EP3214198B1 - Ferrite-based stainless steel with high resistance to corrosiveness caused by exhaust gas and condensation and high brazing properties and method for manufacturing same - Google Patents

Ferrite-based stainless steel with high resistance to corrosiveness caused by exhaust gas and condensation and high brazing properties and method for manufacturing same Download PDF

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EP3214198B1
EP3214198B1 EP15855321.4A EP15855321A EP3214198B1 EP 3214198 B1 EP3214198 B1 EP 3214198B1 EP 15855321 A EP15855321 A EP 15855321A EP 3214198 B1 EP3214198 B1 EP 3214198B1
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amount
exhaust gas
stainless steel
corrosion resistance
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German (de)
English (en)
French (fr)
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EP3214198A1 (en
EP3214198A4 (en
Inventor
Masatoshi Abe
Junichi Hamada
Nobuhiko Hiraide
Norihiro Kanno
Shigeo Fukumoto
Shigeru Kaneko
Atsutaka HAYASHI
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Nippon Steel Stainless Steel Corp
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Nippon Steel Stainless Steel Corp
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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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    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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Definitions

  • the present invention relates to a ferrite-based stainless steel (ferritic stainless steel sheet) that is used in exhaust gas-condensate environments (environments of exhaust gas condensate water) and a method for manufacturing the same.
  • exhaust gas-condensate environments environments of exhaust gas condensate water
  • members that are exposed to exhaust gas-condensate environments include automobile mufflers, exhaust heat recovery devices, and exhaust gas recirculation apparatuses such as exhaust gas recirculation (EGR) coolers.
  • EGR exhaust gas recirculation
  • exhaust heat recovery device that recovers exhaust heat
  • exhaust gas heat is transferred to cooling water by means of a heat exchange, and heat energy is recovered and reused; and as a result, the temperature of the cooling water is increased.
  • performance for heating the inside of vehicles is improved, and gas mileage performance is improved by shortening the time required for warming up engines.
  • the exhaust heat recovery devices are also referred to as exhaust heat recirculation systems.
  • exhaust gas recirculation apparatuses include EGR coolers.
  • EGR cooler exhaust gas from engines is cooled using engine cooling water or air, and then the cooled exhaust gas is returned to the intake side and is re-combusted. Thereby, the combustion temperature is lowered, and the amount of NO x which is harmful gas is decreased.
  • a ferritic stainless steel containing 17% or more of Cr such as SUS430LX, SUS436J1L, or SUS436L has been used.
  • corrosion resistance that is higher than or equal to that of the above-described ferritic stainless steel is required.
  • EGR coolers are, generally, assembled by brazing, and thus parts being used need to have high brazing properties (brazeability).
  • the wettability of the surfaces is important. Ti is more easily oxidized than Fe and Cr and Ti forms an oxide film with poor wettability on the surface. Therefore, the amount of Ti is desirably set to be low.
  • Al forms an oxide film with poor wettability on the surface.
  • the amount of Al as well as the amount of Ti is low.
  • the surface roughness of a steel sheet also has a great influence on wettability, it is also extremely important to control surface properties by controlling manufacturing conditions.
  • a brazing thermal treatment when the temperature of a brazing thermal treatment is high, the temperature reaches approximately 1,200°C, and, in this high-temperature environment, crystal grains in a stainless steel grow and coarsen. Since the coarsening of crystal grains has an influence on mechanical characteristics such as thermal fatigue and the like, a stainless steel on which a brazing thermal treatment is carried out needs to have characteristics in which crystal grains do not easily coarsen even at high temperatures.
  • a steel that is used in the EGR coolers needs to have high corrosion resistance and favorable brazeability.
  • Patent Document 1 discloses an inexpensive ferritic stainless steel material which is used as muffler-constituting members or water-wanning device members that form welded portions and has high corrosion resistance.
