EP1297192B1 - Steel compositions, method for obtaining same and parts made from same - Google Patents

Steel compositions, method for obtaining same and parts made from same Download PDF

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Publication number
EP1297192B1
EP1297192B1 EP01949617A EP01949617A EP1297192B1 EP 1297192 B1 EP1297192 B1 EP 1297192B1 EP 01949617 A EP01949617 A EP 01949617A EP 01949617 A EP01949617 A EP 01949617A EP 1297192 B1 EP1297192 B1 EP 1297192B1
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Prior art keywords
composition according
steel
weight
same
parts
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German (de)
French (fr)
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EP1297192A1 (en
Inventor
Jacques Frey
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Aubert and Duval SA
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Aubert and Duval SA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • 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
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • 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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/004—Dispersions; Precipitations

Definitions

  • the invention relates to a steel more particularly intended for the production of mechanical parts that can be used in severe conditions of use, in nuclear installations but also in industries such as the food industry, energy or mechanical engineering. .
  • cobalt-based alloys pose both economic and technical problems. Indeed, cobalt is an expensive raw material whose sources of supply are few. Moreover, this element is highly undesirable in the nuclear environment because it forms long-lived isotopes which are released by the wear of parts and are one of the main sources of radiation exposure of people working in these facilities. The cobalt content must therefore be limited to the maximum in steels or alloys which are used in this industry for the manufacture of valve seats.
  • the patent US 3,912,503 discloses stainless steel compositions resistant to wear and corrosion. They comprise 0.12% by weight of carbon at the most, 7 to 13% by weight of manganese, 3 to 5% by weight of silicon, 12 to 19% by weight of chromium, 4 to 12% by weight of nickel, 0.3 to 0.3% by weight of nitrogen, the balance being iron. These compositions have a coefficient of friction close to that of the cobalt base alloys but have a hardness at room temperature of only 200 Vickers, hardness which drops to 150 Vickers from 200 ° C. In addition, their ductility is much too large to allow use for the production of mechanical parts subjected to high stresses.
  • the patent US 4,814,140 describes the same type of steel as the patent US 3,912,503 and improves the resistance to seizure.
  • the claimed compositions comprise 0.25% by weight of carbon at most, 2 to 7% by weight of manganese, 1 to 5% by weight of silicon, 12 to 20% by weight of chromium, 2 to 7.75% by weight nickel, 0.35% by weight of nitrogen at most, the balance being iron.
  • the mechanical properties which include ductility, hardness at room temperature and hot, are similar to that of the compositions of the patent. US 3,912,503 and are therefore also insufficient for the intended applications.
  • the present invention therefore essentially aims to provide such a material.
  • a first object of the invention is constituted by a steel composition comprising, expressed in percentages by weight: VS 0.30 - 1.00% Yes 3.50 - 4.50% mn 7.00 - 10.00% Or 3.50 - 4.50% Cr 20.00 - 27.00% W 0.50 - 4.50% Nb 0 - 2.50% Co 0 - 1.00% NOT 0.20 - 0.50%, the complement consisting mainly of iron and impurities inevitable.
  • the steel composition comprises, expressed in percentages by weight: VS 0.50 - 0.80% Yes 3.50 - 4.50% mn 7.00 - 10.00% Or 3.50 - 4.50% Cr 24.00 - 26.00% W 0.50 - 1.50% Nb 0 - 2.50% Co 0 - 0.50% NOT 0.20 - 0.50%, the complement being mainly iron and unavoidable impurities.
  • unavoidable impurities include sulfur and phosphorus that should be maintained at the lowest level compatible with the manufacturing process or the raw materials used.
  • the carbon is present at a relatively high content of 0.30 to 1.00% by weight. This in particular makes it possible to obtain the hardness necessary for the mechanical parts, in particular thanks to the formation of carbide type precipitates which strengthens the structure of the material. A good hardness makes it possible, among other things, to obtain a steel that is resistant to wear. Depending on the compositions and the heat treatment applied, the hardnesses obtained with the steels according to the invention are between 350 and 550 Vickers.
  • the carbon content of the steels according to the invention is between 0.40 and 0.50% by weight, when the parts to be produced do not require a hardness and a resistance to corrosion. very high wear.
  • the carbon content of the steels according to the invention is between 0.50 and 0.60% by weight, when the parts to be produced require a hardness and a resistance to wear a bit higher.
  • the carbon content is between 0.70 and 0.80% by weight for applications in which the hardness and wear resistance must be high. It can therefore be seen that these two characteristics of steel can be adjusted by varying this carbon content, within certain predefined limits.
  • Silicon is present at a level of 3.50 to 4.00% by weight. It plays a role in the improvement of friction and resistance to galling due to the formation of adherent oxide film on the surface of the parts. It also has a favorable role in the resistance to corrosion.
  • Nickel is a gamma element that participates in balancing the composition. It is present at a level of 3.50 to 4.50% by weight and provides the steel compositions with good resistance to corrosion.
  • the manganese is present at a content of 7.00 to 10.00% by weight. Its role is similar to that of nickel.
  • Chromium is present in an amount of 20.00 to 27.00% by weight, preferably 24 to 26% by weight. It also plays an important role in the good resistance against corrosion of steels according to the invention. It may be possible to replace some of the chromium present in the composition with molybdenum on the basis of 1% molybdenum to 3% chromium.
  • Tungsten is present in an amount of from 0.50 to 4.50% by weight, preferably from 0.50 to 1.50% by weight. It makes it possible in particular to obtain a good heat resistance of the compositions according to the invention.
  • Niobium is present in an amount of 0 to 2.5% by weight. It is a carburizing element that contributes to the hardness of the grade while having a favorable action on the hot performance of the steel compositions.
  • the nitrogen is present in an amount of from 0.20 to 0.50% by weight in the compositions according to the invention. It contributes to the balance of the composition by its gammagenic influence, and to the hardness of its participation in the formation of niobium carbonitrides in particular.
  • Cobalt is an undesirable element whose content is limited to a maximum of 1% by weight, preferably 0.5% by weight. Its content will be limited as much as possible technically and will be more preferably reduced to trace.
  • This centrifugal molding process is traditionally used to shape cobalt-based alloys because it has great advantages. It consists of gradually introducing the mass of molten metal in a heated folder in rotation, so that a very thin layer of metal, of the order of a tenth of a millimeter is deposited at each turn inside shirt. Each layer solidifies therefore independently of the previously deposited layers which allows to obtain a fine structure and isotropic blank, without micro-porosities. The finished parts obtained after machining the blank are free of sink holes, very strong and have a very good surface finish.
  • the present inventors have therefore found quite surprisingly that it was perfectly possible to mold by centrifugation the mechanical parts to be produced in the compositions according to the invention.
  • the melting of the steel compositions it can be carried out by any known method, in particular in an arc furnace.
  • the steel compositions according to the invention can in particular be in three different forms depending on their thermal state. This is the so-called “raw state of casting", of the state dissolved in temperatures of 1050 to 1150 ° C. and of the stabilized state obtained by practicing one or more stabilization treatments of 700 at 900 ° C on a piece in the raw state of casting or in the dissolved state.
  • the thermal state essentially depends on the conditions under which the part will be used.
  • an aging stabilization treatment will preferably be carried out, comprising dissolving followed by slow cooling in a fluid such as air. This treatment allows the formation of precipitates in the matrix of the steel which will not then vary in hardness or dimensions.
  • a third subject of the invention consists of the mechanical parts produced in the compositions and / or with the aid of the processes described above. Examples include valve, valve seats, friction rings and discs, gas turbine components, hot work cutters and cutters, knives and shear blades. working at high temperature.
  • grade ES a steel composition according to the invention whose composition is as follows: VS 0.50% Yes 3.50% mn 9.00% Or 4.00% Cr 26.00% W 1.20% Nb 1.50% Co 0.12% NOT 0.25%, the complement being made of iron.
  • the reference material of the prior art chosen for comparison is a cobalt base alloy CoCr29W5, the composition of which is as follows: VS 1.10% Cr 29.00% W 5.00%, the complement consisting of cobalt.
  • the steels according to the invention are non-magnetic for the raw casting conditions and put into solution, which allows their use for certain sensitive parts, such as submarine parts, especially.

