WO2014147655A1 - フェライト系ステンレス鋼板 - Google Patents
フェライト系ステンレス鋼板 Download PDFInfo
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- WO2014147655A1 WO2014147655A1 PCT/JP2013/001824 JP2013001824W WO2014147655A1 WO 2014147655 A1 WO2014147655 A1 WO 2014147655A1 JP 2013001824 W JP2013001824 W JP 2013001824W WO 2014147655 A1 WO2014147655 A1 WO 2014147655A1
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- 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
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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- C21D6/002—Heat treatment of ferrous alloys containing Cr
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
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- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- 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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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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- 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
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
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- 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
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
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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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0273—Final recrystallisation annealing
Definitions
- the present invention relates to a ferritic stainless steel sheet that can be preferably applied to various uses such as automobile parts, household products, kitchen appliances, electrical appliances, etc., and has excellent formability and corrosion resistance.
- Ferritic stainless steel is widely used as a material with excellent corrosion resistance in various fields including automobile parts and household goods. In general, this ferritic stainless steel is cheaper than austenitic stainless steel containing a large amount of Ni, but is inferior in formability. For example, ferritic stainless steel has a problem that irregularities called earrings occur at the edge of a molded member when deep drawing is performed. For this reason, ferritic stainless steel that has both corrosion resistance and formability such as deep drawing is required.
- Patent Document 1 As a technique for improving the formability of ferritic stainless steel, for example, in Patent Document 1, C: 0.03 mass% or less, Si: 2.0 mass% or less, Mn: 0.8 mass% or less, S : 0.03 mass% or less, Cr: 6 to 25 mass%, N: 0.03 mass% or less, Al: 0.3 mass% or less, Ti: 0.4 mass% or less, V: 0.02 to 0 4 mass%, B: 0.0002 to 0.0050 mass% in a range satisfying the formulas: Ti / 48> N / 14 + C / 12, V / B> 10, with the balance being Fe and inevitable impurities
- a ferritic stainless hot-rolled steel sheet characterized by comprising: This ferritic stainless steel hot-rolled steel sheet is said to have excellent skin resistance after forming and high temperature fatigue properties.
- Patent Document 2 C: 0.03 to 0.08 mass%, Si: 1.0 mass% or less, Mn: 1.0 mass% or less, P: 0.05 mass% or less, S: 0 .015 mass% or less, Al: 0.10 mass% or less, N: 0.02 mass% or less, Cr: 5 to 60 mass%, Ti: 4 ⁇ (C content + N content) to 0.5 % By mass, Nb: 0.003-0.020% by mass, B: 0.0002-0.005% by mass, the balance being Fe and inevitable impurities, and ⁇ r being 0.3 or less
- a featured chromium steel sheet is disclosed. This chromium steel sheet is said to be excellent in deep drawability and secondary work brittleness resistance.
- the techniques described in the above patent documents have the following problems.
- the in-plane anisotropy (hereinafter simply referred to as ⁇ r) of the plastic strain ratio (hereinafter simply referred to as r value) is not sufficiently improved.
- the technique described in Patent Document 1 has a problem that earrings are generated at the edge of the molded member when deep drawing is performed.
- the influence on the corrosion resistance due to the addition of B has not been studied, and the corrosion resistance of the ferritic stainless steel hot rolled steel sheet may be lowered.
- the technique disclosed in Patent Document 2 although the r value and ⁇ r are improved, the influence on the corrosion resistance by adding B has not been studied, and the corrosion resistance of the chromium steel sheet may be lowered. is there.
- An object of the present invention is to provide a ferritic stainless steel sheet that solves the above-described problems of the prior art and has excellent formability and corrosion resistance.
- the present inventors have made various studies in order to achieve the above-described problems. As a result, a ferritic stainless steel sheet having both formability such as deep drawing and corrosion resistance can be obtained by adjusting the V content and B content to appropriate ranges and adjusting V / B to 15.0 or more. As a result, the present invention has been completed.
- Example 1 (0.009 to 0.012)% C [C content in Table 1 means in the range of 0.009 to 0.012 mass%. The same applies hereinafter. ], (0.08 to 0.12)% Si, (0.19 to 0.23)% Mn, (0.033 to 0.037)% P, (0.001 to 0.002)% S, (17.2 to 17.5)% Cr, (0.02 to 0.03)% Al, (0.009 to 0.012)% N, (0.08 to 0.12)% Ni, (0 .25 to 0.27)% Ti, (0.010 to 0.016)% V, and (0.0002 to 0.0010)% B, changing the V / B ratio, the balance being Fe and inevitable impurities Stainless steel made of was melted in a 50 kg small vacuum melting furnace.
- the combined cycle corrosion test is based on JASO M 609-91, salt spray (5% NaCl, 35 ° C., 2 h) ⁇ dry (60 ° C., relative humidity 20-30%) ⁇ wet (50 ° C., 2 h, relative humidity) 30 cycles of corrosion test with 1 cycle of ⁇ 95%) were performed.
- an area ratio of 20% or more was determined to be unacceptable and less than 20% was determined to be acceptable.
- Table 1 From Table 1, it can be seen that the corrosion resistance is improved by setting the V / B ratio to 15.0 or more.
