WO2014069543A1 - Feuille d'acier inoxydable ferritique avec une excellente résistance à la chaleur - Google Patents

Feuille d'acier inoxydable ferritique avec une excellente résistance à la chaleur Download PDF

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WO2014069543A1
WO2014069543A1 PCT/JP2013/079461 JP2013079461W WO2014069543A1 WO 2014069543 A1 WO2014069543 A1 WO 2014069543A1 JP 2013079461 W JP2013079461 W JP 2013079461W WO 2014069543 A1 WO2014069543 A1 WO 2014069543A1
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less
stainless steel
temperature
ferritic stainless
grain boundary
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PCT/JP2013/079461
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English (en)
Japanese (ja)
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慎一 寺岡
章宏 福田
小林　雅明
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新日鐵住金ステンレス株式会社
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Priority to KR1020157010546A priority Critical patent/KR101690441B1/ko
Priority to JP2014544565A priority patent/JP6223351B2/ja
Priority to BR112015009634-4A priority patent/BR112015009634B1/pt
Priority to US14/439,456 priority patent/US20150292068A1/en
Priority to CN201380056855.XA priority patent/CN104769144B/zh
Priority to EP13851279.3A priority patent/EP2915894B1/fr
Priority to ES13851279T priority patent/ES2787353T3/es
Publication of WO2014069543A1 publication Critical patent/WO2014069543A1/fr

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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Definitions

  • the present invention relates to a material for a thin plate structure used at a high temperature, and particularly to a ferritic stainless steel that is not easily embrittled by being used at a high temperature as well as corrosion resistance at a normal temperature, such as an automobile exhaust system material. is there.
  • Ferritic stainless steel is inferior in workability, toughness and high-temperature strength compared to austenitic stainless steel, but it is inexpensive because it does not contain a large amount of Ni, and its thermal expansion is small. It is used for applications where thermal distortion becomes a problem, such as materials and automotive exhaust system parts that become hot. Particularly when used as an exhaust system part material for automobiles, high temperature strength, corrosion resistance at normal temperature, and high toughness associated with high temperature use are important.
  • steel types such as SUH409L, SUS429, SUS430LX, SUS436J1L, SUS432, and SUS444 are used as ferritic stainless steel suitable for these applications.
  • Patent Document 1 discloses a material having a high temperature strength increased by using 0.05 to 2% of Sn.
  • Patent Document 2 discloses a technique for improving the surface quality of a stainless steel plate by adding 0.005 to 0.10% Sn. In recent years, a large amount of Sn exceeding 0.05% has been contained in stainless steel as an unavoidable impurity by using scrap iron including a surface-treated steel sheet as a raw material.
  • JP 2000-169943 A Japanese Patent Laid-Open No. 11-92872
  • An object of the present invention is to provide a ferritic stainless steel that does not deteriorate toughness at room temperature even when exposed to a high temperature for a long time, such as an automobile exhaust system material.
  • the present inventors have made various studies on the reduction in toughness at room temperature after high-temperature and long-term aging of Sn-containing ferritic stainless steel.
  • SUS430LX contained 0.3% of Sn
  • the toughness drop was caused by using in any temperature range, and it was found that the temperature was 500 to 800 ° C.
  • the temperature at which the toughness drop occurs particularly in a short time is 700 ° C., and the toughness drop significantly occurs in only 1 hour.
  • the fracture surface form in which brittle fracture occurred was different from a general cleavage fracture surface and had a characteristic of showing a grain boundary fracture surface.
  • the ferritic stainless steel sheet of the present invention is as follows.
  • the grain boundary Sn concentration when the balance is Fe and inevitable impurities, and the heat treatment is performed at a temperature of 600 to 750 ° C. so that the L value represented by Formula 3 is 1.91 ⁇ 10 4 or more.
  • the stainless steel having the composition described in (1) (3) or (4) is annealed at a cold-rolled sheet annealing temperature of 850 ° C. to 1100 ° C., and then cooled from the cold-rolled plate annealing temperature,
  • the ferritic stainless steel containing Sn of the present invention since the stabilizing elements Nb and Ti are optimized, the stainless steel is excellent in corrosion resistance with little deterioration in toughness even when used at high temperatures. A steel plate can be obtained.
