WO2018181060A1 - フェライト系ステンレス鋼板およびその製造方法、ならびに、排気部品 - Google Patents
フェライト系ステンレス鋼板およびその製造方法、ならびに、排気部品 Download PDFInfo
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- WO2018181060A1 WO2018181060A1 PCT/JP2018/011884 JP2018011884W WO2018181060A1 WO 2018181060 A1 WO2018181060 A1 WO 2018181060A1 JP 2018011884 W JP2018011884 W JP 2018011884W WO 2018181060 A1 WO2018181060 A1 WO 2018181060A1
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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
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
Definitions
- the present invention relates to a ferritic stainless steel sheet, a method for producing the same, and an exhaust part.
- Exhaust system members such as automobile exhaust manifolds, front pipes, and center pipes pass high-temperature exhaust gas exhausted from the engine, so the materials that make up the exhaust members have various characteristics such as oxidation resistance, high-temperature strength, and thermal fatigue characteristics. Is required.
- Patent Document 1 discloses a high Cr, Mo-added steel.
- Patent Document 2 discloses an exhaust guide part of a nozzle vane type turbocharger using austenitic stainless steel added with 2 to 4% of Si.
- steel components are defined in consideration of hot workability at the time of steel production, it cannot be said that the high temperature characteristics required for the above parts are sufficiently satisfied, and the punched hole is expanded. However, the steel components specified from the hot workability could not obtain sufficient hole expansibility.
- the caster stainless steel is used for the turbocharger housing, there is a need to reduce the thickness and weight due to the large thickness.
- austenitic stainless steel has excellent heat resistance and workability, but because of its large thermal expansion coefficient, when applied to a member that repeatedly receives heating and cooling, such as an exhaust manifold, Fatigue failure is likely to occur.
- ferritic stainless steel has a smaller coefficient of thermal expansion than austenitic stainless steel, it is excellent in thermal fatigue characteristics and scale peel resistance. Further, compared with austenitic stainless steel, it does not contain Ni, so the material cost is low, and it is used for exhaust parts that substitute an exhaust manifold.
- ferritic stainless steel has lower high-temperature strength than austenitic stainless steel, a technique for improving high-temperature strength has been developed. For example, SUS430J1 (Nb-added steel), Nb—Si-added steel, and SUS444 (Nb—Mo-added steel) are all assumed to be added with Nb. This increased the high temperature strength by solid solution strengthening or precipitation strengthening with Nb.
- Patent Documents 3 to 6 disclose techniques for adding Cu or Cu—V composite as an alloy that contributes to improving high-temperature strength in addition to Nb.
- Cu addition in Patent Document 3 has been studied for addition of 0.5% or less for improving low-temperature toughness, and is not an addition from the viewpoint of heat resistance.
- Patent Documents 4 to 6 disclose techniques for improving high-temperature strength in a temperature range of 600 ° C. or 700 to 800 ° C. using precipitation hardening by Cu precipitates.
- Patent Documents 7 to 9 disclose steel containing B as a ferritic stainless steel having excellent high temperature characteristics.
- Patent Documents 10 to 15 disclose technologies related to ferritic stainless steel to which W is added as a countermeasure for increasing the temperature of exhaust gas.
- Patent Documents 16 and 17 disclose that high temperature strength of ferritic stainless steel is secured by setting Mo + W within a predetermined range.
- Patent Document 18 discloses a technique in which P is contained up to 0.1% as being effective for high temperature and high strength by high solid solution strengthening.
- the amount of P precipitated as FeTiP is 0.01% or less in order to increase the high-temperature strength by the solid solution strengthening action of P.
- JP 2013-069220 A Japanese Patent No. 4937277 JP 2006-37176 A International Publication No. 2003/004714 Japanese Patent No. 3468156 Japanese Patent No. 3397167 JP-A-9-279312 JP 2000-169943 A Japanese Patent Laid-Open No. 10-204590 JP 2009-215648 A JP 2009-235555 A JP 2005-206944 A JP 2008-189974 A JP 2009-120893 A JP 2009-120894 A JP 2009-197306 A JP 2009-197307 A Japanese Patent No. 30216656 JP 2000-336462 A
- the ferritic stainless steel containing B has a problem that the yield strength is high, there is a problem of sensitization, and manufacturability is deteriorated.
- W added in the techniques of Patent Documents 10 to 15 is known as an element that improves high-temperature strength.
- the addition of W has a problem in that workability (elongation) is deteriorated and parts processing becomes difficult. There was a problem in terms of cost.
- bonds with Fe and precipitates as the Laves phase mentioned later at high temperature when the Laves phase coarsened, there existed a subject which cannot improve heat resistance effectively.
- Patent Documents 18 and 19 both increase the high-temperature strength by the solid solution strengthening action of P in ferritic stainless steel. These techniques aim to suppress the formation of P compounds (for example, FeP, FeTiP, FeNbP) from the viewpoint of high-temperature strength. On the other hand, there is a problem that the workability at room temperature deteriorates due to an increase in the solid solution P. .
- normal temperature workability indicates normal temperature ductility and yield strength, and if the ductility is low or the yield strength is high, it is extremely difficult to process exhaust parts.
- the above-described exhaust manifold, turbocharger housing, and the like are designed to have a complicated shape in order to increase thermal efficiency and control exhaust loss. With materials with low processability at room temperature, it becomes difficult to process complex shaped parts.
