EP0649913B1 - High strength stainless austenitic steel with high structural stability and its uses - Google Patents

High strength stainless austenitic steel with high structural stability and its uses Download PDF

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EP0649913B1
EP0649913B1 EP94402202A EP94402202A EP0649913B1 EP 0649913 B1 EP0649913 B1 EP 0649913B1 EP 94402202 A EP94402202 A EP 94402202A EP 94402202 A EP94402202 A EP 94402202A EP 0649913 B1 EP0649913 B1 EP 0649913B1
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steel according
stainless steel
corrosion
chemical composition
manufacturing
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German (de)
French (fr)
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EP0649913A1 (en
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François Dupoiron
Jean-Christophe Gagnepain
Richard Cozar
Bernard Mayonobe
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Creusot Loire SA
Creusot Loire Industrie SA
TECPHY
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Creusot Loire SA
Creusot Loire Industrie SA
TECPHY
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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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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 resistance, high corrosion resistance and very good structural stability.
  • High austenitic stainless steels mechanical characteristics and high resistance to known corrosion also have the disadvantage of not be able to be used in the form of solid parts. In effect, when parts cool, instability of the structure causes intermetallic precipitation which very markedly deteriorate the resistance to corrosion and mechanical properties of steel.
  • the purpose of the present invention is to provide high austenitic stainless steel mechanical and which simultaneously has a very large corrosion resistance in a chlorinated medium and a very good structural stability.
  • the subject of the invention is an austenitic stainless steel with high mechanical characteristics, high resistance to corrosion and having great structural stability, the chemical composition of which comprises by weight: 23% ⁇ Cr ⁇ 28% 15% ⁇ Ni ⁇ 28% 0.5% ⁇ Mn ⁇ 6% 0% ⁇ Cu ⁇ 5% 0% ⁇ C ⁇ 0.06% 0% ⁇ If ⁇ 1% 0% ⁇ Nb ⁇ 0.5% 0% ⁇ V ⁇ 0.5% 0% ⁇ Al ⁇ 0.1% 3% ⁇ Mo ⁇ 8% 0.35% ⁇ N ⁇ 0.8% 1% ⁇ W ⁇ 5% the rest being made up of iron and impurities linked to the production.
  • the chemical composition of the steel comprises by weight: 23% ⁇ Cr ⁇ 26% 21% ⁇ Ni ⁇ 23% 2% ⁇ Mn ⁇ 3.5% 1% ⁇ Cu ⁇ 2% 0% ⁇ C ⁇ 0.03% 0% ⁇ If ⁇ 0.4% 0% ⁇ Nb ⁇ 0.5% 0% ⁇ Al ⁇ 0.1% 4.5% ⁇ Mo ⁇ 6.5% 0.4% ⁇ N ⁇ 0.55% 2% ⁇ W ⁇ 3.5% the rest being made up of iron and impurities linked to the production.
  • the chemical composition of the steel must, preferably satisfy the relationship: 113 + 16 (% Mo + 0.7% W) + 525% N> 420
  • this steel can be used for the production of solid parts. He can also be used for manufacturing equipment for massive oil rigs or for manufacturing equipment for chemical plants, for pulp mills paper, pollution control facilities or for manufacture of containers for transporting products corrosive, or finally, for the manufacture of ship. This steel can also be used to make clad sheets.
  • stainless steels austenitics which are alloys based on iron and high chromium and nickel content which have a structure naturally austenitic in the solid state practically at any temperature.
  • the structure is not 100% austenitic near the solidification point but becomes solid as soon as the temperature lowers.
  • superaustenitic the structure is 100% austenitic upon solidification.
  • the inventors unexpectedly found that by simultaneously adding to these steels contents high in nitrogen: from 0.35% by weight to 0.8% by weight, and preferably from 0.4% to 0.55% and in tungsten: from 1% by weight at 5% by weight, and preferably 2% to 3.5%, we obtained at the same time high mechanical characteristics, very high resistance to corrosion in the environment chlorinated and very good structural stability, i.e. kinetics of precipitation of intermetallic phases at very slow high temperature.
  • Such steels always contain a little carbon, silicon and aluminum. Carbon content must be less than 0.06% and preferably less 0.03% to avoid precipitation of carbide at grain boundaries.
  • the silicon and aluminum that served as deoxidizers during processing are limited to 1% for silicon and 0.1% for aluminum.
  • the corrosion rate in hydrochloric medium is 100 MDJ (mg / dm 2 / day); after hyper quenching followed by an sensitization treatment by maintaining at 800 ° C. for 15 min, the corrosion rate under the same conditions is 200 MDJ.
  • the steel according to the invention is much less sensitive to thermal cycles of sensitization. It results that it is possible to produce clad sheets consisting of a layer of steel according to the invention and a layer of structural steel, the properties of which of stainless plating are comparable to the properties a massive stainless steel sheet made in the same shade.
  • the steel according to the invention having a large structural stability can be used to manufacture including molded parts, forgings, rolled bars, rolled sheets, profiles, seamless tubes and welded tubes in particular when these objects are massive, that is to say when they are used in the form of thick pieces i.e. minimum thickness greater than 4 mm, especially when these are pieces thicker than 4 mm and less than 40 mm; they then present a good homogeneity of characteristics in thickness; for thicknesses greater than 40 mm, very good stability structural maintains high levels of resilience and ductility in thickness.

