EP0626460B1 - Austenitic stainless steel with high resistance against corrosion in chloride and sulfuric environments, and uses of this steel - Google Patents

Austenitic stainless steel with high resistance against corrosion in chloride and sulfuric environments, and uses of this steel Download PDF

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Publication number
EP0626460B1
EP0626460B1 EP94401110A EP94401110A EP0626460B1 EP 0626460 B1 EP0626460 B1 EP 0626460B1 EP 94401110 A EP94401110 A EP 94401110A EP 94401110 A EP94401110 A EP 94401110A EP 0626460 B1 EP0626460 B1 EP 0626460B1
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Prior art keywords
stainless steel
austenitic stainless
steel according
steel
equipment
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German (de)
French (fr)
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EP0626460A1 (en
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François Dupoiron
Jean-Christophe Gagnepain
Michel Verneau
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Industeel Creusot
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Creusot Loire SA
Creusot Loire Industrie SA
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese

Definitions

  • the present invention relates to stainless steel austenitic with high mechanical strength and high corrosion resistance.
  • stainless steels with high mechanical resistance and high corrosion resistance in chlorinated media and sulfuric media or even in media at a time chlorinated and sulfuric are superaustenitic steels, austenoferritic steels or superaustenitic steels with a high nitrogen content.
  • superaustenitic steels with a high nitrogen content are, for these applications, the steels which offer the better performance in terms of combination of characteristics mechanical and corrosion resistance. They are described by two European patents: EP-A-0.438.992 and EP-A-0.342.574.
  • the subject of the present invention is an austenitic stainless steel with high mechanical strength and high corrosion resistance, characterized in that it contains by weight: 23% ⁇ Cr ⁇ 28% 25% ⁇ Ni ⁇ 28% 4.5% ⁇ Mo ⁇ 7% 0.35% ⁇ N ⁇ 0.8% 0.5% ⁇ Mn ⁇ 5.4% C ⁇ 0.06% S ⁇ 0.010% If ⁇ 1% 0.5% ⁇ Cu ⁇ 3%, and at least one of the elements B, Nb, V, Al in the following contents: B 0.0001 to 0.003%, Nb 0.001 to 0.3%, V 0.001 to 0.3% and Al 0.001 to 0.1 %, the rest, with the exception of iron, being made up of impurities resulting from processing.
  • the carbon content is less than 0.04%.
  • this steel can contain from 1% to 2% copper.
  • the composition of the steel according to the invention is as follows: 25% ⁇ Cr ⁇ 26% 25% ⁇ Ni ⁇ 26% 6% ⁇ Mo ⁇ 7% 0.4% ⁇ N ⁇ 0.5% 2.5% ⁇ Mn ⁇ 3.5% C ⁇ 0.03% If ⁇ 0.3% 1% ⁇ Cu ⁇ 2%, the rest, with the exception of iron, being constituted by impurities resulting from the production.
  • the invention also relates to the use steel according to the invention for the manufacture of equipment pollution control from thermal power plants and household waste incineration plants, especially gas or smoke washing towers, gas lines or smoke and chimneys; for manufacturing equipment delignification, in particular by the process bisulfite, filtration and bleaching of the pulp paper; for manufacturing equipment for industry chemical in chlorinated or acidic medium and in particular for the manufacture of tanks, reservoirs, reactors, tubes pump casing and pump shafts; for the manufacture off-shore platform equipment subject to corrosion by sea water and / or hydrocarbons and in particular supports for flares, heat exchangers, separators, tubular plates, piping transport of sea water, pipes used for the transport of hydrocarbons, elements of protection of pylon areas in the vicinity of the free surface from the sea, mace rods, pump shafts, flanges connection, wellheads, manifolds and risers; for the manufacture road or rail transport tanks of chlorides or highly corrosive acids.
  • Such steel must contain less than 0.06% of carbon to avoid precipitation of carbides to grain boundaries which deteriorate corrosion resistance and it is preferable to limit this content to 0.04% and even better at 0.03%.
  • the steel always contains a little sulfur must be up to 0.010% which is favorable to machinability but which promotes corrosion by bites, too, it's better to have a sulfur content less than 0.01%.
  • copper between 0.5% and 3% and preferably between 1% and 2%; copper also has the advantage of improving machinability.
  • Additions of copper, vanadium, niobium, boron, aluminum are optional and can be made alone or in combination.
  • the main alloying elements have, for certain properties, effects all the more favorable as their content is high and for other properties, effects all the less unfavorable as the content is lower; therefore, it is preferable to choose the chemical composition in a composition range which is not too wide.
  • the domains of chromium, nickel and molybdenum must be limited to: 23% ⁇ Cr ⁇ 28% 25% ⁇ Ni ⁇ 28% 4.5% ⁇ Mo ⁇ 7%.
  • This steel may also contain Nb, V, B or Al as previously stated.
  • the steel according to the invention has an additional advantage which comes from the fact that the product A x R of the elongation at break by the break limit is very high (two times more than for the steels of the prior art used for transport) so that resistance to impact of the walls made with this steel is very high and in particular much higher than for steels of prior art.
  • This feature has the advantage of allowing to make tanks, containers or pipes for transporting much safer corrosives in the event of an impact, that the equivalent equipment produced with steels according to the prior art.
  • This steel makes it particularly suitable for the manufacture of reactors (scrubbers, washing tower, filter tanks, attack tanks), tubes (welded and seamless), chimneys, parts junction such as flanges, manifolds, flow lines, separators and road or rail transport tanks, for industries in which this equipment is subject to very severe corrosion by chlorinated media and / or pure or polluted sulfuric and in particular for off-shore oil exploitation platforms, for combustion smoke abatement facilities thermal power plants or incineration of household waste, for the preparation of paper pulp in particular by the process called "bisulfite", and in particular for filtration, bleaching and delignification equipment, for the chemical industry and more particularly for hydrometallurgy equipment and the industry fertilizer using mineral attack by media concentrated sulfurics.
  • This steel also makes it possible to carry out any part subject to abrasion / corrosion in environments chlorides and / or acids.