  • This ferritic stainless steel material contains C: 0.025% or less, Si: 2% or less, Mn: 1% or less, P: 0.045% or less, S: 0.01% or less, Cr: 16% to 25%, Al: less than 0.04%, and N: 0.025% or less, and further contains one or more element selected from Ni: 1% or less, Cu: 1% or less, Mo: less than 1%, Nb: 0.5% or less, Ti: 0.4% or less, and V: 0.5% or less, with a remainder of Fe and inevitable impurities.
  • the ferritic stainless steel material has an oxide film in which the composition of an outermost layer contains a total amount of Si and Cr of 15 atom% to 40 atom% and 5 atom% of Fe in terms of the atomic ratio including oxygen on the surface, and the composition of the outermost layer is measured by an X-ray photoelectron spectrometry (XPS).
  • XPS X-ray photoelectron spectrometry
  • Patent Document 2 discloses a ferritic stainless steel with high brazeability in the case where the ferritic stainless steel is brazed in an environment of a high temperature and a low oxygen partial pressure as is the case with Ni brazing and Cu brazing.
  • This ferritic stainless steel contains C: 0.03% or less, N: 0.05% or less, C+N: 0.015% or more, Si: 0.02% to 1.5%, Mn: 0.02% to 2%, Cr: 10% to 22%, Nb: 0.03% to 1%, and Al: 0.5% or less, with a remainder of Fe and inevitable impurities.
  • the ferritic stainless steel contains an amount of Ti that satisfies Expression: Ti-3N ⁇ 0.03 and Expression: 10(Ti-3N)+Al ⁇ 0.5 or further contains, as a substitute for a part of Fe, one or more of Mo: 3% or less, Ni: 3% or less, Cu: 3% or less, V: 3% or less, W: 5% or less, Ca: 0.002% or less, Mg: 0.002% or less, and B: 0.005% or less.
  • Patent Document 3 discloses a ferritic stainless steel for a automobile exhaust system member having favorable resistance to initial rusting at a low cost without impairing the intrinsic functions of automobile exhaust system members such as high-temperature strength, resistance against scale spallation, formabiliy, corrosion resistance against exhaust gas condensate water, and corrosion resistance against salt damage environments.
  • This ferritic stainless steel contains, by mass%, C: ⁇ 0.0100%, Si: 0,05% to 0.80%, Mn: ⁇ 0.8%, P: ⁇ 0.050%, S: ⁇ 0.0030%, Cr: 11.5% to 13.5%, Ti: 0.05% to 0.50%, Al: ⁇ 0.100%, and N: ⁇ 0.02% with a remainder of Fe and inevitable impurities.
  • the number of inclusions containing Ca per square millimeter of an arbitrary cross-section is less than 10, and furthermore, preferably, the proportion of the number of Mn-based sulfides to the total number of Ti-based sulfides and the Mn-based sulfides is 50% or less.
  • Patent Document 4 discloses a ferritic stainless steel having excellent localized corrosion resistance.
  • This ferritic stainless steel contains, by mass%, C: 0.030%) or less, N: 0.030% or less, Si: 0.30% or less, Mn: 0.30% or less, P: 0.040% or less, S: 0.020% or less, Cr: 16% to 26%, Al: 0.015% to 0.5%, Ti: 0.05% to 0.50%, Nb: 0.05% to 0.50%, and Mo: 0.5% to 3.0%, with a remainder of Fe and inevitable impurities.
  • the ratio of the amount of Al to the amount of Si is represented by Al/Si, the following expression (1) is satisfied.
  • Patent Document 5 discloses a ferritic stainless steel with high corrosion resistance.
  • This ferritic stainless steel contains, by mass%, C: 0.030% or less, N: 0.030% or less, Si: 0.01% to 0.50%, Mn: 1.5% or less, P: 0.04% or less, S: 0.01% or less, Cr: 12% to 25%, Nb: 0.01% to 1.0%, V: 0.010% to 0.50%, Ti: 0.60% or less, and Al: 0.80% or less, with a remainder of Fe and inevitable impurities.