  • the ferritic stainless steel and comparative steel in this embodiment were subjected to a Charpy impact test after being heat-treated at 700 ° C. for 1 hour with a hot rolled annealed sheet having a thickness of 4.0 mm. It is a fracture surface photograph of a test piece. After subjecting the ferritic stainless steel and the comparative steel in this embodiment to a hot-rolled annealed sheet having a thickness of 4.0 mm and a hot-rolled annealed sheet held at 700 ° C. for 1 hour, a V-notch Charpy impact test is performed. It is the graph which showed the ductile-brittle transition temperature measured with the subsize test piece of plate
  • the V-notch Charpy impact test piece is a sub-size test piece having a thickness of 4.0 mm. It is a graph which shows the relationship between the ductility-brittle transition temperature (DBTT) and the parameter
  • DBTT ductility-brittle transition temperature
  • GBSV parameter
  • the Sn concentration at the grain boundary fracture surface is measured by AES, and the Charpy impact test is performed. It is a graph which measures the ductility-brittle transition temperature (DBTT), and shows the relationship between Sn density
  • DBTT ductility-brittle transition temperature
  • the upper limit is made 0.015%.
  • the lower limit may be 0.001%. From the viewpoint of corrosion resistance, it is desirable that the lower limit is 0.002% and the upper limit is 0.009%.
  • N 0.020% or less N, like C, deteriorates formability, corrosion resistance, and hot-rolled sheet toughness, so the smaller the content, the more preferable, so 0.02% or less.
  • the lower limit should be 0.001%.
  • the upper limit is preferably set to 0.018%, and more preferably set to 0.015%.
  • Si 1.5% or less Excessive addition of Si lowers the room temperature ductility, so the upper limit is made 1.5%.
  • Si is an element that is also useful as a deoxidizer and is an element that improves high-temperature strength and oxidation resistance. The deoxidation effect is improved with an increase in the amount of Si, and the effect is manifested at 0.01% or more and stable at 0.05% or more. Therefore, the lower limit may be set to 0.01%.
  • Mn 1.5% or less
  • Mn is an element added as a deoxidizer and an element contributing to an increase in high-temperature strength in the middle temperature range.
  • Mn-based oxides form on the surface layer during long-time use, and are also elements that contribute to the adhesion of scale (oxide) and the effect of suppressing abnormal oxidation.
  • Mn may be added so that the Mn content of the stainless steel of the present invention is 0.01% or more. In consideration of high temperature ductility, scale adhesion, and suppression of abnormal oxidation, it is more desirable to set the lower limit to 0.1 and the upper limit to 1.0%.
  • P 0.035% or less
  • P is an element having a large solid solution strengthening ability, but it is a ferrite stabilizing element and is also an element harmful to corrosion resistance and toughness.
  • P is contained as an impurity in ferrochrome which is a raw material of stainless steel. Since it is very difficult to remove P from the molten steel, it may be 0.010% or more.
  • the P content is almost determined by the purity and amount of the ferrochrome raw material to be used.
  • the content of P in the ferrochrome raw material is preferably low. However, since low P ferrochrome is expensive, it is set to 0.035% or less, which is a range in which the material and corrosion resistance are not greatly deteriorated. In addition, Preferably it is 0.030% or less.
  • the S content is preferably as small as possible, and the upper limit is made 0.015% in consideration of the range that does not affect the corrosion resistance. Further, the smaller the S content, the better the corrosion resistance. However, the lowering of the S content increases the desulfurization load and the manufacturing cost, so the lower limit may be 0.001%. Preferably, the lower limit is 0.001% and the upper limit is 0.008%.
  • Cr 13.0-21.0%
  • Cr is an essential element for ensuring oxidation resistance and corrosion resistance. If it is less than 13.0%, these effects do not appear. On the other hand, if it exceeds 21.0%, workability and toughness are deteriorated, so the lower limit is 13.0 and the upper limit is 21.0%. To do. Furthermore, if manufacturability and high temperature ductility are taken into consideration, it is desirable that the upper limit be 18.0%.
  • Sn 0.01 to 0.50%
  • Sn is an element effective for improving corrosion resistance and high temperature strength.
  • the lower limit is made 0.01%.
  • the contribution to the high-temperature strength is stably expressed by addition of 0.05% or more, so the preferable lower limit is made 0.05%.
  • the upper limit is made 0.50%.
  • the lower limit is preferably 0.1%.
  • the upper limit is preferably set to 0.3%.