Abstract

The steel contains, in proportions by weight, from 20 to 30 % of chromium, 25 to 32 % of nickel, from 3 to 7 % of molybdenum, from 0.35 to 0.8 % of nitrogen, from 0.5 to 5.4 % of manganese, up to 0.06 % of carbon and up to 1 % of silicon. As a result of its great versatility in corrosion resistance, the steel can be employed in particular for the manufacture of equipment for decontamination of fumes, the paper pulp industry, for the chemical industry or for oil exploration, seawater plants and for the manufacture of tankers for transporting corrosive products. The steel has a very high structural stability.

Description

La présente invention concerne un acier inoxydable austénitique à haute résistance mécanique et haute résistance à la corrosion.The present invention relates to stainless steel austenitic with high mechanical strength and high corrosion resistance.

Pour fabriquer des équipements destinés notamment à l'épuration des fumées de centrales électriques thermiques ou destinés à des plate-formes pétrolières travaillant au contact de l'eau de mer et de milieux contenant des gaz acides ou encore pour la fabrication de pâte à papier ou pour l'industrie chimique, on utilise des aciers inoxydables à haute résistance mécanique et à haute résistance à la corrosion dans les milieux chlorurés et les milieux sulfuriques ou même dans des milieux à la fois chlorurés et sulfuriques. Ces aciers inoxydables sont des aciers superausténitiques, des aciers austénoferritiques ou des aciers superausténitiques à forte teneur en azote. Les aciers superausténitiques à forte teneur en azote sont, pour ces applications, les aciers qui offrent les meilleures performances en terme de combinaison de caractéristiques mécaniques et de résistance à la corrosion. Ils sont décrits par deux brevets européens : EP-A-0.438.992 et EP-A-0.342.574.To manufacture equipment intended in particular the purification of fumes from power plants thermal or intended for oil platforms working in contact with sea water and environments containing acid gases or for the manufacture of pulp or for the chemical industry, we use stainless steels with high mechanical resistance and high corrosion resistance in chlorinated media and sulfuric media or even in media at a time chlorinated and sulfuric. These stainless steels are superaustenitic steels, austenoferritic steels or superaustenitic steels with a high nitrogen content. Superaustenitic steels with a high nitrogen content are, for these applications, the steels which offer the better performance in terms of combination of characteristics mechanical and corrosion resistance. They are described by two European patents: EP-A-0.438.992 and EP-A-0.342.574.

Mais ces aciers (décrits par EP-A-0.438.992 et EP-A-0.342.574) présentent des inconvénients. D'une part si l'amélioration de la résistance à la corrosion en milieu chloruré de ces aciers est effective, la résistance à la corrosion en milieux sulfuriques concentrés pollués ou non de ces nouvelles nuances est moyenne si bien que l'aptitude de ces aciers à une utilisation polyvalente dans des milieux corrosifs variés ou renfermant des agents corrosifs différents par exemple chlorurés et sulfuriques est moins bonne que celle des aciers connus antérieurement qui avaient par contre des caractéristiques mécaniques plus faibles.But these steels (described by EP-A-0.438.992 and EP-A-0.342.574) have drawbacks. Firstly if improving the corrosion resistance in chlorinated medium of these steels is effective, the resistance corrosion in concentrated polluted sulfuric media or not of these new shades is average so much so that the suitability of these steels for versatile use in various corrosive environments or containing agents different corrosives for example chlorides and sulfurics is not as good as that of previously known steels which on the other hand had mechanical characteristics weaker.

D'autre part, lorsqu'on utilise le type d'acier décrit par le brevet EP-A-0.438.992 pour fabriquer des pièces épaisses, il apparaít au cours de la fabrication de ces pièces, des phénomènes de ségrégation ou de précipitation de phases intermétalliques qui détériorent très notablement les propriétés mécaniques notamment la résilience et la tenue à la corrosion.On the other hand, when using the type of steel described by patent EP-A-0.438.992 for manufacturing thick parts, it appears during the manufacture of these parts, phenomena of segregation or precipitation of intermetallic phases which very significantly deteriorate the mechanical properties, in particular the resilience and resistance to corrosion.

On connaít, par le document EP-A-0.292.061, des aciers polyvalents à haute teneur en nickel, mais, d'une part ils sont très coûteux et d'autre part ils n'ont pas de caractéristiques mécaniques suffisantes pour répondre aux exigences des applications envisagées dans la présente description.We know, from document EP-A-0.292.061, versatile steels high in nickel, but on the one hand they are very expensive and on the other hand they do not have sufficient mechanical characteristics to meet the requirements of the applications envisaged in the present description.

