furnace, and then induction heating is used to heat the rolling material before tilt rolling. After heating at 3 m/s, tilt rolling, in-line heat treatment, bar and wire rolling, offline heat treatment at 1100°C for 30 minutes (water cooling), pickling, and bar steel with a diameter of 20.0 mm. was made.
- AA 0.0005% or more and less than 0.0010%
- A 0.0001% or more and less than 0.0005%
- B 0.0001%. % less than C.
- CC coarse borides were formed due to excessive B content, it was rated as CC.
- AA is 5 or less
- A is 5 to 30, B is 30 to 50
- C is more than 50.
- tensile strength AA is 500 MPa or less
- A is more than 500 MPa and 620 MPa or less
- B is more than 620 MPa and 700 MPa or less
- C is more than 700 MPa.
- AA is 80% or more, A is 70% or more and less than 80%, B is 60% or more and less than 70%, and C is less than 60%.
- 20 m/min or more is AA
- 10 m/min or more and less than 20 m/min is A
- 1 m/min or more and less than 10 m/min is B
- less than 1 m/min is C.
- AA indicates 95% or more
- A indicates 90% or more and less than 95%
- B indicates 80% or more and less than 90%
- C indicates less than 80%.
- AA indicates 70% or more, A indicates 60% or more and less than 70%
- B indicates 50% or more and less than 60%
- C indicates less than 50%. Evaluation results are shown in Tables 10 and 11.
- Inventive Example No. 1 to 39 have the chemical composition, the amount of precipitated B as borides, and the aspect ratio of sulfides specified in the second invention, and have tensile strength, critical compressibility, and VL-1000. , the relative tensile strength and reduction of area after cold working were either AA, A, or B, and were good.
- Comparative Example No. For 40 to 50 and 52 to 56, one of the components is outside the second invention range, the amount of precipitated B as borides and the aspect ratio of sulfides are outside the second invention range, and as a result, the tensile strength It was C in all of the strength, critical compressibility, VL-1000, relative tensile strength and reduction of area after cold working.
- comparative example No. In 51 coarse borides are formed due to excessive B content, and the coarse borides become the starting point of fracture, and as a result, tensile strength, critical compressibility, VL-1000, relative after cold working Both tensile strength and area of drawing were C.
- Example 2-2 Using steel type P in Table 7 as the chemical composition, the induction heating conditions before tilt rolling were set to the conditions shown in Table 12, and other manufacturing conditions were the same as in Example 2-1 above to produce a bar steel.
- invention example No. 55 to 64 have the manufacturing method under the suitable conditions of the second invention, have the chemical composition specified in the second invention, the amount of precipitated B as borides, and the aspect ratio of sulfides, and have tensile strength and limit All of compressibility, relative tensile strength and reduction of area after cold working were AA, A, or B, and were good.
- Comparative Example No. For 65 to 70, one of the production conditions is out of the preferred range of the second invention, the amount of precipitated B as borides and the aspect ratio of sulfides are out of the scope of the second invention, and as a result, the tensile strength , critical compressibility, VL-1000, relative tensile strength and reduction of area after cold working were all C.
- Example 3-1 When the steel was smelted, assuming AOD smelting, which is a low-cost stainless steel smelting process, the steel was melted in a 100 kg vacuum melting furnace and cast into a slab with a diameter of 180 mm. Thereafter, stainless steel rods having a diameter of 20.0 mm and chemical compositions shown in Tables 13 and 14 were manufactured under the following manufacturing conditions. In Tables 13 to 17, items outside the scope of the third invention and items outside the preferred manufacturing conditions of the third invention are underlined.
- the cast slab is subjected to heating, tilt rolling, and in-line heat treatment, the temperature at the entry side of rough rolling is adjusted to 1130 ° C., rough rolling is performed, and the average time between stands for rough rolling is 1.8 s.
- heat treatment at 1100° C. for 30 minutes was performed as a solution treatment, followed by pickling to produce a steel bar with a diameter of 20.0 mm. From this bar steel material ( ⁇ 20 mm), an L cross section of ⁇ 20 ⁇ 30 mm was taken for corrosion resistance evaluation, and a test piece of ⁇ 8 ⁇ 12 mm was taken for the end face restraint compression test from the D (diameter) / 4 part position of the steel material C cross section 12 mm in the L direction. Taken long.
- the L cross section of the solution-treated bar ( ⁇ 20 mm) was used, and the method described above was used.
- a test piece with a diameter of ⁇ 20 ⁇ 30 mm was used, and the method as described above was used.
- Tensile strength was evaluated by an ordinary method using solution-treated bar steel ( ⁇ 20 mm).
- a test piece of ⁇ 8 ⁇ 12 mm was used for the limit compressibility measurement method, and the method as described above was used.
- the above-mentioned method is used using a bar steel material of ⁇ 9 mm obtained by cold drawing the bar steel material subjected to the above solution heat treatment at a cross-sectional reduction rate of 80%. board.
- the B grain boundary occupancy rate was AA when 15% or more, A when 5% or more and less than 15%, B when 1% or more and less than 5%, and C when less than 1%.
- Corrosion resistance was rated AA when 0.20V or more, A when 0.10V or more and less than 0.20V, B when 0.05V or more and less than 0.10V, and C when less than 0.05V.
- AA is 500 MPa or less
- A is more than 500 MPa and 620 MPa or less
- B is more than 620 MPa and 700 MPa or less
- C is more than 700 MPa.
- AA is 80% or more, A is 70% or more and less than 80%, B is 60% or more and less than 70%, and C is less than 60%.
- AA indicates 1.03 or less, A indicates more than 1.03 and 1.05 or less, B indicates more than 1.05 and 1.10 or less, and C indicates more than 1.10. Evaluation results are shown in Tables 15 and 16.
- Inventive Example No. 1 to 39 have the chemical composition and B grain boundary occupancy specified in the third invention, corrosion resistance, tensile strength, critical compressibility, relative magnetic permeability after cold working, were either AA, A, or B, and were good.
- Comparative Example No. for 40 to 54, one of the components is outside the third invention range, and the B grain boundary occupation ratio is outside the third invention range, resulting in corrosion resistance, tensile strength, critical compressibility, and after cold working Both of the relative magnetic permeability of
- Example 3-2 Using steel type P in Table 13 as the chemical composition, the temperature at the entry side of rough rolling, the average time between rough rolling stands, and the presence or absence of passivation treatment of test pieces during corrosion resistance evaluation (if not, as polished) are changed. 16, and the other manufacturing conditions were the same as in Example 3-1, steel rods were manufactured and test pieces were prepared.
- invention example No. 55 to 64 have the manufacturing method under the preferred conditions of the third invention, have the chemical composition and the B grain boundary occupation ratio specified in the third invention, and have corrosion resistance, tensile strength, critical compressibility, and cold working. All of the subsequent relative magnetic permeability were either AA, A, or B, and were good.
- Comparative Example No. For 65 to 68 and 70, one of the manufacturing conditions is out of the preferred range of the third invention, and the B grain boundary occupation rate is out of the range of the third invention, resulting in corrosion resistance, tensile strength, and critical compressibility. , the relative magnetic permeability after cold working, were both C. Comparative example no. For No. 69, passivation treatment was not performed, passivation in the Cr-deficient region was not promoted, and the B grain boundary occupation ratio was outside the scope of the third invention, resulting in poor corrosion resistance, tensile strength, Both the critical compressibility and the relative magnetic permeability after cold working were C.
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Abstract
Description
本発明は、ステンレス鋼であって、特に、冷間鍛造性と冷間加工後の耐水素脆化特性の両方を満足することのできるステンレス鋼に関するものである。本発明はまた、ステンレス鋼であって、特に、冷間鍛造性、切削性と冷間加工後の耐水素脆化特性のすべてを満足することのできるステンレス鋼に関するものである。本発明はさらに、ステンレス鋼であって、特に、耐食性と冷間鍛造性に優れる非磁性ステンレス鋼に関するものである。 The present invention relates to stainless steel, and particularly to stainless steel that can satisfy both cold forgeability and resistance to hydrogen embrittlement after cold working. The present invention also relates to stainless steel, and more particularly to stainless steel that can satisfy all of cold forgeability, machinability, and resistance to hydrogen embrittlement after cold working. The present invention further relates to stainless steel, and more particularly to non-magnetic stainless steel that is excellent in corrosion resistance and cold forgeability.
燃料電池自動車、あるいは水素燃料を取り扱う水素ステーションには、高圧ガス状態の水素に接触する金属部品が多数用いられている。高圧水素ガスに接する金属部品は、金属中に水素が侵入して水素脆化を起こしやすい。そのため、高圧水素環境において、機械的強度や耐食性を具備するとともに、耐水素脆化特性を備えることが求められている。 Fuel cell vehicles and hydrogen stations that handle hydrogen fuel use many metal parts that come into contact with hydrogen in a high-pressure gas state. Metal parts that come into contact with high-pressure hydrogen gas are prone to hydrogen embrittlement due to penetration of hydrogen into the metal. Therefore, in a high-pressure hydrogen environment, it is required to have mechanical strength and corrosion resistance as well as hydrogen embrittlement resistance.
従来、高圧水素ガスに接触する部位に用いられるステンレス鋼としては、SUS316、SUS316L等のオーステナイト系ステンレス鋼が一般的である。SUS316、SUS316LはMoを含有している。これに対して、特許文献1では、Moを含有しない成分系において、機械的強度及び耐食性に優れ、-40℃の低温においても水素脆化感受性が低く、かつ安価な高圧水素用オーステナイト系ステンレス鋼が開示されている。実施例では、冷間加工率0~25%で冷間引抜加工を行った試験片について、SSRT(Slow Strain Rate Test)による水素脆化感受性評価を行っている。 Conventionally, austenitic stainless steels such as SUS316 and SUS316L are generally used as stainless steels used for parts that come into contact with high-pressure hydrogen gas. SUS316 and SUS316L contain Mo. On the other hand, Patent Document 1 discloses austenitic stainless steel for high-pressure hydrogen that is excellent in mechanical strength and corrosion resistance, has low hydrogen embrittlement susceptibility even at a low temperature of -40 ° C., and is inexpensive in a composition system that does not contain Mo. is disclosed. In the examples, hydrogen embrittlement susceptibility is evaluated by SSRT (Slow Strain Rate Test) for test pieces that have been cold drawn at a cold working rate of 0 to 25%.
特許文献2には、所定の成分を有するオーステナイト系ステンレス鋼で構成され、所定の冷間加工がなされ、その加工後の格子結晶構造が面心立方晶(fcc)を有することを特徴とする耐水素性ばね用ステンレス鋼線が開示されている。実施例では、固溶加熱処理後に最終加工率が0~75%の冷間伸線を行い、試験片に水素チャージをした上で曲げ応力と引張応力の評価を行っている。 Patent Document 2 discloses a water-resistant steel made of austenitic stainless steel having a predetermined composition, subjected to a predetermined cold working, and having a face-centered cubic (fcc) lattice crystal structure after the working. A stainless steel wire for elemental springs is disclosed. In the examples, after the solid-solution heat treatment, cold wire drawing was performed with a final working ratio of 0 to 75%, and the test pieces were charged with hydrogen and then evaluated for bending stress and tensile stress.
非特許文献1には、オーステナイトステンレス鋼のオーステナイト安定度の評価指標として、Md30が提示されている。Md30とは、オーステナイト単相の試料に0.30の引張真ひずみを与えたときに組織が50%マルテンサイト相に変態する温度(℃)である。この値が高温であるほど材料が不安定であることを示す。非特許文献1では、成分組成の関数としてMd30の式を提示している。 Non-Patent Document 1 presents Md30 as an evaluation index for the austenite stability of austenitic stainless steel. Md30 is the temperature (° C.) at which the structure transforms into 50% martensite phase when a tensile true strain of 0.30 is applied to an austenite single phase sample. The higher the value, the more unstable the material. Non-Patent Document 1 presents the formula for Md30 as a function of component composition.
特許文献3には、C:0.15~0.80%、Ni:8.0~20.0%、Cr:8.0~18.0%、Mo:0.05~0.50%、V:0.50~3.00%、Al:0.001~1.000%を含む所定の成分を有する鋼であって、非特許文献1に記載の上記Md30式を変形した(3)式の値を-100以下とし、50nm以下のV(C、N)析出物が、3.5×10-2μm2中に50個以上、分散して存在することを特徴とする安価で優れた耐水素脆性、機械的性質および耐食性を兼備した高硬度非磁性鋼が開示されている。 In Patent Document 3, C: 0.15 to 0.80%, Ni: 8.0 to 20.0%, Cr: 8.0 to 18.0%, Mo: 0.05 to 0.50%, A steel having a predetermined composition containing V: 0.50 to 3.00% and Al: 0.001 to 1.000%, and is a modified formula (3) of the Md30 formula described in Non-Patent Document 1 is -100 or less, and 50 or more V (C, N) precipitates of 50 nm or less are present dispersedly in 3.5 × 10 -2 μm 2 . A high hardness non-magnetic steel is disclosed that combines hydrogen embrittlement resistance, mechanical properties and corrosion resistance.
特許文献4には、傾斜圧延が開示されている。傾斜圧延は、3個のワークロールを被圧延材を中心にして同方向に捩って傾斜したロール軸に配置している。各ワークロールが被圧延材の周囲を自転しながら公転する。これにより、被圧延材は前進しながらスパイラル状に圧延される。 Patent Document 4 discloses tilt rolling. In the tilt rolling, three work rolls are twisted in the same direction around the material to be rolled and arranged on the roll axes tilted. Each work roll revolves around the material to be rolled while rotating. As a result, the material to be rolled is spirally rolled while moving forward.
従来、非磁性部位に用いられるステンレス鋼としては、SUS316、SUS316L等のオーステナイト系ステンレス鋼が一般的である。これに対して、特許文献3、5では、C:0.15~0.80%、Ni:8.0~20.0%、Cr:8.0~18.0%、Mo:0.05~0.50%、V:0.50~3.00%、Al:0.001~1.000%を含む所定の成分を有する鋼であって、非特許文献1に記載の上記Md30式を変形した(3)式の値を-100以下とし、50nm以下のV(C、N)析出物が、3.5×10-2μm2中に50個以上、分散して存在することを特徴とする安価で優れた耐水素脆性、機械的性質および耐食性を兼備した高硬度非磁性鋼が開示されている。 Conventionally, austenitic stainless steels such as SUS316 and SUS316L are generally used as stainless steels used for non-magnetic parts. On the other hand, in Patent Documents 3 and 5, C: 0.15 to 0.80%, Ni: 8.0 to 20.0%, Cr: 8.0 to 18.0%, Mo: 0.05 0.50%, V: 0.50 to 3.00%, Al: 0.001 to 1.000%. The value of the modified formula (3) is set to −100 or less, and 50 or more V(C, N) precipitates of 50 nm or less are dispersed in 3.5×10 −2 μm 2 . A high-hardness non-magnetic steel that is inexpensive and has excellent hydrogen embrittlement resistance, mechanical properties and corrosion resistance is disclosed.
SUS316、SUS316L、あるいは特許文献1~3に記載のオーステナイト系ステンレス鋼を用いることにより、耐水素脆化特性に優れるとともに、機械的強度及び耐食性に優れる鋼が実現している。これらの鋼は、熱間加工後、あるいは冷間加工を行いさらに固溶熱処理を行った鋼については、いずれも優れた耐水素脆化特性を有している。冷間加工後においても、特許文献1では冷間加工率25%以下、特許文献2では最終加工率75%以下の冷間加工を施した鋼について、優れた耐水素脆化特性を有することが示されている。 By using SUS316, SUS316L, or the austenitic stainless steel described in Patent Documents 1 to 3, steel with excellent hydrogen embrittlement resistance, mechanical strength and corrosion resistance is realized. All of these steels have excellent resistance to hydrogen embrittlement after hot working or steels subjected to cold working followed by solid solution heat treatment. Even after cold working, the steel subjected to cold working at a cold working rate of 25% or less in Patent Document 1 and at a final working rate of 75% or less in Patent Document 2 has excellent hydrogen embrittlement resistance. It is shown.
ところが、これら従来から知られていた鋼においては、冷間鍛造性と冷間加工後の耐水素脆化特性の両方を満足することが難しいことがわかった。特に、従来技術では冷間鍛造前の材料強度が高いため、工具寿命が短く、太径棒鋼での鍛造荷重が増える。そのため、これら要因に起因し冷間鍛造性が悪化することが判明した。また、冷間鍛造のような高ひずみでの加工では、従来の鋼において材料の加工限界(割れ)が生じてしまうことも判明した。 However, it was found that it was difficult to satisfy both cold forgeability and resistance to hydrogen embrittlement after cold working with these conventionally known steels. In particular, in the conventional technology, the material strength before cold forging is high, so the tool life is short and the forging load increases with large diameter steel bars. Therefore, it was found that the cold forgeability deteriorated due to these factors. In addition, it has been found that the processing limit (cracking) of the material occurs in conventional steel in high-strain processing such as cold forging.
本発明は、引張強さを下げ冷間鍛造性を高め、更に冷間加工後の耐水素脆化特性を高めることのできる、ステンレス鋼を提供することを第1の目的とする。 The first object of the present invention is to provide a stainless steel that can lower tensile strength, improve cold forgeability, and further improve hydrogen embrittlement resistance after cold working.
前記従来から知られていた鋼においてはまた、冷間鍛造性と切削性、冷間加工後の耐水素脆化特性のすべてを満足することが難しいことがわかった。特に、従来技術では冷間鍛造前の材料強度が高いため、工具寿命が短く、太径棒鋼での鍛造荷重が増える。そのため、これら要因に起因し冷間鍛造性が悪化するとともに、切削性が悪化することが判明した。また、冷間鍛造のような高ひずみでの加工では、従来の鋼において材料の加工限界(割れ)が生じてしまうことも判明した。 It has also been found that it is difficult for the conventionally known steels to satisfy all of cold forgeability, machinability, and resistance to hydrogen embrittlement after cold working. In particular, in the conventional technology, the material strength before cold forging is high, so the tool life is short and the forging load increases with large diameter steel bars. Therefore, it was found that cold forgeability and machinability deteriorated due to these factors. In addition, it has been found that the processing limit (cracking) of the material occurs in conventional steel in high-strain processing such as cold forging.
本発明は、引張強さを下げ冷間鍛造性を高め、切削性を向上するとともに、更に冷間加工後の耐水素脆化特性を高めることのできる、ステンレス鋼を提供することを第2の目的とする。 The second object of the present invention is to provide a stainless steel that can lower tensile strength, improve cold forgeability, improve machinability, and further improve hydrogen embrittlement resistance after cold working. aim.
SUS316、SUS316L、あるいは特許文献3、5に記載のオーステナイト系ステンレス鋼を用いることにより、機械的強度に優れる非磁性鋼が実現している。ところが、これら従来から知られていた鋼においては、耐食性と冷間鍛造性と冷間加工後の非磁性を同時に満足することが難しいことがわかった。特に、従来技術では、高Cに起因し鋭敏化などを生じ耐食性が劣化する。また、冷間鍛造前の材料強度が高いため、工具寿命が短く、太径棒鋼での鍛造荷重が増える。そのため、これら要因に起因し冷間鍛造性が悪化することが判明した。更に、冷間鍛造のような高ひずみでの加工では、従来の鋼において材料の加工限界(割れ)が生じてしまうことも判明した。 By using SUS316, SUS316L, or the austenitic stainless steel described in Patent Documents 3 and 5, non-magnetic steel with excellent mechanical strength is realized. However, it has been found that it is difficult to simultaneously satisfy corrosion resistance, cold forgeability, and non-magnetism after cold working in these conventionally known steels. In particular, in the prior art, the corrosion resistance deteriorates due to sensitization due to the high C content. In addition, since the strength of the material before cold forging is high, the tool life is short and the forging load for large steel bars increases. Therefore, it was found that the cold forgeability deteriorated due to these factors. Furthermore, it has been found that the processing limit (cracking) of the material occurs in conventional steel in high-strain processing such as cold forging.
本発明は、耐食性を高め、引張強さを下げ冷間鍛造性を高め、更に冷間加工後の非磁性特性を高めることのできる、ステンレス鋼を提供することを第3の目的とする。 A third object of the present invention is to provide a stainless steel that can improve corrosion resistance, lower tensile strength, improve cold forgeability, and further improve non-magnetic properties after cold working.
本発明において、上記第1の目的に対応する以下の第1発明、第2の目的に対応する第2発明、第3の目的に対応する第3発明の3つの発明に至った。
即ち、本発明の要旨とするところは以下のとおりである。
In the present invention, the following three inventions, a first invention corresponding to the first object, a second invention corresponding to the second object, and a third invention corresponding to the third object, were achieved.
That is, the gist of the present invention is as follows.
[1]<第1発明>
化学組成が、質量%で、
C:0.0010~0.15%、Si:0.01~2.00%、Mn:0.01~10.00%、Ni:8.00~30.00%、Cr:9.0~21.0%、Mo:0.01~3.00%、Cu:0.01~5.00%、N:0.0010~0.10%、
Ti:0~2.00%、Nb:0~2.00%、Sn:0~2.5%、V:0~2.0%、W:0~3.0%、Ga:0~0.05%、Co:0~2.5%、Sb:0~2.5%、Ta:0~2.5%、Ca:0~0.05%、Mg:0~0.012%、Zr:0~0.012%、REM:0~0.05%、Pb:0~0.30%、Se:0~0.80%、Te:0~0.30%、Bi:0~0.50%、S:0~0.50%、P:0~0.30%を含有し、さらに、
Al:0.001~2.0%、B:0.0001~0.05%から選択される一種以上を含有し、残部:Feおよび不純物であり、
下記式(a)で示されるA値が-100以下であり、
鋼材表層~D/4のミクロひずみが平均で0.0040以下であるステンレス鋼。
A値=551-462(C+N)-9.2Si―8.1Mn―29(Ni+Cu)-13.7Cr―18.5Mo (a)
但し、式(a)中の元素記号は、当該元素の鋼中における含有量(質量%)を意味する。また、式(a)中の元素の含有量が0%である場合は、該当記号箇所には「0」を代入して算出する。
ここで、Dは鋼材の直径または厚みであり、前記ミクロひずみとは、X線回折で得られる半価幅から算出される格子ひずみを意味する。
[1] <First invention>
The chemical composition, in mass %,
C: 0.0010-0.15%, Si: 0.01-2.00%, Mn: 0.01-10.00%, Ni: 8.00-30.00%, Cr: 9.0- 21.0%, Mo: 0.01-3.00%, Cu: 0.01-5.00%, N: 0.0010-0.10%,
Ti: 0-2.00%, Nb: 0-2.00%, Sn: 0-2.5%, V: 0-2.0%, W: 0-3.0%, Ga: 0-0 .05%, Co: 0-2.5%, Sb: 0-2.5%, Ta: 0-2.5%, Ca: 0-0.05%, Mg: 0-0.012%, Zr : 0-0.012%, REM: 0-0.05%, Pb: 0-0.30%, Se: 0-0.80%, Te: 0-0.30%, Bi: 0-0. 50%, S: 0-0.50%, P: 0-0.30%, and
Al: 0.001 to 2.0%, containing one or more selected from B: 0.0001 to 0.05%, the balance being Fe and impurities,
The A value represented by the following formula (a) is −100 or less,
A stainless steel having an average microstrain of 0.0040 or less from the surface layer to D/4 of the steel material.
A value = 551-462 (C+N)-9.2Si-8.1Mn-29(Ni+Cu)-13.7Cr-18.5Mo (a)
However, the symbol of an element in the formula (a) means the content (% by mass) of the element in the steel. Further, when the content of the element in the formula (a) is 0%, the calculation is performed by substituting "0" in the corresponding symbol.
Here, D is the diameter or thickness of the steel material, and the micro strain means the lattice strain calculated from the half width obtained by X-ray diffraction.
