EP0076745A1 - Process for treating the surfaces of steels against wear, and coating obtained - Google Patents

Process for treating the surfaces of steels against wear, and coating obtained Download PDF

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Publication number
EP0076745A1
EP0076745A1 EP82401774A EP82401774A EP0076745A1 EP 0076745 A1 EP0076745 A1 EP 0076745A1 EP 82401774 A EP82401774 A EP 82401774A EP 82401774 A EP82401774 A EP 82401774A EP 0076745 A1 EP0076745 A1 EP 0076745A1
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Prior art keywords
chromium
layer
molybdenum
iron
sulfide
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German (de)
French (fr)
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EP0076745B1 (en
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Guy Nicolas
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Nicolas Guy
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12576—Boride, carbide or nitride component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12597—Noncrystalline silica or noncrystalline plural-oxide component [e.g., glass, etc.]
    • Y10T428/12604—Film [e.g., glaze, etc.]

Definitions

  • Tectonic scope of the present invention is that of surface treatment of the surface layers of steel parts in order to im- li orer their mechanical properties. More particularly, the technical sector of the present invention relates to treatments which aim to increase the resistance to wear of structural steel and tool steel parts subjected to friction.
  • coatings are obtained which have good wear resistance. These coatings generally consist of layers based on chromium carbides M 23 C 6 and M 7 C 3 , M denoting a metal which apart from chromium (Cr) can be iron (Fe), molybdenum (Mo) vanadium (V) etc ...
  • the layers obtained have a limited thickness; for example, the layers obtained by chromizing treatment on steels having a carbon content of at least 0.15% have a total thickness of carbides of the order of 10 to 15 ⁇ m.
  • the lifetime of a system, thus treated, and subjected to friction depends on the kinetics of wear of this layer of carbides. For a given stressing rode, this lifetime is linked, on the one hand, to the total thickness of the hard surface layer, on the other hand, to the crystallization morphology of the carbides M 7 C 3 .
  • M 7 C 3 has a columnar structure which is harmful to good wear resistance. Furthermore, in the case of dry friction contact with antagonists of lesser hardness, these undergo very significant wear.
  • the aim of the present invention is to produce a surface coating of steel parts which improves the wear resistance of the part subjected to friction and makes it possible to increase the service life of systems solicited in friction while by limiting the wear of the antagonists in contact by friction with said parts.
  • the subject of the present invention is a method of treatment against surface wear of steel parts with a carbon content of at least 0.15%, characterized in that a supply of sulfur and an vaporization control.
  • the sulfur is preferably added by depositing a metal sulphide on the steel surface, for example by depositing a varnish based on molybdenum disulphide or by depositing an iron-molybdenum alloy sulphide of formulation (Fe - Mo) 3 S 4 .
  • an iron-mlyndene deposition is carried out prior to the deposition of iron-molybdenum sulfide.
  • Chromization is carried out at 950 ° C for 15 hours and without the flow of hydrogen.
  • hydrogen can desulfurize the deposit by the formation of H 2 S and thus prevent the formation of chromium sulfide on the substrate surface.
  • the subject of the invention is also a surface coating against wear of steel parts with a carbon content greater than or equal to 0.15%, characterized in that it consists of a surface layer of chromium sulfide and a layer underlying the surface layer consisting of chromium carbides M 23 C 6 and M 7 C 3 .
  • all the percentages are percentages by mass.
  • the coating obtained by the process according to the invention is characterized in that it consists of a surface layer of chromium-molybdenum sulphide, the molybdenum being substituted in the hexagonal network of chromium sulphide at a mass content less than 18% and a layer underlying the surface layer consisting of chromium carbides M 23 C 6 and M 7 C 3 .
  • the carbide layer is made up of two sublayers consisting successively of chromium carbide M 23 C 6 and chromium carbide M 7 C 3 .
  • the chromium carbide M 7 C 3 sublayer is recrystallized over part of its thickness from the substrate.
  • the steel used for this description is the low alloy steel 35CD4, widely used in industrial manufacturing. Any other steel with a carbon content of at least 0.15% could be used.
  • the sequenced processing according to the invention comprises two parts, the order of which must be respected.
  • the first part of this treatment consists of a treatment making it possible to deposit a sulphide of the iron-molybdenum sulphide or molybdenum sulphide type.
  • the treatment mode only matters with regard to the uniformity in thickness and distribution of the deposit. It is thus possible to make deposits of the varnish type based on molybdenum disulphide or to carry out deposits by the "sprettering-magnetron" technique of (Fe-Mo) 3 S 4 .
  • the latter technique allows good control of the thickness and distribution of the initial deposit.
  • a deposit of at least 5 ⁇ m is necessary to obtain good results.
  • a thickness of 8 to 15 ⁇ m is best suited to subsequent chromizing conditions.
  • the chromizing treatment is carried out according to average parameters such as:
  • the external sulphide layer formed from the (Cr, Mo) S phase which crystallizes in the hexagonal system, is quite heterogeneous as regards its distribution of molybdenum and sulfur.
  • the iron is almost zero in content and Mo at a rate of at most 18%.
  • the underlying carbide layer is divided into two carbide sublayers M 23 C 6 and M 7 C 3 .
  • the latter carbide, rich in molybdenum, is partially recrystallized.
  • the general morphology of the layers is in the form of crystals with a spherular front. These crystals are distributed in domains separated by fairly shallow "channels".
  • the coating is divided into two main layers A and B with respective thicknesses of 9 ⁇ m.
  • Layer A has a two-phase appearance with basaltic domains. These areas are generally set back from the outside surface. They correspond to channels.
  • Layer B is made up of two sublayers B 1 and B 2 Reversed after basic attack, these sublayers correspond to carbides; the sublayer 13 2 has the typical morphology of the carbide M 7 C 3 with recrystallization.
  • Layer A consists essentially of the elements chromium, sulfur, molybdenum.
  • the two-phase aspect observed in metallography seems to be due only to relative variations in sulfur and molybdenum.
  • the iron is almost zero in content, and molybdenum up to 18%.
  • Layer B is made up of two layers formed of carbides where no sulfur is detected.
  • the chromium concentration levels and the shape of the carbon distribution profiles indicate that the sublayers B 1 and B 2 correspond respectively to the carbides M 23 C 6 and M 7 C 3 . It should be noted that the molybdenum content in these carbides is high. But molybdenum can largely replace this type of phase.
  • the coating is divided into two main sub-layers with respective thickness of 9 ⁇ m, for a total thickness of 18 ⁇ m.
  • the surface layer consists of the (Cr, Mo) S phase.
  • the hardness of this phase is 770 + 50 Hv 0.02 .
  • the second layer revealed by metallographic attack in basic medium, consists of chromium carbides enriched in molybdenum M 23 C 6 and M 7 C 3 .
  • the carbide M 7 C 3 is in this case partially recrystallized, which ensures an increase in toughness to this layer of carbide.
  • the hardness of carbide M 23 C 6 is 1400 + 200 Hv 0.02
  • that of carbide M 7 C 3 is 2700 + 500 Hv v0.02 for the recrystallized domain.
  • the advantage of the invention resides in the fact that it is possible to increase the overall performance of wear resistance of systems subjected to dry friction or poorly lubricated. Furthermore, this gain in quality can be acquired from various implementation techniques without fundamentally modifying the characteristics obtained. A change in technology for carrying out the conventional chromization treatment requires only a fine-tuning of the parameters, which is of obvious interest from an economic point of view.
  • the economic benefit also lies in improving the lifespans and reliability of the parts.
  • the invention can be applied to any moving mechanical system, made of steel, in particular weapon mechanisms or engine transmission mechanisms, etc.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

