US20040265162A1 - Ferritic stainless steel and use thereof in the manufacture for high temperature resistant products - Google Patents
Ferritic stainless steel and use thereof in the manufacture for high temperature resistant products Download PDFInfo
- Publication number
- US20040265162A1 US20040265162A1 US10/491,044 US49104404A US2004265162A1 US 20040265162 A1 US20040265162 A1 US 20040265162A1 US 49104404 A US49104404 A US 49104404A US 2004265162 A1 US2004265162 A1 US 2004265162A1
- Authority
- US
- United States
- Prior art keywords
- steel
- hot
- cold rolling
- ferritic stainless
- stainless steel
- 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.)
- Abandoned
Links
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 37
- 239000010959 steel Substances 0.000 claims abstract description 37
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052729 chemical element Inorganic materials 0.000 claims abstract description 5
- 238000005097 cold rolling Methods 0.000 claims description 13
- 238000005098 hot rolling Methods 0.000 claims description 13
- 238000005554 pickling Methods 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- 238000005242 forging Methods 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000010936 titanium Substances 0.000 description 8
- 239000011651 chromium Substances 0.000 description 7
- 239000010955 niobium Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000004901 spalling Methods 0.000 description 2
- 239000002436 steel type Substances 0.000 description 2
- 238000005382 thermal cycling Methods 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- -1 Chromium nitrides Chemical class 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
Definitions
- the present invention refers to the field of the ferritic stainless steels usable in the manufacture of high temperature resistant products.
- Object of the present invention is a ferritic stainless steel that, by virtue of its composition and of suitable thermo-mechanical treatments, is suitable for the manufacture of products exhibiting high performances at high temperatures, in particular for the manufacture of vehicle exhaust manifold systems.
- ferritic stainless steels by virtue of their smaller thermal expansion coefficient, are preferred to the austenitic ones.
- ferritic stainless steels are adopted for the manufacture of vehicle exhaust system components working at temperatures reaching 750° C.
- cast iron had longtime been preferred to ferritic stainless steels.
- the adoption of the former material proved unsatisfactory due to the occurrence of drawbacks related to the weight increases, the entailed fuel consumption, and the design difficulty due to the high thickness of the component thus manufactured.
- object of the present invention is a ferritic stainless steel, comprising the following chemical elements expressed in percentage by weight: Cr 14.0-20.0 Al 0.50-1.50 Zr 0.10-0.50 Si 0.30-1.50 Ti 0.10-0.35 Nb 0.25-0.55 C ⁇ 0.035 N ⁇ 0.035
- the ferritic stainless steel according to the present invention may also comprise Yttrium and/or rare earth elements in a percentage by weight comprised in the range 0.10-0.30.
- the present invention further encompasses strips or sheets made of steel according to the invention, weldable, formable and highly resistant to oxidation and creep.
- a further object of the present invention is a process for the preparing of the strips or sheets, wherein the steel according to the invention is subjected to the following steps:
- the present invention encompasses the use of the ferritic stainless steel according to the invention for the manufacture of products in form of flat bloom, strip, ingot, casting, forging or semimanufactured item, as well as the flat blooms, the strips, the ingots, the castings, the forgings and the semimanufactured items made therewith.
- the present invention further refers to the use of the steel strip or sheet according to the invention for the production of pipes or of pipe-derivable products.
- the pipes thus manufactured can be weldless or welded, even longitudinally welded. Also the pipes and the pipe-derivable products manufactured with said steel strips or sheets are an object of the present invention.
- the invention also refers to high temperature exhaust system components, in particular to vehicle exhaust manifolds.
- the ferritic stainless steel of the invention exhibits the desired features, in particular a resistance to hot cyclic oxidation, by virtue of an apt synergy of chemical elements like Chromium, Aluminum, Zirconium, Silicon, Titanium, Niobium, Carbon, Nitrogen and optionally Yttrium and/or rare earth elements.
- These features, desired at high temperatures are enhanced by the hot and/or cold rolling and by the subsequent annealing treatment of sheets and/or strips thus obtainable, during which a Zircon carbonitride precipitation occurs, optionally followed by a pickling treatment.
- Chromium in the indicated percentages by weight, remarkably increases resistance to oxidation without promoting the formation of brittle phases.
- Silicon and Aluminum stabilize the ferritic matrix and are accountable for the increase of resistance to hot oxidation.
- An employ of these elements above the upper limits set forth is detrimental to steel quality in terms of formation of intermetallic phases and of increased manufacturing problems.
- Zircon forms stable carbonitrides, whose presence influences the microstructural development during annealing of the cold-rolled items.