Le but de la présente invention est de remédier à ces inconvénients en proposant un acier inoxydable à hautes caractéristiques mécaniques et notamment à limite d'élasticité supérieure à 400 MPa et à haute résistance à la corrosion dans les milieux chlorurés et les milieux sulfuriques purs ou pollués et notamment ayant un indice de résistance à la corrosion par piqûre PREN = % Cr + 3,3 % Mo + 16 % N supérieur à 50, qui ait une très bonne aptitude à une utilisation polyvalente dans des milieux corrosifs variés contenant des agents corrosifs différents par exemple chlorurés et sulfuriques et qui permette de fabriquer des pièces épaisses qui aient une très bonne résilience et résistance à la corrosion à coeur.The object of the present invention is to remedy these drawbacks by offering stainless steel with high mechanical characteristics and in particular with elastic limit higher than 400 MPa and high resistance to corrosion in chlorinated media and pure sulfuric media or polluted and in particular having an index of resistance to pitting corrosion PREN =% Cr + 3.3% Mo + 16% N greater than 50, which has a very good suitability for versatile use in various corrosive environments containing different corrosive agents such as chlorides and sulfurics and which allows to make thick parts which have a very good resilience and corrosion resistance at its core.

A cet effet, la présente invention a pour objet un acier inoxydable austénitique à haute résistance mécanique et haute résistance à la corrosion caractérisé en ce qu'il contient en poids : 23 % ≤ Cr ≤ 28 % 25 % ≤ Ni ≤ 28 % 4,5 % ≤ Mo ≤ 7 % 0,35 % ≤ N ≤ 0,8 % 0,5 % ≤ Mn ≤ 5,4 % C ≤ 0,06 % S ≤ 0,010% Si ≤ 1 % 0,5 % ≤ Cu ≤ 3 %, et l'un au moins des éléments B, Nb, V, Al dans les teneurs suivantes : B 0,0001 à 0,003 %, Nb 0,001 à 0,3 %, V 0,001 à 0,3 % et Al 0,001 à 0,1 %, le reste, à l'exception du fer, étant constitué par des impuretés résultant de l'élaboration.To this end, the subject of the present invention is an austenitic stainless steel with high mechanical strength and high corrosion resistance, characterized in that it contains by weight: 23% ≤ Cr ≤ 28% 25% ≤ Ni ≤ 28% 4.5% ≤ Mo ≤ 7% 0.35% ≤ N ≤ 0.8% 0.5% ≤ Mn ≤ 5.4% C ≤ 0.06% S ≤ 0.010% If ≤ 1% 0.5% ≤ Cu ≤ 3%, and at least one of the elements B, Nb, V, Al in the following contents: B 0.0001 to 0.003%, Nb 0.001 to 0.3%, V 0.001 to 0.3% and Al 0.001 to 0.1 %, the rest, with the exception of iron, being made up of impurities resulting from processing.

De préférence, la teneur en carbone est inférieure à 0,04 %. Pour améliorer sa résistance à la corrosion, cet acier peut comporter de 1 % à 2 % de cuivre. Preferably, the carbon content is less than 0.04%. For improve its corrosion resistance, this steel can contain from 1% to 2% copper.

De manière préférentielle, la composition de l'acier selon l'invention est la suivante : 25 % ≤ Cr ≤ 26 % 25 % ≤ Ni ≤ 26 % 6 % ≤ Mo ≤ 7 % 0,4 % ≤ N ≤ 0,5 % 2,5 % ≤ Mn ≤ 3,5 % C ≤ 0,03 % Si ≤ 0,3 % 1 % ≤ Cu ≤ 2 %, le reste, à l'exception du fer, étant constitué par des impuretés résultant de l'élaboration.Preferably, the composition of the steel according to the invention is as follows: 25% ≤ Cr ≤ 26% 25% ≤ Ni ≤ 26% 6% ≤ Mo ≤ 7% 0.4% ≤ N ≤ 0.5% 2.5% ≤ Mn ≤ 3.5% C ≤ 0.03% If ≤ 0.3% 1% ≤ Cu ≤ 2%, the rest, with the exception of iron, being constituted by impurities resulting from the production.

Enfin, la composition chimique de l'acier doit de préférence satisfaire les relations suivantes : 95 < kP = % Cr + 0,3 % Ni + 9 % Si + 27 % Mo + 130 % P - 8 % N < 232 et de préférence : 95 < kP < 210 et 319 < kC = 3,3 % Cr + 10 % Ni + % Mo + 1,5 % Cu < 432 et de préférence : 355 < kC < 432. Finally, the chemical composition of the steel must preferably satisfy the following relationships: 95 <kP =% Cr + 0.3% Ni + 9% Si + 27% Mo + 130% P - 8% N <232 and preferably: 95 <kP <210 and 319 <kC = 3.3% Cr + 10% Ni +% Mo + 1.5% Cu <432 and preferably: 355 <kC <432.

L'invention a également pour objet l'utilisation de l'acier selon l'invention pour la fabrication d'équipements de dépollution des fumées de centrales thermiques et d'usines d'incinération d'ordures ménagères, notamment les tours de lavage de gaz ou de fumées, les conduites de gaz ou fumées et les cheminées ; pour la fabrication d'équipements de délignification, notamment par le procédé au bisulfite, de filtration et de blanchiement de la pâte à papier ; pour la fabrication d'équipements pour l'industrie chimique en milieu chloruré ou acide et notamment pour la fabrication de cuves, réservoirs, réacteurs, tubes corps de pompe et arbres de pompe ; pour la fabrication d'équipements de plate-formes off-shore soumis à la corrosion par l'eau de mer et/ou des hydrocarbures et notamment les supports de torchères, d'échangeurs de chaleur, de séparateurs, de plaques tubulaires, de tuyauteries de transport d'eau de mer, de tuyauteries utilisées pour le transport des hydrocarbures, d'éléments de protection des zones des pylones situées au voisinage de la surface libre de la mer, de masses tiges, d'arbres de pompe, de brides de raccordement, de têtes de puits, de collecteurs (manifolds) et de colonnes montantes (risers) ; pour la fabrication de citernes de transport routier ou ferroviaire de produits chlorurés ou acides très corrosifs.The invention also relates to the use steel according to the invention for the manufacture of equipment pollution control from thermal power plants and household waste incineration plants, especially gas or smoke washing towers, gas lines or smoke and chimneys; for manufacturing equipment delignification, in particular by the process bisulfite, filtration and bleaching of the pulp paper; for manufacturing equipment for industry chemical in chlorinated or acidic medium and in particular for the manufacture of tanks, reservoirs, reactors, tubes pump casing and pump shafts; for the manufacture off-shore platform equipment subject to corrosion by sea water and / or hydrocarbons and in particular supports for flares, heat exchangers, separators, tubular plates, piping transport of sea water, pipes used for the transport of hydrocarbons, elements of protection of pylon areas in the vicinity of the free surface from the sea, mace rods, pump shafts, flanges connection, wellheads, manifolds and risers; for the manufacture road or rail transport tanks of chlorides or highly corrosive acids.