  • polishing marks with an arithmetic average roughness value Ra of the surface in a range of 0.35 ⁇ m to 5.0 ⁇ m are provided, and the color difference L ⁇ value of the surface is 70 or more. 0.35 ⁇ Nb + 5 V ⁇ 2.0
  • Patent Documents 1 to 5 are not capable of having both of excellent corrosion resistance against exhaust gas condensate water and excellent brazeability.
  • JP 2014-145097 A discloses ferritic stainless steel sheets for an automotive exhaust system member.
  • the present invention aims to provide a ferrite-based stainless steel (ferritic stainless steel sheet) with high resistance to corrosiveness caused by exhaust gas and condensation (corrosion resistance against exhaust gas condensate water) and high brazing properties (brazeability) in environments in which the ferritic stainless steel is used for automobile mufflers, exhaust heat recovery devices, EGR coolers, or the like, and a method for manufacturing the same.
  • the present invention it is possible to provide a ferritic stainless steel with high corrosion resistance against exhaust gas condensate water and high brazeability in the case where the ferritic stainless steel is used in automobile parts exposed to exhaust gas-condensate environments (environments of exhaust gas condensate water) such as automobile mufflers, exhaust heat recovery devices, EGR coolers, or the like.
  • FIG. 1 is a view showing a relationship between the amounts of Si, Al, and Ti in steel sheets and the results of the condensate water corrosion test.
  • the present inventors produced steels in which the amount of Ai or the amount of Ti was decreased to a variety of concentrations under a variety of cold rolling conditions or a variety of annealing conditions of cold-rolled sheets. Then, corrosion resistance, brazeability, surface roughness, and an amount of change in crystal grain size before and after a brazing thermal treatment were investigated. As a result, it was found that the brazeability is improved as the concentration of Al or the concentration of Ti in a steel is decreased. However, regarding improvement of corrosion resistance against exhaust gas condensate water, no effects were developed in a method in which the concentration of Al or the concentration of Ti in a steel was simply decreased.
  • the maximum corrosion pit depth of 100 ⁇ m was used as a boundary value, and 100 ⁇ m was the maximum corrosion pit depth of the sample in which the notable growth of corrosion pits was confirmed under the test conditions used in examples described below.
  • a steel in which the maximum corrosion pit depth was 100 ⁇ m or more was evaluated as C (bad) and plotted with a reference sign "X" in FIG. 1 .
  • a steel in which the maximum corrosion pit depth was less than 100 ⁇ m was evaluated as B (good) and plotted with a reference sign "O" in FIG. 1 .
  • the Ti-based oxide is a hard inclusion, the Ti-based oxide does not deform together with the base material during cold rolling, and voids are likely to be formed in the interfaces between the inclusions and the base material.
  • the formed voids are considered to serve as starting points of pitting corrosion and degrade the corrosion resistance against condensate water of the steel.
  • Al 2 O 3 -MgO is also a hard inclusion, but it is considered that no voids are formed in the interfaces between the inclusions and the base material due to the deformation of CaO-Al 2 O 3 in the rolling direction which is present in the vicinity of Al 2 O 3 -MgO, and the corrosion resistance against condensate water does not deteriorate.
  • Si increases the activity of Ti; and thereby, Si assists the generation of the Ti-based oxide. Therefore, it is desirable to decrease the amount of Si in, particularly, low-Al materials (materials with a small amount of Al).
  • Al 2 O 3 -MgO inclusions which do not serve as starting points of corrosion are preferentially generated.
  • Al, Ti, and Si are effective elements for deoxidation, in the case where the amounts of these elements are decreased, there is a concern of an increase in the concentration of O in the steel. In this case. Mg is added to perform deoxidation; and thereby, the formation of oxides in the steel is inhibited, and furthermore, it is possible to prevent the deterioration of corrosion resistance against condensate water.
