EP1297192A1 - Steel compositions, method for obtaining same and parts made from same - Google Patents

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

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Publication number
EP1297192A1
EP1297192A1 EP01949617A EP01949617A EP1297192A1 EP 1297192 A1 EP1297192 A1 EP 1297192A1 EP 01949617 A EP01949617 A EP 01949617A EP 01949617 A EP01949617 A EP 01949617A EP 1297192 A1 EP1297192 A1 EP 1297192A1
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EP
European Patent Office
Prior art keywords
weight
composition according
steel
mechanical
parts
Prior art date
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Granted
Application number
EP01949617A
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German (de)
French (fr)
Other versions
EP1297192B1 (en
Inventor
Jacques Frey
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Aubert and Duval SA
Original Assignee
Industrielle De Metallurgie Avancee (sima) Ste
Aubert and Duval SA
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Publication of EP1297192A1 publication Critical patent/EP1297192A1/en
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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 which can be used under 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.
  • cobalt is an expensive raw material with few sources of supply.
  • this element is highly undesirable in the nuclear environment because it forms isotopes with long lifespan which are released by the wear of the parts and are one of the main sources of exposure to radiations of the people working in these installations.
  • the cobalt content must therefore be limited as much as possible in the steels or alloys which are used in particular in this industry for the production of valve seats.
  • US Patent 3,912,503 describes compositions of stainless steels resistant to wear and corrosion. They include 0.12% by weight of carbon at 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 , 03 to 0.3% by weight of nitrogen, the balance consisting of iron. These compositions have a coefficient of friction close to that of cobalt-based 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 great to allow use for the production of mechanical parts subjected to high stresses.
  • US Patent 4,814,140 describes the same type of steel as US Patent 3,912,503 and makes it possible to improve the resistance to seizing.
  • 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 of nickel, 0.35% by weight of nitrogen at most, the remainder consisting of iron.
  • the mechanical properties which include ductility, hardness at room temperature and when hot, are similar to that of the compositions of US Pat. No. 3,912,503 and are therefore also insufficient for the applications envisaged.
  • the main object of the present invention is therefore to provide such a material.
  • a first object of the invention consists of a steel composition comprising, expressed in percentages by weight:
  • the steel composition comprises, expressed in percentages by weight:
  • unavoidable impurities mention will be made in particular of sulfur and phosphorus which should be kept at the lowest level compatible with the manufacturing process or the raw materials used.
  • 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 hardness and resistance to l '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 hardness and resistance to slightly higher wear. 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 the resistance to wear 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.
  • the silicon is present at a content of 3.00 to 4.50% by weight, preferably 3.50 to 4.00% by weight. It plays a role in improving friction and seizure resistance due to the formation of adherent oxide film on the surface of the parts. It also has a favorable role in corrosion resistance.
  • Nickel is a gamma element which participates in balancing the composition. It is present in a content of 3.50 to 4.50% by weight and provides the steel compositions with good corrosion resistance.
  • Manganese is present at a content of 7.00 to 10.00% by weight. Its role is similar to that of nickel.
  • the 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 the steels according to the invention. It may be possible to replace part of the chromium present in the composition with molybdenum on the basis of 1% molybdenum for 3% chromium.
  • the tungsten is present in an amount of 0.50 to 4.50% by weight, preferably 0.50 to 1.50% by weight. It makes it possible in particular to obtain good heat resistance of the compositions according to the invention.
  • the niobium is present in an amount of 0 to 2.5% by weight. It is a carburetor element which contributes to the hardness of the shade while having a favorable action on the heat resistance of steel compositions.
  • the nitrogen is present in an amount of 0.20 to 0.50% by weight in the compositions according to the invention. It contributes to the balance of the composition by its gamma influence, and to the hardness by its participation in the formation of niobium carbonitrides in particular.
  • Cobalt is an undesirable element the content of which is limited to a maximum of 1% by weight, preferably 0.5% by weight. Its content will be limited technically as much as possible and will be more particularly reduced to a trace state.
