EP0388283B1 - Acier inoxydable ferritique et procédé pour l'élaboration d'un tel acier - Google Patents

Acier inoxydable ferritique et procédé pour l'élaboration d'un tel acier Download PDF

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Publication number
EP0388283B1
EP0388283B1 EP90400666A EP90400666A EP0388283B1 EP 0388283 B1 EP0388283 B1 EP 0388283B1 EP 90400666 A EP90400666 A EP 90400666A EP 90400666 A EP90400666 A EP 90400666A EP 0388283 B1 EP0388283 B1 EP 0388283B1
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EP
European Patent Office
Prior art keywords
less
steel
titanium
niobium
nickel
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.)
Expired - Lifetime
Application number
EP90400666A
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German (de)
English (en)
French (fr)
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EP0388283A1 (fr
Inventor
Pierre Bourgain
Jean-Claude Bavay
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.)
Ugine SA
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Ugine SA
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Filing date
Publication date
Application filed by Ugine SA filed Critical Ugine SA
Publication of EP0388283A1 publication Critical patent/EP0388283A1/fr
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Publication of EP0388283B1 publication Critical patent/EP0388283B1/fr
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    • 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
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • 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
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper

Definitions

  • the present invention relates to a ferritic stainless steel very resistant to corrosion in a neutral or weakly acidic chlorinated medium and more particularly suitable for the manufacture of heat exchangers for industry, in particular those cooled by brackish water and water from sea.
  • the present invention also relates to a process for the preparation of such a steel.
  • FR-A-2,377,457 discloses a ferritic steel with chromium nickel molybdenum resistant to corrosion and containing in particular from 18 to 32% of chromium, from 0.1 to 6% of molybdenum, from 0.5 to 5% nickel and not more than 3% copper.
  • the examples of steel described in this document relate to steels containing 1.99 to 2.15% molybdenum. Furthermore, it is specified, on page 9 lines 27 to 32, that the steels having the best alloy compositions are those containing 28% chromium, 2% molybdenum and 4% nickel, as well as those containing 20% chromium , 5% molybdenum and 2% nickel, because they have sufficient structural stability and can be produced economically on an industrial scale.
  • FR-A-2,352,893 is a ferritic stainless steel containing from 0.01 to 0.025% by weight of carbon, from 0.005 to 0.025% by weight of nitrogen, from 20 to 30% by weight of chromium , 3 to 5% molybdenum, 3.2 to 4.8% nickel, 0.1 to 1% copper, 0.2 to 0.7% titanium and / or 0.2 to 1% niobium.
  • This document claims more particularly a high nickel content of between 3.2 to 4.8% associated with a limitation of the copper content of between 0.1 to 1% to obtain the temperature ambient high ductility values.
  • FR-A-2,473,069 also discloses an iron-based ferritic stainless steel containing up to 0.08% by weight of carbon, up to 0.060% by weight of nitrogen, from 25 to 35% in weight of chromium, from 3.60 to 5.60% by weight of molybdenum, up to 2% by weight of nickel, up to 2% by weight of titanium, niobium and zirconium according to the following equation: % Ti / 6 +% Zr / 7 +% cb / 8>% C +% N
  • FR-A-2,473,068 discloses a ferritic stainless steel which has the same composition as the preceding steel, but whose nickel content by weight is between 2 and 5%.
  • nickel is an expensive element which accelerates the formation of embrittling intermetallic phases and reduces the resistance to cavernous corrosion in chlorinated medium.
  • the present invention therefore relates to a ferritic stainless steel in which the addition of copper is limited to a value between 0.5 to 2% by weight so as to reinforce the impact resistance of the alloy while reducing the speed for the formation of hard and embrittling intermetallic phases of the sigma and chi type which can form during heat treatments for manufacturing welding.
  • the steel contains less than 0.010% of carbon and less than 0.015% of nitrogen, the sum of the carbon and of the nitrogen being less than 0.025%.
  • the invention also relates to a process for the production of a ferritic stainless steel from which a steel strip is formed which is hot rolled, characterized in that the hot rolled steel strip is subjected annealing at a temperature between 900 and 1200 ° C., then the steel strip is subjected to a first cold rolling followed by an intermediate annealing at a temperature between 900 and 1200 ° C. and finally the steel strip is subjected to a second cold rolling followed by a final annealing at a temperature between 900 and 1200 ° C.
  • the examples which led to the present invention were obtained from 30 kg ingots produced in the vacuum induction furnace. Slabs from these ingots were heated between 1100 and 1250 ° C for hot rolling to a thickness of 5 mm.
  • the hot-rolled strips are then annealed between 1000 and 1200 ° C followed by cold rolling to a thickness of 2 millimeters. After this cold rolling, annealing on the order of 20 s to 5 min is carried out continuously at a temperature between 900 and 1200 ° C.
  • Additional cold rolling makes it possible to obtain strips of a thickness of 0.8 millimeters which then undergo a final annealing of the order of 20 s to 5 min and at a temperature between 900 and 1200 ° C.