[2]前記化学組成が、質量%でさらに、
A群として、Ti:0.01~2.00%、Nb:0.01~2.00%、Sn:0.0001~2.5%、V:0.001~2.0%、W:0.05~3.0%、Ga:0.0004~0.05%、Co:0.05~2.5%、Sb:0.01~2.5%、およびTa:0.01~2.5%から選択される一種以上、
B群として、Ca:0.0002~0.05%、Mg:0.0002~0.012%、Zr:0.0002~0.012%、およびREM:0.0002~0.05%から選択される一種以上、
C群として、Pb:0.0001~0.30%、Se:0.0001~0.80%、Te:0.0001~0.30%、Bi:0.0001~0.50%、S:0.0001~0.50%、P:0.0001~0.30%から選択される一種以上、
のA群~C群の一群以上を含有する、[1]に記載のステンレス鋼。
[2] The chemical composition is further, in mass %,
As group A, Ti: 0.01 to 2.00%, Nb: 0.01 to 2.00%, Sn: 0.0001 to 2.5%, V: 0.001 to 2.0%, W: 0.05-3.0%, Ga: 0.0004-0.05%, Co: 0.05-2.5%, Sb: 0.01-2.5%, and Ta: 0.01-2 one or more selected from .5%,
Group B selected from Ca: 0.0002 to 0.05%, Mg: 0.0002 to 0.012%, Zr: 0.0002 to 0.012%, and REM: 0.0002 to 0.05% one or more
As group C, Pb: 0.0001 to 0.30%, Se: 0.0001 to 0.80%, Te: 0.0001 to 0.30%, Bi: 0.0001 to 0.50%, S: 0.0001 to 0.50%, P: one or more selected from 0.0001 to 0.30%,
The stainless steel according to [1], containing one or more of Groups A to C of
[3]引張強さが700MPa以下である、[1]又は[2]に記載のステンレス鋼。
[4]限界圧縮率が60%以上である、[1]~[3]のいずれか1つに記載のステンレス鋼。
[5]冷間加工後の高圧水素中の相対引張強さが80%以上である、[1]~[4]のいずれか1つに記載のステンレス鋼。
[6]冷間加工後の高圧水素中の相対絞りが50%以上である、[1]~[5]のいずれか1つに記載のステンレス鋼。
[3] The stainless steel according to [1] or [2], which has a tensile strength of 700 MPa or less.
[4] The stainless steel according to any one of [1] to [3], which has a critical compressibility of 60% or more.
[5] The stainless steel according to any one of [1] to [4], which has a relative tensile strength of 80% or more in high-pressure hydrogen after cold working.
[6] The stainless steel according to any one of [1] to [5], which has a relative reduction in area of 50% or more in high-pressure hydrogen after cold working.
[7]<第2発明>
化学組成が、質量%で、
C:0.0010~0.15%、Si:0.01~2.00%、Mn:0.01~10.00%、Ni:8.00~30.00%、Cr:9.0~21.0%、Mo:0.01~3.00%、Cu:0.01~5.00%、N:0.0010~0.10%、B:0.0001~0.05%、S:0.0001~0.50%、
Ti:0~2.00%、Nb:0~2.00%、Sn:0~2.5%、V:0~2.0%、W:0~3.0%、Ga:0~0.05%、Co:0~2.5%、Sb:0~2.5%、Ta:0~2.5%、Mg:0~0.012%、Zr:0~0.012%、REM:0~0.05%、Pb:0~0.30%、Se:0~0.80%、Te:0~0.30%、Bi:0~0.50%、P:0~0.30%、
を含有し、さらに、
Al:0.001~2.0%、Ca:0.0001~0.05%、から選択される一種以上を含有し、残部:Feおよび不純物であり、
下記式(a)で示されるA値が-100以下であり、
ホウ化物としての析出B量が0.0001%以上であり、硫化物のアスペクト比が50以下であることを特徴とするステンレス鋼。
A値=551-462(C+N)-9.2Si―8.1Mn―29(Ni+Cu)-13.7Cr―18.5Mo (a)
但し、式(a)中の元素記号は、当該元素の鋼中における含有量(質量%)を意味する。また、式(a)中の元素の含有量が0%である場合は、該当記号箇所には「0」を代入して算出する。
[7] <Second invention>
The chemical composition, in mass %,
C: 0.0010-0.15%, Si: 0.01-2.00%, Mn: 0.01-10.00%, Ni: 8.00-30.00%, Cr: 9.0- 21.0%, Mo: 0.01-3.00%, Cu: 0.01-5.00%, N: 0.0010-0.10%, B: 0.0001-0.05%, S : 0.0001 to 0.50%,
Ti: 0-2.00%, Nb: 0-2.00%, Sn: 0-2.5%, V: 0-2.0%, W: 0-3.0%, Ga: 0-0 .05%, Co: 0-2.5%, Sb: 0-2.5%, Ta: 0-2.5%, Mg: 0-0.012%, Zr: 0-0.012%, REM : 0-0.05%, Pb: 0-0.30%, Se: 0-0.80%, Te: 0-0.30%, Bi: 0-0.50%, P: 0-0. 30%,
and further
Al: 0.001 to 2.0%, Ca: 0.0001 to 0.05%, containing one or more selected from, the balance being Fe and impurities,
The A value represented by the following formula (a) is −100 or less,
A stainless steel characterized by having an amount of precipitated B as borides of 0.0001% or more and an aspect ratio of sulfides of 50 or less.
A value = 551-462 (C+N)-9.2Si-8.1Mn-29(Ni+Cu)-13.7Cr-18.5Mo (a)
However, the symbol of an element in the formula (a) means the content (% by mass) of the element in the steel. Further, when the content of the element in the formula (a) is 0%, the calculation is performed by substituting "0" in the corresponding symbol.
[8]前記化学組成が、質量%でさらに、
A群として、Ti:0.01~2.00%、Nb:0.01~2.00%、Sn:0.0001~2.5%、V:0.001~2.0%、W:0.05~3.0%、Ga:0.0004~0.05%、Co:0.05~2.5%、Sb:0.01~2.5%、およびTa:0.01~2.5%、から選択される一種以上、
B群として、Mg:0.0002~0.012%、Zr:0.0002~0.012%、およびREM:0.0002~0.05%、から選択される一種以上、
C群として、Pb:0.0001~0.30%、Se:0.0001~0.80%、Te:0.0001~0.30%、Bi:0.0001~0.50%、P:0.0001~0.30%、から選択される一種以上、
のA群~C群の一群以上を含有する、[7]に記載のステンレス鋼。
[8] The chemical composition is further, in mass %,
As group A, Ti: 0.01 to 2.00%, Nb: 0.01 to 2.00%, Sn: 0.0001 to 2.5%, V: 0.001 to 2.0%, W: 0.05-3.0%, Ga: 0.0004-0.05%, Co: 0.05-2.5%, Sb: 0.01-2.5%, and Ta: 0.01-2 .5%, one or more selected from
As group B, one or more selected from Mg: 0.0002 to 0.012%, Zr: 0.0002 to 0.012%, and REM: 0.0002 to 0.05%,
As group C, Pb: 0.0001 to 0.30%, Se: 0.0001 to 0.80%, Te: 0.0001 to 0.30%, Bi: 0.0001 to 0.50%, P: 0.0001 to 0.30%, one or more selected from
The stainless steel according to [7], containing one or more of Groups A to C of
[9]引張強さが700MPa以下である、[7]又は[8]に記載のステンレス鋼。
[10]限界圧縮率が60%以上である、[7]~[9]のいずれか1つに記載のステンレス鋼。
[11]ドリル加工寿命指標のVL-1000が1m/min以上である、[7]~[10]のいずれか1つに記載のステンレス鋼。
[12]冷間加工後の高圧水素中の相対引張強さが80%以上である、[7]~[11]のいずれか1つに記載のステンレス鋼。
[13]冷間加工後の高圧水素中の相対絞りが50%以上である、[7]~[12]のいずれか1つに記載のステンレス鋼。
[9] The stainless steel according to [7] or [8], which has a tensile strength of 700 MPa or less.
[10] The stainless steel according to any one of [7] to [9], which has a critical compressibility of 60% or more.
[11] The stainless steel according to any one of [7] to [10], which has a drilling life index VL-1000 of 1 m/min or more.
[12] The stainless steel according to any one of [7] to [11], which has a relative tensile strength of 80% or more in high-pressure hydrogen after cold working.
[13] The stainless steel according to any one of [7] to [12], which has a relative reduction in area of 50% or more in high-pressure hydrogen after cold working.
[14]<第3発明>
化学組成が、質量%で、
C:0.0010~0.15%、Si:0.01~2.00%、Mn:0.01~10.00%、Ni:8.00~30.00%、Cr:9.0~21.0%、Mo:0.01~3.00%、Cu:0.01~5.00%、N:0.0010~0.10%、B:0.0001~0.05%、
Al:0~2.0%、Ti:0~2.00%、Nb:0~2.00%、Sn:0~2.5%、V:0~2.0%、W:0~3.0%、Ga:0~0.05%、Co:0~2.5%、Sb:0~2.5%、Ta:0~2.5%、Ca:0~0.05%、Mg:0~0.012%、Zr:0~0.012%、REM:0~0.05%、Pb:0~0.30%、Se:0~0.80%、Te:0~0.30%、Bi:0~0.50%、S:0~0.50%、P:0~0.30%を含有し、残部:Feおよび不純物であり、
下記式(a)で示されるA値が-100以下であり、
B粒界占有率が1%以上であるステンレス鋼。
A値=551-462(C+N)-9.2Si―8.1Mn―29(Ni+Cu)-13.7Cr―18.5Mo (a)
但し、式(a)中の元素記号は、当該元素の鋼中における含有量(質量%)を意味する。また、式(a)中の元素の含有量が0%である場合は、該当記号箇所には「0」を代入して算出する。
[14] <Third invention>
The chemical composition, in mass %,
C: 0.0010-0.15%, Si: 0.01-2.00%, Mn: 0.01-10.00%, Ni: 8.00-30.00%, Cr: 9.0- 21.0%, Mo: 0.01-3.00%, Cu: 0.01-5.00%, N: 0.0010-0.10%, B: 0.0001-0.05%,
Al: 0-2.0%, Ti: 0-2.00%, Nb: 0-2.00%, Sn: 0-2.5%, V: 0-2.0%, W: 0-3 .0%, Ga: 0-0.05%, Co: 0-2.5%, Sb: 0-2.5%, Ta: 0-2.5%, Ca: 0-0.05%, Mg : 0-0.012%, Zr: 0-0.012%, REM: 0-0.05%, Pb: 0-0.30%, Se: 0-0.80%, Te: 0-0. 30%, Bi: 0 to 0.50%, S: 0 to 0.50%, P: 0 to 0.30%, the balance is Fe and impurities,
The A value represented by the following formula (a) is −100 or less,
A stainless steel having a B grain boundary occupancy of 1% or more.
A value = 551-462 (C+N)-9.2Si-8.1Mn-29(Ni+Cu)-13.7Cr-18.5Mo (a)
However, the symbol of an element in the formula (a) means the content (% by mass) of the element in the steel. Further, when the content of the element in the formula (a) is 0%, the calculation is performed by substituting "0" in the corresponding symbol.
[15]前記化学組成が、質量%でさらに、
A群として、Al:0.001~2.0%、Ti:0.01~2.00%、Nb:0.01~2.00%、Sn:0.0001~2.5%、V:0.001~2.0%、W:0.05~3.0%、Ga:0.0004~0.05%、Co:0.05~2.5%、Sb:0.01~2.5%、およびTa:0.01~2.5%、から選択される一種以上、
B群として、Ca:0.0002~0.05%、Mg:0.0002~0.012%、Zr:0.0002~0.012%、およびREM:0.0002~0.05%、から選択される一種以上、
C群として、Pb:0.0001~0.30%、Se:0.0001~0.80%、Te:0.0001~0.30%、Bi:0.0001~0.50%、S:0.0001~0.50%、P:0.0001~0.30%、から選択される一種以上、
のA群~C群の1群以上を含有する、[14]に記載のステンレス鋼。
[15] The chemical composition is further, in mass %,
As group A, Al: 0.001 to 2.0%, Ti: 0.01 to 2.00%, Nb: 0.01 to 2.00%, Sn: 0.0001 to 2.5%, V: 0.001-2.0%, W: 0.05-3.0%, Ga: 0.0004-0.05%, Co: 0.05-2.5%, Sb: 0.01-2. 5%, and one or more selected from Ta: 0.01 to 2.5%,
As group B, Ca: 0.0002-0.05%, Mg: 0.0002-0.012%, Zr: 0.0002-0.012%, and REM: 0.0002-0.05%, from one or more selected
As group C, Pb: 0.0001 to 0.30%, Se: 0.0001 to 0.80%, Te: 0.0001 to 0.30%, Bi: 0.0001 to 0.50%, S: One or more selected from 0.0001 to 0.50%, P: 0.0001 to 0.30%,
The stainless steel according to [14], containing one or more of Groups A to C of
[16] 孔食電位が0.05V以上である、[14]又は[15]に記載のステンレス鋼。
[17]引張強さが700MPa以下である、[14]~[16]のいずれか1項に記載のステンレス鋼。
[18]限界圧縮率が60%以上である、[14]~[17]のいずれか1つに記載のステンレス鋼。
[19]冷間加工後の比透磁率が1.10以下である、[14]~[18]のいずれか1つに記載のステンレス鋼。
[16] The stainless steel according to [14] or [15], which has a pitting potential of 0.05 V or higher.
[17] The stainless steel according to any one of [14] to [16], which has a tensile strength of 700 MPa or less.
[18] The stainless steel according to any one of [14] to [17], which has a critical compressibility of 60% or more.
[19] The stainless steel according to any one of [14] to [18], which has a relative magnetic permeability of 1.10 or less after cold working.
第1発明のステンレス鋼は、所定の成分を含有し、さらにAlとBの一方または両方を含有し、鋼材表層~D/4のミクロひずみが0.0040以下であることにより、冷間鍛造性と冷間加工後の耐水素脆化特性の両方を満足することが可能になる。 The stainless steel of the first invention contains predetermined components, further contains one or both of Al and B, and has a micro strain of 0.0040 or less from the surface layer to D/4 of the steel material. and hydrogen embrittlement resistance after cold working.
第2発明のステンレス鋼は、所定の成分を含有し、さらにAlとCaの一方または両方を含有し、ホウ化物としての析出B量が0.0001%以上であり、硫化物のアスペクト比が50以下であることにより、冷間鍛造性、切削性と冷間加工後の耐水素脆化特性のすべてを満足することが可能になる。 The stainless steel of the second invention contains predetermined components, further contains one or both of Al and Ca, has an amount of B precipitated as borides of 0.0001% or more, and has a sulfide aspect ratio of 50. By having the following, it becomes possible to satisfy all of cold forgeability, machinability and resistance to hydrogen embrittlement after cold working.
第3発明のステンレス鋼は、所定の成分を含有し、B粒界占有率が1%以上であることにより、耐食性と冷間鍛造性と冷間加工後の非磁性特性を満足することが可能になる。 The stainless steel of the third invention contains predetermined components and has a B grain boundary occupancy of 1% or more, so that it can satisfy corrosion resistance, cold forgeability, and non-magnetic properties after cold working. become.
本発明のステンレス鋼は、棒形状、板形状のいずれであっても適用することができる。中でも、棒状鋼材として使用するときに特に好適に用いることができる。棒状鋼材とは、「棒鋼」、「線材」、「鋼線」、「異形線」、「異形棒鋼」などを含む。本発明のステンレス鋼は、オーステナイト系ステンレス鋼である。 The stainless steel of the present invention can be applied in either bar shape or plate shape. Above all, it can be used particularly suitably when used as a bar-shaped steel material. Steel bars include "steel bars", "wire rods", "steel wires", "deformed wires", "deformed steel bars" and the like. The stainless steel of the present invention is austenitic stainless steel.
第1発明は、前述のように、冷間鍛造性と冷間加工後の耐水素脆化特性の両方を満足することのできる、ステンレス鋼、特に棒状鋼材の提供を目的とする。 As described above, the first invention aims to provide a stainless steel, particularly a bar steel, which can satisfy both cold forgeability and hydrogen embrittlement resistance after cold working.
第2発明は、前述のように、冷間鍛造性、切削性と冷間加工後の耐水素脆化特性のすべてを満足することのできる、ステンレス鋼、特に棒状鋼材の提供を目的とする。 The purpose of the second invention is to provide a stainless steel, particularly a bar steel, which can satisfy all of cold forgeability, machinability, and resistance to hydrogen embrittlement after cold working, as described above.
第3発明は、前述のように、耐食性と冷間鍛造性と冷間加工後の非磁性特性を満足することのできる、ステンレス鋼、特に棒状鋼材の提供を目的とする。 As described above, the third invention aims to provide stainless steel, particularly bar steel, which can satisfy corrosion resistance, cold forgeability, and non-magnetic properties after cold working.
冷間鍛造性については、φ8×12mmの試験片を用い、端面拘束圧縮試験(加工温度:RT(室温)、ひずみ速度:10/s)を行ったときに、圧縮加工後の試験片側面に割れの生じない最大圧縮率を限界圧縮率と定義し、限界圧縮率が60%以上となることを目標とする。 For cold forgeability, a test piece of φ8 × 12 mm was used, and an end face restraint compression test (processing temperature: RT (room temperature), strain rate: 10 / s) was performed. The maximum compressibility at which cracks do not occur is defined as the limit compressibility, and the goal is to achieve the limit compressibility of 60% or more.
冷間加工後の耐水素脆化特性については、まず、溶体化熱処理を行った上で、冷間加工率が80%の冷間加工を行った試料を準備する。同じ加工条件で2つの試験片を準備し、一方を水素試験片、他方を大気試験片とする。水素試験片については、水素雰囲気、-40℃、70MPaの環境で、ひずみ速度1×10-5/sで引張試験を行う。大気試験片については、大気雰囲気で同じひずみ速度で引張試験を行う。それぞれ強度と絞りを評価し、水素試験片での評価結果を大気試験片での評価結果で除した値の%表示を、それぞれ「相対強度」「相対絞り」とする。相対強度が80%以上、かつ、相対絞りが50%以上の実現を、第1、第2発明の目標とする。 For the hydrogen embrittlement resistance after cold working, first, a sample is prepared by performing solution heat treatment and then cold working at a cold working rate of 80%. Two test pieces are prepared under the same processing conditions, one being a hydrogen test piece and the other an air test piece. A hydrogen test piece is subjected to a tensile test at a strain rate of 1×10 −5 /s in a hydrogen atmosphere, −40° C., 70 MPa. For atmospheric specimens, tensile tests are performed at the same strain rate in atmospheric conditions. The strength and reduction of area are evaluated, respectively, and the percentage display of the value obtained by dividing the evaluation result of the hydrogen test piece by the evaluation result of the air test piece is defined as "relative strength" and "relative reduction of area", respectively. The goals of the first and second inventions are to achieve a relative strength of 80% or more and a relative reduction of area of 50% or more.
切削性については、ドリル加工寿命指標のVL-1000(累積穴深さ1000mm穿孔可能な最大外周速度(m/min))によって評価を行う。VL-1000が1m/min以上となることを第2発明の目標とする。 The machinability is evaluated by the drilling life index VL-1000 (maximum peripheral speed (m/min) that can be drilled to a cumulative hole depth of 1000 mm). A target of the second invention is to achieve VL-1000 of 1 m/min or more.
耐食性については、φ20×30mmの試験片のL断面中心部(20幅×30長×1mm厚)を評価面として用い、評価面を含め、不働態化処理は15%硝酸の30分浸漬の条件にて実施した。その後、評価面についてJISG 0577(3.5%NaCl,30℃,N=3の平均、V vs Ag/AgCl,飽和KCl)に従った孔食電位試験を行い、孔食電位を測定した。孔食電位が0.05V以上となることを第3発明の目標とする。なお、実施例において、比較材の不働態化処理なしでは、研磨まま直後に孔食電位の測定を行った。 For corrosion resistance, the center of the L cross section (20 width x 30 length x 1 mm thickness) of a φ20 x 30 mm test piece was used as the evaluation surface, and the passivation treatment including the evaluation surface was immersed in 15% nitric acid for 30 minutes. It was carried out at After that, the evaluation surface was subjected to a pitting potential test according to JISG 0577 (3.5% NaCl, 30°C, N=3 average, V vs Ag/AgCl, saturated KCl) to measure the pitting potential. A target of the third invention is to achieve a pitting potential of 0.05 V or higher. In the examples, the pitting potential was measured immediately after polishing without the passivation treatment of the comparative material.
冷間加工後の非磁性特性については、まず、溶体化熱処理として1100℃×30分(水冷)の熱処理を行った上で、冷間加工率(断面減少率)が80%の冷間加工を行った試料を準備し、1000[Oe]における比透磁率を測定する。比透磁率が1.10以下の実現を、第3発明の目標とする。 Regarding the non-magnetic properties after cold working, first, after performing heat treatment at 1100 ° C. for 30 minutes (water cooling) as solution heat treatment, cold working with a cold working rate (area reduction rate) of 80% is performed. A sample is prepared and the relative permeability at 1000 [Oe] is measured. The objective of the third invention is to achieve a relative permeability of 1.10 or less.
以下、第1発明、第2発明、第3発明の順に、詳細について説明する。 Details will be described below in the order of the first invention, the second invention, and the third invention.
<第1発明>
《第1発明のステンレス鋼のミクロひずみ》
本発明者らは、ステンレス鋼、特に棒状鋼材において、冷間鍛造性と冷間加工後の耐水素脆化特性の両方を満足する手段として、鋼材の表面近傍のミクロひずみを制御することを着想した。ミクロひずみとはX線ラインプロファイル解析で得られる半価幅から算出される格子ひずみであり、鋼材中の格子欠陥や固溶元素などに起因し格子ひずみの大きさは決まる。ミクロひずみが小さいと、結晶格子がひずみ難く、冷間鍛造などの高ひずみ加工においてひずみの蓄積が小さくなり、高ひずみでの変形応力が小さくなり、冷間鍛造での工具寿命の長寿命化が可能になるとともに、鍛造荷重低減に起因して太径棒状鋼材の冷間鍛造が可能になると考えた。また、金属組織内の局所的なひずみ集中も小さくなることで、冷間鍛造時の破壊の抑制や、水素雰囲気中での破壊の抑制につながることを着想した。
<First Invention>
<<Micro strain of the stainless steel of the first invention>>
The present inventors conceived the idea of controlling the micro-strain near the surface of stainless steel, particularly bar steel, as a means of satisfying both cold forgeability and hydrogen embrittlement resistance after cold working. bottom. Microstrain is lattice strain calculated from the half width obtained by X-ray line profile analysis, and the magnitude of lattice strain is determined by lattice defects and solid solution elements in the steel material. If the micro strain is small, the crystal lattice will not be easily distorted, and the accumulation of strain in high strain processing such as cold forging will be small. In addition, we thought that cold forging of large-diameter bar steel would be possible due to the reduction of the forging load. In addition, it was conceived that by reducing the local strain concentration in the metal structure, it would lead to suppression of fracture during cold forging and suppression of fracture in a hydrogen atmosphere.
ミクロひずみの評価はX線ラインプロファイル解析で測定した。鋼材のL断面(棒状鋼材であればその中心線を含む断面)において、鋼材表層~D/4位置において、X線回折にてCuKα線を用いて測定を行い、(111)、(200)、(220)(311)の半価幅を測定し、得られた半価幅を以下のDirect-Fitting法の式(A)へ代入する。ここで、Dは鋼材の直径または厚みである。
ΔK=α+ε(K/ω) ・・・(A)
なお、式(A)において、εがミクロひずみであり、αは結晶子サイズに関する値である。また、KおよびΔK、ωは、下記の通りである。
K=2sinθ/λ、
ΔK=2βcosθ/λ
1/ω=(1/ωh00)-Γ{(1/ωh00)-1}/0.276
上記式において、β、θおよびλは、それぞれ各回折線の半値幅(rad)、ブラッグ反射角(rad)およびX線波長(CuKα=0.15405nm)である。Γは回折線の指数h,k,lの関数であり下記の通りである。
Γ=(h2k2+k2l2+l2h2)/(h2+k2+l2)2
ωh00は定数であり、式(A)のΔKと(K/ω)を直線近似した際の誤差が最小となるようにωh00を決定する。その後、上記のΔKと(K/ω)の直線近似の傾きがミクロひずみεとして算出される。
Evaluation of microstrain was measured by X-ray line profile analysis. In the L cross section of the steel material (the cross section including the center line in the case of a bar steel material), the steel material surface layer to the D/4 position are measured by X-ray diffraction using CuKα rays, and (111), (200), The half-value widths of (220) and (311) are measured, and the obtained half-value widths are substituted into the following formula (A) of the Direct-Fitting method. where D is the diameter or thickness of the steel.