  • the development of the embrittlement phenomenon at high temperature use becomes remarkable when 0.05% or more of Sn is contained, but the embrittlement phenomenon caused by the inclusion of Sn can be suppressed by adding Nb described below in combination. .
  • the upper limit of the Sn content is more preferably 0.21%.
  • Nb 0.05 to 0.60%
  • Nb is an element having an effect of suppressing sensitization due to precipitation of chromium carbonitride in stainless steel and deterioration of corrosion resistance by forming carbonitride. This effect is manifested at 0.05% or more.
  • the present inventors have found that it has an effect of suppressing grain boundary embrittlement in Sn-containing steel. Since both effects of improving corrosion resistance and suppressing grain boundary embrittlement are manifested at 0.05% or more, the lower limit is made 0.05%. In order to obtain the effect more reliably, it is preferably set to 0.09% or more, and if it is 0.2% or more, the effect can be obtained almost certainly.
  • the upper limit of Nb is set to 0.60%. Furthermore, from the viewpoint of weldability and workability with a thin plate, the lower limit may be 0.3% and the upper limit may be 0.5%. Moreover, the grain boundary embrittlement suppressing effect in the Sn-containing steel can be obtained even when Ti and Nb are added in combination. Also in this case, the effect is obtained when the amount of Nb added is 0.05% or more. However, it is necessary to adjust the CI value, which will be described later, to be within a predetermined range both when adding Nb alone and when adding Ti and Nb.
  • Ti and Nb form carbonitrides and suppress deterioration of corrosion resistance due to formation and sensitization of chromium carbonitrides. That is, the addition amount corresponding to the amount of C and N in steel is necessary.
  • the CI value is an index for precipitating C and N in steel as Ti and Nb carbonitrides to suppress sensitization, and as the CI value increases, sensitization is suppressed.
  • CI In order to stably suppress precipitation of chromium carbonitride even in a welding heat cycle, CI is required to be 8 or more. However, if Ti and Nb are added excessively, large inclusions are formed and the workability is lowered, so the CI is made 26 or less. In order to ensure stable corrosion resistance and workability, the CI is preferably 10 or more and 20 or less.
  • GBSV Sn + Ti-2Nb-0.3Mo-0.2 is 0 or less.
  • GBSV Sn-2Nb-0.2 is set to 0 or less.
  • GBSV is an index indicating the grain boundary segregation tendency of Sn, and the grain boundary segregation becomes more prominent as the value is larger.
  • the coefficient of the elements constituting GBSV is an evaluation of the effect on grain boundary segregation.
  • Sn is an element effective for high-temperature strength and corrosion resistance, but lowers the toughness of the material at 400 ° C. or lower due to grain boundary segregation.
  • Nb and Mo have the effect of increasing the grain boundary strength in addition to the action of suppressing the grain boundary segregation of Sn, and the action of suppressing embrittlement due to the grain boundary segregation of Sn.
  • the ductility-brittle transition temperature decreases, and when the GBSV becomes 0 or less, the ductile-brittle transition temperature is 150 in a hot-rolled annealed sheet having a thickness of 4.0 mm. It can be seen that the toughness is greatly improved at a temperature below °C. For this reason, GBSV was made 0 or less.
  • the Sn concentration (atomic%) of the grain boundary fracture surface was used as an index of the grain boundary segregation of Sn, and the relationship with the ductile brittle transition temperature was examined. As shown in FIG. 4, it was found that when the Sn concentration at the grain boundary exceeds 2.0 atomic%, the ductile-brittle transition temperature increases rapidly and the grain boundary embrittlement is likely to occur. Even in a high temperature use environment, it is important for the Sn concentration at the grain boundary to be 2.0 atomic% or less in order to suppress grain boundary embrittlement due to Sn.
  • an L value represented by Formula 3 that is usually used as an evaluation index for heat treatment was introduced.
  • heat treatment is performed at a temperature of 600 to 750 ° C. so that the L value shown in Formula 3 is 1.91 ⁇ 10 4 or more
  • Sn segregation to the grain boundary is noticeably observed when Ti is added.
  • the present inventors have found that the Sn segregation of N will adversely affect the characteristics (transition temperature).
  • the present inventors also confirmed that the grain boundary Sn concentration is 2 atomic% or less when heat treatment is performed with an L value of 1.91 ⁇ 10 4 or more in the case of the component composition in the present invention. did.
