WO2020203939A1 - Stainless steel sheet - Google Patents
Stainless steel sheet Download PDFInfo
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- WO2020203939A1 WO2020203939A1 PCT/JP2020/014407 JP2020014407W WO2020203939A1 WO 2020203939 A1 WO2020203939 A1 WO 2020203939A1 JP 2020014407 W JP2020014407 W JP 2020014407W WO 2020203939 A1 WO2020203939 A1 WO 2020203939A1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
-
- 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
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
-
- 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
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
Definitions
- the present invention relates to stainless steel.
- SUS304N2-X which is an austenitic stainless steel
- SUS329J4L which is a duplex stainless steel
- Stainless steel is used as a countermeasure against corrosion in river structures, industrial machinery, chemical industry tanks, etc.
- a high-strength material is required for the purpose of weight reduction by thinning, so austenitic stainless steel SUS304N2-X containing N in SUS304 and omitting solution heat treatment is used. May be used.
- Two-phase stainless steel is said to have lower expensive Ni content and higher strength than austenitic stainless steel.
- duplex stainless steels that have undergone solution heat treatment do not have the strength of SUS304N2-X.
- SUS329J4L which is a typical steel type of duplex stainless steel, precipitation of ⁇ phase is unavoidable during hot rolling. Therefore, if solution heat treatment is omitted in order to obtain strength, ⁇ phase remains in the product. Corrosion resistance and toughness are greatly deteriorated.
- Patent Document 1 The stainless steel shown in Patent Document 1 has been proposed as a duplex stainless steel having increased strength by omitting solution heat treatment. This steel saves Mo and focuses on suppressing the precipitation of Cr nitrides.
- River structures, industrial machinery, chemical industry tanks, etc. may be in a severe corrosive environment due to chloride ions and acids in the contacting fluid. In such a place, the amount of Cr is small, and the desired corrosion resistance cannot be secured with SUS304N2-X that does not contain Mo.
- ⁇ -phase precipitation has a great influence on toughness and corrosion resistance.
- Cr nitride is a compound that precipitates by the interaction of Cr and N, and reduction of N and inclusion of austenite phase-forming elements (for example, Ni and Mn) are effective for suppressing precipitation of Cr nitride.
- the ⁇ phase is an intermetallic compound precipitated by the interaction of Cr and Mo, and Ni accelerates the precipitation of the ⁇ phase.
- Mn is an element that is effective in suppressing Cr nitride precipitation but deteriorates corrosion resistance.
- the hot-rolled steel sheet disclosed in Patent Document 1 has a limit in corrosion resistance because it does not consider deterioration of toughness and corrosion resistance due to precipitation of the ⁇ phase, and a steel sheet having further enhanced corrosion resistance and toughness is required. Has been done.
- the present inventors have sufficient corrosion resistance to be applied to structures such as river structures, industrial machinery, and chemical industry tanks, and further have strength and toughness equal to or higher than that of SUS304N2-X.
- the subject is to obtain a stainless steel plate.
- the present inventors have high strength even if solution heat treatment is omitted by designing a component that can avoid ⁇ phase precipitation during hot rolling while ensuring corrosion resistance.
- a stainless steel sheet with excellent corrosion resistance and toughness could be obtained. That is, a new estimation formula was found for the ⁇ -phase precipitation temperature TS, and using steel materials with different TSs according to this formula, the entry side temperature TF of the final finish rolling pass of hot rolling and 800 ° C. after the completion of hot rolling The cooling rate in the section of 600 ° C. was changed, and the strength, impact characteristics, and corrosion resistance of the obtained hot-rolled steel sheet were evaluated.
- the present invention has been completed, which clearly indicates the stainless hot-rolled steel sheet without the solution heat treatment.
- the gist of the present invention is as follows. [1] By mass% C: 0.001 to 0.030%, Si: 0.05 to 1.50%, Mn: 0.10 to 3.00%, Cr: 22.00 to 27.00%, Ni: 4.00 to 7.00%, Mo: 0.50 to 2.50%, W: 0 to 1.50%, N: 0.10 to 0.25%, Co: 0 to 1.00%, Cu: 0 to 3.00%, V: 0 to 1.00%, Nb: 0 to 0.200%, Ta: 0 to 0.200%, Ti: 0 to 0.030%, Zr: 0 to 0.050%, Hf: 0 to 0.100%, B: 0 to 0.0050%, Al: 0 to 0.050%, Ca: 0 to 0.0050%, Mg: 0 to 0.0050%, REM: 0 to 0.100%, and Sn: 0 to 0.100%, The rest is Fe and unavoidable impurities, O as an impurity: 0.006% or less, P
- the component in the stainless steel sheet is mass%, Co: 0.01-1.00%, Cu: 0.01-3.00%, V: 0.01-1.00%, Nb: 0.005 to 0.200%, Ta: 0.005 to 0.200%, Ti: 0.001 to 0.030%, Zr: 0.001 to 0.050%, Hf: 0.001 to 0.100%, B: 0.0001 to 0.0050%, Al: 0.003 to 0.050%, Ca: 0.0005-0.0050%, Mg: 0.0001 to 0.0050%, REM: 0.005 to 0.100%, and Sn: 0.005 to 0.100%
- the stainless steel sheet according to [1] which contains one or more of them.