La présente invention a pour objet un procédé de traitement contre l'usure de surface de piêces en aciers à teneur en carbone d'au moins 0,15% et le revêtement obtenu. Le procédé est caractérisé en ce qu'on effectue successivement sur la surface à traiter un apport de soufre par example par dépôt de sulfure métallique et une chromisation en phase vapeur. Le revêtement obtenu est caractérisé par la présence d'une couche de sulfure de chrome en surface et par la recristallisation partielle de la couche de carbure de chrome M7C3 sous-jacente. L'invention peut s'appliquer à tout système mécanique en mouvement soumis à frottement. Son intérêt est d'augmenter la résistance à l'usure et la durée de vie du système traité tout en limitant l'usure de l'antagoniste non traité en frottement.The present invention relates to a method of treatment against surface wear of parts made of steels with a carbon content of at least 0.15% and the coating obtained. The process is characterized in that a supply of sulfur is carried out successively on the surface to be treated, for example by deposition of metallic sulfide and chromization in the vapor phase. The coating obtained is characterized by the presence of a layer of chromium sulfide on the surface and by the partial recrystallization of the layer of underlying chromium carbide M7C3. The invention can be applied to any mechanical system in motion subjected to friction. Its advantage is to increase the resistance to wear and the lifetime of the treated system while limiting the wear of the untreated antagonist in friction.

Description

Le secteur tectonique de la présente invention est celui des traitements de surface des couches superficielles de pièces en acier en vue d'amé- liorer leurs proprietes mécaniques. Plus particulièrement le secteur technique de la présente invention concerne les traitements qui visent à accroître la résistance à l'usure de pieces en acier de construction et acier à outils soumises à frottement.Tectonic scope of the present invention is that of surface treatment of the surface layers of steel parts in order to im- li orer their mechanical properties. More particularly, the technical sector of the present invention relates to treatments which aim to increase the resistance to wear of structural steel and tool steel parts subjected to friction.

Les principaux traitements de ce type actuellement pratiqués sur les aciers à outils sont la nitruration, l'oxydation, la chromisation, le chromage dur et la boruration. La sulfuration directe d'un substrat n'a jamais éte employée pour des traitements de ce type car cet élément conduit à la fragilisation des aciers. Le soufre est utilisé sous forme combinée au molyb- dène ou au fer en vue d'application antifriction cemne lubrifiant solide et non pas en résistance à l'usure.The main treatments of this type currently practiced on tool steels are nitriding, oxidation, chromium plating, hard chromium plating and boriding. Direct sulfurization of a substrate has never been used for treatments of this type because this element leads to the embrittlement of steels. Sulfur is used in combined form the molybdate d ene or iron for antifriction cemne solid lubricant application and not in wear resistance.

