Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
• • 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
  • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
• • 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
• • 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
• • 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
• • 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
  • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
• • 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 Cr-containing steel, and in particular, an exhaust pipe of a motor vehicle, a exhaust case of a motorcycle, a converter case, and a thermal electric power plant.
• High heat resistance thermal fatigue resistance, oxidation resistance
• suitable for exhaust system members used in high-temperature environments such as ducts (exhaust air duct) and base metal
• the present invention relates to ferritic stainless steel having excellent toughness.
• Exhaust manifolds, exhaust pipes, compressor cases, mufflers, and other exhaust system members used in the exhaust system environment of automobiles are subject to thermal fatigue, rawness and oxidation resistance (hereinafter referred to as “exhaust manifold”). Both specialties are collectively referred to as “heat resistance.”)
• heat resistance Both specialties are collectively referred to as “heat resistance.”
• Cr-containing such as Ty pe 429 (14 C r -0.9 S i -0.4 Nb series)
• the exhaust gas temperature rises to a temperature exceeding 900 ° C. It was.
• WO 2003/004714 pamphlet has 10-20 mass% Cr steel, Nb: 0.5 Oma ss% or less, Cu: 0.8-2 Oma ss%, V
• Ferritic stainless steel for automobile exhaust gas flow channel members with 0.03 to 0.2 Oma ss% added discloses 10 to 20 ma ss% Cr steel.
• T i 0.05 to 0.30 ma ss%
• Nb 0.1 to 0.60 ma ss%
• Cu 0.8 to 2.
• B 0.0005 to 0.02 ma ss%
• No. 7355 discloses ferritic stainless steel for automotive exhaust system parts in which Cu: 1 to 3 mass% is added to 15 to 25 nxas s s% Cr steel. All of these steels are characterized by improved thermal fatigue properties by adding Cu.
• the object of the present invention is to develop a technique for preventing the decrease in oxidation resistance due to the addition of Cu, thereby improving thermal fatigue characteristics and oxidation resistance without adding expensive elements such as Mo and W. It is to provide a ferritic stainless steel having excellent toughness equivalent to or better than that of Type 429.
• excellent oxidation resistance and thermal fatigue characteristics J as used in the present invention means that it has the same or better characteristics than SUS 444. Specifically, the oxidation resistance is 9
• Oxidation resistance at 50 ° C and thermal fatigue characteristics are 100 ° C-8 Repeated thermal fatigue characteristics between 50 ° C and SUS 444 are equivalent or better.
• the toughness equivalent to Ty pe 429 means that the brittle fracture surface ratio of a cold-rolled sheet with a thickness of 2 mm when it is subjected to a Charpy impact test at 140 ° C is equivalent to Ty pe 429.
• C 0.0 15 mass% or less
• Mn 0.5 mass% or less
• P 0.04 mass% or less
• Cr 16 to 20 mass% or less
• N 0.015 mass% or less
• N b 0.3 to 0.55 mass%
• T i 0.01 mass% or less
• Mo 0.1 mass% or less
• W 0.1 mass% or less
• Cu l. 0 to 2.5 mass%
• a 1 0.2 to 1.2 mass%, the balance being Fe and Ferritic stainless steel made of inevitable impurities.
• the fluorescent stainless steel of the present invention further includes B: 0.003 mass% or less, REM: 0.08 mass% or less, Zr: 0.5 mass% or less, V: It is characterized by containing one or more selected from 0.5 mass% or less, Co: 0.5 mass% or less, and Ni: 0.5 mass% or less.
• heat resistance thermal fatigue characteristics, oxidation resistance
• Ty pe 429 presentative components are steels in Table 1
• Ferritic stainless steel with toughness equivalent to or better than No. 24 can be obtained at low cost. Therefore, the steel of the present invention is suitable for use in automobile exhaust system members.
• Fig. 1 is a diagram illustrating a thermal fatigue test piece.
• Fig. 2 is a diagram for explaining temperature and restraining conditions in a thermal fatigue test.
• Figure 3 A graph showing the effect of Cu content on thermal fatigue properties.
