WO2009096244A1 - 耐食性と加工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 - Google Patents
耐食性と加工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 Download PDFInfo
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- WO2009096244A1 WO2009096244A1 PCT/JP2009/050607 JP2009050607W WO2009096244A1 WO 2009096244 A1 WO2009096244 A1 WO 2009096244A1 JP 2009050607 W JP2009050607 W JP 2009050607W WO 2009096244 A1 WO2009096244 A1 WO 2009096244A1
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- corrosion resistance
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- stainless steel
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- ferritic stainless
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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
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
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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
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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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
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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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
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
Definitions
- the present invention relates to a ferritic stainless steel excellent in corrosion resistance and workability and a method for producing the same.
- Ferritic stainless steel is used in a wide range of fields, including kitchen equipment, home appliances, and electronic equipment. However, since it is inferior in workability compared to austenitic stainless steel, it may be limited to its use. In recent years, with the improvement of refined technology in steel production, it has become possible to reduce impurity elements such as P and S in combination with extremely low carbon, nitrogen, and low Si, and processing by adding stabilizing elements such as Ti Ferritic stainless steel (hereinafter referred to as high-purity ferritic stainless steel) with improved properties is being applied to a wide range of processing applications. This is because ferritic stainless steels are more economical than austenitic stainless steels that contain a large amount of Ni, which has seen a dramatic increase in prices in recent years.
- High purity ferritic stainless steel is compared with SUS 3 0 4 (1 8 Cr-8 N i), which is a typical austenitic stainless steel, as can be seen from JIS standard SUS 4 3 0 LX. Then, there are many cases where the amount of Cr is low, and there is a problem in corrosion resistance.
- kitchen appliances such as stainless steel sinks and household electrical appliances that require design properties often suffer from deterioration of the surface properties due to corrosion such as pitting corrosion.
- alloy Cr, Mo, etc. To improve the above-mentioned corrosion resistance problem, alloy Cr, Mo, etc. And a method of modifying the film formed on the steel surface by bright annealing.
- the former is not preferable because it causes an increase in cost due to alloying and also becomes a factor that hinders workability.
- the latter is an effective method from the viewpoint of suppressing an increase in material cost and a decrease in workability, and various inventions have been proposed for film modification using bright annealing.
- P is a factor that hinders manufacturability, workability, and weldability, and is not suitable for applications that require workability.
- Japanese Patent Laid-Open No. 2 00 0-1 6 9 94 3 discloses a ferritic stainless steel excellent in high-temperature strength containing a trace element of SnSb and a method for producing the same.
- This Japanese Patent No. 2 0 0 0 — 1 6 9 9 4 3 Most of the examples shown in the report are low ⁇ 1 "steels with Cr: 10 to 12%, and Cr: over 12% to ensure high temperature strength. Addition of V, Mo, etc. The effect of Sn and Sb is to improve high-temperature strength, and it is questioned because there is no disclosure of whether sufficient corrosion resistance can be secured.
- Japanese Patent Laid-Open No. 2 0 0 1 — 2 8 8 5 4 3 and Japanese Patent Laid-Open No. 2 0 0 1 — 2 8 8 5 4 4 the surface characteristics and corrosion resistance of Mg and Ca as trace elements are excellent. Ferrite stainless steel and its manufacturing method are disclosed. Sn is a selective additive element and is described as an element preferable for corrosion resistance.
- the steels shown in the examples of Japanese Patent Laid-Open No. 2 0 0 1 1 2 8 8 5 4 3 and Japanese Patent Laid-Open No. 2 0 1 1 2 8 8 5 4.4 have Sn and high-cost Co. Combined addition.
- These steels are 11.6% Cr steel or 16% Cr steel containing a lot of impurity elements such as C, and their pitting corrosion potentials are 0.0 8 6 V and 0.1 2 V, respectively. Are listed. This pitting corrosion potential is lower than the pitting corrosion potential equivalent to SUS304 (targeted by the present invention) (over 0.2 V).