- the present invention aims to provide a ferritic stainless steel sheet having both heat resistance and workability, a method for producing the same, and an exhaust part in order to solve the above-described problems of the prior art.
- the present inventors have conducted a detailed investigation mainly on the production conditions and room temperature workability of Nb and Cu-containing ferritic stainless steel sheets. As a result, the steel components are limited to a predetermined range and cold rolled. It has been found that by controlling the precipitation of the P compound to an appropriate amount in the plate annealing step, a low yield strength and high ductility material can be obtained without impairing the high temperature strength.
- the amount of solid solution P is reduced by precipitating a P compound in the cooling process after obtaining a recrystallized structure, and this acts on strengthening at room temperature.
- the solid solution P By reducing the solid solution P, the normal temperature workability of the steel sheet is improved.
- the high temperature strength is improved by the precipitated P compound, heat resistance is also ensured.
- the present inventors have found a heat-resistant ferritic stainless steel sheet that has both high-temperature characteristics and room-temperature processability that can be applied to the above-described complicated exhaust parts.
- the gist of the present invention is as follows.
- [1] Steel has a chemical composition of mass%, C: 0.02% or less, N: 0.02% or less, Si: more than 0.10% and 3.0% or less, Mn: 1.0% or less, P: 0.02 to 0.05%, Cr: 11.0 to 18.0%, B: 0.0001 to 0.0010%, Al: 0.01 to 1.0% Nb and / or Cu: 0.3 to 4.0% in total, Ti: 0 to 0.5%, Mo: 0 to 3.0%, W: 0-2.0%, V: 0 to 1.0%, Sn: 0 to 0.5% Ni: 0 to 1.0%, Mg: 0 to 0.01%, Sb: 0 to 0.5%, Zr: 0 to 0.3%, Ta: 0 to 0.3%, Hf: 0 to 0.3% Co: 0 to 0.3% Ca: 0 to 0.01%, REM: 0 to 0.2%, Ga: 0 to 0.3%, The remainder: Fe and inevitable impurities In the steel, the content of P existing as a P compound is 0.005% or more
- the chemical composition is mass%, Ti: 0.05 to 0.5%, Mo: 0.01 to 3.0%, W: 0.1-2.0%, V: 0.05 to 1.0%, Sn: 0.01 to 0.5%, Ni: 0.05 to 1.0%, Mg: 0.0002 to 0.01%, Sb: 0.01 to 0.5%, Zr: 0.01 to 0.3%, Ta: 0.01-0.3% Hf: 0.01 to 0.3%, Co: 0.01 to 0.3% Ca: 0.0001 to 0.01%, REM: 0.001 to 0.2%, Ga: containing one or more selected from 0.0002 to 0.3%, The ferritic stainless steel sheet according to the above [1].
- [4] The method for producing a ferritic stainless steel sheet according to any one of [1] to [3], wherein the following steps (1) to (3) are sequentially performed.
- (1) a step of heating the cold-rolled steel sheet having the chemical composition according to the above [1] or [2] to 870 to 1100 ° C. (2) cooling the cold-rolled steel sheet from the heating temperature to 800 ° C. at an average cooling rate of 1 ° C./s or less, and (3) A step of cooling the cold-rolled steel sheet from 800 ° C. to 350 ° C. at an average cooling rate of 5 ° C./s or more.
- FIG. 1 shows the relationship between the precipitation amount of a P compound and cold ductility in a cold-rolled steel sheet (1.5 mm thickness).
- the ferritic stainless steel sheet according to the present invention has the following chemical composition. “%” For the content of each element means “mass%”.
- the upper limit is preferably 0.009%. However, excessive reduction leads to an increase in refining costs, so the lower limit is preferably 0.001%.
- N 0.02% or less N, like C, deteriorates moldability and corrosion resistance and lowers the high-temperature strength. Therefore, the lower the content, the better.
- the upper limit is preferably 0.015%. However, excessive reduction leads to an increase in refining costs, so the lower limit is preferably 0.003%.
- Si more than 0.10% and not more than 3.0% Si is an element useful as a deoxidizer and an element that improves high-temperature strength and oxidation resistance.
- High temperature strength and oxidation resistance improve with increasing Si content, and the effect is manifested at over 0.10%.
- the upper limit is made 3.0%.
- the upper limit is preferably 1.0%.
- the lower limit is preferably 0.2%.
- Mn 1.0% or less Mn is an element useful as a deoxidizing agent and contributes to an increase in high-temperature strength in the intermediate temperature range.
- the upper limit is made 1.0%.
- the upper limit is desirably set to 1.0% in consideration of pickling properties and ductility at room temperature.
- the lower limit is preferably 0.05%.
- P 0.02 to 0.05%
- P is an important element for controlling the precipitation of P compounds (FeP, FeTiP and FeNbP).
- P P compounds
- FeP, FeTiP and FeNbP P compounds
- the cost increases due to the use of a low P raw material. To do.
- addition of more than 0.05% remarkably hardens, and corrosion resistance, toughness and pickling properties deteriorate, so 0.05% is made the upper limit.