- the hot-rolled sheet was annealed at 1020 ° C. ⁇ 60 sec, then shot blasted, pickled with a mixed acid of hydrofluoric acid and nitric acid, and cold rolled into a cold-rolled sheet having a thickness of 0.7 mm. .
- the obtained cold-rolled sheet was subjected to finish annealing at 980 ° C. ⁇ 40 sec to obtain a cold-rolled annealed sheet.
- a test piece of 60 mm ⁇ 80 mm was cut out from the obtained cold-rolled annealed plate, the surface was polished with # 600 count, and corrosion resistance was evaluated by a combined cycle corrosion test. In the combined cycle corrosion test, the above corrosion test cycle was performed 30 times.
- a hot-rolled sheet having a thickness of 0.0 mm was used. These hot-rolled sheets were subjected to hot-rolled sheet annealing at 930 ° C. ⁇ 60 sec, then pickled, and then cold-rolled to obtain cold-rolled sheets having a thickness of 0.7 mm. Further, these cold-rolled plates were subjected to finish annealing at 880 ° C. ⁇ 40 sec, and then pickled to obtain cold-rolled annealed pickled plates. About the obtained cold-rolled annealing pickling board, the tension test (JIS Z 2201) was done and elongation, r value, and (DELTA) r were calculated
- an elongation of 30.0% or more, an r value of 1.50 or more, and ⁇ r of 0.30 or less were determined to be acceptable.
- the surface of the test piece cut out from the cold rolled annealed pickling plate was polished with # 600 count, and the corrosion resistance was evaluated by a combined cycle corrosion test.
- the above corrosion test cycle was performed 30 times.
- an area ratio of 20% or more was determined to be unacceptable and less than 20% was determined to be acceptable.
- FIG. 1 shows the relationship between the V / B and cold-rolled annealed pickling plate forming processability (elongation, r value, ⁇ r) and the corrosion resistance evaluation results. From FIG. 1, it was found that by satisfying V / B ⁇ 15.0, all of El, r value, ⁇ r, and corrosion resistance evaluation satisfy the determination criteria. In particular, it was found that r value and ⁇ r were excellent when V / B ⁇ 30.0.
- the present invention provides the following.
- V 0.010-0.040%
- B 0.0001-0.0010%
- ratio of V content to B content (V / B) ⁇ 15.0 When it is contained within a range satisfying Ti: 0.20% or more and 0.40% or less and Ti% + Nb% ⁇ 0.70, Ti is contained or Ti and Nb are contained, and Nb : 0.40% or more and 0.60% or less, Nb contained within a range satisfying Ti% + Nb% ⁇ 0.70, or a small amount when Nb and Ti are contained Satisfy one Kutomo, ferritic stainless steel sheet balance being Fe and unavoidable impurities.
- the ferritic stainless steel sheet of the present invention has excellent formability (formability) and excellent corrosion resistance. Specifically, the ferritic stainless steel sheet of the present invention has a formability satisfying an elongation of 30.0% or more, an r value of 1.50 or more, and ⁇ r of 0.30 or less, and was polished by # 600. Corrosion resistance satisfying a cracking area ratio of less than 20% in a combined cycle corrosion test (30 cycles) in accordance with JASO M 609-91 on the surface of a steel plate.
- C 0.003-0.013%
- the lower the C content the better from the viewpoint of corrosion resistance and moldability.
- the lower limit of the C content is 0.003%.
- the C content is in the range of 0.003 to 0.013%. More preferably, it is 0.004 to 0.011%.
- Si 0.01 to 0.95%
- Si is an element useful as a deoxidizer for steel.
- the Si content is 0.01% or more.
- the Si content exceeds 0.95%, the rolling load increases in the hot rolling process, and a scale is very easily generated.
- the pickling property is lowered due to the formation of a scale in which Si is concentrated on the surface layer of the steel sheet.
- the Si content is in the range of 0.01 to 0.95%. More preferably, it is 0.05 to 0.50%.
- the Ti content to be described later is 0.25% or more, the pickling property is significantly reduced by Si.
- the preferable range of the Si content is 0.05 to 0.20%. It is.
- Mn 0.01 to 0.40% Mn combines with S present in the steel to form MnS and lowers the corrosion resistance. Therefore, the Mn content is set to 0.40% or less. On the other hand, if the content of Mn is decreased more than necessary, the refining cost increases. For this reason, the Mn content is preferably 0.01% or more. In order to achieve particularly high corrosion resistance while suppressing refining costs, the preferable range of the Mn content is 0.05 to 0.35%.
- P 0.020 to 0.040%
- P is an element inevitably contained in steel. Since P is an element harmful to corrosion resistance and moldability, the P content is preferably low. In particular, if the P content exceeds 0.040%, the formability of the steel sheet decreases due to solid solution strengthening. For this reason, content of P is 0.040% or less. On the other hand, in order to make the P content less than 0.020%, it is necessary to perform refining over time, and making the P content less than 0.020% is not preferable in production. Therefore, the P content is in the range of 0.020 to 0.040%. Preferably, it is in the range of 0.025 to 0.035%.
- S 0.010% or less S combines with Mn to form MnS.
- MnS expands by hot rolling or the like and exists as precipitates (inclusions) at ferrite grain boundaries and the like.