Par les traitements de chromisation connus on obtient des revêtements ayant une bonne résistance à l'usure. Ces revêtement se composent généralement ue couches à base de carbures de chrome M23 C6 et M7 C3, M désignant un métal qui à part le chrome (Cr) peut être le fer (Fe) , le molybdène (Mo) le vanadium (V) etc... Les couches obtenues ont une épaisseur limitée; par exemple les cou- cnes obtenues par traitement de chromisation sur des aciers ayant une teneur en carbone d'au moins 0,15% ont une épaisseur totale de carbures de l'ordre de 10 à 15 µm.By the known chromizing treatments, coatings are obtained which have good wear resistance. These coatings generally consist of layers based on chromium carbides M 23 C 6 and M 7 C 3 , M denoting a metal which apart from chromium (Cr) can be iron (Fe), molybdenum (Mo) vanadium (V) etc ... The layers obtained have a limited thickness; for example, the layers obtained by chromizing treatment on steels having a carbon content of at least 0.15% have a total thickness of carbides of the order of 10 to 15 μm.

Or, la durée de vie d'un système, ainsi traité, et sollicité en frottement, dépend de la cinétique d'usure de cette couche de carbures. Pour un rode de sollicitation donné, cette durée de vie est liée, d'une part, à l'épaisseur totale de la couche dure superficielle, d'autre part, à la morphologie de cristallisation des carbures M7C3. Dans ces traitements de chromisation connus, M7C3 a une structure colonnaire néfaste à une bonne résistance à l'usure. Par ailleurs, dans le cas de contact en frottement sec avec des antagonistes de moindre dureté, ceux-ci subissent une usure très importante.However, the lifetime of a system, thus treated, and subjected to friction, depends on the kinetics of wear of this layer of carbides. For a given stressing rode, this lifetime is linked, on the one hand, to the total thickness of the hard surface layer, on the other hand, to the crystallization morphology of the carbides M 7 C 3 . In these known chromizing treatments, M 7 C 3 has a columnar structure which is harmful to good wear resistance. Furthermore, in the case of dry friction contact with antagonists of lesser hardness, these undergo very significant wear.

Le but de la présente invention est la réalisation d'un revêtement de surface de pièces en acier qui améliore la resistance à l'usure de la pièce soumise à frottement et permette d'augmenter la durée de vie des systèmes soli- cités en frottement tout en limitant l'usure des antagonistes en contact par frottement avec lesdites pièces.The aim of the present invention is to produce a surface coating of steel parts which improves the wear resistance of the part subjected to friction and makes it possible to increase the service life of systems solicited in friction while by limiting the wear of the antagonists in contact by friction with said parts.

La présent invention a pour objet un procédé de traitement contre l'usure de surface de pièces en acier à teneur en carbone d'au moins 0,15%, caractérisé en ce qu'on effectue successivement sur cette surface un apport de soufre et une cnrcmisation en phase vapeur.The subject of the present invention is a method of treatment against surface wear of steel parts with a carbon content of at least 0.15%, characterized in that a supply of sulfur and an vaporization control.

Par apport préalable de soufre sur l'acier de base, on modifie les conditions d'échange entre le chromé déposé au cours de la chromisation ultérieure et les éléments du substrat et on permet ainsi au soufre de se combiner avec le chrome. On obtient en effet une couche superficielle originale composée de sulfure de chrome. La surface ainsi traitée présente une résistance à l'usure satisfaisante et offre en outre l'avantage de réduire très largement l'usure de l'antagoniste en acier non revêtu. Au cours du frottement, le soufre réagit par contact avec l'antagoniste et forme sur ce dernier des couches de transfert riches en espèces soufrées favorisant sa moindre usure. Ce traitement permet d'autre part d'augmenter l'épaisseur totale de la couche dure en surface. La teneur en carbone supérieure ou égale à 0,15% est nécessaire pour la constitution de sous-couches de carbures qui participent à la résistance à l'usure.By prior supply of sulfur on the base steel, the exchange conditions between the chromium deposited during the subsequent chromization and the elements of the substrate are modified and the sulfur is thus allowed to combine with the chromium. An original surface layer composed of chromium sulfide is obtained. The surface thus treated has satisfactory wear resistance and also offers the advantage of greatly reducing the wear of the antagonist in uncoated steel. During friction, the sulfur reacts by contact with the antagonist and forms on the latter transfer layers rich in sulfur species favoring its least wear. This treatment also makes it possible to increase the total thickness of the hard layer on the surface. The carbon content greater than or equal to 0.15% is necessary for the constitution of sublayers of carbides which participate in the resistance to wear.

L'apport de soufre se fait préférentiellement par dépôt en surface de l'acier d'un sulfure métallique, par exemple par dépôt d'un vernis à base de bisulfure de molybdène ou par dépôt d'un sulfure d'alliage de fer-molybdène de formulation (Fe - Mo)3S4.The sulfur is preferably added by depositing a metal sulphide on the steel surface, for example by depositing a varnish based on molybdenum disulphide or by depositing an iron-molybdenum alloy sulphide of formulation (Fe - Mo) 3 S 4 .