- W 0 2 0 0 7/1 2 9 7 0 3 has an excellent resistance to crevice corrosion with Sn and Sb as trace elements for the purpose of improving the perforated life of automobile parts and the like.
- Ferritic stainless steel is disclosed. Most of the steels shown in the examples of this W 0 2 0 0 7/1 2 9 7 0 3 publication are Sn and Ni in order to improve the pore resistance of the gaps. Compound is added. The 16% Cr steel to which Sn is added alone has a high amount of Si, and does not fall under the high purity ferritic stainless steel targeted by the present invention.
- the conventional technology for improving corrosion resistance using trace elements is a combination of P alone, Sn and Sb, and expensive rare elements such as Co and Ni, and paragraph 0 0 0 2 High purity ferritic stainless steel to be described There is a problem from the viewpoint of manufacturability, workability, and material cost, not for steel. Disclosure of the invention
- the object of the present invention is for high-purity ferritic stainless steel, and does not reduce manufacturability or workability, and does not rely on the addition of rare elements.
- the purpose of this study is to provide high-purity ferritic stainless steel that has improved surface quality degradation due to corrosion such as pitting and rusting to a level comparable to or exceeding that of SUS304.
- the present invention has been made to solve the above problems, and the gist thereof is as follows. (1) By mass%, C: 0.0 1% or less, S i: 0.0 1 to 0.20
- T i 0.05 to 0.35%, A10.0.05 to 0.05 0%
- the steel is further mass%, Ni: 0.5% or less, Cu: 0
- the stainless steel ingot having the steel component described in (1) or (2) above is hot-rolled by hot forging or hot rolling, and after annealing the hot-rolled steel, cold working and annealing are performed.
- the steel material stays for one minute or more in the temperature range of 200 to 700 ° (1) to (4)
- Figure 1 shows the relationship between the pitting potential of 13Cr-0.1.7 Ti steel and the amount of Sn added.
- Figure 2 shows an example of an anodic polarization curve in diluted sulfuric acid.
- Sn is a solid solution strengthening element that increases the strength of the material and decreases the elongation.
- Cr is a solid solution strengthening element that increases the strength of the material and decreases the elongation.
- Sn is a solid solution strengthening element that increases the strength of the material and decreases the elongation.
- S n is a low melting point metal and assumed to induce melt embrittlement during hot working. However, since Sn has a large diffusion in the temperature range during hot working and also has a solubility in steel, it was confirmed that it does not hinder manufacturability unless excessive addition exceeding 1% is added.
- the pitting potential is measured in 30 t :, 3.5% aqueous sodium chloride solution, and the steel surface is polished with emery paper # 600.
- the electrode is AgC1, and the value of the pitting corrosion potential V'c100 is measured.
- the strength and elongation of the material are the values obtained for a tensile speed of 2 O mmZmin when a J I S 13 B tensile specimen was taken from the rolling direction in the case of a sheet.
- the presence state of Sn in the passive film and directly under the film can be analyzed by an X-ray photoelectron spectrometer (X P S).
- the polished sample surface is used as the analysis surface, and the presence of Sn can be confirmed by detecting peaks from around 484 to 487 eV.
- the content of C deteriorates workability and corrosion resistance, so its content is preferably as low as possible. Therefore, the upper limit is set to 0.0 10%. However, excessive reduction leads to increase in cost, so the lower limit is preferably set to 0.001%. More preferably, considering the corrosion resistance and the manufacturing cost, the content is made 0.0% to 0.05%.
- S i may be added as a deoxidizing element.
- the upper limit is set to 0.2%.
- the lower limit is set to 0.0 1%.
- the content is set to 0.03 to 0.15%.
- Mn like S1
- the upper limit is made 0.3% in order to suppress the decrease in elongation.
- the lower limit is set to 0.0 1%.
- the content is set to 0.03 to 0.15%.
- P like Si and Mn, is a solid solution strengthening element, so the lower the content, the better.
