EP0655512B1 - Procédé pour la formation de couches d'oxydes unitaires sur des substrats métalliques et dispositif pour réaliser le procédé - Google Patents

Procédé pour la formation de couches d'oxydes unitaires sur des substrats métalliques et dispositif pour réaliser le procédé Download PDF

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Publication number
EP0655512B1
EP0655512B1 EP94116881A EP94116881A EP0655512B1 EP 0655512 B1 EP0655512 B1 EP 0655512B1 EP 94116881 A EP94116881 A EP 94116881A EP 94116881 A EP94116881 A EP 94116881A EP 0655512 B1 EP0655512 B1 EP 0655512B1
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EP
European Patent Office
Prior art keywords
process according
theoretical value
oxidising
oxidation
gas supply
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Expired - Lifetime
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EP94116881A
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German (de)
English (en)
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EP0655512A1 (fr
Inventor
B. Dr. Edenhofer
W. Dr. Lerche
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Ipsen International GmbH
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Ipsen International GmbH
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    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/06—Surface hardening
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/34—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in more than one step

Definitions

  • the invention relates to a method for producing uniform oxidation layers on metallic workpieces following a nitriding or Nitrocarburizing process, the workpieces after nitriding or Nitrocarburizing at a given temperature for a given time Oxidation atmosphere are exposed.
  • the generic methods are used to improve the wear or. the corrosion resistance of the surfaces of components made of ferrous materials.
  • the nitrocarburizing process is carried out as a special nitriding process at temperatures between 570 ° C and 700 ° C. This minimizes the delay.
  • the workpieces are exposed to an oxidation atmosphere.
  • the post-oxidation can significantly increase the wear resistance and in particular the corrosion resistance of the nitrocarburized surfaces.
  • the workpieces are oxidized in an oxygen-containing atmosphere in an atmosphere-sphere furnace after the nitriding or nitrocarburizing.
  • This post-oxidation normally takes place at temperatures between 500 ° C and 550 ° C, but is not limited to this range. Air, water vapor, CO 2 , nitrous oxide and mixtures of these gases with nitrogen or ammonia are primarily used for the oxidation.
  • the aim of the post-oxidation is to convert the outer edge layer of the workpieces, which essentially consists of iron nitrides or carbonitrides, into a thin iron oxide layer.
  • an iron oxide layer of the form Fe 3 O 4 is sought, the so-called magnetite. Desired oxidation layer thicknesses are between 0.5 and 2 ⁇ m in the case of predominantly corrosive stress, or between 1 and 3 ⁇ m in the case of predominant wear and tear.
  • the oxide layers are too thick and can flake off. If the oxidation effect of the oxidation atmosphere is set incorrectly, other iron oxide modifications also arise, such as Fe 2 O 3 or FeO. These iron oxide modifications do not improve the corrosion and wear behavior of the workpieces, they can even worsen it. The setting of such iron oxides should therefore be avoided during post-oxidation. Generating Fe 3 O 4 layers that are too thick can also be harmful, particularly in the case of corrosion, as practice has shown. The targeted setting of the desired layer modification and thickness setting during post-oxidation is therefore of particular importance.
  • the object of the invention is to improve a method for producing uniform oxidation layers of the generic type in such a way that defined, uniform oxidation layers and workpiece surface properties are achieved. Furthermore, an apparatus for performing the method is to be provided.
  • the method according to the invention is further developed in that the oxygen potential present in the oxidation atmosphere is continuously determined, the measurement result is compared with a predetermined target value and, in the event of deviations, the oxidation atmosphere is modified until the measurement result matches the target value, the target value being so It is determined that the oxygen potential at the given oxidation temperature is always above the formation limit of Fe 3 O 4 oxide, but below the formation limit of other iron oxides.
  • the oxide layers have a uniform appearance and that Surface properties are defined and can be easily reproduced.
  • the measured oxygen potential is below the specified target value, further oxidizing agent is fed. If the measured oxygen potential value is above of the predetermined target value, then according to a proposal of the invention the supply of the oxidant stopped. Alternatively or additionally, the Oxidation atmosphere can also be supplied with a reducing agent.