- Such sulfide-based precipitates (inclusions) reduce the elongation of the steel sheet, and sometimes cause cracks in the steel sheet during bending of the steel sheet. For this reason, it is desirable to reduce the S content as much as possible, and the allowable S content is up to 0.010%.
- a preferable S content is 0.005% or less.
- Al 0.01 to 0.45%
- Al is an element useful as a deoxidizer for steel.
- the Al content needs to be 0.01% or more.
- the range of Al content is set to 0.01 to 0.45%.
- a preferable range of the Al content is 0.01 to 0.10%.
- a more preferred range is 0.02 to 0.04%.
- Cr 14.5-21.5%
- Cr is an element that contributes to improving corrosion resistance, and is an element included as an essential element in a stainless steel plate.
- the Cr content is less than 14.5%, a steel sheet having sufficient corrosion resistance cannot be obtained.
- the Cr content exceeds 21.5%, in addition to the toughness of the steel sheet being lowered, the steel is too hard and the elongation of the steel sheet is also significantly reduced. Therefore, the Cr content range is 14.5 to 21.5%. Further, from the viewpoint of corrosion resistance and manufacturability, the preferable range of the Cr content is 16.0 to 21.5%.
- Ni 0.01 to 0.60% Ni has an effect of reducing crevice corrosion. In order to obtain this effect, the Ni content must be 0.01% or more. However, in addition to Ni being an expensive element, even if Ni exceeds 0.60%, the above effect is saturated and the hot workability is reduced. Therefore, the range of Ni content is set to 0.01 to 0.60%. A preferable range of the Ni content is 0.10 to 0.40%.
- N 0.005 to 0.012% N combines with V to form nitrides or carbonitrides, refines the crystal grains of the final product plate, and contributes to the improvement of the r-value characteristics.
- the N content is less than 0.005%, the effect of refining crystal grains due to fine precipitation of V (C, N) carbonitride cannot be obtained.
- the N content exceeds 0.012%, the Cr nitride amount or the Cr carbonitride amount increases, the steel plate becomes hard and the elongation decreases. Therefore, the range of N content is set to 0.005 to 0.012%.
- the preferable range of the N content is 0.006 to 0.010%.
- V 0.010 to 0.040%
- B 0.0001 to 0.0010%
- V / B 15.0 or more
- V and B are extremely important elements in the present invention.
- V is combined with N to form nitrides and carbonitrides such as VN and V (C, N), and has an effect of suppressing coarsening of crystal grains of the hot-rolled annealing plate.
- B has an effect of assisting the grain growth suppression by concentrating on the ferrite grain boundary and delaying the grain boundary movement. Due to the combined effect of V and B, the crystal grains of the hot-rolled annealing plate are refined.
- the area of the grain boundary which is the preferential nucleation site of ⁇ 111 ⁇ recrystallized orientation grains after cold rolling annealing, increases the ⁇ 111 ⁇ orientation, thereby improving the r value. It is considered that the ⁇ r value decreases.
- V content is less than 0.010%, the effect of refining crystal grains due to fine precipitation of VN or V (C, N) cannot be obtained.
- B content is less than 0.0001%, there is no effect of suppressing grain growth.
- V content exceeds 0.040% or the B content exceeds 0.0010% the effect of refinement of crystal grains during growth and suppression of growth and improvement of moldability are only saturated. On the contrary, the material is hardened, the ductility is lowered, and the formability of the steel sheet is deteriorated. Therefore, the content range of V is 0.010 to 0.040%, and the content range of B is 0.0001 to 0.0010%.
- V / B The content ratio of V and B affects the balance between the ferrite crystal grain size and the ferrite grain interfacial area and the precipitation behavior of Cr 2 B at the grain boundaries, and affects the moldability and corrosion resistance. It is conceivable that. As described in Tables 1 and 2 and FIG. 1, when the V / B ratio is less than 15.0, B combines with Cr and precipitates as Cr 2 B at the grain boundary. As a result, the effect of suppressing grain growth is reduced, and the r value is insufficiently improved. Furthermore, the Cr concentration in the vicinity of the grain boundary decreases, and the corrosion resistance of the steel sheet deteriorates. Therefore, (V / B) is set to 15.0 or more. In addition, from a viewpoint of ensuring high moldability, the preferable range of V / B is 30.0 or more.
- Ti 0.20% or more and 0.40% or less, Ti in a range satisfying Ti% + Nb% ⁇ 0.70, or Ti and Nb, and Nb: 0.40% or more and 0.60 % Or less, when Nb is contained in a range satisfying Ti% + Nb% ⁇ 0.70, or Nb and Ti are contained Ti and Nb are both solid solution C and N are fixed as a compound to fix the corrosion resistance of the steel sheet. And has the effect of improving moldability. For this reason, it is necessary to use either Ti or Nb alone or to use both Ti and Nb. Specifically, in order to acquire the said effect, it is necessary to contain Ti: 0.20% or more or Nb: 0.40% or more.
- the Ti amount is 0.40% or less, the Nb amount is 0.60% or less, and Ti% + Nb% ⁇ 0.70 (in the present invention, all of Ti amount, Nb amount, Ti% + Nb% Must be less than or equal to the upper limit).
- the Ti content is 0.35% or less, the Nb content is 0.55% or less, and Ti% + Nb% ⁇ 0.65.