Description

L'invention concerne un acier plus particulièrement destiné à la réalisation de pièces mécaniques pouvant être utilisées dans des conditions d'utilisation sévères, dans des installations nucléaires mais aussi dans les industries tels que l'agro-alimentaire, l'énergie ou la construction mécanique.The invention relates to a steel more particularly intended for the production of mechanical parts that can be used in severe conditions of use, in nuclear installations but also in industries such as the food industry, energy or mechanical engineering. .

En effet, lorsque des pièces mécaniques doivent être soumises à des contraintes d'usage nécessitant une forte résistance à l'usure par abrasion ou érosion, une forte résistance à la corrosion et une bonne tenue à chaud jusqu'à 900°C, les seuls matériaux susceptibles de convenir dans de telles conditions sont les alliages base cobalt. On peut d'ailleurs remarquer que même lorsque seules deux de ces qualités sont requises, il n'existe pas non plus à l'heure actuelle d'alternative satisfaisante à ces alliages.Indeed, when mechanical parts must be subjected to wear constraints requiring a high resistance to abrasion or erosion wear, a high resistance to corrosion and a good heat resistance up to 900 ° C, the only ones materials that may be suitable under such conditions are cobalt-based alloys. It can also be noted that even when only two of these qualities are required, there is no satisfactory alternative to these alloys at present.

Hors, les alliages base cobalt posent des problèmes à la fois économiques et techniques. En effet, le cobalt est une matière première onéreuse dont les sources d'approvisionnement sont peu nombreuses. Par ailleurs, cet élément est hautement indésirable dans le milieu du nucléaire car il forme des isotopes à longue durée de vie qui sont libérés par l'usure des pièces et sont une des principales sources d'exposition aux radiations des personnes travaillant dans ces installations. La teneur en cobalt doit donc être limitée au maximum dans les aciers ou alliages qui sont notamment utilisés dans cette industrie pour la réalisation de sièges de vanne.Outside, cobalt-based alloys pose both economic and technical problems. Indeed, cobalt is an expensive raw material whose sources of supply are few. Moreover, this element is highly undesirable in the nuclear environment because it forms long-lived isotopes which are released by the wear of parts and are one of the main sources of radiation exposure of people working in these facilities. The cobalt content must therefore be limited to the maximum in steels or alloys which are used in this industry for the manufacture of valve seats.