• Figure 4 A graph showing the effect of A 1 content on oxidation resistance (weight gain by oxidation).
• Figure 5 A graph showing the effect of A 1 content on oxidation resistance (spoiling amounts of scale).
• Fig. 6 Graph showing the effect of Si content on oxidation resistance (scale peeling)
• Fig. 7 Graph showing the effect of Mn content on toughness (brittle fracture surface ratio) It is.
• Fig. 8 is a graph showing the effect of A 1 content on toughness (brittle fracture surface ratio).
• Figure 9 Graph showing the effect of Ti content on toughness (brittle fracture surface ratio).
• the inventors have prevented the deterioration of oxidation resistance due to Cu addition in the prior art, and without adding expensive elements such as Mo and W, they have excellent thermal fatigue characteristics and oxidation resistance, and are also tough.
• Nb is changed from 0.3 to 0. & 3 3%, ⁇ 11 in the range of 1.0 to 2.5 mass%, high high-temperature strength can be obtained in a wide temperature range, thermal fatigue characteristics can be improved, and addition of Cu
• the decrease in oxidation resistance can be prevented by adding more than 0.2 mass% of A 1. Therefore, by controlling Nb, Cu and A 1 within the proper range, Mo and W can be added.
• this sheet bar was forged into a par with a cross section of 35 mm X 35 mm, annealed at a temperature of 1030 ° C, machined, and the thermal fatigue test specimen with the dimensions shown in Fig. 1 (thermal fatigue test specimen) ) was produced. Then, as shown in Fig. 2, a thermal treatment was performed by repeatedly applying a heat treatment in which a restraint ratio was 0.35 at a temperature of 100 ° C-850 at 100 ° C-850, and the thermal fatigue life was measured. The thermal fatigue life is
• Figure 3 shows the results of the thermal fatigue test. From this figure, by adding more than 1.0 mass% of ⁇ 11, thermal fatigue life equal to or better than that of SUS 444 (about 1 100 cycles) can be obtained, thus improving thermal fatigue characteristics. It can be seen that it is effective to add Cu by lma ss% or more.
• a 3 OmmX 20 mm test piece was cut out from the cold-rolled steel sheet obtained as described above, a 4 ⁇ hole was drilled at the top of the test piece, and the surface and end face were polished with # 320 emery paper, degreased. Later, it was subjected to the following test.
• the above test piece is kept in a furnace at 950 ° C in an air atmosphere for 300 hours and heated. The difference in the mass of the test piece before and after the test was measured, and the increase in oxidation per unit area (gZm 2 ) was determined.
• Figure 4 shows the measurement results of the increase in oxidation.
• Fig. 5 shows the measurement results of the amount of scale peeling. From these figures, by adding more than 0.2 mass% of A 1, oxidation resistance equal to or better than SUS 444 (oxidation increase: 27 gZm 2 or less, scale peeling: less than 4 g / in 2 ) Is obtained.
• C 0.006 ⁇ 0.007ma ss%
• N 0.00 6 ⁇ 0.00 00 7m ass%
• S i 0.3ma ss%
• C r 1 7ma ss%
• Nb 0.
• a 50 kg steel ingot was prepared by laboratory smelting steel with various contents of Mn, A 1 and Ti based on the composition of 45 mass% and Cu: 1.5 mass%.
• the steel ingot was hot-rolled, hot-rolled sheet annealed, cold-rolled, and finish-annealed to obtain a cold-rolled annealed sheet with a thickness of 2 mm.
• a sub-size Charpy impact test specimen was taken from this cold-rolled annealed plate and subjected to a Charpy impact test at a temperature of 40 ° C. The brittle fracture surface ratio was measured and the toughness was evaluated.
• Figure 7 shows the effect of Mn content on toughness at A 1: 0.25 mass% and T i: 0.006 mass%.
• Figure 8 shows the effect of Mn: 0.1 mass% and Ti: 0. The effect of A 1 content on toughness at 0 05 ma ss%.