ΔK=α+ε(K/ω) (A)
In formula (A), ε is microstrain and α is a value related to crystallite size. K, ΔK, and ω are as follows.
K=2 sin θ/λ,
ΔK=2β cos θ/λ
1/ω=(1/ω h00 )−Γ{(1/ω h00 )−1}/0.276
In the above formula, β, θ and λ are the half width (rad), Bragg reflection angle (rad) and X-ray wavelength (CuKα=0.15405 nm) of each diffraction line, respectively. Γ is a function of diffraction line indices h, k, and l, and is given below.
Γ=(h 2 k 2 +k 2 l 2 +l 2 h 2 )/(h 2 +k 2 +l 2 ) 2
ω h00 is a constant, and is determined so as to minimize the error when linearly approximating ΔK and (K/ω) in Equation ( A). After that, the slope of the linear approximation of the above ΔK and (K/ω) is calculated as the micro strain ε.
そして、鋼材の直径または厚みをDとして、鋼材表層~D/4のミクロひずみが平均で0.0040以下であれば、上記目標とする、冷間鍛造性と冷間加工後の耐水素脆化特性の両方を満足できることが判明した。鋼材表層~D/4のミクロひずみが平均で0.0020以下であればより好ましく、0.0010以下は更に好ましく、0.0005以下が更に好ましい。鋼材表層近傍は冷間鍛造において破壊起点となりやすいが、鋼材表層~D/4のミクロひずみを小さく制御することで、冷間鍛造時に鋼材の変形能を高めるため、鋼材表層~D/4のミクロひずみ制御が重要となる。鋼材表層~D/4のミクロひずみは鋼材表層~D/4位置における平均の値である。 Then, if the diameter or thickness of the steel material is D, and the average microstrain of the steel material surface layer to D/4 is 0.0040 or less, the above target cold forgeability and resistance to hydrogen embrittlement after cold working It was found that both characteristics were satisfied. The average microstrain from the surface layer to D/4 of the steel material is more preferably 0.0020 or less, still more preferably 0.0010 or less, and even more preferably 0.0005 or less. The vicinity of the steel material surface layer tends to be a fracture starting point in cold forging, but by controlling the micro strain of the steel material surface layer to D/4 to be small, the deformability of the steel material is increased during cold forging. Strain control becomes important. The micro strain from the surface layer to D/4 of the steel material is the average value at the position from the surface layer to D/4 of the steel material.
《第1発明のステンレス鋼の成分組成》
次に、第1発明のステンレス鋼の成分組成について説明する。成分組成において、第2、第3発明を含め、%は質量%を意味する。
<<Component composition of the stainless steel of the first invention>>
Next, the chemical composition of the stainless steel of the first invention will be explained. In the component composition, % means % by mass, including the second and third inventions.
(Al:0.001~2.0%、B:0.0001~0.05%から選択される一種以上)
第1発明のステンレス鋼は、Al:0.001~2.0%、B:0.0001~0.05%から選択される一種以上を含有する。これにより、ミクロひずみを下げ、冷間鍛造性を向上し、耐水素脆化特性を高める。またAlは脱酸元素として有効である。
過剰にAlを添加すると、粗大AlNなどが形成し、冷間鍛造性と耐水素脆化特性が劣化する。そのため、Al含有量の上限値を2.0%とし、好ましくは1.0%以下であり、更に好ましくは0.5%以下、更に好ましくは0.05%以下とする。
Bの下限値理由は前記載の通りであることに加え、B系析出物を形成し切削性を高める効果があり、0.0001%以上とする。好ましくは0.0005%以上である。過剰にBを添加すると、粗大B系析出物などが形成し、冷間鍛造性と耐水素脆化特性が劣化する。そのため、B含有量の上限値を0.05%とし、好ましくは0.02%以下であり、更に好ましくは0.015%以下とする。
Al、Bをともに含有しない、あるいは下限値を外れると、ミクロひずみが本発明範囲から外れ、引張強さ、限界圧縮率、冷間加工後の相対引張強さと絞りが不良となる。
(At least one selected from Al: 0.001 to 2.0%, B: 0.0001 to 0.05%)
The stainless steel of the first invention contains one or more selected from Al: 0.001 to 2.0% and B: 0.0001 to 0.05%. This reduces microstrain, improves cold forgeability, and enhances resistance to hydrogen embrittlement. Also, Al is effective as a deoxidizing element.
Excessive addition of Al results in the formation of coarse AlN and the like, degrading cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Al content is set to 2.0%, preferably 1.0% or less, more preferably 0.5% or less, further preferably 0.05% or less.
The reason for the lower limit of B is as described above, and in addition, it has the effect of forming B-based precipitates to improve machinability. Preferably it is 0.0005% or more. Excessive addition of B forms coarse B-based precipitates and the like, deteriorating cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the B content is set to 0.05%, preferably 0.02% or less, and more preferably 0.015% or less.
If neither Al nor B is contained, or if the lower limit is exceeded, the microstrain will be outside the range of the present invention, and the tensile strength, critical compressibility, relative tensile strength after cold working, and reduction of area will be poor.
(C:0.0010~0.15%)
Cは加工誘起マルテンサイトの形成を抑制し、耐水素脆化特性を高めるため、0.0010%以上とする。過剰にCを添加すると、ミクロひずみを高め、冷間鍛造性と耐水素脆化特性が劣化する。そのため、C含有量の上限値を0.15%とし、好ましくは0.12%以下であり、更に好ましくは0.05%以下とし、更に好ましくは0.02%以下とする。C上限を0.15%未満とすると好ましい。
(C: 0.0010 to 0.15%)
C is made 0.0010% or more in order to suppress the formation of deformation-induced martensite and improve hydrogen embrittlement resistance. Excessive addition of C increases microstrain and deteriorates cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the C content is set to 0.15%, preferably 0.12% or less, more preferably 0.05% or less, still more preferably 0.02% or less. It is preferable to set the upper limit of C to less than 0.15%.
(Si:0.01~2.00%)
Siは脱酸元素として添加し、0.01%以上とする。過剰にSiを添加すると、ミクロひずみを高め、冷間鍛造性と耐水素脆化特性が劣化する。そのため、Si含有量の上限値を2.0%とし、好ましくは1.2%以下であり、更に好ましくは0.6%以下とし、更に好ましくは0.5%以下とする。
(Si: 0.01 to 2.00%)
Si is added as a deoxidizing element to be 0.01% or more. Excessive addition of Si increases microstrain and deteriorates cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Si content is set to 2.0%, preferably 1.2% or less, more preferably 0.6% or less, still more preferably 0.5% or less.
(Mn:0.01~10.00%)
Mnは加工誘起マルテンサイトの形成を抑制し、耐水素脆化特性を高めるため、0.01%以上とする。過剰にMnを添加すると、ミクロひずみを高め、冷間鍛造性と耐水素脆化特性が劣化する。そのため、Mn含有量の上限値を10.0%とし、好ましくは2.5%以下であり、更に好ましくは1.5%以下とし、更に好ましくは1.0%以下とする。
(Mn: 0.01 to 10.00%)
Mn is made 0.01% or more in order to suppress the formation of deformation-induced martensite and improve hydrogen embrittlement resistance. Excessive addition of Mn increases microstrain and deteriorates cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Mn content is set to 10.0%, preferably 2.5% or less, more preferably 1.5% or less, still more preferably 1.0% or less.
(Ni:8.00~30.00%)
Niは加工誘起マルテンサイトの形成を抑制し、耐水素脆化特性を高める。また、ミクロひずみを下げ、冷間鍛造性を高めるため、Ni含有量を8.00%以上とする。好ましくは10.00%以上であり、更に好ましくは13.00%以上であり、更に好ましくは15.00%以上である。過剰にNiを添加すると、逆にミクロひずみを高め、冷間鍛造性と耐水素脆化特性が劣化する。そのため、Ni含有量の上限値を30.00%とし、好ましくは25.00%以下とする。
(Ni: 8.00-30.00%)
Ni suppresses the formation of deformation-induced martensite and enhances hydrogen embrittlement resistance. Also, in order to reduce microstrain and improve cold forgeability, the Ni content is made 8.00% or more. It is preferably 10.00% or more, more preferably 13.00% or more, and still more preferably 15.00% or more. Excessive addition of Ni, on the contrary, increases microstrain and deteriorates cold forgeability and resistance to hydrogen embrittlement. Therefore, the upper limit of the Ni content is 30.00%, preferably 25.00% or less.
(Cr:9.0~21.0%)
Crは加工誘起マルテンサイトの形成を抑制し、耐水素脆化特性を高める。また、耐食性を高めるため、Cr含有量を9.0%以上とする。好ましくは10.5%以上である。過剰にCrを添加すると、ミクロひずみを高め、冷間鍛造性と耐水素脆化特性が劣化する。そのため、Cr含有量の上限値を21.0%とし、好ましくは19.5%以下であり、更に好ましくは15.0%以下である。
(Cr: 9.0 to 21.0%)
Cr suppresses the formation of deformation-induced martensite and enhances hydrogen embrittlement resistance. Moreover, in order to improve corrosion resistance, the Cr content is set to 9.0% or more. Preferably it is 10.5% or more. Excessive addition of Cr increases microstrain and degrades cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Cr content is set to 21.0%, preferably 19.5% or less, more preferably 15.0% or less.
(Mo:0.01~3.00%)
Moは加工誘起マルテンサイトの形成を抑制し、耐水素脆化特性を高める。また、耐食性を高めることに加え、ミクロひずみを下げ、冷間鍛造性を高めるため、Mo含有量を0.01%以上とする。過剰にMoを添加すると、逆にミクロひずみを高め、冷間鍛造性と耐水素脆化特性が劣化する。そのため、Mo含有量の上限値を3.0%とし、好ましくは2.8%以下であり、更に好ましくは2.5%以下であり、更に好ましくは1.0%以下である。
(Mo: 0.01 to 3.00%)
Mo suppresses the formation of deformation-induced martensite and enhances hydrogen embrittlement resistance. In addition to improving corrosion resistance, the Mo content is set to 0.01% or more in order to reduce microstrain and improve cold forgeability. Excessive addition of Mo, on the contrary, increases microstrain and deteriorates cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Mo content is 3.0%, preferably 2.8% or less, more preferably 2.5% or less, and even more preferably 1.0% or less.
(Cu:0.01~5.00%)
Cuは加工誘起マルテンサイトの形成を抑制し、耐水素脆化特性を高める。また、ミクロひずみを下げ、冷間鍛造性を高めるため、Cu含有量を0.01%以上とする。好ましくは1.00%以上であり、更に好ましくは2.00%以上である。過剰にCuを添加すると、逆にミクロひずみを高め、冷間鍛造性と耐水素脆化特性が劣化し、また、熱間脆性を引き起こす。そのため、Cu含有量の上限値を5.00%とし、好ましくは3.50%以下とする。
(Cu: 0.01 to 5.00%)
Cu suppresses the formation of deformation-induced martensite and enhances hydrogen embrittlement resistance. Also, in order to reduce microstrain and improve cold forgeability, the Cu content is made 0.01% or more. It is preferably 1.00% or more, more preferably 2.00% or more. Excessive addition of Cu conversely increases microstrain, degrades cold forgeability and hydrogen embrittlement resistance, and causes hot shortness. Therefore, the upper limit of the Cu content is set to 5.00%, preferably 3.50% or less.
(N:0.0010~0.10%)
Nは加工誘起マルテンサイトの形成を抑制し、耐水素脆化特性を高めるため、0.0010%以上とする。過剰にNを添加すると、ミクロひずみを高め、冷間鍛造性と耐水素脆化特性が劣化する。そのため、N含有量の上限値を0.10%とし、好ましくは0.08%以下であり、更に好ましくは0.05%以下とし、更に好ましくは0.03%以下とする。
(N: 0.0010 to 0.10%)
N is made 0.0010% or more in order to suppress the formation of deformation-induced martensite and improve hydrogen embrittlement resistance. Excessive addition of N increases microstrain and deteriorates cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the N content is set to 0.10%, preferably 0.08% or less, more preferably 0.05% or less, still more preferably 0.03% or less.
第1発明のステンレス鋼は、上記成分を含有し、残部はFe及び不純物である。さらに、下記成分から選択される一種以上を含有することとしても良い。 The stainless steel of the first invention contains the above components, and the balance is Fe and impurities. Furthermore, it may contain one or more selected from the following components.
(Ti:0~2.00%)
Tiはミクロひずみを高めるC,Nの固定のために添加してもよい。一方、過剰にTiを添加すると粗大Ti系析出物などが形成し、冷間鍛造性と耐水素脆化特性が劣化する。そのため、Ti含有量の上限値を2.00%とし、好ましくは1.0%以下であり、更に好ましくは0.7%以下とし、更に好ましくは0.5以下である。Tiの好ましい下限は0.03%以上であり、更に好ましくは0.05%以上である。
(Ti: 0 to 2.00%)
Ti may be added for fixing C and N which enhance microstrain. On the other hand, if Ti is added excessively, coarse Ti-based precipitates and the like are formed, degrading cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Ti content is set to 2.00%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less. A preferable lower limit of Ti is 0.03% or more, more preferably 0.05% or more.
(Nb:0~2.00%)
Nbはミクロひずみを高めるC,Nの固定のために添加してもよい。一方、過剰にNbを添加すると粗大Nb系析出物などが形成し、冷間鍛造性と耐水素脆化特性が劣化する。そのため、Nb含有量の上限値を2.00%とし、好ましくは1.0%以下であり、更に好ましくは0.7%以下とし、更に好ましくは0.5%以下である。Nbの好ましい下限は0.03%以上であり、更に好ましくは0.05%以上である。
(Nb: 0 to 2.00%)
Nb may be added for fixing C and N to enhance microstrain. On the other hand, if Nb is added excessively, coarse Nb-based precipitates and the like are formed, degrading cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Nb content is set to 2.00%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less. A preferable lower limit of Nb is 0.03% or more, more preferably 0.05% or more.
(Sn:0~2.5%)
Snは、耐食性を向上させるのに有効な元素であるため、含有させてもよい。しかしながら、Snを過剰に含有させると、その効果は飽和し、逆に冷間鍛造性と耐水素脆化特性が劣化するおそれがある。そのため、Snを含有させる場合の上限を2.5%とする。より好ましくは、1.0%以下であり、更に好ましくは0.2%以下である。前記効果を発現させるには、Sn量を0.0001%以上が好ましく、0.01%以上とすることが更に好ましい。より好ましくは、0.05%以上である。
(Sn: 0-2.5%)
Since Sn is an effective element for improving corrosion resistance, it may be contained. However, excessive Sn content saturates the effect, and conversely, there is a possibility that the cold forgeability and the hydrogen embrittlement resistance deteriorate. Therefore, the upper limit of the content of Sn is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.2% or less. In order to exhibit the above effects, the Sn content is preferably 0.0001% or more, more preferably 0.01% or more. More preferably, it is 0.05% or more.
(V:0~2.0%)
Vはミクロひずみを高めるC,Nの固定のために添加してもよい。一方、過剰にVを添加すると粗大V系析出物などが形成し、冷間鍛造性と耐水素脆化特性が劣化する。そのため、V含有量の上限値を2.0%とし、好ましくは1.0%以下であり、更に好ましくは0.7%以下とし、更に好ましくは0.5以下である。Vの好ましい下限は0.001%である。
(V: 0-2.0%)
V may be added for fixing C and N which enhances microstrain. On the other hand, excessive addition of V forms coarse V-based precipitates and the like, deteriorating cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the V content is set to 2.0%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less. A preferable lower limit of V is 0.001%.
(W:0~3.0%)
Wは、耐食性を向上させるのに有効な元素であるため、含有させてもよい。しかしながら、Wを過剰に含有させると、その効果は飽和し、逆に冷間鍛造性と耐水素脆化特性が劣化するおそれがある。そのため、Wを含有させる場合の上限を3.0%とする。より好ましくは、2.0%以下であり、更に好ましくは1.5%以下である。前記効果を発現させるには、W量を0.05%以上とすることが好ましい。より好ましくは、0.10%以上である。
(W: 0-3.0%)
Since W is an effective element for improving corrosion resistance, it may be contained. However, if W is contained excessively, the effect is saturated, and the cold forgeability and hydrogen embrittlement resistance may deteriorate. Therefore, when W is contained, the upper limit is set to 3.0%. More preferably, it is 2.0% or less, and still more preferably 1.5% or less. In order to exhibit the above effects, it is preferable to set the W amount to 0.05% or more. More preferably, it is 0.10% or more.
(Ga:0~0.05%)
Gaは、耐食性を向上させるのに有効な元素であるため、含有させてもよい。しかしながら、Gaを過剰に含有させると、その効果は飽和し、逆に冷間鍛造性と耐水素脆化特性が劣化するおそれがある。そのため、Gaを含有させる場合の上限を、0.05%とする。前記効果を発現させるには、Ga量を0.0004%以上とすることが好ましい。
(Ga: 0 to 0.05%)
Ga is an effective element for improving corrosion resistance, so it may be contained. However, if Ga is contained excessively, the effect is saturated, and the cold forgeability and hydrogen embrittlement resistance may deteriorate. Therefore, the upper limit when Ga is contained is set to 0.05%. In order to exhibit the above effect, it is preferable to set the amount of Ga to 0.0004% or more.
(Co:0~2.5%)
Coは、耐食性を向上させる効果を有するため、含有させてもよい。しかしながら、Coを過剰に含有させると、その効果は飽和し、逆に冷間鍛造性と耐水素脆化特性が劣化するおそれがある。そのため、Coを含有させる場合の上限を2.5%とする。より好ましくは、1.0%以下であり、更に好ましくは0.8%以下である。前記効果を発現させるには、Co量を0.05%以上とすることが好ましく、0.10%以上含有させることがより好ましい。
(Co: 0-2.5%)
Co has the effect of improving the corrosion resistance, so it may be contained. However, if Co is contained excessively, the effect is saturated, and the cold forgeability and hydrogen embrittlement resistance may deteriorate. Therefore, the upper limit of the content of Co is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.8% or less. In order to exhibit the above effects, the Co content is preferably 0.05% or more, more preferably 0.10% or more.
(Sb:0~2.5%)
Sbは、耐食性を向上させる効果を有するため、含有させてもよい。しかしながら、Sbを過剰に含有させると、その効果は飽和し、逆に冷間鍛造性と耐水素脆化特性が劣化するおそれがある。そのため、Sbを含有させる場合の上限を2.5%とする。より好ましくは、1.0%以下であり、更に好ましくは0.8%以下である。前記効果を発現させるには、Sb量を0.01%以上とすることが好ましく、0.05%以上含有させることがより好ましい。
(Sb: 0-2.5%)
Since Sb has an effect of improving corrosion resistance, it may be contained. However, if Sb is contained excessively, the effect is saturated, and the cold forgeability and hydrogen embrittlement resistance may deteriorate. Therefore, the upper limit when Sb is contained is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.8% or less. In order to exhibit the above effect, the Sb content is preferably 0.01% or more, more preferably 0.05% or more.
(Ta:0~2.5%)
Taはミクロひずみを高めるC,Nの固定のために添加してもよい。一方、過剰にTaを添加すると粗大Ta系析出物などが形成し、冷間鍛造性と耐水素脆化特性が劣化する。そのため、Ta含有量の上限値を2.5%とし、好ましくは1.0%以下であり、更に好ましくは0.7%以下とし、更に好ましくは0.5%以下である。Taの好ましい下限は0.01%である。
(Ta: 0-2.5%)
Ta may be added for fixing C and N to enhance microstrain. On the other hand, if Ta is added excessively, coarse Ta-based precipitates and the like are formed, degrading cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Ta content is set to 2.5%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less. A preferable lower limit of Ta is 0.01%.
(Ca:0~0.05%)
Caは脱酸のため必要に応じて含有させてよい。一方、過剰にCaを添加すると粗大Ca系介在物などが形成し、冷間鍛造性と耐水素脆化特性が劣化する。そのため、Ca含有量の上限値を0.05%とし、好ましくは0.010%以下であり、更に好ましくは0.005%以下である。Caの好ましい下限は0.0002%である。
(Ca: 0-0.05%)
Ca may be contained as needed for deoxidation. On the other hand, if Ca is added excessively, coarse Ca-based inclusions and the like are formed, degrading cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Ca content is 0.05%, preferably 0.010% or less, and more preferably 0.005% or less. A preferable lower limit of Ca is 0.0002%.
(Mg:0~0.012%)
Mgは脱酸のため必要に応じて含有させてよい。一方、過剰にMgを添加すると粗大Mg系介在物などが形成し、冷間鍛造性と耐水素脆化特性が劣化する。そのため、Mg含有量の上限値を0.012%とし、好ましくは0.010%以下であり、更に好ましくは0.005%以下である。Mgの好ましい下限は0.0002%である。
(Mg: 0-0.012%)
Mg may be contained as necessary for deoxidation. On the other hand, if Mg is excessively added, coarse Mg-based inclusions and the like are formed, degrading cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Mg content is 0.012%, preferably 0.010% or less, and more preferably 0.005% or less. A preferred lower limit for Mg is 0.0002%.
(Zr:0~0.012%)
Zrは脱酸のため必要に応じて含有させてよい。一方、過剰にZrを添加すると粗大Zr系介在物などが形成し、冷間鍛造性と耐水素脆化特性が劣化する。そのため、Zr含有量の上限値を0.012%とし、好ましくは0.010%以下であり、更に好ましくは0.005%以下である。Zrの好ましい下限は0.0002%である。
(Zr: 0 to 0.012%)
Zr may be contained as necessary for deoxidation. On the other hand, if Zr is excessively added, coarse Zr-based inclusions and the like are formed, degrading cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Zr content is 0.012%, preferably 0.010% or less, and more preferably 0.005% or less. A preferable lower limit of Zr is 0.0002%.
(REM:0~0.05%)
REMは脱酸のため必要に応じて含有させてよい。一方、過剰にREMを添加すると粗大REM系介在物などが形成し、冷間鍛造性と耐水素脆化特性が劣化する。そのため、REM含有量の上限値を0.05%とし、好ましくは0.010%以下であり、更に好ましくは0.005%以下である。REMの好ましい下限は0.0002%である。
(REM: 0-0.05%)
REM may optionally be included for deacidification. On the other hand, if REM is excessively added, coarse REM inclusions and the like are formed, degrading cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the REM content is 0.05%, preferably 0.010% or less, and more preferably 0.005% or less. A preferred lower limit for REM is 0.0002%.
(Pb:0~0.30%)
Pbは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にPbを添加すると冷間鍛造性と耐水素脆化特性が劣化する。そのため、Pb含有量の上限値を0.30%とし、好ましくは0.10%以下であり、更に好ましくは0.05%以下である。Pbの好ましい下限は0.0001%である。
(Pb: 0 to 0.30%)
Pb is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of Pb deteriorates the cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Pb content is set to 0.30%, preferably 0.10% or less, and more preferably 0.05% or less. A preferable lower limit of Pb is 0.0001%.
(Se:0~0.80%)
Seは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にSeを添加すると冷間鍛造性と耐水素脆化特性が劣化する。そのため、Se含有量の上限値を0.80%とし、好ましくは0.1%以下であり、更に好ましくは0.05%以下である。Seの好ましい下限は0.0001%である。
(Se: 0 to 0.80%)
Se is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of Se deteriorates cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Se content is 0.80%, preferably 0.1% or less, and more preferably 0.05% or less. A preferred lower limit for Se is 0.0001%.
(Te:0~0.30%)
Teは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にTeを添加すると冷間鍛造性と耐水素脆化特性が劣化する。そのため、Te含有量の上限値を0.30%とし、好ましくは0.1%以下であり、更に好ましくは0.05%以下である。Teの好ましい下限は0.0001%である。
(Te: 0 to 0.30%)
Te is an element that enhances machinability and may be contained as necessary. On the other hand, if Te is added excessively, cold forgeability and hydrogen embrittlement resistance deteriorate. Therefore, the upper limit of the Te content is set to 0.30%, preferably 0.1% or less, and more preferably 0.05% or less. A preferable lower limit of Te is 0.0001%.