Le brevet US 3 912 503 décrit des compositions d'aciers inoxydables résistants à l'usure et à la corrosion. Elle comprennent 0,12% en poids de carbone au maximum, 7 à 13% en poids de manganèse, 3 à 5% en poids de silicium, 12 à 19% en poids de chrome, 4 à 12% en poids de nickel, 0,03 à 0,3% en poids d'azote, le complément étant constitué de fer. Ces compositions ont un coefficient de frottement proche de celui des alliages base cobalt mais présentent une dureté à température ambiante de 200 Vickers seulement, dureté qui tombe à 150 Vickers dès 200°C. De plus, leur ductilité est beaucoup trop grande pour permettre une utilisation pour la réalisation de pièces mécaniques soumises à de fortes contraintes.The patent US 3,912,503 discloses stainless steel compositions resistant to wear and corrosion. They comprise 0.12% by weight of carbon at the most, 7 to 13% by weight of manganese, 3 to 5% by weight of silicon, 12 to 19% by weight of chromium, 4 to 12% by weight of nickel, 0.3 to 0.3% by weight of nitrogen, the balance being iron. These compositions have a coefficient of friction close to that of the cobalt base alloys but have a hardness at room temperature of only 200 Vickers, hardness which drops to 150 Vickers from 200 ° C. In addition, their ductility is much too large to allow use for the production of mechanical parts subjected to high stresses.

Le brevet US 4 814 140 décrit le même type d'acier que le brevet US 3 912 503 et permet d'améliorer la résistance au grippage. Les compositions revendiquées comprennent 0,25% en poids de carbone au maximum, 2 à 7% en poids de manganèse, 1 à 5% en poids de silicium, 12 à 20% en poids de chrome, 2 à 7,75% en poids de nickel, 0,35% en poids d'azote au maximum, le complément étant constitué de fer. Mais, les propriétés mécaniques, parmi lesquelles figurent la ductilité, la dureté à température ambiante et à chaud, sont semblables à celle des compositions du brevet US 3 912 503 et sont donc elles-aussi insuffisantes pour les applications envisagées.The patent US 4,814,140 describes the same type of steel as the patent US 3,912,503 and improves the resistance to seizure. The claimed compositions comprise 0.25% by weight of carbon at most, 2 to 7% by weight of manganese, 1 to 5% by weight of silicon, 12 to 20% by weight of chromium, 2 to 7.75% by weight nickel, 0.35% by weight of nitrogen at most, the balance being iron. However, the mechanical properties, which include ductility, hardness at room temperature and hot, are similar to that of the compositions of the patent. US 3,912,503 and are therefore also insufficient for the intended applications.

Il existe donc un besoin pour un matériau métallique de substitution aux alliages base cobalt qui en contienne le moins possible, voire pas du tout, mais qui présente l'association des caractéristiques de ce type d'alliage, à savoir une résistance à l'abrasion et à l'usure élevée, une bonne résistance à la corrosion et une bonne dureté à température ambiante et à chaud pour des température allant de 300 à 900°C, en les améliorant si possible.There is therefore a need for a metallic material of substitution with cobalt-base alloys which contains as little as possible, if at all, but which has the combination of the characteristics of this type of alloy, namely a resistance to abrasion. and high wear, good corrosion resistance and good hardness at room temperature and hot for temperatures ranging from 300 to 900 ° C, improving them if possible.

La présente invention a donc essentiellement pour but de mettre à disposition un tel matériau.The present invention therefore essentially aims to provide such a material.

A cet effet, un premier objet dé l'invention est constitué par une composition d'acier comprenant, exprimés en pourcentages en poids : C 0,30 - 1,00 % Si 3,50 - 4,50 % Mn 7,00 - 10,00 % Ni 3,50 - 4,50 % Cr 20,00 - 27,00 % W 0,50 - 4,50 % Nb 0 - 2,50 % Co 0 - 1,00 % N 0,20 - 0,50 %, le complément étant principalement constitué de fer et d'impuretés inévitables.For this purpose, a first object of the invention is constituted by a steel composition comprising, expressed in percentages by weight: VS 0.30 - 1.00% Yes 3.50 - 4.50% mn 7.00 - 10.00% Or 3.50 - 4.50% Cr 20.00 - 27.00% W 0.50 - 4.50% Nb 0 - 2.50% Co 0 - 1.00% NOT 0.20 - 0.50%, the complement consisting mainly of iron and impurities inevitable.

Dans un mode de réalisation préféré de l'invention, la composition d'acier comprend, exprimés en pourcentages en poids : C 0,50 - 0,80 % Si 3,50 - 4,50 % Mn 7,00 - 10,00 % Ni 3,50 - 4,50 % Cr 24,00 - 26,00 % W 0,50 - 1,50 % Nb 0 - 2,50 % Co 0 - 0,50 % N 0,20 - 0,50 %, le complément étant principalement constitué de fer et d'impuretés inévitables.In a preferred embodiment of the invention, the steel composition comprises, expressed in percentages by weight: VS 0.50 - 0.80% Yes 3.50 - 4.50% mn 7.00 - 10.00% Or 3.50 - 4.50% Cr 24.00 - 26.00% W 0.50 - 1.50% Nb 0 - 2.50% Co 0 - 0.50% NOT 0.20 - 0.50%, the complement being mainly iron and unavoidable impurities.