• Figure 9 shows the toughness of Ti content at A 1: 25 mass% and Mn: 0.1 mass%. It shows the effect on From these figures, to obtain toughness equivalent to or better than Ty pe 42 9, Mn: 0 ⁇ 3 mass% or less, A 1: 1 ⁇ 2 ma ss ° / 0 or less, T i: 0.0 lma ss% It turns out that it must be:
• the present invention has been completed by further studying the above findings.
• C is an element effective for increasing the strength of steel, but if it exceeds 0.015 mass%, the toughness and formability deteriorate significantly. Therefore, in the present invention, C is set to not more than 0.015 ma s s%. From the viewpoint of ensuring moldability, the lower the C, the better.
• the lower limit is preferably 0.008 ma s s%.
• C is preferably 0.001 lma s s% or more. More preferably, it is in the range of 0., 002 to 0.008 ma s s%.
• Si is added as a deoxidizer. It is preferable to add more than 0.05 mass%. In addition, Si has an effect of improving the oxidation resistance which is the main subject of the present invention, but cannot be as effective as A 1. On the other hand, as can be seen from FIG. 6, excessive addition of Si exceeding 0.5 mass% reduces the scale peel resistance and does not provide oxidation resistance equal to or better than SUS444. Therefore, the upper limit of S i is 0.5 ma s s%.
• Mn 0.5 ma s s. /. Less than
• Mn is an element that increases the strength of steel and also has a function as a deoxidizer. It is preferable to add 0.05 mass% or more. However, excessive addition tends to generate ⁇ y phase at high temperatures, which reduces heat resistance. Also, as can be seen from Figure 7, 0.5ina s If added in excess of s%, a toughness equal to or higher than that of Type 4 29 cannot be obtained, and the object of the present invention cannot be achieved. Therefore, in the present invention, Mn is set to 0.5 mass% or less.
• P is a harmful element that lowers toughness and should be reduced as much as possible. Therefore, in the present invention, P is set to 0.04 mass% or less. Preferably, it is 0.03 mass% or less.
• S is a harmful element that lowers the elongation value and adversely affects the formability and lowers the corrosion resistance, which is a basic characteristic of stainless steel, so it is desirable to reduce it as much as possible. Therefore, in the present invention, S is set to 0.006 mass s s% or less. Preferably, it is 0.003 s s% or less.
• Cr is an important element effective for improving the corrosion resistance and oxidation resistance characteristic of stainless steel, but if it is less than 16 mass%, sufficient oxidation resistance cannot be obtained.
• Cr is an element that solidifies and strengthens steel at room temperature and hardens' low ductility.In particular, when it exceeds 20% by mass, the above-mentioned adverse effects become significant, and it is equivalent to or higher than Ty pe 429. The toughness cannot be obtained. Therefore: In the present invention, Cr is in the range of 16-20 mass%. Preferably, it is in the range of 16 to 19 mass%.
• N is an element that lowers the toughness and formability of steel, and when the content exceeds 0.015 mass%, the above reduction becomes significant. Therefore, N is set to 0.01 5 ma s s% or less. Note that N is further reduced when higher toughness is required, and is preferably less than 0.010 mass%.
• Nb forms and fixes carbon nitride with C and N, has the effect of improving corrosion resistance and formability, and intergranular corrosion resistance of welds, and also increases the high temperature strength and improves thermal fatigue properties. It is an element that has fruit. Such an effect is recognized with addition of 0.3 mass% or more. 4707. On the other hand, if it exceeds 0.55 mass%, the Laves phase tends to precipitate and the brittleness decreases. Therefore, Nb is in the range of 0.3 to 0.55 mass%. Preferably, it is in the range of 0.4 to 0.5 ma ss%.
• T i is an element that easily binds to N and forms coarse T i N compared to Nb, and this coarse T i N acts as a notch and significantly reduces toughness. In particular, as shown in FIG. 9, this adverse effect becomes significant when the Ti content exceeds 0.01 mass%. Therefore, in the present invention, it is limited to T 3 ⁇ 40.0.1% or less.
• Mo is an expensive element and is not actively added for the purpose of the present invention. However, it may be mixed in less than 0.1 ma s s% from the raw material scrap. Therefore, Mo is set to 0.1 m a s s% or less.