  • the grain boundary Sn concentration after heat treatment at 700 ° C. for 1 hour is preferably 2.0 atomic% or less.
  • the Sn concentration of the grain boundary is measured by breaking in an AES apparatus under ultra high vacuum. Since Auger electrons are emitted not only from the surface but also from atoms within several nm from the surface, this value does not represent only the Sn concentration at the grain boundary. Moreover, the analysis accuracy differs for each apparatus. However, in principle, the Sn concentration at the cleavage fracture surface is the same as the average Sn concentration of the base material. Therefore, the Sn concentration at the grain boundary was determined by calibrating the measured value of the Sn concentration on the cleavage fracture surface so that the Sn concentration measured on the cleavage fracture surface becomes the average Sn concentration of the base material.
  • the Sn concentration at the grain boundary In order to stably reduce grain boundary embrittlement, it is preferable to set the Sn concentration at the grain boundary to 1.7 atomic% or less. Moreover, since it is difficult to make it below the Sn concentration of the base material, it is preferable to set 0.02 atomic% as the lower limit.
  • Ti 0.32% or less Ti is an element that suppresses deterioration of sensitization and corrosion resistance due to precipitation of chromium carbonitride in stainless steel by forming carbonitride similarly to Nb.
  • Nb since it has a greater effect of promoting grain boundary embrittlement in Sn-containing steel than Nb, it is an element to be reduced in Sn-containing steel. The influence of Sn on grain boundary segregation appears when the Ti content exceeds 0.05%.
  • Nb is contained, adverse effects due to Ti can be reduced. In the case of adding Nb in combination, it was confirmed that the Sn grain boundary concentration was 2.0 atomic% or less in the heat treatment if the upper limit was 0.32%.
  • a preferable upper limit in the case of containing Nb is 0.15%.
  • Ni 1.5% or less Ni is mixed as an inevitable impurity in the alloy raw material of ferritic stainless steel and is generally contained in the range of 0.03 to 0.10%. Moreover, it is an element effective in suppressing the progress of pitting corrosion, and the effect is stably exhibited by addition of 0.05% or more. Therefore, the lower limit is preferably 0.05%. More preferably, the lower limit is 0.1%. On the other hand, since a large amount of addition may cause material hardening due to solid solution strengthening, the upper limit is made 1.5%. In consideration of the alloy cost, the upper limit is preferably 1.0%. More preferably, the upper limit is 0.5%. From the above, Ni is preferably 0.1 to 0.5%.
  • Ni is an element that improves the corrosion resistance by a synergistic effect with Sn. It is useful to add together with Sn. Further, Ni also has an effect of improving the decrease in workability (elongation, r value) accompanying the addition of Sn. When combined with Sn, it is preferable that the lower limit of Ni is 0.2 and the upper limit is 0.4%.
  • Cu 1.5% or less
  • Cu is effective in improving the corrosion resistance. This is particularly effective in reducing the rate of progress after crevice corrosion. It is desirable to contain 0.1% or more in order to improve corrosion resistance. However, excessive addition deteriorates workability. Therefore, it is desirable to contain Cu with a lower limit of 0.1 and an upper limit of 1.5%.
  • Cu is an element that improves the corrosion resistance by a synergistic effect with Sn. It is useful to add together with Sn. Further, Cu also has an effect of improving a decrease in workability (elongation, r value) accompanying the addition of Sn. When combined with Sn, it is preferable to contain Cu with a lower limit of 0.1 and an upper limit of 0.5%.
  • Cu is also an element necessary for increasing the high-temperature strength required for use as a high-temperature environment member typified by a high-temperature exhaust system of an automobile.
  • Cu mainly exhibits precipitation strengthening ability at 500 to 750 ° C., and at higher temperatures, it suppresses plastic deformation of the material by solid solution strengthening and exhibits a function of improving thermal fatigue characteristics.
  • Such precipitation hardening effect and solid solution strengthening of Cu are manifested by addition of 0.2% or more.
  • the upper limit is made 1.5%.
  • the lower limit is 0.5 and the upper limit is 1.0%.
  • Mo 2.0% or less Mo may be added as necessary in order to improve the high temperature strength and thermal fatigue characteristics.
  • the lower limit is preferably made 0.01%.
  • excessive addition may cause the generation of a Laves phase, which may cause a reduction in hot-rolled sheet toughness.