Parmi les impuretés inévitables, on citera notamment le soufre et le phosphore qu'il convient de maintenir au plus bas niveau compatible avec le procédé de fabrication ou les matières premières employées.Among the unavoidable impurities include sulfur and phosphorus that should be maintained at the lowest level compatible with the manufacturing process or the raw materials used.

Les excellentes propriétés observées pour les compositions d'acier selon invention sont obtenues grâce à l'équilibrage précis des éléments.The excellent properties observed for the steel compositions according to the invention are obtained thanks to the precise balancing of the elements.

Le carbone est présent à une teneur relativement élevée de 0,30 à 1,00% en poids. Ceci permet notamment d'obtenir la dureté nécessaire aux pièces mécaniques, en particulier grâce à la formation de précipités de type carbure qui renforce la structure du matériau. Une bonne dureté permet entre autres d'obtenir un acier résistant à l'usure. En fonction des compositions et du traitement thermique appliqué, les duretés obtenues avec les aciers selon invention sont comprises entre 350 et 550 Vickers.The carbon is present at a relatively high content of 0.30 to 1.00% by weight. This in particular makes it possible to obtain the hardness necessary for the mechanical parts, in particular thanks to the formation of carbide type precipitates which strengthens the structure of the material. A good hardness makes it possible, among other things, to obtain a steel that is resistant to wear. Depending on the compositions and the heat treatment applied, the hardnesses obtained with the steels according to the invention are between 350 and 550 Vickers.

Dans un mode de réalisation préféré de l'invention, la teneur en carbone des aciers selon l'invention est comprise entre 0,40 et 0,50% en poids, lorsque les pièces à réaliser ne nécessitent pas une dureté et une résistance à l'usure très élevée. Dans un autre mode de réalisation préféré de l'invention, la teneur en carbone des aciers selon l'invention est comprise entre 0,50 et 0,60% en poids, lorsque les pièces à réaliser nécessitent une dureté et une résistance à l'usure un peu plus élevée. Dans un autre mode de réalisation préféré de l'invention, la teneur en carbone est comprise entre 0,70 et 0,80% en poids pour des applications dans lesquelles, la dureté et la résistance à l'usure doivent être élevées. On constate donc que l'on peut ajuster ces deux caractéristiques de l'acier en jouant sur cette teneur en carbone, dans certaines limites prédéfinies.In a preferred embodiment of the invention, the carbon content of the steels according to the invention is between 0.40 and 0.50% by weight, when the parts to be produced do not require a hardness and a resistance to corrosion. very high wear. In another preferred embodiment of the invention, the carbon content of the steels according to the invention is between 0.50 and 0.60% by weight, when the parts to be produced require a hardness and a resistance to wear a bit higher. In another mode preferred embodiment of the invention, the carbon content is between 0.70 and 0.80% by weight for applications in which the hardness and wear resistance must be high. It can therefore be seen that these two characteristics of steel can be adjusted by varying this carbon content, within certain predefined limits.

Le silicium est présent à une teneur de 3,50 à 4,00% en poids. Il joue un rôle dans l'amélioration du frottement et la résistance au grippage du fait de la formation de film adhérent d'oxyde en surface des pièces. Il a également un rôle favorable dans la résistance à la corrosion.Silicon is present at a level of 3.50 to 4.00% by weight. It plays a role in the improvement of friction and resistance to galling due to the formation of adherent oxide film on the surface of the parts. It also has a favorable role in the resistance to corrosion.

Le nickel est un élément gammagène qui participe à l'équilibrage de la composition. Il est présent à une teneur de 3,50 à 4,50% en poids et assure aux compositions d'acier une bonne résistance à la corrosion.Nickel is a gamma element that participates in balancing the composition. It is present at a level of 3.50 to 4.50% by weight and provides the steel compositions with good resistance to corrosion.

Le manganèse est présent à une teneur de 7,00 à 10,00 % en poids. Son rôle est similaire à celui du nickel.The manganese is present at a content of 7.00 to 10.00% by weight. Its role is similar to that of nickel.

Le chrome est présent en une quantité de 20,00 à 27,00% en poids, de préférence 24 à 26% en poids. Il joue lui-aussi un rôle important dans la bonne résistance contre la corrosion des aciers selon l'invention. On pourra éventuellement remplacer une partie du chrome présent dans la composition par du molybdène sur la base de 1% de molybdène pour 3% de chrome.Chromium is present in an amount of 20.00 to 27.00% by weight, preferably 24 to 26% by weight. It also plays an important role in the good resistance against corrosion of steels according to the invention. It may be possible to replace some of the chromium present in the composition with molybdenum on the basis of 1% molybdenum to 3% chromium.

Le tungstène est présent en une quantité de 0,50 à 4,50% en poids, de préférence de 0,50 à 1,50% en poids. Il permet notamment d'obtenir une bonne tenue à chaud des compositions selon l'invention.Tungsten is present in an amount of from 0.50 to 4.50% by weight, preferably from 0.50 to 1.50% by weight. It makes it possible in particular to obtain a good heat resistance of the compositions according to the invention.

Le niobium est présent en une quantité de 0 à 2,5% en poids. C'est un élément carburigène qui contribue à la dureté de la nuance tout en ayant une action favorable sur le tenue à chaud des compositions d'acier.Niobium is present in an amount of 0 to 2.5% by weight. It is a carburizing element that contributes to the hardness of the grade while having a favorable action on the hot performance of the steel compositions.