- the ferritic stainless steel sheet of the present invention contains the essential components described above, with the balance being Fe and inevitable impurities.
- the ferritic stainless steel sheet of the present invention further includes one or more selected from one or two of Cu and Mo, Zr, REM, W, Co, Mg, and Ca, if necessary. You may contain in the following range.
- Cu 0.01 to 1.40%
- Cu is an element that improves the corrosion resistance.
- Cu is an element that is particularly effective for improving the corrosion resistance when the steel sheet is in an aqueous solution or when weakly acidic water droplets adhere to the steel sheet. This effect is obtained by containing 0.01% or more of Cu, and increases as the Cu content increases.
- the Cu content exceeds 1.40%, the hot workability deteriorates and Cu-derived oxide called red scale is generated on the hot-rolled slab during hot rolling, resulting in surface defects. Therefore, it is not preferable.
- the Cu content exceeds 1.40%, descaling after annealing becomes difficult, which is not preferable for production. Therefore, when Cu is contained, the content range is preferably 0.01 to 1.40%. Further, the more preferable range of the Cu content is 0.10 to 1.00%, and the most preferable range is 0.30 to 0.50%.
- Mo 0.01 to 1.62%
- Mo is an element that significantly improves the corrosion resistance of the stainless steel plate. This effect is obtained by adding 0.01% or more of Mo to the steel sheet, and the effect improves as the Mo content increases. However, if the Mo content exceeds 1.62%, the hot workability deteriorates and surface defects frequently occur during hot rolling. Moreover, since Mo is an expensive element, an increase in the Mo content increases the manufacturing cost. Therefore, when Mo is contained, the content range is preferably 0.01 to 1.62%. A more preferable content range is 0.30 to 1.62%, and most preferably 0.40 to 1.20%.
- the Mo content is preferably 0.30 to 1.40%. More preferably, it is in the range of 0.40 to 1.00%.
- the said component in the case of containing the 1 type (s) or 2 or more types chosen from Zr, REM, W, Co, Mg, Ca is demonstrated.
- Zr 0.01-0.20%
- Zr binds to C and N and has the effect of suppressing sensitization. This effect is obtained when the Zr content is 0.01% or more.
- the content of Zr exceeds 0.20%, the workability of the steel sheet decreases. Further, since Zr is an expensive element, an increase in the Zr content increases the manufacturing cost. Therefore, when Zr is contained, the content range is preferably 0.01 to 0.20%.
- REM 0.001 to 0.100% REM has the effect of improving oxidation resistance. This effect is obtained by containing REM 0.001% or more. On the other hand, if REM is contained in an amount exceeding 0.100%, hot rollability is lowered and surface defects frequently occur, which is not preferable. Therefore, when it is contained, the content range of REM is preferably 0.001 to 0.100%, and more preferably 0.001 to 0.050%.
- W 0.01-0.20% W has the effect of improving the corrosion resistance like Mo. This effect is obtained when the W content is 0.01% or more. On the other hand, when the amount of W exceeds 0.20%, the strength increases, and the productivity decreases due to an increase in rolling load or the like. Therefore, the range of W content is preferably 0.01 to 0.20%, and more preferably 0.01 to 0.10%.
- Co 0.01-0.20%
- Co has the effect of improving the corrosion resistance. This effect is obtained when the Co content is 0.01% or more.
- the range of Co content is preferably 0.01 to 0.20%, and more preferably 0.01 to 0.10%.
- Mg 0.0001 to 0.0010%
- Mg is an element that improves the equiaxed crystal ratio of the slab and is effective in improving formability and toughness. This effect is obtained when the Mg content is 0.0001% or more. On the other hand, if the Mg content exceeds 0.0010%, Mg-based inclusions increase and the surface properties are deteriorated. Therefore, the content range of Mg is preferably 0.0001 to 0.0010%, more preferably 0.0002 to 0.0004%.
- Ca 0.0003 to 0.0030%
- Ca is an effective component for preventing nozzle clogging due to precipitation of Ti-based inclusions that are likely to occur during continuous casting. The effect is obtained when the Ca content is 0.0003% or more. However, when the Ca content exceeds 0.0030%, the corrosion resistance decreases due to the generation of CaS. Therefore, the preferable content range of Ca is 0.0003 to 0.0030%, more preferably 0.0005 to 0.0020%, and most preferably 0.0005 to 0.0015%. .
- the manufacturing method of the ferritic stainless steel of this invention is not limited to the following embodiment.
- the molten steel having the above composition is melted in a generally known converter or electric furnace, and further refined by vacuum degassing (RH), VOD, AOD, etc., and then preferably cast by a continuous casting method to obtain a rolled material (slab Etc.).
- the rolled material is heated and hot rolled to obtain a hot rolled sheet.
- the slab heating temperature for hot rolling is preferably in the temperature range of 1050 ° C. to 1250 ° C., and the finishing temperature for hot rolling is preferably 750 to 900 ° C.
- a hot-rolled sheet can perform hot-rolled sheet annealing as needed. When hot-rolled sheet annealing is performed, it is preferable to perform short-term continuous annealing in the temperature range of 850 to 1150 ° C.
- a hot-rolled sheet can be descaled and used as a product as it is, or can be used as a material for cold rolling.