- Titanium and Niobium form stable carbides and nitrides, and prevent the precipitation of Chromium nitrides and carbides onto the edge of the grains and the entailed dechroming (sensitizing) of the matrix in the vicinities thereof, further promoting the presence of an entirely ferritic structure at all temperatures, as reducing the dissolved Carbon and Nitrogen quantities.
- Yttrium and/or rare earth elements enhance the resistance to hot oxidation in the presence of thermal and mechanical shocks due to the increased adhesion of the oxide onto the metal substrate.
- FIG. 1 shows the weight variation per surface unit effected on samples of austenitic and of ferritic steels in order to identify a steel known to the state of the art apt to provide the best features in terms of resistance to hot cyclic oxidation, carrying out for this purpose a cyclic oxidation test according to the number of cycles at temperatures equal to 1000° C.
- FIG. 2 shows the weight variation per surface unit in an AISI 441 steel sample of a composition known to the art, identified as apt to provide the best features to hot cyclic oxidation, carrying out for this purpose a cyclic oxidation test according to the number of cycles at temperatures equal to 1000° C.
- FIG. 3 shows the weight variation per surface unit in a steel sample according to the invention, carrying out for this purpose a cyclic oxidation test according to the number of cycles at temperatures equal to 1000° C.
- Ferritic stainless steels 441, 436, 429, and austenitic steels 321, 309, 310, 4828 operating at a 1000° C. temperature were tested.
- FIG. 1 shows the weight variation per surface unit of the various steel types according to the number of cycles.
- austenitic steels exhibit a worse behavior, with a swift weight decrease due to spalling.
- steel 321 has a high instability and decays over a very short time.
- steel 441 undergoes a slight weight increase, with respect to 436 and 429 steels that instead exhibit a slight weight decrease after the test.
- the steel 441 apt to provide the best performances among known steels, was used as comparison to the steel advanced according to the present invention.
- This conventional steel AISI 441 was prepared according to the following composition expressed as percentage by weight: C 0.016; Cr 18.18; Si 0.60; Al 0.09; Nb 0.42; Ti 0.18; Mn 0.18; Cu 0.08; N 0.012, and iron q.s. to 100.
- Post pickling the hot strips were forwarded to cold rolling down to a 1.5 mm thickness and then annealed 40 sec at a 1080° C. temperature.
- a steel according to the present invention is prepared, having the following composition expressed as percentage by weight: Cr 17.68; Al 0.94; Zr 0.15; Si 1.16; Ti 0.21; Nb 0.40; C 0.022; N 0.013, and substantially iron q.s. to 100.
- the steel is cast by a casting process into flat blooms having thin thicknesses typically ranging from 50 to 90 mm, and in the example being equal to 60 mm.
- This flat bloom obtained according to the abovedisclosed composition was heated to 1150° C., and by a subsequent hot rolling thereof strips having a thickness equal to 5 mm were produced.
- a steel according to the present invention is prepared, having the following composition expressed as percentage by weight:
- the steel was cast by a traditional casting process into flat blooms that were first heated to 1150° C. Then, by a subsequent hot-rolling, 5 mm thick strips were made.
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 Sheet Steel (AREA)
- Catalysts (AREA)
- Heat Treatment Of Steel (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2001RM000584A ITRM20010584A1 (it) | 2001-09-26 | 2001-09-26 | Acciaio inossidabile ferritico e suo uso nella fabbricazione di manufatti per impieghi ad elevate temperature. |
| ITRM2001A000584 | 2001-09-26 | ||
| PCT/IT2002/000613 WO2003027343A1 (en) | 2001-09-26 | 2002-09-26 | Ferritic stainless steel and use thereof in the manufacture for high temperature resistant products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20040265162A1 true US20040265162A1 (en) | 2004-12-30 |
Family
ID=11455801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/491,044 Abandoned US20040265162A1 (en) | 2001-09-26 | 2002-09-26 | Ferritic stainless steel and use thereof in the manufacture for high temperature resistant products |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20040265162A1 (de) |
