WO2016117458A1 - 加熱後耐食性に優れた排気系部材用フェライト系ステンレス鋼 - Google Patents

加熱後耐食性に優れた排気系部材用フェライト系ステンレス鋼 Download PDF

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WO2016117458A1
WO2016117458A1 PCT/JP2016/051086 JP2016051086W WO2016117458A1 WO 2016117458 A1 WO2016117458 A1 WO 2016117458A1 JP 2016051086 W JP2016051086 W JP 2016051086W WO 2016117458 A1 WO2016117458 A1 WO 2016117458A1
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stainless steel
corrosion resistance
heating
ferritic stainless
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PCT/JP2016/051086
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English (en)
French (fr)
Japanese (ja)
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信彦 平出
裕史 浦島
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新日鐵住金ステンレス株式会社
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Priority to JP2016570601A priority Critical patent/JP6779790B2/ja
Priority to KR1020197022451A priority patent/KR20190092621A/ko
Priority to US15/544,476 priority patent/US20180016655A1/en
Priority to KR1020177020528A priority patent/KR20170101262A/ko
Priority to CN201680006170.8A priority patent/CN107208213B/zh
Priority to MX2017009376A priority patent/MX2017009376A/es
Priority to PL16740065T priority patent/PL3249067T3/pl
Priority to EP16740065.4A priority patent/EP3249067B1/en
Priority to ES16740065T priority patent/ES2837114T3/es
Publication of WO2016117458A1 publication Critical patent/WO2016117458A1/ja

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    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/005—Ferrite

Definitions

  • the present invention relates to a ferritic stainless steel and an exhaust system member excellent in corrosion resistance after heating for exhaust system members of passenger cars, motorcycles, commercial vehicles, construction machines, and the like, and methods for producing them.
  • the present invention relates to a ferritic stainless steel used in a state in which an oxide film is formed on the surface by heating to 573 to 1073K.
  • Ferritic stainless steel is often used for exhaust system members such as passenger cars, motorcycles, commercial vehicles, and construction machinery.
  • C and N are fixed with Ti and SUH409L steel containing 11% Cr, C and N with Ti SUS430LX that is fixed and contains about 17% Cr, and SUS436J1L and SUS436L that further contain Mo are often used.
  • HAZ weld heat affected zone
  • the corrosion resistance here refers to the corrosion resistance against exhaust gas condensate on the inner surface side and the corrosion resistance against salt damage on the outer surface side.
  • the generation of holes is regarded as a problem. Therefore, although resistance to perforation is regarded as important among the corrosion resistances, in addition to this, appearance deterioration due to rusting has recently started to be regarded as a problem.
  • Patent Document 1 C: 0.015% or less, N: 0.02% or less, Si: 1.0% or less, Ni: more than 0.6 to 3.0%, Cr: 16.0 to 25 0.0%, Mo: 3.0% or less and Cu: 2.0% or less, if necessary, Mn: 2.0% or less, Mn: 2.0% or less, Ti: 0.5 %: Nb: 0.5% or less, Al: 0.5% or less, and B: 0.01% or less, including one or more, P: 0.04% or less, S: 0.02 A stainless steel plate with improved crevice corrosion resistance in which a matrix limited to not more than 1% exhibits a ferrite single phase structure is disclosed.
  • Patent Document 2 C: 0.001 to 0.02%, N: 0.001 to 0.02%, Si: 0.01 to 0.3%, Mn: 0.05 to 1%, P : 0.04% or less, Ni: 0.15 to 2%, Cr: 11 to 22%, Ti: 0.01 to 0.5%, Mo: 0.5 to 3.0%, Nb: 0 0.02 to 0.6%, Cu: containing 0.1 or 1.5% of Mo, Nb, or Cu in a range satisfying Cr + 3Mo + 6 (Ni + Nb + Cu) ⁇ 22
  • Both Patent Document 1 and Patent Document 2 relate to stainless steel containing Ni and improving crevice corrosion resistance, and are characterized by suppressing the growth rate of corrosion and increasing resistance to perforation. There is no description about the corrosion resistance in the state in which the oxide film is formed by heating.
  • Patent Document 3 C: 0.0010 to 0.30%, N: 0.0010 to 0.050%, Si: 0.01 to 1.0%, Mn: 0.01 to 1.0%, P : 0.04% or less, S: 0.010% or less, Ni: 1.0% or less, Cr: 10.0 to 30.0%, O: 0.010% or less, Sn, Sb 1 Ferritic stainless steel containing 0.005 to 0.10% of seeds or more, and optionally containing Ti: 0.0050 to 0.5% and Nb: 0.01 to 1.0% Steel is disclosed. The inclusion of one or more of Sn and Sb prevents P grain boundary segregation and prevents surface scratches caused by grain boundary corrosion during sulfuric acid pickling.