- Cr 11.0 to 18.0% Cr is an essential element for ensuring oxidation resistance and corrosion resistance. If it is less than 11.0%, oxidation resistance cannot be particularly secured. If it exceeds 18.0%, workability and toughness are deteriorated, so 11.0 to 18.0%. Furthermore, in consideration of manufacturability and scale peelability, it is desirable that the lower limit is 13.0% and the upper limit is 17.5%.
- B 0.0001 to 0.0010% B is an element that improves the secondary workability during product press working. Further, in the present invention, the P compound is utilized to improve the room temperature workability and the high temperature strength. However, the addition of B suppresses the coarsening of the P compound under a high temperature use environment, and the strength when used in a high temperature environment. The effect of increasing stability appears. This is because B is segregated at the grain boundaries during the recrystallization process in the cold-rolled sheet annealing step, and the precipitates that precipitate when exposed to a subsequent high temperature environment are less likely to precipitate at the grain boundaries. This is thought to promote fine precipitation inside.
- the long-term stability of precipitation strengthening is expressed, and it contributes to suppression of strength reduction and improvement of thermal fatigue life.
- This effect is manifested at 0.0001% or more.
- excessive content deteriorates the hardness, intergranular corrosion resistance and oxidation resistance, and also causes weld cracks, so the content was made 0.0001 to 0.0010%.
- the lower limit is 0.0001% and the upper limit is 0.0005%.
- Al 0.01 to 1.0%
- Al is an element that improves oxidation resistance. Further, it is useful as a solid solution strengthening element for improving the strength at 600 to 700 ° C. The effect is stably expressed at a content of 0.01% or more, but excessive content hardens to significantly reduce uniform elongation and toughness to remarkably decrease, so the upper limit was made 1.0%. Furthermore, considering the occurrence of surface defects, weldability, and manufacturability, it is desirable that the lower limit be 0.01% and the upper limit be 0.2%.
- Nb and / or Cu 0.3 to 4.0% in total Nb is an element effective for improving the high-temperature strength by strengthening solid solution and strengthening precipitates.
- C and N are fixed as carbonitrides, contributing to the development of the recrystallization texture that affects the corrosion resistance and r value of the product plate.
- it also has the effect of promoting the production
- the upper limit of the total content is set to 4.0% in order to remarkably harden and deteriorate manufacturability.
- the lower limit is 0.4% and the upper limit is 2.0%.
- a more preferable upper limit is 1.5%, and a further preferable upper limit is 0.6%.
- the Cu contributes to precipitation strengthening by ⁇ -Cu precipitation
- Cu may be contained. At this time, the Cu content is 0.3% or more.
- the high temperature strengthening works effectively because the Cu precipitation rate is increased by using the P compound as a nucleation site.
- the exhaust gas temperature is 800 ° C. or higher, it is desirable to increase the Cu content, and 1.0% or higher is desirable.
- the lower limit is 1.1% and the upper limit is 1.6%.
- Ti 0 to 0.5%
- Ti is an element that combines with C, N, and S to improve corrosion resistance, intergranular corrosion resistance, room temperature ductility and deep drawability, and may be contained.
- the content exceeds 0.5%, the amount of dissolved Ti increases and the room temperature ductility decreases, and a coarse Ti-based precipitate is formed, which becomes the starting point of cracking during hole expansion processing, and press workability Deteriorate.
- the Ti content is set to 0.5% or less.
- the lower limit is 0.05% and the upper limit is 0.2%.
- Mo 0 to 3.0% Mo is an element effective for solid solution strengthening at 950 ° C., and may be included to improve corrosion resistance. This effect becomes remarkable at 0.01% or more. Excessive content significantly deteriorates the room temperature ductility and oxidation resistance, so the content was made 3.0% or less. Considering thermal fatigue characteristics and manufacturability, it is desirable that the lower limit is 0.2% and the upper limit is 2.7%.
- W 0-2.0% W, like Mo, is an element effective for solid solution strengthening at 950 ° C., and also generates a Laves phase (Fe 2 W) to bring about precipitation strengthening.
- the Laves phase of Fe 2 (Nb, Mo, W) is precipitated.
- these Laves phases tend to become fine due to the coexistence with Fe-P-based precipitates. For this reason, you may contain W.
- V 0 to 1.0%
- V is an element that improves the corrosion resistance, and may be contained. This effect becomes remarkable when the content is 0.05% or more. If the content is excessive, the precipitate becomes coarse and the high temperature strength decreases, and the oxidation resistance deteriorates, so the upper limit was made 1.0%. Furthermore, considering the manufacturing cost and manufacturability, it is desirable that the lower limit is 0.08% and the upper limit is 0.5%.
- Sn 0 to 0.5%
- Sn is an element that improves the corrosion resistance, and may be contained in order to improve the high temperature strength in the middle temperature range. These effects become significant at 0.01% or more. An excessive content significantly reduces manufacturability, so the upper limit was made 0.5%. Furthermore, considering the oxidation resistance and manufacturing cost, it is desirable that the lower limit is 0.1% and the upper limit is 0.5%.
- Ni 0 to 1.0%
- Ni is an element that improves acid resistance and toughness, and may be contained. These effects become significant at 0.05% or more. An excessive content increases the cost, so the upper limit was made 1.0%. Further, in consideration of manufacturability, it is desirable that the lower limit is 0.1% and the upper limit is 0.5%.