| EP (1) | EP1436440B1 (de) |
| CN (1) | CN1274864C (de) |
| AT (1) | ATE300627T1 (de) |
| CA (1) | CA2461869A1 (de) |
| DE (1) | DE60205269T2 (de) |
| ES (1) | ES2248625T3 (de) |
| IT (1) | ITRM20010584A1 (de) |
| WO (1) | WO2003027343A1 (de) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160115562A1 (en) * | 2012-09-03 | 2016-04-28 | Aperam Stainless France | Ferritic stainless steel sheet, method for the production thereof, and use of the same, especially in exhaust lines |
| EP3438313A4 (de) * | 2016-03-30 | 2019-08-21 | Nippon Steel Nisshin Co., Ltd. | Nb-haltiges ferritisches edelstahlblech und herstellungsverfahren dafür |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE528027C2 (sv) * | 2004-04-16 | 2006-08-08 | Sandvik Intellectual Property | Användning av ett ferritiskt stål i katalysatorer för dieselmotorer |
| CN103725971B (zh) * | 2011-08-11 | 2016-01-20 | 丹阳市华龙特钢有限公司 | 机车制动电阻带的制备方法 |
| US11111570B2 (en) * | 2017-02-28 | 2021-09-07 | Nippon Steel Corporation | Ferritic stainless steel sheet, hot coil, and automobile exhaust flange member |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3782925A (en) * | 1971-12-14 | 1974-01-01 | Deutsche Edelstahlwerke Gmbh | Ferritic heat-resistant steel |
| US3923696A (en) * | 1973-08-22 | 1975-12-02 | Int Nickel Co | Catalyst structure |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0145471B1 (de) * | 1983-12-12 | 1989-11-29 | Armco Advanced Materials Corporation | Warmfester ferritischer Stahl |
| JPS61117251A (ja) * | 1984-11-09 | 1986-06-04 | Daido Steel Co Ltd | 耐熱鋼 |
| JP3541458B2 (ja) * | 1993-10-15 | 2004-07-14 | Ｊｆｅスチール株式会社 | 高温塩害特性に優れたフェライト系ステンレス鋼 |
| FR2790485B1 (fr) * | 1999-03-05 | 2002-02-08 | Usinor | Procede de coulee continue entre cylindres de bandes d'acier inoxydable ferritique a haute ductilite, et bandes minces ainsi obtenues |
-
2001
- 2001-09-26 IT IT2001RM000584A patent/ITRM20010584A1/it unknown
-
2002
- 2002-09-26 CN CN02821307.6A patent/CN1274864C/zh not_active Expired - Lifetime
- 2002-09-26 DE DE60205269T patent/DE60205269T2/de not_active Expired - Lifetime
- 2002-09-26 ES ES02783530T patent/ES2248625T3/es not_active Expired - Lifetime
- 2002-09-26 AT AT02783530T patent/ATE300627T1/de active
- 2002-09-26 WO PCT/IT2002/000613 patent/WO2003027343A1/en not_active Application Discontinuation
- 2002-09-26 EP EP02783530A patent/EP1436440B1/de not_active Expired - Lifetime
- 2002-09-26 US US10/491,044 patent/US20040265162A1/en not_active Abandoned
- 2002-09-26 CA CA002461869A patent/CA2461869A1/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3782925A (en) * | 1971-12-14 | 1974-01-01 | Deutsche Edelstahlwerke Gmbh | Ferritic heat-resistant steel |
| US3923696A (en) * | 1973-08-22 | 1975-12-02 | Int Nickel Co | Catalyst structure |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160115562A1 (en) * | 2012-09-03 | 2016-04-28 | Aperam Stainless France | Ferritic stainless steel sheet, method for the production thereof, and use of the same, especially in exhaust lines |
| US9873924B2 (en) * | 2012-09-03 | 2018-01-23 | Aperam Stainless France | Ferritic stainless steel sheet, method for the production thereof, and use of the same, especially in exhaust lines |
| EP3438313A4 (de) * | 2016-03-30 | 2019-08-21 | Nippon Steel Nisshin Co., Ltd. | Nb-haltiges ferritisches edelstahlblech und herstellungsverfahren dafür |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1436440A1 (de) | 2004-07-14 |
| ATE300627T1 (de) | 2005-08-15 |
| CN1274864C (zh) | 2006-09-13 |
| ES2248625T3 (es) | 2006-03-16 |
| CN1575347A (zh) | 2005-02-02 |
| DE60205269T2 (de) | 2006-05-24 |
| DE60205269D1 (de) | 2005-09-01 |
| ITRM20010584A0 (it) | 2001-09-26 |
| EP1436440B1 (de) | 2005-07-27 |
| CA2461869A1 (en) | 2003-04-03 |
| ITRM20010584A1 (it) | 2003-03-26 |
| WO2003027343A1 (en) | 2003-04-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: THYSSENKRUPP ACCIAI SPECIALI TERNI S.P.A., ITALY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SONGINI, GIANNI;BARTERI, MASSIMO;REEL/FRAME:015673/0362 Effective date: 20040701 |
|
| STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |