EP2737961A1 - Method for producing austenitic stainless steel - Google Patents

Method for producing austenitic stainless steel Download PDF

Info

Publication number
EP2737961A1
EP2737961A1 EP20120819669 EP12819669A EP2737961A1 EP 2737961 A1 EP2737961 A1 EP 2737961A1 EP 20120819669 EP20120819669 EP 20120819669 EP 12819669 A EP12819669 A EP 12819669A EP 2737961 A1 EP2737961 A1 EP 2737961A1
Authority
EP
European Patent Office
Prior art keywords
stainless steel
temperature
hot
hot rolling
slab
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP20120819669
Other languages
German (de)
French (fr)
Other versions
EP2737961A4 (en
EP2737961B1 (en
Inventor
Hayato Kita
Masayuki Shibuya
Shuuji Yoshida
Tomoyuki SUKAWA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Corp
Original Assignee
Nippon Steel and Sumitomo Metal Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Steel and Sumitomo Metal Corp filed Critical Nippon Steel and Sumitomo Metal Corp
Priority to SI201230842A priority Critical patent/SI2737961T1/en
Publication of EP2737961A1 publication Critical patent/EP2737961A1/en
Publication of EP2737961A4 publication Critical patent/EP2737961A4/en
Application granted granted Critical
Publication of EP2737961B1 publication Critical patent/EP2737961B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/005Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21BROLLING OF METAL
    • B21B1/00Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/02Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling heavy work, e.g. ingots, slabs, blooms, or billets, in which the cross-sectional form is unimportant ; Rolling combined with forging or pressing
    • B21B1/026Rolling
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/004Heat treatment of ferrous alloys containing Cr and Ni
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/008Heat treatment of ferrous alloys containing Si
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226Hot rolling
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/28Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21BROLLING OF METAL
    • B21B1/00Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/02Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling heavy work, e.g. ingots, slabs, blooms, or billets, in which the cross-sectional form is unimportant ; Rolling combined with forging or pressing
    • B21B2001/028Slabs
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/001Austenite
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/004Dispersions; Precipitations