- Mg 0 to 0.01% Mg may be added as a deoxidizing element, and is an element that contributes to improving the formability by refining the slab structure. Further, the Mg oxide becomes a precipitation site for carbonitrides such as Ti (C, N) and Nb (C, N), and has an effect of finely dispersing and depositing them. Furthermore, there is an effect of improving toughness. For this reason, you may contain Mg. These effects become significant at 0.0002% or more. Excessive inclusion leads to deterioration of weldability and corrosion resistance, so the upper limit was made 0.01%. Considering refining costs, it is desirable that the lower limit is 0.0003% and the upper limit is 0.0010%.
- Sb 0 to 0.5% Sb may be contained because it contributes to the improvement of corrosion resistance and high-temperature strength. The above effect becomes significant at 0.01% or more. An excessive content may cause excessive slab cracking or ductility reduction during the production of the steel sheet, so the upper limit was made 0.5%. Furthermore, considering refining costs and manufacturability, it is desirable that the lower limit is 0.01% and the upper limit is 0.15%.
- Zr 0 to 0.3%
- Zr is a carbonitride-forming element, is an element that improves corrosion resistance and deep drawability, and may be contained. These effects become significant at 0.01% or more. If the content is excessive, the manufacturability is remarkably deteriorated, so the upper limit was made 0.3%. Furthermore, considering the cost and surface quality, it is desirable that the lower limit is 0.1% and the upper limit is 0.3%.
- Ta 0 to 0.3%
- Hf 0 to 0.3%
- Ta and Hf may be contained because they combine with C and N to contribute to improvement of toughness. This effect becomes remarkable at 0.01% or more. Excessive content increases costs and significantly degrades manufacturability, so the upper limit of each element is set to 0.3%. Furthermore, considering refining costs and manufacturability, the lower limit of each element is preferably 0.01% and the upper limit is preferably 0.08%.
- Co 0 to 0.3% Co contributes to the improvement of the high-temperature strength and may be contained. This effect becomes remarkable at 0.01% or more. Since excessive inclusion leads to toughness deterioration, the upper limit was made 0.3%. Furthermore, considering refining costs and manufacturability, the lower limit is preferably 0.01% and the upper limit is preferably 0.1%.
- Ca 0 to 0.01% Since Ca has a desulfurization effect, Ca may be contained. This effect becomes significant at 0.0001% or more. An excessive content generates coarse CaS and degrades toughness and corrosion resistance, so the upper limit was made 0.01%. Furthermore, considering refining costs and manufacturability, the lower limit is preferably 0.0003% and the upper limit is preferably 0.0020%.
- REM 0 to 0.2% REM may be contained from the viewpoint of improving toughness and oxidation resistance by refining various precipitates. This effect becomes significant at 0.001% or more. Excessive content significantly deteriorates castability and lowers ductility, so the upper limit was made 0.2%. Furthermore, considering refining costs and manufacturability, it is desirable that the lower limit is 0.001% and the upper limit is 0.05%.
- REM rare earth element refers to a generic name of two elements of scandium (Sc) and yttrium (Y) and 15 elements (lanthanoids) from lanthanum (La) to lutetium (Lu). It may be added alone or as a mixture. The REM content means the total content of these elements.
- Ga 0 to 0.3% Ga may be contained in a range of 0.3% or less in order to improve corrosion resistance and suppress hydrogen embrittlement. These effects become significant at 0.0002%. From the viewpoints of manufacturability and cost, and from the viewpoints of ductility and toughness, 0.0020% or less is preferable.
- the ferritic stainless steel sheet according to the present invention contains each of the above elements, with the balance being Fe and inevitable impurities.
- the inevitable impurities mean components mixed due to raw materials such as ore and scrap and other factors when industrially producing steel materials.
- Other elements are not particularly specified, but in the present invention, Bi or the like may be contained in an amount of 0.001 to 0.1% as necessary. Note that it is preferable to reduce general harmful elements and impurity elements such as As and Pb as much as possible.
- P content present as P compound 0.005% or more (mass%)
- P compound include FeP, FeTiP, FeNbP, and the like.
- FIG. 1 shows the relationship between the content of P existing as a P compound in a cold-rolled steel sheet (1.5 mm thick) (hereinafter referred to as “P amount in P compound”) and room temperature ductility.
- P amount in P compound a cold-rolled steel sheet
- FIG. 1 is the result of having heat-processed with the various temperature pattern about the steel containing 0.03% of P, and having investigated the relationship between the amount of P in a P compound, and normal temperature ductility according to the test method shown in an Example. .
- the normal temperature ductility is 30% or more. If the room temperature ductility is 30% or more, it is at a level that can be sufficiently molded for various exhaust parts currently manufactured.
- the improvement in ductility due to the formation of the P compound is due to a decrease in the amount of dissolved P.
- the reduction in the amount of solid solution Nb due to FeNbP precipitation and in the case of Ti-containing steel, the reduction in the amount of solid solution Ti due to FeTiP precipitation has an influence.
- the above-mentioned P compound contributes to the improvement of high-temperature strength.
- the precipitates hinder dislocation at high temperature, and the Laves phase and Cu precipitates (bcc-Cu, fcc-Cu) precipitate finely in the high-temperature tensile process with the P compound as the nucleus, and the high-temperature precipitation strengthening ability This is because it increases further.