  • Table 1 shows the relationships between the cold rolling conditions in the final pass and the arithmetic average roughness values in the respective directions and the brazeability.
  • Steel Nos. in Table 1 are the same as Steel Nos. in Tables 3A to 3D shown below.
  • Brazeability was evaluated as described below. 0.2 g of Ni brazing filler metal was placed on the surface of a steel sheet produced by a method described below and was heated at 1,200°C for ten minutes in a vacuum atmosphere of 5 ⁇ 10 -3 torr. Next, the test specimen was cooled to normal temperature, and the area of the brazing filler metal (brazing filler metal area) in the heated test specimen was measured.
  • brazing filler metal when the average value of roughness on a sheet surface (in-plane roughness) is decreased and the difference in roughness on the sheet surface (in-plane roughness) is decreased, the two-dimensional spreading of brazing filler metal becomes easy (the brazing filler metal can easily spread in two-dimensional directions).
  • (Ra L +Ra C +2Ra V )/4 is an index indicating the average value of arithmetic average roughness values in three directions
  • is an index indicating the difference between arithmetic average roughness values in three directions. Brazeability is improved by setting the average value of arithmetic average roughness values in three directions to be 0.50 or less and setting the difference between the arithmetic average roughness values in three directions to be 0.10 or less.
  • the final pass is carried out using a roll with a roll roughness of #60 or more, the rolling reduction in the final pass is set to 15.0% or less, and the cold rolling speed in the final pass is set to 800 m/min or less.
  • preferred surface properties defined in the present embodiment are realized.
  • a flat surface is formed by transferring cold rolling roll marks while eliminating defects (shot blast flaws, intergranular corrosion grooves, pickling pits, and the like) on the surface of a base material.
  • the average value of arithmetic average roughness values in three directions and the difference between arithmetic average roughness values in three directions are smaller than predetermined values.
  • the surface of a roll being used in the final pass is rough, the grinding marks of the roll are transferred, and the surface of a stainless steel also becomes rough, and thus, in the final pass, a roll with a roughness of #60 or more is used.
  • the roll roughness is more desirably #80 or more. In the case where the roll roughness is more than #1,000, further improvement of the effect cannot be expected, and thus the roll roughness is desirably set to #1,000 or less.
  • the rolling reduction in the final pass is desirably set to 15.0% or less.
  • the rolling reduction in the final pass is more desirably 14.5% or less, and, when productivity or steel sheet shapes are taken into account, the rolling reduction is desirably 10.0% or more.
  • the rolling reduction in the final pass is more desirably 12.0% or more.
  • the rolling speed (cold rolling speed) in the final pass in the present embodiment is desirably set to 800 m/min or less.
  • the rolling oil In the inlet of the roll caliber tool, the rolling oil remains in surface recesses that remain in the rolled material, the oil is discharged in the roll caliber tool, and thus roll marks are transferred to the steel sheet.
  • the rolling speed is fast, sufficient time is not obtained for discharging the oil, thus, recesses are insufficiently eliminated, and it becomes difficult to decrease the roughness, particularly, at recess portions.
  • the cold rolling speed in the final pass is desirably set to 800 m/min or less.
  • the cold rolling speed in the final pass is more desirably 600 m/min or less and still more desirably 500 m/min or less.
  • the cold rolling speed in the final pass is desirably 150 m/min or more.
  • the rolling oil may be paraffinum liquidum or water-soluble oil.
  • Table 2 shows the annealing conditions of the cold-rolled sheets and grain size numbers (GSN) before and after a brazing thermal treatment.
  • Steel Nos. in Table 2 are the same as Steel Nos. in Tables 3A to 3D shown below.
  • the grain size number was evaluated as described below. A steel sheet produced using a method described below was cut so that a surface parallel to the rolling direction could be observed and was implanted in a resin. The grain size number was measured using an optical microscope and a cutting method.