(Bi:0~0.50%)
Biは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にBiを添加すると冷間鍛造性と耐水素脆化特性が劣化する。そのため、Bi含有量の上限値を0.50%とし、好ましくは0.1%以下であり、更に好ましくは0.05%以下である。Biの好ましい下限は0.0001%である。
(Bi: 0 to 0.50%)
Bi is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of Bi degrades cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Bi content is 0.50%, preferably 0.1% or less, and more preferably 0.05% or less. A preferable lower limit of Bi is 0.0001%.
(S:0~0.50%)
Sは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にSを添加すると冷間鍛造性と耐水素脆化特性が劣化する。そのため、S含有量の上限値を0.50%とし、好ましくは0.1%以下であり、更に好ましくは0.05%以下である。Sの好ましい下限は0.0001%である。なお、Sは製鋼原料から混入する不純物として、通常は鋼中に含有している。
(S: 0-0.50%)
S is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of S degrades cold forgeability and resistance to hydrogen embrittlement. Therefore, the upper limit of the S content is 0.50%, preferably 0.1% or less, and more preferably 0.05% or less. A preferred lower limit for S is 0.0001%. Incidentally, S is usually contained in steel as an impurity mixed from steelmaking raw materials.
(P:0~0.30%)
Pは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にPを添加すると冷間鍛造性と耐水素脆化特性が劣化する。そのため、P含有量の上限値を0.30%とし、好ましくは0.1%以下であり、更に好ましくは0.05%以下である。Pの好ましい下限は0.0001%である。
(P: 0-0.30%)
P is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of P degrades cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the P content is 0.30%, preferably 0.1% or less, and more preferably 0.05% or less. A preferred lower limit for P is 0.0001%.
<第2発明>
《第2発明の鋼材へのホウ化物としての析出B量》
本発明者らは、ステンレス鋼材において、冷間鍛造性、切削性と冷間加工後の耐水素脆化特性のすべてを満足する手段として、鋼材へのホウ化物としての析出B量を制御することを着想した。冷間鍛造性について、ホウ化物形成によって固溶元素(Nなど)が低減し、軟質化する結果、冷間鍛造時の限界圧縮率が向上し、冷間鍛造性が改善する。また、ホウ化物が微細に析出するため割れの起点となりがたく、この点でも冷間鍛造性を改善する。切削性について、ホウ化物の潤滑作用によって切削時の工具寿命が長くなる。耐水素脆化特性について、ホウ化物形成によって軟質化し転位易動度が増すことに加え、ホウ化物が水素のトラップサイトとして寄与することで耐水素脆化特性が良好になる。そして、ホウ化物としての析出B量を0.0001質量%以上とすることにより、下記硫化物のアスペクト比の規定と相まって、冷間鍛造性、切削性と冷間加工後の耐水素脆化特性のすべてを満足することができる。
<Second invention>
<<Amount of precipitated B as borides on the steel material of the second invention>>
The inventors of the present invention have found that as a means of satisfying all of the cold forgeability, machinability, and resistance to hydrogen embrittlement after cold working in stainless steel materials, the amount of B precipitated as borides in steel materials is controlled. was conceived. With regard to cold forgeability, the formation of borides reduces solute elements (such as N) and softens the steel. In addition, since borides are finely precipitated, they are less likely to initiate cracks, which also improves the cold forgeability. Regarding machinability, the lubricating action of borides prolongs the tool life during cutting. Regarding the resistance to hydrogen embrittlement, the formation of borides softens the material and increases the mobility of dislocations. In addition, the borides contribute as trap sites for hydrogen, thereby improving the resistance to hydrogen embrittlement. By setting the amount of precipitated B as a boride to 0.0001% by mass or more, together with the definition of the aspect ratio of the sulfide described below, cold forgeability, machinability, and hydrogen embrittlement resistance after cold working can satisfy all of
鋼材中のホウ化物としての析出B量の評価については、鋼材に対し電解抽出残渣を行い、ホウ化物を抽出させ、ホウ化物のB量(Bpre)を測定することとして行うことができる。 The amount of B precipitated as borides in the steel can be evaluated by subjecting the steel to electrolytic extraction residue, extracting the borides, and measuring the amount of B (Bpre) in the borides.
《第2発明の鋼材中の硫化物のアスペクト比》
本発明者らは、ステンレス鋼において、冷間鍛造性、切削性と冷間加工後の耐水素脆化特性のすべてを満足する手段として、鋼材中の硫化物のアスペクト比を制御することを着想した。鋼材中の硫化物のアスペクト比が小さいと、破壊起点となりがたいため、冷間鍛造性と耐水素脆化特性が向上する。また、硫化物のアスペクト比が小さいと、潤滑作用が増し、工具寿命が長くなるため、切削性が向上する。そして、硫化物のアスペクト比が50以下であると、上記ホウ化物としての析出B量の規定と相まって、冷間鍛造性、切削性と冷間加工後の耐水素脆化特性のすべてを満足することができる。なお、アスペクト比とは、硫化物の圧延方向の長さ(L)と、硫化物の圧延方向と垂直方向の長さ(W)から、L/Wとして算出される値を意味する。
<<Aspect ratio of sulfide in the steel material of the second invention>>
The present inventors conceived the idea of controlling the aspect ratio of sulfides in steel materials as a means of satisfying all of the cold forgeability, machinability, and resistance to hydrogen embrittlement after cold working in stainless steel. bottom. When the aspect ratio of sulfides in the steel material is small, it is difficult to act as a fracture starting point, so cold forgeability and hydrogen embrittlement resistance are improved. Also, when the aspect ratio of the sulfide is small, the lubricating effect increases and the tool life increases, thus improving the machinability. When the aspect ratio of the sulfide is 50 or less, together with the regulation of the amount of precipitated B as the boride, all of cold forgeability, machinability, and hydrogen embrittlement resistance after cold working are satisfied. be able to. The aspect ratio means a value calculated as L/W from the length (L) of the sulfide in the rolling direction and the length (W) of the sulfide in the direction perpendicular to the rolling direction.
硫化物のアスペクト比の評価については、鋼材のL断面(鋼材の中心線を含む断面)において、表層部、中心部、および表層部と中心部との間に存在する1/4深さ位置部において、200倍の視野で、1視野以上測定を行い、光学顕微鏡から同視野の硫化物の上記アスペクト比L/Wの平均値を算出することとして行うことができる。 Regarding the evaluation of the aspect ratio of sulfide, in the L cross section of the steel material (the cross section including the center line of the steel material), the surface layer, the central part, and the 1/4 depth position part existing between the surface layer and the central part In , one or more fields of view are measured in a field of view of 200 times, and the average value of the aspect ratio L/W of the sulfides in the same field of view is calculated from an optical microscope.
《第2発明のステンレス鋼の成分組成》
次に、第2発明のステンレス鋼の成分組成について説明する。成分組成において、%は質量%を意味する。
<<Component composition of the stainless steel of the second invention>>
Next, the chemical composition of the stainless steel of the second invention will be explained. In the component composition, % means % by mass.
(B:0.0001~0.05%)
Bは、上記ホウ化物としての析出B量を確保するために必要である。Bを0.0001%以上含有することにより、後記製造方法の規定と相まって、ホウ化物としての析出B量を確保することができる。B含有量は、0.0005%以上であるとより好ましい。0.0020%以上であるとさらに好ましい。一方、B含有量が0.05%を超えると、鋼中に粗大ホウ化物が形成され、粗大ホウ化物が破壊の起点となるため、冷間鍛造性や切削性、耐水素脆化特性を劣化させるので、0.05%を上限とする。B含有量は、0.02%以下であるとより好ましい。0.015%以下であるとさらに好ましい。
(B: 0.0001 to 0.05%)
B is necessary in order to secure the amount of precipitated B as the boride. By containing 0.0001% or more of B, it is possible to ensure the amount of precipitated B as borides, coupled with the regulation of the manufacturing method described later. The B content is more preferably 0.0005% or more. More preferably, it is 0.0020% or more. On the other hand, if the B content exceeds 0.05%, coarse borides are formed in the steel, and the coarse borides become fracture starting points, so cold forgeability, machinability, and hydrogen embrittlement resistance deteriorate. Therefore, the upper limit is set to 0.05%. The B content is more preferably 0.02% or less. It is more preferably 0.015% or less.
(S:0.0001~0.50%)
Sは鋼中に硫化物を形成し、切削性を高める元素であり、0.0001%以上含有させる。一方、過剰にSを添加すると冷間鍛造性、切削性と耐水素脆化特性が劣化するため、上限値を0.50%とし、好ましくは0.1%以下であり、更に好ましくは0.05%以下である。なお、Sは製鋼原料から混入する不純物として、通常は鋼中に含有している。
(S: 0.0001 to 0.50%)
S is an element that forms sulfides in steel and improves machinability, and is contained in an amount of 0.0001% or more. On the other hand, if S is added excessively, cold forgeability, machinability, and resistance to hydrogen embrittlement deteriorate, so the upper limit is made 0.50%, preferably 0.1% or less, more preferably 0.5%. 05% or less. Incidentally, S is usually contained in steel as an impurity mixed from steelmaking raw materials.
(Al:0.001~2.0%、Ca:0.0001~0.05%から選択される一種以上)
第2発明のステンレス鋼は、Al:0.001~2.0%、Ca:0.0001~0.05%から選択される一種以上を含有する。AlとCaの一種以上を上記下限値以上に含有することにより、AlもしくはCa系の酸化物を形成し、上記Sの含有及び後記製造方法の規定と相まって、硫化物の核となり、微細な硫化物を形成させ、圧延後の硫化物のアスペクト比を50以下とすることができる。
過剰にAlを添加すると、粗大AlNなどが形成し、冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、Al含有量の上限値を2.0%とし、好ましくは1.0%以下であり、更に好ましくは0.5%以下、更に好ましくは0.05%以下とする。
過剰にCaを添加すると粗大Ca系介在物などが形成し、その周辺に形成される硫化物も大きくなり、圧延時に硫化物が展伸することで硫化物のアスペクト比が大きくなるとともに、冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、Ca含有量の上限値を0.05%とする。Caは好ましくは0.010%以下であり、更に好ましくは0.005%以下である。
Al、Caをともに含有しない、あるいは下限値を外れると、硫化物のアスペクト比が本発明範囲から外れ、引張強さ、限界圧縮率、切削性、冷間加工後の相対引張強さと絞りが不良となる。
(At least one selected from Al: 0.001 to 2.0% and Ca: 0.0001 to 0.05%)
The stainless steel of the second invention contains one or more selected from Al: 0.001 to 2.0% and Ca: 0.0001 to 0.05%. By containing one or more of Al and Ca in an amount equal to or higher than the above lower limit, an Al- or Ca-based oxide is formed, and together with the above-mentioned content of S and the provisions of the production method described later, it becomes the nucleus of sulfide and fine sulfidation. The aspect ratio of the sulfide after rolling can be 50 or less.
Excessive addition of Al forms coarse AlN and the like, deteriorating cold forgeability, machinability, and resistance to hydrogen embrittlement. Therefore, the upper limit of the Al content is set to 2.0%, preferably 1.0% or less, more preferably 0.5% or less, further preferably 0.05% or less.
When excessive Ca is added, coarse Ca-based inclusions and the like are formed, and the sulfides formed around them also become large. Forgeability, machinability and resistance to hydrogen embrittlement deteriorate. Therefore, the upper limit of Ca content is set to 0.05%. Ca is preferably 0.010% or less, more preferably 0.005% or less.
If neither Al nor Ca is contained, or if the lower limit is exceeded, the aspect ratio of the sulfide will be outside the range of the present invention, and the tensile strength, critical compressibility, machinability, relative tensile strength after cold working, and drawing will be poor. becomes.
(C:0.0010~0.15%)
Cは加工誘起マルテンサイトの形成を抑制し、耐水素脆化特性を高めるため、0.0010%以上とする。過剰にCを添加すると、冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、C含有量の上限値を0.15%とし、好ましくは0.12%以下であり、更に好ましくは0.05%以下とし、更に好ましくは0.02%以下とする。C上限を0.15%未満とすると好ましい。
(C: 0.0010 to 0.15%)
C is made 0.0010% or more in order to suppress the formation of deformation-induced martensite and improve hydrogen embrittlement resistance. Excessive addition of C degrades cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the C content is set to 0.15%, preferably 0.12% or less, more preferably 0.05% or less, still more preferably 0.02% or less. It is preferable to set the upper limit of C to less than 0.15%.
(Si:0.01~2.00%)
Siは脱酸元素として添加し、0.01%以上とする。過剰にSiを添加すると、冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、Si含有量の上限値を2.0%とし、好ましくは1.2%以下であり、更に好ましくは0.6%以下とし、更に好ましくは0.5%以下とする。
(Si: 0.01 to 2.00%)
Si is added as a deoxidizing element to be 0.01% or more. Excessive addition of Si deteriorates cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the Si content is set to 2.0%, preferably 1.2% or less, more preferably 0.6% or less, still more preferably 0.5% or less.
(Mn:0.01~10.00%)
Mnは加工誘起マルテンサイトの形成を抑制し、耐水素脆化特性を高めるため、0.01%以上とする。過剰にMnを添加すると、冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、Mn含有量の上限値を10.0%とし、好ましくは2.5%以下であり、更に好ましくは1.5%以下とし、更に好ましくは1.0%以下とする。
(Mn: 0.01 to 10.00%)
Mn is made 0.01% or more in order to suppress the formation of deformation-induced martensite and improve hydrogen embrittlement resistance. Excessive addition of Mn deteriorates cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the Mn content is set to 10.0%, preferably 2.5% or less, more preferably 1.5% or less, still more preferably 1.0% or less.
(Ni:8.00~30.00%)
Niは加工誘起マルテンサイトの形成を抑制し、耐水素脆化特性を高める。また、冷間鍛造性を高めるため、Ni含有量を8.00%以上とする。好ましくは10.00%以上であり、更に好ましくは13.00%以上であり、更に好ましくは15.00%以上である。過剰にNiを添加すると、逆に冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、Ni含有量の上限値を30.00%とし、好ましくは25.00%以下とする。
(Ni: 8.00-30.00%)
Ni suppresses the formation of deformation-induced martensite and enhances hydrogen embrittlement resistance. Moreover, in order to improve cold forgeability, the Ni content is set to 8.00% or more. It is preferably 10.00% or more, more preferably 13.00% or more, and still more preferably 15.00% or more. If Ni is added excessively, cold forgeability, machinability and resistance to hydrogen embrittlement deteriorate. Therefore, the upper limit of the Ni content is 30.00%, preferably 25.00% or less.
(Cr:9.0~21.0%)
Crは加工誘起マルテンサイトの形成を抑制し、耐水素脆化特性を高める。また、耐食性を高めるため、Cr含有量を9.0%以上とする。好ましくは10.5%以上である。過剰にCrを添加すると、冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、Cr含有量の上限値を21.0%とし、好ましくは19.5%以下であり、更に好ましくは15.0%以下である。
(Cr: 9.0 to 21.0%)
Cr suppresses the formation of deformation-induced martensite and enhances hydrogen embrittlement resistance. Moreover, in order to improve corrosion resistance, the Cr content is set to 9.0% or more. Preferably it is 10.5% or more. Excessive addition of Cr deteriorates cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the Cr content is set to 21.0%, preferably 19.5% or less, more preferably 15.0% or less.
(Mo:0.01~3.00%)
Moは加工誘起マルテンサイトの形成を抑制し、耐水素脆化特性を高める。また、耐食性を高めることに加え、冷間鍛造性を高めるため、Mo含有量を0.01%以上とする。過剰にMoを添加すると、逆に冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、Mo含有量の上限値を3.0%とし、好ましくは2.8%以下であり、更に好ましくは2.5%以下であり、更に好ましくは1.0%以下である。
(Mo: 0.01 to 3.00%)
Mo suppresses the formation of deformation-induced martensite and enhances hydrogen embrittlement resistance. In addition to improving corrosion resistance, the Mo content is set to 0.01% or more in order to improve cold forgeability. Excessive addition of Mo deteriorates cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the Mo content is 3.0%, preferably 2.8% or less, more preferably 2.5% or less, and even more preferably 1.0% or less.
(Cu:0.01~5.00%)
Cuは加工誘起マルテンサイトの形成を抑制し、耐水素脆化特性を高める。また、冷間鍛造性を高めるため、Cu含有量を0.01%以上とする。好ましくは1.00%以上であり、更に好ましくは2.00%以上である。過剰にCuを添加すると、逆に冷間鍛造性、切削性と耐水素脆化特性が劣化し、また、熱間脆性を引き起こす。そのため、Cu含有量の上限値を5.00%とし、好ましくは3.50%以下とする。
(Cu: 0.01 to 5.00%)
Cu suppresses the formation of deformation-induced martensite and enhances hydrogen embrittlement resistance. Moreover, in order to improve the cold forgeability, the Cu content is made 0.01% or more. It is preferably 1.00% or more, more preferably 2.00% or more. Excessive addition of Cu deteriorates cold forgeability, machinability and resistance to hydrogen embrittlement, and causes hot shortness. Therefore, the upper limit of the Cu content is set to 5.00%, preferably 3.50% or less.
(N:0.0010~0.10%)
Nは加工誘起マルテンサイトの形成を抑制し、耐水素脆化特性を高めるため、0.0010%以上とする。過剰にNを添加すると、冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、N含有量の上限値を0.10%とし、好ましくは0.08%以下であり、更に好ましくは0.05%以下とし、更に好ましくは0.03%以下とする。
(N: 0.0010 to 0.10%)
N is made 0.0010% or more in order to suppress the formation of deformation-induced martensite and improve hydrogen embrittlement resistance. Excessive addition of N degrades cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the N content is set to 0.10%, preferably 0.08% or less, more preferably 0.05% or less, still more preferably 0.03% or less.
第2発明のステンレス鋼は、上記成分を含有し、残部はFe及び不純物である。さらに、下記成分から選択される一種以上を含有することとしても良い。 The stainless steel of the second invention contains the above components, and the balance is Fe and impurities. Furthermore, it may contain one or more selected from the following components.
(Ti:0~2.00%)
Tiはミクロひずみを高めるC,Nの固定のために添加してもよい。一方、過剰にTiを添加すると粗大Ti系析出物などが形成し、冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、Ti含有量の上限値を2.00%とし、好ましくは1.0%以下であり、更に好ましくは0.7%以下とし、更に好ましくは0.5以下である。Tiの好ましい下限は0.01%以上であり、更に好ましくは0.05%以上である。
(Ti: 0 to 2.00%)
Ti may be added for fixing C and N which enhance microstrain. On the other hand, if Ti is added excessively, coarse Ti-based precipitates and the like are formed, degrading cold forgeability, machinability, and resistance to hydrogen embrittlement. Therefore, the upper limit of the Ti content is set to 2.00%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less. A preferable lower limit of Ti is 0.01% or more, more preferably 0.05% or more.
(Nb:0~2.00%)
NbはC,Nの固定のために添加してもよい。一方、過剰にNbを添加すると粗大Nb系析出物などが形成し、冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、Nb含有量の上限値を2.00%とし、好ましくは1.0%以下であり、更に好ましくは0.7%以下とし、更に好ましくは0.5以下である。Nbの好ましい下限は0.01%以上であり、更に好ましくは0.05%以上である。
(Nb: 0 to 2.00%)
Nb may be added for fixing C and N. On the other hand, if Nb is added excessively, coarse Nb-based precipitates and the like are formed, deteriorating cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the Nb content is set to 2.00%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less. A preferable lower limit of Nb is 0.01% or more, more preferably 0.05% or more.
(Sn:0~2.5%)
Snは、耐食性を向上させるのに有効な元素であるため、含有させてもよい。しかしながら、Snを過剰に含有させると、その効果は飽和し、逆に冷間鍛造性、切削性と耐水素脆化特性が劣化するおそれがある。そのため、Snを含有させる場合の上限を2.5%とする。より好ましくは、1.0%以下であり、更に好ましくは0.2%以下である。前記効果を発現させるには、Sn量を0.0001%以上が好ましく、0.01%以上とすることが更に好ましい。より好ましくは、0.05%以上である。
(Sn: 0-2.5%)
Since Sn is an effective element for improving corrosion resistance, it may be contained. However, if Sn is contained excessively, the effect is saturated, and cold forgeability, machinability, and resistance to hydrogen embrittlement may deteriorate. Therefore, the upper limit of the content of Sn is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.2% or less. In order to exhibit the above effects, the Sn content is preferably 0.0001% or more, more preferably 0.01% or more. More preferably, it is 0.05% or more.
(V:0~2.0%)
VはC,Nの固定のために添加してもよい。一方、過剰にVを添加すると粗大V系析出物などが形成し、冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、V含有量の上限値を2.0%とし、好ましくは1.0%以下であり、更に好ましくは0.7%以下とし、更に好ましくは0.5%以下である。Vの好ましい下限は0.001%である。
(V: 0-2.0%)
V may be added for fixing C and N. On the other hand, excessive addition of V forms coarse V-based precipitates and the like, deteriorating cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the V content is 2.0%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less. A preferable lower limit of V is 0.001%.
(W:0~3.0%)
Wは、耐食性を向上させるのに有効な元素であるため、含有させてもよい。しかしながら、Wを過剰に含有させると、その効果は飽和し、逆に冷間鍛造性、切削性と耐水素脆化特性が劣化するおそれがある。そのため、Wを含有させる場合の上限を3.0%とする。より好ましくは、2.0%以下であり、更に好ましくは1.5%以下である。前記効果を発現させるには、W量を0.05%以上とすることが好ましい。より好ましくは、0.10%以上である。
(W: 0-3.0%)
Since W is an effective element for improving corrosion resistance, it may be contained. However, if W is contained excessively, the effect is saturated, and cold forgeability, machinability, and resistance to hydrogen embrittlement may deteriorate. Therefore, when W is contained, the upper limit is set to 3.0%. More preferably, it is 2.0% or less, and still more preferably 1.5% or less. In order to exhibit the above effects, it is preferable to set the W amount to 0.05% or more. More preferably, it is 0.10% or more.
(Ga:0~0.05%)
Gaは、耐食性を向上させるのに有効な元素であるため、含有させてもよい。しかしながら、Gaを過剰に含有させると、その効果は飽和し、逆に冷間鍛造性、切削性と耐水素脆化特性が劣化するおそれがある。そのため、Gaを含有させる場合の上限を、0.05%とする。前記効果を発現させるには、Ga量を0.0004%以上とすることが好ましい。
(Ga: 0 to 0.05%)
Ga is an effective element for improving corrosion resistance, so it may be contained. However, if Ga is contained excessively, the effect is saturated, and the cold forgeability, machinability, and resistance to hydrogen embrittlement may deteriorate. Therefore, the upper limit when Ga is contained is set to 0.05%. In order to exhibit the above effect, it is preferable to set the amount of Ga to 0.0004% or more.
(Co:0~2.5%)
Coは、耐食性を向上させる効果を有するため、含有させてもよい。しかしながら、Coを過剰に含有させると、その効果は飽和し、逆に冷間鍛造性、切削性と耐水素脆化特性が劣化するおそれがある。そのため、Coを含有させる場合の上限を2.5%とする。より好ましくは、1.0%以下であり、更に好ましくは0.8%以下である。前記効果を発現させるには、Co量を0.05%以上とすることが好ましく、0.10%以上含有させることがより好ましい。
(Co: 0-2.5%)
Co has the effect of improving the corrosion resistance, so it may be contained. However, if Co is contained excessively, the effect is saturated, and cold forgeability, machinability, and resistance to hydrogen embrittlement may deteriorate. Therefore, the upper limit of the content of Co is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.8% or less. In order to exhibit the above effects, the Co content is preferably 0.05% or more, more preferably 0.10% or more.
(Sb:0~2.5%)
Sbは、耐食性を向上させる効果を有するため、含有させてもよい。しかしながら、Sbを過剰に含有させると、その効果は飽和し、逆に冷間鍛造性、切削性と耐水素脆化特性が劣化するおそれがある。そのため、Sbを含有させる場合の上限を2.5%とする。より好ましくは、1.0%以下であり、更に好ましくは0.8%以下である。前記効果を発現させるには、Sb量を0.01%以上とすることが好ましく、0.05%以上含有させることがより好ましい。
(Sb: 0-2.5%)
Since Sb has an effect of improving corrosion resistance, it may be contained. However, if Sb is contained excessively, the effect is saturated, and cold forgeability, machinability, and resistance to hydrogen embrittlement may deteriorate. Therefore, the upper limit when Sb is contained is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.8% or less. In order to exhibit the above effect, the Sb content is preferably 0.01% or more, more preferably 0.05% or more.