- the hot-rolled sheet of the material for cold rolling is subjected to cold rolling at a cold rolling reduction ratio of 30% or more to obtain a cold-rolled sheet.
- the cold rolling reduction ratio is preferably 50 to 95%.
- recrystallization annealing finish annealing at 800 to 1100 ° C.
- the finish of the cold-rolled sheet can be 2D, 2B, BA and various types of polishing defined by Japan industrial Standard (JIS) G4305.
- the steel plate as used in this invention shall contain a steel strip and foil material.
- Example 1 Molten steel having the composition shown in Table 3 (the balance being Fe) was melted by a converter and secondary refining (VOD), and a slab was formed by a continuous casting method. After these slabs were heated to 1120 ° C., hot rolling was performed at a finishing temperature of 800 ° C. to obtain hot rolled sheets having a thickness of 4.0 mm. These hot-rolled sheets were subjected to hot-rolled sheet annealing at 940 ° C. ⁇ 60 sec, and then pickled and cold-rolled to obtain cold-rolled sheets. Next, these cold-rolled plates were subjected to finish annealing at 900 ° C.
- ElL, ElD, and ElC represent elongations in the L direction, the D direction, and the C direction, respectively.
- rL, rD, and rC represent r values in the L direction, the D direction, and the C direction, respectively.
- Corrosion resistance A test piece of 60 mm x 80 mm was cut out from the obtained cold-rolled annealed plate, the surface was polished with # 600 count, a test piece for corrosion resistance evaluation was produced, and corrosion resistance evaluation was performed by a combined cycle corrosion test. In the combined cycle corrosion test, the above-described corrosion test cycle was performed 30 times, and an area ratio of 20% or more was rejected, and less than 20% was determined to be acceptable.
- Example 2 Molten steel having the composition shown in Table 4 was melted by a converter and secondary refining (VOD) to obtain a slab by a continuous casting method. After these slabs were heated to 1120 ° C., hot rolling was performed at a finishing temperature of 800 ° C. to obtain hot rolled sheets having a thickness of 4.0 mm. These hot-rolled sheets were subjected to hot-rolled sheet annealing at 1020 ° C. ⁇ 60 sec, followed by pickling and cold rolling to obtain cold-rolled sheets. Next, these cold-rolled plates were subjected to finish annealing at 1000 ° C. ⁇ 40 sec, and then pickled to obtain cold-rolled annealed pickled plates having a thickness of 0.7 mm. About the obtained cold-rolled annealing pickling board, forming processability and corrosion resistance evaluation were performed. The evaluation method is as follows.
- Table 5 shows the results obtained in Example 1, and Table 6 shows the results obtained in Example 2.