  • Patent Document 4 C: 0.02% or less, N: 0.02% or less, Cr: 3 to 30%, and one or two of Ti and Nb satisfy (Ti + Nb) / (C + N) ⁇ 8.
  • a method for producing a high-purity Cr-containing steel sheet that is excellent in press formability, in which the ferrite grain size of the slab and the coiling temperature in hot rolling are defined within a certain range is disclosed, and is caused by Cr carbonitride It is said that containing 0.5% or less of Sn is effective in suppressing intergranular corrosion.
  • Patent Document 5 C: 0.001 to 0.02%, N: 0.001 to 0.02%, Si: 0.01 to 0.5%, Mn: 0.05 to 1%, P : 0.04% or less, S: 0.01% or less, Cr: 12 to 25%, one or two of Ti and Nb: Ti: 0.02 to 0.5%, Nb: 0.02 to 1 %, And one or two of Sn and Sb are included in the range of Sn: 0.005 to 2% and Sb: 0.005 to 1%. Ferrite with excellent crevice corrosion resistance Stainless steel is disclosed.
  • Patent Document 1 Similar to Ni in Patent Document 1 and Patent Document 2, it relates to stainless steel that has improved crevice corrosion resistance by containing Sn and Sb, and has increased resistance to perforation by suppressing the growth rate of corrosion. It is characterized by.
  • Patent Documents 3 to 5 mentions corrosion resistance in a state where an oxide film is formed by heating.
  • Patent Document 6 C: 0.015% or less, N: 0.015% or less, Si: 0.10 to 0.50%, Mn: 0.05 to 0.50%, P: 0.050% or less , S: 0.0100% or less, Cr: 10.5 to 16.5%, one or two of Ti and Nb: Ti: 0.03 to 0.30%, Nb: 0.03 to 0.30 %, 1 or 2 of Sn and Sb are included in the range of Sn: 0.03-0.50%, Sb: 0.03-0.50%, Cr + Si + 0.5Mn + 10Al + 15 (Sn + Sb) ⁇ 13
  • Patent Document 7 C: 0.015% or less, N: 0.015% or less, Si: 0.01 to 0.50%, Mn: 0.01 to 0.50%, P: 0.050% or less , S: 0.010% or less, Cr: 16.5 to 22.5%, Al: 0.01 to 0.100%, one or two of Ti and Nb being Ti: 0.03 to 0.30 %, Nb: In the range of 0.03-0.30%, one or two of Sn and Sb are contained in Sn: 0.03-1.00%, Sb: 0.05-1.00% A reduced Mo type ferritic stainless steel for automobile exhaust system members having excellent post-heating corrosion resistance is disclosed.
  • Patent Document 8 C: 0.015% or less, N: 0.015% or less, Si: 0.01 to 0.50%, Mn: 0.01 to 0.50%, P: 0.050% or less S: 0.010% or less, Ni: 0.5-2.0%, Cr: 16.5-22.5%, Al: 0.010-0.100%, Sn: 0.01-0. 50%, ferrite for automobile exhaust system member containing 1 or 2 of Ti and Nb in the range of Ti: 0.03-0.30% and Nb: 0.03-0.30% Stainless steel is disclosed.
  • Patent Documents 6 to 8 all describe the corrosion resistance in a state where an oxide film is formed by heating, but do not mention the composition and formation conditions of the oxide film.
  • Exhaust system parts such as passenger cars, two-wheeled vehicles, commercial vehicles, and construction machines have a need to reduce the thickness and weight and extend the life, and the exhaust system downstream members are required to have improved corrosion resistance. Although these members are practically heated by welding and heated during running, an oxide film is locally formed, but the corrosion resistance is inferior to that when no oxide film is formed. The influence on fertility is great. Therefore, improving the corrosion resistance in the state where the oxide film is formed is effective in reducing the thickness, extending the life and maintaining the appearance.
  • the present invention has been proposed in view of these problems, and provides a ferritic stainless steel and an exhaust system member excellent in post-heating corrosion resistance that can be suitably used as a material for an exhaust system member, and a method for producing the same. With the goal.
  • the gist of the present invention aimed at solving the above problems is as follows. (1) By mass%, C: 0.015% or less, N: 0.02% or less, Si: 0.03-1.0%, Mn: 1.0% or less, P: 0.04% or less, S: 0.01% or less, Cr: 10.5 to 22.5%, Sn: 0.02 to 0.5%, Al: 0.003 to 0.2%, and Ti: 0.
  • the ferrite system for exhaust system members having excellent corrosion resistance after heating, characterized in that a layer containing 2 to 15 nm of Sn more than twice the base material concentration is formed when heated in the air under conditions satisfying the above formula Stainless steel.
  • An exhaust system member excellent in corrosion resistance after heating comprising a ferritic stainless steel, wherein a layer containing Sn having a concentration twice or more is formed in a thickness of 2 to 15 nm.
  • the ferritic stainless steel of the present invention is composed of the ferritic stainless steel of the present invention, characterized in that the Sn content is 0.02% to less than 0.05% and / or 0.07% to 0.3% by mass.
  • the finish annealing temperature for cold rolling is set to 1030 ° C. or lower, and the cooling rate in the range of 800 to 600 ° C. is set to 20 ° C. for cooling from the cold rolled sheet annealing temperature.
  • the method for producing a ferritic stainless steel for exhaust system members having excellent post-heating corrosion resistance according to the present invention characterized by being less than / s.
  • the finish annealing temperature for cold rolling is set to 1030 ° C. or lower, and the cooling rate in the range of 800 to 600 ° C. is set to 5 ° C. for cooling from the cold rolled sheet annealing temperature.
  • the method for producing a ferritic stainless steel for exhaust system members having excellent post-heating corrosion resistance according to the present invention characterized by being less than / s.
  • the finish annealing temperature of cold rolling is set to 1030 ° C. or less, and the cooling from the cold rolled sheet annealing temperature is in the range of 800 to 600 ° C.
  • the manufacturing method of the exhaust system member excellent in the corrosion resistance after a heating comprised from the ferritic stainless steel of this invention characterized by making the cooling rate in less than 20 degrees C / s.
  • the finish annealing temperature of cold rolling is set to 1030 ° C. or less, and the cooling from the cold rolled sheet annealing temperature is in the range of 800 to 600 ° C.
  • the manufacturing method of the exhaust system member excellent in the corrosion resistance after a heating comprised from the ferritic stainless steel of this invention characterized by making the cooling rate in less than 5 degrees C / s.
  • the ferritic stainless steel excellent in corrosion resistance after heating according to the present invention is suitable as a material for exhaust system parts of passenger cars, motorcycles, commercial vehicles, construction machines and the like. Since the ferritic stainless steel of the present invention improves the corrosion resistance of the part that is practically heated including the welded portion, it can contribute to the weight reduction by extending the life of the exhaust system member and reducing the thickness.
  • the inventors of the present invention investigated in detail the corrosion resistance after heating, paying attention to the oxide film formed by heating. This is because the corrosion resistance is deteriorated by heating, but it is considered that the main factor is the formation state of the oxide film.
  • ferritic stainless steel When ferritic stainless steel is heated in the air at 573 to 1073K, an oxide film with an outer layer rich in Fe and an inner layer Cr-rich is formed on the surface. This oxide film is inferior in the effect of shielding the material from the corrosive environment as compared with the passive film of stainless steel that is not heated. Therefore, if the chemical composition of the material is the same, the heat resistance after heating is inferior. Therefore, it was thought that the corrosion resistance after heating could be improved if the formation state of the oxide film could be improved.
  • ferritic stainless steel is mostly composed of Fe and Cr, it is difficult to avoid the formation of an oxide film mainly composed of these two elements, so the use of a third element other than Fe and Cr Thought.
  • an oxide film of about 20 nm to sub-micron order mainly composed of Fe and Cr as main elements is formed.
  • a metal element added in a trace amount in steel is oxidized. It is difficult to concentrate on the entire film. Therefore, it was considered to concentrate an element effective for improving the corrosion resistance near the boundary between the oxide film and the base material.
  • elements that are more difficult to oxidize than Fe and Cr it is possible to concentrate these elements in a metal state under the condition that Fe and Cr are oxidized as in the atmosphere. Therefore, Cu, Ni, and Sn were focused as such elements from the viewpoint of corrosion resistance.
  • Ferritic stainless steel sheet with Sn content varied in the range of 0 to 0.5% by mass was prepared and used as the raw material. After heat treatment in the atmosphere under the condition of 673K ⁇ 24h, two kinds of salt dry and wet repeated A test was conducted. Note that the cooling rate in the range of 800 to 600 ° C. was set to 15 ° C./s during the cooling from the finish annealing temperature during the manufacturing process of the steel sheet. Moreover, the crystal grain size of the steel sheet surface Z plane was 6.5.