  • a second object of the invention consists of a process for the preparation of mechanical parts, characterized in that it comprises the following steps: a - constitution of a charge intended to obtain a chemical composition according to any of the variants previously exposed , b - preparation of said load, c - shaping of a blank of said mechanical part by molding, d- machining of said mechanical part from the blank, e - optional, heat treatment for use of said mechanical piece.
  • a process for the preparation of mechanical parts comprises the following stages: a - constitution of a charge intended to obtain a chemical composition according to any of the variants previously exposed, b - melting of said charge in a crucible, c - "molding" by centrifugation of a blank of said mechanical part, and machining of said mechanical part from the blank, e - as an option, heat treatment using said mechanical part.
  • This centrifugal molding process is traditionally used to form cobalt-based alloys, since it has great advantages, it consists in gradually introducing the mass of molten metal into a jacket heated in rotation, so that that a very thin layer of metal, on the order of a tenth of a millimeter, is deposited on the inside of the liner each turn. ie therefore independently of the previously deposited layers, which makes it possible to obtain a blank with a fine and isotropic structure, without micro-porosities.
  • the finished parts obtained after machining the blank are free from shrinkage, very resistant and have a very good surface condition.
  • the present inventors have therefore found, quite surprisingly, that it is perfectly possible to centrifuge mold 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 process, 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. These are the so-called “raw pouring” state, the state dissolved in temperatures from 1050 to 1150 ° C. and the stabilized state obtained by practicing one or more stabilization treatments of 700 at 900 ° C on a part in the raw casting state or in the dissolved state.
  • the thermal state essentially depends on the conditions under which the part will be used.
  • a stabilization treatment by aging comprising dissolving followed by slow cooling in a fluid such as air. This treatment allows the formation of precipitates in the steel matrix which will then no longer vary in hardness or dimensions.
  • a third object of the invention consists of the mechanical parts produced in the compositions and / or using the methods described above. Examples include valve seats, valve seats, friction rings and discs, gas turbine components, punches and cutting tools for hot work, knives and shear blades working at high temperature.
  • R p o, 2 conventional elastic limit at 0.2% deformation
  • A elongation
  • Z necking
  • HV Vickers hardness
  • HRC Rockwell hardness
  • grade ES the composition of which is as follows:
  • the tests were carried out on steel samples in the three previously defined thermal states, namely the raw casting state, the dissolved state and the stabilized state.
  • the reference material of the prior art chosen for comparison is a cobalt base alloy CoCr29W5, the composition of which is as follows: C 1, 10%
  • - 8 corresponds to a material having a few spots around the bites.

Abstract

The invention concerns steel compositions comprising expressed in weight percentages: C 0.30-1.00 %; Si 3.00-4-50 %; 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 rest mainly consisting of iron and unavoidable impurities. The invention also concerns a method for obtaining same and parts made from said compositions.

Description

Compositions d'acier, procédé pour son obtention et pièces fabriquées à partir de ces compositions.Steel compositions, process for obtaining them and parts made from these compositions.
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 which can be used under 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.In fact, when mechanical parts must be subjected to usage constraints requiring high resistance to abrasion or erosion wear, high corrosion resistance and good heat resistance up to 900 ° C, the only ones materials likely to 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 also currently no satisfactory alternative to these alloys.
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.However, cobalt-based alloys pose both economic and technical problems. In fact, cobalt is an expensive raw material with few sources of supply. In addition, this element is highly undesirable in the nuclear environment because it forms isotopes with long lifespan which are released by the wear of the parts and are one of the main sources of exposure to radiations of the people working in these installations. The cobalt content must therefore be limited as much as possible in the steels or alloys which are used in particular in this industry for the production 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.US Patent 3,912,503 describes compositions of stainless steels resistant to wear and corrosion. They include 0.12% by weight of carbon at 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 , 03 to 0.3% by weight of nitrogen, the balance consisting of iron. These compositions have a coefficient of friction close to that of cobalt-based 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 great 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.US Patent 4,814,140 describes the same type of steel as US Patent 3,912,503 and makes it possible to improve the resistance to seizing. 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 of nickel, 0.35% by weight of nitrogen at most, the remainder consisting of iron. However, the mechanical properties, which include ductility, hardness at room temperature and when hot, are similar to that of the compositions of US Pat. No. 3,912,503 and are therefore also insufficient for the applications envisaged.