  • the amount of change in grain size number before and after the brazing thermal treatment is desirably decreased to 5.0 or less.
  • the amount of change in grain size number before and after the brazing thermal treatment is more desirably 4.0 or less. Since the amount of change in grain size number before and after the brazing thermal treatment is preferably low, it is not necessary to set the lower limit value. However, since it is difficult to set the amount of change in grain size number to zero, the lower limit value is desirably set to more than zero.
  • the annealing step preferably includes a step of maintaining the steel sheet at a temperature of 650°C to 950°C for 5.0 s or longer and a step of maintaining the steel sheet at a temperature of 950°C to 1,050°C for 80.0 s or shorter. It was found that, in such a case, it becomes possible to sufficiently precipitate the fine Laves phase which is effective for pinning crystal grains.
  • the annealing step more desirably includes a step of maintaining the steel sheet at a temperature of 650°C to 950°C for 8.0 s (seconds) or longer and a step of maintaining the steel sheet at a temperature of 950°C to 1,050°C for 60.0 s (seconds) or shorter.
  • the holding time during which the steel sheet is maintained at a temperature of 650°C to 950°C is preferably 50 s or shorter.
  • the holding time during which the steel sheet is maintained at a temperature of 950°C to 1,050°C is preferably 10 s or longer.
  • the amount of C is set to 0.030%.
  • an excessively low amount of C assists the coarsening of crystal grains during brazing and increases refinement costs, and thus the amount of C is set to 0.001% or more.
  • the amount of C is more desirably 0.004% to 0.020%.
  • Si is a useful deoxidation element, but Si increases the activity of Ti; and thereby, Si assists the generation of a hard Ti-based oxide. Therefore, the amount of Si is set to 0.01% to 1.00%. The amount of Si is more desirably 0.10% to 0.60%.
  • Mn is a useful deoxidation element, but in the case where an excess amount of Mn is added, Mn deteriorates corrosion resistance, and thus the amount of Mn is set to 0.01% to 2.00%.
  • the amount of Mn is more desirably 0.10% to 1.00%.
  • P is an element that deteriorates workability and weldability, and thus it is necessary to limit the amount of P. Therefore, the amount of P is set to 0.050% or less. The amount of P is more desirably set to 0.030% or less.
  • S is an element that deteriorates corrosion resistance, and thus it is necessary to limit the amount of S. Therefore, the amount of S is set to 0.0100% or less. The amount of S is more desirably set to 0.0050% or less.
  • Cr examples of possible corrosive environments include atmospheric environments, cooling water environments, exhaust gas-condensate environments, and the like. In order to ensure corrosion resistance in the above-described environments, at least 11.0% or more of Cr is required. As the amount of Cr is increased, the corrosion resistance is improved, but the workability and manufacturability are degraded, and thus the amount of Cr is set to 30.0% or less. The amount of Cr is more desirably 15.0% to 23.0%.
  • Mo In order to improve corrosion resistance against condensate water, 0.01% or more of Mo is required. However, in the case where an excess amount of Mo is added, workability is degraded and costs are increased due to the expensive price of Mo, and thus the amount of Mo is set to 3.00% or less. The amount of Mo is more desirably 0.10% to 2.50%.
  • Ti forms an oxide film with poor wettability on the surface and degrades brazeability. Therefore, the amount of Ti is set to 0.001% to 0.050%. The amount of Ti is more desirably 0.001% to 0.030%.
  • Al has a deoxidation effect or the like, Al is a useful element for refinement, and Al has an effect of improving moldability. In order to stably obtain these effects, 0.001 % or more of Al is included. However, in the case where a large amount of Al is included, an oxide film with poor wettability is formed on the surface, and brazeability is impaired. Therefore, the amount of Al is set to 0.030% or less. The amount of Al is more desirably 0.001% to 0.015%.