La sulfuration directe du substrat est en effet à éviter car le soufre conduit à la fragilisation des aciers. D'autre pait, par réaction d'échange avec les éléments métalliques, il est possible d'assurer le transport du chrome à partir d'un halogènure de chrome en phase vapeur.Direct sulfurization of the substrate is indeed to be avoided since sulfur leads to the embrittlement of steels. On the other hand, by exchange reaction with metallic elements, it is possible to transport chromium from a chromium halide in the vapor phase.

Avantageusement, on effectue préalablement au dépôt de sulfure de fer-molybdène, un dépôt de fer-mlyndène.Advantageously, an iron-mlyndene deposition is carried out prior to the deposition of iron-molybdenum sulfide.

Si le dépôt de sulfure de fer-molybdène est mis en oeuvre directement sur la pièce, son adhérence dans le temps est assez faible. Par contre un dépôt préalable sans soufre accroît notablement l'adhérence.If the deposit of iron-molybdenum sulphide is applied directly to the part, its adhesion over time is quite weak. On the other hand, a prior sulfur-free deposit significantly increases adhesion.

La chromisation est effectuée à 950°C pendant 15 heures et sans débit d'hydrogène.Chromization is carried out at 950 ° C for 15 hours and without the flow of hydrogen.

En effet,l'hydrogène peut désulfurer le dépôt par formation de H2S et ainsi empêcher la formation de sulfure de chrome en surface de substrat.Indeed, hydrogen can desulfurize the deposit by the formation of H 2 S and thus prevent the formation of chromium sulfide on the substrate surface.

Les traitements thermiques usuels peuvent être pratiqués sur les aciers traités par ce procédé. Cependant, la trempe à l'eau est déconseillée, car elle peut introduire des fissurations dans le revêtement effectué selon l'invention.The usual heat treatments can be practiced on steels treated by this process. However, water quenching is not recommended, as it can introduce cracks in the coating made according to the invention.

L'invention a également pour-objet un revêtement de surface contre l'usure de pièces en acier à teneur en carbone supérieure ou égale à 0,15%, caractérisé en ce qu'il est constitué par une couche superficielle de sulfure de chrome et une couche sous-jacente à la couche superficielle constituée de carbures de chrome M23 C6 et M7 C3. Dans la suite de la description, tous les pourcentages sont des pourcentages en masse.The subject of the invention is also a surface coating against wear of steel parts with a carbon content greater than or equal to 0.15%, characterized in that it consists of a surface layer of chromium sulfide and a layer underlying the surface layer consisting of chromium carbides M 23 C 6 and M 7 C 3 . In the following description, all the percentages are percentages by mass.

Le revêtement obtenu par le procédé selon l'invention est caractérisé en ce qu'il est constitué par une couche superficielle de sulfure de chrome-molybdène, le molybdène étant substitué dans le réseau hexagonal de sulfure de chrome à raison d'une teneur en masse inférieure à 18% et une couche sous-jacente à la couche superficielle constituée de carbures de chrome M23 C6 et M7 C 3.The coating obtained by the process according to the invention is characterized in that it consists of a surface layer of chromium-molybdenum sulphide, the molybdenum being substituted in the hexagonal network of chromium sulphide at a mass content less than 18% and a layer underlying the surface layer consisting of chromium carbides M 23 C 6 and M 7 C 3 .

La couche de carbure se compose de deux sous-couches constituées successivement par du carbure de chrome M23C6 et du carbure de chrome M7C3.The carbide layer is made up of two sublayers consisting successively of chromium carbide M 23 C 6 and chromium carbide M 7 C 3 .

La sous-couche de carbure de chrome M7C3 est recristallisée sur une partie de son épaisseur à partir du substrat.The chromium carbide M 7 C 3 sublayer is recrystallized over part of its thickness from the substrate.

On constate en effet une modification du mode de cristallisation des carbures M7C3. Le molybdène codiffuse avec le chrome dans les carbures M7C3 permettant ainsi de réduire la quantité de chrome dans cette phase et d'at- teindre la teneur critique de 60% de chrome pour laquelle se produit la recristallisation de M7C3. Celle-ci accroît la ténacité de la couche de carbure et par ce fait sa résistance à l'usure.There is indeed a change in the crystallization mode of M 7 C 3 carbides. Molybdenum codiffuses with chromium in M 7 C 3 carbides, thus making it possible to reduce the quantity of chromium in this phase and to reach the critical content of 60% of chromium for which the recrystallization of M 7 C 3 occurs. This increases the toughness of the carbide layer and thereby its wear resistance.

D'autres avantages et caractéristiques de l'invention apparaîtront dans la description d'un mode de réalisation de l'invention non limitatif qui va suivre.Other advantages and characteristics of the invention will appear in the description of an embodiment of the invention which is not limiting, which follows.