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. La présente invention a donc essentiellement pour but de mettre à disposition un tel matériau.There is therefore a need for a metal material to replace cobalt-based alloys which contains as little as possible, if at all, but which has the association of the characteristics of this type of alloy, namely abrasion resistance. 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. The main object of the present invention is therefore to provide such a material.
A cet effet, un premier objet de l'invention est constitué par une composition d'acier comprenant, exprimés en pourcentages en poids :To this end, a first object of the invention consists of a steel composition comprising, expressed in percentages by weight:
C 0,30 - 1,00 %C 0.30 - 1.00%
Si 3,00 - 4,50 %If 3.00 - 4.50%
Mn 7,00 - 10,00 %Mn 7.00 - 10.00%
Ni 3,50 - 4,50 %Ni 3.50 - 4.50%
Cr 20,00 - 27,00 %Cr 20.00 - 27.00%
W 0,50 - 4,50 %W 0.50 - 4.50%
Nb 0 - 2,50 %Nb 0 - 2.50%
Co 0 - 1 ,00 %Co 0 - 1.00%
N 0,20 - 0,50 %, le complément étant principalement constitué de fer et d'impuretés inévitables.N 0.20 - 0.50%, the balance 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 :In a preferred embodiment of the invention, the steel composition comprises, expressed in percentages by weight:
C 0,50 - 0,80 %C 0.50 - 0.80%
Si 3,00 - 4,50 %If 3.00 - 4.50%
Mn 7,00 - 10,00 %Mn 7.00 - 10.00%
Ni 3,50 - 4,50 %Ni 3.50 - 4.50%
Çr 24,00 - 26,00 %Çr 24.00 - 26.00%
W 0,50 - 1,50 %W 0.50 - 1.50%
Nb 0 - 2,50 %Nb 0 - 2.50%
Co 0 - 0,50 %Co 0 - 0.50%
N 0,20 - 0,50 %. le complément étant principalement constitué de fer et d'impuretés inévitables. 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.N 0.20 - 0.50%. the remainder mainly consisting of iron and unavoidable impurities. Among the unavoidable impurities, mention will be made in particular of sulfur and phosphorus which should be kept at the lowest level compatible with the manufacturing process or the raw materials used.
Les excellentes propriétés observées pour les compositions d'acier selon l'invention sont obtenues grâce à l'équilibrage précis des éléments. Le carbone est présent à une teneur relativement élevée de 0,30 àThe excellent properties observed for the steel compositions according to the invention are obtained thanks to the precise balancing of the elements. Carbon is present at a relatively high content of 0.30 to
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 l'invention sont comprises entre 350 et 550 Vickers.1.00% by weight. This makes it possible in particular to obtain the hardness necessary for mechanical parts, in particular thanks to the formation of carbide-type precipitates which reinforces the structure of the material. Good hardness allows, among other things, to obtain a wear-resistant steel. 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 hardness and resistance to l '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 hardness and resistance to slightly higher wear. 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 the resistance to wear 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 3,00 à 4,50% en poids, de préférence 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.The silicon is present at a content of 3.00 to 4.50% by weight, preferably 3.50 to 4.00% by weight. It plays a role in improving friction and seizure resistance due to the formation of adherent oxide film on the surface of the parts. It also has a favorable role in corrosion resistance.
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 which participates in balancing the composition. It is present in a content of 3.50 to 4.50% by weight and provides the steel compositions with good corrosion resistance.