L'azote est présent en une quantité de 0,20 à 0,50% en poids dans les compositions selon l'invention. Il contribue à l'équilibre de la composition par son influence gammagène, et à la dureté de par sa participation à la formation de carbonitrures de niobium en particulier.The nitrogen is present in an amount of from 0.20 to 0.50% by weight in the compositions according to the invention. It contributes to the balance of the composition by its gammagenic influence, and to the hardness of its participation in the formation of niobium carbonitrides in particular.

Le cobalt est un élément indésirable dont la teneur est limitée à 1% en poids au maximum, de préférence 0,5% en poids. Sa teneur sera limitée autant que possible techniquement et sera de façon plus particulièrement préférée réduite à l'état de traces.Cobalt is an undesirable element whose content is limited to a maximum of 1% by weight, preferably 0.5% by weight. Its content will be limited as much as possible technically and will be more preferably reduced to trace.

Un second objet de l'invention est constitué par un procédé de préparation de pièces mécaniques caractérisé en ce qu'il comprend les étapes suivantes :

  • a - constitution d'une charge destinée à obtenir une composition chimique selon l'une quelconque des variantes précédemment exposées,
  • b - élaboration de ladite charge,
  • c - mise en forme d'une ébauche de ladite pièce mécanique par moulage,
  • d- usinage de ladite pièce mécanique à partir de l'ébauche,
  • e - en option, traitement thermique d'emploi de ladite pièce mécanique.
A second subject of the invention consists of a process for preparing mechanical parts, characterized in that it comprises the following steps:
  • a - constitution of a filler intended to obtain a chemical composition according to any one of the variants previously exposed,
  • b - elaboration of said charge,
  • c - forming a blank of said mechanical part by molding,
  • machining said mechanical part from the blank,
  • e - optional heat treatment of use of said mechanical part.

Dans un mode de réalisation préféré, un procédé de préparation de pièces mécaniques est caractérisé en ce qu'il comprend les étapes suivantes :

  • a - constitution d'une charge destinée à obtenir une composition chimique selon l'une quelconque des variantes précédemment exposées,
  • b - fusion de ladite charge dans un creuset,
  • c - moulage par centrifugation d'une ébauche de ladite pièce mécanique, et
  • d- usinage de ladite pièce mécanique à partir de l'ébauche,
  • e - en option, traitement thermique d'emploi de ladite pièce mécanique.
In a preferred embodiment, a method for preparing mechanical parts is characterized in that it comprises the following steps:
  • a - constitution of a filler intended to obtain a chemical composition according to any one of the variants previously exposed,
  • b - melting said charge in a crucible,
  • c - centrifugally molding a blank of said mechanical part, and
  • machining said mechanical part from the blank,
  • e - optional heat treatment of use of said mechanical part.

Ce procédé de moulage par centrifugation est traditionnellement utilisé pour mettre en forme les alliages base cobalt, car il présente de grands avantages. Il consiste à introduire progressivement la masse de métal en fusion dans une chemise chauffée en rotation, de telle sorte qu'une couche très fine de métal, de l'ordre d'un dixième de millimètre se dépose à chaque tour à l'intérieur de la chemise. Chaque couche se solidifie donc indépendamment des couches précédemment déposées ce qui permet d'obtenir une ébauche à structure fine et isotrope, sans micro-porosités. Les pièces finies obtenues après usinage de l'ébauche sont exemptes de retassures, très résistantes et présentent un très bon état de surface.This centrifugal molding process is traditionally used to shape cobalt-based alloys because it has great advantages. It consists of gradually introducing the mass of molten metal in a heated folder in rotation, so that a very thin layer of metal, of the order of a tenth of a millimeter is deposited at each turn inside shirt. Each layer solidifies therefore independently of the previously deposited layers which allows to obtain a fine structure and isotropic blank, without micro-porosities. The finished parts obtained after machining the blank are free of sink holes, very strong and have a very good surface finish.

Les présents inventeurs ont donc constaté de façon tout à fait surprenante qu'il était parfaitement possible de mouler par centrifugation les pièces mécaniques à réaliser dans les compositions selon l'invention.The present inventors have therefore found quite surprisingly that it was perfectly possible to mold by centrifugation the mechanical parts to be produced in the compositions according to the invention.

Il est cependant bien entendu possible de mouler ces pièces mécaniques en coulée statique, en particulier pour les pièces de grande taille pour lesquelles la centrifugation n'est pas possible en raison de la taille limitée de la chemise chauffée. Le moulage à la cire perdue est lui-aussi tout à fait réalisable.However, it is of course possible to mold these mechanical parts in static casting, especially for large parts for which centrifugation is not possible due to the limited size of the heated jacket. The lost wax casting is also quite feasible.

Quant à la fusion des compositions d'acier, elle peut être réalisée par tout procédé connu, en particulier dans un four à arc.As for the melting of the steel compositions, it can be carried out by any known method, in particular in an arc furnace.

Les compositions d'acier selon l'invention peuvent notamment se trouver sous trois formes différentes en fonction de leur état thermique. Il s'agit de l'état dit "brut de coulée", de l'état mis en solution à des températures de 1 050 à 1 150°C et de l'état stabilisé obtenu en pratiquant un ou plusieurs traitements de stabilisation de 700 à 900°C sur une pièce à l'état brut de coulée ou à l'état mis en solution.The steel compositions according to the invention can in particular be in three different forms depending on their thermal state. This is the so-called "raw state of casting", of the state dissolved in temperatures of 1050 to 1150 ° C. and of the stabilized state obtained by practicing one or more stabilization treatments of 700 at 900 ° C on a piece in the raw state of casting or in the dissolved state.