- the stainless steel sheet obtained by the present invention has strength equal to or higher than that of SUS304N2-X, sufficient toughness as a structural material, and corrosion resistance higher than that of SUS304N2-X.
- the alloy cost is also reasonable, so the economy is good.
- C is limited to a content of 0.030% or less in order to ensure the corrosion resistance of stainless steel. If it is contained in excess of 0.030%, Cr carbides are generated during hot rolling, and corrosion resistance and toughness deteriorate. On the other hand, 0.001% is set as the lower limit from the viewpoint of cost of reducing the amount of C in stainless steel.
- Si is contained in an amount of 0.05% or more due to deoxidation. Preferably, it is 0.20% or more. On the other hand, if it is contained in excess of 1.50%, the toughness deteriorates. Therefore, it should be 1.50% or less. Preferably, it is 1.00% or less.
- Mn has the effect of increasing the austenite phase and lowering the ⁇ phase precipitation temperature, so it is preferable to contain Mn at 0.10% or more.
- Mn is an element that lowers the corrosion resistance of stainless steel, so Mn should be 3.0% or less.
- Cr is contained in an amount of 22.00% or more in order to ensure basic corrosion resistance. Preferably 23.00% or more, 24.00% or more, 25.00% or more, 25.10% or more, 25.20% or more, 25.30% or more, 25.40% or more, or 25.50% or more. It is good to set it to. On the other hand, since Cr is an element that promotes the precipitation of the ⁇ phase, the content is limited to 27.00% or less. It is preferably 26.90% or less, 26.80% or less, 26.70% or less, 26.60% or less, or 26.50% or less.
- Ni is an element that promotes the formation of an austenite structure and at the same time has the effect of suppressing the formation of Cr nitrides and has the effect of improving the corrosion resistance to various acids. Therefore, it is preferable to contain 4.00% or more. Preferably, the content is 4.50% or more, 5.00% or more, 5.10% or more, 5.20% or more, 5.30% or more, 5.40% or more, or 5.50% or more.
- Ni is an element that promotes the precipitation of the ⁇ phase, and when the ⁇ phase is precipitated, a Cr-deficient phase is formed and the local corrosion resistance deteriorates. Therefore, it is preferable to contain Ni in 7.00% or less. It is preferably 6.90% or less, 6.80% or less, 6.70% or less, 6.60% or less, or 6.50% or less.
- Mo is a very effective element that enhances the corrosion resistance of stainless steel, and it is preferable to contain 0.50% or more in order to impart corrosion resistance of 304N2-X or more.
- Mo is an element that promotes the precipitation of the ⁇ phase, and the local corrosion resistance deteriorates. Therefore, it is preferable to contain Mo in an amount of 2.50% or less. It is preferably 2.40% or less, 2.30% or less, 2.10% or less, and 2.00% or less.
- W has the effect of improving the corrosion resistance of stainless steel, similar to Mo.
- it is preferable to contain 1.50% as the upper limit for the purpose of enhancing the corrosion resistance.
- the preferable content is preferably 0.02% or more.
- N nitrogen
- N is an effective element that enhances the strength and corrosion resistance of stainless steel, so it is recommended that it be contained in an amount of 0.10% or more. It is preferably 0.15% or more.
- N produces Cr nitride and inhibits corrosion resistance, its content is preferably 0.25% or less. Preferably, it is 0.20% or less.
- the rest is Fe and unavoidable impurities.
- the unavoidable impurities are elements contained in the raw material, elements unintentionally contained during production, and the like. Of the impurities, O, P, and S are limited for the following reasons.
- O oxygen
- the O content is preferably 0.006% or less.
- P is an element that is inevitably mixed from the raw material, and since it deteriorates hot workability and toughness, it should be as small as possible and limited to 0.05% or less. Preferably, it is 0.03% or less.
- S is an element that is inevitably mixed from the raw material, and it also deteriorates hot workability, toughness, and corrosion resistance. Therefore, it should be as small as possible, and the upper limit should be 0.003% or less.
- Fe one or more of the following elements (Co, Cu, V, Nb, Ta, Ti, Zr, Hf, B, Al, Ca, Mg, REM, Sn) are contained. May be good. Since these elements do not have to be contained, the content range includes 0%.
- Co is an element effective for enhancing the corrosion resistance of steel and may be contained. Even if Co is contained in an amount of more than 1.00%, it is an expensive element and therefore an effect commensurate with the cost is not exhibited. Therefore, it is preferable to contain Co in an amount of 1.00% or less. It is preferably contained in an amount of 0.50% or less. In order to obtain the effect, it is preferable to contain 0.01% or more, preferably 0.03% or more.
- Cu may be contained because it is an element that additionally enhances the corrosion resistance of stainless steel to acid. If Cu is contained in an amount of more than 3.0%, ⁇ Cu is precipitated in excess of the solid solubility during cooling after hot rolling and embrittlement occurs. Therefore, it is preferable to contain Cu in an amount of 3.00% or less. It is preferably contained in an amount of 2.00% or less. When Cu is contained, it is preferable to contain it in an amount of 0.01% or more, preferably 0.20% or more in order to obtain the effect.
- V, Nb, and Ta are elements that form carbides and nitrides in steel and additionally enhance corrosion resistance, they may be contained. On the other hand, if a large amount is contained, the toughness will be inhibited by excessively formed carbides and nitrides. Therefore, the contents of V, Nb and Ta are 1.00% or less, 0.200% or less and 0, respectively. .200% or less is recommended. When these elements are contained, they are preferably contained in an amount of 0.01% or more, 0.005% or more, and 0.005% or more, respectively, in order to obtain the effect.
- Ti, Zr, and Hf may be contained because they are elements that form carbides and nitrides in steel to refine crystal grains. On the other hand, if a large amount is contained, the toughness will be inhibited by excessively formed carbides and nitrides. Therefore, the contents of Ti, Zr, and Hf are 0.030% or less, 0.050% or less, and 0, respectively. It should be 100% or less. When these elements are contained, they are preferably contained in an amount of 0.001% or more, 0.001% or more, and 0.001% or more, respectively, in order to obtain the effect.
- B is an element that improves the hot workability of steel and may be contained. On the other hand, if it is contained in a large amount, the nitride of B is precipitated and the toughness is inhibited. Therefore, the content may be 0.0050% or less. When B is contained, it is preferable to contain 0.0001% or more, preferably 0.0005% or more in order to obtain the effect.
- Al is an element for deoxidizing steel and may be contained. On the other hand, if it is contained in excess, Al nitride is generated and the toughness is inhibited. Therefore, the content should be 0.050% or less. It is preferably 0.030% or less. When Al is contained, it is preferably 0.003% or more, preferably 0.005% or more in order to obtain the effect.
- Ca and Mg may be contained in order to enhance hot workability. On the other hand, if it is excessively contained, the hot workability is adversely affected. Therefore, the Ca and Mg contents are preferably 0.0050% or less and 0.0050% or less, respectively. When these elements are contained, it is preferable to set them to 0.0005% or more and 0.0001% or more, respectively, in order to obtain the effect.
- REM may be contained because it is an element that improves the hot workability of steel. On the other hand, excessive content lowers hot workability and toughness, so when REM is contained, it is preferably 0.100% or less. When REM is contained, 0.005% or more may be contained in order to obtain the effect.
- the content of REM is the sum of the contents of lanthanoid rare earth elements such as La and Ce.
- Sn may be contained because it is an element that enhances the corrosion resistance of steel to acid. On the other hand, if it is contained in excess, it impairs hot workability. Therefore, when Sn is contained, it is preferably 0.100% or less. When Sn is contained, it is preferable to make it 0.005% or more in order to obtain the effect.
- PREW is an index for the pitting corrosion resistance of stainless steel, and is calculated by Equation 1 using the contents (%) of the alloying elements Cr, Mo, W, and N. If the PREW of stainless steel is less than 25.0, it cannot exhibit corrosion resistance in brackish water / seawater environment and chloride ion environment such as chemical industry tank. The upper limit is not particularly limited, but if the alloying element is contained in excess of 36.0, the cost will increase. Therefore, the PREW range is preferably 25.0 or more and 36.0 or less.
- PREW Cr + 3.3 (Mo + 0.5W) + 16N (Equation 1) However, each element symbol in the formula 1 indicates the content (mass%) of the element, and if it is not contained, 0 is substituted.
- the PREW value may be 25.0 or more by containing Cr, Mo, N, and W.
- the lower limit of PREW is preferably 26.0, 27.0, 28.0, 29.0, 29.5, 30.0, 30.5, or 31.0.
- the upper limit of PREW should be 36.0.
- the precipitation temperature of the ⁇ phase is determined by the chemical composition of the steel, and the temperature range in which the ⁇ phase can precipitate in a chemical equilibrium state can be estimated by thermodynamic calculation. For example, it can be calculated using commercially available software called Thermocalc (registered trademark) and a thermodynamic database (FE-DATA version 6 or the like). Using the above software and database, the present inventors obtained Equation 2 for estimating the upper limit of the ⁇ -phase precipitation temperature region (hereinafter referred to as ⁇ -phase precipitation temperature, which is indicated by TS). Further, in order to suppress the precipitation of the ⁇ phase and obtain the desired characteristics, the TS is preferably 950 ° C. or lower.
- the TS is 930 ° C or lower, or 910 ° C or lower.
- the lower the TS the more difficult it is for the ⁇ phase to precipitate, but this leads to a decrease in Cr, Mo, and W, resulting in insufficient corrosion resistance. Therefore, the lower limit of TS may be set to 800 ° C. It is preferably 820 ° C. or higher, 830 ° C. or higher, or 840 ° C. or higher.
- TS (° C.) 4Cr + 25Ni-11 (Mo + W) x (Mo + W) + 100 (Mo + W) + 5Si-6Mn-30N + 550 (Equation 2)
- each element symbol in the formula 2 indicates the content (mass%) of the element, and if it is not contained, 0 is substituted.
- the following formula 2' may be used as the estimation formula for the ⁇ phase precipitation temperature TS.
- Equation 2'and Equation 2 are equivalent.
- TS (° C.) 4Cr + 25Ni + 71 (Mo + W) -11.4 (Mo-1.3) * (Mo-1.3) + 5Si-6Mn-30N + 569 (Equation 2')
- the hot rolling process will be described below.
- the slab heating temperature before the start of rolling may be appropriately determined, for example, in the range of 1150 to 1250 ° C.
- the finishing temperature TF (steel surface temperature at the entrance of the final pass of hot rolling) is too high and is close to the solution heat treatment temperature, sufficient strain does not remain in the hot-rolled steel sheet, and the desired hardness is obtained. Cannot be obtained.
- the TF is too low, precipitation of the ⁇ phase is unavoidable.
- TS is an estimated value of the ⁇ -phase precipitation temperature when the steel sheet is held in a chemical equilibrium state, that is, for an infinite time, the actual hot rolling is completed in a finite time, so that the TF does not need to exceed TS. Equation 3 may be satisfied as long as the component range is specified in the present invention.
- the conditions other than the finishing temperature are not particularly limited, and for example, the rolling amount for each pass may be determined according to the capacity of the rolling mill.
- cooling may be performed at a cooling rate of 1 ° C./s or more in the section of 800 ° C. to 600 ° C. within the component range specified in the present invention.
- the cooling method is not particularly limited, and water cooling or air cooling may be used depending on the plate thickness. As described above, it is not necessary to carry out solution heat treatment on the hot-rolled steel sheet thus obtained.
- the strength should be equal to or higher than SUS304N2-X, that is, 0.2% proof stress of 450 MPa or higher. It may be preferably 480 MPa or more.
- Stainless steel is used outdoors as a river structure and in chemical plants together with cooling equipment, so it may be exposed to temperatures below room temperature. In order to use it as a structural member in such an environment, toughness at low temperature is required, and specifically, the Charpy impact value of the hot-rolled steel sheet at ⁇ 20 ° C. may be 70 J / cm 2 or more.
- the pitting potential of a hot-rolled steel sheet at 50 ° C. is 0.40 V vs. It may be SSE or higher.
- vs. SSE indicates that the potential is based on a silver-silver chloride reference electrode using a saturated KCl aqueous solution at 25 ° C. as an electrolyte.
- the ones that affect the corrosion resistance are those precipitated during the hot rolling and subsequent cooling processes. Therefore, hot rolling and subsequent hot rolling are performed based on the difference ⁇ Cr between the amount of Cr extraction residue of the hot-rolled steel sheet and the amount of Cr extraction residue of the steel sheet obtained by subjecting the hot-rolled steel sheet to solution heat treatment at 1000 to 1100 ° C. and then water-cooling. The effect of precipitation during the cooling process was quantified. As a result, when ⁇ Cr exceeds 0.010% in terms of Cr content in the steel sheet, the corrosion resistance of the hot-rolled steel sheet tends to decrease. Therefore, it is preferable that ⁇ Cr is 0.010% or less.
- Table 1 shows the chemical composition, PREW, and TS of the test steel.
- the components not shown in Table 1 are Fe and unavoidable impurity elements. These steels were obtained using a vacuum melting furnace. Regarding the components shown in Table 1, the portion where the content is not described is the unavoidable impurity level.
- REM means lanthanoid rare earth elements, and the content indicates the total of these elements.
- the slabs obtained by vacuum melting were heated at 1200 ° C. for 2 hours, and then hot forged to obtain steel ingots having a predetermined shape.
- the shape of the ingot was 110 mm width ⁇ 150 mm length ⁇ 60 mm thickness when the plate thickness after finish rolling was 20 mm or less, and 110 mm width ⁇ 150 mm length ⁇ 100 mm thickness when the plate thickness exceeded 20 mm.
- Table 2 shows the conditions of the hot rolling and the subsequent cooling rate performed to make the ingot into a steel sheet, and the values of 0.2% strength, Charpy absorption energy, and pitting corrosion potential of the obtained hot-rolled steel sheet.
- the ingot obtained by the above-mentioned forging was soaked in heat at 1200 ° C. for 60 minutes.
- the TF was reduced to the temperature shown in Table 2 and cooled so that the cooling rate in the section of 800 ° C. to 600 ° C. became the value shown in the table.
- the cooling method was water cooling.
- the method of measuring 0.2% proof stress is described.
- the No. 4 test piece described in JIS Z2241: 2011 was cut out from the steel plate after hot rolling by machining.
- the measurement method was carried out in accordance with JIS Z2241: 2011.
- the method of measuring Charpy absorbed energy is described.
- the test piece described in JIS Z2242: 2018 was cut out from the steel sheet after hot rolling by machining.
- the notch shape was a V notch.
- a subsize test piece was collected as shown in Table 2.
- the measurement was carried out in accordance with JIS Z2242: 2018. However, the test temperature was ⁇ 20 ° C.
- the method of measuring the pitting potential is described below.
- a sample having a width of 15 mm, a length of 30 mm, and a thickness of 2 mm was cut out by machining from the surface layer of the steel sheet after hot rolling, and after grinding 0.5 mm from the surface layer, a test piece having a measurement surface of # 600 wet polishing finish was prepared.
- a resin was applied to this test piece, leaving a portion of 10 mm ⁇ 10 mm on the measurement surface.
- the test was carried out using this test piece according to the method of JIS G0577: 2014. However, in JIS G0577: 2014, the temperature of the test was changed from 30 ° C to 50 ° C. The measurement was carried out until the anode current density reached 1 mA / cm 2 , and the pitting potential was the potential at the time when the current density exceeded 100 ⁇ A / cm 2 .
- the stainless steel sheet according to the present invention has strength equal to or higher than that of existing stainless steels (SUS304N2-X and SUS329J4L), has toughness and corrosion resistance suitable for structural members, and is also excellent in economy. It can be used for all industrial equipment and structures such as for chemical plants.
Abstract
Description
以上の実験を通じて、溶体化熱処理を省略したステンレス熱延鋼板について明示した本発明の完成に至った。 In order to solve the above problems, the present inventors have high strength even if solution heat treatment is omitted by designing a component that can avoid σ phase precipitation during hot rolling while ensuring corrosion resistance. However, it was thought that a stainless steel sheet with excellent corrosion resistance and toughness could be obtained. That is, a new estimation formula was found for the σ-phase precipitation temperature TS, and using steel materials with different TSs according to this formula, the entry side temperature TF of the final finish rolling pass of hot rolling and 800 ° C. after the completion of hot rolling The cooling rate in the section of 600 ° C. was changed, and the strength, impact characteristics, and corrosion resistance of the obtained hot-rolled steel sheet were evaluated.
Through the above experiments, the present invention has been completed, which clearly indicates the stainless hot-rolled steel sheet without the solution heat treatment.