- This effect is effective not only for high temperature strength but also for high cycle fatigue and low cycle fatigue (thermal fatigue) required for exhaust parts.
- the P compound necessary for strengthening at high temperature is effective if it is 0.005% or more, but excessive precipitation may promote the origin of fatigue fracture and crack propagation, so the upper limit is 0.100%. It is good to do.
- the lower limit of the amount of P in the P compound is 0.006% and the upper limit is 0.05% in consideration of manufacturability. Is desirable.
- the amount of P in the P compound means the content (mass%) of P contained in the steel as undissolved P precipitates.
- extraction residue analysis is performed and the amount of P in a P compound is measured. Specifically, first, the steel is electrolyzed in a tetramethylammonium chloride solution and filtered using a 0.2 ⁇ m diameter filter to obtain a residue. Subsequently, the extracted residue is dissolved and then analyzed by ICP to measure the amount of P in the P compound.
- the method for producing a steel sheet according to the present invention comprises the steps of steelmaking, hot rolling, annealing, pickling, cold rolling, annealing and pickling.
- steelmaking a method in which the steel containing the above essential components and components added as necessary is subjected to furnace melting followed by secondary refining.
- the molten steel is made into a slab according to a known casting method (continuous casting).
- the slab is heated to a predetermined temperature and hot-rolled to a predetermined plate thickness by continuous rolling.
- Hot rolling is rolled up after being rolled by a hot rolling mill comprising a plurality of stands.
- the coiling temperature is not specified, it is preferably 400 to 750 ° C. from the viewpoint of microstructure refinement.
- Annealing after the hot rolling process may be omitted, and the steel sheet is cold-rolled to a predetermined thickness after pickling.
- both a tandem rolling mill and a Sendzimir rolling mill may be used.
- the rolling reduction may be selected as appropriate.
- the recrystallization temperature of the steel having the above chemical composition is 870 to 1100 ° C., it is heated to this temperature.
- the heating temperature it is preferable that the crystal grain size number is about 5 to 8 considering the normal temperature material, so the lower limit is preferably 880 ° C. and the upper limit is preferably 1050 ° C.
- the cooling method after heating it is important to control the cooling method after heating to appropriately precipitate the P compound and improve the normal temperature workability.
- the average cooling rate from the heating temperature to 800 ° C. is set to 1 ° C./s or less, and during this period, a P compound is generated to reduce the amount of dissolved P. If the average cooling rate is too slow, a coarse Laves phase is generated in the Nb-added steel, and coarse ⁇ -Cu is precipitated in the Cu-added steel, thereby deteriorating the toughness.
- the lower limit is desirably set to 0.1 ° C./s. Furthermore, considering the productivity, the lower limit is preferably 0.2 ° C./s.
- the cooling method may be water cooling or forced air cooling. Moreover, what is necessary is just to select the cold-rolled sheet annealing atmosphere suitably, and you may provide temper rolling and a tension leveler after cold rolling and annealing. Furthermore, as for the pickling method, an existing pickling method may be applied.
- Extract residue analysis A precipitate in steel was extracted using a tetramethylammonium chloride solution and a 0.2 ⁇ m diameter filter and analyzed by ICP to measure the amount of P in the P compound. In the extraction residue analysis, 2 g of a test piece having a surface area of 30 mm ⁇ 20 mm was dissolved.
- Examples A1 to A17 satisfying the chemical composition and the amount of P compound defined in the present invention were excellent in normal temperature ductility and high temperature fatigue properties.
- Examples B1 to B9 which do not satisfy these conditions the normal temperature ductility and the high temperature fatigue properties were deteriorated.
- Examples A21 to A25 produced under the conditions satisfying the provisions of the present invention, the amount of P in the P compound is within the range defined by the present invention, and normal temperature ductility and high temperature fatigue properties are exhibited. It was excellent. In Examples B21 to B25 that do not satisfy these conditions, the normal temperature ductility and the high temperature fatigue properties were deteriorated.
- the ferritic stainless steel plate according to the present invention is suitable for use in, for example, automobile exhaust parts.