  • Nb Since carbonitrides of Nb prevents the coarsening of crystal grains due to heating during brazing and thus a decrease in the strength of members is prevented, Nb is an important element. In addition, Nb is useful for improving high-temperature strength or improving the intergranular corrosion resistance of welded portions, but in the case where an excess amount of Nb is added, workability or manufacturability is degraded, and thus the amount of Nb is set to 0.010% to 1.000%. The amount of Nb is more desirably 0.100% to 0.600%.
  • O is an element that is inevitably included in a stainless steel. However, when O is present in the base material of a stainless steel, there is a possibility that O causes the formation of inclusions such as oxides and degrades a variety of characteristics such as ductility or corrosion resistance. Therefore, the amount of O is decreased to be 0.020% or less. The amount of O is more desirably 0.010% or less.
  • N is a useful element for pitting corrosion resistance, but N degrades intergranular corrosion resistance and workability, and thus it is necessary to decrease the amount of N at a low level. Therefore, the amount of N is set to 0.050% or less. The amount of N is more desirably 0.030% or less.
  • the ferritic stainless steel may further include the following elements as necessary.
  • Ni In order to improve corrosion resistance, 3.00% or less of Ni may be included. In order to stably obtain the effects, the amount of Ni needs to be 0.01% or more. The amount of Ni is more desirably 0.05% to 2.00%.
  • Cu In order to improve corrosion resistance, 1.500% or less of Cu may be included. In order to stably obtain the effects, the amount of Cu needs to be 0.050% or more. The amount of Cu is more desirably 0.100% to 1.000%.
  • W In order to improve corrosion resistance, 1.000% or less of W may be included. In order to stably obtain the effects, the amount of W needs to be 0.010% or more. The amount of W is more desirably 0.020% to 0.800%.
  • V In order to improve corrosion resistance, 0.300% or less of V may be included. In order to stably obtain the effects, the amount of V needs to be 0.010% or more. The amount of V is more desirably 0.020% to 0.050%.
  • Sn In order to improve corrosion resistance, 0.500% or less of Sn may be included. In the case where Sn is included, the amount of Sn is 0.005% or more at which the effects can be obtained stably. The amount of Sn is more desirably 0.01% to 0.300%.
  • Sb In order to improve general corrosion resistance. 0.5000% or less of Sb may be included. In the case where Sb is included, the amount of Sb is 0.0050% or more at which the effects can be obtained stably. The amount of Sb is more desirably 0.0100% to 0.3000%.
  • Mg has a deoxidation effect or the like and is a useful element for refinement. In addition, Mg minimizes the structure and Mg is also useful for improving workability and toughness, and 0.0030% or less of Mg may be included as necessary. In the case where Mg is included, the amount of Mg is 0.0001% or more at which the effects can be obtained stably. The amount of Mg is more desirably 0.0001% to 0.001%.
  • the total amount of one or more of Ni, Cu, W, V, Sn, Sb, and Mg is desirably 6% or less from the viewpoint of an increase in costs.
  • B is a useful element for improving secondary workability, and 0.0030% or less of B may be included.
  • the amount of B is 0.0002% or more at which the effects can be obtained stably.
  • the amount of B is more desirably 0.0005% to 0.0010%.
  • Ca is added in order for desulfurization, but in the case where an excess amount of Ca is added, a water-insoluble inclusion CaS is generated and corrosion resistance is degraded. Therefore, 0.0002% to 0.0100% of Ca may be added. The amount of Ca is more desirably 0.0002% to 0.0050%.
  • Zr In order to improve corrosion resistance, 0.300% or less of Zr may be included as necessary. In the case where Zr is included, the amount of Zr is 0.010% or more at which the effects can be obtained stably. The amount of Zr is more desirably 0.020% to 0.200%,
  • Co In order to improve secondary workability and toughness, 0.300% or less of Co may be included as necessary. In the case where Co is included, the amount of Co is 0.010% or more at which the effects can be obtained stably. The amount of Co is more desirably 0.020% to 0.200%.