- the upper limit is set to 0.0 40% in order to suppress the decrease in elongation.
- the lower limit is preferably set to 0.005%. More preferably, considering the manufacturing cost and workability, the content is made 0.00 to 0.020%.
- the upper limit is set to 0.0 1 0%.
- the lower limit is preferably set to 0.0 0 0 1. More preferably, considering the corrosion resistance and the manufacturing cost, it is set to 0.0 0 10 0 to 0.0 0 50%.
- C r is an essential element for ensuring corrosion resistance, and the lower limit is set to 13% to ensure the pitting potential of the present invention.
- the addition of more than 22% leads to an increase in material costs and a decrease in workability and manufacturability. Therefore, the upper limit of C r is 2 2%.
- the corrosion resistance, workability and manufacturability 15 to 18%.
- the upper limit is set to 0.0 20%.
- the lower limit is set to 0.0 0 1%.
- workability and corrosion resistance Considering the characteristics, it is set to 0.0 0 3 to 0.0 1 2%.
- T i is an extremely effective element for softening by fixing C and N and improving the elongation and r value, so the lower limit is set to 0.05%.
- T i is also a solid solution strengthening element, and excessive addition leads to a decrease in elongation. Therefore, the upper limit is 0.35%.
- the content is made 0.10 to 0.20%.
- a 1 is an effective element as a deoxidizing element
- the lower limit was set to 0.0 0%.
- the upper limit was set to 0.05%.
- it is set to 0.0 1 to 0.03%.
- the lower limit was set to 0.0 0 1%.
- the upper limit was set to 1%.
- the upper limit is preferably 0.8% or less in consideration of workability and manufacturability. More preferably, it is set to 0.05 to 0.5% from the balance between corrosion resistance and workability and manufacturability.
- Ni and Cu are elements that improve the corrosion resistance by a synergistic effect with Sn, and are added as necessary. In addition, these elements also have the effect of improving the workability (elongation, r-value) degradation associated with the addition of Sn. If added, the effect should be 0.05% or more. However, if it exceeds 0.5%, the material cost will increase and the workability will decrease, so the upper limit is made 0.5%. More preferably, the content is 0.1 to 0.3%.
- N b improves the elongation and r-value as well as T i, and is effective in improving corrosion resistance. It is an effective element and should be added as necessary. If added, the effect should be 0.05% or more. However, excessive addition increases the material strength and decreases elongation, so the upper limit is set to 0.5%. Preferably, considering the workability and corrosion resistance, 0.2 to 0.4%
- Mg forms Mg oxide with A 1 in the molten steel and acts as a deoxidizer, and also acts as a crystallization nucleus of Ti N.
- TIN becomes a solidification nucleus of the ferrite phase during the solidification process, and by promoting the crystallization of TiN, the ferrite phase can be finely generated during solidification.
- miniaturizing the solidified structure it can prevent surface defects caused by coarse solidified structure such as lysine globing of products, and it is added as necessary to improve workability. When added, the effect is 0.000%. However, if it exceeds 0.0 0 5%, the manufacturability deteriorates, so the upper limit is set to 0.0 0 5%.
- the content is set to 0.003 to 0.02%.
- B is an element that improves hot workability and secondary workability, and its addition to Ti-added steel is effective. Since Ti-added steel fixes C with T i, the grain boundary strength decreases, and intergranular cracking is likely to occur during secondary processing. When added, the effect should be 0.000% or more. However, excessive addition causes a decrease in elongation, so the upper limit is made 0.05%. Preferably, considering the material cost and workability, the content is made 0.0% 0 to 0.002%.
- Ca is an element that improves hot workability and steel cleanliness, and is added as necessary. When added, the effect should be 0.000% or more. However, excessive addition leads to a decrease in manufacturability and a decrease in corrosion resistance due to water-soluble inclusions such as C a S, so the upper limit is made 0.05%. Preferably, considering the manufacturability and corrosion resistance, 0.0 0 0 3 to 0. 0 0 1 5%.
