(19)
(11)EP 2 163 658 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
06.05.2020 Bulletin 2020/19

(21)Application number: 08765822.5

(22)Date of filing:  18.06.2008
(51)Int. Cl.: 
C22C 38/02  (2006.01)
C22C 38/42  (2006.01)
C22C 38/44  (2006.01)
C21D 8/02  (2006.01)
C22C 38/00  (2006.01)
C22C 38/04  (2006.01)
C22C 38/48  (2006.01)
C22C 38/50  (2006.01)
C21D 9/46  (2006.01)
(86)International application number:
PCT/JP2008/061501
(87)International publication number:
WO 2008/156195 (24.12.2008 Gazette  2008/52)

(54)

FERRITIC STAINLESS STEEL SHEET HAVING EXCELLENT CORROSION RESISTANCE AGAINST SULFURIC ACID, AND METHOD FOR PRODUCTION THEREOF

FERRITISCHES EDELSTAHLBLECH MIT HERVORRAGENDER KORROSIONSBESTÄNDIGKEIT GEGENÜBER SCHWEFELSÄURE UND HERSTELLUNGSVERFAHREN DAFÜR

TÔLE D'ACIER INOXYDABLE FERRITIQUE AYANT UNE EXCELLENTE RÉSISTANCE À LA CORROSION À L'ENCONTRE DE L'ACIDE SULFURIQUE, ET SON PROCÉDÉ DE FABRICATION


(84)Designated Contracting States:
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

(30)Priority: 21.06.2007 JP 2007163418
06.07.2007 JP 2007178097

(43)Date of publication of application:
17.03.2010 Bulletin 2010/11

(73)Proprietor: JFE Steel Corporation
Tokyo 100-0011 (JP)

(72)Inventors:
  • ISHII, Tomohiro
    Tokyo 100-0011 (JP)
  • FUNAKAWA, Yoshimasa
    Tokyo 100-0011 (JP)
  • UJIRO, Takumi
    Tokyo 100-0011 (JP)
  • OHTA, Masayuki
    Tokyo 100-0011 (JP)

(74)Representative: Grünecker Patent- und Rechtsanwälte PartG mbB 
Leopoldstraße 4
80802 München
80802 München (DE)


(56)References cited: : 
EP-A1- 0 547 626
JP-A- 6 041 695
JP-A- 9 041 094
JP-A- 09 003 606
JP-A- 10 298 720
JP-A- 2001 003 144
JP-A- 2001 181 808
JP-A- 2001 293 990
JP-A- 2002 020 845
JP-A- 2007 092 163
GB-A- 2 075 549
JP-A- 8 199 314
JP-A- 06 228 710
JP-A- 10 102 212
JP-A- 56 146 857
JP-A- 2001 020 046
JP-A- 2001 254 153
JP-A- 2001 294 990
JP-A- 2002 194 507
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Technical Field



    [0001] The present invention relates to a ferritic stainless steel sheet having a superior corrosion resistance against sulfuric acid. In addition, besides the above corrosion resistance, the present invention relates to a ferritic stainless steel sheet which has a low degree of rough surface at a bent part which is formed by a bending work performed at an angle of 90° or more and to a method for manufacturing the above ferritic stainless steel sheet.

    Background Art



    [0002] Fossil fuels, such as petroleum and coal, contain sulfur (hereinafter represented by "S"). Hence, when a fossil fuel is combusted, S is oxidized, and sulfur oxides such as SO2 are mixed in an exhaust gas. When the temperature of an exhaust gas decreases in a pipe, such as a gas duct, a chimney pipe, or an exhaust gas desulfurizer, fitted to an apparatus (such as an industrial boiler) in which a fossil fuel is combusted, this SOx gas reacts with moisture in the exhaust gas to form sulfuric acid, and as a result, dewdrops thereof are formed on an inner surface of the pipe. This sulfuric acid in the form of dewdrops enables corrosion (hereinafter referred to as "sulfate corrosion") of the pipe to progress.

    [0003] Various techniques to prevent the sulfate corrosion have been investigates, and for example, there has been used a technique in which a pipe for an exhaust gas is formed from low-alloy steel or a technique in which the temperature of an exhaust gas is controlled to 150°C or more.

    [0004] However, by the techniques described above, although the sulfate corrosion may be suppressed, it is difficult to stop the progression thereof.

    [0005] In recent years, concomitant with an expansion of automobile market in Asia, iron steel has been increasingly in demand, and the amount of fossil fuels consumed in blast furnaces, heat treat furnaces, and the like of steel industry has also been increased. Hence, development of techniques to prevent the sulfate corrosion has become an urgent requirement in the steel industry. In addition, since gasoline contains S, the sulfate corrosion is also generated in pipes for exhaust gases emitted from automobile engines. Accordingly, exhaust gas pipes of automobiles also require a technique to prevent the sulfate corrosion. In addition, many of these pipes are subjected to a severe bending work.

    [0006] Since high-temperature exhaust gases pass through exhaust gas pipes of blast furnaces, heat treat furnaces, and automobiles, low-alloy steel has not been used in order to prevent high-temperature oxidation, but ferritic stainless steel has been used in many cases. Hence, various techniques to improve the resistance against the sulfate corrosion (hereinafter referred to as "sulfate corrosion resistance") of ferritic stainless steel have been studied.

    [0007] For example, In Japanese Unexamined Patent Application Publication No. 56-146857, a technique has been disclosed in which acid resistance is improved by decreasing the S content of ferritic stainless steel to 0.005 mass percent or less. However, in Japanese Unexamined Patent Application Publication No. 56-146857, the acid resistance is investigated by dipping ferritic stainless steel in boiling hydrochloric acid, and the sulfate corrosion resistance has not been disclosed.

    [0008] Different steel compositions are further disclosed in JP 9 041094 A, JP 2002 02845 A, GB 2 075 549 A, EP 0 547 626 A1, JP 10 102212, JP 2001 294990, JP 2001 020046 A, JP 2001 181808, JP 201 254153 A, JP 2001 254153 A, JP 2001 003144, JP 10 298720 A, and JP 8 199314 A.

    [0009] In Japanese Unexamined Patent Application Publication No. 7-188866, a technique has been disclosed In which in order to suppress intergranular corrosion caused by nitric acid, the contents of C and N of ferritic stainless steel are decreased, and the contents of Mn, Ni, and B are also de fined. However, according to the generation mechanism of intergranular corrosion caused by nitric acid, an environmental potential becomes positive due to the presence of nitric ions, and hence the breakage behavior of a passivation film of stainless steel and the stability of corrosion products are different from those caused by the sulfate corrosion. Accordingly, in order to apply the technique disclosed in Japanese Unexamined Patent Application Publication No. 7-188866 to prevent the sulfate corrosion, further study must be carried out.

    [0010] An object of the present invention is to provide a ferritic stainless steel sheet having a superior sulfate corrosion resistance even in a high-temperature atmosphere.

    [0011] It is also provided a ferritic stainless steel sheet which has a low degree of rough surface at a bent part which is formed by a bending work performed at an angle of 90° or more.

    [0012] In order to improve the formability of a ferritic stainless steel sheet, there has been investigated a technique in which the amounts of C and N are considerably decreased in a refining step of molten steel which is used as a raw material or a technique in which C and/or N is stabilized by the formation of carbides and/or nitrides by addition of Ti and/or Nb to molten steel. As a result, a ferritic stainless steel sheet having superior deep drawing characteristics to those of an austenite stainless steel sheet has been developed. However, according to a related ferritic stainless steel sheet having superior deep drawing characteristics, the formability by a deep drawing work, which is evaluated, for example, by a Lankford value (so-called r value), is improved.