L'invention va maintenant être décrite de façon plus précise mais non limitative.The invention will now be described in a manner more precise but not limiting.

L'acier inoxydable austénitique selon l'invention doit contenir (teneurs exprimées en % en poids) :

  • du chrome : de 23 % pour obtenir une bonne résistance à la corrosion localisée et inférieure ou égal à 28 % pour avoir une cinétique de précipitation des carbures et/ou phases intermétalliques pas trop rapide ; de préférence, on choisira une teneur en chrome comprise entre 25 % et 26 %.
  • du nickel : de 25 % pour obtenir une résistance à la corrosion dans des milieux très divers et notamment dans les milieux sulfuriques purs ou pollués et/ou les gaz acides et jusqu'à 28 % pour ne pas trop diminuer la solubilité de l'azote ; on choisira de préférence une teneur en nickel comprise entre 25 % et 26 %.
  • du molybdène : de 4,5 % pour améliorer la résistance à la corrosion localisée et jusqu'à 7 % pour limiter les ségrégations dans les produits épais qui détériorent la résilience et la tenue à la corrosion ; de préférence on choisira un molybdène supérieur à 6 %.
  • de l'azote : de 0,35 % pour obtenir un niveau de caractéristiques mécaniques élevées, améliorer la stabilité structurale et augmenter la résistance à la corrosion et jusqu'à 0,8 % pour éviter de trop détériorer la résilience par précipitation de nitrures ; de préférence on choisira une teneur en azote comprise entre 0,4 % et 0,5 %.
  • du manganèse : de 0,5 % pour améliorer la solubilité de l'azote et jusqu'à 5,4 % car une trop forte teneur en manganèse détériore la stabilité structurale de l'acier et dégrade les réfractaires d'aciérie pendant l'élaboration.
The austenitic stainless steel according to the invention must contain (contents expressed in% by weight):
  • chromium: 23% to obtain good resistance to localized corrosion and less than or equal to 28% to have a kinetics of precipitation of carbides and / or intermetallic phases not too fast; preferably, a chromium content of between 25% and 26% will be chosen.
  • nickel: 25% to obtain corrosion resistance in a wide variety of media, especially in pure or polluted sulfuric media and / or acid gases and up to 28% so as not to reduce the nitrogen solubility too much ; preferably, a nickel content of between 25% and 26% will be chosen.
  • molybdenum: 4.5% to improve resistance to localized corrosion and up to 7% to limit segregation in thick products which deteriorate resilience and resistance to corrosion; preferably, a molybdenum greater than 6% will be chosen.
  • nitrogen: 0.35% to obtain a high level of mechanical characteristics, improve structural stability and increase resistance to corrosion and up to 0.8% to avoid damaging the resilience by precipitation of nitrides; preferably, a nitrogen content of between 0.4% and 0.5% will be chosen.
  • manganese: from 0.5% to improve the solubility of nitrogen and up to 5.4% because too high a manganese content deteriorates the structural stability of the steel and degrades the steelworks refractories during production .

Un tel acier doit contenir moins de 0,06 % de carbone pour éviter la précipitation de carbures aux joints de grains qui détériorent la résistance à la corrosion et il est préférable de limiter cette teneur à 0,04 % et encore mieux à 0,03 %.Such steel must contain less than 0.06% of carbon to avoid precipitation of carbides to grain boundaries which deteriorate corrosion resistance and it is preferable to limit this content to 0.04% and even better at 0.03%.

L'acier contient toujours un peu de soufre doit être jusqu'à 0.010 % qui est favorable à l'usinabilité mais qui favorise la corrosion par piqures, aussi, il est préférable d'avoir une teneur en soufre inférieure à 0,01 %. The steel always contains a little sulfur must be up to 0.010% which is favorable to machinability but which promotes corrosion by bites, too, it's better to have a sulfur content less than 0.01%.

Pour améliorer la résistance à la corrosion en milieu sulfurique et en milieu chloruré acide on peut ajouter du cuivre entre 0,5 % et 3 % et de préférence entre 1% et 2 % ; le cuivre a l'avantage également d'améliorer l'usinabilité.To improve corrosion resistance by sulfuric medium and in acid chlorinated medium one can add copper between 0.5% and 3% and preferably between 1% and 2%; copper also has the advantage of improving machinability.

Pour améliorer les caractéristiques mécaniques on peut ajouter entre 0,001 % et 0,3 % de niobium ou de vanadium.To improve mechanical characteristics between 0.001% and 0.3% of niobium or vanadium.