  • Combinations of the proposed measures are also part of the Invention possible.
  • the oxidant path connection and the reducing agent connection made both simultaneously and alternately.
  • the oxidant connection is undershot and the reducing agent path circuit also both made simultaneously and alternately.
  • Air, water, CO 2 , N 2 O and the like are advantageously supplied as the oxidizing agent, these oxidizing agents mentioned being able to be supplied individually but also in the context of gas mixtures from these components.
  • H 2 , NH 3 , CH 4 or CO are advantageously proposed as reducing agents. These components can also be used individually or as a gas mixture.
  • a device for post-oxidation after nitrocarburizing comprises or nitriding an atmosphere furnace, which is a heater and has at least one gas supply line.
  • atmosphere furnaces which are a heater and has at least one gas supply line.
  • the device according to the invention for carrying out the method of manufacture uniform oxidation layers on metallic workpieces further developed in that an oxygen probe is arranged in the furnace chamber and that a control device is connected to the oxygen probe which is, depending on the measured value, the gas supply to the atmosphere furnace regulates.
  • the oxygen potential can be determined with this oxygen probe determined at any time and depending on the time evaluate the temperature and the like.
  • the control device acts in the range of Valves in the gas supply lines.
  • a particularly advantageous device-side solution for controlling the Oxygen potential during post-oxidation is through the use of a Endexo retort marked.
  • Such retorts are used to generate Carrier gas in nitrocarburizing furnaces already known.
  • Using the Endexo retort Endogas is usually produced during nitrocarburization.
  • Nitriding agent for example ammonia
  • the Endexo retort is then carried out in such a way that when the target value is undershot of the oxygen potential in the oxidation atmosphere is the natural gas supply switched off, or if the setpoint is exceeded, the natural gas supply is switched on again with constant air supply to the retort.
  • the furnace 1 shows an atmosphere furnace 1 known per se, consisting of a furnace housing 2, which is arranged on a frame 3. Internally the furnace 1 has a furnace chamber 4 which comprises a batch space 5. A circulation fan 6, which is driven by a thermally insulated drive 7 is driven, sucks the atmospheric gas from the batch space and it rolls into the space surrounding the furnace chamber, in which not shown Heating elements are arranged. The gas then comes out with the right one Put the temperature back into batch room 5 from below.
  • the atmospheric furnace 1 comprises a gas supply line 8, into which the gases required in each case are fed into the furnace space via corresponding valves.
  • the regulating valve 9a NH 3 , the regulating valve 9b, the endogas or exogas, the regulating valve 9c, nitrogen and the regulating valve 9d, air, water or another oxidizing agent can be supplied.
  • An oxygen probe is used to determine the oxygen potential in the furnace chamber 4 10 provided with which the oxygen potential is measured becomes. From a control device, not shown, the measured value with compared to a target value. If a discrepancy is found, the Control device 13 controls the respective valves 9a, 9b and 9d to modify the oxidation atmosphere in the furnace chamber 4.
  • FIG. 2 A corresponding embodiment is shown in FIG. 2.
  • the atmosphere furnace 1 is constructed in the manner described.
  • the figure shows the use a so-called endexo retort.
  • Oxygen probe 10 is also possible by means of a gas discharge line 12 to discharge so-called sample gas and outside the atmosphere furnace 1 to be measured using an oxygen probe ( ⁇ probe), not shown.
  • About the Control valve 9a can, for example, ammonia via a separate Feed line 8 are introduced into the furnace. During post-oxidation this valve remains closed. Natural gas is produced via the control valve 9b fed. If the measured oxygen potential value exceeds the setpoint, valve 9b is opened. If the value falls below the setpoint, the Natural gas supply switched off. Via the oxygen source 11 and the valve 9c only oxidant is supplied to the furnace chamber 4.
  • the diagram shown in FIG. 3 shows the control range according to the invention, which is to be maintained by the setpoint determination.
  • the diagram shows the oxygen probe voltage mV over the temperature in ° C.
  • the desired range in which in the oxidation atmosphere at the given oxidation temperature the oxidation is always just above the formation limit of Fe 3 O 4 oxide, but regularly below the formation limit of the other iron oxides, can be shown, for example, in FIG specify the temperature range from approximately 450 ° C to approximately 650 ° C with an oxygen probe voltage between approximately 1100 mV and 800 mV (hatched area).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Chemically Coating (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Claims (13)