Definitions

  • the present invention relates to a method for manufacturing austenitic stainless steel exhibiting corrosion resistance to a concentrated nitric acid. More specifically, the present invention relates to a method for manufacturing high Si-containing austenitic stainless steel usable in a concentrated nitric acid environment at a high temperature.
  • Materials employed at a nitric acid production plant are exposed to a highly-concentrated nitric acid environment at a high temperature.
  • stainless steel is used as a corrosion resistant material for the plant.
  • Stainless steel forms a passive film stable in a nitric acid, and exhibits excellent corrosion resistance.
  • the highly-concentrated nitric acid at a high temperature has so strong oxidizability that trans-passive corrosion occurs in common stainless steel.
  • the trans-passive corrosion results in general corrosion due to dissolution of Cr 2 O 3 that forms the passive film, and results in intergranular corrosion in the vicinity of sensitized grain boundaries (having increased susceptibility to intergranular attack).
  • high-Si austenitic stainless steel such as 17Cr-14Ni-4Si (Patent Document 1) and 11Cr-17Ni-6Si (Patent Document 2)
  • high-Si austenitic stainless steel such as 17Cr-14Ni-4Si (Patent Document 1) and 11Cr-17Ni-6Si (Patent Document 2)
  • Si resolved in a trans-passive region due to corrosion is re-oxidized, thereby forming a silicate film, which exhibits excellent corrosion resistance against a nitric acid.
  • One or more types of elements selected from Nb, Ta, Ti, and Zr tend to be added to this high-Si stainless steel.
  • These additive elements have an effect of immobilizing C in steel, and suppressing sensitization. Particularly, they are effective for suppression of sensitization in a welded heat affected zone, and have a significant effect of improving intergranular corrosion resistance in a highly-concentrated nitric acid.
  • a heating temperature of a slab in hot working is preferably as high as possible in view of productivity.
  • high-Si stainless steel there is a problem of cracking caused in the slab during the hot working if upon heated at a higher temperature than a predetermined temperature during the hot working because Si has low solid solubility relative to an austenite phase, and as the Si content becomes more increased, a brittle phase, such as an intermetallic compound and ⁇ ferrite, is more likely to be generated at a high temperature, which deteriorates high-temperature ductility. Accordingly, in order to stably manufacture high-Si stainless steel industrially, it is necessary to appropriately control a heating temperature in the hot working.
  • Patent Document 3 discloses a method of hot-rolling or hot-forging an ingot of high-Si stainless steel containing Si of 5 to 8% (in this description, unless otherwise specified, percent with respect to chemical composition means mass percent) within a temperature range of at least 900°C after soaking in a temperature range that satisfies: 1050 to 1100°C; and T(°C) ⁇ 1470 - 35 x Si - 5 x Ni (%).
  • the soaking temperature is determined so as to prevent such cracking.
  • Non Patent Document 1 reports that, regarding a relation between an intermetallic compound and hot workability in high-Si stainless steel (6.5Si-17Cr-22Ni-0.01Pd), (a) an Si-Ni rich intermetallic compound is crystallized in an interdendritic region of a cast structure, and existence of a large amount of such crystallization deteriorates the hot workability, and (b) if an ingot where the intermetallic compound is crystallized is soaked at a temperature of 1000 to 1150°C, the intermetallic compound is partially melted at a temperature of 1150°C, and cracking occurs; but soaking at a temperature of 1100°C exhibits no fusion of the intermetallic compound, so that the cracking in the hot working can be prevented by dissolving the intermetallic compound.
  • the Ni-Si based intermetallic compound having a low fusion point becomes partially melted at a temperature of more than 1100°C, and propagation of cracking along grain boundaries causes cracking, and thus the heating temperature in the hot working is substantially controlled to be at most 1100°C.
  • Patent Document 4 discloses that soaks at a temperature of at least 1100°C and at most 1250°C for at least two hours a slab of high-Si stainless steel containing Si of 4 to 10% in which S and O are restricted to be at most 30 ppm, and then hot-rolls this steel; finishes the hot rolling at a temperature of at least 950°C; and subjects this steel to solution heat treatment at a temperature of at least 1000°C and at most 1200°C.
  • Patent Document 4 discloses that (1) impurity elements such as S and O, and (2) an intermetallic compound that precipitates during cooling a slab affect high-temperature ductility of high-Si austenitic stainless steel, and also discloses that the intermetallic compound is removed by reduction of S and O, and by soaking of the slab, thereby improving hot workability.
  • a composition of this intermetallic compound is not clearly described, but it is estimated that this is an Ni-Si intermetallic compound having a low melting point as similar to that of Non-Patent Document 1.
  • Patent Document 3 and Patent Document 4 improve hot workability by setting a heating temperature to be not more than a fusing temperature of the Ni-Si intermetallic compound.
  • a heating temperature to be not more than a fusing temperature of the Ni-Si intermetallic compound.
  • Si in high-Si austenitic stainless steel used in a highly-concentrated nitric acid environment at a high-temperature, a great deal of Si thereof deteriorates solid solubility of C, so that sensitization likely occurs, and consequently, intergranular corrosion resistance in the highly-concentrated nitric acid is poor.
  • Each high-Si stainless steel disclosed in Patent Document 1 and Patent Document 2 contains Nb, Ta, Ti, and Zr so as to suppress sensitization, and to greatly improve the nitric acid corrosion resistance, but this brings up another problem of surface defects called as scab that is likely to be generated in the hot rolling process.
  • An object of the present invention is to ensure manufacturing high-Si containing austenitic stainless steel having corrosion resistance suitable for use in a highly-concentrated nitric acid environment at a high temperature without generating scab in a hot rolling process.
  • the present inventors have conducted studies on conditions to ensure manufacturing high Si-containing austenitic stainless steel (austenitic stainless steel is also referred to simply as “stainless steel", hereinafter) suitable for use in a highly-concentrated nitric acid environment at a high temperature without generating fractures in a hot rolling process, and as a result, the following (i) to (iii) have been found.
  • the scabs in the hot rolling process are generated by the aforementioned Ni-Si-X ternary system intermetallic compound as a starting point, and occur by propagation of the cracking to the surface.
  • Containing Si and X elements is essential for corrosion prevention in the highly-concentrated nitric environment, and thus a method of suppressing the above described propagation of the cracking in the vicinity of the surface have been studied.
  • the present invention based on the above findings is a method for manufacturing austenitic stainless steel which heats and hot-rolls a slab of stainless steel at a heating temperature T h during the hot rolling, wherein the slab of stainless steel includes a chemical composition containing C: 0.04% or less; Cr: 7 to 20%, Ni: 10 to 22%, Si: 2.5 to 7%, Mn: 10% or less, sol.
  • the method according to the present invention further includes subjecting the hot-rolled austenitic stainless steel to heat treatment within a temperature range of 1100 to 1160°C, and thereafter, cooling this austenitic stainless steel at cooling rate of 100°C/min. or more.
  • % relating to the chemical composition of steel means mass%.
  • the remainder of the chemical composition of the steel includes Fe and impurities.
  • the C content is an element for increasing strength of steel, but producing Cr carbide at grain boundaries in a welded heat affected zone, which causes sensitization, and deteriorates corrosion resistance. Accordingly, the C content is controlled to be at most 0.04%. The C content is preferably at most 0.03%, and more preferably at most 0.02%.
  • Cr is a basic element for improving the corrosion resistance of the stainless steel, and the Cr content is controlled to be at least 7% and at most 20%.
  • the Cr content of less than 7% cannot achieve adequate corrosion resistance.