Pour améliorer la forgeabilité et ainsi faciliter les opérations de laminage à chaud ou de forgeage à chaud, il est préférable d'ajouter de 0,001 % à 0,1 % d'aluminium et éventuellement de 0,0001 % à 0,003 % de bore.To improve forgeability and thus facilitate hot rolling or forging operations warm, it is best to add from 0.001% to 0.1% aluminum and possibly from 0.0001% to 0.003% of boron.

De préférence, l'acier contient moins de 0,04 % de carbone. Cet acier a l'avantage d'avoir, simultanément :

  • une résistance mécanique élevée et notamment une limite d'élasticité supérieure à 400 MPa,
  • une bonne résilience en particulier lorsqu'il est utilisé pour réaliser des pièces épaisses ou massives telles que des tôles fortes ou des pièces forgées, du fait en particulier d'une teneur en molybdène limitée à 7 % maximum,
  • une bonne résistance à la corrosion localisée en milieu chloruré, il est notamment caractérisé par un indice de piqure P.R.E.N. = % Cr + 3,3 % Mo + 16 % N > 50
  • une bonne résistance à la corrosion dans les milieux à la fois chlorurés et sulfuriques, du fait de sa teneur en nickel élevée (> 25 %).
Preferably, the steel contains less than 0.04% carbon. This steel has the advantage of having simultaneously:
  • high mechanical strength and in particular an elastic limit greater than 400 MPa,
  • good resilience, in particular when it is used to produce thick or massive parts such as heavy plates or forgings, due in particular to a molybdenum content limited to a maximum of 7%,
  • good resistance to localized corrosion in a chlorinated environment, it is in particular characterized by a bite index PREN =% Cr + 3.3% Mo + 16% N> 50
  • good corrosion resistance in both chlorinated and sulfuric media, due to its high nickel content (> 25%).

En ajoutant de 0,5 % à 3 % de cuivre à cet acier, on obtient un acier dont la résistance à la corrosion et l'usinabilité sont améliorées.By adding 0.5% to 3% copper to this steel, a steel is obtained whose corrosion resistance and machinability are improved.

Lorsqu'aux aciers précédemment définis, on ajoute 0,001 % à 0,3 % de niobium ou 0,001 % à 0,3 % de vanadium on obtient un acier dont les caractéristiques mécaniques sont améliorées.When the steels previously defined, we add 0.001% to 0.3% niobium or 0.001% to 0.3% vanadium a steel is obtained whose characteristics mechanics are improved.

Avec une addition supplémentaire de 0,001 % à 0,1 % d'aluminium et/ou de 0,0001 % à 0,003 % de bore, on obtient un acier dont la forgeabilité est améliorée.With an additional addition of 0.001% to 0.1% aluminum and / or 0.0001% to 0.003% boron, we obtains a steel whose forgeability is improved.

Les additions de cuivre, vanadium, niobium, bore, aluminium sont optionnelles et peuvent être faites seules ou en combinaison.Additions of copper, vanadium, niobium, boron, aluminum are optional and can be made alone or in combination.

Les principaux éléments d'alliage ont, pour certaines propriétés, des effets d'autant plus favorables que leur teneur est élevée et pour d'autres propriétés, des effets d'autant moins défavorables que la teneur est moins élevée ; aussi, il est préférable de choisir la composition chimique dans un domaine de composition pas trop large. Ainsi, dans tous les cas il faut limiter les domaines du chrome, du nickel et du molybdène à : 23 % ≤ Cr ≤ 28 % 25 % ≤ Ni ≤ 28 % 4,5 % ≤ Mo ≤ 7 %. The main alloying elements have, for certain properties, effects all the more favorable as their content is high and for other properties, effects all the less unfavorable as the content is lower; therefore, it is preferable to choose the chemical composition in a composition range which is not too wide. Thus, in all cases, the domains of chromium, nickel and molybdenum must be limited to: 23% ≤ Cr ≤ 28% 25% ≤ Ni ≤ 28% 4.5% ≤ Mo ≤ 7%.

Les inventeurs ont constaté que les meilleurs résultats étaient obtenus avec un acier dont la composition est la suivante : 25 % ≤ Cr ≤ 26 % 25 % ≤ Ni ≤ 26 % 6 % ≤ Mo ≤ 7 % 0,4 % ≤ N ≤ 0,5 % 2,5 % ≤ Mn ≤ 3,5 % 1 % ≤ Cu ≤ 2 % C ≤ 0,03 % Si ≤ 0,3 %. et, S ≤ 0,01 %, le reste, à l'exception du fer, étant constitué par des impuretés résultant de l'élaboration.The inventors have found that the best results are obtained with a steel whose composition is as follows: 25% ≤ Cr ≤ 26% 25% ≤ Ni ≤ 26% 6% ≤ Mo ≤ 7% 0.4% ≤ N ≤ 0.5% 2.5% ≤ Mn ≤ 3.5% 1% ≤ Cu ≤ 2% C ≤ 0.03% If ≤ 0.3%. and, S ≤ 0.01%, the rest, with the exception of iron, being constituted by impurities resulting from the production.

Cet acier peut contenir en outre du Nb, V, B ou Al comme indiqué précédemment.This steel may also contain Nb, V, B or Al as previously stated.