- the present invention by optimizing the component composition, in particular, the V and B contents, a ferritic stainless steel sheet having excellent forming processability and corrosion resistance can be produced, and an industrially remarkable effect is achieved.
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Abstract
Description
表1に示す(0.009~0.012)%C[Cの含有量が0.009~0.012質量%の範囲にあることを意味する。以下同様である。]、(0.08~0.12)%Si、(0.19~0.23)%Mn、(0.033~0.037)%P、(0.001~0.002)%S、(17.2~17.5)%Cr、(0.02~0.03)%Al、(0.009~0.012)%N、(0.08~0.12)%Ni、(0.25~0.27)%Ti、(0.010~0.016)%V、(0.0002~0.0010)%Bで、V/B比を変化させ、残部がFe及び不可避的不純物からなるステンレス鋼を50kg小型真空溶解炉にて溶製した。これらの鋼塊を1100℃に加熱後、熱間圧延を施して4.0mmの熱延板とした。次いで、上記熱延板を930℃×60secの焼鈍を施した後、ショットブラストを行い、弗酸と硝酸の混合酸で酸洗し、冷間圧延により板厚0.7mmの冷延板とした。得られた冷延板に対し、880℃×40secの仕上焼鈍を施して、冷延焼鈍板とした。得られた冷延焼鈍板から60mm×80mmの試験片を切り出し、表面を#600番手で研磨したのち、複合サイクル腐食試験による耐食性評価を行った。複合サイクル腐食試験は、JASO M 609-91に準拠し、塩水噴霧(5%NaCl、35℃、2h)→乾燥(60℃、相対湿度20~30%)→湿潤(50℃、2h、相対湿度≧95%)を1サイクルとする腐食試験サイクルを30サイクル行った。複合サイクル腐食試験では、発銹面積率20%以上を不合格、20%未満を合格と判定した。得られた結果を表1に合わせて示す。表1から、V/B比を15.0以上とすることにより、耐食性が改善されることがわかる。
表2に示す(0.009~0.012)%C、(0.82~0.89)%Si、(0.35~0.40)%Mn、(0.024~0.027)%P、(0.001~0.003)%S、(14.5~14.9)%Cr、(0.01~0.02)%Al、(0.009~0.012)%N、(0.15~0.20)%Ni、(0.40~0.43)%Nb、(0.011~0.017)%V、(0.0002~0.0010)%Bで、V/B比を変化させ、残部がFe及び不可避的不純物からなるステンレス鋼を50kg小型真空溶解炉にて溶製した。これらの鋼塊を1100℃に加熱後、熱間圧延を施して4.0mmの熱延板とした。次いで、上記熱延板を1020℃×60secの焼鈍を施した後、ショットブラストを行い、弗酸と硝酸の混合酸で酸洗し、冷間圧延により板厚0.7mmの冷延板とした。得られた冷延板に対し、980℃×40secの仕上焼鈍を施して、冷延焼鈍板とした。得られた冷延焼鈍板から60mm×80mmの試験片を切り出し、表面を#600番手で研磨したのち、複合サイクル腐食試験による耐食性評価を行った。複合サイクル腐食試験は、上記腐食試験サイクルを、30サイクル行った。複合サイクル腐食試験では、発銹面積率20%以上を不合格、20%未満を合格と判定した。得られた結果を表2に合わせて示す。表2から、V/B比を15.0以上とすることにより、耐食性が改善されることがわかる。
Cの含有量は、耐食性および成形性の観点から低いほど好ましい。しかし、Cの含有量を0.003%未満にするには精錬を長時間行う必要がある。所望の生産性を確保する観点から、Cの含有量の下限は0.003%である。一方、Cの含有量が0.013%を超えると、フェライト系ステンレス鋼板の成形性および耐食性の低下が顕著になる。よって、Cの含有量は0.003~0.013%の範囲とする。より好ましくは0.004~0.011%である。
Siは、鋼の脱酸剤として有用な元素である。この効果を得るためには、Siの含有量は0.01%以上である。しかし、Siの含有量が0.95%を超えると、熱間圧延工程において圧延荷重が増大するとともに、スケールが非常に生成しやすくなる。また、焼鈍工程においては鋼板表層でのSiが濃化したスケールの形成による酸洗性の低下も生じる。このため、Siの含有量が0.95%を超えると、表面欠陥が増加したり、製造コストが上昇したりするため好ましくない。よって、Siの含有量は0.01~0.95%の範囲とする。より好ましくは、0.05~0.50%である。特に後述するTiの含有量が0.25%以上の場合には、Siによる酸洗性の低下が顕著になるので、この場合Siの含有量の好ましい範囲は、0.05~0.20%である。
Mnは、鋼中に存在するSと結合して、MnSを形成し、耐食性を低下させる。よって、Mnの含有量は0.40%以下とする。一方、必要以上に、Mnの含有量を低下させようとすると、精錬コストが増大する。このため、Mnの含有量は0.01%以上が好ましい。なお、精錬コストを抑えつつ、特に高い耐食性を実現するためには、Mnの含有量の好ましい範囲は0.05~0.35%である。
Pは、鋼に不可避的に含まれる元素である。Pは耐食性および成形性に対して有害な元素であるため、Pの含有量は低いことが好ましい。特に、Pの含有量が0.040%を超えると固溶強化により鋼板の成形性が低下する。このためPの含有量は0.040%以下である。一方、Pの含有量を0.020%未満にするためには、時間を掛けて精錬を行う必要があり、Pの含有量を0.020%未満にすることは製造上好ましくない。よって、Pの含有量は0.020~0.040%の範囲とする。好ましくは、0.025~0.035%の範囲である。