L'acier retenu pour cette description est l'acier faiblement allié 35CD4, largement utilisé dans les fabrications industrielles. Tout autre acier dont la teneur en carbone serait d'au moins 0,15%, pourrait être employé.The steel used for this description is the low alloy steel 35CD4, widely used in industrial manufacturing. Any other steel with a carbon content of at least 0.15% could be used.

Le traitement séquencé selon l'invention comprend deux parties, dont l'ordre doit être respecté. La première partie de ce traitement consiste en un traitement permettant d'effectuer un dépôt de sulfure de type sulfure de fer-molybdène ou sulfure de molybdène. Le mode de traitement n'a d'importance que vis à vis de l'homogénéité en épaisseur et en répartition du dépôt. On peut ainsi effectuer des dépôts du type vernis à base de bisulfure de molybdène ou procéder à des dépôts par la technique "sprettering-magnétron" de (Fe-Mo)3S4. Cette dernière technique permet une bonne maîtrise de l'épaisseur et de la répartition du dépôt initial.The sequenced processing according to the invention comprises two parts, the order of which must be respected. The first part of this treatment consists of a treatment making it possible to deposit a sulphide of the iron-molybdenum sulphide or molybdenum sulphide type. The treatment mode only matters with regard to the uniformity in thickness and distribution of the deposit. It is thus possible to make deposits of the varnish type based on molybdenum disulphide or to carry out deposits by the "sprettering-magnetron" technique of (Fe-Mo) 3 S 4 . The latter technique allows good control of the thickness and distribution of the initial deposit.

Un dépôt d'au moins 5 µm est nécessaire pour obtenir de bons résultats. Une épaisseur de 8 à 15 µm est la mieux adaptée aux conditions de chromisation ultérieures.A deposit of at least 5 µm is necessary to obtain good results. A thickness of 8 to 15 µm is best suited to subsequent chromizing conditions.

Quand les pièces sont traitées sans dépôt préalaLle de fer-molybdène, on observe des faiençages de dépôt, avant chranisation. Des traitements avec dépôt préalable de fer-molybdène ont donc été effectués. Ils n'ont pas présentés de défaut d'adhérence.When the parts are treated without prior iron-molybdenum deposition, deposit faience is observed before chranization. Treatments with prior deposition of iron-molybdenum were therefore carried out. They did not show any lack of adhesion.

Après dépôt de la couche de sulfure, on procède au traitement de chromisation selon des paramètres moyens tels que :

Figure imgb0001
After depositing the sulphide layer, the chromizing treatment is carried out according to average parameters such as:
Figure imgb0001

Si l'on veut éviter la formation superficielle d'une couche de chrome exempte de soufre, il est nécessaire dans ce cas de supprimer le débit d'hydrogène habituellement assuré dans ces types de traitement.If one wishes to avoid the surface formation of a sulfur-free chromium layer, it is necessary in this case to suppress the flow of hydrogen usually provided in these types of treatment.

Il est à noter que le type de cément et le mode statique ou dynamique de transport ne conditionnent pas ici la nature du revêtement; ils n'en modulent que les épaisseurs de couches relatives.It should be noted that the type of cement and the static or dynamic mode of transport do not condition the nature of the coating here; they only modulate the thicknesses of relative layers.

Deux couches principales d'égales épaisseurs, respectivement à base de sulfure et de carbures de chrome, composent le revêtement obtenu après chromisation.Two main layers of equal thicknesses, respectively based on sulfide and chromium carbides, make up the coating obtained after chromization.

La couche externe de sulfure, formée de la phase (Cr, Mo) S qui cristallise dans le système hexagonal, est assez hétérogène quant à sa répartition en molybdène et soufre. Le fer y est en teneur quasiment nulle et Mo à raison d'au plus 18%.The external sulphide layer, formed from the (Cr, Mo) S phase which crystallizes in the hexagonal system, is quite heterogeneous as regards its distribution of molybdenum and sulfur. The iron is almost zero in content and Mo at a rate of at most 18%.

La couche sous-jacente de carbures se répartit en deux sous-couches de carbures M23C6 et M7C3. Ce dernier carbure riche en molybdène, est partiellement recristallisé.The underlying carbide layer is divided into two carbide sublayers M 23 C 6 and M 7 C 3 . The latter carbide, rich in molybdenum, is partially recrystallized.

Au cours des échanges, le fer a donc été pompé du dépôt initial de fer-molybdène-soufre, pour donner lieu à dépôt de chrome. Ce dernier élément, diffusant à travers l'ensemble du dépôt initial, a migré jusqu'à l'interface du substrat pour y former avec le carbone de l'acier, la séquence de carbures obtenue en chromisation classique, avec toutefois quelques caractéristiques différentes. La sous-couche de carbure M23C6 est ici beaucoup plus importante; et le carbure M7C3 est partiellement recristallisé.During the exchanges, the iron was therefore pumped from the initial deposit of iron-molybdenum-sulfur, to give rise to deposit of chromium. This last element, diffusing through the whole of the initial deposit, has migrated to the interface of the substrate to form there with the carbon of the steel, the sequence of carbides obtained in conventional chromization, with however some different characteristics. The M 23 C 6 carbide undercoat is much larger here; and the carbide M 7 C 3 is partially recrystallized.