    [0013] In addition, in order to reduce the degree of rough surface (so-called orange peel) at a bent part formed by stretch forming, a technique has been investigated to improve a method for forming a ferritic stainless steel sheet into a predetermined shape (for example, see Japanese Unexamined Patent Application Publication No. 2005-139533). However, the rough surface at a bent part is not only generated by stretch forming but is also generated, for example, by a bending work, and research on a technique for reducing the degree of rough surface at a bent part by improving components of a ferritic stainless steel sheet and a manufacturing method therefor has not been sufficiently carried out.

    [0014] The rough surface is a collective term including various surface defects, and in a ferritic stainless steel sheet, a rough surface, which is called ridging, is frequently generated. The ridging indicates a surface defect which is caused by the difference in deformation between individual textures which is generated when the textures are processed in a rolling direction generated by rolling. Although steel which suppresses the generation of ridging has been disclosed in many reports, even when the steel described above is used, a rough surface at a bent part may be apparently observed in some cases. Accordingly, it is believed that the generation mechanism of the rough surface at a bent part is different from that of the ridging, and hence measures suitable for the respective problems are separately required. In particular, when a bending work is performed at an angle of 90° or more, the rough surface is apparently generated.

    [0015] Accordingly, an object of the present invention is to provide a ferritic stainless steel sheet and a method for manufacturing the same, the ferritic stainless steel sheet having a superior sulfate corrosion resistance even in a high-temperature atmosphere and may further have a low degree of rough surface at a bent part formed by a bending work performed at an angle of 90° or more.

    Disclosure of Invention



    [0016] The inventors of the present invention carried out an intensive research on the generation mechanism of sulfate corrosion of a ferritic stainless steel sheet. It has been understood that inclusions containing S (hereinafter referred to as "sulfur-containing inclusions") function as initiation points of the sulfate corrosion. However, since the sulfur-containing inclusions are dissolved when being brought into contact with sulfuric acid, the sulfur-containing inclusions are not frequently observed at portions at which the sulfate corrosion occurs. Accordingly, the inventors of the present invention focused on the sulfur-containing inclusions before the sulfate corrosion occurs and investigated the influence of the grain diameter of the sulfur-containing inclusions on the progression of the sulfate corrosion.

    [0017] As a result, the following findings which are effective to prevent the sulfate corrosion are obtained. They are:
    1. (a) the S content is decreased to suppress precipitation of the sulfur-containing inclusions;
    2. (b) fine NbC grains are dispersed and precipitated by maintaining the Nb content in an appropriate range, and the sulfur-containing inclusions (such as MnS) are made to adhere to the precipitated NbC grains so that the sulfur-containing inclusions are refined; and
    3. (c) a passivation film is modified by maintaining the Cu content in an appropriate range so as to suppress dissolution of base iron.


    [0018] In addition, the inventors of the present invention also investigated the mechanism in which the rough surface (different from the ridging) is generated at a bent part formed by performing a bending work on a ferritic stainless steel sheet. As a result, the relationship between the average grain diameter of ferrite crystal grains at a bent part and a rough-surface depth was discovered. That is, it was found that as the average grain diameter of ferrite crystal grains at a bent part is decreased, the rough-surface depth at the bent part is decreased.

    [0019] In addition, it was also found that when dislocation movement caused by a bending work is disturbed by dispersing fine NbC grains to generate work hardening at a bent part, the bent part is uniformly processed, and the degree of rough surface is reduced.

    [0020] The present invention was made based on the findings described above.

    [0021] In order to solve the aforementioned problems, the present invention provides a ferritic stainless cold-rolled steel sheet having the features defined in claim 1. A further preferred embodiment of the ferritic stainless steel is defined in claim 2. Moreover, a method for manufacturing a ferritic stainless cold-rolled steel sheet, said method has the features defined in claim 3. A further preferred embodiment of this method is defined in claim 4.

    [0022] The ferritic stainless steel sheet of the present invention is a ferritic stainless steel sheet in which in the composition described above, the Ni content is 0.3 mass percent or less, and the Nb content is 0.20 to 0.50 mass percent.

    [0023] In addition, the ferritic stainless steel sheet of the present invention is a ferritic stainless steel sheet in which in addition to the above composition, at least one selected from the group consisting of 0,005 to 0.5 mass percent of Ti, 0.5 mass percent or less of Zr, and 1.0 mass percent or less of Mo is contained.

    [0024] In addition, in the method for manufacturing a ferritic stainless steel sheet of the present invention, the finishing temperature is 700°C to 900°C, and the coiling is performed at a coiling temperature of 570°C or less.

    [0025] According to the present invention, a ferritic stainless steel sheet having a superior sulfate corrosion resistance even in a high-temperature atmosphere can be obtained.

    [0026] In addition, a ferritic stainless steel sheet can be obtained which has a low degree of rough surface at a bent part formed by a bending work performed at an angle of 90° or more as well as the characteristics described above.

    Brief Description of Drawings



    [0027] 

    [Fig. 1] Fig. 1 is a graph showing the relationship between the grain diameter of sulfur-containing inclusions and the solution probability of base iron.

    [Fig. 2] Fig. 2 is a schematic view showing a method for measuring a rough-surface depth at a bent part.


    Best Modes for Carrying Out the Invention



    [0028] First, the reasons for limiting components of a ferritic stainless steel sheet of the present invention will be described.

    C: 0.001 to 0.02 mass percent



    [0029] C is an element to increase the strength of a ferritic stainless steel sheet. In order to obtain the above effect, the content is 0.001 mass percent or more. However, when the C content is more than 0.02 mass percent, since a ferritic stainless steel sheet is hardened, the press formability is degraded, and in addition, since C binds to Nb and N, which will be described later, to precipitate a coarse Nb carbonitride, the sulfate corrosion resistance is degraded. Hence, the C content is set to 0.02 mass percent or less. More preferably, the content is 0.015 mass percent or less.

    [0030] In addition, in view of the degree of rough surface at a bent part, when the C content is less than 0.001 mass percent, precipitation of NbC grains which function as production nuclei of ferrite crystal grains is disturbed. On the other hand, when the C content is more than 0.02 mass percent, the formability and the corrosion resistance are not only degraded, but also NbC grains are coarsened. Hence, the C content is set in the range of 0.001 to 0.02 mass percent. More preferably, the content is 0.002 to 0.015 mass percent.

    Si: 0.05 to 0.8 mass percent



    [0031] Si is used as a deoxidizing agent in a steelmaking process for forming ferritic stainless steel. When the Si content is less than 0.05 mass percent, a sufficient deoxidizing effect cannot be obtained. Hence, a large amount of oxides is precipitated on a manufactured ferritic stainless steel sheet, and the weldability and the press formability are degraded. On the other hand, when the content is more than 0.8 mass percent, since a ferritic stainless steel sheet is hardened, the workability is degraded, and as a result, manufacturing of a ferritic stainless steel sheet may have some problems. Hence, the Si content is set in the range of 0.05 to 0.8 mass percent. More preferably, the content is 0.05 to 0.3 mass percent. Even more preferably, the content is 0.06 to 0.28 mass percent.

    Mn: 0.01 to 0.5 mass percent



    [0032] Mn is used as a deoxidizing agent in a steelmaking process for forming a ferritic stainless steel. In order to obtain the above effect, the content is 0.01 mass percent or more. When the Mn content is more than 0.5 mass percent, the workability of a ferritic stainless steel sheet is degraded by solid solution strengthening. In addition, Mn binds to S which will be described later to facilitate precipitation of MnS, and as a result, the sulfate corrosion resistance is degraded. Hence, the Mn content is set to 0.5 mass percent or less. More preferably, the content is 0.3 mass percent or less.