  • the excessive Cr content produces a two-phase structure in which a large amount of ferrite precipitates under the coexistence of Si and Nb, which causes deterioration of workability and impact resistance; and thus the upper limit of the Cr content is controlled to be 20%.
  • the lower limit of the Cr content is preferably 10%, and more preferably 11%.
  • the upper limit of the Cr content is preferably 19%, and more preferably 18%.
  • Ni is a stabilizing element of the austenite phase, and also has an effect of increasing the zero ductility temperature.
  • the Ni content is controlled to be at least 10% and at most 22% or less.
  • the Ni content of less than 10% cannot achieve desired corrosion resistance and toughness.
  • the Ni content of more than 22% causes significant increase in cost.
  • the lower limit of the Ni content is preferably 12%, and more preferably 13%.
  • the upper limit of the Ni content is preferably 20%, and more preferably 16%.
  • Si is contained at a content of at least 2.5% and at most 7% for the purpose of increasing the corrosion resistance in a concentrated nitric acid.
  • Si is contained at a content of at least 2.5% so as to form a silicate film for achieving the corrosion resistance in the nitric acid.
  • An excessive Si content decreases the zero ductility temperature. This excessive content not only increases the cost but also deteriorates weldability; therefore, the upper limit of the Si content is controlled to be 7%.
  • the lower limit of the Si content is preferably 3.0%, and more preferably 3.5%.
  • the upper limit of the Si content is preferably 6%, and more preferably 5%.
  • Mn is an austenite stabilizing element, and is contained as a deoxidizing agent; therefore, the Mn content is controlled to be at most 10%.
  • the Mn content of more than 10% causes deterioration of the corrosion resistance, hot cracking upon welding, as well as deterioration of workability.
  • the upper limit of the Mn content is preferably 6%, and more preferably 4%.
  • the Mn content is preferably at least 0.5%, and more preferably at least 1.0%.
  • Al is contained as a deoxidizing agent in the steel, but produces a toxic inclusion if Al is excessively contained; therefore, the sol. Al content is controlled to be at most 0.03%.
  • P and S are both undesirable elements for the corrosion resistance and the weldability, and each content thereof is preferably as small as possible.
  • the P content is controlled to be at most 0.03%, and the S content is controlled to be at most 0.03%.
  • N has a high affinity to Nb, Ti, Ta, and Zr, and hinders immobility of C by these elements; and thus the N content is preferably as small as possible.
  • the N content is controlled to be at most 0.035%.
  • Total amount of one or more types of elements selected from Nb, Ti, Ta, and Zr 0.05% to 0.7%
  • All ofNb, Ti, Ta, and Zr have an effect of immobilizing C, and suppressing deterioration of intergranular corrosion resistance caused by sensitization, and they are particularly effective for improving the corrosion resistance in the welded heat affected zone.
  • a total amount of these elements of less than 0.05% cannot achieve an effect of improving the intergranular corrosion resistance, and increases hot-working cracking caused by formation of a low melting point Ni-Si based intermetallic compound.
  • the total amount of these elements of more than 0.7% deteriorates the workability. Accordingly, the total amount of one or more types of these elements is controlled to be at least 0.05% and at most 0.7%.
  • each test piece having a parallel portion of 8 mm in diameter and a length of 30 mm was fixed at its one end while being held at a predetermined temperature, and a torsion force was applied to the test piece in one direction with an axial force of 0 kgf at a rotational rate of 300 rpm (strain rate: 4.2 sec -1 ) until the test piece was ruptured; and the number of rotations until the test piece was ruptured was defied as torsion cycles of this test piece.
  • test piece 1 in Table 1 a result of the high-temperature torsion test using a test piece of high-Si stainless steel having a chemical composition indicated as the test piece 1 in Table 1 is shown in Figure 1 in a relation between the heating temperature and the torsion cycles.
  • Test piece 1 Chemical Composition of Test Piece (Mass%, Remainder: Fe and Impurities) No.
  • Test Piece 1 0.03 4.12 1.2 0.006 0.014 0.010 17.8 14.05 0.009 0.70
  • Test Piece 2 0.14 4.33 1.0 0.002 0.019 0.004 17.0 13.98 0.017 0.58
  • Test Piece 3 0.12 5.95 0.76 0.011 0.011 0.009 11.1 17.06 0.010 0.70
  • Test Piece 4 0.02 4.16 1.02 0.009 0.014 0.008 17.1 14.12 0.012 0.10 0.51
  • each forged slab After being heated at a predetermined temperature, each forged slab was hot-rolled to have a thickness of 4 mm. Thereafter, scales were removed by pickling, and then the scab occurrence ratio was investigated in the following methods.
  • a surface of each steel sheet was segmented into meshes each having a size of 100 ⁇ 100 mm, and a percentage of the number of meshes where scabs occurred relative to total meshes that were investigated was defined as the scab occurrence ratio (%). If the scab occurrence ratio is 5% , only simper treatment may be required prior to the subsequent step.
  • the scab occurrence ratio becomes 5% if the heating temperature T h during the hot rolling is set to satisfy ⁇ T ⁇ 30°C. To the contrary, if ⁇ T is less than 30°C, and as ⁇ T becomes closer to the zero ductility temperature, the scab occurrence ratio becomes abruptly increased.
  • the heating temperature T h during the hot rolling such that ⁇ T is at least 30°C, preferably at least 60°C.
  • Time duration of holding the stainless steel at this heating temperature is not limited to a specific one.
  • setting of the heating temperature is carried out for the purpose of preventing scabs from being generated after the hot rolling; and thus it is only required to control the temperature on the surface of the slab.
  • the heating time duration required for this state depends on the dimension of the slab; and generally, it is preferable to set the heating time duration to be at least 60 minutes.
  • the upper limit of ⁇ T is not limited. In a common hot rolling plant, it is possible to carry out the hot rolling if the hot-rolling finishing temperature is at least 700°C. Preferably, this finishing temperature is set to be at least 950°C.
  • the hot rolling may be performed in a single stage or in multiple stages. In the case of using multiple stages, heating may be applied between roll stands if necessary. At this time, the heating temperature is unnecessary to satisfy ⁇ T of at least 30°C, but it may be preferable to set ⁇ T to be at least 30°C. This process refines grain in the surface during the subsequent hot rolling, so that propagation of the cracking hardly occurs, thereby further suppressing the scab occurrence. After the hot rolling, oxide scales on the surface of the rolled material are removed by pickling with a conventional method.
  • the stainless steel sheet manufactured through the hot rolling can be adjusted in mechanical property (ductility, yield strength) by performing heat treatment for annealing; therefore, it is preferable to subject the stainless steel sheet to heat treatment after the hot rolling.
  • Increase in heat treatment temperature improves the ductility, but reduces the yield strength.
  • Slow cooling rate after the heat treatment allows chrome carbide to precipitate, which causes deterioration of the corrosion resistance. Accordingly, the heat treatment temperature and the subsequent cooling rate should be set so as to achieve both the ductility and the yield strength, as well as to prevent sensitization.
  • Figure 3 shows relations of the heat treatment temperature with 0.2% yield strength, and with ductility of the test piece 1.
  • black solid circles indicate the 0.2% yield strength (MPa)
  • black solid squares indicate the ductility (%).
  • Each test piece 1 to 5 having a corresponding chemical composition shown in Table 1 was melted by a high-frequency electric furnace into an ingot of 10 kg, and a slab produced by forging this ingot was heated at a corresponding predetermined temperature shown in Table 2 for 120 minutes, and thereafter was hot-rolled into a steel sheet having a thickness of 4 mm through a two-stage rolling mill. Each obtained stainless steel sheet was pickled to remove scales therefrom, and thereafter, the scab occurrence ratio on a surface of each steel sheet was investigated in the aforementioned methods. Total results of the investigation are shown in Table 2. [Table 2] Test Piece Heating Temperature during Hot Rolling (°C) No.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Sheet Steel (AREA)

Abstract

It is possible to securely produce high Si-containing austenitic stainless steel having corrosion resistance usable in a highly-concentrated nitric acid environment at a high temperature without generating scabs by heating and hot-rolling a slab of stainless steel at a heating temperature during the hot rolling, and subsequently, carrying out heat treatment to heat the hot-rolled stainless steel at a temperature of 1100 to 1160°C, and thereafter, to cool this stainless steel at cooling rate of at least 100°C/min. , wherein the slab of stainless steel has a chemical composition containing: C: at most 0.04% ; Cr: 7 to 20%, Ni: 10 to 22%, Si: 2.5 to 7%, Mn: at most 10% , sol. Al: at most 0.03% , P: at most 0.03% , S: at most 0.03% ; N: at most 0.035% , a total amount of one or more types of elements selected from Nb, Ti, Ta, and Zr: 0.05 to 0.7%; and the remainder being Fe and impurities, and the heating temperature during the hot rolling is defined as Th in which ΔT of Formula (1): Th = 1135 - 90Si - 2.9Cr + 40Ni - ΔT is at least 30°C.

Description

    Technical Field
  • The present invention relates to a method for manufacturing austenitic stainless steel exhibiting corrosion resistance to a concentrated nitric acid. More specifically, the present invention relates to a method for manufacturing high Si-containing austenitic stainless steel usable in a concentrated nitric acid environment at a high temperature.
  • Background Art
  • Materials employed at a nitric acid production plant are exposed to a highly-concentrated nitric acid environment at a high temperature. In general, stainless steel is used as a corrosion resistant material for the plant. Stainless steel forms a passive film stable in a nitric acid, and exhibits excellent corrosion resistance. The highly-concentrated nitric acid at a high temperature has so strong oxidizability that trans-passive corrosion occurs in common stainless steel. The trans-passive corrosion results in general corrosion due to dissolution of Cr2O3 that forms the passive film, and results in intergranular corrosion in the vicinity of sensitized grain boundaries (having increased susceptibility to intergranular attack).
  • As a corrosion resistant material having even in such an environment, high-Si austenitic stainless steel, such as 17Cr-14Ni-4Si (Patent Document 1) and 11Cr-17Ni-6Si (Patent Document 2), has been known. In such high-Si stainless steel, Si resolved in a trans-passive region due to corrosion is re-oxidized, thereby forming a silicate film, which exhibits excellent corrosion resistance against a nitric acid. One or more types of elements selected from Nb, Ta, Ti, and Zr tend to be added to this high-Si stainless steel. These additive elements have an effect of immobilizing C in steel, and suppressing sensitization. Particularly, they are effective for suppression of sensitization in a welded heat affected zone, and have a significant effect of improving intergranular corrosion resistance in a highly-concentrated nitric acid.
  • A heating temperature of a slab in hot working is preferably as high as possible in view of productivity. In high-Si stainless steel, however, there is a problem of cracking caused in the slab during the hot working if upon heated at a higher temperature than a predetermined temperature during the hot working because Si has low solid solubility relative to an austenite phase, and as the Si content becomes more increased, a brittle phase, such as an intermetallic compound and δ ferrite, is more likely to be generated at a high temperature, which deteriorates high-temperature ductility. Accordingly, in order to stably manufacture high-Si stainless steel industrially, it is necessary to appropriately control a heating temperature in the hot working.
  • Patent Document 3 discloses a method of hot-rolling or hot-forging an ingot of high-Si stainless steel containing Si of 5 to 8% (in this description, unless otherwise specified, percent with respect to chemical composition means mass percent) within a temperature range of at least 900°C after soaking in a temperature range that satisfies: 1050 to 1100°C; and T(°C) < 1470 - 35 x Si - 5 x Ni (%). With increase in Si content, an intermetallic compound having a low melting point is generated in casting solidification structure, and the intermetallic compound becomes partially fused at a higher soaking temperature, and thus cracking occurs during the hot working. The soaking temperature is determined so as to prevent such cracking.
  • Non Patent Document 1 reports that, regarding a relation between an intermetallic compound and hot workability in high-Si stainless steel (6.5Si-17Cr-22Ni-0.01Pd), (a) an Si-Ni rich intermetallic compound is crystallized in an interdendritic region of a cast structure, and existence of a large amount of such crystallization deteriorates the hot workability, and (b) if an ingot where the intermetallic compound is crystallized is soaked at a temperature of 1000 to 1150°C, the intermetallic compound is partially melted at a temperature of 1150°C, and cracking occurs; but soaking at a temperature of 1100°C exhibits no fusion of the intermetallic compound, so that the cracking in the hot working can be prevented by dissolving the intermetallic compound.
  • Specifically, in the high-Si stainless steel of Non Patent Document 1, it is estimated that the Ni-Si based intermetallic compound having a low fusion point becomes partially melted at a temperature of more than 1100°C, and propagation of cracking along grain boundaries causes cracking, and thus the heating temperature in the hot working is substantially controlled to be at most 1100°C.
  • In Patent Document 4 discloses that soaks at a temperature of at least 1100°C and at most 1250°C for at least two hours a slab of high-Si stainless steel containing Si of 4 to 10% in which S and O are restricted to be at most 30 ppm, and then hot-rolls this steel; finishes the hot rolling at a temperature of at least 950°C; and subjects this steel to solution heat treatment at a temperature of at least 1000°C and at most 1200°C. Patent Document 4 discloses that (1) impurity elements such as S and O, and (2) an intermetallic compound that precipitates during cooling a slab affect high-temperature ductility of high-Si austenitic stainless steel, and also discloses that the intermetallic compound is removed by reduction of S and O, and by soaking of the slab, thereby improving hot workability. A composition of this intermetallic compound is not clearly described, but it is estimated that this is an Ni-Si intermetallic compound having a low melting point as similar to that of Non-Patent Document 1.
  • Techniques disclosed in Patent Document 3 and Patent Document 4 improve hot workability by setting a heating temperature to be not more than a fusing temperature of the Ni-Si intermetallic compound. In high-Si austenitic stainless steel used in a highly-concentrated nitric acid environment at a high-temperature, a great deal of Si thereof deteriorates solid solubility of C, so that sensitization likely occurs, and consequently, intergranular corrosion resistance in the highly-concentrated nitric acid is poor.
  • Each high-Si stainless steel disclosed in Patent Document 1 and Patent Document 2 contains Nb, Ta, Ti, and Zr so as to suppress sensitization, and to greatly improve the nitric acid corrosion resistance, but this brings up another problem of surface defects called as scab that is likely to be generated in the hot rolling process.
  • The cause of this is unclear, and the surface defects tend to be reduced by controlling a heating temperature of a slab lower, but it may be difficult to sufficiently achieve this reduction effect depending on the chemical composition of the steel in some cases; therefore, it is required to heat the slab at an unnecessarily low temperature, or to provide treatment such as cutting for removing the scab after the hot rolling, which causes significant increase in cost.
  • Prior Art Documents
    • Patent Document 1: Japanese Patent Publication No. 3237132
    • Patent Document 2: Japanese Patent Publication No. 1119398
    • Patent Document 3: Japanese Patent Laid-Open No. 6-93389
    • Patent Document 4: Japanese Patent Laid-Open No. 5-51633
    Non Patent Document
    • Non Patent Document 1: NKK Technical Report, No. 154, 1996, pp. 14-19
    Summary of Invention
  • An object of the present invention is to ensure manufacturing high-Si containing austenitic stainless steel having corrosion resistance suitable for use in a highly-concentrated nitric acid environment at a high temperature without generating scab in a hot rolling process.
  • The present inventors have conducted studies on conditions to ensure manufacturing high Si-containing austenitic stainless steel (austenitic stainless steel is also referred to simply as "stainless steel", hereinafter) suitable for use in a highly-concentrated nitric acid environment at a high temperature without generating fractures in a hot rolling process, and as a result, the following (i) to (iii) have been found.
    1. (i) Upon manufacturing stainless steel containing a large amount of Si, an Ni-Si intermetallic compound is produced. As disclosed in Non Patent Document 1, its melting point is estimated to be within a range from 1100 to 1150°C, and this intermetallic compound causes great slab cracking that hinders hot rolling.
    2. (ii) If stainless steel having a great content of Si contains Nb, Ta, Ti, Zr, and the like, Ni-Si-X (X = Nb, Ti, Zr) is produced as the intermetallic compound. Its melting point is within a range of approximately 1150 to 1200°C, and this is approximately 1160°C for Ni-Si-Nb based on a calculated result of a state diagram calculation thereof, for example. Since Nb, Ta, Ti, Zr and the like are elements that hardly segregate in the steel, an Ni-Si-X ternary system (X = Nb, Ta, Ti, Zr) intermetallic compound is finely dispersed. Because the Ni-Si-X intermetallic compound is finely dispersed at a high melting point, this causes no slab cracking great enough to hinder the rolling.
    3. (iii) Despite the above, if cracking occurs in the vicinity of the slab surface from the Ni-Si-X intermetallic compound as a starting point, this cracking propagates to the surface, and the inside of the cracking is oxidized, resulting in generation of a number of scabs. Because the Ni-Si-X intermetallic compound is finely dispersed, the amount thereof is so great that a large number of scabs occur.
  • Based on the above result, it has been found that the scabs in the hot rolling process are generated by the aforementioned Ni-Si-X ternary system intermetallic compound as a starting point, and occur by propagation of the cracking to the surface. Containing Si and X elements is essential for corrosion prevention in the highly-concentrated nitric environment, and thus a method of suppressing the above described propagation of the cracking in the vicinity of the surface have been studied.
  • In general, if ductility is deteriorated with excessively high temperature, the cracking likely propagate; therefore, a relation between the composition and the ductility of the steel has been studied. As a result, the following findings have been obtained.
    • (A) Defects (scabs) of the product surface can be prevented by controlling the heating temperature during the hot rolling based on the relation among the contents of Si, Cr, and Ni in the chemical composition of the steel.
    • (B) Sensitization can be suppressed as well as achieving ductility and yield strength by controlling a temperature range and a cooling method of finishing annealing after the rolling.
  • The present invention based on the above findings is a method for manufacturing austenitic stainless steel which heats and hot-rolls a slab of stainless steel at a heating temperature Th during the hot rolling, wherein the slab of stainless steel includes a chemical composition containing C: 0.04% or less; Cr: 7 to 20%, Ni: 10 to 22%, Si: 2.5 to 7%, Mn: 10% or less, sol. Al: 0.03% or less, P: 0.03% or less, S: 0.03% or less; N: 0.035% or less, a sum of one or more types of elements selected from Nb, Ti, Ta, and Zr: 0.05 to 0.7%; and the balance being Fe and impurities, and the heating temperature Th is defined as Th, in which ΔT of Formula (1): Th = 1135 - 90Si -2.9Cr + 40 Ni - ΔT is 30°C or more.
  • In a preferable aspect of the present invention, the method according to the present invention further includes subjecting the hot-rolled austenitic stainless steel to heat treatment within a temperature range of 1100 to 1160°C, and thereafter, cooling this austenitic stainless steel at cooling rate of 100°C/min. or more.
  • According to the present invention, it is possible to securely manufacture high Si-containing austenitic stainless steel suitable for use in a highly-concentrated nitric acid environment at a high temperature without generating scabs in the hot rolling process.
  • Brief Description of Drawings
    • Figure 1 is a graph showing a test result of a torsion test on a test piece 1.
    • Figure 2 is a graph showing a relation between ΔT and a scab occurrence ratio in the test piece 1.
    • Figure 3 is a graph showing relations of a heat treatment temperature after hot rolling with 0.2% yield strength, and with ductility in the test piece 1.
    Description of Embodiment
  • The method for manufacturing austenitic stainless steel according to the present invention will be explained in greater detail while referring to the attached drawings. As described above, "%" relating to the chemical composition of steel means mass%. The remainder of the chemical composition of the steel includes Fe and impurities.
  • [Chemical composition of steel] [C: at most 0.04%]
  • C is an element for increasing strength of steel, but producing Cr carbide at grain boundaries in a welded heat affected zone, which causes sensitization, and deteriorates corrosion resistance. Accordingly, the C content is controlled to be at most 0.04%. The C content is preferably at most 0.03%, and more preferably at most 0.02%.
  • [Cr: 7 to 20%]
  • Cr is a basic element for improving the corrosion resistance of the stainless steel, and the Cr content is controlled to be at least 7% and at most 20%. The Cr content of less than 7% cannot achieve adequate corrosion resistance. On the other hand, the excessive Cr content produces a two-phase structure in which a large amount of ferrite precipitates under the coexistence of Si and Nb, which causes deterioration of workability and impact resistance; and thus the upper limit of the Cr content is controlled to be 20%. The lower limit of the Cr content is preferably 10%, and more preferably 11%. The upper limit of the Cr content is preferably 19%, and more preferably 18%.
  • [Ni: 10 to 22%]
  • Ni is a stabilizing element of the austenite phase, and also has an effect of increasing the zero ductility temperature. The Ni content is controlled to be at least 10% and at most 22% or less. The Ni content of less than 10% cannot achieve desired corrosion resistance and toughness. The Ni content of more than 22% causes significant increase in cost. The lower limit of the Ni content is preferably 12%, and more preferably 13%. The upper limit of the Ni content is preferably 20%, and more preferably 16%.
  • [Si: 2.5 to 7%]
  • Si is contained at a content of at least 2.5% and at most 7% for the purpose of increasing the corrosion resistance in a concentrated nitric acid. Si is contained at a content of at least 2.5% so as to form a silicate film for achieving the corrosion resistance in the nitric acid. An excessive Si content decreases the zero ductility temperature. This excessive content not only increases the cost but also deteriorates weldability; therefore, the upper limit of the Si content is controlled to be 7%. The lower limit of the Si content is preferably 3.0%, and more preferably 3.5%. The upper limit of the Si content is preferably 6%, and more preferably 5%.
  • [Mn: at most 10%]
  • Mn is an austenite stabilizing element, and is contained as a deoxidizing agent; therefore, the Mn content is controlled to be at most 10%. The Mn content of more than 10% causes deterioration of the corrosion resistance, hot cracking upon welding, as well as deterioration of workability. The upper limit of the Mn content is preferably 6%, and more preferably 4%. In order to securely achieve the above effect of Mn, the Mn content is preferably at least 0.5%, and more preferably at least 1.0%.
  • [sol. Al: at most 0.03%]
  • Al is contained as a deoxidizing agent in the steel, but produces a toxic inclusion if Al is excessively contained; therefore, the sol. Al content is controlled to be at most 0.03%.
  • [P: at most 0.03%, S: at most 0.03%]
  • P and S are both undesirable elements for the corrosion resistance and the weldability, and each content thereof is preferably as small as possible. The P content is controlled to be at most 0.03%, and the S content is controlled to be at most 0.03%.
  • [N: at most 0.035%]
  • N has a high affinity to Nb, Ti, Ta, and Zr, and hinders immobility of C by these elements; and thus the N content is preferably as small as possible. The N content is controlled to be at most 0.035%.
  • [Total amount of one or more types of elements selected from Nb, Ti, Ta, and Zr: 0.05% to 0.7%]
  • All ofNb, Ti, Ta, and Zr have an effect of immobilizing C, and suppressing deterioration of intergranular corrosion resistance caused by sensitization, and they are particularly effective for improving the corrosion resistance in the welded heat affected zone. A total amount of these elements of less than 0.05% cannot achieve an effect of improving the intergranular corrosion resistance, and increases hot-working cracking caused by formation of a low melting point Ni-Si based intermetallic compound. On the other hand, the total amount of these elements of more than 0.7% deteriorates the workability. Accordingly, the total amount of one or more types of these elements is controlled to be at least 0.05% and at most 0.7%.
  • [Manufacturing Condition]
  • The method for manufacturing the austenitic stainless steel according to the present invention includes: a hot rolling step of heating and hot-rolling a slab of stainless steel having the aforementioned chemical composition at a heating temperature Th during the hot rolling, wherein the heating temperature Th is defined as Th in which ΔT of Formula (1): Th = 1135 - 90Si -2.9Cr + 40 Ni - ΔT is at least 30°C; and a heat treatment step (annealing step) of preferably further subjecting the stainless steel to heat treatment within a temperature range of 1100 to 1160°C, and thereafter, cooling the stainless steel at cooling rate of at least 100°C/min..
  • [Hot rolling step]
  • For the purpose of finding an optimum heating temperature range for the hot rolling, a relation between the chemical composition and a high-temperature deformability has been studied through a high-temperature torsion test. Through this test, the zero ductility in the hot rolling can be investigated.
  • In the hot torsion test, each test piece having a parallel portion of 8 mm in diameter and a length of 30 mm was fixed at its one end while being held at a predetermined temperature, and a torsion force was applied to the test piece in one direction with an axial force of 0 kgf at a rotational rate of 300 rpm (strain rate: 4.2 sec-1) until the test piece was ruptured; and the number of rotations until the test piece was ruptured was defied as torsion cycles of this test piece.
  • As an example, a result of the high-temperature torsion test using a test piece of high-Si stainless steel having a chemical composition indicated as the test piece 1 in Table 1 is shown in Figure 1 in a relation between the heating temperature and the torsion cycles. [Table 1]
    Chemical Composition of Test Piece (Mass%, Remainder: Fe and Impurities)
    No. C Si Mn Al P S Cr Ni N Nb+Ta Ti Zr
    Test Piece 1 0.03 4.12 1.2 0.006 0.014 0.010 17.8 14.05 0.009 0.70
    Test Piece 2 0.14 4.33 1.0 0.002 0.019 0.004 17.0 13.98 0.017 0.58
    Test Piece 3 0.12 5.95 0.76 0.011 0.011 0.009 11.1 17.06 0.010 0.70
    Test Piece 4 0.02 4.16 1.02 0.009 0.014 0.008 17.1 14.12 0.012 0.10 0.51
    Test Piece 5 0.007 4.03 1.83 0.010 0.016 0.0005 17.7 15.05 0.014 0.11
  • In Figure 1, a maximum value of the torsion cycles appears at approximately 1100°C, the torsion cycles greatly drop at a temperature more than 1100°C, and the test piece was ruptured at the beginning of applying torsion at 1275°C. This shows that the temperature where the high-Si stainless steel shown as the test piece 1 in Table 1 has zero ductility is approximately 1275°C (referred to as a "zero ductility temperature", hereinafter).
  • Each of high-Si stainless steel having various chemical composition containing one or more types of elements selected from Nb, Ta, Ti, and Zr was subjected to the above high-temperature torsion test in the same way so as to investigate the zero ductility temperature thereof. As a result, it was found that the zero ductility temperature (T0) can be expressed by the following regression equation (2) as a relation of the zero ductility temperature (T0) with concentrations of Si, Cr, and Ni. T 0 = 1135 - 90 Si - 2.9 Cr + 40 Ni
    Figure imgb0001
  • The heating temperature (Th) in the hot working is set to be less than the zero ductility temperature (T0) by at least 30°C, that is, the heating temperature (Th) is set to be a temperature in which ΔT of Formula (1): Th = 1135 - 90Si - 2.9Cr + 40 Ni - ΔT is at least 30°C so that cracking generated from an Ni-Si-X ternary system (X = Nb, Ta, Ti, Zr) intermetallic compound as a starting point hardly occurs, and scabs are reduced. Reducing scabs provides simpler surface treatment prior to a subsequent step, which is excellent in economy.
  • After being heated at a predetermined temperature, each forged slab was hot-rolled to have a thickness of 4 mm. Thereafter, scales were removed by pickling, and then the scab occurrence ratio was investigated in the following methods.
  • A surface of each steel sheet was segmented into meshes each having a size of 100 × 100 mm, and a percentage of the number of meshes where scabs occurred relative to total meshes that were investigated was defined as the scab occurrence ratio (%). If the scab occurrence ratio is 5% , only simper treatment may be required prior to the subsequent step.
  • With the chemical composition of the test piece 1 in Table 1, the zero ductility temperature To = 1275°C was obtained by Formula (2). A relation between ΔT of the test piece 1 (Table 1) and the scab occurrence ratio is shown in Figure 2.
  • As shown in a graph of Figure 2, the scab occurrence ratio becomes 5% if the heating temperature Th during the hot rolling is set to satisfy ΔT ≥ 30°C. To the contrary, if ΔT is less than 30°C, and as ΔT becomes closer to the zero ductility temperature, the scab occurrence ratio becomes abruptly increased.
  • Accordingly, in order to minimize the scab occurrence, it is preferable to set the heating temperature Th during the hot rolling such that ΔT is at least 30°C, preferably at least 60°C. Time duration of holding the stainless steel at this heating temperature is not limited to a specific one. In the present invention, setting of the heating temperature is carried out for the purpose of preventing scabs from being generated after the hot rolling; and thus it is only required to control the temperature on the surface of the slab. In order to prevent hindrance in the hot rolling, it is preferable to heat the slab until its central portion substantially has a uniform temperature. The heating time duration required for this state depends on the dimension of the slab; and generally, it is preferable to set the heating time duration to be at least 60 minutes.
  • The upper limit of ΔT is not limited. In a common hot rolling plant, it is possible to carry out the hot rolling if the hot-rolling finishing temperature is at least 700°C. Preferably, this finishing temperature is set to be at least 950°C.
  • The hot rolling may be performed in a single stage or in multiple stages. In the case of using multiple stages, heating may be applied between roll stands if necessary. At this time, the heating temperature is unnecessary to satisfy ΔT of at least 30°C, but it may be preferable to set ΔT to be at least 30°C. This process refines grain in the surface during the subsequent hot rolling, so that propagation of the cracking hardly occurs, thereby further suppressing the scab occurrence. After the hot rolling, oxide scales on the surface of the rolled material are removed by pickling with a conventional method.
  • [Heat treatment step]
  • The stainless steel sheet manufactured through the hot rolling can be adjusted in mechanical property (ductility, yield strength) by performing heat treatment for annealing; therefore, it is preferable to subject the stainless steel sheet to heat treatment after the hot rolling. Increase in heat treatment temperature improves the ductility, but reduces the yield strength. Slow cooling rate after the heat treatment allows chrome carbide to precipitate, which causes deterioration of the corrosion resistance. Accordingly, the heat treatment temperature and the subsequent cooling rate should be set so as to achieve both the ductility and the yield strength, as well as to prevent sensitization.
  • Figure 3 shows relations of the heat treatment temperature with 0.2% yield strength, and with ductility of the test piece 1. In a graph of Figure 3, black solid circles indicate the 0.2% yield strength (MPa), and black solid squares indicate the ductility (%).
  • As shown in Figure 3, through the heat treatment at a temperature of at least 1100°C and at least 1160°C, it is possible to achieve the stainless steel having preferable ductility and sufficient yield strength, specifically, ductility of 50 to 53%, and 0.2% yield strength of 325 to 290 MPa.
  • Slow cooling rate after the heat treatment causes sensitization, and increases susceptibility to intergranular corrosion. It is possible to achieve the stainless steel causing no sensitization and exhibiting preferable nitric acid resistance by setting the cooling rate to be at least 100°C/min..
  • According to the present invention, it is possible to surely manufacture high Si-containing austenitic stainless steel suitable for use in a highly-concentrated nitric acid environment at a high temperature without generating scabs in the hot rolling process.
  • Example
  • Each test piece 1 to 5 having a corresponding chemical composition shown in Table 1 was melted by a high-frequency electric furnace into an ingot of 10 kg, and a slab produced by forging this ingot was heated at a corresponding predetermined temperature shown in Table 2 for 120 minutes, and thereafter was hot-rolled into a steel sheet having a thickness of 4 mm through a two-stage rolling mill. Each obtained stainless steel sheet was pickled to remove scales therefrom, and thereafter, the scab occurrence ratio on a surface of each steel sheet was investigated in the aforementioned methods. Total results of the investigation are shown in Table 2. [Table 2]
    Test Piece Heating Temperature during Hot Rolling (°C)
    No. T0(°C) 1300 1250 1200 1150
    Test Piece 1 1275 × Δ
    Test Piece 2 1255 × ×
    Test Piece 3 1250 × ×
    Test Piece 4 1276 × Δ
    Test Piece 5 1323 Δ
    Scab Occurrence Ratio
    × : at least 20%, Δ: more than 5% to less than 20%, ○: at most 5%
  • As shown in Table 2, all test piece having the heating temperature during the hot rolling less than the zero ductility temperature To (°C), which was calculated based on the chemical composition, by at least 30°C had a scab occurrence ratio of 5% .
  • To the contrary, every test piece having a heating temperature during the hot rolling more than a temperature less than the zero ductility temperature To (°C), which is calculated based on the chemical composition, by 30°C had a scab occurrence ratio of more than 5%; therefore, it was not possible to ensure manufacturing high Si-containing austenitic stainless steel suitable for use in a highly-concentrated nitric acid environment at a high temperature without generating scabs in the hot rolling process.

Claims (2)

  1. A method for manufacturing austenitic stainless steel comprising
    a hot rolling step of heating and hot-rolling a slab of stainless steel at a heating temperature Th during the hot rolling
    wherein
    the slab of stainless steel has a chemical composition containing: by mass%, C: at most 0.04% ; Cr: 7 to 20%, Ni: 10 to 22%, Si: 2.5 to 7%, Mn: at most 10% , sol. Al: at most 0.03% , P: at most 0.03% , S: a at most 0.03% ; N: at most 0.035% , a total amount of one or more types of elements selected from Nb, Ti, Ta, and Zr: 0.05 to 0.7%; and the remainder being Fe and impurities,
    and
    the heating temperature Th is defined as Th in which ΔT of Formula (1): Th = 1135 - 90Si - 2.9Cr + 40Ni - ΔT is at least 30°C or more.
  2. The method for manufacturing austenitic stainless steel according to claim 1, further comprising
    a heat treatment step of subjecting the austenitic stainless steel obtained through the hot rolling to heat treatment within a temperature range of 1100 to 1160°C, and thereafter, cooling the austenitic stainless steel at cooling rate of at least 100°C/min..
EP12819669.8A 2011-07-29 2012-07-26 Method for producing austenitic stainless steel Active EP2737961B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI201230842A SI2737961T1 (en) 2011-07-29 2012-07-26 Method for producing austenitic stainless steel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011166361 2011-07-29
PCT/JP2012/068905 WO2013018628A1 (en) 2011-07-29 2012-07-26 Method for producing austenitic stainless steel

Publications (3)

Publication Number Publication Date
EP2737961A1 true EP2737961A1 (en) 2014-06-04
EP2737961A4 EP2737961A4 (en) 2015-06-03
EP2737961B1 EP2737961B1 (en) 2016-12-14

Family

ID=47629153

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12819669.8A Active EP2737961B1 (en) 2011-07-29 2012-07-26 Method for producing austenitic stainless steel

Country Status (7)

Country Link
US (1) US20140261917A1 (en)
EP (1) EP2737961B1 (en)
JP (1) JP5418734B2 (en)
KR (1) KR101495483B1 (en)
CN (1) CN103826766B (en)
SI (1) SI2737961T1 (en)
WO (1) WO2013018628A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103849715B (en) * 2014-03-18 2015-10-28 河北师范大学 A kind of heat treating method reducing austenitic stainless cast steel part magnetic
JP6341053B2 (en) * 2014-10-20 2018-06-13 新日鐵住金株式会社 High Si austenitic stainless steel containing composite non-metallic inclusions
CN107217215A (en) * 2017-05-26 2017-09-29 黄曦雨 Austenitic stainless steel and its application and bead-welding technology
JP2020104145A (en) * 2018-12-27 2020-07-09 ヤマコー株式会社 Method for molding high-silicon stainless steel
CN110257690B (en) * 2019-06-25 2021-01-08 宁波宝新不锈钢有限公司 Resource-saving austenitic heat-resistant steel and preparation method thereof