SはMnと結合しMnSを形成する。MnSは熱間圧延等により展伸し、フェライト粒界等に析出物(介在物)として存在する。このような硫化物系析出物(介在物)は、鋼板の伸びを低下させ、特に鋼板の曲げ加工時において鋼板に亀裂を発生させる場合がある。このためSの含有量はできるだけ低減することが望ましく、許容できるSの含有量は0.010%までである。なお、好ましいSの含有量は0.005%以下である。
Alは、鋼の脱酸剤として有用な元素である。この効果を得るためには、Alの含有量を0.01%以上にする必要がある。しかし、Alの含有量が多くなり過ぎると、Al系介在物の増加により、表面疵を招く原因となる。以上よりAlの含有量の範囲は0.01~0.45%とする。また、Alの含有量の好ましい範囲は、0.01~0.10%である。さらに好ましい範囲は、0.02~0.04%である。
Crは耐食性向上に寄与する元素であり、ステンレス鋼板に必須元素として含まれる元素である。しかし、Crの含有量が14.5%未満では、十分な耐食性を持つ鋼板が得られない。一方、Crの含有量が21.5%を超えると、鋼板の靭性が低下することに加えて、鋼が硬質化しすぎて鋼板の伸びも顕著に低下する。よって、Crの含有量の範囲は14.5~21.5%とする。さらに、耐食性と製造性の観点から、Crの含有量の好ましい範囲は16.0~21.5%である。
Niは、隙間腐食を低減させる効果を有する。この効果を得るためには、Niの含有量を0.01%以上にすることが必要である。しかし、Niは高価な元素であることに加え、0.60%を超えるNiを含有しても、上記効果は飽和し、熱間加工性を低下させる。よって、Niの含有量の範囲は0.01~0.60%とする。また、Niの含有量の好ましい範囲は、0.10~0.40%である。
Nは、Vと結合して、窒化物や炭窒化物を形成し、最終的な製品板の結晶粒を微細化して、r値特性向上に寄与する。しかし、Nの含有量が0.005%未満では、V(C、N)の炭窒化物の微細析出による結晶粒の微細化効果が得られない。一方、Nの含有量が0.012%を超える場合、Cr窒化物量、あるいはCr炭窒化物量が増加して、鋼板が硬質化し伸びが低下する。よって、Nの含有量の範囲は0.005~0.012%とする。また、Nの含有量の好ましい範囲は、0.006~0.010%である。
VおよびBは、本発明において極めて重要な元素である。Vは、Nと結びついて、VNやV(C、N)といった窒化物や炭窒化物を形成し、熱延焼鈍板の結晶粒の粗大化を抑制する効果がある。また、Bはフェライト粒界に濃化し、粒界移動を遅れさせることにより、粒成長抑制を補助する効果がある。これらのVとBの複合効果により、熱延焼鈍板の結晶粒が微細化する。この結果、冷延焼鈍後の{111}再結晶方位粒の優先核生成サイトである粒界の面積が増加することにより、{111}方位が高集積化することで、r値が向上するとともにΔr値が低減するものと考えられる。
Ti、Nbはいずれも、固溶C、Nを化合物として固定することにより、鋼板の耐食性や成形性を向上させる効果を有している。このため、Ti、Nbのいずれかを単独で使用するか、Ti及びNbの両方を使用することが必要である。具体的には上記効果を得るために、Ti:0.20%以上を含有するか、Nb:0.40%以上を含有する必要がある。好ましくは、Ti:0.25%以上を含有するか、Nb:0.45%以上を含有する場合である。一方、Tiの含有量、Nbの含有量、TiとNbの合計量が多過ぎる場合には、表面品質の低下や再結晶温度の上昇による製造性の低下を招き好ましくない。このため、Ti量は0.40%以下、Nb量は0.60%以下、及びTi%+Nb%≦0.70とする(本発明においては、Ti量、Nb量、Ti%+Nb%の全てが上限値以下でなければならない)。好ましくは、Ti量は0.35%以下、Nb量は0.55%以下、及びTi%+Nb%≦0.65の場合である。
Cuは、耐食性を向上させる元素であり、具体的には、鋼板が水溶液中にある場合や弱酸性の水滴が鋼板に付着した場合に耐食性を向上させるのに特に有効な元素である。この効果は、Cuを0.01%以上含有させることにより得られ、Cuの含有量が多いほど高くなる。しかし、Cuの含有量が1.40%を超えると、熱間加工性が低下するとともに、熱間圧延時に赤スケールと呼ばれるCu起因の酸化物が熱延スラブ上に生成し、表面欠陥を生じるため好ましくない。さらには、Cuの含有量が1.40%を超えると、焼鈍後の脱スケールが困難となるため製造上好ましくない。そのため、Cuを含有する場合、その含有量の範囲は0.01~1.40%であることが好ましい。また、Cu含有量のより好ましい範囲は0.10~1.00%であり、最も好ましい範囲は0.30~0.50%である。
Moはステンレス鋼板の耐食性を顕著に向上させる元素である。この効果は、鋼板にMoを0.01%以上含有させることによって得られ、その効果はMoの含有量が多いほど向上する。しかし、Mo含有量が1.62%を超えると、熱間加工性が低下して熱間圧延時に表面欠陥が多発するようになる。また、Moは高価な元素であることから、Mo含有量の増加は製造コストを増大させる。そのため、Moを含有する場合は、その含有量の範囲を0.01~1.62%とすることが好ましい。より好ましい含有量の範囲は0.30~1.62%であり、最も好ましくは0.40~1.20%である。特に熱延板靭性が低下するTi含有鋼ではMoの添加によりさらに靭性が低下して、良好な熱延板焼鈍を得ることが困難になるので、Tiを0.15%以上含有している場合にはMoの含有量を0.30~1.40%にするのが好ましい。より好ましくは0.40~1.00%の範囲である。
ZrはCやNと結合して鋭敏化を抑制する効果がある。この効果はZrの含有量が0.01%以上で得られる。一方、Zrの含有量が0.20%を超えると鋼板の加工性が低下する。また、Zrは高価な元素であるため、Zr含有量の増加は製造コストを増大させる。そのため、Zrを含有する場合は、その含有量の範囲を0.01~0.20%とすることが好ましい。
REMは耐酸化性を向上させる効果がある。この効果は、REMを0.001%以上含有させることによって得られる。一方、0.100%を超える量のREMを含有させると熱間圧延性が低下して表面欠陥が多発するので好ましくない。そのため、含有する場合は、REMの含有量の範囲を0.001~0.100%とするのが好ましく、より好ましくは、0.001~0.050%である。