Abstract

The steel contains, by weight, from 0.35 to 0.8 % of nitrogen and from 1 to 5 % of tungsten. The chemical composition of the steel preferably comprises, in weight contents, 23 to 28 % of Cr, 15 to 28 % of Ni, 0.5 to 6 % of Mn, from 3 to 8 % of Mo, in addition to the nitrogen and tungsten. As a result of its high corrosion resistance the steel can be employed for the manufacture of massive components for any application, especially for the manufacture of equipment for oil platforms and for chemical factories, of containers for the transport of corrosive products, of ships' hulls and of plated sheets.

Description

La présente invention concerne un acier inoxydable austénitique à haute résistance mécanique, haute résistance à la corrosion et très bonne stabilité structurale.The present invention relates to stainless steel austenitic with high mechanical resistance, high corrosion resistance and very good structural stability.

Pour la fabrication d'équipements destinés notamment à des installations de dépollution de fumées, à des plates-formes pétrolières, à l'industrie chimique, à celle de la pâte à papier, on utilise des aciers inoxydables austénitiques ou superausténitiques à haute résistance mécanique et à haute résistance à la corrosion. Ces aciers inoxydables contiennent en général de fortes proportions d'azote et de molybdène. De tels aciers ont été décrits notamment dans deux brevets européens : EP-A-0.438.992 et EP-A-0.342.574 et dans la demande de brevet français FR-93-06468. Mais ces aciers présentent l'inconvénient d'une certaine incompatibilité entre une bonne tenue à la corrosion et une bonne stabilité structurale. Il en résulte par exemple une certaine difficulté à concilier les opérations de fabrication d'équipements tels que le soudage ou le formage à chaud et une très haute résistance à la corrosion de toutes les parties de ces équipements.For the manufacture of equipment intended in particular to smoke abatement installations, from oil rigs, to the chemical industry, to that of paper pulp, we use stainless steels high strength austenitics or superaustenitics mechanical and with high corrosion resistance. These stainless steels generally contain strong proportions of nitrogen and molybdenum. Such steels have have been described in particular in two European patents: EP-A-0.438.992 and EP-A-0.342.574 and in the patent application French FR-93-06468. But these steels have the disadvantage of a certain incompatibility between a good corrosion resistance and good structural stability. This results, for example, in some difficulty in reconcile equipment manufacturing operations such as than hot welding or forming and a very high corrosion resistance of all parts of these equipment.

Les aciers inoxydables austénitiques à hautes caractéristiques mécaniques et haute résistance à la corrosion connus ont également l'inconvénient de ne pas pouvoir être utilisés sous forme de pièces massives. En effet, lors du refroidissement des pièces, l'instabilité de la structure provoque des précipitations intermétalliques qui détériorent très notablement la résistance à la corrosion et les propriétés mécaniques de l'acier.High austenitic stainless steels mechanical characteristics and high resistance to known corrosion also have the disadvantage of not be able to be used in the form of solid parts. In effect, when parts cool, instability of the structure causes intermetallic precipitation which very markedly deteriorate the resistance to corrosion and mechanical properties of steel.

Le but de la présente invention est de proposer un acier inoxydable austénitique à hautes caractéristiques mécaniques et qui présente simultanément une très grande résistance à la corrosion en milieu chloruré et une très bonne stabilité structurale. The purpose of the present invention is to provide high austenitic stainless steel mechanical and which simultaneously has a very large corrosion resistance in a chlorinated medium and a very good structural stability.