(Ta:0~2.5%)
TaはC,Nの固定のために添加してもよい。一方、過剰にTaを添加すると粗大Ta系析出物などが形成し、冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、Ta含有量の上限値を2.5%とし、好ましくは1.0%以下であり、更に好ましくは0.7%以下とし、更に好ましくは0.5%以下である。Taの好ましい下限は0.01%である。
(Ta: 0-2.5%)
Ta may be added for fixing C and N. On the other hand, if Ta is added excessively, coarse Ta-based precipitates and the like are formed, degrading cold forgeability, machinability, and hydrogen embrittlement resistance. Therefore, the upper limit of the Ta content is set to 2.5%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less. A preferable lower limit of Ta is 0.01%.
(Mg:0~0.012%)
Mgは脱酸のため必要に応じて含有させてよい。一方、過剰にMgを添加すると粗大Mg系介在物などが形成し、冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、Mg含有量の上限値を0.012%とし、好ましくは0.010%以下であり、更に好ましくは0.005%以下である。Mgの好ましい下限は0.0002%である。
(Mg: 0-0.012%)
Mg may be contained as necessary for deoxidation. On the other hand, if Mg is excessively added, coarse Mg-based inclusions and the like are formed, deteriorating cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the Mg content is 0.012%, preferably 0.010% or less, and more preferably 0.005% or less. A preferred lower limit for Mg is 0.0002%.
(Zr:0~0.012%)
Zrは脱酸のため必要に応じて含有させてよい。一方、過剰にZrを添加すると粗大Zr系介在物などが形成し、冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、Zr含有量の上限値を0.012%とし、好ましくは0.010%以下であり、更に好ましくは0.005%以下である。Zrの好ましい下限は0.0002%である。
(Zr: 0 to 0.012%)
Zr may be contained as necessary for deoxidation. On the other hand, if Zr is added excessively, coarse Zr-based inclusions and the like are formed, degrading cold forgeability, machinability, and resistance to hydrogen embrittlement. Therefore, the upper limit of the Zr content is 0.012%, preferably 0.010% or less, and more preferably 0.005% or less. A preferable lower limit of Zr is 0.0002%.
(REM:0~0.05%)
REMは脱酸のため必要に応じて含有させてよい。一方、過剰にREMを添加すると粗大REM系介在物などが形成し、冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、REM含有量の上限値を0.05%とし、好ましくは0.010%以下であり、更に好ましくは0.005%以下である。REMの好ましい下限は0.0002%である。
(REM: 0-0.05%)
REM may optionally be included for deacidification. On the other hand, if REM is added excessively, coarse REM inclusions and the like are formed, deteriorating cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the REM content is 0.05%, preferably 0.010% or less, and more preferably 0.005% or less. A preferred lower limit for REM is 0.0002%.
(Pb:0~0.30%)
Pbは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にPbを添加すると冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、Pb含有量の上限値を0.30%とし、好ましくは0.10%以下であり、更に好ましくは0.05%以下である。Pbの好ましい下限は0.0001%である。
(Pb: 0 to 0.30%)
Pb is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of Pb deteriorates cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the Pb content is set to 0.30%, preferably 0.10% or less, and more preferably 0.05% or less. A preferable lower limit of Pb is 0.0001%.
(Se:0~0.80%)
Seは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にSeを添加すると冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、Se含有量の上限値を0.80%とし、好ましくは0.1%以下であり、更に好ましくは0.05%以下である。Seの好ましい下限は0.0001%である。
(Se: 0 to 0.80%)
Se is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of Se deteriorates cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the Se content is 0.80%, preferably 0.1% or less, and more preferably 0.05% or less. A preferred lower limit for Se is 0.0001%.
(Te:0~0.30%)
Teは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にTeを添加すると冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、Te含有量の上限値を0.30%とし、好ましくは0.1%以下であり、更に好ましくは0.05%以下である。Teの好ましい下限は0.0001%である。
(Te: 0 to 0.30%)
Te is an element that enhances machinability and may be contained as necessary. On the other hand, if Te is added excessively, cold forgeability, machinability and resistance to hydrogen embrittlement deteriorate. Therefore, the upper limit of the Te content is set to 0.30%, preferably 0.1% or less, and more preferably 0.05% or less. A preferable lower limit of Te is 0.0001%.
(Bi:0~0.50%)
Biは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にBiを添加すると冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、Bi含有量の上限値を0.50%とし、好ましくは0.1%以下であり、更に好ましくは0.05%以下である。Biの好ましい下限は0.0001%である。
(Bi: 0 to 0.50%)
Bi is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of Bi degrades cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the Bi content is 0.50%, preferably 0.1% or less, and more preferably 0.05% or less. A preferable lower limit of Bi is 0.0001%.
(P:0~0.30%)
Pは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にPを添加すると冷間鍛造性、切削性と耐水素脆化特性が劣化する。そのため、P含有量の上限値を0.30%とし、好ましくは0.1%以下であり、更に好ましくは0.05%以下である。Pの好ましい下限は0.0001%である。
(P: 0-0.30%)
P is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of P degrades cold forgeability, machinability and resistance to hydrogen embrittlement. Therefore, the upper limit of the P content is 0.30%, preferably 0.1% or less, and more preferably 0.05% or less. A preferred lower limit for P is 0.0001%.
<第3発明>
《第3発明のステンレス鋼のB粒界占有率》
本発明者らは、ステンレス鋼、特に棒状鋼材において、耐食性と冷間鍛造性、冷間加工後の非磁性特性を満足する手段として、鋼材のB粒界占有率を制御することを着想した。B粒界占有率(%)とは、全結晶粒界(A)に対し有限B量の存在する結晶粒界(B)が占める割合(B/A×100)である。B粒界占有率が大きいと、粒界Cr系析出物によるCr欠乏領域に対し不働態化を促進し耐食性が向上し、粒界での塑性変形が容易となり冷間鍛造性が向上し、粒界での局所変形が抑制され磁性相の加工誘起α’マルテンサイトの生成を抑制し非磁性を保つことを着想した。
<Third invention>
<<B Grain Boundary Occupancy of the Stainless Steel of the Third Invention>>
The present inventors came up with the idea of controlling the B grain boundary occupancy of stainless steel, particularly bar steel, as a means of satisfying corrosion resistance, cold forgeability, and non-magnetic properties after cold working. The B grain boundary occupation ratio (%) is the ratio (B/A×100) occupied by the grain boundaries (B) in which a finite amount of B exists with respect to all the grain boundaries (A). When the B grain boundary occupancy is large, passivation is promoted in the Cr-deficient region due to grain boundary Cr-based precipitates, improving corrosion resistance, facilitating plastic deformation at grain boundaries, and improving cold forgeability. It was conceived that the local deformation in the field is suppressed, suppressing the formation of deformation-induced α'-martensite in the magnetic phase, and maintaining the non-magnetism.
B粒界占有率の評価はEPMA解析で測定した。鋼材のL断面(棒状鋼材であればその中心線を含む断面)において、任意視野領域における結晶粒界の総長さ(A)を測定し、次いで同視野においてB濃度の面分析を行い、粒内母相に比べ高B濃度となる粒界をB粒界占有と定義し、B粒界占有の長さ(B)を算出し、上記式よりB粒界占有率を算出した。 The evaluation of the B grain boundary occupation rate was measured by EPMA analysis. In the L cross section of the steel material (the cross section including the center line if it is a bar steel material), the total length (A) of the grain boundary in an arbitrary field of view is measured. A grain boundary having a higher B concentration than the parent phase was defined as a B grain boundary occupancy, the B grain boundary occupancy length (B) was calculated, and the B grain boundary occupancy was calculated from the above formula.
そして、鋼材のB粒界占有率が1%以上であれば、上記目標とする、耐食性と冷間鍛造性と冷間加工後の非磁性特性を満足できることが判明した。B粒界占有率が平均で5%以上であればより好ましく、15%以上は更に好ましく、20%以上が更に好ましい。 It was also found that if the B grain boundary occupation ratio of the steel material is 1% or more, the above-mentioned targets of corrosion resistance, cold forgeability, and non-magnetic properties after cold working can be satisfied. The average B grain boundary occupation rate is more preferably 5% or more, more preferably 15% or more, and even more preferably 20% or more.
《第3発明のステンレス鋼の成分組成》
次に、第3発明のステンレス鋼の成分組成について説明する。成分組成において、%は質量%を意味する。
<<Component composition of the stainless steel of the third invention>>
Next, the chemical composition of the stainless steel of the third invention will be explained. In the component composition, % means % by mass.
(C:0.0010~0.15%)
Cは加工誘起マルテンサイトの形成を抑制し、非磁性特性を高めるため、0.0010%以上とする。過剰にCを添加すると、B粒界占有率を下げ、耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、C含有量の上限値を0.15%とし、好ましくは0.12%以下であり、更に好ましくは0.05%以下とし、更に好ましくは0.02%以下とする。C上限を0.15%未満とすると好ましい。
(C: 0.0010 to 0.15%)
C is made 0.0010% or more in order to suppress the formation of deformation-induced martensite and improve non-magnetic properties. Excessive addition of C lowers the B grain boundary occupancy and deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the C content is set to 0.15%, preferably 0.12% or less, more preferably 0.05% or less, still more preferably 0.02% or less. It is preferable to set the upper limit of C to less than 0.15%.
(Si:0.01~2.00%)
Siは脱酸元素として添加し、0.01%以上とする。過剰にSiを添加すると、B粒界占有率を下げ、耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、Si含有量の上限値を2.0%とし、好ましくは1.2%以下であり、更に好ましくは0.6%以下とし、更に好ましくは0.5%以下とする。
(Si: 0.01 to 2.00%)
Si is added as a deoxidizing element to be 0.01% or more. Excessive addition of Si lowers the B grain boundary occupancy and deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Si content is set to 2.0%, preferably 1.2% or less, more preferably 0.6% or less, still more preferably 0.5% or less.
(Mn:0.01~10.00%)
Mnは加工誘起マルテンサイトの形成を抑制し、非磁性特性を高めるため、0.01%以上とする。過剰にMnを添加すると、B粒界占有率を下げ、耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、Mn含有量の上限値を10.0%とし、好ましくは2.5%以下であり、更に好ましくは1.5%以下とし、更に好ましくは1.0%以下とする。
(Mn: 0.01 to 10.00%)
Mn is made 0.01% or more in order to suppress the formation of deformation-induced martensite and improve non-magnetic properties. Excessive addition of Mn lowers the B grain boundary occupancy and deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Mn content is set to 10.0%, preferably 2.5% or less, more preferably 1.5% or less, still more preferably 1.0% or less.
(Ni:8.00~30.00%)
Niは加工誘起マルテンサイトの形成を抑制し、非磁性特性を高める。また、冷間鍛造性を高めるため、Ni含有量を8.00%以上とする。好ましくは10.00%以上であり、更に好ましくは13.00%以上であり、更に好ましくは15.00%以上である。過剰にNiを添加すると、B粒界占有率を下げ、耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、Ni含有量の上限値を30.00%とし、好ましくは25.00%以下とする。
(Ni: 8.00-30.00%)
Ni suppresses the formation of deformation-induced martensite and enhances non-magnetic properties. Moreover, in order to improve cold forgeability, the Ni content is set to 8.00% or more. It is preferably 10.00% or more, more preferably 13.00% or more, and still more preferably 15.00% or more. Excessive addition of Ni lowers the B grain boundary occupancy and deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Ni content is 30.00%, preferably 25.00% or less.
(Cr:9.0~21.0%)
Crは加工誘起マルテンサイトの形成を抑制し、非磁性特性を高める。また、耐食性を高めるため、Cr含有量を9.0%以上とする。好ましくは10.5%以上である。過剰にCrを添加すると、B粒界占有率を下げ、耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、Cr含有量の上限値を21.0%とし、好ましくは19.5%以下であり、更に好ましくは15.0%以下である。
(Cr: 9.0 to 21.0%)
Cr suppresses the formation of deformation-induced martensite and enhances non-magnetic properties. Moreover, in order to improve corrosion resistance, the Cr content is set to 9.0% or more. Preferably it is 10.5% or more. Excessive addition of Cr lowers the B grain boundary occupancy and deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Cr content is set to 21.0%, preferably 19.5% or less, more preferably 15.0% or less.
(Mo:0.01~3.00%)
Moは加工誘起マルテンサイトの形成を抑制し、非磁性特性を高める。また、耐食性を高めることに加え、冷間鍛造性を高めるため、Mo含有量を0.01%以上とする。過剰にMoを添加すると、B粒界占有率を下げ、耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、Mo含有量の上限値を3.0%とし、好ましくは2.8%以下であり、更に好ましくは2.5%以下であり、更に好ましくは1.0%以下である。
(Mo: 0.01 to 3.00%)
Mo suppresses the formation of deformation-induced martensite and enhances non-magnetic properties. In addition to improving corrosion resistance, the Mo content is set to 0.01% or more in order to improve cold forgeability. Excessive addition of Mo lowers the B grain boundary occupancy and deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Mo content is 3.0%, preferably 2.8% or less, more preferably 2.5% or less, and even more preferably 1.0% or less.
(Cu:0.01~5.00%)
Cuは加工誘起マルテンサイトの形成を抑制し、非磁性特性を高める。また、冷間鍛造性を高めるため、Cu含有量を0.01%以上とする。好ましくは1.00%以上であり、更に好ましくは2.00%以上である。過剰にCuを添加すると、B粒界占有率を下げ、耐食性と冷間鍛造性、非磁性特性が劣化し、また、熱間脆性を引き起こす。そのため、Cu含有量の上限値を5.00%とし、好ましくは3.50%以下とする。
(Cu: 0.01 to 5.00%)
Cu suppresses the formation of deformation-induced martensite and enhances non-magnetic properties. Moreover, in order to improve the cold forgeability, the Cu content is made 0.01% or more. It is preferably 1.00% or more, more preferably 2.00% or more. Excessive addition of Cu lowers the B grain boundary occupancy, degrades corrosion resistance, cold forgeability, and non-magnetic properties, and causes hot shortness. Therefore, the upper limit of the Cu content is set to 5.00%, preferably 3.50% or less.
(N:0.0010~0.10%)
Nは加工誘起マルテンサイトの形成を抑制し、非磁性特性を高めるため、0.0010%以上とする。過剰にNを添加すると、B粒界占有率を下げ、耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、N含有量の上限値を0.10%とし、好ましくは0.08%以下であり、更に好ましくは0.05%以下とし、更に好ましくは0.03%以下とする。
(N: 0.0010 to 0.10%)
N is made 0.0010% or more in order to suppress the formation of deformation-induced martensite and improve non-magnetic properties. Excessive addition of N lowers the B grain boundary occupancy and deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the N content is set to 0.10%, preferably 0.08% or less, more preferably 0.05% or less, still more preferably 0.03% or less.
(B:0.0001~0.05%)
BはB粒界占有率を高める主元素であり、耐食性と冷間鍛造性、非磁性特性を高めるため、0.0001%以上とする。好ましくは0.0005%以上である。過剰にBを添加すると、粗大B系析出物などが形成し、逆に耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、B含有量の上限値を0.05%とし、好ましくは0.02%以下であり、更に好ましくは0.015%以下とする。
(B: 0.0001 to 0.05%)
B is the main element that increases the B grain boundary occupation ratio, and is made 0.0001% or more in order to improve corrosion resistance, cold forgeability, and non-magnetic properties. Preferably it is 0.0005% or more. Excessive addition of B causes the formation of coarse B-based precipitates and conversely deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the B content is set to 0.05%, preferably 0.02% or less, and more preferably 0.015% or less.
第3発明のステンレス鋼は、上記成分を含有し、残部はFe及び不純物である。さらに、下記成分から選択される一種以上を含有することとしても良い。 The stainless steel of the third invention contains the above components, and the balance is Fe and impurities. Furthermore, it may contain one or more selected from the following components.
(Al:0~2.0%)
AlはB粒界占有率を下げるNの固定のために添加してもよい。一方、過剰にAlを添加すると粗大Al系析出物などが形成し、耐食性と冷間鍛造性と非磁性特性が劣化する。そのため、Al含有量の上限値を2.0%とし、好ましくは1.0%以下であり、更に好ましくは0.5%以下、更に好ましくは0.05%以下とする。Alの好ましい下限は0.001%以上である。
(Al: 0-2.0%)
Al may be added for fixing N which lowers the B grain boundary occupancy. On the other hand, if Al is added excessively, coarse Al-based precipitates are formed, and corrosion resistance, cold forgeability, and non-magnetic properties deteriorate. Therefore, the upper limit of the Al content is set to 2.0%, preferably 1.0% or less, more preferably 0.5% or less, further preferably 0.05% or less. A preferable lower limit of Al is 0.001% or more.
(Ti:0~2.00%)
TiはB粒界占有率を下げるC,Nの固定のために添加してもよい。一方、過剰にTiを添加すると粗大Ti系析出物などが形成し、耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、Ti含有量の上限値を2.00%とし、好ましくは1.0%以下であり、更に好ましくは0.7%以下とし、更に好ましくは0.5以下である。Tiの好ましい下限は0.01%以上であり、更に好ましくは0.05%以上である。
(Ti: 0 to 2.00%)
Ti may be added for fixing C and N which lowers the B grain boundary occupancy. On the other hand, if Ti is added excessively, coarse Ti-based precipitates and the like are formed, degrading corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Ti content is set to 2.00%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less. A preferable lower limit of Ti is 0.01% or more, more preferably 0.05% or more.
(Nb:0~2.00%)
NbはB粒界占有率を下げるC,Nの固定のために添加してもよい。一方、過剰にTiを添加すると粗大Nb系析出物などが形成し、耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、Nb含有量の上限値を2.00%とし、好ましくは1.0%以下であり、更に好ましくは0.7%以下とし、更に好ましくは0.5以下である。Nbの好ましい下限は0.01%以上であり、更に好ましくは0.05%以上である。
(Nb: 0 to 2.00%)
Nb may be added for fixing C and N which lowers the B grain boundary occupancy. On the other hand, if Ti is added excessively, coarse Nb-based precipitates and the like are formed, degrading corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Nb content is set to 2.00%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less. A preferable lower limit of Nb is 0.01% or more, more preferably 0.05% or more.
(Sn:0~2.5%)
Snは、耐食性を向上させるのに有効な元素であるため、含有させてもよい。しかしながら、Snを過剰に含有させると、その効果は飽和し、逆に耐食性と冷間鍛造性、非磁性特性が劣化するおそれがある。そのため、Snを含有させる場合の上限を2.5%とする。より好ましくは、1.0%以下であり、更に好ましくは0.2%以下である。前記効果を発現させるには、Sn量を0.0001%以上が好ましく、0.01%以上とすることが更に好ましい。より好ましくは、0.05%以上である。
(Sn: 0-2.5%)
Since Sn is an effective element for improving corrosion resistance, it may be contained. However, excessive Sn content saturates the effect, and conversely, the corrosion resistance, cold forgeability, and non-magnetic properties may deteriorate. Therefore, the upper limit of the content of Sn is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.2% or less. In order to exhibit the above effects, the Sn content is preferably 0.0001% or more, more preferably 0.01% or more. More preferably, it is 0.05% or more.
(V:0~2.0%)
VはB粒界占有率を下げるC,Nの固定のために添加してもよい。一方、過剰にVを添加すると粗大V系析出物などが形成し、耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、V含有量の上限値を2.0%とし、好ましくは1.0%以下であり、更に好ましくは0.7%以下とし、更に好ましくは0.5以下である。Vの好ましい下限は0.001%である。
(V: 0-2.0%)
V may be added for fixing C and N which lower the B grain boundary occupation rate. On the other hand, excessive addition of V forms coarse V-based precipitates and the like, deteriorating corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the V content is set to 2.0%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less. A preferable lower limit of V is 0.001%.
(W:0~3.0%)
Wは、耐食性を向上させるのに有効な元素であるため、含有させてもよい。しかしながら、Wを過剰に含有させると、その効果は飽和し、逆に耐食性と冷間鍛造性、非磁性特性が劣化するおそれがある。そのため、Wを含有させる場合の上限を3.0%とする。より好ましくは、2.0%以下であり、更に好ましくは1.5%以下である。前記効果を発現させるには、W量を0.05%以上とすることが好ましい。より好ましくは、0.10%以上である。
(W: 0-3.0%)
Since W is an effective element for improving corrosion resistance, it may be contained. However, if W is contained excessively, the effect is saturated, and the corrosion resistance, cold forgeability, and non-magnetic properties may deteriorate. Therefore, when W is contained, the upper limit is set to 3.0%. More preferably, it is 2.0% or less, and still more preferably 1.5% or less. In order to exhibit the above effects, it is preferable to set the W amount to 0.05% or more. More preferably, it is 0.10% or more.
(Ga:0~0.05%)
Gaは、耐食性を向上させるのに有効な元素であるため、含有させてもよい。しかしながら、Gaを過剰に含有させると、その効果は飽和し、逆に耐食性と冷間鍛造性、非磁性特性が劣化するおそれがある。そのため、Gaを含有させる場合の上限を、0.05%とする。前記効果を発現させるには、Ga量を0.0004%以上とすることが好ましい。
(Ga: 0 to 0.05%)
Ga is an effective element for improving corrosion resistance, so it may be contained. However, if Ga is contained excessively, the effect is saturated, and the corrosion resistance, cold forgeability, and non-magnetic properties may deteriorate. Therefore, the upper limit when Ga is contained is set to 0.05%. In order to exhibit the above effect, it is preferable to set the amount of Ga to 0.0004% or more.
(Co:0~2.5%)
Coは、耐食性を向上させる効果を有するため、含有させてもよい。しかしながら、Coを過剰に含有させると、その効果は飽和し、逆に耐食性と冷間鍛造性、非磁性特性が劣化するおそれがある。そのため、Coを含有させる場合の上限を2.5%とする。より好ましくは、1.0%以下であり、更に好ましくは0.8%以下である。前記効果を発現させるには、Co量を0.05%以上とすることが好ましく、0.10%以上含有させることがより好ましい。
(Co: 0-2.5%)
Co has the effect of improving the corrosion resistance, so it may be contained. However, if Co is contained excessively, the effect is saturated, and the corrosion resistance, cold forgeability, and non-magnetic properties may deteriorate. Therefore, the upper limit of the content of Co is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.8% or less. In order to exhibit the above effects, the Co content is preferably 0.05% or more, more preferably 0.10% or more.
(Sb:0~2.5%)
Sbは、耐食性を向上させる効果を有するため、含有させてもよい。しかしながら、Sbを過剰に含有させると、その効果は飽和し、逆に耐食性と冷間鍛造性、非磁性特性が劣化するおそれがある。そのため、Sbを含有させる場合の上限を2.5%とする。より好ましくは、1.0%以下であり、更に好ましくは0.8%以下である。前記効果を発現させるには、Sb量を0.01%以上とすることが好ましく、0.05%以上含有させることがより好ましい。
(Sb: 0-2.5%)
Since Sb has an effect of improving corrosion resistance, it may be contained. However, if Sb is contained excessively, the effect is saturated, and the corrosion resistance, cold forgeability, and non-magnetic properties may deteriorate. Therefore, the upper limit when Sb is contained is set to 2.5%. More preferably, it is 1.0% or less, and still more preferably 0.8% or less. In order to exhibit the above effect, the Sb content is preferably 0.01% or more, more preferably 0.05% or more.
(Ta:0~2.5%)
TaはB粒界占有率を下げるC,Nの固定のために添加してもよい。一方、過剰にTaを添加すると粗大Ta系析出物などが形成し、耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、Ta含有量の上限値を2.5%とし、好ましくは1.0%以下であり、更に好ましくは0.7%以下とし、更に好ましくは0.5%以下である。Taの好ましい下限は0.01%である。
(Ta: 0-2.5%)
Ta may be added for fixing C and N which lowers the B grain boundary occupancy. On the other hand, if Ta is added excessively, coarse Ta-based precipitates and the like are formed, degrading corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Ta content is set to 2.5%, preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.5% or less. A preferable lower limit of Ta is 0.01%.