  • the first test in the salt dry / wet repeat test is 35 ° C, 5% NaCl spray, 2h-60 ° C, dry, 4h-50 in accordance with JASO M609-91 for the purpose of evaluating the pore resistance. 120 cycles of a test with 1 cycle of C, wet and 2 h were performed. After completion of the test, the corrosion products were removed using an aqueous solution of ammonium dihydrogen citrate. Thereafter, the maximum pitting depth was measured by a microscope depth of focus method.
  • FIG. 1 shows the effect of Sn content on the maximum pitting depth measured in the first test.
  • the maximum pitting depth is clearly reduced by adding 0.02 mass% or more of Sn, and then the maximum pitting depth is reduced as the Sn content is increased.
  • the second test when the Sn content was 0.001%, it was RN5, but by including 0.02 mass% or more of Sn, the glazing level was improved and RN6 or more was shown. .
  • RN5 When RN5 is reached, it can be easily confirmed and deterioration in appearance becomes clear. Therefore, the boundary condition between RN5 and RN6 is set to be superior or inferior. From the above, it has been clarified that the inclusion of 0.02 mass% or more of Sn improves the weather resistance in addition to the hole resistance.
  • a material containing 0.021 mass% of Sn was subjected to heat treatment under the same conditions as in the corrosion test and investigated by XPS.
  • the outer layer having a thickness of about 40 nm was Fe-rich on the surface, and the inner layer was Cr.
  • a rich oxide film was formed, and 0.02 to 0.04 at% Sn was present in the cation fraction over a range of about 2 nm near the boundary between the oxide film and the base material.
  • the Sn content in the vicinity of the boundary between the oxide film and the base material increases as the Sn content of the material increases.
  • the cation fraction is 0.47 to 0.00. 7 at% Sn was detected over about 10 nm.
  • the Sn amount in the base material corresponds to about 0.22 at%, so it is clear that Sn is concentrated near the boundary between the oxide film and the base material.
  • a layer in which Sn is thicker than the Sn concentration of the base material in the vicinity of the boundary between the oxide film and the base material is hereinafter referred to as an Sn concentrated layer.
  • the thickness of Sn concentration layer is 2 nm or more and Sn concentration in Sn concentration layer is 2 times or more of a base material, it turned out that the corrosion-resistance improvement effect of this invention can be exhibited.
  • the thickness of the Sn concentrated layer was about 15 nm.
  • Sn acts as an inhibitor (corrosion inhibitor) by being dissolved and ionized.
  • corrosion inhibitor corrosion inhibitor
  • the progress of the pitting corrosion is reduced to reduce the depth of pitting corrosion, and the progress of small pitting corrosion that has just occurred can be stopped to improve the weather resistance.
  • Sn having a higher concentration than the base material exists in the metallic state in the vicinity of the boundary between the oxide film and the base material, so that it is considered that corrosion of the base material can be more effectively suppressed.
  • the oxidation of Fe and Cr by heating causes the Sn concentration to increase near the boundary between the oxide film and the base material.
  • the grain boundary diffusion is the main component. Therefore, when the particles are made finer, the diffusion of Sn is promoted and the concentration of Sn proceeds.
  • the grain size number is 6.5 or more, and more desirably 7 or more.
  • forming a processed layer on the surface by polishing or the like before heating is also effective for concentrating Sn.
  • the upper limit of the C content is 0.015%, preferably 0.012%.
  • the lower limit of the C content is preferably 0.002%, more preferably 0.003%.
  • N (N: 0.02% or less) N is an element useful for pitting corrosion resistance, but its content needs to be kept low in order to reduce intergranular corrosion resistance and workability. For this reason, the upper limit of the content of N is set to 0.02%, preferably 0.018%. However, excessively reducing the N content increases the scouring cost as well as the required strength cannot be obtained. For this reason, it is preferable to make the minimum of content of N into 0.002%, More preferably, it is 0.003%.
  • Si (Si: 0.03% or more, 1.0% or less) Si is effective in improving the oxidation resistance and has the effect of improving the corrosion resistance after heating, so it is necessary to contain 0.03% or more.
  • the lower limit of Si is preferably 0.05%, more preferably 0.1%, and still more preferably 0.2%.
  • the upper limit of the Si content is set to 1.0%.
  • the upper limit of Si is preferably 0.8%, more preferably 0.6%, and still more preferably 0.5%.