A cet effet, l'invention a pour objet un acier inoxydable austénitique à hautes caractéristiques mécaniques, haute résistance à la corrosion et présentant une grande stabilité structurale dont la composition chimique comporte en poids : 23 % ≤ Cr ≤ 28 % 15 % ≤ Ni ≤ 28 % 0,5 % ≤ Mn ≤ 6 % 0 % ≤ Cu ≤ 5 % 0 % ≤ C ≤ 0,06% 0 % ≤ Si ≤ 1 % 0 % ≤ Nb ≤ 0,5 % 0 % ≤ V ≤ 0,5 % 0 % ≤ Al ≤ 0,1 % 3 % ≤ Mo ≤ 8 % 0,35 % ≤ N ≤ 0,8 % 1 % ≤ W ≤ 5 % le reste étant constitué par du fer et des impuretés liées à l'élaboration.To this end, the subject of the invention is an austenitic stainless steel with high mechanical characteristics, high resistance to corrosion and having great structural stability, the chemical composition of which comprises by weight: 23% ≤ Cr ≤ 28% 15% ≤ Ni ≤ 28% 0.5% ≤ Mn ≤ 6% 0% ≤ Cu ≤ 5% 0% ≤ C ≤ 0.06% 0% ≤ If ≤ 1% 0% ≤ Nb ≤ 0.5% 0% ≤ V ≤ 0.5% 0% ≤ Al ≤ 0.1% 3% ≤ Mo ≤ 8% 0.35% ≤ N ≤ 0.8% 1% ≤ W ≤ 5% the rest being made up of iron and impurities linked to the production.

De préférence, la composition chimique de l'acier comporte en poids : 23 % ≤ Cr ≤ 26 % 21 % ≤ Ni ≤ 23 % 2 % ≤ Mn ≤ 3,5 % 1 % ≤ Cu ≤ 2 % 0 % ≤ C ≤ 0,03% 0 % ≤ Si ≤ 0,4 % 0 % ≤ Nb ≤ 0,5 % 0 % ≤ Al ≤ 0,1 % 4,5 % ≤ Mo ≤ 6,5 % 0,4 % ≤ N ≤ 0,55 % 2 % ≤ W ≤ 3,5 % le reste étant constitué par du fer et des impuretés liées à l'élaboration.Preferably, the chemical composition of the steel comprises by weight: 23% ≤ Cr ≤ 26% 21% ≤ Ni ≤ 23% 2% ≤ Mn ≤ 3.5% 1% ≤ Cu ≤ 2% 0% ≤ C ≤ 0.03% 0% ≤ If ≤ 0.4% 0% ≤ Nb ≤ 0.5% 0% ≤ Al ≤ 0.1% 4.5% ≤ Mo ≤ 6.5% 0.4% ≤ N ≤ 0.55% 2% ≤ W ≤ 3.5% the rest being made up of iron and impurities linked to the production.

De préférence, la composition chimique de l'acier selon l'invention satisfait la formule suivante : CP = 20 x % Cr + 0,3 x % Ni + 30 x % Si + 40 x % Mo + 5 x % W + 10 x % Mn + 50 x % C - 200 x % N < 710 ce qui assure que la cinétique de précipitation des phases intermétalliques sera la plus lente possible.Preferably, the chemical composition of the steel according to the invention satisfies the following formula: CP = 20 x% Cr + 0.3 x% Ni + 30 x% Si + 40 x% Mo + 5 x% W + 10 x% Mn + 50 x% C - 200 x% N <710 which ensures that the kinetics of precipitation of the intermetallic phases will be as slow as possible.

En outre, afin d'obtenir la meilleure résistance à la corrosion possible, la composition chimique de l'acier doit vérifier : PRENW = % Cr + 3,3 x % Mo + 16 x % N + 1,7 % W > 47. In addition, in order to obtain the best possible corrosion resistance, the chemical composition of the steel must check: PRENW =% Cr + 3.3 x% Mo + 16 x% N + 1.7% W> 47.

Enfin et pour obtenir des caractéristiques mécaniques très élevées, la composition chimique de l'acier doit, de préférence satisfaire la relation : 113 + 16 (% Mo + 0,7 % W) + 525 % N > 420 Finally and to obtain very high mechanical characteristics, the chemical composition of the steel must, preferably satisfy the relationship: 113 + 16 (% Mo + 0.7% W) + 525% N> 420

Suivant l'invention, cet acier peut être utilisé pour la fabrication de pièces massives. Il peut également être utilisé pour la fabrication d'équipements pour plates-formes pétrolières massives ou pour la fabrication d'équipements pour usines chimiques, pour usines de pâte à papier, d'installations de dépollution ou encore pour la fabrication de récipients pour le transport de produits corrosifs, ou enfin, pour la fabrication de coques de navire. Cet acier peut également servir à fabriquer des tôles plaquées.According to the invention, this steel can be used for the production of solid parts. He can also be used for manufacturing equipment for massive oil rigs or for manufacturing equipment for chemical plants, for pulp mills paper, pollution control facilities or for manufacture of containers for transporting products corrosive, or finally, for the manufacture of ship. This steel can also be used to make clad sheets.

L'invention va maintenant être décrite en détail mais de façon non limitative.The invention will now be described in detail. but not limited to.

L'homme du métier connaít les aciers inoxydables austénitiques qui sont les alliages à base de fer et à forte teneur en chrome et en nickel qui ont une structure naturellement austénitique à l'état solide pratiquement à toute température. Pour la plupart de ces aciers, la structure n'est pas 100 % austénitique au voisinage du point de solidification mais le devient dès que la température s'abaisse. Pour certains de ces aciers, dits superausténitiques, la structure est 100 % austénitique dès la solidification. Ces aciers sont supposés connus.A person skilled in the art knows stainless steels austenitics which are alloys based on iron and high chromium and nickel content which have a structure naturally austenitic in the solid state practically at any temperature. For most of these steels, the structure is not 100% austenitic near the solidification point but becomes solid as soon as the temperature lowers. For some of these steels, called superaustenitic, the structure is 100% austenitic upon solidification. These steels are assumed to be known.

Les inventeurs ont constaté de façon inattendue qu'en ajoutant simultanément à ces aciers des teneurs élevées en azote : de 0,35 % en poids à 0,8 % en poids, et de préférence de 0,4 % à 0,55 % et en tungstène : de 1 % en poids à 5 % en poids, et de préférence 2 % à 3,5 %, on obtenait tout à la fois de hautes caractéristiques mécaniques, une très grande résistance à la corrosion en milieu chloruré et une très bonne stabilité structurale, c'est-à-dire une cinétique de précipitation de phases intermétalliques à haute température très lente.The inventors unexpectedly found that by simultaneously adding to these steels contents high in nitrogen: from 0.35% by weight to 0.8% by weight, and preferably from 0.4% to 0.55% and in tungsten: from 1% by weight at 5% by weight, and preferably 2% to 3.5%, we obtained at the same time high mechanical characteristics, very high resistance to corrosion in the environment chlorinated and very good structural stability, i.e. kinetics of precipitation of intermetallic phases at very slow high temperature.

La très bonne stabilité structurale permet de fabriquer des pièces massives notamment : tôles fortes, tubes épais, pièces forgées, pièces moulées ou des assemblages soudés dont les propriétés mécaniques et de tenue à la corrosion sont en tous points, y compris au voisinage des soudures, excellentes.The very good structural stability allows manufacture massive parts, in particular: heavy plates, thick tubes, forgings, castings or assemblies welded with mechanical and holding properties corrosion are everywhere, including in the vicinity welds, excellent.

Il est préférable que ces aciers contiennent en poids, outre l'azote et le tungstène dans les teneurs déjà citées, les éléments indiqués ci-dessous.

  • Chrome : plus de 23 % pour assurer une bonne résistance à la corrosion localisée et une bonne solubilité de l'azote, moins de 28 % et de préférence moins de 26 % pour limiter les risques de précipitation de carbures de chrome.
  • Nickel : plus de 15 % et préférentiellement plus de 21 % pour assurer une solidification austénitique qui garantit une bonne solubilité de l'azote, pour obtenir une bonne résistance à la corrosion en milieu sulfurique et pour limiter la propagation de la corrosion localisée, moins de 28 % et de préférence moins de 23 % pour ne pas trop réduire la solubilité de l'azote, et parce que le nickel est un métal cher.
  • Manganèse : plus de 0,5 % et de préférence plus de 2 % pour obtenir une solubilité suffisante de l'azote et pour limiter la susceptibilité à la fissuration à chaud, moins de 6 % et de préférence moins de 3,5 % pour limiter les risques de précipitation de phases intermétalliques et limiter l'usure des réfractaires lors de l'élaboration.
  • Cuivre : de 0 % à 5 % et de préférence de 1 % à 2 % pour améliorer la résistance à la corrosion en milieu sulfurique et chloruré acide.
  • Molybdène : La teneur pondérale de l'acier en molybdène doit être de plus de 3 % et de préférence de plus de 4,5 % afin d'améliorer la résistance à la corrosion localisée, la solubilité de l'azote, les caractéristiques mécaniques à la température ambiante et à haute température et limiter les risques de fissuration à chaud au soudage ; mais cette teneur doit être de moins de 8 % et de préférence de moins de 6,5 % pour éviter la formation de ségrégations et la précipitation de phases intermétalliques.
It is preferable that these steels contain by weight, in addition to nitrogen and tungsten in the contents already mentioned, the elements indicated below.
  • Chromium : more than 23% to ensure good resistance to localized corrosion and good nitrogen solubility, less than 28% and preferably less than 26% to limit the risk of precipitation of chromium carbides.
  • Nickel : more than 15% and preferably more than 21% to ensure an austenitic solidification which guarantees good nitrogen solubility, to obtain good resistance to corrosion in sulfuric medium and to limit the spread of localized corrosion, less than 28% and preferably less than 23% so as not to reduce the solubility of nitrogen too much, and because nickel is an expensive metal.
  • Manganese : more than 0.5% and preferably more than 2% to obtain sufficient nitrogen solubility and to limit the susceptibility to hot cracking, less than 6% and preferably less than 3.5% to limit the risks of precipitation of intermetallic phases and limit the wear of refractories during production.
  • Copper : from 0% to 5% and preferably from 1% to 2% to improve the resistance to corrosion in sulfuric and acid chlorinated medium.
  • Molybdenum : The molybdenum content by weight of steel must be more than 3% and preferably more than 4.5% in order to improve the resistance to localized corrosion, the solubility of nitrogen, the mechanical characteristics to ambient temperature and high temperature and limit the risk of hot cracking during welding; but this content must be less than 8% and preferably less than 6.5% to avoid the formation of segregations and the precipitation of intermetallic phases.