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Abstract
Description
C:0.02%以下、
N:0.02%以下、
Si:0.10%を超え3.0%以下、
Mn:1.0%以下、
P:0.02~0.05%、
Cr:11.0~18.0%、
B:0.0001~0.0010%、
Al:0.01~1.0%、
Nbおよび/またはCu:合計で0.3~4.0%、
Ti:0~0.5%、
Mo:0~3.0%、
W:0~2.0%、
V:0~1.0%、
Sn:0~0.5%、
Ni:0~1.0%、
Mg:0~0.01%、
Sb:0~0.5%、
Zr:0~0.3%、
Ta:0~0.3%、
Hf:0~0.3%、
Co:0~0.3%、
Ca:0~0.01%、
REM:0~0.2%、
Ga:0~0.3%、
残部:Feおよび不可避的不純物であり、
前記鋼中において、P化合物として存在するPの含有量が、質量%で、0.005%以上である、
フェライト系ステンレス鋼板。
Ti:0.05~0.5%、
Mo:0.01~3.0%、
W:0.1~2.0%、
V:0.05~1.0%、
Sn:0.01~0.5%、
Ni:0.05~1.0%、
Mg:0.0002~0.01%、
Sb:0.01~0.5%、
Zr:0.01~0.3%、
Ta:0.01~0.3%、
Hf:0.01~0.3%、
Co:0.01~0.3%、
Ca:0.0001~0.01%、
REM:0.001~0.2%、
Ga:0.0002~0.3%から選択される1種以上を含有する、
上記〔1〕に記載のフェライト系ステンレス鋼板。
上記〔1〕または〔2〕に記載のフェライト系ステンレス鋼板。
(1)上記〔1〕または〔2〕に記載の化学組成を有する冷延鋼板を、870~1100℃に加熱する工程、
(2)上記冷延鋼板を、上記加熱温度から800℃まで、1℃/s以下の平均冷却速度で冷却する工程、および、
(3)上記冷延鋼板を、800℃から350℃まで、5℃/s以上の平均冷却速度で冷却する工程。
排気部品。
本発明に係るフェライト系ステンレス鋼板は、下記の化学組成を有する。なお、各元素の含有量についての「%」は「質量%」を意味する。
Cは、成形性と耐食性を劣化させ、高温強度の低下をもたらすため、その含有量は少ないほど良く、0.02%以下とした。上限は0.009%とするのが好ましい。但し、過度の低減は精錬コストの増加に繋がるため、その下限は0.001%とするのが好ましい。
Nは、Cと同様、成形性と耐食性を劣化させ、高温強度の低下をもたらすため、その含有量は少ないほど良く、0.02%以下とした。上限は0.015%とするのが好ましい。但し、過度の低減は精錬コストの増加に繋がるため、その下限は0.003%とするのが好ましい。
Siは、脱酸剤として有用な元素であるとともに、高温強度と耐酸化性を改善する元素である。高温強度および耐酸化性は、Si量の増加とともに向上し、その効果は0.10%超で発現する。特に、Cu添加した場合は、その効果が顕著である。しかしながら、過度な含有は常温延性を低下させるためその上限を3.0%とする。酸洗性や靭性を考慮すると、上限は1.0%とするのが望ましい。上記の効果を得るためには、下限は0.2%とするのが好ましい。
Mnは、脱酸剤として有用な元素であるとともに、中温域での高温強度上昇に寄与する。しかし、その含有量が過剰な場合には、高温でMn系酸化物表層に形成し、スケール密着性や異常酸化が生じ易くなる。特に、MoやWと複合添加した場合は、Mn量に対して異常酸化が生じやすくなる傾向にある。そのため、上限を1.0%とする。更に、鋼板製造における酸洗性や常温延性を考慮すると、上限は1.0%とするのが望ましい。上記の効果を得るためには、下限は0.05%とするのが好ましい。
Pは、P化合物(FeP、FeTiPおよびFeNbP)の析出制御を行なうために、重要な元素である。通常、Pは加工性の観点から極力低減することが望ましいとされているが、0.02%未満にするためには、低P原料の使用によるコストアップが生じるため、0.02%以上とする。一方、0.05%超の含有により著しく硬質化する他、耐食性、靭性および酸洗性が劣化するため、0.05%を上限とする。
Crは、耐酸化性や耐食性確保のために必須な元素である。11.0%未満では、特に耐酸化性が確保できず、18.0%超では加工性の低下や靭性の劣化をもたらすため、11.0~18.0%とした。更に、製造性やスケール剥離性を考慮すると、下限は13.0%、上限は17.5%とするのが望ましい。
Bは、製品のプレス加工時の2次加工性を向上させる元素である。また、本発明では、P化合物を活用して常温加工性と高温強度を向上させるが、B添加により高温での使用環境下におけるP化合物の粗大化が抑制され、高温環境での使用時の強度安定性が高くなる効果が発現する。これは、冷延板焼鈍工程において再結晶処理時にBが結晶粒界に偏析することで、その後の高温環境に曝された際に析出する上記析出物が結晶粒界に析出し難くなり、粒内に微細析出を促すためと考えられる。これにより析出強化の長期安定性を発現させ、強度低下の抑制や熱疲労寿命の向上に寄与する。この効果は0.0001%以上で発現するが、過度な含有は硬質化や粒界腐食性と耐酸化性を劣化させる他、溶接割れが生じるため、0.0001~0.0010%とした。更に、耐食性や製造コストを考慮すると、下限は0.0001%、上限は0.0005%とするのが望ましい。