  • the upper limit of Mo is set to 2.0%. Further, from the viewpoint of productivity and manufacturability, it is desirable that the lower limit is 0.05% and the upper limit is 1.5%.
  • V 0.3% or less V is mixed as an inevitable impurity in ferritic stainless steel alloy raw materials and is difficult to remove in the refining process, so it is generally contained in the range of 0.01 to 0.1%. Is done. Moreover, since it has the effect which forms a fine carbonitride and a precipitation strengthening effect
  • action produces and contributes to a high temperature strength improvement, it is an element also added intentionally as needed. Since the effect is stably manifested by addition of 0.03% or more, the lower limit is preferably 0.03%. On the other hand, if added excessively, the precipitates may be coarsened. As a result, the high-temperature strength decreases and the thermal fatigue life decreases, so the upper limit is made 0.3%. In view of manufacturing cost and manufacturability, it is desirable that the lower limit is 0.03% and the upper limit is 0.1%.
  • Al 0.3% or less
  • Al is an element that improves oxidation resistance. Further, it is useful as a solid solution strengthening element for improving the strength at 600 to 700 ° C. Since the action is stably expressed from 0.01%, the lower limit is preferably set to 0.01%. On the other hand, excessive addition hardens and significantly reduces the uniform elongation, and also significantly reduces the toughness, so the upper limit is made 0.3%. Furthermore, considering the occurrence of surface flaws, weldability and manufacturability, the lower limit is preferably 0.01% and the upper limit is preferably 0.07%.
  • B 0.0020% or less B is effective for fixing N which is harmful to workability and improving secondary workability, and is added at 0.0003% or more as necessary. Further, even if added over 0.0020%, the effect is saturated, and the workability deterioration and corrosion resistance due to B are reduced, so 0.0003 to 0.002% is added. In consideration of workability and manufacturing cost, it is desirable that the lower limit is 0.0005% and the upper limit is 0.0015%.
  • W 0.20% or less W is effective in improving the high-temperature strength, and is added at 0.01% or more as necessary. Further, if added over 0.20%, the solid solution strengthening is too large and the mechanical properties are lowered, so 0.01 to 0.20% is added. Considering the manufacturing cost and hot-rolled sheet toughness, it is desirable that the lower limit is 0.02% and the upper limit is 0.15%.
  • Zr 0.20% or less Zr is added in an amount of 0.01% or more as necessary in order to form a carbonitride and suppress the formation of Cr carbonitride and improve the corrosion resistance like Nb and Ti. To do. Further, even if added over 0.20%, the effect is saturated and the formation of large oxides may cause surface defects, so 0.01% to 0.20% is added. Since it is an expensive element compared with Ti and Nb, considering the manufacturing cost, it is desirable that the lower limit is 0.02% and the upper limit is 0.05%.
  • Sb 0.5% or less Sb is effective in improving sulfuric acid resistance, and is added at 0.001% or more as necessary. Even if added over 0.5%, the effect is saturated and embrittlement occurs due to segregation of Sb grain boundaries, so 0.001 to 0.20% is added. In consideration of workability and manufacturing cost, it is desirable to set the lower limit to 0.002% and the upper limit to 0.05%.
  • Co 0.5% or less Co is effective for improving wear resistance and high-temperature strength, and is added at 0.01% or more as necessary. Moreover, even if added over 0.5%, the effect is saturated, and mechanical properties are deteriorated due to solid solution strengthening, so 0.01 to 0.5% is added. From the viewpoint of production cost and high temperature strength stability, it is desirable that the lower limit is 0.05% and the upper limit is 0.20%.
  • Ca 0.01% or less Ca is an important desulfurization element in the steelmaking process, and also has a deoxygenating effect, so is added at 0.0003% or more as necessary. Further, even if added over 0.01%, the effect is saturated, resulting in a decrease in corrosion resistance due to Ca granulated materials and a deterioration in workability due to oxides. Add in%. Considering manufacturability such as slag treatment, it is desirable that the lower limit is 0.0005% and the upper limit is 0.0015%.
  • Mg 0.01% or less Mg is an element effective for refining the solidified structure in the steel making process, and is added in an amount of 0.0003% or more as necessary. Even if added over 0.01%, the effect is saturated, and the corrosion resistance due to Mg sulfide or oxide tends to be reduced. Therefore, it is added at 0.0003 to 0.01%.