(Ca:0~0.05%)
Caは脱酸のため必要に応じて含有させてよい。一方、過剰にCaを添加すると粗大Ca系介在物などが形成し、耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、Ca含有量の上限値を0.05%とし、好ましくは0.010%以下であり、更に好ましくは0.005%以下である。Caの好ましい下限は0.0002%である。
(Ca: 0-0.05%)
Ca may be contained as needed for deoxidation. On the other hand, if Ca is added excessively, coarse Ca-based inclusions and the like are formed, degrading corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Ca content is 0.05%, preferably 0.010% or less, and more preferably 0.005% or less. A preferable lower limit of Ca is 0.0002%.
(Mg:0~0.012%)
Mgは脱酸のため必要に応じて含有させてよい。一方、過剰にMgを添加すると粗大Mg系介在物などが形成し、冷間鍛造性と耐水素脆化特性が劣化する。そのため、Mg含有量の上限値を0.012%とし、好ましくは0.010%以下であり、更に好ましくは0.005%以下である。Mgの好ましい下限は0.0002%である。
(Mg: 0-0.012%)
Mg may be contained as necessary for deoxidation. On the other hand, if Mg is excessively added, coarse Mg-based inclusions and the like are formed, degrading cold forgeability and hydrogen embrittlement resistance. Therefore, the upper limit of the Mg content is 0.012%, preferably 0.010% or less, and more preferably 0.005% or less. A preferred lower limit for Mg is 0.0002%.
(Zr:0~0.012%)
Zrは脱酸のため必要に応じて含有させてよい。一方、過剰にZrを添加すると粗大Zr系介在物などが形成し、耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、Zr含有量の上限値を0.012%とし、好ましくは0.010%以下であり、更に好ましくは0.005%以下である。Zrの好ましい下限は0.0002%である。
(Zr: 0 to 0.012%)
Zr may be contained as necessary for deoxidation. On the other hand, if Zr is added excessively, coarse Zr-based inclusions and the like are formed, degrading corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Zr content is 0.012%, preferably 0.010% or less, and more preferably 0.005% or less. A preferable lower limit of Zr is 0.0002%.
(REM:0~0.05%)
REMは脱酸のため必要に応じて含有させてよい。一方、過剰にREMを添加すると粗大REM系介在物などが形成し、耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、REM含有量の上限値を0.05%とし、好ましくは0.010%以下であり、更に好ましくは0.005%以下である。REMの好ましい下限は0.0002%である。
(REM: 0-0.05%)
REM may optionally be included for deacidification. On the other hand, if REM is added excessively, coarse REM-based inclusions are formed, and corrosion resistance, cold forgeability, and non-magnetic properties deteriorate. Therefore, the upper limit of the REM content is 0.05%, preferably 0.010% or less, and more preferably 0.005% or less. A preferred lower limit for REM is 0.0002%.
(Pb:0~0.30%)
Pbは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にPbを添加すると耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、Pb含有量の上限値を0.30%とし、好ましくは0.10%以下であり、更に好ましくは0.05%以下である。Pbの好ましい下限は0.0001%である。
(Pb: 0 to 0.30%)
Pb is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of Pb deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Pb content is set to 0.30%, preferably 0.10% or less, and more preferably 0.05% or less. A preferable lower limit of Pb is 0.0001%.
(Se:0~0.80%)
Seは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にSeを添加すると耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、Se含有量の上限値を0.80%とし、好ましくは0.1%以下であり、更に好ましくは0.05%以下である。Seの好ましい下限は0.0001%である。
(Se: 0 to 0.80%)
Se is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of Se deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Se content is 0.80%, preferably 0.1% or less, and more preferably 0.05% or less. A preferred lower limit for Se is 0.0001%.
(Te:0~0.30%)
Teは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にTeを添加すると耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、Te含有量の上限値を0.30%とし、好ましくは0.1%以下であり、更に好ましくは0.05%以下である。Teの好ましい下限は0.0001%である。
(Te: 0 to 0.30%)
Te is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of Te deteriorates corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Te content is set to 0.30%, preferably 0.1% or less, and more preferably 0.05% or less. A preferable lower limit of Te is 0.0001%.
(Bi:0~0.50%)
Biは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にBiを添加すると耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、Bi含有量の上限値を0.50%とし、好ましくは0.1%以下であり、更に好ましくは0.05%以下である。Biの好ましい下限は0.0001%である。
(Bi: 0 to 0.50%)
Bi is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of Bi degrades corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the Bi content is 0.50%, preferably 0.1% or less, and more preferably 0.05% or less. A preferable lower limit of Bi is 0.0001%.
(S:0~0.50%)
Sは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にSを添加すると耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、S含有量の上限値を0.50%とし、好ましくは0.1%以下であり、更に好ましくは0.05%以下である。Sの好ましい下限は0.0001%である。なお、Sは製鋼原料から混入する不純物として、通常は鋼中に含有している。
(S: 0-0.50%)
S is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of S degrades corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the S content is 0.50%, preferably 0.1% or less, and more preferably 0.05% or less. A preferred lower limit for S is 0.0001%. Incidentally, S is usually contained in steel as an impurity mixed from steelmaking raw materials.
(P:0~0.30%)
Pは切削性を高める元素であり必要に応じて含有させてよい。一方、過剰にPを添加すると耐食性と冷間鍛造性、非磁性特性が劣化する。そのため、P含有量の上限値を0.30%とし、好ましくは0.1%以下であり、更に好ましくは0.05%以下である。Pの好ましい下限は0.0001%である。
(P: 0-0.30%)
P is an element that enhances machinability and may be contained as necessary. On the other hand, excessive addition of P degrades corrosion resistance, cold forgeability, and non-magnetic properties. Therefore, the upper limit of the P content is 0.30%, preferably 0.1% or less, and more preferably 0.05% or less. A preferred lower limit for P is 0.0001%.
<第1~第3発明に共通>
《式(a)のA値》
非特許文献1に記載のMd30の式をベースとし、下記式(a)を導入した。
A値=551-462(C+N)-9.2Si―8.1Mn―29(Ni+Cu)-13.7Cr―18.5Mo (a)
式(a)中の元素記号は、当該元素の鋼中における含有量(質量%)を意味する。また、式(a)中の元素の含有量が0%である場合は、該当記号箇所には「0」を代入して算出する。上記式(a)は、非特許文献1に記載のMd30の式から、Nbの項を削除したものに相当する。Nbの項を削除した理由は、Nbの添加割合が小さく、Md30へのその寄与度が小さいためである。
第1~第3発明においては、上記式(a)で示されるA値が-100以下である。A値を-100以下とすることにより、加工誘起マルテンサイトの生成を抑制し、加工硬化を低減させることで、軟質化し、また割れ発生を抑制するので冷間鍛造性が向上する。さらに第1発明はミクロひずみの低減と耐水素脆化特性が向上するとの効果を得ることができる。第2発明は軟質化することで切削抵抗が低減し、切削性が向上する。耐水素脆化特性については、破壊起点の加工誘起マルテンサイトが低減するため、耐水素脆化特性が改善する。第3発明は非磁性特性が向上するとの効果を得ることができる。
<Common to the first to third inventions>
<<A value of formula (a)>>
Based on the formula for Md30 described in Non-Patent Document 1, the following formula (a) was introduced.
A value = 551-462 (C+N)-9.2Si-8.1Mn-29(Ni+Cu)-13.7Cr-18.5Mo (a)
The symbol of an element in formula (a) means the content (% by mass) of the element in steel. Further, when the content of the element in the formula (a) is 0%, the calculation is performed by substituting "0" in the corresponding symbol. The above formula (a) corresponds to the Md30 formula described in Non-Patent Document 1 with the Nb term removed. The reason for deleting the Nb term is that the addition ratio of Nb is small and its contribution to Md30 is small.
In the first to third inventions, the A value represented by the above formula (a) is -100 or less. By setting the A value to −100 or less, the formation of strain-induced martensite is suppressed, and work hardening is reduced, which softens the steel and suppresses the occurrence of cracks, thereby improving the cold forgeability. Furthermore, the first invention can obtain the effects of reducing microstrain and improving hydrogen embrittlement resistance. In the second invention, softening reduces cutting resistance and improves machinability. As for the resistance to hydrogen embrittlement, since deformation-induced martensite at the starting point of fracture is reduced, the resistance to hydrogen embrittlement is improved. The third invention can obtain the effect of improving the non-magnetic properties.
《第1~第3発明の鋼材の品質》
本発明のステンレス鋼、特に棒状鋼材は、上記成分組成と、さらに第1発明は鋼材表層~D/4のミクロひずみを具備する結果として、第2発明はホウ化物としての析出B量、硫化物のアスペクト比を具備する結果として、第3発明は鋼材のB粒界占有率を具備する結果として、以下の品質を実現することができる。
<<Quality of the steel materials of the first to third inventions>>
The stainless steel of the present invention, particularly the bar steel, has the above-mentioned chemical composition, and the first invention has a micro strain of D/4 from the surface layer of the steel material. As a result of having the aspect ratio of , the third invention can realize the following qualities as a result of having the B grain boundary occupancy of the steel material.
<第1~第3発明に共通>
引張強さが700MPa以下のステンレス鋼とすることができる。
<第1~第3発明に共通>
限界圧縮率が60%以上のステンレス鋼とすることができる。ここで、限界圧縮率の評価については、テストピースの形状、圧縮試験の内容、限界圧縮率の定義のいずれも、前述のとおりの方法を用いるものとする。
<Common to the first to third inventions>
It can be stainless steel with a tensile strength of 700 MPa or less.
<Common to the first to third inventions>
A stainless steel having a critical compressibility of 60% or more can be used. Here, regarding the evaluation of the critical compressibility, the above-described method is used for all of the shape of the test piece, the contents of the compression test, and the definition of the critical compressibility.
<第1~第2発明に共通>
冷間加工後の高圧水素中の相対引張強さが80%以上であるステンレス鋼とすることができる。
<第1~第2発明に共通>
冷間加工後の高圧水素中の相対絞りが50%以上であるステンレス鋼とすることができる。
ここで、上記冷間加工は、冷間加工率(減面率)が80%である。また、高圧水素中の引張強さと絞りの評価は、水素雰囲気、-40℃、70MPaの環境で、ひずみ速度1×10-5/sで引張試験を行う。こうして得られた水素雰囲気での引張強さと絞り値を、大気雰囲気で同じひずみ速度で評価した引張強さと絞り値で除した値の%表示が、高圧水素中の相対引張強さ、高圧水素中の相対絞りである。
<Common to the first and second inventions>
A stainless steel having a relative tensile strength of 80% or more in high-pressure hydrogen after cold working can be used.
<Common to the first and second inventions>
A stainless steel having a relative reduction in area of 50% or more in high-pressure hydrogen after cold working can be used.
Here, the cold working rate (area reduction rate) of the cold working is 80%. For the evaluation of tensile strength and reduction in area in high-pressure hydrogen, a tensile test is performed at a strain rate of 1×10 −5 /s in a hydrogen atmosphere at −40° C. and 70 MPa. The % display of the value obtained by dividing the tensile strength and reduction of area in the hydrogen atmosphere obtained in this way by the tensile strength and reduction of area evaluated at the same strain rate in the air atmosphere is the relative tensile strength in high pressure hydrogen, and the value in high pressure hydrogen. is the relative aperture of
<第2発明>
ドリル加工寿命指標のVL-1000が1m/min以上のステンレス鋼とすることができる。
<Second invention>
Stainless steel having a drilling life index VL-1000 of 1 m/min or more can be used.
<第3発明>
孔食電位が0.05V以上のステンレス鋼とすることができる。
<Third invention>
Stainless steel having a pitting potential of 0.05 V or higher can be used.
<第3発明>
冷間加工後の比透磁率が1.10以下であるステンレス鋼とすることができる。
ここで、上記冷間加工は、冷間加工率(減面率)が80%である。
<Third invention>
Stainless steel having a relative magnetic permeability of 1.10 or less after cold working can be used.
Here, the cold working rate (area reduction rate) of the cold working is 80%.
《第1~第3発明の鋼材の製造方法》
以下、第1~第3発明の鋼材の製造方法について、順番に説明する。
<<Manufacturing method of steel materials according to the first to third inventions>>
Hereinafter, the steel material manufacturing methods of the first to third inventions will be described in order.
<第1発明>
第1発明のステンレス鋼、特に棒状鋼材を製造する上で、熱間加工方法として傾斜圧延を採用し、傾斜圧延前の素材の加熱に誘導加熱を用いる方法が好適である。
<First Invention>
In producing the stainless steel of the first invention, particularly the bar-shaped steel, it is preferable to use tilt rolling as the hot working method and use induction heating to heat the raw material before tilt rolling.
鋼材の圧延素材を加熱する誘導加熱装置において、設定温度が設けられている。この設定温度を1000~1400℃に特定した上で、圧延素材の誘導加熱装置通材時間を10~300秒の範囲内とする。設定温度が1000~1300℃の範囲内、通材時間が10~200秒の範囲内であるとより好ましい。設定温度について更に好ましくは1050~1300℃であり、更に好ましくは1100~1300℃である。通材時間について更に好ましくは20~200秒であり、更に好ましくは20~150秒である。これにより、鋼材表層~D/4位置の鋼材温度を均一に設定温度とすることができる。 A set temperature is provided in the induction heating device that heats the rolled steel material. After specifying this set temperature to be 1000 to 1400° C., the time for passing the material to be rolled through the induction heating device is set within the range of 10 to 300 seconds. It is more preferable that the set temperature is in the range of 1000 to 1300° C. and the passing time is in the range of 10 to 200 seconds. The set temperature is more preferably 1050 to 1300°C, more preferably 1100 to 1300°C. The passage time is more preferably 20 to 200 seconds, more preferably 20 to 150 seconds. As a result, the steel material temperature from the steel material surface layer to the D/4 position can be uniformly set to the set temperature.
誘導加熱装置の設定温度が1000℃未満であると、熱間圧延中に鋼材へのひずみが累積し、鋼材表層~D/4のミクロひずみが大きくなることに加え、粗大未固溶析出物が残留し、冷間鍛造性と耐水素脆化特性が劣化する。1400℃を超えると未固溶析出物が固溶し、固溶元素増大によって鋼材のミクロひずみが増大する。また、高温加熱によって、鋼材の酸化による歩留まり低下が生じ、あるいは、通材中に鋼材がクリープ変形し圧延不良となる。また、圧延素材の誘導加熱装置通材時間が10秒未満であると、鋼材表層~D/4での鋼材温度が設定温度に均一に達しなく、熱間圧延中に鋼材へのひずみが累積し、鋼材表層~D/4のミクロひずみが大きくなることに加え、粗大未固溶析出物が残留し、冷間鍛造性と耐水素脆化特性が劣化する。誘導加熱装置通材時間が300秒を超えると、鋼材表層~D/4での鋼材温度が設定温度に対し不均一に局所的に過加熱され、未固溶析出物が固溶し、固溶元素増大によって鋼材のミクロひずみが増大する。また、高温加熱によって鋼材の酸化による歩留まり低下が生じ、あるいは、通材中に鋼材がクリープ変形し圧延不良となる。なお、誘導加熱装置の設定温度とは、具体的には鋼材が通材する誘導加熱装置内での出力温度を意味する。 If the set temperature of the induction heating device is less than 1000 ° C., the strain on the steel material accumulates during hot rolling, and in addition to the large micro strain of the steel material surface layer to D / 4, coarse undissolved precipitates are formed. It remains and deteriorates cold forgeability and hydrogen embrittlement resistance. When the temperature exceeds 1400°C, the undissolved precipitates are dissolved, and the increase in the dissolved elements increases the micro strain of the steel material. In addition, high-temperature heating causes a reduction in yield due to oxidation of the steel material, or creep deformation of the steel material during rolling, resulting in poor rolling. In addition, if the rolling material passes through the induction heating device for less than 10 seconds, the steel material temperature does not uniformly reach the set temperature in the steel material surface layer to D/4, and the strain in the steel material accumulates during hot rolling. In addition to the increase in micro strain in the steel material surface layer to D/4, coarse undissolved precipitates remain, resulting in deterioration of cold forgeability and hydrogen embrittlement resistance. When the induction heating device passing time exceeds 300 seconds, the steel material temperature in the steel material surface layer to D/4 is locally overheated non-uniformly with respect to the set temperature, and the undissolved precipitates dissolve into solid solution. An increase in the number of elements increases the micro strain of the steel. In addition, high-temperature heating causes a decrease in yield due to oxidation of the steel material, or creep deformation of the steel material during rolling, resulting in poor rolling. The set temperature of the induction heating device specifically means the output temperature in the induction heating device through which the steel material passes.
圧延素材をこのように加熱した上で、傾斜圧延を行う。傾斜圧延は、例えば特許文献4に開示されているとおり、3個のワークロールを被圧延材を中心にして同方向に捩って傾斜したロール軸に配置し、各ワークロールが被圧延材の周囲を自転しながら公転する。これにより、被圧延材は前進しながらスパイラル状に圧延される。傾斜圧延を行うに際しての圧延素材の温度分布について、鋼材表層~D/4位置の鋼材温度が均一に設定温度に一致するような温度分布とする。これにより、鋼材表層~D/4での再結晶によってひずみ累積を低減させるとのメカニズムにより、鋼材表層~D/4のミクロひずみを0.0040以下とすることができる。また、上記プロセスによって、粗大未固溶析出物が消失し、析出物が微細化することも、冷間鍛造性と耐水素脆化特性を高めることへ寄与する。 After heating the rolled material in this way, tilt rolling is performed. In tilt rolling, for example, as disclosed in Patent Document 4, three work rolls are arranged on roll axes that are tilted in the same direction around the material to be rolled, and each work roll rotates the material to be rolled. It revolves around itself while rotating. As a result, the material to be rolled is spirally rolled while moving forward. Regarding the temperature distribution of the material to be rolled when tilt rolling is performed, the temperature distribution is such that the steel material temperature from the steel material surface layer to the D/4 position uniformly coincides with the set temperature. As a result, the micro strain of the steel material surface layer to D/4 can be reduced to 0.0040 or less by the mechanism of reducing the strain accumulation by recrystallization in the steel material surface layer to D/4. In addition, the above process eliminates coarse undissolved precipitates and refines the precipitates, which also contributes to the enhancement of cold forgeability and hydrogen embrittlement resistance.
傾斜圧延後はインライン熱処理・熱間圧延・熱処理・酸洗などを施すことが好ましい。その後、鋼材のピーリング、引抜加工などで鋼材の形状調整などを行ってもよい。 It is preferable to perform in-line heat treatment, hot rolling, heat treatment, pickling, etc. after tilt rolling. After that, the shape of the steel material may be adjusted by peeling or drawing of the steel material.
第1発明の鋼材の製造方法において、上記のように傾斜圧延を用い、熱間加工されるのが好ましい。なお、熱間加工は傾斜圧延に限定されず、同様の熱加工履歴を辿る方法であればよく、例えば分塊圧延(ブレークダウン)であっても、同様の熱加工履歴を取れれば用いることができる。 In the steel manufacturing method of the first invention, it is preferable that hot working is performed using tilt rolling as described above. Note that hot working is not limited to tilt rolling, and any method that follows a similar heat working history may be used. For example, blooming rolling (breakdown) can be used as long as a similar heat working history can be obtained. can.
<第2発明>
第2発明のステンレス鋼、特に棒状鋼材を製造する上で、熱間加工方法として傾斜圧延を採用し、傾斜圧延前の素材の加熱に誘導加熱を用いる方法が好適である。
<Second invention>
In producing the stainless steel of the second invention, particularly the bar steel, it is preferable to employ tilt rolling as the hot working method and use induction heating to heat the raw material before tilt rolling.
鋼材の圧延素材を加熱する誘導加熱装置において、設定温度が設けられている。この設定温度を1000~1400℃に特定した上で、圧延素材の誘導加熱装置通材速度を0.003~4.0m/sの範囲内とする。設定温度が1000~1300℃の範囲内、通材速度が0.005~2.0m/sの範囲内であるとより好ましい。設定温度について更に好ましくは1050~1300℃であり、更に好ましくは1100~1300℃である。通材速度について更に好ましくは0.01~2.0m/sであり、更に好ましくは0.1~1.0m/sである。
誘導加熱装置の設定温度と通材速度を上記範囲内とすることにより、鋼中にBを含有することと相まって、鋼中のホウ化物としての析出B量を0.0001%以上とすることができる。
また、誘導加熱装置の設定温度と通材速度を上記範囲内とすることにより、鋼中にSを含有するとともにAlとCaの一種以上を含有することと相まって、硫化物のアスペクト比を50以下とすることができる。
A set temperature is provided in an induction heating device that heats a rolled steel material. After specifying this set temperature to be 1000 to 1400° C., the speed at which the material to be rolled passes through the induction heating device is set within the range of 0.003 to 4.0 m/s. It is more preferable that the set temperature is in the range of 1000 to 1300° C. and the feed speed is in the range of 0.005 to 2.0 m/s. The set temperature is more preferably 1050 to 1300°C, more preferably 1100 to 1300°C. The threading speed is more preferably 0.01 to 2.0 m/s, more preferably 0.1 to 1.0 m/s.
By setting the set temperature of the induction heating device and the feeding speed within the above ranges, coupled with containing B in the steel, it is possible to make the amount of precipitated B as borides in the steel 0.0001% or more. can.
In addition, by setting the set temperature of the induction heating device and the feed speed within the above ranges, the aspect ratio of the sulfides is reduced to 50 or less, coupled with the inclusion of S in the steel and the inclusion of one or more types of Al and Ca. can be
誘導加熱装置の設定温度が1000℃未満であると、析出B量が低下し、硫化物のアスペクト比が大きくなるとともに、粗大未固溶析出物が残留するため、冷間鍛造性、切削性と耐水素脆化特性が劣化する。1400℃を超えると、析出B量の低下と硫化物の伸長による高アスペクト比化によって、冷間鍛造性、切削性と耐水素脆化特性が劣化する。また、高温加熱によって鋼材の酸化による歩留まり低下が生じ、あるいは、通材中に鋼材がクリープ変形し圧延不良となる。また、圧延素材の誘導加熱装置通材速度が0.003m/s未満であると、析出B量の低下と硫化物の伸長が生じ、これにより、硫化物が高アスペクト比化し、冷間鍛造性、切削性と耐水素脆化特性がそれぞれ劣化する。誘導加熱装置通材速度が4.0m/sを超えると、析出B量が低下し、硫化物のアスペクト比が大きくなるとともに、粗大未固溶析出物が残留するため、冷間鍛造性、切削性と耐水素脆化特性が劣化する。また、高温加熱によって鋼材の酸化による歩留まり低下が生じ、あるいは、通材中に鋼材がクリープ変形し圧延不良となる。なお、誘導加熱装置の設定温度とは、具体的には鋼材が通材する誘導加熱装置内での出力温度を意味する。 If the set temperature of the induction heating device is less than 1000°C, the amount of precipitated B decreases, the aspect ratio of sulfides increases, and coarse undissolved precipitates remain, resulting in poor cold forgeability and machinability. Hydrogen embrittlement resistance deteriorates. If the temperature exceeds 1400° C., cold forgeability, machinability, and resistance to hydrogen embrittlement deteriorate due to a decrease in the amount of precipitated B and an increase in aspect ratio due to elongation of sulfides. In addition, high-temperature heating causes a decrease in yield due to oxidation of the steel material, or creep deformation of the steel material during rolling, resulting in poor rolling. In addition, when the speed of passing through the induction heating device of the rolled material is less than 0.003 m / s, the amount of precipitated B decreases and the sulfide is elongated, which causes the sulfide to have a high aspect ratio and cold forgeability. , the machinability and hydrogen embrittlement resistance deteriorate. If the induction heating device passing speed exceeds 4.0 m / s, the amount of precipitated B decreases, the aspect ratio of sulfide increases, and coarse undissolved precipitates remain, so cold forgeability and machinability properties and hydrogen embrittlement resistance deteriorate. In addition, high-temperature heating causes a decrease in yield due to oxidation of the steel material, or creep deformation of the steel material during rolling, resulting in poor rolling. The set temperature of the induction heating device specifically means the output temperature in the induction heating device through which the steel material passes.