  • Mn 1.0% or less Since Mn deteriorates the corrosion resistance, it is necessary to limit its content. Therefore, the upper limit of the Mn content is 1.0%, preferably 0.5%. However, extremely reducing the Mn content leads to an increase in cost. For this reason, it is preferable to make the minimum of content of Mn into 0.03%, More preferably, it is 0.05%.
  • P 0.04% or less Since P is an element that deteriorates workability and weldability, its content needs to be limited. Therefore, the upper limit of the P content is 0.04%. However, extremely reducing the P content leads to an increase in cost. For this reason, it is preferable that the minimum of content of P shall be 0.02%.
  • S (S: 0.01% or less) Since S is an element that deteriorates the corrosion resistance, the content thereof needs to be limited. Therefore, the upper limit of the S content is 0.01%, preferably 0.005%, and more preferably 0.002%.
  • Cr 10.5% or more, 22.5% or less
  • the lower limit of the Cr content needs to be 10.5%. Preferably it is 11.0% or more, More preferably, it is 12.5% or more, More preferably, it is 14.0% or more.
  • the corrosion resistance can be improved as the content of Cr is increased. However, excessive addition of Cr decreases workability and manufacturability. For this reason, the Cr content is 22.5% or less, preferably 20.5% or less, more preferably 19.5% or less, and still more preferably 18.0% or less.
  • Sn 0.02% or more, 0.5% or less
  • Sn is extremely useful in improving the corrosion resistance after heating, and is the most important element in the present invention. Therefore, the lower limit of the Sn content is 0.02%, desirably 0.05%, more desirably 0.07%, and still more preferably 0.1%.
  • the corrosion resistance after heating can be improved as the Sn content is increased, but excessive addition of Sn deteriorates workability and manufacturability. Therefore, the Sn content is 0.5% or less, preferably 0.4% or less, more preferably 0.3% or less, and further preferably 0.25% or less. It is also desirable to adjust the Sn content according to the required post-heating corrosion resistance level.
  • 0.02% or more and less than 0.05% when the required level of post-heating corrosion resistance is low 0.07% or more and 0.3% or less in a general case, and 0 when the level is high. It is preferable to set it to 3% or more and 0.5% or less. Among these, in a general case, it is more preferably 0.1% or less.
  • Al 0.003% or more, 0.2% or less
  • Al is useful as a deoxidizing element and needs to be contained by 0.003% or more. Preferably it is 0.005% or more, More preferably, it is 0.01%. Excessive addition degrades toughness and manufacturability, so the upper limit of Al content is 0.2%. Preferably it is 0.15%, More preferably, it is 0.1% or less.
  • the stainless steel of the present invention contains one or two of Ti and Nb in the following component ranges.
  • Ti 0.03% or more, 0.35% or less
  • Ti has the effect of suppressing intergranular corrosion by fixing C and N as carbonitrides. Moreover, it has the effect
  • the lower limit of the Ti content is 0.03%, preferably 0.05%, more preferably 0.07%. Excessive addition adversely affects workability and manufacturability, so the upper limit is made 0.35%. Preferably it is 0.32%, more preferably 0.28%.
  • it is preferable to contain Ti 4 (C + N) + 3S or more.
  • Nb 0.03% or more, 0.6% or less
  • Nb like Ti
  • the lower limit of the Nb content is 0.03%, preferably 0.1%, more preferably 0.2%.
  • the upper limit is made 0.6%. Preferably it is 0.55%, More preferably, it is 0.5%.
  • Cu 0.05% or more, 1.5% or less
  • Cu can be contained in an amount of 0.05% or more as necessary in order to improve corrosion resistance and strength. Preferably it is 0.2% or more, More preferably, it is 0.3% or more. However, since excessive addition of Cu decreases workability, the upper limit of Cu content is preferably 1.5% or less. Moreover, it is preferable that it is 1.0% or less, More preferably, it is 0.8% or less.
  • Ni 0.1% or more, 1.2% or less
  • Ni can be contained in an amount of 0.1% or more as necessary in order to improve the corrosion resistance. Preferably it is 0.2% or more, More preferably, it is 0.3% or more. However, excessive addition of Ni reduces workability and is expensive, leading to an increase in cost. Therefore, the Ni content is preferably 1.2% or less, more preferably 0.9% or less, and even more preferably less than 0.5%.
  • Mo 0.03% to 36%
  • Mo can be contained in an amount of 0.03% or more as necessary in order to improve the corrosion resistance and strength. Preferably it is 0.1% or more, More preferably, it is 0.3% or more, More preferably, it is 0.7% or more.
  • the Mo content is preferably 3% or less, more preferably 2.2% or less, and even more preferably 1.8% or less.