En surface, la morphologie générale des couches se présente sous la forme de cristaux à front sphérulaire. Ces cristaux sont répartis en domaines séparés par des "canaux" assez peu profonds.On the surface, the general morphology of the layers is in the form of crystals with a spherular front. These crystals are distributed in domains separated by fairly shallow "channels".

En coupe, le revêtement. se répartit en deux couches principales A et B d'épaisseurs respectives de 9 µm.In section, the coating. is divided into two main layers A and B with respective thicknesses of 9 µm.

La couche A a un aspect biphasé avec des domaines à caractère basaltique. Ces domaines sont en général en retrait par rapport à la surface extérieure. Ils correspondent à des canaux.Layer A has a two-phase appearance with basaltic domains. These areas are generally set back from the outside surface. They correspond to channels.

La couche B se compose de deux sous-couches B1 et B2 Réverées après attaque basique, ces sous-couches correspondent à des carbures; la sous-couche 132 a la morphologie typique du carbure M7C3 avec recristallisation.Layer B is made up of two sublayers B 1 and B 2 Reversed after basic attack, these sublayers correspond to carbides; the sublayer 13 2 has the typical morphology of the carbide M 7 C 3 with recrystallization.

La couche A se compose essentiellement des éléments chrome, soufre, molybdène. L'aspect biphasé observé en métallographie ne semble dû qu'à des variations relatives du soufre et du molybdène. Le fer y est en teneur quasiment nulle, et le molybdène jusqu'à 18%.Layer A consists essentially of the elements chromium, sulfur, molybdenum. The two-phase aspect observed in metallography seems to be due only to relative variations in sulfur and molybdenum. The iron is almost zero in content, and molybdenum up to 18%.

Sur la base des données du diagramme binaire chrome-soufre, il apparaît d'après le niveau de concentration du chrome dans cette couche que la phase dont elle se compose, est le sulfure'de chrome CrS. Cette phase cristallise dans le système hexagonal (a=3,45 A, c=5,76A c/a = 1,67).Based on the data in the chromium-sulfur binary diagram, it appears from the level of chromium concentration in this layer that the phase of which it is composed is chromium sulfide CrS. This phase crystallizes in the hexagonal system (a = 3.45 A, c = 5.76A c / a = 1.67).

La couche B se compose de deux couches formées de carbures où l'on ne détecte pas de soufre. Les niveaux de concentration en chrome et l'allure des profils de répartition du carbone indiquent que les sous-couches B1 et B2 correspondent respectivement aux carbures M23C6 et M7C3. Ils est à remarquer que la teneur en molybdène dans ces carbures est élevée. Mais le molybdène peut se substituer largement dans ce type de phase.Layer B is made up of two layers formed of carbides where no sulfur is detected. The chromium concentration levels and the shape of the carbon distribution profiles indicate that the sublayers B 1 and B 2 correspond respectively to the carbides M 23 C 6 and M 7 C 3 . It should be noted that the molybdenum content in these carbides is high. But molybdenum can largely replace this type of phase.

A l'inverse des résultats enregistrés lors des précédentes analyses, on s'aperçoit ici que le molybdène au lieu d'être pompé dans le substrat pour migrer vers les carbures en formation, a en fait diffusé jusque dans celui-ci à partir du dépôt initial.Contrary to the results recorded during the previous analyzes, we notice here that the molybdenum instead of being pumped in the substrate to migrate towards the carbides in formation, in fact diffused until in this one starting from the deposit initial.

En coupe, le revêtement se répartit en deux sous-couches principales d'égaisseur respective de 9 µm, soit une épaisseur totale de 18 µm.In section, the coating is divided into two main sub-layers with respective thickness of 9 µm, for a total thickness of 18 µm.

La couche superficielle, dont l'aspect biphasé n'est dû qu'à des variations relatives en molybdène se compose de la phase (Cr, Mo)S. La dureté de cette phase est de 770 + 50 Hv0,02.The surface layer, the two-phase appearance of which is only due to relative variations in molybdenum, consists of the (Cr, Mo) S phase. The hardness of this phase is 770 + 50 Hv 0.02 .

La seconde couche, révélée par attaque métallographique en milieu basique, se compose des carbures de chrome enrichis en molybdène M23C6 et M7C3. Le carbure M7C3 est dans ce cas partiellement recristallisé, ce qui assure un accroissement de ténacité à cette couche de carbure. La dureté du carbure M23 C6 est de 1400 + 200 Hv0,02, celle du carbure M7C3 est de 2700 + 500 Hvv0,02 pour le domaine recristallisé.The second layer, revealed by metallographic attack in basic medium, consists of chromium carbides enriched in molybdenum M 23 C 6 and M 7 C 3 . The carbide M 7 C 3 is in this case partially recrystallized, which ensures an increase in toughness to this layer of carbide. The hardness of carbide M 23 C 6 is 1400 + 200 Hv 0.02 , that of carbide M 7 C 3 is 2700 + 500 Hv v0.02 for the recrystallized domain.