- High-purity ferritic stainless steel with the composition of the present invention has a pitting potential> 0.2 V, 0.2% proof stress, less than 300 MPa, rupture elongation ⁇ 30%
- the corrosion resistance is not inferior to that of SUS 3 0 4 or better than that.
- the conditions for measuring the pitting potential and 0.2% resistance to elongation at break are those described in paragraph 0 0 28.
- the reason why the finish annealing is set to 700 or more is to ensure workability by recrystallizing the cold-worked steel.
- An excessive increase in the annealing temperature leads to a coarse crystal grain size and a decrease in surface quality such as rough skin due to processing.
- the upper limit of the annealing temperature is 9 5 0.
- the cooling rate After finishing annealing, adjust the cooling rate to keep the residence time in the temperature range of 200 to 700 to 1 minute or more, or reheat to 20 00 to 700 and hold for 1 minute or more It doesn't matter. If it exceeds 700, precipitates containing Ti and P will precipitate and lead to a decrease in corrosion resistance, so the upper limit is set to 700. If it is less than 200, the effect of further improving the corrosion resistance described in paragraphs 0 0 26 cannot be expected. Therefore, the lower limit is 2 0 0. More preferably, it is in the range of 300 to 600.
- the residence time between 2 00 and 700 is preferably 1 minute or longer.
- the upper limit is not particularly specified, but it is preferably 5 minutes or less when using an industrial continuous annealing facility. More preferably, it is 3 minutes or less.
- a ferritic stainless steel having the components shown in Table 1 was melted and hot-rolled at a heating temperature of 1 1550 to 1200 to obtain a hot-rolled steel sheet having a thickness of 3.8 mm.
- the hot-rolled steel sheet was annealed, and after pickling, it was cold-rolled to a thickness of 0.8 mm and subjected to finish annealing for evaluation of corrosion resistance and mechanical properties.
- the components of the steel were also carried out in the range specified in the present invention and others. Cooling after the finish annealing was performed under the conditions limited in the present invention and other conditions.
- S U S 3 0 4 (1 8% C r-8% N i) was used as the comparative steel.
- Corrosion resistance was evaluated by measuring the pitting potential, salt spray test, and cast test.
- the pitting corrosion potential was measured by the method described in paragraphs 0 0 28.
- the salt spray test and the cast test were conducted in accordance with J I S Z 2 3 7 1.
- a steel sheet (material) that had been annealed and a work product that had been deep-drawn from the cylinder were used.
- the surface of the material was polished with the paper # 600 as in the measurement of the pitting potential, and the test surface was used.
- Cylindrical deep drawing was performed with a blank diameter of 80 mm, a punch diameter of 40 mm, a die diameter of 42 mm, and a crease pressure I ton, and a film was used for lubrication.
- the number of test days was 15 days (360 hours).
- the degree of fire was evaluated as “ ⁇ ” when it was good, “ ⁇ ” when it was inferior, and “X” when it was inferior.
- the mechanical properties were measured by the method described in
- test numbers 1 to 9 are high-purity ferritic stainless steels that satisfy the components of the present invention, and the pitting corrosion potential V c '100 is 0.2 V (Vv.s.AG CL ) Excessive 0.2% resistance: less than 300 MPa, elongation at break: 30% or more mechanical properties. These steel plates are comparable to SUS 3 0 4 of test number 1 2 in salt spray or cascading acceleration tests, or It has higher corrosion resistance.
- test numbers 10 and 11 correspond to 31 of standard 3; 3 4 3 0 L X and are steel plates not added with Sn as defined in the present invention.
- Test No. 10 is 0.2% resistance: less than 300 MPa, elongation at break: poor corrosion resistance compared to SUS304 having mechanical properties of 30% or more.
- test number 1 1 has corrosion resistance comparable to SUS 3 0 4 but does not satisfy the mechanical properties defined in the present invention.
- Test Nos. 1 to 9 of the inventive example showed a marked improvement in corrosion resistance without impairing the good mechanical properties (soft and high elongation) of JIS standard steel.