L'état thermique dépend essentiellement des conditions dans lesquelles la pièce sera utilisée. Ainsi pour une utilisation à chaud, on réalisera de préférence un traitement de stabilisation par vieillissement, comprenant une mise en solution suivie d'un refroidissement lent dans un fluide tel que l'air. Ce traitement permet la formation de précipités dans la matrice de l'acier qui ne variera ensuite plus en dureté ou en dimensions.The thermal state essentially depends on the conditions under which the part will be used. Thus, for hot use, an aging stabilization treatment will preferably be carried out, comprising dissolving followed by slow cooling in a fluid such as air. This treatment allows the formation of precipitates in the matrix of the steel which will not then vary in hardness or dimensions.

Un troisième objet de l'invention est constitué par les pièces mécaniques réalisées dans les compositions et/ou à l'aide des procédés précédemment décrits. On citera en particulier, à titre d'exemples, les sièges de soupape, de vanne, les bagues et disques de frottement, les composants de turbine à gaz, les poinçons et outils de découpe pour travail à chaud, les couteaux et lames de cisaille travaillant à haute température.A third subject of the invention consists of the mechanical parts produced in the compositions and / or with the aid of the processes described above. Examples include valve, valve seats, friction rings and discs, gas turbine components, hot work cutters and cutters, knives and shear blades. working at high temperature.

ESSAISTESTS

Les symboles utilisés dans la suite ont les significations suivantes :

Rm =
résistance maximale,
Rp0,2=
limite élastique conventionnelle à 0,2% de déformation,
A =
allongement,
Z =
striction,
HV =
dureté Vickers,
HRC =
dureté Rockwell.
The symbols used in the following have the following meanings:
R m =
maximum resistance,
R p0,2 =
conventional elastic limit at 0.2% deformation,
A =
elongation,
Z =
necking,
HV =
Vickers hardness,
HRC =
Rockwell hardness.

Tous les pourcentages mentionnés sont des pourcentages en poids.All percentages mentioned are percentages by weight.

Les différents essais ont été réalisés sur une composition d'acier selon l'invention appelée nuance ES dont la composition est la suivante : C 0,50 % Si 3,50 % Mn 9,00 % Ni 4,00 % Cr 26,00 % W 1,20 % Nb 1,50 % Co 0,12 % N 0,25 %, le complément étant constitué de fer.The various tests were carried out on a steel composition according to the invention called grade ES whose composition is as follows: VS 0.50% Yes 3.50% mn 9.00% Or 4.00% Cr 26.00% W 1.20% Nb 1.50% Co 0.12% NOT 0.25%, the complement being made of iron.

Les essais ont été réalisés sur des échantillons d'acier se trouvant dans les trois états thermiques précédemment définis, à savoir l'état brut de coulée, l'état mis en solution et l'état stabilisé.The tests were carried out on steel samples in the three previously defined thermal states, namely the raw state of casting, the state in solution and the stabilized state.

Le matériau de référence de l'art antérieur choisi à titre de comparaison est un alliage base cobalt CoCr29W5, dont la composition est la suivante : C 1,10 % Cr 29,00 % W 5,00 %, le complément étant constitué de cobalt.The reference material of the prior art chosen for comparison is a cobalt base alloy CoCr29W5, the composition of which is as follows: VS 1.10% Cr 29.00% W 5.00%, the complement consisting of cobalt.

1. Caractéristiques mécaniques à température ambiante1. Mechanical characteristics at room temperature

Au moyen des tests classiques bien connus de l'homme du métier, on a déterminé les caractéristiques mécaniques à température ambiante respectives de trois échantillons de la nuance ES dans différents états thermiques et d'un échantillon d'alliage base cobalt. Les résultats sont rassemblés dans le tableau 1. Tableau 1 Nuance ES selon l'invention CoCr29W5 BC1) MS2) S3) S3) Dureté
(HV) 340 320 460 450 Rm
(MPa) 820 850 900 900 Rp0,2 (MPa) 550 600 680 650 A
(%) 5 8 2 2 Z
(%) 8 10 4 2,5 1) état brut de coulée
2) état mis en solution
3) état stabilisé Using standard tests well known to those skilled in the art, the respective room temperature mechanical characteristics of three samples of the ES grade in different thermal states and a cobalt base alloy sample were determined. The results are summarized in Table 1. <u> Table 1 </ u> Nuance ES according to the invention CoCr29W5 BC 1) MS 2) S 3) S 3) Hardness
(H V) 340 320 460 450 rm
(MPa) 820 850 900 900 Rp 0.2 (MPa) 550 600 680 650 AT
(%) 5 8 2 2 Z
(%) 8 10 4 2.5 1) raw state of casting
2) state in solution
3) stabilized state

On constate que les caractéristiques mécaniques à température ambiante des compositions d'acier selon l'invention sont tout à fait similaires à celles obtenues avec les alliages à base cobalt tel que le CoCr29W5.It is found that the mechanical characteristics at ambient temperature of the steel compositions according to the invention are quite similar to those obtained with cobalt-based alloys such as CoCr29W5.