  • the lower limit is preferably 0.0005% and the upper limit is preferably 0.0015%.
  • REM 0.1% or less REM is effective in improving oxidation resistance, and is added at 0.001% or more as necessary. Further, even if added over 0.1%, the effect is saturated and the corrosion resistance is lowered due to the REM granulated material, so 0.001 to 0.1% is added. Considering the workability and manufacturing cost of the product, it is desirable that the lower limit is 0.002% and the upper limit is 0.05%.
  • the grain size number after cold rolling annealing is set to 5.0 or more and 9.0 or less.
  • the toughness is not completely reduced.
  • grain boundary embrittlement can be alleviated by increasing the area of grain boundaries where Se segregates.
  • the crystal grain size number needs to be 5 or more.
  • the mechanical properties become low ductility and high strength due to fine graining, so 5.0 or more and 9.0 or less.
  • the value be 6.0 or more and 8.5 or less.
  • the cold-rolled sheet annealing temperature is set to 850 ° C. or more at which Sn grain boundary segregation does not easily occur, and is set to 1100 ° C. or less at which crystal grain size coarsening hardly occurs. It is desirable that the cooling rate is 5 ° C./s or higher in the temperature range.
  • steels having the component compositions shown in Table 1-1 and Table 1-2 were melted and cast into slabs.
  • the slab was heated to 1190 ° C. and then hot-rolled to a sheet thickness of 4 mm with a finishing temperature in the range of 800 to 950 ° C. to obtain a hot-rolled steel sheet.
  • Table 1-1 and Table 1-2 values outside the scope of the present invention are underlined.
  • the hot-rolled steel sheet was cooled to 500 ° C. by air-water cooling and then wound into a coil.
  • examples of the present invention and comparative examples that do not contain Ti and Mo have Ti and Mo contents indicated by a symbol “-”.
  • the CI and GBSV values of the inventive examples and comparative examples not containing Ti and Mo were calculated based on the above-described formulas 1 and 2, respectively. Further, the CI and GBSV values of the inventive examples and comparative examples containing Ti and Mo were calculated based on the above-described formulas 1 'and 2', respectively.
  • the hot rolled coil was annealed at 900 to 1100 ° C. and cooled to room temperature. At this time, the average cooling rate in the range of 800 to 550 ° C. was set to 20 ° C./s or more. Subsequently, the hot-rolled annealed plate was pickled and cold-rolled to obtain a thin plate having a thickness of 1.5 mm, and then the cold-rolled plate was annealed and pickled to obtain a thin plate product. No. in Table 1-1. 1 to 34 are examples of the present invention, No. 1 in Table 1-2. 35 to 56 are comparative examples.
  • the hot-rolled annealed sheet thus obtained was heat-treated at 700 ° C. for 1 hour (L value: 19460), and then subjected to a Charpy impact test in accordance with JIS Z 2242 to obtain a ductile-brittle transition.
  • the temperature (DBTT) was measured.
  • Table 2-1 and Table 2-2 The measurement results are shown in Table 2-1 and Table 2-2.
  • the test piece in a present Example is a subsize test piece with the plate
  • the hot-rolled annealing board in each Example is obtained by dividing absorbed energy by a cross-sectional area (unit cm 2 ).
  • the toughness was compared and evaluated.
  • the evaluation criteria of toughness made ductility-brittle transition temperature (DBTT) 150 degrees C or less favorable.
  • test piece of 14 ⁇ 4 ⁇ 4 mm was prepared from the hot-rolled annealed plate for Auger electron spectroscopy (AES).
  • a notch having a depth of 1 mm and a width of 0.2 mm was placed in the center of the test piece in the longitudinal direction.
  • AES apparatus In ultra-high vacuum in the AES apparatus, it was cooled with liquid nitrogen, ruptured by impact, and the Sn concentration at the grain boundary fracture surface was measured. The measurement results are shown in Tables 2-1 and 2-2 as “grain boundary Sn concentration (at%)”.
  • SAM-670 PHI, FE type
  • the beam size was 0.05 ⁇ m.
  • the concentration was calibrated so that the analytical value on the cleavage plane was the same as the concentration of the base material. Auger electrons are emitted not only from the outermost surface of the grain boundary fracture surface, but also from a depth of several nanometers. In this method, the Sn concentration of the grain boundary is not accurate, but this method is used as a general measurement value. 2 atomic% (at%) or less was considered good.