Les inventeurs ont également constaté que pour que ces aciers aient des propriétés optimales, il fallait que leurs compositions chimiques satisfassent aux relations suivantes :

  • pour garantir une faible ségrégation et peu de précipitation de carbures et/ou phases intermétalliques : 95 < kP = % Cr + 0,3 % Ni + 9 % Si + 27 % Mo + 130 % P - 8 % N < 232 et de préférence 95 < kP < 210
  • pour avoir une bonne polyvalence de la résistance à la corrosion (en particulier en milieux sulfuriques purs ou pollués et en milieux chlorurés) : 319 < kC = 3,3 % Cr + 10 % Ni + % Mo + 1,5 % Cu < 432 et de préférence : 355 < kC < 432.
The inventors have also found that for these steels to have optimal properties, their chemical compositions had to satisfy the following relationships:
  • to guarantee a low segregation and little precipitation of carbides and / or intermetallic phases: 95 <kP =% Cr + 0.3% Ni + 9% Si + 27% Mo + 130% P - 8% N <232 and preferably 95 <kP <210
  • to have good versatility in corrosion resistance (in particular in pure or polluted sulfuric media and in chlorinated media): 319 <kC = 3.3% Cr + 10% Ni +% Mo + 1.5% Cu <432 and preferably: 355 <kC <432.

L'acier selon l'invention présente un avantage supplémentaire qui provient du fait que le produit A x R de l'allongement à la rupture par la limite de rupture est très élevé (deux fois plus environ que pour les aciers de l'art antérieur utilisés pour le transport) si bien que la résistance au choc des parois réalisées avec cet acier est très élevée et notamment beaucoup plus élevée que pour les aciers de l'art antérieur. The steel according to the invention has an additional advantage which comes from the fact that the product A x R of the elongation at break by the break limit is very high (two times more than for the steels of the prior art used for transport) so that resistance to impact of the walls made with this steel is very high and in particular much higher than for steels of prior art.

Cette caractéristique a l'avantage de permettre de réaliser des citernes, des récipients ou des tuyaux pour le transport de produits corrosifs beaucoup plus sûrs en cas de choc que les équipements équivalents réalisés avec des aciers selon l'art antérieur.This feature has the advantage of allowing to make tanks, containers or pipes for transporting much safer corrosives in the event of an impact, that the equivalent equipment produced with steels according to the prior art.

Les propriétés de cet acier le rendent particulièrement apte à la fabrication de réacteurs (laveurs, tour de lavage, cuves à filtres, cuves d'attaque), de tubes (soudés et sans soudure), de cheminées, de pièces de jonction telles que des brides, des collecteurs (manifolds), des canalisations (flow lines), de séparateurs et de citernes de transport routier ou ferroviaire, pour les industries dans lesquelles ces équipements sont soumis à des corrosions très sévères par des milieux chlorurés et/ou sulfuriques purs ou pollués et notamment pour les plate-formes off-shore d'exploitations pétrolières, pour les installations de dépollution de fumées de combustion de centrales thermiques ou d'incinération d'ordures ménagères, pour la préparation de la pâte à papier en particulier par le procédé dit "au bisulfite", et notamment pour les équipements de filtration, blanchiement et délignification, pour l'industrie chimique et plus particulièrement pour les équipements d'hydrométallurgie et industrie des engrais utilisant l'attaque des minerais par des milieux sulfuriques concentrés.The properties of this steel make it particularly suitable for the manufacture of reactors (scrubbers, washing tower, filter tanks, attack tanks), tubes (welded and seamless), chimneys, parts junction such as flanges, manifolds, flow lines, separators and road or rail transport tanks, for industries in which this equipment is subject to very severe corrosion by chlorinated media and / or pure or polluted sulfuric and in particular for off-shore oil exploitation platforms, for combustion smoke abatement facilities thermal power plants or incineration of household waste, for the preparation of paper pulp in particular by the process called "bisulfite", and in particular for filtration, bleaching and delignification equipment, for the chemical industry and more particularly for hydrometallurgy equipment and the industry fertilizer using mineral attack by media concentrated sulfurics.

Plus particulièrement :

  • dans les plate-formes off-shore pour l'exploitation de champs pétroliers ou gaziers sous-marins, l'acier selon l'invention est utilisé pour réaliser des équipements de process soumis à la corrosion par l'eau de mer notamment les supports de torchères, les échangeurs de chaleur et les séparateurs, et notamment, les plaques tubulaires, les tuyauteries de transport d'eau de mer et les tuyauteries utilisées pour le traitement du pétrole ou du gaz, les protections de la zone des pylones qui est au voisinage de la surface libre de la mer, les masses-tiges, les arbres de pompe et les brides de raccordement soumises à la corrosion par l'eau de mer, les têtes de puits, les collecteurs (manifolds), les colonnes montantes (risers).
  • dans les industries de la dépollution pour réaliser les équipements soumis à une corrosion soit par l'acide chlorhydrique soit par l'acide sulfurique soit par des mélanges de ces acides avec parfois présence d'acide fluorhydrique et notamment pour la réalisation des tours de lavage des gaz ou fumées de combustion des centrales thermiques et des usines d'incinération d'ordure ainsi que pour la fabrication des conduites menant aux cheminées ; dans le cas particulier des tours de lavage des gaz d'une centrale thermique, les équipements sont en particulier, le réacteur, le présaturateur, la structure interne de l'absorbeur et la cheminée.
  • dans l'industrie de la pâte à papier pour la fabrication des équipements de délignification en particulier par le procédé au bisulfite et des équipements de filtration et de blanchiement par des composés chlorés très oxydants tels que Cl2 et ClO2 et également par des composés du type peroxyde d'hydrogène et ozone ; pour la délignification il s'agit notamment des préchauffeurs, des lessiveurs, des imprégnateurs et des lessiveurs continus ; pour le lavage et le blanchiement, il s'agit notamment du laveur, du bac de filtration, de la tour de blanchiement au chlore et au dioxyde de chlore ainsi que ses équipements de diffusion, lavage et filtration et la tour de blanchiement à l'hypochlorite avec son laveur et son bac de filtration.
  • dans l'industrie chimique, l'acier selon l'invention peut être utilisé avantageusement pour réaliser notamment des bacs, des réservoirs, des réacteurs, des tubes, des corps de pompe, des arbres de pompe qui sont en contact avec des milieux fortement chlorurés ou des milieux acides.
More specifically:
  • in off-shore platforms for the exploitation of underwater oil or gas fields, the steel according to the invention is used to produce process equipment subjected to corrosion by sea water, in particular the supports of flares, heat exchangers and separators, and in particular, tubular plates, piping for seawater transport and piping used for the treatment of oil or gas, protections for the pylon area which is in the vicinity of the free surface of the sea, the drill rods, the pump shafts and the connection flanges subjected to corrosion by sea water, the well heads, the manifolds (manifolds), the risers (risers) .
  • in the depollution industries to produce equipment subject to corrosion either by hydrochloric acid or by sulfuric acid or by mixtures of these acids with sometimes the presence of hydrofluoric acid and in particular for the realization of washing towers for gases or fumes from combustion of thermal power stations and refuse incineration plants as well as for the manufacture of pipes leading to chimneys; in the particular case of the gas washing towers of a thermal power plant, the equipment is in particular, the reactor, the presaturator, the internal structure of the absorber and the stack.
  • in the pulp industry for the manufacture of delignification equipment, in particular by the bisulfite process and of filtration and bleaching equipment with highly oxidizing chlorine compounds such as Cl 2 and ClO 2 and also with compounds of the hydrogen peroxide and ozone type; for delignification, these are in particular preheaters, digesters, impregnators and continuous digesters; for washing and bleaching, these are in particular the washer, the filtration tank, the chlorine and chlorine dioxide bleaching tower as well as its diffusion, washing and filtration equipment and the bleaching tower. hypochlorite with its washer and its filtration tank.
  • in the chemical industry, the steel according to the invention can be advantageously used to produce in particular tanks, reservoirs, reactors, tubes, pump bodies, pump shafts which are in contact with highly chlorinated media or acidic media.

Cet acier permet également de réaliser toute pièce soumise à l'abrasion/corrosion dans les milieux chlorurés et/ou acides.This steel also makes it possible to carry out any part subject to abrasion / corrosion in environments chlorides and / or acids.

Pour toutes ces applications en effet, l'homme du métier cherche constamment l'acier qui ait les plus hautes caractéristiques mécaniques possibles et la résistance à la corrosion la plus élevée possible sans toutefois que son prix soit exorbitant afin de réaliser des équipements les plus fiables possibles ayant la durée de vie la plus longue possible et celà à un prix compatible avec leur exploitation industrielle. De ce point de vue l'acier selon l'invention, de par sa composition chimique et ses propriétés est beaucoup plus intéressant que les superalliages à base nickel.For all these applications indeed, man of the trade is constantly looking for the steel that has the most high possible mechanical characteristics and resistance to the highest possible corrosion without however that its price is exorbitant in order to achieve most reliable equipment possible with the duration of the longest possible life and this at a compatible price with their industrial exploitation. From this point of view the steel according to the invention, by virtue of its chemical composition and its properties is much more interesting than nickel-based superalloys.

Les applications décrites ne sont pas limitatives et l'homme du métier saura choisir cet acier lorsqu'il le jugera utile.The applications described are not limiting and the skilled person will be able to choose this steel when he will find it useful.

Claims (10)

  1. Austenitic stainless steel with high mechanical strength and high corrosion resistance, characterised in that it contains by weight: 23 % ≤ Cr ≤ 28 % 25 % ≤ Ni ≤ 28 % 4.5 % ≤ Mo ≤ 7 % 0.35% ≤ N ≤ 0.8% 0.5 % ≤ Mn ≤ 5.4% C ≤ 0.06% S ≤ 0.010% Si ≤ 1 % 0.5 % ≤ Cu ≤ 3 %, and at least one of the elements B, Nb, V and Al in the following amounts: B 0.0001 to 0.003%, Nb 0.001 to 0.3%, V 0.001 to 0.3% and Al 0.001 to 0.1%, the remainder, with the exception of the iron, being made up of impurities resulting from the manufacturing process.
  2. Austenitic stainless steel according to claim 1, characterised in that C ≤ 0.04%.
  3. Austenitic stainless steel according to claim 1 or 2, characterised in that it contains from 1 to 2% copper.
  4. Austenitic stainless steel according to claim 1, characterised in that it preferably contains: 25 % ≤ Cr ≤ 26 % 25 % ≤ Ni ≤ 26 % 6 % ≤ Mo ≤ 7 % 0.4 % ≤ N ≤ 0.5% 2.5 % ≤ Mn ≤ 3.5% C ≤ 0.03% Si ≤ 0.3% and furthermore 1 % ≤ Cu ≤ 2 %, the remainder, with the exception of the iron, consisting of impurities resulting from the manufacturing process.
  5. Austenitic stainless steel according to any one of the preceding claims, characterised in that the chemical composition satisfies the following equations: 95 < kP = % Cr + 0.3% Ni + 9% Si + 27% Mo + 130 % P - 8% N < 232 and preferably: 95 < kP < 210 319 < kC = 3.3% Cr + 10% Ni + % Mo + 1.5% Cu < 432 and preferably: 355 < kC < 432.
  6. Use of an austenitic stainless steel according to any one of claims 1 to 5 for the manufacture of equipment for depolluting smoke from thermal power stations and factories for incinerating household waste, notably gas or smoke washing towers, gas or smoke pipes and chimneys.
  7. Use of an austenitic stainless steel according to any one of claims 1 to 5 for the production of equipment for delignification, notably by the bisulphite process, for filtration and bleaching of paper pulp.
  8. Use of an austenitic stainless steel according to any one of claims 1 to 5 for the manufacture of equipment for the chemical industry in a chloride-containing or acidic medium and particularly the production of vats, reservoirs, reactors, tubes, pump bodies and pump shafts.
  9. Use of an austenitic stainless steel according to any one of claims 1 to 8 for the production of equipment for offshore platforms exposed to marine corrosion and particularly flare stack supports, heat exchangers, separators, tube plates, seawater transporting pipes, pipes used for the process of treating petroleum or gas, for protecting the zones of pylons located close to the open surface of the sea, drill collars, pump shafts, connecting flanges, wellheads, collectors (manifolds) and (risers).
  10. Use of an austenitic stainless steel according to any one of claims 1 to ≤ for the manufacture of tankers for transporting chloride-containing products or highly corrosive acids by road or rail.
EP94401110A 1993-05-28 1994-05-18 Austenitic stainless steel with high resistance against corrosion in chloride and sulfuric environments, and uses of this steel Expired - Lifetime EP0626460B1 (en)