2. Dureté à chaud2. Hot hardness

On a testé des échantillons stabilisés de la nuance ES et de CoCr29W5 pour des températures allant de 100 à 600°C. Les résultats sont rassemblés dans le tableau 2. Tableau 2 Dureté (HRC) Nuance ES CoCr29W5 à 100°C 42 40 à 200°C 38,5 37,5 à 300°C 35 35 à 400°C 31 32 à 500°C 27 28,5 à 600°C 23,5 25,5 Stabilized samples of ES grade and CoCr29W5 were tested for temperatures ranging from 100 to 600 ° C. The results are collated in Table 2. <b><u> Table 2 </ u></b> Hardness (HRC) Nuance ES CoCr29W5 at 100 ° C 42 40 at 200 ° C 38.5 37.5 at 300 ° C 35 35 at 400 ° C 31 32 at 500 ° C 27 28.5 at 600 ° C 23.5 25.5

3. Tenue à la corrosion3. Corrosion resistance

Trois échantillons de la nuance ES et un échantillon de CoCr29W5 ont été soumis à un essai en brouillard salin suivant la norme NFX 41-002. Les résultats, qui sont rassemblés dans le tableau 3, sont donnés sous la forme d'un nombre correspondant à l'aspect du matériau à l'issue de l'essai:

  • 10 correspond à un matériau sans aucune trace de corrosion,
  • 9 correspond à un matériau présentant quelques piqûres dispersées, et
  • 8 correspond à un matériau présentant quelques spots autour des piqûres.
Tableau 3 Nuance ES selon l'invention CoCr29W5 Temps d'exposition BC1) MS2) S3) S3) 24 heures 9 10 10 10 56 heures 8 10 9 10 288 heures 8 10 9 10 1) état brut de coulée
2) état mis en solution
3) état stabilisé Three samples of grade ES and a sample of CoCr29W5 were subjected to a salt spray test according to NFX 41-002. The results, which are collected in Table 3, are given in the form of a number corresponding to the appearance of the material at the end of the test:
  • 10 corresponds to a material without any trace of corrosion,
  • 9 corresponds to a material having a few scattered bites, and
  • 8 corresponds to a material having some spots around the bites.
<b><u> Table 3 </ u></b> Nuance ES according to the invention CoCr29W5 Exposure time BC 1) MS 2) S 3) S 3) 24 hours 9 10 10 10 56 hours 8 10 9 10 288 hours 8 10 9 10 1) raw state of casting
2) state in solution
3) stabilized state

On constate que là-aussi la tenue à la corrosion atteinte par les compositions selon l'invention est du même niveau que celle obtenue avec l'alliage base cobalt.It is noted that here too the resistance to corrosion achieved by the compositions according to the invention is of the same level as that obtained with the cobalt base alloy.

4. Essais de frottement et de résistance à l'usure4. Friction and wear resistance tests

Les essais ont été réalisés sur des échantillons stabilisés de la nuance ES et du CoCr29W5 selon la norme ASTM G99-95a, à l'aide d'un tribomètre de type pion-disque, sous une charge maximale de 10 N, à sec et avec une vitesse linéaire de contact de 0,1 m/s pour une distance totale parcourue de 1008 m. Les résultats sont rassemblés dans le tableau 4. Tableau 4 Nuance ES CoCr29W5 Coefficient de frottement Essai 1 0,705 0,684 Essai 2 0,710 0,625 Essai 3 0,702 0,703 Moyenne 0,707 0,671 Usure
(10-3 mm3) Essai 1 5 10 Essai 2 5 9 Essai 3 6 13 Moyenne 5,33 10,66 The tests were carried out on stabilized samples of grade ES and CoCr29W5 according to ASTM G99-95a, using a pion-disk tribometer, under a maximum load of 10 N, dry and with a linear contact velocity of 0.1 m / s for a total distance of 1008 m. The results are summarized in Table 4. <u> Table 4 </ u> Nuance ES CoCr29W5 Coefficient of friction Trial 1 0.705 0,684 Trial 2 0.710 0.625 Trial 3 0.702 0,703 Average 0.707 0.671 Wear
(10 -3 mm 3 ) Trial 1 5 10 Trial 2 5 9 Trial 3 6 13 Average 5.33 10.66

On constate tout d'abord que le coefficient de frottement des nuances selon l'invention est similaire à celui du CoCr29W5. Par contre, le taux d'usure de ces mêmes compositions est deux fois moindre que celui du CoCr29W5, ce qui est tout à fait surprenant.It is first noted that the coefficient of friction of the shades according to the invention is similar to that of CoCr29W5. On the other hand, the wear rate of these same compositions is two times lower than that of CoCr29W5, which is quite surprising.

On notera également la grande reproductibilité des essais lorsqu'ils portent sur les nuances selon l'invention, contrairement à ce qui se produit avec l'alliage base cobalt. Cette caractéristique peut notamment s'avérer avantageuse pour l'élaborateur lorsqu'il doit fournir les caractéristiques d'une pièce ou d'un produit semi-fini, car il n'est alors pas nécessaire d'effectuer plusieurs essais pour déterminer le coefficient de frottement et/ou le taux d'usure.Note also the great reproducibility of the tests when they relate to the grades of the invention, unlike what occurs with the cobalt base alloy. This characteristic may in particular prove to be advantageous for the manufacturer when he has to provide the characteristics of a part or a semi-finished product, since it is then not necessary to carry out several tests to determine the coefficient of friction and / or wear rate.