[1]
質量%で、
C:0.001~0.030%、
Si:0.05~1.50%、
Mn:0.10~3.00%、
Cr:22.00~27.00%、
Ni:4.00~7.00%、
Mo:0.50~2.50%、
W:0~1.50%、
N:0.10~0.25%、
Co:0~1.00%、
Cu:0~3.00%、
V:0~1.00%、
Nb:0~0.200%、
Ta:0~0.200%、
Ti:0~0.030%、
Zr:0~0.050%、
Hf:0~0.100%、
B:0~0.0050%、
Al:0~0.050%、
Ca:0~0.0050%、
Mg:0~0.0050%、
REM:0~0.100%、および
Sn:0~0.100%を含み、
残部がFeおよび不可避的不純物であり、
不純物として
O:0.006%以下、
P:0.05%以下、
S:0.003%以下に制限した鋼であり、
式1で求められるPREWが25.0以上36.0以下であり
式2で求められるσ相析出温度TS(℃)が800℃以上、950℃以下であり、
0.2%耐力が450MPa以上、
-20℃におけるシャルピー衝撃値が70J/cm2以上、
50℃で測定した孔食電位が0.40V vs. SSE以上
であることを特徴とするステンレス鋼板。
PREW=Cr+3.3(Mo+0.5W)+16N (式1)
TS(℃)=4Cr+25Ni-11(Mo+W)×(Mo+W)+100(Mo+W)+5Si-6Mn-30N+550 (式2)
ただし、式1、式2における各元素記号は、当該元素の含有量(質量%)を示し、含有しない場合は0を代入する。
[2]
前記ステンレス鋼板における成分が、質量%で、
Co:0.01~1.00%、
Cu:0.01~3.00%、
V:0.01~1.00%、
Nb:0.005~0.200%、
Ta:0.005~0.200%、
Ti:0.001~0.030%、
Zr:0.001~0.050%、
Hf:0.001~0.100%、
B:0.0001~0.0050%、
Al:0.003~0.050%、
Ca:0.0005~0.0050%、
Mg:0.0001~0.0050%、
REM:0.005~0.100%、および
Sn:0.005~0.100%
うち1種または2種以上を含有する[1]に記載のステンレス鋼板。 That is, the gist of the present invention is as follows.
[1]
By mass%
C: 0.001 to 0.030%,
Si: 0.05 to 1.50%,
Mn: 0.10 to 3.00%,
Cr: 22.00 to 27.00%,
Ni: 4.00 to 7.00%,
Mo: 0.50 to 2.50%,
W: 0 to 1.50%,
N: 0.10 to 0.25%,
Co: 0 to 1.00%,
Cu: 0 to 3.00%,
V: 0 to 1.00%,
Nb: 0 to 0.200%,
Ta: 0 to 0.200%,
Ti: 0 to 0.030%,
Zr: 0 to 0.050%,
Hf: 0 to 0.100%,
B: 0 to 0.0050%,
Al: 0 to 0.050%,
Ca: 0 to 0.0050%,
Mg: 0 to 0.0050%,
REM: 0 to 0.100%, and Sn: 0 to 0.100%,
The rest is Fe and unavoidable impurities,
O as an impurity: 0.006% or less,
P: 0.05% or less,
S: Steel limited to 0.003% or less,
The PREW obtained by the formula 1 is 25.0 or more and 36.0 or less, and the σ phase precipitation temperature TS (° C.) obtained by the formula 2 is 800 ° C. or more and 950 ° C. or less.
0.2% proof stress is 450MPa or more,
Charpy impact value at -20 ° C is 70 J / cm 2 or more,
The pitting potential measured at 50 ° C. is 0.40 V vs. A stainless steel plate characterized by being SSE or higher.
PREW = Cr + 3.3 (Mo + 0.5W) + 16N (Equation 1)
TS (° C.) = 4Cr + 25Ni-11 (Mo + W) x (Mo + W) + 100 (Mo + W) + 5Si-6Mn-30N + 550 (Equation 2)
However, each element symbol in the formulas 1 and 2 indicates the content (mass%) of the element, and if it is not contained, 0 is substituted.
[2]
The component in the stainless steel sheet is mass%,
Co: 0.01-1.00%,
Cu: 0.01-3.00%,
V: 0.01-1.00%,
Nb: 0.005 to 0.200%,
Ta: 0.005 to 0.200%,
Ti: 0.001 to 0.030%,
Zr: 0.001 to 0.050%,
Hf: 0.001 to 0.100%,
B: 0.0001 to 0.0050%,
Al: 0.003 to 0.050%,
Ca: 0.0005-0.0050%,
Mg: 0.0001 to 0.0050%,
REM: 0.005 to 0.100%, and Sn: 0.005 to 0.100%
The stainless steel sheet according to [1], which contains one or more of them.