  • W can be contained in an amount of 0.03% or more as necessary in order to improve the corrosion resistance.
  • the content is preferably 0.2% or more, and more preferably 0.5% or more. Excessive addition of W deteriorates processability and increases the cost because it is expensive. For this reason, the W content is preferably 1% or less, and more preferably 0.8% or less.
  • V 0.05% or more, 0.5% or less
  • V can be contained in an amount of 0.05% or more as necessary in order to improve the corrosion resistance. Moreover, it is preferable to make it contain 0.1% or more. However, excessive addition of V deteriorates processability and is expensive, leading to an increase in cost. For this reason, the content of V is preferably 0.5% or less, and more preferably 0.3% or less.
  • Sb can be contained in an amount of 0.01% or more as needed in order to improve the corrosion resistance. It is preferable to contain 0.03% or more, and more preferably 0.05% or more. However, excessive addition of Sb reduces processability and manufacturability. For this reason, the Sb content is preferably 0.5% or less, and more preferably 0.3% or less.
  • Zr 0.03% or more, 0.5% or less
  • Zr can be contained in an amount of 0.03% or more as necessary in order to improve the corrosion resistance, particularly the intergranular corrosion resistance. It is preferable to contain 0.05% or more, and more preferably 0.1% or more. Excessive addition of Zr degrades workability and increases costs because it is expensive. For this reason, the content of Zr is preferably 0.5% or less, and more preferably 0.3% or less.
  • Co (Co: 0.02% or more, 0.2% or less) Co can be contained in an amount of 0.02% or more as needed in order to improve secondary workability and toughness.
  • the content is preferably 0.05% or more, and more preferably 0.08% or more.
  • the content of Co is preferably 0.2% or less, and more preferably 0.18% or less.
  • Ca 0.0002% or more, 0.002% or less
  • Ca is an element useful for scouring because it has a deoxidizing effect and the like, and can be contained in an amount of 0.0002% or more as necessary. Moreover, it is more preferable to make it contain 0.0004% or more. However, in order to form sulfides and deteriorate the corrosion resistance, the Ca content is preferably 0.002% or less, and more preferably 0.0015% or less.
  • Mg is an element useful for scouring because it has a deoxidizing effect, etc., and is effective in improving the workability and toughness by refining the structure. Accordingly, Mg can be contained in an amount of 0.0002% or more as required, and more preferably 0.0005% or more. However, excessive addition degrades the corrosion resistance, so the Mg content is preferably 0.002% or less, and more preferably 0.0015% or less.
  • B can be contained in an amount of 0.0002% or more as necessary in order to improve workability, particularly secondary workability. Moreover, it is more preferable to make it contain 0.0003% or more. Since excessive addition of B reduces the intergranular corrosion resistance, the content of B is preferably 0.005% or less, and more preferably 0.002% or less.
  • REM 0.001% or more, 0.01% or less
  • REM is the total of elements belonging to atomic numbers 57 to 71, such as La, Y, Ce, Pr, and Nd. Since REM has a deoxidizing effect and the like, it is an element useful for scouring and can be contained in an amount of 0.001% or more as necessary. However, since excessive addition leads to an increase in cost, the REM content is preferably 0.01% or less.
  • Ga forms stable sulfides to improve corrosion resistance and also improve hydrogen embrittlement resistance. Therefore, Ga can be contained in an amount of 0.0002% or more as necessary. However, since excessive addition leads to an increase in cost, the Ga content is preferably 0.01% or less.
  • Ta 0.01% or more, 0.5% or less
  • Ta can be contained in an amount of 0.01% or more as needed in order to improve the corrosion resistance. Moreover, it is more preferable to make it contain 0.05% or more, and it is still more preferable to make it contain 0.1% or more. However, excessive addition reduces toughness and increases costs. Therefore, the Ta content is preferably 0.5% or less, more preferably 0.4% or less.
  • the stainless steel of the present invention is basically manufactured by a general method for manufacturing ferritic stainless steel.
  • molten steel having the above chemical composition in a converter or electric furnace, scoured in an AOD furnace or VOD furnace, etc. to form a steel piece by a continuous casting method or an ingot method, It is manufactured through the steps of annealing, pickling, cold rolling, finish annealing, and pickling. If necessary, annealing of the hot-rolled sheet may be omitted, or cold rolling, finish annealing, and pickling may be repeated.
  • using a small-diameter roll of ⁇ 150 mm or less during cold rolling is effective for concentrating Sn near the boundary between the oxide film and the base material.