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FR9306468A FR2705689B1 (en) 1993-05-28 1993-05-28 Austenitic stainless steel with high resistance to corrosion by chlorinated and sulfuric environments and uses.
FR9306468 1993-05-28

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FR2711674B1 (en) * 1993-10-21 1996-01-12 Creusot Loire Austenitic stainless steel with high characteristics having great structural stability and uses.
US5841046A (en) * 1996-05-30 1998-11-24 Crucible Materials Corporation High strength, corrosion resistant austenitic stainless steel and consolidated article
US6168755B1 (en) 1998-05-27 2001-01-02 The United States Of America As Represented By The Secretary Of Commerce High nitrogen stainless steel
WO2001068929A1 (en) * 2000-03-15 2001-09-20 Huntington Alloys Corporation Corrosion resistant austenitic alloy
SE520027C2 (en) * 2000-05-22 2003-05-13 Sandvik Ab Austenitic alloy
US20040156737A1 (en) * 2003-02-06 2004-08-12 Rakowski James M. Austenitic stainless steels including molybdenum
SE527177C2 (en) * 2001-09-25 2006-01-17 Sandvik Intellectual Property Use of an austenitic stainless steel
SE525252C2 (en) * 2001-11-22 2005-01-11 Sandvik Ab Super austenitic stainless steel and the use of this steel
SE528008C2 (en) * 2004-12-28 2006-08-01 Outokumpu Stainless Ab Austenitic stainless steel and steel product
US7658883B2 (en) * 2006-12-18 2010-02-09 Schlumberger Technology Corporation Interstitially strengthened high carbon and high nitrogen austenitic alloys, oilfield apparatus comprising same, and methods of making and using same
US7985304B2 (en) 2007-04-19 2011-07-26 Ati Properties, Inc. Nickel-base alloys and articles made therefrom
US8430075B2 (en) * 2008-12-16 2013-04-30 L.E. Jones Company Superaustenitic stainless steel and method of making and use thereof
JP2014515436A (en) 2011-05-26 2014-06-30 ユナイテッド・パイプラインズ・アジア・パシフィック・プライベイト・リミテッド Austenitic stainless steel
US20150337419A1 (en) * 2014-05-20 2015-11-26 Crs Holdings Inc. Austenitic Stainless Steel Alloy
US10179943B2 (en) 2014-07-18 2019-01-15 General Electric Company Corrosion resistant article and methods of making
KR20230156447A (en) 2015-10-19 2023-11-14 산드빅 인터렉츄얼 프로퍼티 에이비 New austenitic stainless alloy

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* Cited by examiner, † Cited by third party
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JPS55100966A (en) * 1979-01-23 1980-08-01 Kobe Steel Ltd High strength austenite stainless steel having excellent corrosion resistance
SE441455B (en) * 1983-10-21 1985-10-07 Avesta Ab STALL OF AUSTENITIC TYPE
CA1263041A (en) * 1984-11-13 1989-11-21 William Lawrence Mankins Nickel-chromium-molybdenum alloy
US4765957A (en) * 1986-12-29 1988-08-23 Carondelet Foundry Company Alloy resistant to seawater and other corrosive fluids
DE3716665A1 (en) * 1987-05-19 1988-12-08 Vdm Nickel Tech CORROSION RESISTANT ALLOY
EP0342574A1 (en) * 1988-05-17 1989-11-23 Thyssen Edelstahlwerke AG Corrosion-resistant austenitic steel
US4981646A (en) * 1989-04-17 1991-01-01 Carondelet Foundry Company Corrosion resistant alloy
SE465373B (en) * 1990-01-15 1991-09-02 Avesta Ab AUSTENITIC STAINLESS STEEL

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GR3033108T3 (en) 2000-08-31
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ES2141806T3 (en) 2000-04-01
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NO941991L (en) 1994-11-29
FR2705689A1 (en) 1994-12-02
PT626460E (en) 2000-06-30
NO302623B1 (en) 1998-03-30
FI942490A0 (en) 1994-05-27
NO941991D0 (en) 1994-05-27
EP0626460A1 (en) 1994-11-30
FI942490A (en) 1994-11-29
DE69422850T2 (en) 2000-08-17
DE69422850D1 (en) 2000-03-09
FI110010B (en) 2002-11-15
FR2705689B1 (en) 1995-08-25

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