  • Molybdenum is a much more efficient alloying element than chromium because a Mo / Cr equivalent coefficient equal to 3.3 is generally accepted to qualify the improvement in resistance to pitting corrosion due to the action of molybdenum.
  • the increase in the chromium content also accelerates the precipitation of the embrittling phases as shown in the diagram in Figure 2.
  • the curves shown in this diagram show the influence of the holding time at 900 ° C on the elongation A% to rupture at room temperature of an experimental alloy at 29Cr 4Mo 4Ni Ti and 25Cr 4Mo 4Ni Ti.
  • the alloy with approximately 25% chromium, 4% molybdenum, 4% nickel and 0.5% titanium does not exhibit brittleness when cold between 0 and -50 ° C. unlike the alloy containing approximately 29 % of chromium, 4% of molybdenum, 4% of nickel and 0.5% of titanium as it appears on the diagram of figure 5 which shows the evolution of the resistance to the impact rupture according to the temperature and the chromium content.
  • the alloy according to the present invention contains no voluntary addition of nickel which is considered to be an element residual. This absence of a significant amount of nickel allows the adoption of high chromium contents greater than 28.5% and molybdenum greater than 3.5% necessary for obtaining optimal resistance to cavernous and pitting corrosion.
  • ferritic stainless steel containing titanium and niobium for ferritic stainless steel containing titanium and niobium.
  • up to 3% copper and preferably 0.5 to 2% copper are added to the steel, which according to this patent increases the resistance to corrosion in non-oxidizing acids, and in particular in hot sulfuric acid solutions.
  • the results reveal that copper does not cause any improvement in the resistance to corrosion in chlorinated media. weakly acid analogous to corrosive media that form in caves.
  • This diagram shows the corrosion rates (mm / year) deducted from the weight losses observed after 24 hours of immersion in NaCl 2M-0.2M HCl medium deaerated by nitrogen bubbling, at the temperature of 30 ° C respectively for the alloys 6 and 7 of Table 1 above.
  • 0.5 to 2% of copper is added to ferritic stainless steel with a high chromium and molybdenum content and containing titanium or niobium.
  • the diagram in FIG. 7, the curves of which show the influence of 1% of copper on impact resistance, indicates that the addition of approximately 1% of copper to an alloy containing approximately 29% of chromium, 4% of molybdenum and 0.5% of titanium results in a decrease of the order of 20 ° C in the transition temperature between the brittle state characterized by very low breaking energies and the ductile state corresponding to high breaking energies . This results in a very significant improvement in the impact resistance of the alloy due to the addition of copper.
  • an alloy of 0.018% carbon, 0.027% nitrogen, 28.90% chromium, 3.75% molybdenum, 0.035% nickel and 0.56% titanium only has an elongation at break of 6% at room temperature while an alloy of 0.03% carbon, 0.010% nitrogen, 28.90% chromium, 3.97% molybdenum, 0.041% nickel and 0.21% titanium has an elongation at break of 26%.
  • the present invention voluntarily excludes the addition of nickel, which is an expensive element and which accelerates the formation of embrittling intermetallic phases and reduces the resistance to cavernous corrosion in chlorinated medium.
  • ferritic stainless steels according to the present invention are all the more resistant to shocks and have structural stability in the range between 650 and 1000 ° C, the higher the lower the contents of C, N, Ti and Nb.
  • the contents of titanium and / or niobium to be added must be equal to the minimum necessary to fix carbon and nitrogen and take into account the fact that titanium and / or niobium solid solution in ferrite do not participate in the sequestration of carbon and nitrogen.
  • the titanium content must satisfy the following equation: % Ti> 0.10 + 4x (% C) + 3.4 x (% N) and in particular to the equation: % Ti> 0.15 + 4 x (% C) + 3.4 x (% N) so that the resistance to intergranular corrosion is optimal.
  • the coefficients 4 and 3,4 logically follow the approximate values of the atomic masses of titanium (48), carbon (12) and nitrogen (14) as well as the formulas of titanium carbide and titanium nitride, respectively TiC and TiN.
  • the atomic mass of niobium being taken equal to 93 grams.
  • the addition of copper is limited to less than 2%, the precipitation of copper-rich particles resulting in a significant degradation of hot forgeability when the copper content is greater than 2%.
  • An addition of aluminum to the ferritic stainless steel according to the present application can be added during the preparation for deoxidation purposes.
  • the ferritic alloy according to the present invention is particularly suitable for the use in the form of sheets and strips whose thickness may be greater than that generally used in practice (less than one mm) for a steel.
  • ferritic stainless with the same chromium and molybdenum content containing titanium or niobium.
  • the stainless steel described by the present invention is particularly intended for the manufacture of welded tubes for heat exchangers conveying chlorinated water. It can, for example, be produced by the steel, electrical, AOD and / or vacuum refining, continuous casting and hot rolling on strip train industry.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Heat Treatment Of Steel (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
EP90400666A 1989-03-16 1990-03-13 Acier inoxydable ferritique et procédé pour l'élaboration d'un tel acier Expired - Lifetime EP0388283B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8903472 1989-03-16
FR8903472A FR2644478B1 (sr) 1989-03-16 1989-03-16