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5737669B2 (en) * 1973-10-30 1982-08-11
JPS5591960A (en) * 1978-12-28 1980-07-11 Sumitomo Chem Co Ltd High silicon-nickel-chromium steel with resistance to concentrated
JPS56139616A (en) * 1980-04-02 1981-10-31 Sumitomo Chem Co Ltd Surface detect improving method of steel plate for concentrated nitric acid
JPS5915979B2 (en) * 1980-07-03 1984-04-12 新日本製鐵株式会社 Stainless steel alloy with fewer rolling defects during hot rolling
JPH07116556B2 (en) * 1986-09-08 1995-12-13 日新製鋼株式会社 Austenitic heat resistant steel for processing
JPH0613157B2 (en) * 1986-12-03 1994-02-23 住友金属工業株式会社 Welding material for high Si austenitic stainless steel
JPH01119398A (en) 1987-10-30 1989-05-11 Akua Runesansu Gijutsu Kenkyu Kumiai Water treatment equipment
JPH01316418A (en) * 1988-06-16 1989-12-21 Nippon Steel Corp Production of austenitic stainless steel exhibiting excellent integranular corrosion resistance in nitric acid solution
JP3237132B2 (en) 1991-07-12 2001-12-10 住友化学工業株式会社 Stainless steel for concentrated nitric acid with excellent weld toughness and corrosion resistance
JPH0551633A (en) 1991-08-27 1993-03-02 Nippon Steel Corp Production of high si-containing austenitic stainless steel
JPH05156411A (en) * 1991-12-05 1993-06-22 Nippon Stainless Steel Co Ltd High-si austenitic stainless cast steel for concentrated nitric acid having excellent castability and toughness
JP2806145B2 (en) * 1992-04-10 1998-09-30 日本鋼管株式会社 Austenitic stainless steel with excellent nitric acid corrosion resistance
JPH0693389A (en) * 1992-06-23 1994-04-05 Nkk Corp High si stainless steel excellent in corrosion resistance and ductility-toughness and its production
JP2682398B2 (en) * 1993-10-19 1997-11-26 住友金属工業株式会社 Hot rolling method for stainless steel
DE69516336T2 (en) * 1994-01-26 2000-08-24 Kawasaki Steel Co METHOD FOR PRODUCING A STEEL SHEET WITH HIGH CORROSION RESISTANCE
US5716153A (en) * 1995-11-06 1998-02-10 Saf-T Ring, Llc Safety ring binder
JP4176471B2 (en) * 2000-12-14 2008-11-05 義之 清水 High silicon stainless steel
JP4221569B2 (en) * 2002-12-12 2009-02-12 住友金属工業株式会社 Austenitic stainless steel
KR20090130331A (en) * 2007-04-27 2009-12-22 가부시키가이샤 고베 세이코쇼 Austenitic stainless steel excellent in intergranular corrosion resistance and stress corrosion cracking resistance, and method for producing austenitic stainless steel
WO2010110003A1 (en) * 2009-03-27 2010-09-30 住友金属工業株式会社 Austenitic stainless steel

Also Published As

Publication number Publication date
JP5418734B2 (en) 2014-02-19
KR101495483B1 (en) 2015-02-24
EP2737961A4 (en) 2015-06-03
US20140261917A1 (en) 2014-09-18
WO2013018628A1 (en) 2013-02-07
SI2737961T1 (en) 2017-05-31
JPWO2013018628A1 (en) 2015-03-05
CN103826766A (en) 2014-05-28
CN103826766B (en) 2015-11-25
EP2737961B1 (en) 2016-12-14
KR20140037969A (en) 2014-03-27

Similar Documents

Publication Publication Date Title
KR102059886B1 (en) Titanium material for hot rolling
CN110366601B (en) Ferritic stainless steel sheet, hot-rolled coil, and flange member for automobile exhaust system
EP2737961B1 (en) Method for producing austenitic stainless steel
CA3015441C (en) Ti-containing ferritic stainless steel sheet, manufacturing method, and flange
JP6261648B2 (en) Ti-containing ferritic stainless steel sheet for exhaust pipe flange parts and manufacturing method
CN110337503B (en) Ferritic stainless steel sheet, hot-rolled coil, and flange member for automobile exhaust system
JP2010100877A (en) Method for manufacturing hot-rolled ferritic stainless steel sheet excellent in toughness
EP2834381B1 (en) Cost-effective ferritic stainless steel
EP2801631B1 (en) Alpha+beta-type titanium alloy plate for welded pipe, method for producing same, and alpha+beta-type titanium-alloy welded pipe product
JP2001192761A (en) Ferritic heat resistant steel sheet excellent in creep strength and toughness of base metal and welded joint and producing method therefor
JPH0551633A (en) Production of high si-containing austenitic stainless steel
JPH0830253B2 (en) Precipitation hardening type martensitic stainless steel with excellent workability
JP2000119749A (en) Production of chromium-molybdenum seamless steel pipe for machine structure
WO2019151124A1 (en) Ferritic stainless steel
JP3687315B2 (en) B-containing stainless steel and method for producing hot rolled sheet thereof
JP2000160247A (en) Manufacture of duplex stainless steel tube
JPH06184637A (en) Production of steel tube for automotive exhaust system
JP2005008925A (en) Mo-CONTAINING AUSTENITIC STAINLESS STEEL AND ITS MANUFACTURING METHOD
JP2001020041A (en) Tool steel excellent in weldability and machinability and tool and die
JPH0236669B2 (en)
JP4254583B2 (en) Cr-containing alloy with excellent strain aging resistance of welds
JPH0874003A (en) Ferritic stainless steel excellent in slab season cracking resistance and intergranular corrosion resistance and its production
KR20220088157A (en) Ferritic stainless steel excellent in heat resistance and method for manufacturing thereof
JPS61154703A (en) Manufacture of two-phase stainless steel stock
JPH07109006B2 (en) Method for producing A-l containing austenitic stainless steel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140130

AK Designated contracting states

Kind code of ref document: A1

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

DAX Request for extension of the european patent (deleted)
RA4 Supplementary search report drawn up and despatched (corrected)

Effective date: 20150507

RIC1 Information provided on ipc code assigned before grant

Ipc: B21B 1/02 20060101ALI20150429BHEP

Ipc: C21D 9/46 20060101ALI20150429BHEP

Ipc: B21B 3/02 20060101AFI20150429BHEP

Ipc: C22C 38/58 20060101ALI20150429BHEP

Ipc: C22C 38/00 20060101ALI20150429BHEP

Ipc: C22C 38/34 20060101ALI20150429BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20160713

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

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

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 853106

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602012026696

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20161214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170314

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170315

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 853106

Country of ref document: AT

Kind code of ref document: T

Effective date: 20161214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170414

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170314

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170414

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602012026696

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20170915

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170731

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170731

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170726

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170726

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170726

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602012026696

Country of ref document: DE

Representative=s name: GRUND INTELLECTUAL PROPERTY GROUP PATENTANWALT, DE

Ref country code: DE

Ref legal event code: R081

Ref document number: 602012026696

Country of ref document: DE

Owner name: NIPPON STEEL CORPORATION, JP

Free format text: FORMER OWNER: NIPPON STEEL & SUMITOMO METAL CORPORATION, TOKYO, JP

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20120726

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20161214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161214

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230612

Year of fee payment: 12

Ref country code: FR

Payment date: 20230620

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20230613

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20230616

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230601

Year of fee payment: 12

Ref country code: FI

Payment date: 20230712

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SI

Payment date: 20230613

Year of fee payment: 12

Ref country code: DE

Payment date: 20230531

Year of fee payment: 12