PREW=Cr+3.3(Mo+0.5W)+16N (式1)
ただし、式1における各元素記号は、当該元素の含有量(質量%)を示し、含有しない場合は0を代入する。 PREW is an index for the pitting corrosion resistance of stainless steel, and is calculated by Equation 1 using the contents (%) of the alloying elements Cr, Mo, W, and N. If the PREW of stainless steel is less than 25.0, it cannot exhibit corrosion resistance in brackish water / seawater environment and chloride ion environment such as chemical industry tank. The upper limit is not particularly limited, but if the alloying element is contained in excess of 36.0, the cost will increase. Therefore, the PREW range is preferably 25.0 or more and 36.0 or less.
PREW = Cr + 3.3 (Mo + 0.5W) + 16N (Equation 1)
However, each element symbol in the formula 1 indicates the content (mass%) of the element, and if it is not contained, 0 is substituted.
TS(℃)=4Cr+25Ni-11(Mo+W)×(Mo+W)+100(Mo+W)+5Si-6Mn-30N+550 (式2)
ただし、式2における各元素記号は、当該元素の含有量(質量%)を示し、含有しない場合は0を代入する。
なお、σ相析出温度TSの推定式は以下の式2’を用いてもよい。本発明の範囲であれば、式2’も式2でも同等である。
TS(℃)=4Cr+25Ni+71(Mo+W)-11.4(Mo-1.3)*(Mo-1.3)+5Si-6Mn-30N+569 (式2’) The precipitation temperature of the σ phase is determined by the chemical composition of the steel, and the temperature range in which the σ phase can precipitate in a chemical equilibrium state can be estimated by thermodynamic calculation. For example, it can be calculated using commercially available software called Thermocalc (registered trademark) and a thermodynamic database (FE-DATA version 6 or the like). Using the above software and database, the present inventors obtained Equation 2 for estimating the upper limit of the σ-phase precipitation temperature region (hereinafter referred to as σ-phase precipitation temperature, which is indicated by TS). Further, in order to suppress the precipitation of the σ phase and obtain the desired characteristics, the TS is preferably 950 ° C. or lower. Preferably, the TS is 930 ° C or lower, or 910 ° C or lower. The lower the TS, the more difficult it is for the σ phase to precipitate, but this leads to a decrease in Cr, Mo, and W, resulting in insufficient corrosion resistance. Therefore, the lower limit of TS may be set to 800 ° C. It is preferably 820 ° C. or higher, 830 ° C. or higher, or 840 ° C. or higher.
TS (° C.) = 4Cr + 25Ni-11 (Mo + W) x (Mo + W) + 100 (Mo + W) + 5Si-6Mn-30N + 550 (Equation 2)
However, each element symbol in the formula 2 indicates the content (mass%) of the element, and if it is not contained, 0 is substituted.
The following formula 2'may be used as the estimation formula for the σ phase precipitation temperature TS. Within the scope of the present invention, both Equation 2'and Equation 2 are equivalent.
TS (° C.) = 4Cr + 25Ni + 71 (Mo + W) -11.4 (Mo-1.3) * (Mo-1.3) + 5Si-6Mn-30N + 569 (Equation 2')
圧延開始前の鋳片加熱温度は適宜定めればよく、例えば、1150~1250℃の範囲などであればよい。 The hot rolling process will be described below.
The slab heating temperature before the start of rolling may be appropriately determined, for example, in the range of 1150 to 1250 ° C.
TF-TS≧-100 (式3) Next, regarding the pass schedule, if the finishing temperature TF (steel surface temperature at the entrance of the final pass of hot rolling) is too high and is close to the solution heat treatment temperature, sufficient strain does not remain in the hot-rolled steel sheet, and the desired hardness is obtained. Cannot be obtained. On the other hand, if the TF is too low, precipitation of the σ phase is unavoidable. However, since TS is an estimated value of the σ-phase precipitation temperature when the steel sheet is held in a chemical equilibrium state, that is, for an infinite time, the actual hot rolling is completed in a finite time, so that the TF does not need to exceed TS. Equation 3 may be satisfied as long as the component range is specified in the present invention. The conditions other than the finishing temperature are not particularly limited, and for example, the rolling amount for each pass may be determined according to the capacity of the rolling mill.