Publications (2)

Publication Number Publication Date
EP0388283A1 EP0388283A1 (fr) 1990-09-19
EP0388283B1 true EP0388283B1 (fr) 1994-12-28

Family

ID=9379766

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90400666A Expired - Lifetime EP0388283B1 (fr) 1989-03-16 1990-03-13 Acier inoxydable ferritique et procédé pour l'élaboration d'un tel acier

Country Status (11)

Country Link
US (1) US5230752A (sr)
EP (1) EP0388283B1 (sr)
JP (1) JPH04504140A (sr)
AT (1) ATE116379T1 (sr)
AU (1) AU5289090A (sr)
CA (1) CA2050315C (sr)
DE (1) DE69015394T2 (sr)
DK (1) DK0388283T3 (sr)
ES (1) ES2069035T3 (sr)
FR (1) FR2644478B1 (sr)
WO (1) WO1990010723A1 (sr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5824265A (en) * 1996-04-24 1998-10-20 J & L Fiber Services, Inc. Stainless steel alloy for pulp refiner plate
US7842434B2 (en) * 2005-06-15 2010-11-30 Ati Properties, Inc. Interconnects for solid oxide fuel cells and ferritic stainless steels adapted for use with solid oxide fuel cells
US7981561B2 (en) * 2005-06-15 2011-07-19 Ati Properties, Inc. Interconnects for solid oxide fuel cells and ferritic stainless steels adapted for use with solid oxide fuel cells
US8158057B2 (en) * 2005-06-15 2012-04-17 Ati Properties, Inc. Interconnects for solid oxide fuel cells and ferritic stainless steels adapted for use with solid oxide fuel cells
EP1797212A4 (en) * 2004-09-16 2012-04-04 Vladimir Belashchenko DEPOSIT SYSTEM, METHODS AND MATERIALS FOR COMPOSITE COATINGS
UA111115C2 (uk) 2012-04-02 2016-03-25 Ейкей Стіл Пропертіс, Інк. Рентабельна феритна нержавіюча сталь
WO2014103728A1 (ja) * 2012-12-27 2014-07-03 昭和電工株式会社 成膜装置
US10883160B2 (en) 2018-02-23 2021-01-05 Ut-Battelle, Llc Corrosion and creep resistant high Cr FeCrAl alloys
CN115572898B (zh) * 2022-09-23 2023-12-01 成都先进金属材料产业技术研究院股份有限公司 一种高铬铁素体不锈钢的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB465999A (en) * 1935-09-16 1937-05-20 Stahlwerke Roechling Buderus Improvements in articles that are subjected to and must resist attack by solutions containing free chlorine or hypochlorous acid, its salts and solutions thereof
FR2091642A5 (en) * 1970-05-16 1972-01-14 Nippon Steel Corp Stainless steel resistant to pitting corrosion -and suitable for comp - used in sewater
JPS50109809A (sr) * 1974-02-07 1975-08-29
US4360381A (en) * 1980-04-11 1982-11-23 Sumitomo Metal Industries, Ltd. Ferritic stainless steel having good corrosion resistance
ATE12527T1 (de) * 1981-01-16 1985-04-15 Allegheny Ludlum Steel Ferritischer, rostfreier, korrosionsbestaendiger, schweissbarer stahl mit geringem gehalt an zwischengittersubstanzen und verfahren zu seiner herstellung.

Also Published As

Publication number Publication date
DE69015394T2 (de) 1995-08-17
CA2050315C (fr) 1999-04-27
WO1990010723A1 (fr) 1990-09-20
DE69015394D1 (de) 1995-02-09
JPH04504140A (ja) 1992-07-23
US5230752A (en) 1993-07-27
FR2644478B1 (sr) 1993-10-15
EP0388283A1 (fr) 1990-09-19
ATE116379T1 (de) 1995-01-15
ES2069035T3 (es) 1995-05-01
DK0388283T3 (da) 1995-04-03
FR2644478A1 (sr) 1990-09-21
AU5289090A (en) 1990-10-09

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