    P: 0.04 mass percent or less



    [0033] Although not responsible for the sulfate corrosion, P is an element to cause various types of corrosion, and hence the content thereof must be decreased. In particular, when the P content is more than 0.04 mass percent, besides the corrosion problem, due to segregation of P in crystal grain boundaries, the workability of a ferritic stainless steel sheet is degraded. As a result, manufacturing of a ferritic stainless steel sheet may have some problems. Hence, the P content is set to 0.04 mass percent or less. More preferably, the content is 0.03 mass percent or less.

    S : 0.0005 to 0.010 mass percent



    [0034] S is an element which binds to Mn or the like to generate sulfur-containing inclusions (such as MnS). Hence, a lower S content is more preferable; however, when the content is less than 0.0005 mass percent, desulfurization is difficult to be performed, and as a result, a manufacturing load is increased. Accordingly, the content is 0.0005 mass percent or more. When the sulfur-containing inclusions are in contact with sulfuric acid and are dissolved, hydrogen sulfide is generated, the pH locally decreases. A passivation film is not formed just under sulfur-containing inclusions precipitated on a surface of a ferritic stainless steel sheet, and even after the sulfur-containing inclusions are dissolved, no passivation film is formed since the pH is low. As a result, base iron is exposed to sulfuric acid, and the sulfate corrosion progresses. When the S content is more than 0.010 mass percent, a large amount of the sulfur-containing inclusions is precipitated, so that the sulfate corrosion apparently occurs. Hence, the S content is set to 0.010 mass percent or less. More preferably, the content is 0.008 mass percent or less.

    Al: 0.005 to 0.10 mass percent



    [0035] Al is used as a deoxidizing agent in a steelmaking process for forming a ferritic stainless steel. In addition, in the present invention, Al is added to precipitate N in steel in the form of AlN which is precipitated at a higher temperature than that at which a Nb carbonitride is precipitated, and thereby the N amount which binds to Nb is decreased, so that precipitation of a coarse Nb carbonitride is suppressed. Hence, Nb is precipitated in the form of fine NbC grains, and as a result, refining of ferrite crystal grains and suppression of coarsening of the sulfur-containing inclusions are effectively performed. In addition, since precipitated AlN grains are very fine, dislocation movement in a bending work is disturbed, and the work hardening of steel is facilitated, so that uniform deformation of a bent part can be effectively performed. In order to obtain the above effect, the content is 0.005 mass percent or more. However, when the Al content is more than 0.10 mass percent, since Al-based non-metal inclusions are increased, surface defects, such as surface scratches, of a ferritic stainless steel sheet are caused thereby, and the workability is also degraded. Accordingly, the A1 content is set to 0.10 mass percent or less. More preferably, the content is 0.08 mass percent or less.

    Cr : 20.5 to 23 mass percent



    [0036] Cr is an element to improve the sulfate corrosion resistance of a ferritic stainless steel sheet. When the Cr content is less than 20 mass percent, a sufficient sulfate corrosion resistance cannot be obtained. On the other hand, when the content is more than 2 4 mass percent, a σ phase is liable to be generated, and the press formability of a ferritic stainless steel sheet is degraded. Hence, the Cr content is set in the range of 20.5 to 23.0 mass percent.

    Cu : 0.3 to 0.8 mass percent



    [0037] After the sulfate corrosion occurs in a ferritic stainless steel sheet, Cu has a function to suppress the dissolution of base iron caused by an anode reaction. In addition, Cu also has a function to modify a passivation film present around each sulfur-containing inclusion. According to the study carried out by the inventors of the present invention, Cu present in the vicinity of sulfur-containing inclusions generates distortion in a crystal lattice of base iron. A passivation film formed on a distorted crystal lattice becomes denser than a passivation film formed on a normal crystal lattice. When the passivation film is modified as described above, the sulfate corrosion resistance of a ferritic stainless steel sheet is improved. When the Cu content is less than 0.3 mass percent, the above effect cannot be obtained. On the other hand, when the content is more than 0.8 mass percent, Cu is corroded by sulfuric acid, and from the corroded Cu, the sulfate corrosion of a ferritic stainless steel sheet progresses. In addition, since hot workability is degraded, manufacturing of a ferritic stainless steel sheet may have some problems. Hence, the Cu content is set in the range of 0.3 to 0.8 mass percent. More preferably, the content is 0.3 to 0.6 mass percent.

    Ni: 0.05 to 0.5 mass percent



    [0038] Ni has a function to suppress an anode reaction caused by sulfuric acid and to maintain a passivation film even when the pH decreases. In order to obtained the above effect, the content is 0.05 mass percent or more. However, when the Ni content is more than 0.5 mass percent, a ferritic stainless steel sheet is hardened, and the press formability is degraded. Hence, the Ni content is set to 0.5 mass percent or less. More preferably, the content is 0.3 mass percent or less. Even more preferably, the content is 0.2 mass percent or less.

    Nb: 0.20 to 0.55 mass percent



    [0039] Nb fixes C and N and has a function to prevent sensitization to corrosion by a Cr carbonitride. In addition, Nb also has a function to improve resistance to oxidation at a high temperature of a ferritic stainless steel sheet. According to the present invention, besides the effects described above, Nb is an important element that refines ferrite crystal grains by dispersing fine inclusions (that is, NbC). NbC grains function as product nuclei of recrystallization grains when a cold-rolled ferritic stainless steel sheet is annealed. Hence, when NbC grains are dispersed and precipitated, fine ferrite crystal grains are generated. Furthermore, NbC disturbs movement of grain boundaries in a generation process of ferrite crystal grains and disturbs the growth thereof, and hence an effect of maintaining fine ferrite crystal grains can be obtained. That is, when fine NbC grains are dispersed, refining of ferrite crystal grains can be achieved. In addition, fine NbC grains dispersed in and precipitated on a ferritic stainless steel sheet disturbs dislocation movement caused by a bending work and causes work hardening at a bent part. As a result, since deformation by a bending work is sequentially moved to a region having a small deformation resistance, the bent part is uniformly processed, and the degree of rough surface is reduced. In addition, according to the study carried out by the inventors of the present invention, when fine NbC grains are dispersed and precipitated, sulfur-containing inclusions adhere thereto and are precipitated, and the grain diameter thereof is decreased. Even when a sulfur-containing inclusion having a decreased grain diameter is dissolved in sulfuric acid, since the pH is suppressed from decreasing, a solution therearound can maintain a lower limit pH or more at which stainless steel can form a passivation film, and as a result, stainless steel just below the sulfur-containing inclusion can be re-passivated immediately after the sulfur-containing inclusion is dissolved. Hence, dissolution of the S-containing inclusion does not initiate the corrosion, and hence the sulfate corrosion resistance is improved. When the Nb content is less than 0.20 mass percent, the above effect cannot be obtained. On the other hand, when the content is more than 0.55 mass percent, NbC grains are coarsened, and ferrite crystal grains and sulfur-containing inclusions are both coarsened. Hence, the Nb content is set in the range of 0.20 to 0.55 mass percent. More preferably, the content is 0.20 to 0.5 mass percent. Even more preferably, the content is 0.25 to 0.45 mass percent.

    N: 0.001 to 0.02 mass percent



    [0040] N is solid-solved in a ferritic stainless steel sheet and has a function to improve the sulfate corrosion resistance. In order to obtain the above effect, the content is 0.001 mass percent or more. However, when the content is excessive, as in the case of C, since precipitation of a coarse Nb carbonitride is facilitated, the sulfate corrosion resistance of a ferritic stainless steel sheet is degraded, and in addition, the degree of rough surface at a bent part is degraded. In particular, when the N content is more than 0.02 mass percent, besides the sulfate corrosion problem, the press formability of a ferritic stainless steel sheet is also degraded. Hence, the N content is set to 0.02 mass percent or less. More preferably, the content is 0.015 mass percent or less.

    [0041] Furthermore, in the ferritic stainless steel sheet of the present invention, at least one selected from the group consisting of Ti, Zr, and Mo is preferably contained.

    Ti: 0.005 to 0.5 mass percent



    [0042] Since Ti binds to C and N to form a Ti carbonitride, C and N are fixed, and hence, Ti has a function to prevent sensitization to corrosion caused by a Cr carbonitride. Hence, by addition of Ti, the sulfate corrosion resistance can be further improved. When the Ti content is less than 0.005 mass percent, the above effect cannot be obtained. On the other hand, when the content is more than 0.5 mass percent, a ferritic stainless steel sheet is hardened, so that the press formability is degraded. Hence, when Ti is added, the Ti content is in the range of 0.005 to 0.5 mass percent. More preferably, the content is 0.1 to 0.4 mass percent.

    Zr: 0.5 mass percent or less



    [0043] As in the case of Ti, since Zr binds to C and N to form a Zr carbonitride, C and N are fixed, and hence, Zr has a function to prevent sensitization to corrosion caused by a Cr carbonitride. In order to obtain the above effect, the content is preferably 0.01 mass percent or more. Hence, by addition of Zr, the sulfate corrosion resistance can be further improved. However, when the Zr content is more than 0.5 mass percent, a large amount of Zr oxides (that is, ZrO2 and the like) is generated, surface cleanness of a ferritic stainless steel sheet is degraded. Hence, when Zr is added, the Zr content is 0.5 mass percent or less. More preferably, the content is 0.4 mass percent or less.

    Mo: 1.0 mass percent or less



    [0044] Mo has a function to improve the sulfate corrosion resistance. In order to obtain the above effect, the content is preferably 0.1 mass percent or more. However, when the Mo content is more than 1.0 mass percent, the effect is saturated. That is, even when more than 1.0 mass percent of Mo is added, improvement in sulfate corrosion resistance corresponding to the addition amount cannot be expected, and on the other hand, since a large amount of expensive Mo is used, a manufacturing cost of a ferritic stainless steel sheet is increased. Hence, when Mo is added, the Mo content is 1.0 mass percent or less. More preferably, the content is 0.8 mass percent or less.

    [0045] In addition, since Mg has no contribution in the present invention, a lower content is more preferable, and the content is preferably equivalent to or less than that of inevitable impurities.

    [0046] The balance other than those components described above contains Fe and inevitable impurities.

    [0047] Next, the structure of the ferritic stainless steel sheet of the present invention will be described.

    Maximum grain diameter of sulfur-containing inclusions: 5 µm or less



    [0048] The inventors of the present invention manufactured ferritic stainless steel sheets having various components and investigated the relationship between the size of sulfur-containing inclusions and the progression of the sulfate corrosion. The investigation method and the investigation results will be described.

    [0049] After ferritic stainless steel having components shown in Table 1 was formed by melting and was further formed into a slab, hot rolling (finishing temperature: 800°C, coiling temperature: 450°C, and sheet thickness: 4 mm) was performed by heating to 1,170°C, so that a hot-rolled steel sheet was formed. An average cooling rate from finish rolling to coiling (that is, from 800°C to 450°C) was set to 20°C/sec.

    [0050] The hot-rolled steel sheet thus obtained was annealed at 900°C to 1,200°C for 30 to 300 seconds and was further processed by pickling. Next, after cold rolling was performed, annealing was performed at 970°C for 30 to 300 seconds and was further processed by pickling, so that a ferritic stainless steel sheet (sheet thickness: 0.8 mm) was formed.

    [0051] A test piece (width: 30 mm, and length: 50 mm) was cut out of the ferritic stainless steel sheet thus obtained, and two surfaces of the test piece were polished with #600 abrasive paper and were then observed using a scanning electron microscope (so-called SEM). The grain diameter of a Nb carbonitride was approximately several micrometers, and the grain diameter of a Nb carbide was approximately 1 µm. In addition, it was confirmed that sulfur-containing inclusions (such as MnS) adhere to peripheries of the Nb carbonitride and the Nb carbide and are precipitated. The grain diameters of all sulfur-containing inclusions in one arbitrary viewing field having a size of 10 mm square were measured. The grain diameter was defined as the maximum length of the longitudinal axis. The grain diameter of the maximum sulfur-containing inclusion among those thus measured was regarded as the maximum grain diameter.

    [0052] Subsequently, after the test piece was immersed in sulfuric acid (concentration: 10 mass percent, and temperature: 50°C) for 1 hour, the surface of the test piece was observed by a SEM. The Nb carbonitride and the Nb carbide observed before the immersion were dissolved together with the sulfur-containing inclusions, and at the positions thereof, dimples which were supposed to be formed by dissolution of base iron were generated. Although some inclusions remained on the test piece, S was not detected from the inclusions.

    [0053] As described above, the relationship between the grain diameter of the sulfur-containing inclusions before the immersion in sulfuric acid and the solution probability of base iron by the immersion was investigated. The results are shown in Fig. 1. In this case, the solubility probability is a value (=100×M/N) obtained by dividing a number M by a total number N of inclusions having a predetermined size before the immersion, the number M being the number of base-iron dissolution points which are confirmed at places at which the inclusions having a predetermined size are present before the immersion.

    [0054] As apparent from Fig. 1, when the maximum grain diameter of the sulfur-containing inclusions is 5 µm or less, the solution probability of the base iron is considerably decreased. This phenomenon indicates that when the maximum grain diameter of the sulfur-containing inclusions is 5 µm or less, the sulfate corrosion can be prevented. Hence, the maximum grain diameter of the sulfur-containing inclusions is set to 5 µm or less.

    [0055] Next, the structure of the ferritic stainless steel sheet which has a low degree of rough surface at a bent part formed by a bending work will be described.

    Average grain diameter of ferrite crystal grains: 30.0 µm or less



    [0056] A rough-surface depth at a bent part formed by a bending work has the relationship with the average grain diameter of ferrite crystal grains. Since ferrite crystal grains are each formed to have a pancake like shape when receiving a tensile stress by a bending work, spaces are generated between adjacent ferrite crystal grains, so that the rough surface is generated. When a bending work is performed to a predetermined level, the ratio of the major axis of a deformed pancake like ferrite crystal grain to the minor axis thereof is constant regardless of the size of ferrite crystal grains having an approximately spherical shape before a bending work is performed. The rough-surface depth is proportional to the minor axis of a ferrite crystal grain having a pancake like shape, and this minor axis is proportional to the size of the ferrite crystal grain before a bending work is performed. That is, as the average grain diameter of ferrite crystal grains is decreased, the rough-surface depth is decreased. According to the study carried out by the inventors of the present invention, when the average grain diameter of ferrite crystal grains is 30.0 µm or less, even if a bending work is performed at an angle of 90° or more, the degree of rough surface at a bent part can be reduced to a level at which no problems may occur. Hence, the average grain diameter of ferrite crystal grains is set to 30.0 µm or less. More preferably, the average grain diameter is 20.0 µm or less. By the way, the average grain diameter was obtained in accordance with ASTM E 112, and after the grain diameters of ferrite crystal grains in three arbitrary viewing fields were measured by an intercept method, the average value of the grain diameters was calculated.

    Maximum grain diameter of NbC grains: 1 µm or less



    [0057] As described above, when fine NbC grains are dispersed in a ferritic stainless steel sheet, since recrystallization of ferrite crystal grains is facilitated, and the growth thereof is disturbed, the ferrite crystal grains can be refined. According to the study carried out by the inventors of the present invention, when the maximum grain diameter of precipitated NbC grains is more than 1 µm, the above effect cannot be obtained. In addition, when NbC grains are coarsened, a stress is concentrated by a bending work, and as a result, local deformation is liable to occur. Accordingly, the maximum grain diameter of NbC grains is set to 1 µm or less. The grain diameter of the largest one among NbC inclusions observed in one arbitrary viewing field having a size of 10 mm square was measured. The maximum length of the long axis was regarded as the maximum grain diameter.

    [0058] Hereinafter, one example of a method for manufacturing the ferritic stainless steel sheet of the present invention will be described.

    [0059] After a ferritic stainless steel having predetermined components is formed by melting and is further formed into a slab, hot rolling (finishing temperature: 700°C to 950°C, more preferably 900°C or less, and even more preferably 770°C or less; coiling temperature: 600°C or less, preferably 570°C or less, and even more preferably 450°C or less; and sheet thickness: 2.5 to 6 mm) is performed by heating to 1,100°C to 1,200°C, so that a hot-rolled steel sheet is obtained. In order to prevent sulfur-containing inclusions and ferrite crystal grains from being coarsened from finish rolling to coiling, cooling from the finishing temperature to the coiling temperature is performed at an average cooling rate of 20°C/sec or more.

    [0060] A cooling rate after the coiling is not particularly limited. However, since the toughness of the hot-rolled steel sheet is degraded at approximately 475°C (so-called 475°C brittleness), the average cooling rate in a temperature range of 525°C to 425°C is preferably 100°C/hour or more.

    [0061] Next, the hot-rolled steel sheet is annealed at 900°C to 1,200°C and more preferably at 900°C to 1,100°C for 30 to 240 seconds and is further processed by pickling. Furthermore, after cold rolling (preferably at a draft of 50% or more) is performed, annealing and pickling are performed to form a ferritic stainless steel sheet. In order to prevent the sulfur-containing inclusions from being coarsened, annealing after the cold rolling is performed at less than 1,050°C and preferably at less than 900°C for 10 to 240 seconds. When the annealing temperature is 900°C or more, a time at a heating temperature of 900°C or more is preferably set to 1 minute or less.

    [0062] The above-described ferritic stainless steel sheet of the present invention has a superior sulfate corrosion resistance even in a high-temperature atmosphere because of the synergetic effect of the intrinsic characteristics of ferritic stainless steel, that is, superior corrosion resistance in a high-temperature atmosphere, and the intrinsic characteristics according to the present invention, which are disclosed in the above (a) to (c). Furthermore, since the ferrite crystal grains are fine, even when a bending work is performed at an angle of 90° or more, the space between adjacent ferrite crystal grains is decreased to a level at which no problems may occur; hence, the degree of rough surface is reduced.

    Example 1



    [0063] After ferritic stainless steel having components shown in Table 1 was formed by melting and was further formed into a slab, hot rolling (finishing temperature: 800°C, coiling temperature: 450°C, and sheet thickness: 4 mm) was performed by heating to 1,170°C, so that a hot-rolled steel sheet was formed. An average cooling rate from finish rolling to coiling (that is, from 800°C to 450°C) was set to 20°C/sec.

    [0064] The hot-rolled steel sheet thus obtained was annealed at 900°C to 1,200°C for 30 to 300 seconds and was further processed by pickling. Next, after cold rolling was performed, annealing was performed at 970°C for 30 to 300 seconds and was further processed by pickling, so that a ferritic stainless steel sheet (sheet thickness: 0.8 mm) was obtained.

    [0065] The ferritic stainless steel sheet thus obtained was cut into a sheet having a width of 30 mm and a length of 50 mm, and two surfaces of this sheet was polished with #600 abrasive paper, so that a test piece was prepared. This test piece was observed using a scanning electron microscope (so-called SEM), and grain diameters of all sulfur-containing inclusions present in one arbitrary viewing field having a size of 10 mm square were measured. The maximum length of the long axis was regarded as the grain diameter. The grain diameter of the largest one among the measured sulfur-containing inclusions was regarded as the maximum grain diameter. The results are shown in Table 2. Furthermore, the mass of the test piece was measured.

    [0066] Next, after the test piece was immersed in sulfuric acid (concentration: 10 mass percent, and temperature: 50°C) for 48 hours, the mass of the test piece was measured, so that the sulfate corrosion resistance was investigated. For the sulfate corrosion resistance, the change in mass of the test piece before and after the immersion was calculated. When the change in mass of the test piece with respect to the mass thereof before the immersion was less than 10%, it was evaluated as Good (O) , and when the change in mass was 10% or more, it was evaluated as No good (×). The results are shown in Table 2.

    [0067] A1 to A4 shown in Table 2 are examples in which the Cu content was changed. According to A2 and A3 which were within the range of the present invention, a superior sulfate corrosion resistance was obtained. B1 to B4 shown in Table 2 are examples in which the S content was changed. According to B2 to B3 which were within the range of the present invention, a superior sulfate corrosion resistance was obtained. C1 to C5 shown in Table 2 are examples in which the Nb content was changed. According to C2 to C4 which were within the range of the present invention, a superior sulfate corrosion resistance was obtained. D1 to D4 shown in Table 2 are examples in which the maximum grain diameter of the sulfur-containing inclusions was changed. According to D1 and D2 which were within the range of the present invention, a superior sulfate corrosion resistance was obtained. E1 to E7 shown in Table 2 are examples in which at least one of Ti, Zr, and Mo was further added as an additional element. According to E1 to E3 which were within the range of the present invention, a superior sulfate corrosion resistance was obtained.

    [0068] On the other hand, A1 and A4 shown in Table 2 are comparative examples in which the Cu content was out of the range of the present invention. B4 is a comparative example in which the S content was out of the range of the present invention. C1 and C5 are comparative examples in which the Nb content was out of the range of the present invention. D3 and D4 are comparative examples in which the maximum grain diameter of the sulfur-containing inclusions was out of the range of the present invention. In addition, E8 to E10 are comparative examples in which the content of at least one of Al, Cr, Nb, and N was out of the range of the present invention. According to the comparative examples which were out of the range of the present invention, a superior sulfate corrosion resistance could not be obtained.

    Example (Reference example)



    [0069] In addition to the confirmation of the effect on the sulfate corrosion resistance, the effect on the degree of rough surface at a bent part formed by a bending work performed at an angle of 90° or more was further confirmed.

    [0070] After ferritic stainless steel having components shown in Table 3 was formed by melting and was then processed by continuous casting, hot rolling of an obtained slab was performed by heating to 1,170°C. The finishing temperature and the coiling temperature are shown in Table 4. Among slabs of Nos. 1 to 29 shown in Table 3, No. 1 and No. 5 are examples in which the Nb content was out of the range of the present invention; No. 13 is an example in which the Cu content was out of the range of the present invention; No. 28 is an example in which the C content was out of the range of the present invention.

    [0071] Obtained hot-rolled steel sheets were cooled from the finishing temperature to the coiling temperature of the hot rolling at an average cooling rate of 25°C/sec. The hot-rolled steel sheets were annealed at 900°C to 1,100°C (however, only No. 9 was annealed at 1,150°C) and were further processed by pickling to remove scale. Next, after cold rolling was performed, annealing (heating temperature: 970°C, and heating time: 90 seconds) and pickling were further performed, so that ferritic stainless steel sheets (sheet thickness: 0.8 mm) were obtained. The finishing temperature of the hot rolling, the coiling temperature thereof, and the draft of the cold rolling are shown in Table 4. Nos. 9, 17, 21, 25, and 29 are examples in which at least one of the finishing temperature of the hot rolling, the coiling temperature thereof, the annealing temperature for the hot-rolled steel sheet, and the draft of the cold rolling was out of the range of the present invention.

    [0072] After an arbitrary cross section of the ferritic stainless steel sheet was etched with diluted aqua regia, grain diameters of ferrite crystal grains in 3 arbitrary viewing fields were measured by an intercept method in accordance with ASTM E 112, and the average value of the grain diameters was calculated. The results are shown in Table 4.

    [0073] In addition, an arbitrary cross section of the ferritic stainless steel sheet was observed by a scanning electron microscope (so-called SEM), and the maximum grain diameter of precipitated NbC grains was measured. Among NbC inclusions in one arbitrary viewing field having a size of 10 mm square, the grain diameter of the largest one was measured. The maximum long axis length was regarded as the maximum grain diameter. The results are shown in Table 4.

    [0074] Furthermore, after a sample having a width of 20 mm and a length of 70 mm was cut out of the ferritic stainless steel sheet, two surfaces of the sample were polished with #600 abrasive paper, and a bending work was then performed. The bending work was performed in such a way that the sample was bent at angle of 180° by pressing a central portion thereof with a punch having a radius of 10 mm.

    [0075] After the bending work was performed, the cross section of the bent part in 3 arbitrary viewing fields was observed, and the rough-surface depth was measured. A method for measuring the rough-surface depth is shown in Fig. 2. After the cross section of the bent part was enlarged at a magnification of 1,000 using an optical microscope, a photograph of the cross section was taken, and as shown in Fig. 2, the largest difference between adjacent convex and concave portions of the rough surface on the cross section of the observed bent part was regarded as the rough-surface depth. A rough-surface depth of 30 µm or less was evaluated as Good (O), and a rough-surface depth of more than 30 µm was evaluated as No good (×). The results are shown in Table 4.

    [0076] Steels No 2-3, 7-8, 10, 14-16, 18-20, 22-24, 27 are reference examples. Steels No 1, 5-6, 9, 11-13, 17, 21, 25-26, 28-29 are Comparative examples.

    [0077] As apparent from Table 4, according to the reference examples, the rough-surface depths were all 30 µm or less; however, according to comparative examples, 1, 5, 9, 13, 17, 21, 25, 28 and 29 the depths were more than 30 µm.

    [0078] In addition, although not described here, the effect on the sulfate corrosion resistance was also confirmed, and similar effect to that of Example 1 was also confirmed.
    TABLE 1
     COMPOSITION (mass percent)REMARKS
    CSiMnPSAlCrNiCuNbNOTHER ELEMENTS
    A1 0.011 0.11 0.17 0.032 0.002 0.028 20.6 0.28 0.23 0.24 0.010 - COMPARATIVE EXAMPLE
    A2 0.008 0.12 0.16 0.030 0.004 0.024 21.0 0.22 0.33 0.27 0.010 - INVENTION EXAMPLE
    A3 0.008 0.13 0.17 0.031 0.004 0.024 21.4 0.23 0.55 0.27 0.011 - INVENTION EXAMPLE
    A4 0.009 0.14 0.16 0.032 0.007 0.026 21.8 0.29 0.85 0.24 0.012 - COMPARATIVE EXAMPLE
    B1 0.007 0.14 0.18 0.022 0.001 0.029 20.3 0.27 0.42 0.42 0.010 - COMPARATIVE EXAMPLE
    B2 0.007 0.14 0.19 0.020 0.005 0.028 20.5 0.25 0.43 0.38 0.009 - INVENTION EXAMPLE
    B3 0.008 0.15 0.18 0.022 0.008 0.029 20.8 0.25 0.45 0.38 0.009 - INVENTION EXAMPLE
    B4 0.007 0.16 0.18 0.027 0.014 0.029 20.4 0.27 0.43 0.40 0.009 - COMPARATIVE EXAMPLE
    C1 0.008 0.13 0.17 0.031 0.004 0.033 22.4 0.28 0.23 0.16 0.011 - COMPARATIVE EXAMPLE
    C2 0.010 0.12 0.18 0.030 0.008 0.052 22.5 0.27 0.35 0.27 0.014 - INVENTION EXAMPLE
    C3 0.009 0.14 0.16 0.032 0.007 0.049 22.7 0.29 0.33 0.35 0.012 - INVENTION EXAMPLE
    C4 0.009 0.14 0.15 0.032 0.007 0.035 22.7 0.29 0.30 0.46 0.012 - INVENTION EXAMPLE
    C5 0.010 0.12 0.18 0.030 0.008 0.044 22.5 0.26 0.29 0.58 0.014 - COMPARATIVE EXAMPLE
    D1 0.012 0.24 0.28 0.028 0.008 0.025 20.8 0.28 0.32 0.39 0.013 - INVENTION EXAMPLE
    D2 0.011 0.25 0.25 0.027 0.008 0.016 21.0 0.29 0.57 0.41 0.015 - INVENTION EXAMPLE
    D3 0.009 0.24 0.28 0.028 0.009 0.022 20.9 0.28 0.46 0.40 0.008 - COMPARATIVE EXAMPLE
    D4 0.011 0.25 0.24 0.029 0.009 0.021 21.1 0.28 0.45 0.39 0.010 - COMPARATIVE EXAMPLE
    E1 0.011 0.16 0.17 0.029 0.002 0.021 22.1 0.22 0.48 0.25 0.010 Ti:0.08 INVENTION EXAMPLE
    E2 0.016 0.18 0.16 0.030 0.003 0.083 22.2 0.24 0.47 0.28 0.019 Zr:0.03 INVENTION EXAMPLE
    E3 0.014 0.22 0.17 0.030 0.004 0.072 20.8 0.20 0.33 0.33 0.016 Mo:0.14 INVENTION EXAMPLE
    E4 0.011 0.16 0.15 0.029 0.002 0.046 20.1 0.29 0.45 0.27 0.013 Ti:0.23, Zr:0.37 COMPARATIVE EXAMPLE
    E5 0.017 0.18 0.16 0.032 0.001 0.053 23.2 0.27 0.42 0.28 0.014 Zr:0.11, Mo:0.27 COMPARATIVE EXAMPLE
    E6 0.015 0,20 0.17 0.031 0.005 0.022 23.8 0.25 0.38 0.22 0.011 Ti:0.02, Mo:0.71 COMPARATIVE EXAMPLE
    E7 0.018 0.54 0.18 0.029 0.001 0.022 23.7 0.28 0.32 0.23 0.012 Ti:0.10, Zr:0.05, Mo:0.13 COMPARATIVE EXAMPLE
    E8 0.032 0.17 0.16 0.030 0.002 0.023 24.3 0.31 0.55 0.27 0.044 - COMPARATIVE EXAMPLE
    E9 0.008 0.13 0.17 0.031 0.001 0.122 19.0 0.33 0.55 0.27 0.011 - COMPARATIVE EXAMPLE
    E10 0.010 0.12 0.32 0.030 0.015 0.038 24.5 0.32 0.72 0.53 0.014 - COMPARATIVE EXAMPLE
    TABLE 2
     MAXIMUM DIAMETER OF S-CONTAINING INCLUSIONS (µm)CORROSION RESISTANCE IN SULFURIC ACID*1REMARKS
    A1 1.6 × COMPARATIVE EXAMPLE
    A2 2.7 INVENTION EXAMPLE
    A3 2.5 INVENTION EXAMPLE
    A4 3.2 × COMPARATIVE EXAMPLE
    B1 2.5 COMPARATIVE EXAMPLE
    B2 3.1 INVENTION EXAMPLE
    B3 3.3 INVENTION EXAMPLE
    B4 4.9 × COMPARATIVE EXAMPLE
    C1 4.3 × COMPARATIVE EXAMPLE
    C2 2.4 INVENTION EXAMPLE
    C3 2.7 INVENTION EXAMPLE
    C4 3.1 INVENTION EXAMPLE
    C5 4.8 × COMPARATIVE EXAMPLE
    D1 2.3 INVENTION EXAMPLE
    D2 4.4 INVENTION EXAMPLE
    D3 7.5 × COMPARATIVE EXAMPLE
    D4 9.2 × COMPARATIVE EXAMPLE
    E1 1.5 INVENTION EXAMPLE
    E2 1.4 INVENTION EXAMPLE
    E3 1.8 INVENTION EXAMPLE
    E4 1.9 COMPARATIVE EXAMPLE
    E5 1.8 COMPARATIVE EXAMPLE
    E6 2.2 COMPARATIVE EXAMPLE
    E7 0.7 COMPARATIVE EXAMPLE
    E8 4.9 × COMPARATIVE EXAMPLE
    E9 3.6 × COMPARATIVE EXAMPLE
    E10 10.3 × COMPARATIVE EXAMPLE
    *1: A dissolved amount of less than 10% is represented by ○, and a dissolved amount of 10% or more is represented by ×.
    TABLE 3
    NO.COMPOSITION (MASS PERCENT)
    CSiMnPSAlCrNiCuNbN
    1 0.011 0.18 0.18 0.027 0.008 0.016 22.0 0.29 0.57 0.17 0.015
    2 0.009 0.13 0.17 0.031 0.005 0.025 21.5 0.30 0.48 0.28 0.011
    3 0.012 0.18 0.18 0.029 0.001 0.021 20.7 0.28 0.32 0.44 0.010
    4 0.014 0.18 0.16 0.032 0.003 0.031 21.2 0.31 0.47 0.52 0.014
    5 0.011 0.16 0.17 0.029 0.009 0.021 23.1 0.28 0.45 0.59 0.010
    6 0.011 0.16 0.17 0.029 0.002 0.021 23.1 0.28 0.45 0.38 0.010
    7 0.007 0.16 0.18 0.033 0.008 0.029 22.3 0.27 0.43 0.37 0.009
    8 0.007 0.14 0.19 0.031 0.005 0.028 22.5 0.25 0.43 0.39 0.009
    9 0.011 0.18 0.18 0.027 0.008 0.016 22.0 0.29 0.57 0.38 0.014
    10 0.008 0.13 0.17 0.031 0.004 0.024 21.4 0.33   0.52 0.011
    11 0.012 0.19 0.16 0.028 0.008 0.025 23.8 0.33 0.32 0.53 0.013
    12 0.011 0.22 0.17 0.031 0.005 0.022 23.8 0.30 0.33 0.49 0.011
    13 0.011 0.11 0.17 0.032 0.002 0.028 20.6 0.28 0.23 0.51 0.013
    14 0.007 0.16 0.18 0.033 0.009 0.029 22.3 0.27 0.43 0.35 0.009
    15
    16
    17
    18 0.008 0.12 0.16 0.030 0.004 0.024 21.0 0.31 0.33 0.35 0.010
    19
    20
    21
    22 0.007 0.14 0.18 0.031 0.001 0.029 22.3 0.27 0.42 0.36 0.010
    23
    24
    25
    26 0.009 0.14 0.16 0.032 0.007 0.026 23.7 0.29 0.72 0.38 0.012
    27 0.009 0.15 0.16 0.032 0.003 0.027 21.2 0.30 0.41 0.52 0.011
    28 0.032 0.17 0.16 0.030 0.002 0.023 23.3 0.31   0.18 0.044
    29 0.012 0.19 0.16 0.028 0.008 0.025 23.8 0.33 0.32 0.28 0.013
    TABLE 4
    NO.AVERAGE FERRITE GRAIN DIAMETER (µm)MAXIMUM GRAIN DIAMETER OF NbC (µm)FINISHING TEMPERATURE (°C)COILING TEMPERATURE (°C)DRAFR OF COLD ROLLING (%)EVALUATION OF ROUGH SURFACE AT BENT PART *1
    1 17.9 0.25 740 432 75 ×
    2 18.2 0.28 743 430 76
    3 18.3 0.33 736 430 75
    4 19.4 0.35 737 431 75
    5 18.7 0.38 745 435 75 ×
    6 15.4 0.46 752 434 75
    7 18.7 0.48 751 435 76
    8 23.3 0.47 752 432 75
    9 32.2 0.48 753 432 74 ×
    10 18.4 0.45 760 432 75
    11 17.2 0.71 762 431 75
    12 18.4 0.88 765 433 74
    13 17.9 1.21 763 434 75 ×
    14 14.3 0.36 745 433 75
    15 20.2 0.63 752 432 75
    16 25.4 0.84 764 435 74
    17 31.0 1.08 782 436 75 ×
    18 18.3 0.44 758 407 75
    19 21.7 0.43 759 422 74
    20 24.5 0.45 760 446 76
    21 31.8 0.44 758 467 75 ×
    22 16.8 0.32 752 435 85
    23 19.4 0.38 753 435 74
    24 24.7 0.34 752 432 62
    25 30.2 0.36 751 433 48 ×
    26 15.3 0.33 752 438 80
    27 24.4 0.47 753 440 81
    28 34.3 1.55 753 433 88 ×
    29 32.5 1.43 852 512 81 ×
    *1: A rough-surface depth at a bent art of 30 µm or less is represented by ○, and a rough-surface depth of morehan 30 µm is represented by ×.



    Claims

    1. A ferritic stainless cold rolled steel sheet consisting of:

    0.001 to 0.02 mass percent of C, 0.05 to 0.8 mass percent of Si, 0.01 to 0.5 mass percent of Mn, 0.04 mass percent of P, 0.0005 to 0.010 mass percent of S, 0.005 to 0.10 mass percent of Al, 20.5 to 23 mass percent of Cr, 0.3 to 0.8 mass percent of Cu, 0.05 to 0.5 mass percent of Ni, 0.20 to 0.55 mass percent of Nb, 0.001 to 0.02 mass percent of N; optionally at least one selected from the group consisting of 0.005 to 0.5 mass percent of Ti, 0.5 mass percent or less of Zr, and 1.0 mass percent or less of Mo; and the balance being Fe and inevitable impurities;

    and having a structure in which the S-containing inclusions have a maximum grain diameter of 5 µm or less.


     
    2. The ferritic stainless cold rolled steel sheet according to Claim 1, wherein in the composition, the Ni content is 0.3 mass percent or less, and the Nb content is 0.20 to 0.5 mass percent.
     
    3. A method for manufacturing a ferritic stainless cold rolled steel sheet comprising:

    a) heating a slab or an ingot to a temperature in the range of 1100 °C and 1200 °C,

    b) performing hot rolling of a slab or an ingot which consists of 0.001 to 0.02 mass percent of C, 0.05 to 0.8 mass percent of Si, 0.01 to 0.5 mass percent of Mn, 0.04 mass percent or less of P, 0.0005 to 0.010 mass percent of S, 0.005 to 0.10 mass percent of Al, 20.5 to 23 mass percent of Cr, 0.3 to 0.8 mass percent of Cu, 0.05 to 0.5 mass percent of Ni, 0.20 to 0.55 mass percent of Nb, 0.001 to 0.02 mass percent of N,
    optionally at least one selected from the group consisting of 0.005 to 0.5 mass percent of Ti, 0.5 mass percent or less of Zr, and 1.0 mass percent or less of Mo;
    and the balance being Fe and inevitable impurities at a finishing temperature of 700°C to 950°C,

    c) performing cooling at an average cooling rate of 20°C/sec or more from the finishing temperature to a coiling temperature,

    d) performing coiling at a coiling temperature of 600°C or less,

    e) performing annealing at 900°C to 1200°C for 30 to 240 seconds and thereafter performing first pickling,

    f) performing cold rolling after the first pickling,

    g) performing annealing after cold rolling at less than 1050 °C for 10 to 240 seconds and further performing pickling.