Le manganèse est présent à une teneur de 7,00 à 10,00 % en poids. Son rôle est similaire à celui du nickel.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.The 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 the steels according to the invention. It may be possible to replace part of the chromium present in the composition with molybdenum on the basis of 1% molybdenum for 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. Le niobium est présent en une quantité de 0 à 2,5% en poids. C'est un élément carburigene qui contribue à la dureté de la nuance tout en ayant une action favorable sur le tenue à chaud des compositions d'acier.The tungsten is present in an amount of 0.50 to 4.50% by weight, preferably 0.50 to 1.50% by weight. It makes it possible in particular to obtain good heat resistance of the compositions according to the invention. The niobium is present in an amount of 0 to 2.5% by weight. It is a carburetor element which contributes to the hardness of the shade while having a favorable action on the heat resistance of 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 0.20 to 0.50% by weight in the compositions according to the invention. It contributes to the balance of the composition by its gamma influence, and to the hardness by 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 the content of which is limited to a maximum of 1% by weight, preferably 0.5% by weight. Its content will be limited technically as much as possible and will be more particularly reduced to a trace state.
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. 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. 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.A second object of the invention consists of a process for the preparation of mechanical parts, characterized in that it comprises the following steps: a - constitution of a charge intended to obtain a chemical composition according to any of the variants previously exposed , b - preparation of said load, c - shaping of a blank of said mechanical part by molding, d- machining of said mechanical part from the blank, e - optional, heat treatment for use of said mechanical piece. In a preferred embodiment, a process for the preparation of mechanical parts is characterized in that it comprises the following stages: a - constitution of a charge intended to obtain a chemical composition according to any of the variants previously exposed, b - melting of said charge in a crucible, c - "molding" by centrifugation of a blank of said mechanical part, and machining of said mechanical part from the blank, e - as an option, heat treatment using said mechanical part. This centrifugal molding process is traditionally used to form cobalt-based alloys, since it has great advantages, it consists in gradually introducing the mass of molten metal into a jacket heated in rotation, so that that a very thin layer of metal, on the order of a tenth of a millimeter, is deposited on the inside of the liner each turn. ie therefore independently of the previously deposited layers, which makes it possible to obtain a blank with a fine and isotropic structure, without micro-porosities. The finished parts obtained after machining the blank are free from shrinkage, very resistant and have a very good surface condition.
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 is perfectly possible to centrifuge mold 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.It is however of course possible to mold these mechanical parts in static casting, in particular for large parts for which centrifugation is not possible due to the limited size of the heated jacket. The lost wax molding 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 process, 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. These are the so-called "raw pouring" state, the state dissolved in temperatures from 1050 to 1150 ° C. and the stabilized state obtained by practicing one or more stabilization treatments of 700 at 900 ° C on a part in the raw casting state 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, a stabilization treatment by aging is preferably carried out, comprising dissolving followed by slow cooling in a fluid such as air. This treatment allows the formation of precipitates in the steel matrix which will then no longer 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. ESSAISA third object of the invention consists of the mechanical parts produced in the compositions and / or using the methods described above. Examples include valve seats, valve seats, friction rings and discs, gas turbine components, punches and cutting tools for hot work, knives and shear blades working at high temperature. TESTS
Les symboles utilisés dans la suite ont les significations suivantes : Rm = résistance maximale,The symbols used in the following have the following meanings: R m = maximum resistance,
Rpo,2= limite élastique conventionnelle à 0,2% de déformation, A = allongement, Z = striction, HV = dureté Vickers, HRC = dureté Rockwell.R p o, 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. Les différents essais ont été réalisés sur une composition d'acier selon l'invention appelée nuance ES dont la composition est la suivante :All the percentages mentioned are percentages by weight. The various tests were carried out on a steel composition according to the invention called grade ES, the composition of which is as follows:
C 0,50 % Si 3,50 %C 0.50% If 3.50%
Mn 9,00 %Mn 9.00%
Ni 4,00 %Ni 4.00%
Cr 26,00 %Cr 26.00%
W 1 ,20 % Nb 1 ,50 %)W 1, 20% Nb 1, 50%)
Co 0,12 %Co 0.12%
N 0,25 %, le complément étant constitué de fer.N 0.25%, the balance consisting 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 casting state, the dissolved state 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 %The reference material of the prior art chosen for comparison is a cobalt base alloy CoCr29W5, the composition of which is as follows: C 1, 10%
Cr 29,00 %Cr 29.00%
W 5,00 %, le complément étant constitué de cobalt. 1. Caractéristiques mécaniques à température ambianteW 5.00%, the balance consisting of cobalt. 1. 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.By means of standard tests well known to those skilled in the art, the mechanical characteristics at ambient temperature were determined for three samples of the ES grade in different thermal states and for a sample of cobalt-based alloy. The results are collated in Table 1.