Il est à noter que par chromisation directe avec des paramètres identiques de traitement la couche avait une épaisseur totale de carbure de 13 µm.It should be noted that by direct chromization with identical treatment parameters the layer had a total thickness of carbide of 13 μm.

Une caractérisation tribologique de cette couche a été effectuée. En essai standard d'usure sur tribomètre en configuration pion-disques,les paramètres d'essai étaient les suivants :

  • - disque plans en acier 35CD4,
  • - pions cylindriques à bout plat de diamètre 1,5mm en acier 35CD4,traités thermiquement pour une dureté de 310Hv0.5,
  • - effort normal 1N, soit une contrainte statique normale de 0,56 MPa,
  • - vitesse circonférentielle : 500 tr.mn-1
  • - vitesse linéaire de contact : 41 m. mn-1
  • - température de laboratoire : 20°C,
  • - frottement sec,
  • - distance de sollicitation : 50 km.
A tribological characterization of this layer was carried out. In the standard wear test on a tribometer in disc-disc configuration, the test parameters were as follows:
  • - 35CD4 steel flat disc,
  • - cylindrical pins with flat end of 1.5mm diameter in 35CD4 steel, heat treated for a hardness of 310Hv 0.5 ,
  • - normal force 1N, i.e. a normal static stress of 0.56 MPa,
  • - circumferential speed: 500 rpm -1
  • - linear contact speed: 41 m. mn -1
  • - laboratory temperature: 20 ° C,
  • - dry friction,
  • - operating distance: 50 km.

Des essais identiques étant effectués sur disques 35CD4 chromisés directement avec les mênes paramètres de traitement, les résultats du tableau n° montrent que :

  • a) la couche composée de sulfure de chrome est moins usée que la couche obtenue par chromisation directe;
  • b) le pion antagoniste, qui n'a pas de traitement spécifique anti-usure, est ici très peu endommagé. Cette usure particulièrement faible est assurée par un film transfert à base de soufre,oxygène et carbone mis en évidence par spectrométrie Auger.
    Figure imgb0002
Identical tests being carried out on 35CD4 chromized discs directly with the same processing parameters, the results of table n ° show that:
  • a) the layer composed of chromium sulfide is less used than the layer obtained by direct chromization;
  • b) the antagonist counter, which has no specific anti-wear treatment, is very little damaged here. This particularly low wear is ensured by a transfer film based on sulfur, oxygen and carbon highlighted by Auger spectrometry.
    Figure imgb0002

L'intérêt de l'invention réside dans le fait qu'il est possible d'accroître les performances globales de résistance à l'usure des systèmes sollicités en frottement à sec ou mal lubrifiés. Par ailleurs, ce gain de qualité peut être acquis à partir de techniques de mise en oeuvre diverses sans pour autant modifier d'une façon fondamentale les caractéristiques obtenues. Un changement de technologie de réalisation du traitement de chromisation classique ne nécessite qu'une mise au point des paramètres ce qui est d'un intérêt évident du point de vue économique.The advantage of the invention resides in the fact that it is possible to increase the overall performance of wear resistance of systems subjected to dry friction or poorly lubricated. Furthermore, this gain in quality can be acquired from various implementation techniques without fundamentally modifying the characteristics obtained. A change in technology for carrying out the conventional chromization treatment requires only a fine-tuning of the parameters, which is of obvious interest from an economic point of view.

L'intérêt économique réside en outre dans l'amélioration des durées ae vie et de la fiabilité des pièces.The economic benefit also lies in improving the lifespans and reliability of the parts.

L'invention peut s'appliquer à tout système mécanique en mouvement, réalise en acier, notamment les mécanismes d'armes ou les mécanismes de transmission de moteurs etc...The invention can be applied to any moving mechanical system, made of steel, in particular weapon mechanisms or engine transmission mechanisms, etc.

Claims (13)