  • the hot-rolled annealed sheet is cold-rolled to 1.5 mm, pickled after annealing at 840 to 980 ° C. for 100 seconds, Mig bead-on-plate welding is performed on the cold-rolled annealed sheet, and is specified in JIS G 0575.
  • the stainless steel was subjected to a sulfuric acid / copper sulfate corrosion test to investigate the presence or absence of sensitization in the welded HAZ part. However, the sulfuric acid concentration was 0.5%, and the test time was 24 hours. Those in which intergranular corrosion was observed were considered to have failed corrosion resistance. The evaluation results are shown in Tables 2-1 and 2-2 as the “improved Strauss test”.
  • Table 3 shows the results of tests similar to the items described in Table 2-1 and Table 2-2, with different heat treatment conditions for the hot-rolled annealed sheet. Some steels shown in Table 3 were evaluated by a wet and dry repeated test.
  • test tube Semi-immersed.
  • the test tube was put in a warm bath at 80 ° C., and a sample completely dried after 24 hours was lightly washed with distilled water. Then, the test solution was again filled in the newly washed test tube, and the sample was half-immersed again. And holding for 24 hours was performed 14 cycles.
  • Table 4 shows the results of a V-notch Charpy impact test with the plate thickness changed after changing the annealing conditions of the cold-rolled annealed plate to a 1.5 mm thin plate product and aging treatment at 600 ° C. for 1 week. Indicated. At this time, the condition where the ductile-brittle transition temperature was ⁇ 20 ° C. or lower was regarded as acceptable.
  • no. 35, 39 to 41, 43, 44, 46, 49, 50 have GBSV larger than 0, and the grain boundary Sn segregation amount after heat treatment at 700 ° C. for 1 hour is larger than 2 at% by AES measurement.
  • -It has low toughness so that the brittle transition temperature is over 150 ° C.
  • No. 36, 37, 38, 52, 53, and 51 had high Si, Mn, P, Ni, Cu, and Mo, respectively, and their mechanical properties were poor because elongation decreased due to solid solution strengthening.
  • No. No. 39 has a high S. No.
  • No. 40 has low Cr.
  • No. 42 has a low Sn. Since 55 had a high B, the corrosion resistance evaluated in the salt spray test was poor. No. Since No. 42 had low Sn, toughness was good even when GBSV was larger than 0.
  • No. No. 45 has a high Nb. 47, 45, 50 are Ti, No. No. 54 had a high V, so wrinkles caused by large inclusions were generated, and the quality was judged to be poor.
  • No. 41 is Cr, No. No. 56 was judged to be of poor quality because Al was high and hot rolling occurred.
  • Symbols a1 to a3 in Table 3 indicate that the DBTT exceeds 150 ° C. because the grain boundary Sn concentration is 2 atomic% or more after the heat treatment with an L value of 1.91 ⁇ 10 4 or more. And toughness was poor. Further, as in a4, when the L value is less than 1.91 ⁇ 10 4 , Sn does not segregate at the grain boundary, so DBTT is as low as 80 ° C. However, when the L value increases, Sn segregates at the grain boundary. From the fact that DBTT becomes high, it was confirmed that Sn segregation at the grain boundary must be evaluated at an L value of 1.91 ⁇ 10 4 or more.
  • the maximum corrosion depth of all the steels in the range of the present invention was 50 ⁇ m or less.
  • the maximum corrosion depth was 20 ⁇ m or less, indicating a result of extremely excellent corrosion resistance.
  • the thin plate to which the component composition to which the present invention is applied, the grain size number after cold rolling annealing, the cold rolling plate annealing temperature, and the cooling rate are applied has a low ductile-brittle transition temperature and is good. Showed toughness.
  • the symbol b1 has a cold-rolled sheet annealing temperature of 1100 ° C. or higher, and the crystal grain size number defined by the steel-crystal grain size microscopic test method defined in JIS G0551 is less than 5.0.
  • the cooling rate at 20 ° C. was 20 ° C./s, but the ductile-brittle transition temperature was high.
  • the symbol b2 had a cold rolled sheet annealing temperature of less than 850 ° C. and a crystal grain size number exceeding 9.0, so the mechanical properties were poor.