- Test Nos. 2 and 6 in the present invention example are the ones to which the manufacturing method specified in the present invention is applied. Compared with Test Nos. 1 and 5 in which this is not applied, the improvement in corrosion resistance can be confirmed. In Test No. 4, elongation was improved by adding a trace amount of Cu.
- the pitting corrosion potential V c '1 0 0 in an aqueous solution of 30% and 3.5% NaCl is 0.2 V without causing an increase in material cost and a decrease in manufacturability.
- VV. S. AG CL exceeding that of SUS 3 0 4 and exceeding corrosion resistance
- 0.2% proof stress in tensile test is less than 300 MPa and elongation at break is 3
- This has a remarkable effect that it is possible to obtain a high purity ferritic stainless steel having mechanical properties of 0% or more and excellent corrosion resistance and workability.
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES09706158.4T ES2528204T3 (es) | 2008-01-28 | 2009-01-13 | Acero inoxidable ferrítico de alta pureza con excelente resistencia a la corrosión y facilidad para ser trabajado, y método para la producción del mismo |
KR1020107013303A KR101100360B1 (ko) | 2008-01-28 | 2009-01-13 | 내식성과 가공성이 우수한 고순도 페라이트계 스테인리스 강 및 그 제조 방법 |
US12/735,549 US8262815B2 (en) | 2008-01-28 | 2009-01-13 | High-purity ferritic stainless steel with excellent corrosion resistance and workability and method of production of same |
EP09706158.4A EP2246455B1 (en) | 2008-01-28 | 2009-01-13 | High-purity ferritic stainless steel excellent in corrosion resistance and workability and process for production of the same. |
CN200980101432.9A CN101903553B (zh) | 2008-01-28 | 2009-01-13 | 耐腐蚀性和加工性优异的高纯度铁素体系不锈钢及其制造方法 |
BRPI0906716-7 BRPI0906716B1 (pt) | 2008-01-28 | 2009-01-13 | aço inoxidável ferrítico de alta pureza e processo de produção do mesmo |
Applications Claiming Priority (2)
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JP2008016785A JP4651682B2 (ja) | 2008-01-28 | 2008-01-28 | 耐食性と加工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 |
JP2008-016785 | 2008-01-28 |
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WO2009096244A1 true WO2009096244A1 (ja) | 2009-08-06 |
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PCT/JP2009/050607 WO2009096244A1 (ja) | 2008-01-28 | 2009-01-13 | 耐食性と加工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 |
Country Status (9)
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US (1) | US8262815B2 (ja) |
EP (1) | EP2246455B1 (ja) |
JP (1) | JP4651682B2 (ja) |
KR (1) | KR101100360B1 (ja) |
CN (1) | CN101903553B (ja) |
BR (1) | BRPI0906716B1 (ja) |
ES (1) | ES2528204T3 (ja) |
TW (1) | TW200948988A (ja) |
WO (1) | WO2009096244A1 (ja) |
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JP4651682B2 (ja) | 2011-03-16 |
CN101903553A (zh) | 2010-12-01 |
EP2246455A4 (en) | 2013-11-13 |
US8262815B2 (en) | 2012-09-11 |
EP2246455B1 (en) | 2014-12-31 |
ES2528204T3 (es) | 2015-02-05 |
BRPI0906716A2 (pt) | 2015-06-30 |
KR20100087225A (ko) | 2010-08-03 |
TW200948988A (en) | 2009-12-01 |
BRPI0906716B1 (pt) | 2019-12-10 |
TWI346709B (ja) | 2011-08-11 |
JP2009174036A (ja) | 2009-08-06 |
EP2246455A1 (en) | 2010-11-03 |
ES2528204T8 (es) | 2015-02-23 |
CN101903553B (zh) | 2015-09-09 |
US20110236248A1 (en) | 2011-09-29 |
KR101100360B1 (ko) | 2011-12-30 |
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