TF-TS ≧ -100 (Equation 3)
Claims (2)
- 質量%で、
C:0.001~0.030%、
Si:0.05~1.50%、
Mn:0.10~3.00%、
Cr:22.00~27.00%、
Ni:4.00~7.00%、
Mo:0.50~2.50%、
W:0~1.50%、
N:0.10~0.25%、
Co:0~1.00%、
Cu:0~3.00%、
V:0~1.00%、
Nb:0~0.200%、
Ta:0~0.200%、
Ti:0~0.030%、
Zr:0~0.050%、
Hf:0~0.100%、
B:0~0.0050%、
Al:0~0.050%、
Ca:0~0.0050%、
Mg:0~0.0050%、
REM:0~0.100%、および
Sn:0~0.100%を含み、
残部がFeおよび不可避的不純物であり、
不純物として
O:0.006%以下、
P:0.05%以下、
S:0.003%以下に制限した鋼であり、
式1で求められるPREWが25.0以上36.0以下であり
式2で求められるσ相析出温度推定式TS(℃)が800℃以上、950℃以下であり、
0.2%耐力が450MPa以上、
-20℃におけるシャルピー衝撃値が70J/cm2以上、
50℃で測定した孔食電位が0.40V vs. SSE以上
であることを特徴とするステンレス鋼板。
PREW=Cr+3.3(Mo+0.5W)+16N (式1)
TS(℃)=4Cr+25Ni-11(Mo+W)×(Mo+W)+100(Mo+W)+5Si-6Mn-30N+550 (式2)
ただし、式1、式2における各元素記号は、当該元素の含有量(質量%)を示し、含有しない場合は0を代入する。 By mass%
C: 0.001 to 0.030%,
Si: 0.05 to 1.50%,
Mn: 0.10 to 3.00%,
Cr: 22.00 to 27.00%,
Ni: 4.00 to 7.00%,
Mo: 0.50 to 2.50%,
W: 0 to 1.50%,
N: 0.10 to 0.25%,
Co: 0 to 1.00%,
Cu: 0 to 3.00%,
V: 0 to 1.00%,
Nb: 0 to 0.200%,
Ta: 0 to 0.200%,
Ti: 0 to 0.030%,
Zr: 0 to 0.050%,
Hf: 0 to 0.100%,
B: 0 to 0.0050%,
Al: 0 to 0.050%,
Ca: 0 to 0.0050%,
Mg: 0 to 0.0050%,
REM: 0 to 0.100%, and Sn: 0 to 0.100%,
The rest is Fe and unavoidable impurities,
O as an impurity: 0.006% or less,
P: 0.05% or less,
S: Steel limited to 0.003% or less,
The PREW obtained by the formula 1 is 25.0 or more and 36.0 or less, and the σ phase precipitation temperature estimation formula TS (° C.) obtained by the formula 2 is 800 ° C. or more and 950 ° C. or less.
0.2% proof stress is 450MPa or more,
Charpy impact value at -20 ° C is 70 J / cm 2 or more,
The pitting potential measured at 50 ° C. is 0.40 V vs. A stainless steel plate characterized by being SSE or higher.
PREW = Cr + 3.3 (Mo + 0.5W) + 16N (Equation 1)
TS (° C.) = 4Cr + 25Ni-11 (Mo + W) x (Mo + W) + 100 (Mo + W) + 5Si-6Mn-30N + 550 (Equation 2)
However, each element symbol in the formulas 1 and 2 indicates the content (mass%) of the element, and if it is not contained, 0 is substituted. - 前記ステンレス鋼板における成分が、質量%で、
Co:0.01~1.00%、
Cu:0.01~3.00%、
V:0.01~1.00%、
Nb:0.005~0.200%、
Ta:0.005~0.200%、
Ti:0.001~0.030%、
Zr:0.001~0.050%、
Hf:0.001~0.100%、
B:0.0001~0.0050%、
Al:0.003~0.050%、
Ca:0.0005~0.0050%、
Mg:0.0001~0.0050%、
REM:0.005~0.100%、および
Sn:0.005~0.100%
うち1種または2種以上を含有する請求項1に記載のステンレス鋼板。 The component in the stainless steel sheet is mass%,
Co: 0.01-1.00%,
Cu: 0.01-3.00%,
V: 0.01-1.00%,
Nb: 0.005 to 0.200%,
Ta: 0.005 to 0.200%,
Ti: 0.001 to 0.030%,
Zr: 0.001 to 0.050%,
Hf: 0.001 to 0.100%,
B: 0.0001 to 0.0050%,
Al: 0.003 to 0.050%,
Ca: 0.0005-0.0050%,
Mg: 0.0001 to 0.0050%,
REM: 0.005 to 0.100%, and Sn: 0.005 to 0.100%
The stainless steel sheet according to claim 1, which contains one or more of them.
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