  • Ga In order to improve corrosion resistance and hydrogen embrittlement resistance, 0.0100% or less of Ga may be included as necessary. In the case where Ga is included, the amount of Ga is 0.0001% or more at which the effects can be obtained stably. The amount of Ga is more desirably 0.0005% to 0.0050%.
  • Ta In order to improve corrosion resistance, 0.0100% or less of Ta may be included as necessary. In the case where Ta is included, the amount of Ta is 0.0001% or more at which the effects can be obtained stably. The amount of Ta is more desirably 0.0005% to 0.0050%.
  • REM Since REM has a deoxidation effect or the like, REM is a useful element for refinement, and 0.200% or less of REM may be included as necessary. In the case where REM is included, the amount of REM is 0.001% or more at which the effects can be obtained stably. The amount of REM is more desirably 0.002% to 0.100%.
  • rare earth elements refer to, according to the ordinary definition, two elements of scandium (Sc) and yttrium (Y) and fifteen (lanthanoid) elements from lanthanum (La) to lutetium (Lu).
  • REM is one or more elements selected from these rare earth elements, and the amount of REM refers to the total amount of rare earth elements.
  • a manufacturing method of the present embodiment basically, an ordinary method for manufacturing a steel sheet made of a ferritic stainless steel is applied.
  • molten steel having the above-described chemical composition is produced using a converter or an electric furnace and is refined using an AOD furnace, a VOD furnace, or the like.
  • a slab is produced using a continuous casting method or an ingot casting method and then the slab is subjected to steps of hot rolling, annealing of hot-rolled sheets, pickling, cold rolling, finishing annealing, and pickling; and thereby, the ferritic stainless steel of the present embodiment is manufactured.
  • the annealing of hot-rolled sheets may not be carried out as necessary.
  • the cold rolling, the finishing annealing, and the pickling may be repeated.
  • the annealing step of the cold-rolled sheet desirably includes a step of maintaining the steel sheet at a temperature of 650°C to 950°C for 5.0 s or longer and a step of maintaining the steel sheet at a temperature of 950°C to 1,050°C for 80.0 s or shorter.
  • the holding time during which the steel sheet is maintained is maintained at a temperature of 650°C to 950°C to 5.0 s or longer and set the holding time during which the steel sheet is maintained at a temperature of 950°C to 1,050°C to 80.0 s or shorter.
  • test specimens with a 100 mm width and a 100 mm length were cut out from the produced steel sheets.
  • the arithmetic average roughness values of the steel surface in the respective directions of the rolling direction (L direction), the direction perpendicular to the rolling direction (C direction), and the direction inclined at 45° with respect to the rolling direction (V direction) were measured using a surface roughness and shape measurement instrument.
  • the measurement length was set to 4.0 mm
  • the measurement speed was set to 0.30 mm/s
  • the cut-off length was set to 0.8 mm.
  • the average value of three measurement results was used as the arithmetic average roughness value in that direction.
  • the produced steel sheets were cut so that a surface parallel to the rolling direction could be observed and were implanted in a resin.
  • the grain size number (GSN) was measured using the cutting method.
  • test specimens with a 60 mm width and a 100 mm length were cut out from the produced steel sheets, and Ni brazing filler metal (0.2 g) was placed on the surface of each of the test specimens and was heated at 1,200°C for ten minutes in a vacuum atmosphere of 5 ⁇ 10 -3 torr.
  • the test specimen was cooled to normal temperature, and an area of the brazing filler metal (brazing filler metal area) on the surface of the test specimen after heating was measured.
  • Test specimens in which the brazing filler metal area after heating was 2.5 times or more the brazing filler metal area before heating was evaluated as A (excellent).
  • Test specimens in which the brazing filler metal area after heating was 2 times (twice) or more to less than 2.5 times the brazing filler metal area before heating was evaluated as B (good).