• W is an expensive element like Mo, and is not actively added for the purpose of the present invention. However, it may be mixed in less than 0.1 ma s s% from raw materials such as scrap. Therefore, W is less than 0. lma s s%.
• Cu is an extremely effective element for improving thermal fatigue properties. As shown in Fig. 3, it is necessary to add Cu in an amount of 1.0 mass% or more in order to obtain thermal fatigue characteristics equivalent to or better than SUS444. However, if the addition exceeds 2.5 mass%, ⁇ -Cu precipitates during cooling after heat treatment, hardens the steel, and tends to cause embrittlement during hot working. More importantly, the addition of Cu improves the thermal fatigue resistance, but decreases the oxidation resistance of the steel itself, and overall, the heat resistance decreases. The cause of this is not sufficiently clear, but Cu is concentrated in the decreasing Cr layer immediately below the scale, which suppresses the re-diffusion of Cr, an element that improves the inherent oxidation resistance of stainless steel. It is thought to do. Therefore, Cu is in the range of 1.0 to 2.5 mass%. More preferably, it is in the range of 1.1 to 1.8 ma ss%. 4707
• Al is an indispensable element for improving the oxidation resistance of Cu-added steel.
• SUS 444 which is the object of the present invention
• addition of 0.2 mass% or more is necessary.
• the steel becomes hard and no toughness equivalent to Ty pe 42 9 can be obtained, so the upper limit is 1.2 mass% To do.
• it is in the range of 0.3 to 1. Oma s s%.
• the ferritic stainless steel of the present invention further contains one or more selected from B, REM, Zr, V, Co and Ni in the following range. Can be added.
• B is an element effective for improving workability, particularly secondary workability. This remarkable effect can be obtained by addition of 0.005 5 mass% or more. However, if it exceeds 0.03 mass%, BN is formed and workability is lowered. Therefore, when adding B, it should be 0.003 mass s s% or less. More preferably, it is in the range of 0.0 0 0 5 to 0.002 ma s s%.
• REM rare earth element
• Zr are both elements that improve oxidation resistance, and can be added as necessary in the present invention.
• the addition of more than 0.08 mass% of REM causes the steel to become brittle, and the addition of more than 0.5 mass% of Z ⁇ causes the Zr intermetallic compound to precipitate, making the steel brittle. Therefore, when adding REM, it should be less than 0.08 mass%, and when adding Zr, it should be less than 0.5 mass%.
• V 0.5ma s s% or less
• V is an element effective for improving workability and oxidation resistance.
• V is preferably added in an amount of 0.15 mass% or more. Force and 0.5 mas Excessive addition exceeding s% precipitates coarse V (C, N) and degrades the surface properties. Therefore, when V is added, it is preferable to add 0.5 mass% or less, and it is preferable to add in the range of 0.15 to 0.4 mass%.
• Co is an element effective in improving toughness, and it is preferable to add 0.02 mass s s% or more.
• Co is an expensive element, and the above effect is saturated even when added in excess of 0.5 mass%. Therefore, when adding Co, it is preferable to be 0.5 mass% or less. More preferably, it is in the range of 0.02 to 0.2 ma s s%.
• N i 0.5ma s s% or less
• Ni is an element that improves toughness. In order to obtain the effect, 0.05 mass s s% or more is preferable. However, Ni is expensive and is a strong ⁇ -phase-forming element, so it generates a ⁇ -phase at high temperatures and reduces oxidation resistance. Therefore, when Ni is added, the content is preferably 0.5 mass% or less. More preferably, it is in the range of 0.05 to 0.4 ma s s%.
• the method for producing stainless steel of the present invention can be suitably used as long as it is an ordinary method for producing fluorescent stainless steel, and is not particularly limited.
• steel is produced in a known melting furnace such as a converter or an electric furnace, or further subjected to secondary refinement such as ladle or vacuum refinement to obtain steel having the above-described component composition of the present invention,
• the molten steel is made into a steel slab (slab) by continuous forging or ingot lump rolling, hot-rolled to hot-rolled sheet, and subjected to hot-rolled sheet annealing as necessary. It is preferable to produce a cold-rolled annealed plate through steps such as pickling, cold rolling, finish annealing, and pickling.