     
    4. The method for manufacturing a ferritic stainless cold rolled steel sheet according to Claim 3, wherein the finishing temperature is 700°C to 900°C, and the coiling is performed at a coiling temperature of 570°C or less.
     


    Ansprüche

    1. Ferritisches, rostfreies kaltgewalztes Stahlblech, das aus

    0,001 bis 0,02 Masse-% C, 0,05 bis 0,8 Masse-% Si, 0,01 bis 0,5 Masse-% Mn, 0,04 Masse-% P, 0,0005 bis 0,010 Masse-% S, 0,005 bis 0,10 Masse-% Al, 20,5 bis 23 Masse-% Cr, 0,3 bis 0,8 Masse-% Cu, 0,05 bis 0,5 Masse-% Ni, 0,20 bis 0,55 Masse-% Nb, 0,001 bis 0,02 Masse-% N; optional wenigstens einem Bestandteil besteht, der aus der Gruppe ausgewählt wird, die aus 0,005 bis 0,5 Masse-% Ti, 0,5 Masse-% oder weniger Zr sowie 1,0 Masse-% oder weniger Mo besteht; wobei der Rest Fe und unvermeidliche Verunreinigungen sind;

    und das eine Struktur hat, in der die S-haltigen Einschlüsse einen maximalen Korndurchmesser von 5 µm oder weniger haben.


     
    2. Ferritisches, rostfreies kaltgewalztes Stahlblech nach Anspruch 1, wobei in der Zusammensetzung der Ni-Gehalt 0,3 Masse-% oder weniger beträgt und der Nb-Gehalt 0,20 bis 0,5 Masse-% beträgt.
     
    3. Verfahren zum Herstellen eines ferritischen, rostfreien kaltgewalzten Stahlblechs, umfassend:

    a) Erhitzen einer Bramme oder eines Blocks auf eine Temperatur im Bereich von 1100 °C und 1200 °C,

    b) Durchführen von Warmwalzen einer Bramme oder eines Blocks, die/der aus 0,001 bis 0,02 Masse-% C, 0,05 bis 0,8 Masse-% Si, 0,01 bis 0,5 Masse-% Mn, 0,04 Masse-% oder weniger P, 0,0005 bis 0.010 Masse-% S, 0,005 bis 0,10 Masse-% Al, 20,5 bis 23 Masse-% Cr, 0,3 bis 0,8 Masse-% Cu, 0,05 bis 0,5 Masse-% Ni, 0,20 bis 0,55 Masse-% Nb, 0,001 bis 0,02 Masse-% N,
    optional wenigstens einem Bestandteil besteht, der aus der Gruppe ausgewählt wird, die aus 0,005 bis 0,5 Masse-% Ti, 0,5 Masse-% oder weniger Zr sowie 1,0 Masse-% oder weniger Mo besteht;
    wobei der Rest Fe und unvermeidliche Verunreinigungen sind, bei einer Endtemperatur von 700 °C bis 950 °C,

    c) Durchführen von Abkühlen mit einer durchschnittlichen Abkühlgeschwindigkeit von 20°C/s oder mehr von der Endtemperatur auf eine Wickeltemperatur,

    d) Durchführen von Wickeln bei einer Wickeltemperatur von 600°C oder darunter,

    e) Durchführen von Glühen bei 900°C bis 1200°C über 30 bis 240 Sekunden und anschließend Durchführen von erstem Beizen,

    f) Durchführen von Kaltwalzen nach dem ersten Beizen,

    g) Durchführen von Glühen nach Kaltwalzen bei weniger als 1050 °C über 10 bis 240 Sekunden und weiteres Durchführen von Beizen.


     
    4. Verfahren zum Herstellen eines ferritischen, rostfreien kaltgewalzten Stahlblechs nach Anspruch 3, wobei die Endtemperatur 700°C bis 900°C beträgt und das Wickeln bei einer Wickeltemperatur von 570°C oder darunter durchgeführt wird.
     


    Revendications

    1. Tôle d'acier inoxydable ferritique laminée à froid constituée de :

    0,001 à 0,02 pourcent en masse de C, 0,05 à 0,8 pourcent en masse de Si, 0,01 à 0,5 pourcent en masse de Mn, 0,04 pourcent en masse de P, 0,0005 à 0,010 pourcent en masse de S, 0,005 à 0,10 pourcent en masse d'Al, 20,5 à 23 pourcent en masse de Cr, 0,3 à 0,8 pourcent en masse de Cu, 0,05 à 0,5 pourcent en masse de Ni, 0,20 à 0,55 pourcent en masse de Nb, 0,001 à 0,02 pourcent en masse de N ; éventuellement au moins un élément choisi dans un groupe constitué par 0,005 à 0,5 pourcent en masse de Ti, 0,5 pourcent en masse ou moins de Zr et 1,0 pourcent en masse ou moins de Mo ; le reste étant du Fe et des impuretés inévitables ;

    et ayant une structure dans laquelle les inclusions contenant du soufre (S) ont un diamètre maximum de grain inférieur ou égal à 5 µm.


     
    2. Tôle d'acier inoxydable ferritique laminée à froid selon la revendication 1, où dans la composition, la teneur en Ni est inférieure ou égale à 0,3 pourcent en masse et la teneur en Nb va de 0,20 à 0,5 pourcent en masse.
     
    3. Procédé de fabrication d'une tôle d'acier inoxydable ferritique laminée à froid comprenant :

    a) le chauffage d'une brame ou d'un lingot à une température dans la plage de 1100 °C et 1200 °C,

    b) la réalisation d'un laminage à chaud d'une brame ou d'un lingot qui est constitué de 0,001 à 0,02 pourcent en masse de C, 0,05 à 0,8 pourcent en masse de Si, 0,01 à 0,5 pourcent en masse de Mn, 0,04 pourcent en masse de P, 0,0005 à 0,010 pourcent en masse de S, 0,005 à 0,10 pourcent en masse d'Al, 20,5 à 23 pourcent en masse de Cr, 0,3 à 0,8 pourcent en masse de Cu, 0,05 à 0,5 pourcent en masse de Ni, 0,20 à 0,55 pourcent en masse de Nb, 0,001 à 0,02 pourcent en masse de N,
    éventuellement au moins un élément choisi dans un groupe constitué par 0,005 à 0,5 pourcent en masse de Ti, 0,5 pourcent en masse ou moins de Zr et 1,0 pourcent en masse ou moins de Mo ;
    le reste étant du Fe et des impuretés inévitables, à une température de finissage de 700 °C à 950 °C,

    c) la réalisation d'un refroidissement à une vitesse moyenne de refroidissement supérieure ou égale à 20 °C/s depuis la température de finissage jusqu'à une température d'enroulement,

    d) la réalisation d'un enroulement à une température d'enroulement inférieure ou égale à 600 °C,

    e) la réalisation d'un recuit à une température de 900 °C à 1200 °C pendant 30 à 240 secondes, puis la réalisation d'un premier décapage,

    f) la réalisation d'un laminage à froid après le premier décapage,

    g) la réalisation d'un recuit après le laminage à froid à moins de 1050 °C pendant 10 à 240 secondes, puis la réalisation d'un autre décapage.


     
    4. Procédé de fabrication d'une tôle d'acier inoxydable ferritique laminée à froid selon la revendication 3, dans lequel la température de finissage va de 700 °C à 900 °C, et l'enroulement est effectué à une température d'enroulement inférieure ou égale à 570 °C.
     




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    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description