  • Test specimens in which the brazing filler metal area after heating was less than 2 times (twice) the brazing filler metal area before heating was evaluated as C (bad).
  • the steel sheets which had been subjected to a brazing thermal treatment were cut so that a surface parallel to the rolling direction could be observed and were implanted in a resin.
  • the grain size number (GSN) was measured using the cutting method.
  • test specimens with a 25 mm width and a 100 mm length were cut out from the cold-rolled steel sheets, and then all the surfaces of the test specimens were wet-polished using Emery paper of up to #600. These test specimens were evaluated by half-immersion tests.
  • Imitation condensate water used in the half-immersion tests was produced as described below.
  • An aqueous solution containing 300 ppm of Cl - , 1,000 ppm of SO 4 2- , and 1,000 ppm of SO 3 2- was produced using hydrochloric acid, sulfuric acid, and ammonium sulfite as reagents.
  • the pH was adjusted to 2.0 using ammonia water; and thereby the imitation condensate water was obtained.
  • a jig was adjusted so that approximately half of the test specimen was immersed in the imitation condensate water at an angle of 55°.
  • the half of the test specimen was immersed in the imitation condensate water using this jig, and the imitation condensate water was heated to 80°C.
  • the test was carried out for 168 hours, and the solution was renewed everyday on week days.
  • the maximum corrosion pit depth was used. After the end of the tests, the corroded product was removed using an aqueous solution of di-ammonium hydrogen citrate, and the depth of the position in which the test specimen was corroded deepest was measured using a focal depth method. With regard to the determination standard in the half-immersion tests, it was confirmed that growth of corrosion pits became significant under these test conditions in the case where the maximum corrosion pit depth was 100 ⁇ m. Therefore, 100 ⁇ m was used as the boundary value. A steel in which the maximum corrosion pit depth was less than 100 ⁇ m was evaluated as B (good). A steel in which the maximum corrosion pit depth was 100 ⁇ m or more was evaluated as C (bad).
  • EDS energy dispersive X-ray spectroscopy
  • Tables 3D and 3E The test results are shown in Tables 3D and 3E. It is found from Table 3D that steels of Invention Examples were excellent in terms of brazeability and corrosion resistance against condensate water. In addition, it is found from Table 3E that, in the case where the amounts of components were outside the ranges of the present embodiment, the corrosion resistance against condensate water deteriorated except for cases in which the amount of Al or Ti was outside the range of the present embodiment. It is found that, in the case where the amount of Al or Ti was outside the range of the present embodiment, brazeability became poor.
  • the holding time of the steel sheet at 650°C to 950°C was set to 5.0 s or longer, and the holding time of the steel sheet at 950°C to 1,050°C was set to 80.0 s or shorter. It is found that, in steels manufactured under the above-described conditions, the amount of change in grain size number before and after the brazing thermal treatment became 5.0 or less.
  • the ferritic stainless steel with high corrosion resistance against exhaust gas condensate water of the present invention is suitable as members that are used in exhaust gas recirculation apparatuses such as automobile mufflers, exhaust heat recovery devices, and exhaust gas recirculation (EGR) coolers.
  • exhaust gas recirculation apparatuses such as automobile mufflers, exhaust heat recovery devices, and exhaust gas recirculation (EGR) coolers.
  • EGR exhaust gas recirculation

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JP6166540B2 (ja) * 2013-01-28 2017-07-19 新日鐵住金ステンレス株式会社 高温プレス成形に適する自動車排気系部材用のフェライト系ステンレス鋼板およびフェライト系ステンレス鋼成形部品の製造方法
CN105074035B (zh) * 2013-03-27 2018-02-16 新日铁住金不锈钢株式会社 研磨后的表面耐蚀性优异的铁素体系不锈钢及其制造方法
JP5885884B2 (ja) * 2013-03-27 2016-03-16 新日鐵住金ステンレス株式会社 フェライト系ステンレス熱延鋼板とその製造方法及び鋼帯

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