  • the finish annealing temperature is preferably 800 ° C. or higher in order to promote recrystallization, and 1030 ° C. or lower in order to suppress coarsening of crystal grains.
  • the cooling rate in the range of 800 to 600 ° C. is averaged when cooling from the finish annealing temperature. It is preferable to be less than 20 ° C./s. Furthermore, the average is preferably less than 15 ° C / s, and more preferably less than 5 ° C / s on average.
  • the finish annealing temperature for cold rolling is set to an appropriate temperature of 1030 ° C. or lower, and cooling in the range of 800 to 600 ° C. is performed for cooling from the finish annealing temperature.
  • the grain size number of the steel surface is made 6 or more.
  • the finish annealing temperature of cold rolling is set to an appropriate temperature of 1030 ° C. or less, and the cooling from the finish annealing temperature is in the range of 800 to 600 ° C.
  • the average cooling rate in the steel is less than 20 ° C./s, and heating in the air under conditions satisfying the formula (I) makes the steel surface crystal grain size number 6 or more and more than twice the base material concentration.
  • Ferritic stainless steel in which a layer containing Sn of 2 to 15 nm is formed.
  • the heating in the atmosphere under the condition satisfying the formula (I) corresponds to the heating that the exhaust system member receives during traveling. Moreover, it is good also as heating in air
  • the exhaust system member having excellent corrosion resistance after heating according to the present invention is manufactured as a welded pipe by a normal method for manufacturing a stainless steel pipe for exhaust system members such as electric resistance welding, TIG welding, and laser welding using the steel plate as a raw material. .
  • a stainless steel having the composition shown in Table 1-1 is melted in a 180 kg vacuum melting furnace, cast into a 45 kg steel ingot, and then subjected to a hot rolling-hot rolled sheet annealing-shot-cold rolling-finish annealing process to obtain a thickness of 1 mm.
  • a cold-rolled steel sheet was prepared. The hot-rolled sheet was produced by rolling at a material thickness of 50 mm and a heating temperature of 1200 ° C. to a sheet thickness of 5 mm and air cooling. Hot-rolled sheet annealing was performed at 850 to 1050 ° C. for 1 minute with air cooling, and the scale was removed by shot blasting. Thereafter, it was cold-rolled to a thickness of 1 mm, subjected to finish annealing that was held at the temperature shown in Table 1-2 for 1 minute, and then cooled under the conditions shown in Table 1-2.
  • a test piece having a width of 70 mm and a length of 150 mm was cut out from the cold-rolled steel sheet, and the test surface was wet-polished with emery paper to # 600. Thereafter, heat treatment was performed in the air at 673 K for 24 hours. In this case, the left side of the formula (I) is 1.2 ⁇ 10 ⁇ 10 .
  • Comparative Example 5 (steel 7) in Table 1-2 a heat treatment of 15 min in the atmosphere of 523 K was added instead of the heat treatment of 673 K and 24 h. In this case, the left side of the formula (I) is 7.1 ⁇ 10 ⁇ 17 .
  • the distribution of Sn content in the vicinity of the steel sheet surface after the heat treatment was evaluated by XPS.
  • XPS was manufactured by ULVAC-PHI. Elemental analysis in the depth direction was performed by Ar ion sputtering using a mono-AlK ⁇ ray as an X-ray source. The sputtering rate was 1.5 nm / min in terms of SiO 2 .
  • the thickness of the Sn concentrated layer present at the boundary between the oxide film and the base material was measured and is shown in Table 1-2.
  • the thickness of the Sn concentrated layer is the thickness of the region where the Sn concentration higher than the base material Sn concentration is detected, and Table 1-2 shows the minimum Sn concentration in the Sn concentrated layer as atomic%. Indicated. Values obtained by dividing the Sn concentration in the Sn concentrated layer by the Sn concentration of the parent phase are shown in Table 1-2 as “degree of concentration”.
  • Corrosion resistance was evaluated by two types of salt dry and wet test. The first test was conducted in accordance with JASO M609-91, and 120 cycles of a test with 35 ° C., 5% NaCl spray, 2 h-60 ° C., dry, 4 h-50 ° C., wet, and 2 h as one cycle were performed. After the cycle test was completed, the corrosion products were removed using an aqueous solution of ammonium dihydrogen citrate. Thereafter, the maximum pitting depth was measured by a microscope depth of focus method.
  • test piece having a width of 20 mm and a length of 20 mm was cut out from the same cold-rolled steel sheet, and the surface was polished to a mirror surface and then etched to reveal a microstructure.
  • the crystal grain size of the Z plane (plane parallel to the surface) was measured.