Les rôles de l'azote et du tungstène sont les suivants :

  • L'azote permet d'obtenir des caractéristiques mécaniques élevées, une bonne tenue à la corrosion localisée, une bonne stabilité structurale ; mais en excès, il détériore la résilience.
  • Le tungstène permet d'obtenir une bonne résistance à la corrosion en milieux chlorurés acides et réducteurs, une bonne résistance à la corrosion par crevasse lorsqu'il est associé au molybdène et à l'azote, de renforcer les caractéristiques mécaniques à la température ambiante et à haute température ; mais en excès, il provoque des précipitations défavorables aux propriétés d'emploi.
The roles of nitrogen and tungsten are:
  • Nitrogen makes it possible to obtain high mechanical characteristics, good resistance to localized corrosion, good structural stability; but in excess, it deteriorates resilience.
  • Tungsten provides good resistance to corrosion in acidic and reducing chlorinated environments, good resistance to crevice corrosion when combined with molybdenum and nitrogen, to reinforce the mechanical characteristics at room temperature and at high temperature; but in excess, it causes precipitation unfavorable to the properties of use.

De tels aciers contiennent toujours un peu de carbone, de silicium et d'aluminium. La teneur en carbone doit être inférieure à 0,06 % et de préférence inférieure à 0,03 % pour éviter la précipitation de carbure aux joints de grains.Such steels always contain a little carbon, silicon and aluminum. Carbon content must be less than 0.06% and preferably less 0.03% to avoid precipitation of carbide at grain boundaries.

Le silicium et l'aluminium qui ont servi de désoxydants au cours de l'élaboration sont limités à 1 % pour le silicium et 0,1 % pour l'aluminium.The silicon and aluminum that served as deoxidizers during processing are limited to 1% for silicon and 0.1% for aluminum.

D'autres éléments tels le magnésium, le cérium ou le calcium pourront être ajoutés comme agents de désoxydation.Other elements such as magnesium, cerium or calcium can be added as deoxidation.

On peut également ajouter jusqu'à 0,5 % de niobium et/ou vanadium pour améliorer les caractéristiques mécaniques.You can also add up to 0.5% of niobium and / or vanadium to improve the characteristics mechanical.

Pour que les propriétés de l'acier inoxydable selon l'invention soient optimales, la composition chimique doit être ajustée à l'intérieur des fourchettes de composition de façon que :

  • les caractéristiques mécaniques soient élevées, pour cela, il faut que : 113 + 16 (% Mo + 0,7 % W) + 525 % N > 420
  • la résistance à la corrosion localisée soit maximale et pour cela que : PRENW = % Cr + 3,3 (% Mo) + 16 (% N) + 1,7 (% W) > 47
  • la cinétique de précipitation des phases intermétalliques soit très lente, ce qu'on obtient si : CP = 20 % Cr + 0,3 x % Ni + 30 x % Si + 40 x % Mo + 5 x % W + 10 x % Mn + 50 x % C - 200 x % N < 710.
For the properties of the stainless steel according to the invention to be optimal, the chemical composition must be adjusted within the ranges of composition so that:
  • the mechanical characteristics are high, for this, it is necessary that: 113 + 16 (% Mo + 0.7% W) + 525% N> 420
  • the localized corrosion resistance is maximum and for this that: PRENW =% Cr + 3.3 (% Mo) + 16 (% N) + 1.7 (% W)> 47
  • the kinetics of precipitation of the intermetallic phases is very slow, which is obtained if: CP = 20% Cr + 0.3 x% Ni + 30 x% Si + 40 x% Mo + 5 x% W + 10 x% Mn + 50 x% C - 200 x% N <710.

Avec cette composition chimique on obtient un acier inoxydable austénitique dont la limite d'élasticité Rp 0,2 % à l'ambiante est supérieure à 420 MPa, et dont la stabilité structurale caractérisée par la cinétique de précipitation de phases intermétalliques à 850°C est supérieure à celles des nuances par ailleurs équivalentes. Il en résulte que la résistance à la corrosion n'est pas affectée par un cycle thermique correspondant à une mise en oeuvre telle que le soudage, ce qui n'est pas le cas des aciers selon l'art antérieur.With this chemical composition we get a austenitic stainless steel with yield strength 0.2% ambient Rp is greater than 420 MPa, and the structural stability characterized by the kinetics of intermetallic phase precipitation at 850 ° C east higher than those of otherwise equivalent grades. As a result, the corrosion resistance is not affected by a thermal cycle corresponding to a stake implemented such as welding, which is not the case steels according to the prior art.

A titre d'exemple, on a réalisé un acier dont la composition chimique est la suivante : Cr = 23,7 % C = 0,015 % Ni = 21,5 % Mn = 2 % Mo = 5 % Si = 0,2 % N = 0,45 % Nb = 0,02 % W = 2 % V = 0,15 % Cu = 1,5 % Al = 0,02 %. By way of example, a steel has been produced, the chemical composition of which is as follows: Cr = 23.7% C = 0.015% Ni = 21.5% Mn = 2% MB = 5% If = 0.2% N = 0.45% Nb = 0.02% W = 2% V = 0.15% Cu = 1.5% Al = 0.02%.

Cet acier présente une limite d'élasticité de 452 MPa, un coefficient de sensibilité à la corrosion par piqûre PRENW = 50,8 et un coefficient de sensibilité aux précipitations CP = 627 si bien que le temps d'incubation pour la précipitation de composés intermétalliques à 850°C est de 180 s.This steel has an elastic limit of 452 MPa, a coefficient of sensitivity to corrosion by PRENW bite = 50.8 and a coefficient of sensitivity to CP precipitation = 627 so the incubation time for the precipitation of intermetallic compounds at 850 ° C is 180 s.

Après hypertrempe, la vitesse de corrosion en milieu chlorhydrique est de 100 MDJ (mg/dm2/jour) ; après hypertrempe suivie d'un traitement de sensibilisation par maintien à 800°C pendant 15 mn, la vitesse de corrosion dans les mêmes conditions est de 200 MDJ.After hyper quenching, the corrosion rate in hydrochloric medium is 100 MDJ (mg / dm 2 / day); after hyper quenching followed by an sensitization treatment by maintaining at 800 ° C. for 15 min, the corrosion rate under the same conditions is 200 MDJ.

Par comparaison, un acier suivant l'art antérieur et de composition : Cr = 24 Mn = 3 Si = 0,4 Ni = 22 C = 0,01 Al = 0,02 Mo = 7 Nb = 0,2 N = 0,45 V = 0,15 présente une limite d'élasticité de 461 MPa, un PRENW = 54,3, un CP = 716, un temps d'incubation pour la précipitation de 60 s, une vitesse de corrosion après hypertrempe de 99 MDJ et une vitesse de corrosion après sensibilisation à 850° pendant 15 mn de 980 MDJ.By comparison, a steel according to the prior art and of composition: Cr = 24 Mn = 3 If = 0.4 Ni = 22 C = 0.01 Al = 0.02 MB = 7 Nb = 0.2 N = 0.45 V = 0.15 has a yield strength of 461 MPa, a PRENW = 54.3, a CP = 716, an incubation time for precipitation of 60 s, a corrosion rate after hyper quenching of 99 MDJ and a corrosion rate after sensitization at 850 ° for 15 min from 980 MDJ.

L'acier selon l'invention est beaucoup moins sensible à des cycles thermiques de sensibilisation. Il en résulte qu'il est possible de réaliser des tôles plaquées constituées d'une couche d'acier selon l'invention et d'une couche en acier de construction, dont les propriétés du placage inoxydable sont comparables aux propriétés d'une tôle inoxydable massive réalisée dans la même nuance.The steel according to the invention is much less sensitive to thermal cycles of sensitization. It results that it is possible to produce clad sheets consisting of a layer of steel according to the invention and a layer of structural steel, the properties of which of stainless plating are comparable to the properties a massive stainless steel sheet made in the same shade.

L'acier selon l'invention ayant une grande stabilité structurale peut être utilisé pour fabriquer notamment des pièces moulées, des pièces forgées, des barres laminées, des tôles laminées, des profilés, des tubes sans soudure et des tubes soudés, en particulier lorsque ces objets sont massifs, c'est-à-dire lorsqu'ils sont utilisés sous forme de pièces épaisses c'est-à-dire d'épaisseur minimale supérieure à 4 mm, notamment lorsqu'il s'agit de pièces d'épaisseur supérieure à 4 mm et inférieure à 40 mm ; elles présentent alors une bonne homogénéité de caractéristiques dans l'épaisseur ; pour des épaisseurs supérieures à 40 mm, la très bonne stabilité structurale permet de conserver de hauts niveaux de résilience et de ductilité dans l'épaisseur.The steel according to the invention having a large structural stability can be used to manufacture including molded parts, forgings, rolled bars, rolled sheets, profiles, seamless tubes and welded tubes in particular when these objects are massive, that is to say when they are used in the form of thick pieces i.e. minimum thickness greater than 4 mm, especially when these are pieces thicker than 4 mm and less than 40 mm; they then present a good homogeneity of characteristics in thickness; for thicknesses greater than 40 mm, very good stability structural maintains high levels of resilience and ductility in thickness.

Du fait de ses propriétés mécaniques, de résistance à la corrosion, d'aptitude au soudage et à la fabrication de pièces épaisses, l'acier selon l'invention peut être utilisé avantageusement notamment pour fabriquer :

  • des tubes, des brides, des collecteurs, des oléoducs, des gazoducs, des séparateurs, des pompes, des compresseurs, des échangeurs destinés à être utilisés au contact de l'eau de mer ou de fluides contenant des chlorures et de l'H2S, en particulier pour tout équipement de process ou circuit de sécurité incendie véhiculant de l'eau de mer sur des plates-formes pétrolières marines,
  • des tubes, brides, réservoirs, réacteurs, pompes, compresseurs et plus généralement toute pièce ou paroi d'équipement pour l'industrie chimique, la fabrication de la pâte à papier, l'hydrométallurgie, la dépollution travaillant au contact de fluides ou d'effluents corrosifs et notamment lorsqu'il s'agit de corrosion par des milieux chlorurés acides; dans l'industrie de la pâte à papier, sont concernés notamment les filtres de chloration, les tours de blanchiment en particulier les tours de blanchiment par le peroxyde d'hydrogène et l'ozone, les mixeurs, les lessiveurs, les imprégnateurs,
  • des citernes pour le transport routier, ferroviaire ou maritime de produits corrosifs,
  • des coques de navires,
  • des équipements travaillant à haute température et notamment des équipements pour la pétrochimie, la cimenterie, l'incinération d'ordures, les conduites de fumées, les cheminées.
Due to its mechanical properties, resistance to corrosion, ability to weld and to manufacture thick parts, the steel according to the invention can be used advantageously in particular for manufacturing:
  • tubes, flanges, manifolds, oil and gas pipelines, separators, pumps, compressors, exchangers intended to be used in contact with seawater or fluids containing chlorides and H 2 S, in particular for any process equipment or fire safety circuit conveying seawater on marine oil platforms,
  • tubes, flanges, tanks, reactors, pumps, compressors and more generally any part or wall of equipment for the chemical industry, the manufacture of paper pulp, hydrometallurgy, depollution working in contact with fluids or corrosive effluents and in particular when it is corrosion by acid chlorinated media; in the pulp industry, chlorination filters, bleaching towers in particular bleaching towers with hydrogen peroxide and ozone, mixers, digesters, impregnators are concerned,
  • tanks for the road, rail or sea transport of corrosive products,
  • ship hulls,
  • equipment working at high temperature and in particular equipment for petrochemicals, cement works, incineration of garbage, smoke pipes, chimneys.