Wは、Moと同様に耐食性を向上させる効果がある。この効果はWの含有量が0.01%以上で得られる。一方、0.20%を超える量のWを含有させると強度が上昇し、圧延荷重増大等により製造性が低下する。そのため、Wの含有量の範囲は、0.01~0.20%とすることが好ましく、より好ましくは、0.01~0.10%である。
Coは、Moと同様に耐食性を向上させる効果がある。この効果はCoの含有量が0.01%以上で得られる。一方、0.20%を超える量のCoを含有させると成形性が低下する。そのため、Coの含有量の範囲は、0.01~0.20%とすることが好ましく、より好ましくは、0.01~0.10%である。
Mgはスラブの等軸晶率を向上させ、成形性や靭性の向上に有効な元素である。この効果は、Mgの含有量が0.0001%以上で得られる。一方、Mg含有量が0.0010%を超えるとMg系介在物が増加し、表面性状を悪化させる。そのため、Mgの含有量の範囲は、0.0001~0.0010%とすることが好ましく、より好ましくは0.0002~0.0004%である。
Caは、連続鋳造の際に発生しやすいTi系介在物の析出によるノズルの閉塞を防止するのに有効な成分である。その効果はCaの含有量が0.0003%以上で得られる。しかし、Ca含有量が0.0030%を超えた場合、CaSの生成により、耐食性が低下する。そのため、Caの好ましい含有量の範囲は、0.0003~0.0030%であり、より好ましくは0.0005~0.0020%であり、最も好ましくは、0.0005~0.0015%である。
表3に示す組成(残部はFe)の溶鋼を転炉および2次精錬(VOD)で溶製し、連続鋳造法によりスラブとした。これらスラブを1120℃に加熱した後、仕上温度が800℃となる熱間圧延を行い、板厚4.0mmの熱延板とした。これら熱延板に、940℃×60secの熱延板焼鈍を施した後、酸洗、冷間圧延を施し、冷延板とした。次いで、これらの冷延板に900℃×40secの仕上焼鈍を施した後、酸洗し、板厚0.7mmの冷延焼鈍酸洗板とした。得られた冷延焼鈍酸洗板について、成形加工性と耐食性評価を行った。
[評価]
以下に、成形加工性と耐食性の評価方法を示す。
冷延焼鈍酸洗板の各方向[圧延方向(L方向)、圧延直角方向(C方向)および圧延方向から45°方向(D方向)]からJIS13号B試験片を採取した。これら引張試験片を用いて引張試験(JIS Z 2201)を実施し、各方向の伸びを測定した。各方向の伸び値を用いて、次式より伸び(El)の平均値を求めた。Elが30.0%以上を合格とした。
El=(ElL+2×ElD+ElC)/4
ここで、ElL、ElD、ElCは、それぞれL方向、D方向、C方向の伸びを表す。
冷延焼鈍酸洗板の各方向[圧延方向(L方向)、圧延直角方向(C方向)および圧延方向から45°方向(D方向)]からJIS13号B試験片を採取した。これらの試験片に、15%の単軸引張予歪を与えた時の幅歪と板厚歪の比から、各方向のr値(ランクフォード値)を測定し、次式により平均r値、Δrを求めた。r値が1.50以上、Δrが0.30以下を合格とした。
r=(rL+2×rD+rC)/4
Δr=(rL-2×rD+rC)/2
ここで、rL、rD、rCは、それぞれL方向、D方向、C方向のr値を表す。
得られた冷延焼鈍板から60mm×80mmの試験片を切り出し、表面を#600番手で研磨し、耐食性評価用試験片を作製し、複合サイクル腐食試験による耐食性評価を行った。複合サイクル腐食試験は、上記腐食試験サイクルを、30サイクル行い、発銹面積率20%以上を不合格、20%未満を合格と判定した。
表4に示す組成の溶鋼を転炉および2次精錬(VOD)で溶製し、連続鋳造法によりスラブとした。これらスラブを1120℃に加熱した後、仕上温度が800℃となる熱間圧延を行い、板厚4.0mmの熱延板とした。これら熱延板に、1020℃×60secの熱延板焼鈍を施したのち、酸洗、冷間圧延を施し、冷延板とした。ついで、これらの冷延板に1000℃×40secの仕上焼鈍を施した後、酸洗し、板厚0.7mmの冷延焼鈍酸洗板とした。得られた冷延焼鈍酸洗板について、成形加工性と耐食性評価を行った。評価方法は下記の通りである。
Claims (4)
- 質量%で、C:0.003~0.013%、Si:0.01~0.95%、Mn:0.01~0.40%、P:0.020~0.040%、S:0.010%以下、Al:0.01~0.45%、Cr:14.5~21.5%、Ni:0.01~0.60%、N:0.005~0.012%を含有し、
V:0.010~0.040%、B:0.0001~0.0010%を、Vの含有量とBの含有量の比(V/B)≧15.0を満足する範囲で含有し、
更に、Ti:0.20%以上0.40%以下、Ti%+Nb%≦0.70を満足する範囲で、Tiを含有又はTi及びNbを含有する場合、およびNb:0.40%以上0.60%以下、Ti%+Nb%≦0.70を満足する範囲でNbを含有又はNb及びTiを含有する場合の少なくとも一方を満足し、残部がFeおよび不可避的不純物からなることを特徴とするフェライト系ステンレス鋼板。 - V/B≧30.0を満足して含有することを特徴とする請求項1に記載のフェライト系ステンレス鋼板。
- 質量%で、さらに、Cu:0.01~1.40%、Mo:0.01~1.62%の1種または2種を含有することを特徴とする請求項1または2に記載のフェライト系ステンレス鋼板。
- 質量%で、さらに、Zr:0.01~0.20%、REM:0.001~0.100%、W:0.01~0.20%、Co:0.01~0.20%、Mg:0.0001~0.0010%、Ca:0.0003~0.0030%のうちから選ばれる1種または2種以上を含有することを特徴とする請求項1~3のいずれか1項に記載のフェライト系ステンレス鋼板。
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WO2016092713A1 (ja) * | 2014-12-11 | 2016-06-16 | Jfeスチール株式会社 | ステンレス鋼およびその製造方法 |
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