EP0076745A1 - Verfahren zur Oberflächenbehandlung von Stahl gegen Verschleiss und die so erhaltenen Überzüge - Google Patents

Verfahren zur Oberflächenbehandlung von Stahl gegen Verschleiss und die so erhaltenen Überzüge 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
Authority
EP
European Patent Office
Prior art keywords
chromium
layer
molybdenum
iron
sulfide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP82401774A
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English (en)
French (fr)
Other versions
EP0076745B1 (de
Inventor
Guy Nicolas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nicolas Guy
Original Assignee
Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP0076745A1 publication Critical patent/EP0076745A1/de
Application granted granted Critical
Publication of EP0076745B1 publication Critical patent/EP0076745B1/de
Expired legal-status Critical Current

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Classifications

    • 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.

Landscapes

  • 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)
EP82401774A 1981-10-06 1982-09-30 Verfahren zur Oberflächenbehandlung von Stahl gegen Verschleiss und die so erhaltenen Überzüge Expired EP0076745B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8118780A FR2514034A1 (fr) 1981-10-06 1981-10-06 Procede de traitement de surface d'aciers contre l'usure et revetement obtenu
FR8118780 1981-10-06

Publications (2)

Publication Number Publication Date
EP0076745A1 true EP0076745A1 (de) 1983-04-13
EP0076745B1 EP0076745B1 (de) 1985-12-04

Family

ID=9262784

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82401774A Expired EP0076745B1 (de) 1981-10-06 1982-09-30 Verfahren zur Oberflächenbehandlung von Stahl gegen Verschleiss und die so erhaltenen Überzüge

Country Status (4)

Country Link
US (1) US4435227A (de)
EP (1) EP0076745B1 (de)
DE (1) DE3267828D1 (de)
FR (1) FR2514034A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6042949A (en) * 1998-01-21 2000-03-28 Materials Innovation, Inc. High strength steel powder, method for the production thereof and method for producing parts therefrom
CN114196954A (zh) * 2021-12-07 2022-03-18 中国第一汽车股份有限公司 一种复合渗硫层及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH365921A (de) * 1958-11-04 1962-11-30 Berghaus Elektrophysik Anst Verfahren zur Behandlung der Oberfläche von Metallkörpern
FR1535457A (fr) * 1966-11-30 1968-08-09 Applic Des Traitements De Surf Bains ignés pour le traitement des surfaces métalliques
FR2093559A5 (de) * 1970-05-21 1972-01-28 Kito Kk

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH365921A (de) * 1958-11-04 1962-11-30 Berghaus Elektrophysik Anst Verfahren zur Behandlung der Oberfläche von Metallkörpern
FR1535457A (fr) * 1966-11-30 1968-08-09 Applic Des Traitements De Surf Bains ignés pour le traitement des surfaces métalliques
FR2093559A5 (de) * 1970-05-21 1972-01-28 Kito Kk

Also Published As

Publication number Publication date
FR2514034A1 (fr) 1983-04-08
US4435227A (en) 1984-03-06
FR2514034B1 (de) 1984-07-20
DE3267828D1 (en) 1986-01-16
EP0076745B1 (de) 1985-12-04

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