• the cold rolling may be performed once or twice or more with intermediate annealing, and the steps of cold rolling, finish annealing, and pickling may be performed repeatedly. Further, depending on the case, the hot-rolled sheet annealing may be omitted, and when the gloss of the steel sheet surface is required, a skin pass may be applied after cold rolling or after finishing annealing.
• the slab heating temperature before hot rolling is 1000-1250 ° C
• the hot-rolled sheet annealing temperature is 900-1100 ° C
• the final annealing temperature is 900-1 1 2 4707
• a range of 0 ° C. is preferred.
• the ferritic stainless steel of the present invention obtained as described above is then subjected to processing such as cutting, bending, and pressing according to the respective use, and the exhaust pipe of an automobile car pie. It is considered as various exhaust system members used in high temperature environments such as a compressor case and an exhaust duct of a thermal power plant.
• the stainless steel of the present invention used for the above-mentioned member is not limited to a cold-rolled annealed plate, and may be used as a hot-rolled plate or a hot-rolled plate annealed, and further subjected to descaling as necessary. It may be used.
• the welding method for assembling the above-mentioned members is not particularly limited, and normal arc welding such as MIG (Metal Inert Gas), MAG (Metal Active Gas), TIG (Tungsten Inert Gas), or spot welding.
• Methods such as electric resistance welding such as welding and seam welding, high-frequency resistance welding used in electrical welding, high-frequency induction welding, and laser welding can be used.
• the mass of the sample after the test was measured, the difference from the pre-test mass measured in advance was determined, and the scale peeling amount (g / m 2 ) was determined. Each test was conducted twice, and the oxidation resistance was evaluated using the average value.
• Example 1 The remaining steel ingot of 50 kg copper ingot divided into two in Example 1 was heated to 1 1 70 ° C. and hot-rolled to obtain a sheet par of thickness: 3 OmmX width: 150 mm. The sheet par was then forged into a 35 mm par, annealed at a temperature of 1 0303 ⁇ 4, machined, and processed into a thermal fatigue test piece with the dimensions shown in Fig. 1 for the following thermal fatigue test. Provided. As reference examples, as in Example 1, SUS 444, Type 429, and WO 2003/004714 pamphlet, Japanese Patent Application Laid-Open No. 2006-1-17985, and Japanese Patent Application Laid-Open No. 2000-297355. Similarly, a sample was prepared and subjected to a thermal fatigue test. ⁇ Thermal fatigue test> ⁇
• the thermal fatigue life was measured by raising and lowering the temperature between 100 ° C and 850 ° C with a restraint ratio of 0.35. At this time, the heating rate and the cooling rate are 10 ° O sec and the holding time at 100 ° C is 2 mi. n The holding time at 85 ° C. was 5 min. The thermal fatigue life is calculated by dividing the load detected at 100 ° C by the cross-sectional area of the soaking parallel part of the specimen and calculating the stress continuously. Therefore, the minimum number of cycles when the stress began to decrease was determined.
• Table 2 summarizes the results of the atmospheric continuous oxidation test, the atmospheric repeated oxidation test, and the Charpy impact test of Example 1 and the thermal fatigue resistance test of Example 2.
• all of the steels of the inventive examples suitable for the present invention have oxidation resistance and thermal fatigue characteristics equal to or better than SUS 4 4 4, and It has toughness equal to or better than 29 and meets the goals of the present invention.
• comparative steels outside the scope of the present invention or prior art reference steels are not excellent in both oxidation resistance and heat fatigue resistance and toughness of the base metal. The target characteristics of the invention are not obtained. Industrial applicability
• the steel of the present invention is not only suitable for exhaust system members such as automobiles, but is also suitable as a solid oxide type fuel cell member for an exhaust system member of a thermal power generation system that requires similar characteristics. Can be used.
• Reference example 1 Invention steel No.3 of WO2003 / 004714
• Reference example 2 Invention steel No.7 of Kai 2006-117985
• Reference example 3 Invention steel of Kai 2000-297355 o.5

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