  • the test results are shown in Table 1-2.
  • the grain size number is a result of measurement with a test piece cut out from a cold-rolled steel sheet. Moreover, when the grain size number was evaluated also about the heat processing test piece, the same result as the result measured with the cold-rolled steel plate test piece which has not performed heat processing was obtained.
  • Comparative Examples 5 and 6 since the Sn concentrated layer was not formed, the Sn concentration in the vicinity of the boundary between the oxide film and the base material was described.
  • Invention Examples 1 to 18 have excellent corrosion resistance, with a maximum pitting depth of 400 ⁇ m or less and an RN of 6 or more.
  • Comparative Example 1 in which Sn content does not satisfy the present invention Comparative Example 2 in which Cr content does not satisfy the present invention, Comparative Example 3 in which Si content does not satisfy the present invention, Comparison in which heating conditions do not satisfy formula (I)
  • Example 5 and Comparative Example 6 in which the cooling rate in the range of 800 to 600 ° C. in the finish annealing process is 20 ° C./s or more, the maximum pitting depth exceeds 500 ⁇ m and the RN is 5 or less, which is inferior in corrosion resistance.
  • Comparative Example 4 having a grain size number of 4 Sn enriched layer was formed, but Sn concentration was not sufficient due to the influence of grain size number, and as a result, the maximum pitting corrosion depth was 400 to 500 ⁇ m and the resistance to pores. Aperture is secured, but RN is 5 and inferior in weather resistance.
  • the ferritic stainless steel of the present invention is suitable as an exhaust system member for passenger cars, motorcycles, commercial vehicles, construction machines and the like that are practically heated.
  • Suitable exhaust system members include a converter case, a front pipe, a center pipe, a muffler, and the like.

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US15/544,476 US20180016655A1 (en) 2015-01-19 2016-01-15 Ferritic stainless steel for exhaust system member having excellent corrosion resistance after heating
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JP2020050931A (ja) * 2018-09-28 2020-04-02 日鉄ステンレス株式会社 フェライト系ステンレス鋼、フェライト系ステンレス鋼管、管端増肉構造体及び溶接構造体
JP2022513747A (ja) * 2018-12-10 2022-02-09 ポスコ 成形性及び高温特性に優れた低Ｃｒフェライト系ステンレス鋼及びその製造方法

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CN113614269B (zh) * 2019-03-26 2022-10-25 杰富意钢铁株式会社 铁素体系不锈钢板及其制造方法
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JP2010159487A (ja) * 2008-12-09 2010-07-22 Nippon Steel & Sumikin Stainless Steel Corp 耐銹性に優れた高純度フェライト系ステンレス鋼およびその製造方法
JP2011202257A (ja) * 2010-03-26 2011-10-13 Nippon Steel & Sumikin Stainless Steel Corp 耐熱性と加工性に優れたフェライト系ステンレス鋼板およびその製造方法
WO2012036313A1 (ja) * 2010-09-16 2012-03-22 新日鐵住金ステンレス株式会社 耐酸化性に優れた耐熱フェライト系ステンレス鋼板
JP2013204059A (ja) * 2012-03-27 2013-10-07 Nippon Steel & Sumikin Stainless Steel Corp 溶接性に優れた耐熱フェライト系ステンレス鋼板
JP2014162964A (ja) * 2013-02-26 2014-09-08 Nippon Steel & Sumikin Stainless Steel Corp 耐酸化性および耐食性に優れた自動車排気系部材用省合金型フェライト系ステンレス鋼

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WO2019151125A1 (ja) * 2018-01-31 2019-08-08 Ｊｆｅスチール株式会社 フェライト系ステンレス鋼
JP6624347B1 (ja) * 2018-01-31 2019-12-25 Ｊｆｅスチール株式会社 フェライト系ステンレス鋼
JP2020050931A (ja) * 2018-09-28 2020-04-02 日鉄ステンレス株式会社 フェライト系ステンレス鋼、フェライト系ステンレス鋼管、管端増肉構造体及び溶接構造体
JP7213650B2 (ja) 2018-09-28 2023-01-27 日鉄ステンレス株式会社 フェライト系ステンレス鋼管、管端増肉構造体及び溶接構造体
JP2022513747A (ja) * 2018-12-10 2022-02-09 ポスコ 成形性及び高温特性に優れた低Ｃｒフェライト系ステンレス鋼及びその製造方法
JP7174853B2 (ja) 2018-12-10 2022-11-17 ポスコ 成形性及び高温特性に優れた低Ｃｒフェライト系ステンレス鋼及びその製造方法

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