Outre les qualités venant d'être mentionnées, on remarquera également que les aciers selon l'invention sont amagnétiques pour les états brut de coulée et mis en solution, ce qui permet leur utilisation pour certaines pièces sensibles, comme les pièces pour sous-marins, notamment.In addition to the qualities just mentioned, it will also be noted that the steels according to the invention are non-magnetic for the raw casting conditions and put into solution, which allows their use for certain sensitive parts, such as submarine parts, especially.

Il va de soi que les formes de réalisation de l'invention qui ont été décrites ci-dessus ont été données à titre purement indicatif et nullement limitatif, et que de nombreuses modifications peuvent être facilement apportées par l'homme de l'art sans pour autant sortir du cadre de l'invention.It goes without saying that the embodiments of the invention which have been described above have been given for information only and in no way limiting, and that many modifications can easily be made by those skilled in the art without as far out of the scope of the invention.

Claims (12)

  1. Steel composition, characterised in that it comprises, expressed in wt.%: C 0.30 - 1.00 % Si 3.50 - 4.50 % Mn 7.00 - 10.00 % Ni 3.50 - 4.50 % Cr 20.00 - 27.00 % W 0.50 - 4.50 % Nb 0 - 2.50 % Co 0 - 1.00 % N 0.20 - 0.50 %,
    the remainder being iron and unavoidable impurities.
  2. Steel composition according to claim 1, characterised in that it comprises from 24 to 26 wt.% chromium.
  3. Steel composition according to either claim 1 or claim 2, characterised in that it comprises from 0.50 to 1.50% tungsten.
  4. Steel composition according to any one of claims 1 to 3, characterised in that it comprises from 3.50 to 4.00 wt.% silicon.
  5. Steel composition according to any one of claims 1 to 4, characterised in that it comprises from 0.40 to 0.50 wt.% carbon.
  6. Steel composition according to any one of claims 1 to 4, characterised in that it comprises from 0.50 to 0.60 wt.% carbon.
  7. Steel composition according to any one of claims 1 to 4, characterised in that it comprises from 0.70 to 0.80 wt.% carbon.
  8. Steel composition according to claim 1, characterised in that it comprises, expressed in wt.%: C 0.50 - 0.80 % Si 3.50 - 4.50 % Mn 7.00 - 10.00 % Ni 3.50 - 4.50 % Cr 24.00 - 26.00 % W 0.50 - 1.50 % Nb 0 - 2.50 % Co 0 - 0.50 % N 0.20 - 0.50 %,
    the remainder being iron and unavoidable impurities.
  9. Process for the production of mechanical parts, characterised in that it comprises the following steps:
    a - formation of a charge for obtaining a chemical composition according to any one of claims 1 to 8,
    b - production of said charge,
    c - forming of a blank of said mechanical part by casting,
    d - machining of said mechanical part from the blank,
    e - optionally, heat treatment of said mechanical part for use.
  10. Process for the production of mechanical parts according to claim 9, characterised in that it comprises the following steps:
    a - formation of a charge for obtaining a chemical composition according to any one of claims 1 to 8,
    b - melting said charge in a crucible,
    c - centrifugal casting of a blank of said mechanical part, and
    d - machining of said mechanical part from the blank,
    e - optionally, heat treatment of said mechanical part for use.
  11. Steel parts having a composition according to any one of claims 1 to 8.
  12. Steel parts according to claim 11, characterised in that they are obtained by a process according to either claim 9 or claim 10.
EP01949617A 2000-07-04 2001-07-03 Steel compositions, method for obtaining same and parts made from same Expired - Lifetime EP1297192B1 (en)

Applications Claiming Priority (3)

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FR0008698A FR2811336B1 (en) 2000-07-04 2000-07-04 STEEL COMPOSITIONS, PROCESS FOR OBTAINING SAME, AND PARTS MANUFACTURED THEREFROM
FR0008698 2000-07-04
PCT/FR2001/002121 WO2002002830A1 (en) 2000-07-04 2001-07-03 Steel compositions, method for obtaining same and parts made from same

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GB201716640D0 (en) * 2017-10-11 2017-11-22 Rolls Royce Plc Cobalt-free alloys
CN111850428B (en) * 2019-04-28 2022-01-25 重庆三爱海陵实业有限责任公司 Valve alloy material and valve

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US2686116A (en) * 1952-06-18 1954-08-10 Crucible Steel Company Age hardening austenitic steel
FR1314540A (en) * 1961-11-30 1963-01-11 Universal Cyclops Steel Corp Stainless steel alloy
DE3247568A1 (en) * 1981-12-23 1983-06-30 Kubota Ltd., Osaka REACTOR TUBE FOR THERMAL CRACKING OR REFORMING HYDROCARBONS
US4803045A (en) * 1986-10-24 1989-02-07 Electric Power Research Institute, Inc. Cobalt-free, iron-base hardfacing alloys
JP3721637B2 (en) * 1996-04-22 2005-11-30 大同特殊鋼株式会社 Method for producing Ca-containing austenitic heat resistant steel
JPH10280907A (en) * 1997-04-07 1998-10-20 Mitsubishi Heavy Ind Ltd Steam turbine rotor blade

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ES2349399T3 (en) 2011-01-03
AU2001270741A1 (en) 2002-01-14
FR2811336A1 (en) 2002-01-11

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