Tableau 1Table 1
1 ) état brut de coulée1) raw state of casting
2) état mis en solution2) state dissolved
3) état stabilisé3) 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 room 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 2Stabilized samples of grade ES and CoCr29W5 were tested for temperatures ranging from 100 to 600 ° C. The results are collated in Table 2. Table 2
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:Three samples of grade ES and one sample of CoCr29W5 were subjected to a salt spray test according to standard NFX 41-002. The results, which are collated 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 correspond à un matériau sans aucune trace de corrosion,- 10 corresponds to a material without any trace of corrosion,
9 correspond à un matériau présentant quelques piqûres dispersées, et9 corresponds to a material having a few scattered pits, and
- 8 correspond à un matériau présentant quelques spots autour des piqûres.- 8 corresponds to a material having a few spots around the bites.
Tableau 3Table 3
1 ) état brut de coulée 2) état mis en solution1) raw casting state 2) dissolved state
3) état stabilisé 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. 4. Essais de frottement et de résistance à l'usure3) stabilized state It can be seen that here too the corrosion resistance achieved by the compositions according to the invention is of the same level as that obtained with the cobalt base alloy. 4. 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.The tests were carried out on stabilized samples of grade ES and of CoCr29W5 according to standard ASTM G99-95a, using a pawn-disc tribometer, under a maximum load of 10 N, dry and with a linear contact speed of 0.1 m / s for a total distance traveled of 1008 m. The results are collated in Table 4.
Tableau 4Table 4
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.First of all, it can be seen that the coefficient of friction of the grades according to the invention is similar to that of CoCr29W5. On the other hand, the wear rate of these same compositions is two times less 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. 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.Note also the high reproducibility of the tests when they relate to the grades according to the invention, contrary to what occurs with the cobalt base alloy. This characteristic can in particular prove to be advantageous for the producer when he must provide the characteristics of a part or of 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. 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 states of casting and dissolved, which allows their use for certain sensitive parts, such as parts for submarines, 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 purely indicative and in no way limitative, and that many modifications can be easily made by those skilled in the art without as well go beyond the scope of the invention.

Claims

REVENDICATIONS
1. Composition d'acier caractérisée en ce qu'elle comprend, exprimés en pourcentages en poids :1. Steel composition characterized in that it comprises, expressed in percentages by weight:
C 0,30 - 1,00 %C 0.30 - 1.00%
Si 3,00 - 4,50 %If 3.00 - 4.50%
Mn 7,00 - 10,00 %Mn 7.00 - 10.00%
Ni 3,50 - 4,50 %Ni 3.50 - 4.50%
Cr 20,00 - 27,00 %Cr 20.00 - 27.00%
W 0,50 - 4,50 %W 0.50 - 4.50%
Nb 0 - 2,50 %Nb 0 - 2.50%
Co 0 - 1 ,00 %Co 0 - 1.00%
N 0,20 - 0,50 %, le complément étant principalement constitué de fer et d'impuretés inévitables.N 0.20 - 0.50%, the balance consisting mainly of iron and unavoidable impurities.
2. Composition d'acier selon la revendication 1, caractérisée en ce qu'elle comprend 24 à 26% en poids de chrome.2. Steel composition according to claim 1, characterized in that it comprises 24 to 26% by weight of chromium.