Ces applications ne sont pas exhaustives et plus généralement cet acier permet d'obtenir une meilleure tenue en service qu'avec les aciers de l'art antérieur et à moindre coût qu'avec des alliages à base nickel pour toutes les applications :

  • en milieu chloruré oxydant,
  • en milieu contenant des chlorures et de l'H2S,
  • en milieu chloruré acide,
notamment lorsque les pièces réalisées doivent être épaisses ou massives ou lorsque la température d'utilisation est élevée.These applications are not exhaustive and more generally this steel makes it possible to obtain better service life than with the steels of the prior art and at lower cost than with nickel-based alloys for all applications:
  • in an oxidized chlorinated medium,
  • in medium containing chlorides and H 2 S,
  • in an acid chloride medium,
especially when the parts produced must be thick or massive or when the temperature of use is high.

Claims (11)

  1. Stainless austenitic steel which has good mechanical characteristics, is highly resistant to corrosion and has good structural stability, its chemical composition by weight being as follows: 23 % ≤ Cr ≤ 28 % 15 % ≤ Ni ≤ 28 % 0.5 % ≤ Mn ≤ 6 % 0 % ≤ Cu ≤ 5 % 0 % ≤ C ≤ 0.06 % 0 % ≤ Si ≤ 1 % 0 % ≤ Nb ≤ 0.5 % 0 % ≤ V ≤ 0.5 % 0 % ≤ Al ≤ 0.1 % 3 % ≤ Mo ≤ 8 % 0.35 % ≤ N ≤ 0.8 % 1 % ≤ W ≤ 5 % the rest being made up of iron and impurities connected with manufacture.
  2. Stainless steel according to Claim 1, characterized in that its chemical composition by weight is as follows: 23 % ≤ Cr ≤ 26 % 21 % ≤ Ni ≤ 23 % 2 % ≤ Mn ≤ 3.5 % 1 % ≤ Cu ≤ 2 % 0 % ≤ C ≤ 0.03 % 0 % ≤ Si ≤ 0.4 % 0 % ≤ Nb ≤ 0.5 % 0 % ≤ Al ≤ 0.1 % 4.5 % ≤ No ≤ 6.5 % 0.4 % ≤ N ≤ 0.55 % 2 % ≤ W ≤ 3.5 % the rest being made up of iron and impurities linked with manufacture.
  3. Stainless steel according to either one of Claims 1 or 2, characterized in that its chemical composition complies with the following statement: CP = 20 x % Cr + 0.3 x % Ni + 30 x % Si + 40 x % Mo + 5 x % W + 10 x % Mn + 50 x % C - 200 x % N < 710.
  4. Stainless steel according to Claim 3, characterized in that its chemical composition complies with the following statement: PRENW = % Cr + 3.3 x % Mo + 16 x % N + 1.7 % W > 47.
  5. Stainless steel according to Claim 4, characterized in that its chemical composition complies with the following statement: 113 + 16 (% Mo + 0,7 % W) + 525 % N > 420.
  6. Use of a stainless steel according to any one of Claims 1 to 5 for manufacturing solid parts.
  7. Use of a stainless steel according to any one of Claims 1 to 5 for manufacturing equipment for offshore oil rigs.
  8. Use of a stainless steel according to any one of Claims 1 to 5 for manufacturing equipment for chemical works, paper pulp factories, hydrometallurgy installations and pollution control installations.
  9. Use of a stainless steel according to any one of Claims 1 to 5 for manufacturing containers for transporting corrosive products.
  10. Use of a stainless steel according to any one of Claims 1 to 5 for manufacturing ships' hulls.
  11. Use of a stainless steel according to any one of Claims 1 to 5 for manufacturing plated sheet steel made up of one layer of steel according to the invention and one layer of structural steel.
EP94402202A 1993-10-21 1994-10-03 High strength stainless austenitic steel with high structural stability and its uses Expired - Lifetime EP0649913B1 (en)

Applications Claiming Priority (2)

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FR9312578A FR2711674B1 (en) 1993-10-21 1993-10-21 Austenitic stainless steel with high characteristics having great structural stability and uses.
FR9312578 1993-10-21

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DE69422772D1 (en) 2000-03-02
NO943942D0 (en) 1994-10-18
ATE189268T1 (en) 2000-02-15
EP0649913A1 (en) 1995-04-26
ES2141808T3 (en) 2000-04-01
CA2118288A1 (en) 1995-04-22
FR2711674B1 (en) 1996-01-12
DE69422772T2 (en) 2000-06-08
FR2711674A1 (en) 1995-05-05
FI944908A (en) 1995-04-22
CA2118288C (en) 2004-10-05
PT649913E (en) 2000-06-30
US5494636A (en) 1996-02-27
GR3033188T3 (en) 2000-08-31
DK0649913T3 (en) 2000-06-19
FI944908A0 (en) 1994-10-19
FI109032B (en) 2002-05-15
NO943942L (en) 1995-04-24

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