圧延素材をこのように加熱した上で、傾斜圧延を行う。傾斜圧延は、例えば特許文献4に開示されているとおり、3個のワークロールを被圧延材を中心にして同方向に捩って傾斜したロール軸に配置し、各ワークロールが被圧延材の周囲を自転しながら公転する。これにより、被圧延材は前進しながらスパイラル状に圧延される。傾斜圧延を行うに際しての圧延素材の温度分布について、鋼材表層~D/4位置の鋼材温度が均一に設定温度に一致するような温度分布とする。これにより、析出B量の低下と硫化物の伸長の抑制によって、冷間鍛造性、切削性と耐水素脆化特性が改善する。また、上記プロセスによって、粗大未固溶析出物が消失し、析出物が微細化することも、冷間鍛造性、切削性と耐水素脆化特性を高めることへ寄与する。 After heating the rolled material in this way, tilt rolling is performed. In tilt rolling, for example, as disclosed in Patent Document 4, three work rolls are arranged on roll axes that are tilted in the same direction around the material to be rolled, and each work roll rotates the material to be rolled. It revolves around itself while rotating. As a result, the material to be rolled is spirally rolled while moving forward. Regarding the temperature distribution of the material to be rolled when tilt rolling is performed, the temperature distribution is such that the steel material temperature from the steel material surface layer to the D/4 position uniformly coincides with the set temperature. This reduces the amount of precipitated B and suppresses elongation of sulfides, thereby improving cold forgeability, machinability, and resistance to hydrogen embrittlement. In addition, the above process eliminates coarse undissolved precipitates and refines the precipitates, which also contributes to the enhancement of cold forgeability, machinability, and hydrogen embrittlement resistance.
傾斜圧延後はインライン熱処理・熱間圧延・熱処理・酸洗などを施すことが好ましい。その後、鋼材のピーリング、引抜加工などで鋼材の形状調整などを行ってもよい。 It is preferable to perform in-line heat treatment, hot rolling, heat treatment, pickling, etc. after tilt rolling. After that, the shape of the steel material may be adjusted by peeling or drawing of the steel material.
第2発明の鋼材の製造方法において、上記のように傾斜圧延を用い、熱間加工されるのが好ましい。なお、熱間加工は傾斜圧延に限定されず、同様の熱加工履歴を辿る方法であればよく、例えば分塊圧延(ブレークダウン)であっても、同様の熱加工履歴を取れれば用いることができる。 In the steel manufacturing method of the second invention, it is preferable that hot working is performed using tilt rolling as described above. Note that hot working is not limited to tilt rolling, and any method that follows a similar heat working history may be used. For example, blooming rolling (breakdown) can be used as long as a similar heat working history can be obtained. can.
<第3発明>
第3発明のステンレス鋼、特に棒状鋼材を製造する上で、素材の加熱や熱間圧延(傾斜圧延やBD、棒状圧延など)、熱処理、酸洗などを施すことが好ましいが、特に、粗圧延入側温度と粗圧延スタンド間平均時間を制御し、不働態化処理を施すことが好適である。
<Third invention>
In the production of the stainless steel of the third invention, particularly the steel bar, it is preferable to subject the raw material to heating, hot rolling (tilt rolling, BD, bar rolling, etc.), heat treatment, pickling, etc. In particular, rough rolling is preferred. It is preferable to control the entry-side temperature and the average time between rough rolling stands and perform the passivation treatment.
鋼材の粗圧延入側温度を1000~1400℃に特定した上で、圧延素材の粗圧延スタンド間平均時間を0.01~30秒の範囲内とする。粗圧延入側温度が1000~1300℃の範囲内、粗圧延スタンド間平均時間が0.03~10秒の範囲内であるとより好ましい。粗圧延入側温度について更に好ましくは1050~1300℃であり、更に好ましくは1100~1300℃である。粗圧延スタンド間平均時間について更に好ましくは0.05~5秒であり、更に好ましくは0.1~2秒である。粗圧延入側温度が1000℃未満であると、熱間圧延中に鋼材へのひずみが累積し、粒内にB系析出物が生成し、B粒界占有率が小さくなるため、耐食性と冷間鍛造性、非磁性特性が劣化する。粗圧延入側温度が1400℃を超えると粒界に存在しているBが粒内へ拡散し、圧延中に粒内B析出物として生成し、B粒界占有率が小さくなる。また、高温加熱によって鋼材の酸化による歩留まり低下が生じ、あるいは、通材中に鋼材がクリープ変形し圧延不良となる。また、粗圧延スタンド間平均時間が0.01秒未満であると、熱間圧延中に鋼材へのひずみが累積し、粒内にB系析出物が生成し、B粒界占有率が小さくなるため、耐食性と冷間鍛造性、非磁性特性が劣化する。粗圧延スタンド間平均時間が30秒を超えると、粒界に存在しているBが粒内へ拡散し、圧延中に粒内B析出物として生成し、B粒界占有率が小さくなる。また、高温加熱によって鋼材の酸化による歩留まり低下が生じ、あるいは、通材中に鋼材がクリープ変形し圧延不良となる。 After specifying the rough rolling entrance temperature of the steel material to be 1000 to 1400°C, the average time between the rough rolling stands of the rolled material is set within the range of 0.01 to 30 seconds. More preferably, the rough rolling entrance temperature is in the range of 1000 to 1300° C., and the average time between rough rolling stands is in the range of 0.03 to 10 seconds. The entry temperature for rough rolling is more preferably 1050 to 1300°C, more preferably 1100 to 1300°C. The average time between rough rolling stands is more preferably 0.05 to 5 seconds, more preferably 0.1 to 2 seconds. If the rough rolling inlet temperature is less than 1000°C, the strain on the steel material accumulates during hot rolling, B-based precipitates are formed in the grains, and the B grain boundary occupancy decreases, so corrosion resistance and cold rolling are improved. Forgeability and non-magnetic properties deteriorate. When the entry temperature of rough rolling exceeds 1400° C., B present at grain boundaries diffuses into grains and forms intragranular B precipitates during rolling, reducing the B grain boundary occupancy. In addition, high-temperature heating causes a decrease in yield due to oxidation of the steel material, or creep deformation of the steel material during rolling, resulting in poor rolling. In addition, if the average time between rough rolling stands is less than 0.01 seconds, the strain on the steel material accumulates during hot rolling, B-based precipitates are formed in grains, and the B grain boundary occupancy decreases. Therefore, corrosion resistance, cold forgeability, and non-magnetic properties deteriorate. When the average time between rough rolling stands exceeds 30 seconds, B present at grain boundaries diffuses into grains and forms intragranular B precipitates during rolling, reducing the B grain boundary occupancy. In addition, high-temperature heating causes a decrease in yield due to oxidation of the steel material, or creep deformation of the steel material during rolling, resulting in poor rolling.
上記条件で制御された圧延材を熱処理し、表面スケールを除去した後に不働態化処理を施すと、粒界Cr系析出物によるCr欠乏領域に対し不働態化を促進し耐食性が向上する。また、上記条件の圧延-熱処理材では、粒界での塑性変形が容易となり冷間鍛造性が向上し、粒界での局所変形が抑制され磁性相の加工誘起α’マルテンサイトの生成を抑制し非磁性を保つ。ここで不働態化処理は素材を硝酸などの溶液へ浸漬する処理であり、単独処理および酸性工程の内の1処理であってもよい。これはステンレス鋼(特に棒状鋼材)への処理にて効果を示し、また、当該棒状鋼材に二次加工(引抜、鍛造、切削など)された製品への処理においても同様の効果を示す。 When the rolled material controlled under the above conditions is heat-treated, surface scale is removed, and then passivation treatment is performed, passivation is promoted in the Cr-deficient region due to intergranular Cr-based precipitates, and corrosion resistance is improved. In addition, in the rolled and heat-treated material under the above conditions, plastic deformation at grain boundaries is facilitated, cold forgeability is improved, local deformation at grain boundaries is suppressed, and the formation of deformation-induced α' martensite in the magnetic phase is suppressed. and remain non-magnetic. Here, the passivation treatment is a treatment of immersing the material in a solution such as nitric acid, and may be a single treatment or an acid treatment. This is effective in the treatment of stainless steel (especially bar steel), and also in the treatment of products obtained by secondary processing (drawing, forging, cutting, etc.) of the bar steel.
<第1発明>
(実施例1-1)
鋼の溶製の際には、ステンレス鋼の安価な溶製プロセスであるAOD溶製を想定し、100kgの真空溶解炉にて溶解し、直径180mmの鋳片に鋳造した。その後、下記の製造条件により直径20.0mmのステンレス棒状鋼材とし表1~表3に示す化学成分を有する棒状鋼材を製造した。表1~表6において、本発明範囲から外れる項目、本発明の好適な製造条件から外れる項目について、下線を付している。
<First Invention>
(Example 1-1)
When the steel was smelted, assuming AOD smelting, which is a low-cost stainless steel smelting process, the steel was melted in a 100 kg vacuum melting furnace and cast into a slab with a diameter of 180 mm. Thereafter, stainless steel rods having a diameter of 20.0 mm and chemical compositions shown in Tables 1 to 3 were manufactured under the following manufacturing conditions. In Tables 1 to 6, items outside the scope of the present invention and items outside the preferred manufacturing conditions of the present invention are underlined.
鋳造した鋳片を加熱炉にて1130℃で加熱し、その後、傾斜圧延前の圧延素材の加熱には誘導加熱を用い、誘導加熱装置の設定温度を1210℃、誘導加熱装置通材時間を110sとして加熱を行い、傾斜圧延を行い、インライン熱処理、棒線圧延を行った後、1100℃×30分(水冷)のオフライン熱処理を施し、酸洗し、直径20.0mmの棒状鋼材を作製した。 The cast slab is heated in a heating furnace at 1130 ° C., then induction heating is used to heat the rolling material before tilt rolling, the set temperature of the induction heating device is 1210 ° C., and the induction heating device passing time is 110 s. After heating, tilt rolling, in-line heat treatment, bar and wire rolling, offline heat treatment at 1100° C. for 30 minutes (water cooling) and pickling, a bar steel with a diameter of 20.0 mm was produced.
棒状鋼材のミクロひずみ測定方法、限界圧縮率測定方法、冷間加工後の相対引張強さと相対絞りの評価方法については、前述のとおりの方法を用いた。 The methods described above were used for measuring the micro strain of bar steel, measuring the critical compressibility, and evaluating the relative tensile strength and relative reduction of area after cold working.
ミクロひずみについては、0.0005以下をAA、0.0005超0.0020以下をA、0.0020超0.0040以下をB、0.0040超をCとした。
引張強さについては、500MPa以下をAA、500MPa超620MPa以下をA、620MPa超700MPa以下をB、700MPa超をCとした。
限界圧縮率については、80%以上をAA、70%以上80%未満をA、60%以上70%未満をB、60%未満をCとした。
冷間加工後の高圧水素中の相対引張強さについては、95%以上をAA、90%以上95%未満をA、80%以上90%未満をB、80%未満をCとした。
冷間加工後の高圧水素中の相対絞りについては、70%以上をAA、60%以上70%未満をA、50%以上60%未満をB、50%未満をCとした。
評価結果を表4、5に示す。
Regarding the microstrain, AA is 0.0005 or less, A is more than 0.0005 and 0.0020 or less, B is more than 0.0020 and 0.0040 or less, and C is more than 0.0040.
Regarding the tensile strength, AA is 500 MPa or less, A is more than 500 MPa and 620 MPa or less, B is more than 620 MPa and 700 MPa or less, and C is more than 700 MPa.
Regarding the limit compression rate, AA is 80% or more, A is 70% or more and less than 80%, B is 60% or more and less than 70%, and C is less than 60%.
Regarding the relative tensile strength in high-pressure hydrogen after cold working, AA indicates 95% or more, A indicates 90% or more and less than 95%, B indicates 80% or more and less than 90%, and C indicates less than 80%.
Regarding the relative reduction of area in high-pressure hydrogen after cold working, AA indicates 70% or more, A indicates 60% or more and less than 70%, B indicates 50% or more and less than 60%, and C indicates less than 50%.
Evaluation results are shown in Tables 4 and 5.
本発明例No.1~39に記載の棒状鋼材については、第1発明で規定する成分組成とミクロひずみを有しており、引張強さ、限界圧縮率、冷間加工後の相対引張強さと絞り、のいずれも、AA、A、Bのいずれかであり、良好であった。 Inventive Example No. 1 to 39, the steel bars have the chemical composition and microstrain specified in the first invention, and all of the tensile strength, critical compressibility, relative tensile strength and reduction of area after cold working. , AA, A, or B, and was good.
一方、比較例No.40~54については、いずれかの成分が第1発明範囲を外れており、ミクロひずみが第1発明範囲から外れ、結果として、引張強さ、限界圧縮率、冷間加工後の相対引張強さと絞り、のいずれもCであった。 On the other hand, Comparative Example No. For 40 to 54, one of the components is outside the first invention range, and the microstrain is outside the first invention range, resulting in tensile strength, critical compressibility, relative tensile strength after cold working, and Aperture was C in both cases.
(実施例1-2)
成分組成として表1の鋼種Pを用い、傾斜圧延前の誘導加熱条件を表6に示す条件とし、その他の製造条件は上記実施例1-1と同様として棒状鋼材を製造した。
(Example 1-2)
Using steel type P in Table 1 as the chemical composition, induction heating conditions before tilt rolling were set to the conditions shown in Table 6, and other manufacturing conditions were the same as in Example 1-1 above, to produce bar steels.
表6に示すように、本発明例No.55~64は、製造方法が第1発明の好適条件にあり、第1発明で規定する成分組成とミクロひずみを有しており、引張強さ、限界圧縮率、冷間加工後の相対引張強さと絞り、のいずれも、AA、A、Bのいずれかであり、良好であった。 As shown in Table 6, invention example No. 55 to 64 have the manufacturing method under the preferred conditions of the first invention, have the composition and microstrain specified in the first invention, and have tensile strength, critical compressibility, and relative tensile strength after cold working. All of AA, A, and B were good in both of AA, A, and B.
一方、比較例No.65~70については、いずれかの製造条件が第1発明の好適範囲を外れており、ミクロひずみが第1発明範囲から外れ、結果として、引張強さ、限界圧縮率、冷間加工後の相対引張強さと絞り、のいずれもCであった。 On the other hand, Comparative Example No. For 65 to 70, one of the manufacturing conditions is outside the preferred range of the first invention, and the microstrain is outside the range of the first invention, resulting in tensile strength, critical compressibility, relative after cold working Both tensile strength and area of drawing were C.
<第2発明>
(実施例2-1)
鋼の溶製の際には、ステンレス鋼の安価な溶製プロセスであるAOD溶製を想定し、100kgの真空溶解炉にて溶解し、直径180mmの鋳片に鋳造した。その後、下記の製造条件により直径20.0mmのステンレス棒状鋼材とし表7~表9に示す化学成分を有する棒状鋼材を製造した。表7~表12において、第2発明範囲から外れる項目、第2発明の好適な製造条件から外れる項目について、下線を付している。
<Second invention>
(Example 2-1)
When the steel was smelted, assuming AOD smelting, which is a low-cost stainless steel smelting process, the steel was melted in a 100 kg vacuum melting furnace and cast into a slab with a diameter of 180 mm. Thereafter, stainless steel rods having a diameter of 20.0 mm and chemical compositions shown in Tables 7 to 9 were manufactured under the following manufacturing conditions. In Tables 7 to 12, items outside the scope of the second invention and items outside the preferred manufacturing conditions of the second invention are underlined.
鋳造した鋳片を加熱炉にて1130℃で加熱し、その後、傾斜圧延前の圧延素材の加熱には誘導加熱を用い、誘導加熱装置の設定温度を1210℃、誘導加熱装置通材速度を0.3m/sとして加熱を行い、傾斜圧延を行い、インライン熱処理、棒線圧延を行った後、1100℃×30分(水冷)のオフライン熱処理を施し、酸洗し、直径20.0mmの棒状鋼材を作製した。 The cast slab is heated at 1130 ° C. in a heating furnace, and then induction heating is used to heat the rolling material before tilt rolling. After heating at 3 m/s, tilt rolling, in-line heat treatment, bar and wire rolling, offline heat treatment at 1100°C for 30 minutes (water cooling), pickling, and bar steel with a diameter of 20.0 mm. was made.
棒状鋼材のホウ化物としての析出B量、硫化物のアスペクト比の測定方法、限界圧縮率測定方法、ドリル加工寿命指標のVL-1000の評価方法、冷間加工後の相対引張強さと相対絞りの評価方法については、前述のとおりの方法を用いた。 Amount of precipitated B as borides in bar steel, method for measuring aspect ratio of sulfides, method for measuring critical compressibility, method for evaluating VL-1000 drilling life index, relative tensile strength and relative drawing after cold working As for the evaluation method, the method as described above was used.
ホウ化物としての析出B量については質量%で、0.0010%以上をAA、0.0005%以上0.0010%未満をA、0.0001%以上0.0005%未満をB、0.0001%未満をCとした。なお、B含有量過剰に起因して粗大ホウ化物が形成されている場合はCCとした。
硫化物のアスペクト比については、5以下をAA、5超30以下をA、30超50以下をB、50超をCとした。
引張強さについては、500MPa以下をAA、500MPa超620MPa以下をA、620MPa超700MPa以下をB、700MPa超をCとした。
限界圧縮率については、80%以上をAA、70%以上80%未満をA、60%以上70%未満をB、60%未満をCとした。
ドリル加工寿命指標のVL-1000については、20m/min以上をAA、10m/min以上20m/min未満をA、1m/min以上10m/min未満をB、1m/min未満をCとした。
冷間加工後の高圧水素中の相対引張強さについては、95%以上をAA、90%以上95%未満をA、80%以上90%未満をB、80%未満をCとした。
冷間加工後の高圧水素中の相対絞りについては、70%以上をAA、60%以上70%未満をA、50%以上60%未満をB、50%未満をCとした。
評価結果を表10、11に示す。
Regarding the amount of precipitated B as borides, in mass%, 0.0010% or more is AA, 0.0005% or more and less than 0.0010% is A, 0.0001% or more and less than 0.0005% is B, and 0.0001%. % less than C. When coarse borides were formed due to excessive B content, it was rated as CC.
Regarding the aspect ratio of the sulfide, AA is 5 or less, A is 5 to 30, B is 30 to 50, and C is more than 50.
Regarding the tensile strength, AA is 500 MPa or less, A is more than 500 MPa and 620 MPa or less, B is more than 620 MPa and 700 MPa or less, and C is more than 700 MPa.
Regarding the limit compression rate, AA is 80% or more, A is 70% or more and less than 80%, B is 60% or more and less than 70%, and C is less than 60%.
For the VL-1000 drilling life index, 20 m/min or more is AA, 10 m/min or more and less than 20 m/min is A, 1 m/min or more and less than 10 m/min is B, and less than 1 m/min is C.
Regarding the relative tensile strength in high-pressure hydrogen after cold working, AA indicates 95% or more, A indicates 90% or more and less than 95%, B indicates 80% or more and less than 90%, and C indicates less than 80%.
Regarding the relative reduction of area in high-pressure hydrogen after cold working, AA indicates 70% or more, A indicates 60% or more and less than 70%, B indicates 50% or more and less than 60%, and C indicates less than 50%.
Evaluation results are shown in Tables 10 and 11.
本発明例No.1~39に記載の棒状鋼材については、第2発明で規定する成分組成とホウ化物としての析出B量、硫化物のアスペクト比を有しており、引張強さ、限界圧縮率、VL-1000、冷間加工後の相対引張強さと絞り、のいずれも、AA、A、Bのいずれかであり、良好であった。 Inventive Example No. 1 to 39 have the chemical composition, the amount of precipitated B as borides, and the aspect ratio of sulfides specified in the second invention, and have tensile strength, critical compressibility, and VL-1000. , the relative tensile strength and reduction of area after cold working were either AA, A, or B, and were good.
一方、比較例No.40~50、52~56については、いずれかの成分が第2発明範囲を外れており、ホウ化物としての析出B量、硫化物のアスペクト比が第2発明範囲から外れ、結果として、引張強さ、限界圧縮率、VL-1000、冷間加工後の相対引張強さと絞り、のいずれもCであった。なお、比較例No.51は、B含有量過剰に起因して粗大ホウ化物が形成されており、粗大ホウ化物が破壊の起点となり、結果として、引張強さ、限界圧縮率、VL-1000、冷間加工後の相対引張強さと絞り、のいずれもCであった。 On the other hand, Comparative Example No. For 40 to 50 and 52 to 56, one of the components is outside the second invention range, the amount of precipitated B as borides and the aspect ratio of sulfides are outside the second invention range, and as a result, the tensile strength It was C in all of the strength, critical compressibility, VL-1000, relative tensile strength and reduction of area after cold working. In addition, comparative example No. In 51, coarse borides are formed due to excessive B content, and the coarse borides become the starting point of fracture, and as a result, tensile strength, critical compressibility, VL-1000, relative after cold working Both tensile strength and area of drawing were C.
(実施例2-2)
成分組成として表7の鋼種Pを用い、傾斜圧延前の誘導加熱条件を表12に示す条件とし、その他の製造条件は上記実施例2-1と同様として棒状鋼材を製造した。
(Example 2-2)
Using steel type P in Table 7 as the chemical composition, the induction heating conditions before tilt rolling were set to the conditions shown in Table 12, and other manufacturing conditions were the same as in Example 2-1 above to produce a bar steel.
表12に示すように、本発明例No.55~64は、製造方法が第2発明の好適条件にあり、第2発明で規定する成分組成とホウ化物としての析出B量、硫化物のアスペクト比を有しており、引張強さ、限界圧縮率、冷間加工後の相対引張強さと絞り、のいずれも、AA、A、Bのいずれかであり、良好であった。 As shown in Table 12, invention example No. 55 to 64 have the manufacturing method under the suitable conditions of the second invention, have the chemical composition specified in the second invention, the amount of precipitated B as borides, and the aspect ratio of sulfides, and have tensile strength and limit All of compressibility, relative tensile strength and reduction of area after cold working were AA, A, or B, and were good.
一方、比較例No.65~70については、いずれかの製造条件が第2発明の好適範囲を外れており、ホウ化物としての析出B量、硫化物のアスペクト比が第2発明範囲から外れ、結果として、引張強さ、限界圧縮率、VL-1000、冷間加工後の相対引張強さと絞り、のいずれもCであった。 On the other hand, Comparative Example No. For 65 to 70, one of the production conditions is out of the preferred range of the second invention, the amount of precipitated B as borides and the aspect ratio of sulfides are out of the scope of the second invention, and as a result, the tensile strength , critical compressibility, VL-1000, relative tensile strength and reduction of area after cold working were all C.
<第3発明>
(実施例3-1)
鋼の溶製の際には、ステンレス鋼の安価な溶製プロセスであるAOD溶製を想定し、100kgの真空溶解炉にて溶解し、直径180mmの鋳片に鋳造した。その後、下記の製造条件により直径20.0mmのステンレス棒状鋼材とし表13~表14に示す化学成分を有する棒状鋼材を製造した。表13~表17において、第3発明範囲から外れる項目、第3発明の好適な製造条件から外れる項目について、下線を付している。
<Third invention>
(Example 3-1)
When the steel was smelted, assuming AOD smelting, which is a low-cost stainless steel smelting process, the steel was melted in a 100 kg vacuum melting furnace and cast into a slab with a diameter of 180 mm. Thereafter, stainless steel rods having a diameter of 20.0 mm and chemical compositions shown in Tables 13 and 14 were manufactured under the following manufacturing conditions. In Tables 13 to 17, items outside the scope of the third invention and items outside the preferred manufacturing conditions of the third invention are underlined.
鋳造した鋳片を加熱・傾斜圧延・インライン熱処理を行い、粗圧延入側温度を1130℃に調整し、粗圧延を行い、また、粗圧延のスタンド間平均時間は1.8sとし、その後、引き続き棒線圧延を行った後、溶体化処理として1100℃×30分(水冷)の熱処理を施し、酸洗し、直径20.0mmの棒状鋼材を作製した。この棒状鋼材(φ20mm)から、耐食性評価用にφ20×30mmをL断面採取し、端面拘束圧縮試用にφ8×12mmの試験片を鋼材C断面のD(直径)/4部位置からL方向を12mm長とし採取した。 The cast slab is subjected to heating, tilt rolling, and in-line heat treatment, the temperature at the entry side of rough rolling is adjusted to 1130 ° C., rough rolling is performed, and the average time between stands for rough rolling is 1.8 s. After bar rolling, heat treatment at 1100° C. for 30 minutes (water cooling) was performed as a solution treatment, followed by pickling to produce a steel bar with a diameter of 20.0 mm. From this bar steel material (φ20 mm), an L cross section of φ20×30 mm was taken for corrosion resistance evaluation, and a test piece of φ8×12 mm was taken for the end face restraint compression test from the D (diameter) / 4 part position of the steel material C cross section 12 mm in the L direction. Taken long.
棒状鋼材のB粒界占有率測定方法については、溶体化処理された棒状鋼材(φ20mm)のL断面を用い、前述のとおりの方法を用いた。耐食性については、直径φ20×30mmの試験片を用い、前述のとおりの方法を用いた。引張強さについては、溶体化処理された棒状鋼材(φ20mm)を用い、通常の方法で評価を行った。冷間鍛造性に関し、限界圧縮率測定方法については、φ8×12mmの試験片を用い、前述のとおりの方法を用いた。冷間加工後の比透磁率の評価方法については、上記の溶体化熱処理された棒状鋼材を断面減少率80%で冷間伸線されたφ9mmの棒状鋼材を用い、前述のとおりの方法を用いた。 Regarding the method of measuring the B grain boundary occupation ratio of the bar steel, the L cross section of the solution-treated bar (φ20 mm) was used, and the method described above was used. For corrosion resistance, a test piece with a diameter of φ20×30 mm was used, and the method as described above was used. Tensile strength was evaluated by an ordinary method using solution-treated bar steel (φ20 mm). Regarding the cold forgeability, a test piece of φ8×12 mm was used for the limit compressibility measurement method, and the method as described above was used. Regarding the evaluation method of the relative magnetic permeability after cold working, the above-mentioned method is used using a bar steel material of φ9 mm obtained by cold drawing the bar steel material subjected to the above solution heat treatment at a cross-sectional reduction rate of 80%. board.
B粒界占有率は、15%以上をAA、5%以上15%未満をA、1%以上5%未満をB、1%未満をCとした。
耐食性については、0.20V以上をAA、0.10V以上0.20V未満をA、0.05V以上0.10V未満をB、0.05V未満をCとした。
引張強さについては、500MPa以下をAA、500MPa超620MPa以下をA、620MPa超700MPa以下をB、700MPa超をCとした。
限界圧縮率については、80%以上をAA、70%以上80%未満をA、60%以上70%未満をB、60%未満をCとした。
冷間加工後の比透磁率については、1.03以下をAA、1.03超1.05以下をA、1.05超1.10以下をB、1.10超をCとした。
評価結果を表15、表16に示す。
The B grain boundary occupancy rate was AA when 15% or more, A when 5% or more and less than 15%, B when 1% or more and less than 5%, and C when less than 1%.
Corrosion resistance was rated AA when 0.20V or more, A when 0.10V or more and less than 0.20V, B when 0.05V or more and less than 0.10V, and C when less than 0.05V.
Regarding the tensile strength, AA is 500 MPa or less, A is more than 500 MPa and 620 MPa or less, B is more than 620 MPa and 700 MPa or less, and C is more than 700 MPa.
Regarding the limit compression rate, AA is 80% or more, A is 70% or more and less than 80%, B is 60% or more and less than 70%, and C is less than 60%.
Regarding the relative magnetic permeability after cold working, AA indicates 1.03 or less, A indicates more than 1.03 and 1.05 or less, B indicates more than 1.05 and 1.10 or less, and C indicates more than 1.10.
Evaluation results are shown in Tables 15 and 16.
本発明例No.1~39に記載の棒状鋼材については、第3発明で規定する成分組成とB粒界占有率を有しており、耐食性、引張強さ、限界圧縮率、冷間加工後の比透磁率、のいずれも、AA、A、Bのいずれかであり、良好であった。 Inventive Example No. 1 to 39 have the chemical composition and B grain boundary occupancy specified in the third invention, corrosion resistance, tensile strength, critical compressibility, relative magnetic permeability after cold working, were either AA, A, or B, and were good.
一方、比較例No.40~54については、いずれかの成分が第3発明範囲を外れており、B粒界占有率が第3発明範囲から外れ、結果として、耐食性、引張強さ、限界圧縮率、冷間加工後の比透磁率、のいずれもCであった。 On the other hand, Comparative Example No. For 40 to 54, one of the components is outside the third invention range, and the B grain boundary occupation ratio is outside the third invention range, resulting in corrosion resistance, tensile strength, critical compressibility, and after cold working Both of the relative magnetic permeability of
(実施例3-2)
成分組成として表13の鋼種Pを用い、粗圧延入側温度と粗圧延スタンド間平均時間、耐食性評価時の試験片の不働態化処理ありなし(なしの場合、研磨まま)を変化させた表16に示す条件とし、その他の製造条件は上記実施例3-1と同様として棒状鋼材を製造し、試験片を準備した。
(Example 3-2)
Using steel type P in Table 13 as the chemical composition, the temperature at the entry side of rough rolling, the average time between rough rolling stands, and the presence or absence of passivation treatment of test pieces during corrosion resistance evaluation (if not, as polished) are changed. 16, and the other manufacturing conditions were the same as in Example 3-1, steel rods were manufactured and test pieces were prepared.
表17に示すように、本発明例No.55~64は、製造方法が第3発明の好適条件にあり、第3発明で規定する成分組成とB粒界占有率を有しており、耐食性、引張強さ、限界圧縮率、冷間加工後の比透磁率、のいずれも、AA、A、Bのいずれかであり、良好であった。 As shown in Table 17, invention example No. 55 to 64 have the manufacturing method under the preferred conditions of the third invention, have the chemical composition and the B grain boundary occupation ratio specified in the third invention, and have corrosion resistance, tensile strength, critical compressibility, and cold working. All of the subsequent relative magnetic permeability were either AA, A, or B, and were good.
一方、比較例No.65~68、70については、いずれかの製造条件が第3発明の好適範囲を外れており、B粒界占有率が第3発明範囲から外れ、結果として、耐食性、引張強さ、限界圧縮率、冷間加工後の比透磁率、のいずれもCであった。比較例No.69については、不働態化処理を実施しておらず、Cr欠乏領域での不働態化が促進されず、B粒界占有率が第3発明範囲から外れ、結果として、耐食性、引張強さ、限界圧縮率、冷間加工後の比透磁率、のいずれもCであった。 On the other hand, Comparative Example No. For 65 to 68 and 70, one of the manufacturing conditions is out of the preferred range of the third invention, and the B grain boundary occupation rate is out of the range of the third invention, resulting in corrosion resistance, tensile strength, and critical compressibility. , the relative magnetic permeability after cold working, were both C. Comparative example no. For No. 69, passivation treatment was not performed, passivation in the Cr-deficient region was not promoted, and the B grain boundary occupation ratio was outside the scope of the third invention, resulting in poor corrosion resistance, tensile strength, Both the critical compressibility and the relative magnetic permeability after cold working were C.
Claims (19)
C:0.0010~0.15%、
Si:0.01~2.00%、
Mn:0.01~10.00%、
Ni:8.00~30.00%、
Cr:9.0~21.0%、
Mo:0.01~3.00%、
Cu:0.01~5.00%、
N:0.0010~0.10%、
Ti:0~2.00%、
Nb:0~2.00%、
Sn:0~2.5%、
V:0~2.0%、
W:0~3.0%、
Ga:0~0.05%、
Co:0~2.5%、
Sb:0~2.5%、
Ta:0~2.5%、
Ca:0~0.05%、
Mg:0~0.012%、
Zr:0~0.012%、
REM:0~0.05%、
Pb:0~0.30%、
Se:0~0.80%、
Te:0~0.30%、
Bi:0~0.50%、
S:0~0.50%、
P:0~0.30%、
を含有し、さらに、
Al:0.001~2.0%、
B:0.0001~0.05%、
から選択される一種以上を含有し、残部:Feおよび不純物であり、
下記式(a)で示されるA値が-100以下であり、
鋼材表層~D/4のミクロひずみが平均で0.0040以下であるステンレス鋼。
A値=551-462(C+N)-9.2Si―8.1Mn―29(Ni+Cu)-13.7Cr―18.5Mo (a)
但し、式(a)中の元素記号は、当該元素の鋼中における含有量(質量%)を意味する。また、式(a)中の元素の含有量が0%である場合は、該当記号箇所には「0」を代入して算出する。
ここで、Dは鋼材の直径または厚みであり、前記ミクロひずみとは、X線ラインプロファイル解析で得られる半価幅から算出される格子ひずみを意味する。 The chemical composition, in mass %,
C: 0.0010 to 0.15%,
Si: 0.01 to 2.00%,
Mn: 0.01 to 10.00%,
Ni: 8.00 to 30.00%,
Cr: 9.0 to 21.0%,
Mo: 0.01 to 3.00%,
Cu: 0.01 to 5.00%,
N: 0.0010 to 0.10%,
Ti: 0 to 2.00%,
Nb: 0 to 2.00%,
Sn: 0-2.5%,
V: 0 to 2.0%,
W: 0 to 3.0%,
Ga: 0-0.05%,
Co: 0-2.5%,
Sb: 0-2.5%,
Ta: 0-2.5%,
Ca: 0-0.05%,
Mg: 0-0.012%,
Zr: 0 to 0.012%,
REM: 0-0.05%,
Pb: 0 to 0.30%,
Se: 0 to 0.80%,
Te: 0 to 0.30%,
Bi: 0 to 0.50%,
S: 0 to 0.50%,
P: 0 to 0.30%,
and further
Al: 0.001 to 2.0%,
B: 0.0001 to 0.05%,
containing one or more selected from, the balance being Fe and impurities,
The A value represented by the following formula (a) is −100 or less,
A stainless steel having an average microstrain of 0.0040 or less from the surface layer to D/4 of the steel material.
A value = 551-462 (C+N)-9.2Si-8.1Mn-29(Ni+Cu)-13.7Cr-18.5Mo (a)
However, the symbol of an element in the formula (a) means the content (% by mass) of the element in the steel. Further, when the content of the element in the formula (a) is 0%, the calculation is performed by substituting "0" in the corresponding symbol.
Here, D is the diameter or thickness of the steel material, and the micro strain means the lattice strain calculated from the half width obtained by X-ray line profile analysis.
A群として、
Ti:0.01~2.00%、
Nb:0.01~2.00%、
Sn:0.0001~2.5%、
V:0.001~2.0%、
W:0.05~3.0%、
Ga:0.0004~0.05%、
Co:0.05~2.5%、
Sb:0.01~2.5%、および
Ta:0.01~2.5%、
から選択される一種以上、
B群として、
Ca:0.0002~0.05%、
Mg:0.0002~0.012%、
Zr:0.0002~0.012%、および
REM:0.0002~0.05%、
から選択される一種以上、
C群として、
Pb:0.0001~0.30%、
Se:0.0001~0.80%、
Te:0.0001~0.30%、
Bi:0.0001~0.50%、
S:0.0001~0.50%、および
P:0.0001~0.30%、
から選択される一種以上、
のA群~C群の一群以上を含有する、
請求項1に記載のステンレス鋼。 Further, the chemical composition is, in mass %,
As group A,
Ti: 0.01 to 2.00%,
Nb: 0.01 to 2.00%,
Sn: 0.0001 to 2.5%,
V: 0.001 to 2.0%,
W: 0.05 to 3.0%,
Ga: 0.0004 to 0.05%,
Co: 0.05-2.5%,
Sb: 0.01-2.5%, and Ta: 0.01-2.5%,
one or more selected from
As group B,
Ca: 0.0002-0.05%,
Mg: 0.0002-0.012%,
Zr: 0.0002-0.012%, and REM: 0.0002-0.05%,
one or more selected from
As group C,
Pb: 0.0001 to 0.30%,
Se: 0.0001 to 0.80%,
Te: 0.0001 to 0.30%,
Bi: 0.0001 to 0.50%,
S: 0.0001 to 0.50%, and P: 0.0001 to 0.30%,
one or more selected from
containing one or more groups of Groups A to C of
The stainless steel according to claim 1.
C:0.0010~0.15%、
Si:0.01~2.00%、
Mn:0.01~10.00%、
Ni:8.00~30.00%、
Cr:9.0~21.0%、
Mo:0.01~3.00%、
Cu:0.01~5.00%、
N:0.0010~0.10%、
B:0.0001~0.05%、
S:0.0001~0.50%、
Ti:0~2.00%、
Nb:0~2.00%、
Sn:0~2.5%、
V:0~2.0%、
W:0~3.0%、
Ga:0~0.05%、
Co:0~2.5%、
Sb:0~2.5%、
Ta:0~2.5%、
Mg:0~0.012%、
Zr:0~0.012%、
REM:0~0.05%、
Pb:0~0.30%、
Se:0~0.80%、
Te:0~0.30%、
Bi:0~0.50%、
P:0~0.30%、
を含有し、さらに、
Al:0.001~2.0%、
Ca:0.0001~0.05%、
から選択される一種以上を含有し、
残部:Feおよび不純物であり、
下記式(a)で示されるA値が-100以下であり、
ホウ化物としての析出B量が0.0001%以上であり、硫化物のアスペクト比が50以下であることを特徴とするステンレス鋼。
A値=551-462(C+N)-9.2Si―8.1Mn―29(Ni+Cu)-13.7Cr―18.5Mo (a)
但し、式(a)中の元素記号は、当該元素の鋼中における含有量(質量%)を意味する。また、式(a)中の元素の含有量が0%である場合は、該当記号箇所には「0」を代入して算出する。 The chemical composition, in mass %,
C: 0.0010 to 0.15%,
Si: 0.01 to 2.00%,
Mn: 0.01 to 10.00%,
Ni: 8.00 to 30.00%,
Cr: 9.0 to 21.0%,
Mo: 0.01 to 3.00%,
Cu: 0.01 to 5.00%,
N: 0.0010 to 0.10%,
B: 0.0001 to 0.05%,
S: 0.0001 to 0.50%,
Ti: 0 to 2.00%,
Nb: 0 to 2.00%,
Sn: 0-2.5%,
V: 0 to 2.0%,
W: 0 to 3.0%,
Ga: 0-0.05%,
Co: 0-2.5%,
Sb: 0-2.5%,
Ta: 0-2.5%,
Mg: 0-0.012%,
Zr: 0 to 0.012%,
REM: 0-0.05%,
Pb: 0 to 0.30%,
Se: 0 to 0.80%,
Te: 0 to 0.30%,
Bi: 0 to 0.50%,
P: 0 to 0.30%,
and further
Al: 0.001 to 2.0%,
Ca: 0.0001 to 0.05%,
contains one or more selected from
balance: Fe and impurities,
The A value represented by the following formula (a) is −100 or less,
A stainless steel characterized by having an amount of precipitated B as borides of 0.0001% or more and an aspect ratio of sulfides of 50 or less.
A value = 551-462 (C+N)-9.2Si-8.1Mn-29(Ni+Cu)-13.7Cr-18.5Mo (a)
However, the symbol of an element in the formula (a) means the content (% by mass) of the element in the steel. Further, when the content of the element in the formula (a) is 0%, the calculation is performed by substituting "0" in the corresponding symbol.
A群として、
Ti:0.01~2.00%、
Nb:0.01~2.00%、
Sn:0.0001~2.5%、
V:0.001~2.0%、
W:0.05~3.0%、
Ga:0.0004~0.05%、
Co:0.05~2.5%、
Sb:0.01~2.5%、および
Ta:0.01~2.5%、
から選択される一種以上、
B群として、
Mg:0.0002~0.012%、
Zr:0.0002~0.012%、および
REM:0.0002~0.05%、
から選択される一種以上、
C群として、
Pb:0.0001~0.30%、
Se:0.0001~0.80%、
Te:0.0001~0.30%、
Bi:0.0001~0.50%、および
P:0.0001~0.30%、
から選択される一種以上、
のA群~C群の一群以上を含有する、
請求項7に記載のステンレス鋼。 Further, the chemical composition is, in mass %,
As group A,
Ti: 0.01 to 2.00%,
Nb: 0.01 to 2.00%,
Sn: 0.0001 to 2.5%,
V: 0.001 to 2.0%,
W: 0.05 to 3.0%,
Ga: 0.0004 to 0.05%,
Co: 0.05-2.5%,
Sb: 0.01-2.5%, and Ta: 0.01-2.5%,
one or more selected from
As group B,
Mg: 0.0002-0.012%,
Zr: 0.0002-0.012%, and REM: 0.0002-0.05%,
one or more selected from
As group C,
Pb: 0.0001 to 0.30%,
Se: 0.0001 to 0.80%,
Te: 0.0001 to 0.30%,
Bi: 0.0001 to 0.50%, and P: 0.0001 to 0.30%,
one or more selected from
containing one or more groups of Groups A to C of
The stainless steel according to claim 7.
C:0.0010~0.15%、
Si:0.01~2.00%、
Mn:0.01~10.00%、
Ni:8.00~30.00%、
Cr:9.0~21.0%、
Mo:0.01~3.00%、
Cu:0.01~5.00%、
N:0.0010~0.10%、
B:0.0001~0.05%、
Al:0~2.0%、
Ti:0~2.00%、
Nb:0~2.00%、
Sn:0~2.5%、
V:0~2.0%、
W:0~3.0%、
Ga:0~0.05%、
Co:0~2.5%、
Sb:0~2.5%、
Ta:0~2.5%、
Ca:0~0.05%、
Mg:0~0.012%、
Zr:0~0.012%、
REM:0~0.05%、
Pb:0~0.30%、
Se:0~0.80%、
Te:0~0.30%、
Bi:0~0.50%、
S:0~0.50%、
P:0~0.30%、
を含有し、残部:Feおよび不純物であり、
下記式(a)で示されるA値が-100以下であり、
B粒界占有率が1%以上であるステンレス鋼。
A値=551-462(C+N)-9.2Si―8.1Mn―29(Ni+Cu)-13.7Cr―18.5Mo (a)
但し、式(a)中の元素記号は、当該元素の鋼中における含有量(質量%)を意味する。また、式(a)中の元素の含有量が0%である場合は、該当記号箇所には「0」を代入して算出する。 The chemical composition, in mass %,
C: 0.0010 to 0.15%,
Si: 0.01 to 2.00%,
Mn: 0.01 to 10.00%,
Ni: 8.00 to 30.00%,
Cr: 9.0 to 21.0%,
Mo: 0.01 to 3.00%,
Cu: 0.01 to 5.00%,
N: 0.0010 to 0.10%,
B: 0.0001 to 0.05%,
Al: 0 to 2.0%,
Ti: 0 to 2.00%,
Nb: 0 to 2.00%,
Sn: 0-2.5%,
V: 0 to 2.0%,
W: 0 to 3.0%,
Ga: 0-0.05%,
Co: 0-2.5%,
Sb: 0-2.5%,
Ta: 0-2.5%,
Ca: 0-0.05%,
Mg: 0-0.012%,
Zr: 0 to 0.012%,
REM: 0-0.05%,
Pb: 0 to 0.30%,
Se: 0 to 0.80%,
Te: 0 to 0.30%,
Bi: 0 to 0.50%,
S: 0 to 0.50%,
P: 0 to 0.30%,
and the balance is Fe and impurities,
The A value represented by the following formula (a) is −100 or less,
A stainless steel having a B grain boundary occupancy of 1% or more.
A value = 551-462 (C+N)-9.2Si-8.1Mn-29(Ni+Cu)-13.7Cr-18.5Mo (a)
However, the symbol of an element in the formula (a) means the content (% by mass) of the element in the steel. Further, when the content of the element in the formula (a) is 0%, the calculation is performed by substituting "0" in the corresponding symbol.
A群として、
Al:0.001~2.0%、
Ti:0.01~2.00%、
Nb:0.01~2.00%、
Sn:0.0001~2.5%、
V:0.001~2.0%、
W:0.05~3.0%、
Ga:0.0004~0.05%、
Co:0.05~2.5%、
Sb:0.01~2.5%、および
Ta:0.01~2.5%、
から選択される一種以上、
B群として、
Ca:0.0002~0.05%、
Mg:0.0002~0.012%、
Zr:0.0002~0.012%、および
REM:0.0002~0.05%、
から選択される一種以上、
C群として、
Pb:0.0001~0.30%、
Se:0.0001~0.80%、
Te:0.0001~0.30%、
Bi:0.0001~0.50%、
S:0.0001~0.50%、および
P:0.0001~0.30%、
から選択される一種以上、
のA群~C群の一群以上を含有する、
請求項14に記載のステンレス鋼。 Further, the chemical composition is, in mass %,
As group A,
Al: 0.001 to 2.0%,
Ti: 0.01 to 2.00%,
Nb: 0.01 to 2.00%,
Sn: 0.0001 to 2.5%,
V: 0.001 to 2.0%,
W: 0.05 to 3.0%,
Ga: 0.0004 to 0.05%,
Co: 0.05-2.5%,
Sb: 0.01-2.5%, and Ta: 0.01-2.5%,
one or more selected from
As group B,
Ca: 0.0002-0.05%,
Mg: 0.0002-0.012%,
Zr: 0.0002-0.012%, and REM: 0.0002-0.05%,
one or more selected from
As group C,
Pb: 0.0001 to 0.30%,
Se: 0.0001 to 0.80%,
Te: 0.0001 to 0.30%,
Bi: 0.0001 to 0.50%,
S: 0.0001 to 0.50%, and P: 0.0001 to 0.30%,
one or more selected from
containing one or more groups of Groups A to C of
15. The stainless steel of claim 14.
Priority Applications (4)
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| JP2023566088A JP7737034B2 (en) | 2021-12-08 | 2022-08-03 | Stainless steel with excellent cold forging properties, hydrogen embrittlement resistance, corrosion resistance, and non-magnetic properties |
| CN202280079110.4A CN118318056A (en) | 2021-12-08 | 2022-08-03 | Stainless steel excellent in cold forging property, hydrogen embrittlement resistance, corrosion resistance and non-magnetic property |
| JP2024111005A JP7737046B2 (en) | 2021-12-08 | 2024-07-10 | Stainless steel with excellent cold forging properties and hydrogen embrittlement resistance |
| JP2024111006A JP7737047B2 (en) | 2021-12-08 | 2024-07-10 | Stainless steel with excellent cold forging properties, corrosion resistance, and non-magnetic properties |
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| WO2024181512A1 (en) * | 2023-03-02 | 2024-09-06 | 日鉄ステンレス株式会社 | Hot rolled steel material of austenitic stainless steel and method for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004307977A (en) * | 2003-04-10 | 2004-11-04 | Nippon Steel Corp | Nonmagnetic sulfur free-cutting stainless steel wire with excellent cold drawability and corrosion resistance |
| JP2008208430A (en) * | 2007-02-27 | 2008-09-11 | Nippon Steel & Sumikin Stainless Steel Corp | Soft austenitic stainless steel and method for producing the same |
| JP2008240053A (en) * | 2007-03-27 | 2008-10-09 | Nippon Steel & Sumikin Stainless Steel Corp | Austenitic stainless free-cutting steel with excellent cold forgeability and machinability |
| JP2017160520A (en) * | 2016-03-11 | 2017-09-14 | 日新製鋼株式会社 | Austenitic stainless steel |
| JP2018109215A (en) * | 2017-01-05 | 2018-07-12 | 日新製鋼株式会社 | Nonmagnetic austenitic stainless steel sheet and method for producing nonmagnetic member |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004307977A (en) * | 2003-04-10 | 2004-11-04 | Nippon Steel Corp | Nonmagnetic sulfur free-cutting stainless steel wire with excellent cold drawability and corrosion resistance |
| JP2008208430A (en) * | 2007-02-27 | 2008-09-11 | Nippon Steel & Sumikin Stainless Steel Corp | Soft austenitic stainless steel and method for producing the same |
| JP2008240053A (en) * | 2007-03-27 | 2008-10-09 | Nippon Steel & Sumikin Stainless Steel Corp | Austenitic stainless free-cutting steel with excellent cold forgeability and machinability |
| JP2017160520A (en) * | 2016-03-11 | 2017-09-14 | 日新製鋼株式会社 | Austenitic stainless steel |
| JP2018109215A (en) * | 2017-01-05 | 2018-07-12 | 日新製鋼株式会社 | Nonmagnetic austenitic stainless steel sheet and method for producing nonmagnetic member |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024181512A1 (en) * | 2023-03-02 | 2024-09-06 | 日鉄ステンレス株式会社 | Hot rolled steel material of austenitic stainless steel and method for producing same |
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