  • b3 and b6 had a cooling rate of less than 5 ° C./s at 800 to 500, the annealing temperature was appropriate and the crystal grain size number was 8.0, but the ductile-brittle transition temperature was high. Further, since b4 and b5 were comparative example components, the cold-rolled sheet annealing temperature, cooling rate, and crystal grain size number were within the proper ranges, but the ductile-brittle transition temperature was high.
  • the ferritic stainless steel containing Sn of the present invention since the stabilizing elements Nb and Ti are optimized, the toughness is deteriorated even when used at a high temperature. It is possible to manufacture a stainless steel plate that is small and excellent in corrosion resistance of a thin plate. Further, by applying the material to which the present invention is applied to exhaust system members of automobiles and two-wheeled vehicles in particular, it becomes possible to extend the life of parts and increase the social contribution. In other words, the present invention has sufficient industrial applicability.

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Abstract

La présente invention concerne une feuille d'acier inoxydable ferritique contenant du Sn avec une excellente résistance à la chaleur. L'acier inoxydable ferritique contient, en % massique, au plus 0,015 % de C, au plus 1,5 % de Si, au plus 1,5 % de Mn, au plus 0,035 % de P, au plus 0,015% de S, 13-21 % de Cr, 0,01-0,50 % de Sn, 0,05-0,60 % de Nb et au plus 0,020 % de N, le reste étant constitué de Fe et d'impuretés inévitables. L'acier inoxydable ferritique respecte la formule 1 et la formule 2, et a une concentration en Sn de joint de grain d'au plus 2 % atomique lorsqu'il est soumis à un traitement thermique à 600-750 °C dans lequel la valeur de L, selon la formule 3, est supérieure ou égale à 1,91×104. 8 ≤ CI = (Ti+0,52Nb) / (C+N) ≤ 26 (formule 1) GBSV = Sn+Ti-2Nb-0,3Mo-0,2 ≤ 0 (formule 2) L = (273+T) (log(t)+20) (formule 3) T : Température (°C), t : temps (h)
PCT/JP2013/079461 2012-10-30 2013-10-30 Feuille d'acier inoxydable ferritique avec une excellente résistance à la chaleur WO2014069543A1 (fr)

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JP2014544565A JP6223351B2 (ja) 2012-10-30 2013-10-30 フェライト系ステンレス鋼、それを用いた排気系部材及びフェライト系ステンレス鋼の製造方法
BR112015009634-4A BR112015009634B1 (pt) 2012-10-30 2013-10-30 Aços inoxidáveis ferríticos, seus métodos de produção e elementos de sistema de escapamento
US14/439,456 US20150292068A1 (en) 2012-10-30 2013-10-30 Ferritic stainless steel having excellent heat resistance
CN201380056855.XA CN104769144B (zh) 2012-10-30 2013-10-30 耐热性优良的铁素体系不锈钢板
EP13851279.3A EP2915894B1 (fr) 2012-10-30 2013-10-30 Feuille d'acier inoxydable ferritique avec une excellente résistance à la chaleur
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JP2016069677A (ja) * 2014-09-29 2016-05-09 新日鐵住金ステンレス株式会社 穴広げ性に優れたフェライト系ステンレス鋼鈑及びその製造方法
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US10752973B2 (en) 2014-10-31 2020-08-25 Nippon Steel & Sumikin Stainless Steel Corporation Ferrite-based stainless steel with high resistance to corrosiveness caused by exhaust gas and condensation and high brazing properties and method for manufacturing same
WO2023089693A1 (fr) * 2021-11-17 2023-05-25 日鉄ステンレス株式会社 Feuille d'acier inoxydable ferritique

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EP3556880A4 (fr) * 2017-01-26 2019-12-04 JFE Steel Corporation Tôle d'acier inoxydable ferritique, laminée à chaud et procédé de production correspondant
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EP2915894B1 (fr) 2020-03-04
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TW201422828A (zh) 2014-06-16
KR101690441B1 (ko) 2016-12-27
BR112015009634A2 (pt) 2017-07-04
CN104769144B (zh) 2017-10-10
KR20150056656A (ko) 2015-05-26
JPWO2014069543A1 (ja) 2016-09-08
EP2915894A1 (fr) 2015-09-09
JP6223351B2 (ja) 2017-11-08
CN104769144A (zh) 2015-07-08
ES2787353T3 (es) 2020-10-15
TWI504763B (zh) 2015-10-21

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