3. Composition d'acier selon l'une ou l'autre des revendications 1 ou 2, caractérisée en ce qu'elle comprend 0,50 à 1 ,50% de tungstène.3. Steel composition according to either of Claims 1 or 2, characterized in that it comprises 0.50 to 1.50% of tungsten.
4. Composition d'acier selon l'une quelconque des revendications 1 à 3, caractérisée en ce qu'elle comprend 3,50 à 4,00% en poids de silicium. 4. Steel composition according to any one of claims 1 to 3, characterized in that it comprises 3.50 to 4.00% by weight of silicon.
5. Composition d'acier selon l'une quelconque des revendications 1 à 4, caractérisée en ce qu'elle comprend 0,40 à 0,50%o en poids de carbone.5. Steel composition according to any one of claims 1 to 4, characterized in that it comprises 0.40 to 0.50% o by weight of carbon.
6. Composition d'acier selon l'une quelconque des revendications 1 à 4, caractérisée en ce qu'elle comprend 0,50 à 0,60% en poids de carbone.6. Steel composition according to any one of claims 1 to 4, characterized in that it comprises 0.50 to 0.60% by weight of carbon.
7. Composition d'acier selon l'une quelconque des revendications 1 à 4, caractérisée en ce qu'elle comprend 0,70 à 0,80% en poids de carbone.7. Steel composition according to any one of claims 1 to 4, characterized in that it comprises 0.70 to 0.80% by weight of carbon.
8. Composition d'acier selon la revendication 1, caractérisée en ce qu'elle comprend, exprimés en pourcentages en poids : C 0,50 - 0,80 %8. Steel composition according to claim 1, characterized in that it comprises, expressed in percentages by weight: C 0.50 - 0.80%
Si 3,00 - 4,50 %If 3.00 - 4.50%
Mn 7,00 - 10,00 %Mn 7.00 - 10.00%
Ni 3,50 - 4,50 %Ni 3.50 - 4.50%
Cr 24,00 - 26,00 %Cr 24.00 - 26.00%
W 0,50 - 1 ,50 %W 0.50 - 1.50%
Nb 0 - 2,50 %Nb 0 - 2.50%
Co 0 - 0,50 %Co 0 - 0.50%
N 0,20 - 0,50 %, le complément étant principalement constitué de fer et d'impuretés inévitables.N 0.20 - 0.50%, the balance consisting mainly of iron and unavoidable impurities.
9. Procédé de fabrication 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 revendications 1 à 8, 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.9. A method of manufacturing mechanical parts, characterized in that it comprises the following steps: a - constitution of a charge intended to obtain a chemical composition according to any one of claims 1 to 8, b - preparation of said charge , c - shaping of a blank of said mechanical part by molding; d- machining of said mechanical part from the blank, e - as an option, heat treatment for using said mechanical part.
10. Procédé de fabrication de pièces mécaniques selon la revendication 9, 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 revendications 1 à 8, 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. 10. A method of manufacturing mechanical parts according to claim 9, characterized in that it comprises the following steps: a - constitution of a charge intended to obtain a chemical composition according to any one of claims 1 to 8, b - melting of said charge in a crucible, c - centrifugal molding of a blank of said mechanical part, and machining of said mechanical part from the blank, e - optional, heat treatment for using said part mechanical.
11. Pièces d'acier ayant une composition selon l'une quelconque des revendications 1 à 8.11. Steel parts having a composition according to any one of claims 1 to 8.
12. Pièces d'acier selon la revendication 11, caractérisée en ce qu'elle est obtenue par un procédé selon l'une ou l'autre des revendications 9 ou 10. 12. Steel parts according to claim 11, characterized in that it is obtained by a process according to either of claims 9 or 10.
EP01949617A 2000-07-04 2001-07-03 Steel compositions, method for obtaining same and parts made from same Expired - Lifetime EP1297192B1 (en)

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FR0008698 2000-07-04
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