Alは、脱酸元素として添加される他、耐酸化性を向上させる元素である。また、固溶強化元素として600~700℃の強度向上に有用である。その作用は0.01%以上の含有で、安定して発現するが、過度の含有は硬質化して均一伸びを著しく低下させる他、靭性が著しく低下するため、上限を1.0%とした。更に、表面疵の発生や溶接性、製造性を考慮すると、下限は0.01%、上限は0.2%とするのが望ましい。
Nbは、固溶強化および析出物微細化強化による高温強度向上に有効な元素である。また、CやNを炭窒化物として固定し、製品板の耐食性やr値に影響する再結晶集合組織の発達に寄与する役割もある。本発明ではFeとPの化合物の生成を促進する効果も有し、FeNbPが粒内析出して高加工性を発現する。このため、Nbを含有させてもよい。これらの効果は0.3%から発現するため、合計含有量の下限を0.3%とした。一方、合計含有量が4.0%を超える場合には、著しく硬質化する他、製造性も劣化させるため、合計含有量の上限を4.0%とした。また、原料コストや靭性を考慮すると、下限は0.4%、上限は2.0%とするのが望ましい。より好ましい上限は、1.5%であり、更に好ましい上限は0.6%である。
Tiは、C,N,Sと結合して耐食性、耐粒界腐食性、常温延性や深絞り性を向上させる元素であり、含有させてもよい。また、本発明ではFeTiPの析出により常温加工性を向上させる場合、その効果は0.05%以上から顕著となるため、下限を0.05%とするのが好ましい。一方、0.5%超の含有により、固溶Ti量が増加して常温延性が低下する他、粗大なTi系析出物を形成し、穴拡げ加工時の割れの起点になり、プレス加工性を劣化させる。また、耐酸化性も劣化するため、Ti含有量は0.5%以下とした。更に、表面疵の発生や靭性を考慮すると、下限は0.05%、上限は0.2%とするのが望ましい。
Moは、950℃における固溶強化に有効な元素であるとともに、耐食性を向上させるため含有させてもよい。この効果は0.01%以上で顕著となる。過剰な含有は、常温延性と耐酸化性を著しく劣化させるため、その含有量は3.0%以下とした。熱疲労特性や製造性を考慮すると、下限は0.2%、上限は2.7%とするのが望ましい。
WもMo同様、950℃における固溶強化に有効な元素であるとともに、Laves相(Fe2W)を生成して析出強化の作用をもたらす。特に、NbやMoと複合添加した場合、Fe2(Nb,Mo,W)のLaves相が析出するが、Wを添加するとこのLaves相の粗大化が抑制されて析出強化能が向上する。更に、前記のように、Fe-P系の析出物との共存によってこれらのLaves相は微細になる傾向がある。このため、Wを含有させてもよい。これらの効果は0.1%以上の含有で顕著となる。過剰な含有は、コスト高になるとともに、常温延性が低下するため、上限を2.0%とした。更に、製造性、低温靭性および耐酸化性を考慮すると、下限は0.2%、上限は1.5%とするのが望ましい。
Vは、耐食性を向上させる元素であり、含有させてもよい。この効果は0.05%以上の含有で顕著となる。過剰な含有は、析出物が粗大化して高温強度が低下する他、耐酸化性が劣化させるため、上限を1.0%とした。更に、製造コストや製造性を考慮すると、下限は0.08%、上限は0.5%とするのが望ましい。
Snは、耐食性を向上させる元素であり、中温域の高温強度を向上させるため、含有させてもよい。これらの効果は0.01%以上で顕著となる。過剰な含有は、製造性を著しく低下させるため、上限を0.5%とした。更に、耐酸化性や製造コストを考慮すると、下限は0.1%、上限は0.5%とするのが望ましい。
Niは耐酸性や靭性を向上させる元素であり、含有させてもよい。これらの効果は0.05%以上で顕著となる。過剰な含有はコスト高になるため、上限を1.0%とした。更に、製造性を考慮すると、下限は0.1%、上限は0.5%とするのが望ましい。
Mgは、脱酸元素として添加させる場合がある他、スラブの組織を微細化させ、成形性向上に寄与する元素である。また、Mg酸化物はTi(C,N)やNb(C,N)等の炭窒化物の析出サイトになり、これらを微細分散析出させる効果がある。さらに、靭性を向上させる効果もある。このため、Mgを含有させてもよい。これらの効果は0.0002%以上で顕著となる。過度な含有は、溶接性や耐食性の劣化につながるため、上限を0.01%とした。精錬コストを考慮すると、下限は0.0003%、上限は0.0010%とするのが望ましい。
Sbは、耐食性と高温強度の向上に寄与するため、含有させてもよい。上記の効果は0.01%以上で顕著となる。過剰な含有は、鋼板製造時のスラブ割れや延性低下が過度に生じる場合があるため、上限を0.5%とした。更に、精錬コストや製造性を考慮すると、下限は0.01%、上限は0.15%とするのが望ましい。
Zrは、TiやNb同様に炭窒化物形成元素であり、耐食性、深絞り性の向上させる元素であり、含有させてもよい。これらの効果は0.01%以上で顕著となる。過剰な含有は、製造性の劣化が著しいため、上限は0.3%とした。更に、コストや表面品位を考慮すると、下限は0.1%、上限は0.3%とするのが望ましい。
Hf:0~0.3%
TaおよびHfは、CやNと結合して靭性の向上に寄与するため、含有させてもよい。この効果は、0.01%以上で顕著となる。過剰な含有は、コスト増になる他、製造性を著しく劣化させるため、いずれの元素も上限を0.3%とした。更に、精錬コストや製造性を考慮すると、いずれの元素も下限は0.01%、上限は0.08%とするのが望ましい。
Coは、高温強度の向上に寄与するため、含有させてもよい。この効果は、0.01%以上で顕著となる。過剰な含有は靭性劣化につながるため、上限を0.3%とした。更に、精錬コストや製造性を考慮すると、下限は0.01%、上限は0.1%とするのが望ましい。