1 - Procède de traitement, contre l'usure de surface de pièces en acier à teneur en carbone d'au moins 0,15%, caractérisé en ce qu'on effectue successivement sur cette surface un apport de soufre et une chromisation en phase vapeur. 1 - Treatment process, against surface wear of steel parts with carbon content of at least 0.15%, characterized in that successively carries out on this surface a supply of sulfur and chromization in the vapor phase . 2 - Procédé selon la revendication 1, caractérisé en ce que l'apport de soufre se fait par dépôt en surface de l'acier d'un sulfure métallique.2 - A method according to claim 1, characterized in that the addition of sulfur is done by depositing on the surface of the steel a metal sulfide. 3 - Procédé selon la revendication 2, caractérisé en ce qu'on réalise un dépôt de vernis à base de bisulfure de molybdène.3 - Process according to claim 2, characterized in that a varnish deposition based on molybdenum disulfide is carried out. 4 - Procédé selon la revendication 2, caractérisé en ce que l'on effectue un dépôt de sulfure d'alliage fer-malybdène de formulation (Fe-Mo)3S4.4 - Process according to claim 2, characterized in that one carries out a deposition of sulphide of iron-malybdenum alloy of formulation (Fe-Mo) 3 S 4 . 5 - Procédé selon la revendication 3 ou 4, caractérisé en ce qu'on effectue, préalablement au dépôt de sulfure de fer-molybdène, un dépôt de fer-molybdène.5 - Process according to claim 3 or 4, characterized in that one carries out, prior to the deposition of iron-molybdenum sulfide, a deposition of iron-molybdenum. 6 - Procédé selon la revendication 5, caractérisé en ce que l'on dépose tout d'abord une couche de fer-molybdène d'au moins 1 µm d'épaisseur et ensuite une couche de sulfure fer-wlybdène d'au moins 4 µm.6 - Process according to claim 5, characterized in that firstly a layer of iron-molybdenum at least 1 µm thick is deposited and then a layer of iron-wlybdenum sulfide of at least 4 µm . 7 - Procédé selon l'une des revendications 1 à 6, caractérisé en ce qu'on effectue la chromisation à 950°C pendant 15 h et sans débit d'hydrogène.7 - Method according to one of claims 1 to 6, characterized in that the chromization is carried out at 950 ° C for 15 h and without hydrogen flow. 8 - Procédé selon l'une des revendications précédentes, caractérisé en ce qu'on effectue ultérieurement un traitement thermique de trempe-revenu, à l'exception de la trempe à l'eau.8 - Method according to one of the preceding claims, characterized in that a subsequent quenching heat treatment is carried out, with the exception of water quenching. 9 - Revêtement de surface contre l'usure de pièces en acier à teneur en carbone supérieure ou égale à 0,15%,caractérise en ce qu'il est constitué par une couche superficielle de sulfure de chrome et une couche sous-jacente à la couche superficielle constituée de carbures de chrome M23C6 et M7C3.9 - Surface coating against wear of steel parts with carbon content greater than or equal to 0.15%, characterized in that it consists of a surface layer of chromium sulphide and a layer underlying the surface layer consisting of chromium carbides M 23 C 6 and M 7 C 3 . 10 - Revêtement de surface de pièces en acier obtenu par le procédé selon les revendications 1 à 8, caractérisé en ce qu'il est constitué par une couche superficielle de sulfure de chrome-molybdène, le molybdène étant substitué dans le réseau hexagonal du sulfure de chrome à raison d'une teneur en masse jusqu'à 18% une couche sous-jacente à la couche superficielle constituée de carbures de chrome M23C6 et M7C3.10 - Surface coating of steel parts obtained by the method according to claims 1 to 8, characterized in that it consists of a surface layer of chromium-molybdenum sulfide, the molybdenum being substituted in the hexagonal network of the sulfide of chromium at a content of up to 18% by mass, a layer underlying the surface layer consisting of chromium carbides M 23 C 6 and M 7 C 3 . 11 - Revetement de surface selon la revendication 9 ou 10, caractérisé en ce que la couche sous-jacente de carbures se compose de deux sous-couches constituées successivement par du carbure de chrome M23C6 et du carbure de chrome M7C3.11 - Surface coating according to claim 9 or 10, characterized in that the underlying layer of carbides consists of two sublayers constituted successively by chromium carbide M 23 C 6 and chromium carbide M 7 C 3 . 12 - Revêtement de surface selon la revendication 11, caractérisé en ce que la sous-couche de carbure de chrome M7C3 est recristallisée sur une partie de son épaisseur à partir du substrat.12 - Surface coating according to claim 11, characterized in that the underlay of chromium carbide M 7 C 3 is recrystallized over part of its thickness from the substrate. 13 - Revêtement de surface selon l'une des revendications 10 à 12, carac- térisé en ce qu'il se répartit en deux couches principales de sulfure métallique et de carbures métalliques d'épaisseurs respectives de 9 µm au moins, soit une epaisseur totale de 18 µm au moins. 13 - surface covering according to one of claims 10 to 12, charac- t ERI in that it is divided into two main layers of metal sulfide and metal carbides with respective thicknesses of 9 .mu.m at least, a total thickness of at least 18 µm.
EP82401774A 1981-10-06 1982-09-30 Process for treating the surfaces of steels against wear, and coating obtained Expired EP0076745B1 (en)

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CH365921A (en) * 1958-11-04 1962-11-30 Berghaus Elektrophysik Anst Process for treating the surface of metal bodies
FR1535457A (en) * 1966-11-30 1968-08-09 Applic Des Traitements De Surf Igneous baths for the treatment of metal surfaces
FR2093559A5 (en) * 1970-05-21 1972-01-28 Kito Kk

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US2243787A (en) 1938-06-30 1941-05-27 Allegheny Ludlum Steel Colored steel
US3769098A (en) 1971-05-19 1973-10-30 Kito Kk Process of manufacturing fine powders of metal halide
US3987222A (en) 1975-06-20 1976-10-19 Petr Mikhailovich Verkhovykh Method of surface-strengthening of steel parts working in abrasion

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CH365921A (en) * 1958-11-04 1962-11-30 Berghaus Elektrophysik Anst Process for treating the surface of metal bodies
FR1535457A (en) * 1966-11-30 1968-08-09 Applic Des Traitements De Surf Igneous baths for the treatment of metal surfaces
FR2093559A5 (en) * 1970-05-21 1972-01-28 Kito Kk

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