Caは、脱硫効果を有するので、含有させてもよい。この効果は0.0001%以上で顕著となる。過剰な含有は、粗大なCaSを生成させ、靭性や耐食性を劣化させるため、上限を0.01%とした。更に、精錬コストや製造性を考慮すると、下限は0.0003%、上限は0.0020%とするのが望ましい。
REMは、種々の析出物の微細化による靭性向上や耐酸化性の向上の観点から、含有させてもよい。この効果は0.001%以上で顕著となる。過剰な含有は、鋳造性を著しく劣化させ、延性の低下をもたらすので、上限を0.2%とした。更に、精錬コストや製造性を考慮すると、下限は0.001%、上限は0.05%とするのが望ましい。REM(希土類元素)は、スカンジウム (Sc)、イットリウム (Y)の2元素と、ランタン(La)からルテチウム(Lu) までの15元素(ランタノイド)の総称を指す。単独で添加してもよいし、混合物であってもよい。REM含有量は、これらの元素の合計含有量を意味する。
Gaは、耐食性向上や水素脆化抑制のため、0.3%以下の範囲で含有させてもよい。これらの効果は、0.0002%で顕著となる。製造性やコストの観点、ならびに、延性や靭性の観点から0.0020%以下が好ましい。
本発明に係るフェライト系ステンレス鋼板は、Pの化合物を形成させることで、固溶P量を低減し、低耐力化および高延性化を図る。P化合物としては、例えば、FeP、FeTiPおよびFeNbP等が例示される。
本発明の鋼板の製造方法は、製鋼-熱間圧延-焼鈍-酸洗-冷間圧延-焼鈍・酸洗の各工程よりなる。製鋼においては、前記必須成分および必要に応じて添加される成分を含有する鋼を、転炉溶製し続いて2次精錬を行う方法が好適である。溶製した溶鋼は、公知の鋳造方法(連続鋳造)に従ってスラブとする。スラブは、所定の温度に加熱され、所定の板厚に連続圧延で熱間圧延される。熱間圧延は複数スタンドから成る熱間圧延機で圧延された後に巻き取られる。巻取温度の規定はしないが、組織微細化の観点からは400~750℃が望ましい。
テトラメチルアンモニウムクロライド溶液および0.2μm径のフィルターを用いて鋼中の析出物を抽出しICPで分析して、P化合物中のP量を測定した。なお、抽出残渣分析においては、30mm×20mmの表面積の試験片を2g溶解させた。
JIS13B号試験片を作製して圧延方向と平行方向の引張試験を行い、破断伸び(全伸び)を測定した。常温の全伸びは、30%以上のものを良好と判断する。
JIS Z 2275に記載されている金属平板の平面曲げ疲れ試験方法に準拠した方法で、かつ加熱炉が装着されている平面曲げ疲労試験機を用いて、800℃で応力振幅、50MPaを付与し、107回での破断有無を確認した。
Claims (5)
- 鋼の化学組成が、質量%で、
C:0.02%以下、
N:0.02%以下、
Si:0.10%を超え3.0%以下、
Mn:1.0%以下、
P:0.02~0.05%、
Cr:11.0~18.0%、
B:0.0001~0.0010%、
Al:0.01~1.0%、
Nbおよび/またはCu:合計で0.3~4.0%、
Ti:0~0.5%、
Mo:0~3.0%、
W:0~2.0%、
V:0~1.0%、
Sn:0~0.5%、
Ni:0~1.0%、
Mg:0~0.01%、
Sb:0~0.5%、
Zr:0~0.3%、
Ta:0~0.3%、
Hf:0~0.3%、
Co:0~0.3%、
Ca:0~0.01%、
REM:0~0.2%、
Ga:0~0.3%、
残部:Feおよび不可避的不純物であり、
前記鋼中において、P化合物として存在するPの含有量が、質量%で、0.005%以上である、
フェライト系ステンレス鋼板。 - 前記化学組成が、質量%で、
Ti:0.05~0.5%、
Mo:0.01~3.0%、
W:0.1~2.0%、
V:0.05~1.0%、
Sn:0.01~0.5%、
Ni:0.05~1.0%、
Mg:0.0002~0.01%、
Sb:0.01~0.5%、
Zr:0.01~0.3%、
Ta:0.01~0.3%、
Hf:0.01~0.3%、
Co:0.01~0.3%、
Ca:0.0001~0.01%、
REM:0.001~0.2%、
Ga:0.0002~0.3%から選択される1種以上を含有する、
請求項1に記載のフェライト系ステンレス鋼板。 - 排気部品に用いられる、
請求項1または2に記載のフェライト系ステンレス鋼板。 - 下記の(1)~(3)の工程を順に行う、請求項1~3のいずれかに記載のフェライト系ステンレス鋼板の製造方法。
(1)請求項1または2に記載の化学組成を有する冷延鋼板を、870~1100℃に加熱する工程、
(2)上記冷延鋼板を、上記加熱温度から800℃まで、1℃/s以下の平均冷却速度で冷却する工程、および、
(3)上記冷延鋼板を、800℃から350℃まで、5℃/s以上の平均冷却速度で冷却する工程。 - 請求項1または2に記載のフェライト系ステンレス鋼板を用いた、
排気部品。
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KR20190132455A (ko) | 2019-11-27 |
CN110462088A (zh) | 2019-11-15 |
KR102306578B1 (ko) | 2021-09-29 |
JP6796708B2 (ja) | 2020-12-09 |
JPWO2018181060A1 (ja) | 2020-03-26 |
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