  1. Procédé destiné à la réalisation de couches d'oxydation homogènes sur des pièces métalliques suite à un procédé de nitruration ou de nitrocarburation, les pièces étant exposées après la nitruration ou la nitrocarburation durant un temps prédéterminé à une atmosphère d'oxydation à température donnée,
    caractérisé en ce que le potentiel oxygène présent dans l'atmosphère d'oxydation est déterminé en permanence, en ce que le résultat de mesure est comparé avec une valeur de consigne prescrite, et en ce que, lors de différences, l'atmosphère d'oxydation est modifiée jusqu'à ce que le résultat de mesure corresponde à la valeur de consigne, la valeur de consigne étant définie de telle sorte qu'à la température d'oxydation donnée, le potentiel oxygène soit toujours situé au-dessus de la limite de formation d'oxyde Fe3O4, mais au-dessous de la limite de formation d'autres oxydes de fer.
  2. Procédé selon la revendication 1, caractérisé en ce qu'à des températures comprises entre 450 °C et 650 °C, la valeur de consigne pour le potentiel oxygène est réglée entre 1 100 mv et 800 mv.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que de l'agent d'oxydation est amené lorsque la valeur de consigne n'est pas atteinte.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'amenée d'agent d'oxydation est stoppée lors d'un dépassement de la valeur de consigne.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'un agent de réduction est amené lors d'un dépassement de la valeur de consigne.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'amenée d'agent de réduction est stoppée lorsque la valeur de consigne n'est pas atteinte.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que lors d'un dépassement de la valeur de consigne, l'interruption de l'apport d'agent d'oxydation et l'apport d'agent de réduction sont effectués simultanément ou en alternance.
  8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que, lorsque la valeur de consigne n'est pas atteinte, l'apport d'agent d'oxydation et l'interruption d'agent de réduction sont effectués simultanément ou en alternance.
  9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent d'oxydation contient de l'air, de l'H2O, du CO2 et/ou du N2O.
  10. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent de réduction contient de l'H2, du NH3, du CH4 et/ou du CO.
  11. Dispositif destiné à la mise en oeuvre du procédé selon l'une quelconque des revendications 1 à 10, la nitruration ou la nitrocarburation, et l'oxydation consécutive, étant effectuées dans un four atmosphérique (1) comportant au moins une conduite d'amenée (8) de gaz, caractérisé en ce qu'une sonde d'oxygène (10) est disposée dans l'enceinte (4) du four, et en ce qu'un dispositif de commande est relié à la sonde d'oxygène, lequel règle l'amenée de gaz au four atmosphérique (1) en fonction de la valeur de mesure.
  12. Dispositif selon la revendication 11, caractérisé en ce que le dispositif de commande règle l'amenée de gaz par l'intermédiaire de vannes (9a, 9b, 9d).
  13. Dispositif selon l'une des revendications 11 ou 12, caractérisé en ce qu'une cornue Endexo est disposée dans la zone de l'amenée (8) de gaz.
EP94116881A 1993-11-18 1994-10-26 Procédé pour la formation de couches d'oxydes unitaires sur des substrats métalliques et dispositif pour réaliser le procédé Expired - Lifetime EP0655512B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4339404A DE4339404A1 (de) 1993-11-18 1993-11-18 Verfahren zur Herstellung einheitlicher Oxidationsschichten auf metallischen Werkstücken und Vorrichtung zur Durchführung des Verfahrens
DE4339404 1993-11-18

Publications (2)

Publication Number Publication Date
EP0655512A1 EP0655512A1 (fr) 1995-05-31
EP0655512B1 true EP0655512B1 (fr) 2000-07-19

Family

ID=6502908

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94116881A Expired - Lifetime EP0655512B1 (fr) 1993-11-18 1994-10-26 Procédé pour la formation de couches d'oxydes unitaires sur des substrats métalliques et dispositif pour réaliser le procédé

Country Status (4)

Country Link
EP (1) EP0655512B1 (fr)
AT (1) ATE194855T1 (fr)
DE (2) DE4339404A1 (fr)
ES (1) ES2149835T3 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19938009C1 (de) * 1999-08-11 2000-10-26 Ipsen Ind Int Gmbh Vorrichtung zur Wärmebehandlung metallischer Werkstücke
ATE235581T1 (de) * 2000-02-04 2003-04-15 Ipsen Int Gmbh Verfahren zum nitrieren und/oder nitrocarburieren von höher legierten stählen
DE10162339A1 (de) * 2001-12-18 2003-07-10 Messer Griesheim Gmbh Verfahren zur Herstellung einer Oxidschicht auf Metallteilen
DE10235131A1 (de) 2002-08-01 2004-02-19 Ipsen International Gmbh Verfahren und Vorrichtung zum Schwärzen von Bauteilen
DE202005011573U1 (de) * 2005-07-22 2006-11-23 JOH. WINKLHOFER & SÖHNE GMBH & Co. KG Gelenkkette mit nitrierter Lagerfläche mit Oxidationsschicht
ITMI20110366A1 (it) * 2011-03-10 2012-09-11 Sol Spa Procedimento per il trattamento di acciai.
DE102015204656A1 (de) * 2015-03-16 2016-09-22 Aktiebolaget Skf Schichtbildung für Wälzlagerkomponenten
DE102021213888A1 (de) * 2021-12-07 2023-06-07 Robert Bosch Gesellschaft mit beschränkter Haftung Verfahren und Einrichtung zum örtlich begrenzten Nitrieren oder Nitrocarburieren der Oberfläche eines Bauteils

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4439248A (en) * 1982-02-02 1984-03-27 Cabot Corporation Method of heat treating NICRALY alloys for use as ceramic kiln and furnace hardware
GB8310102D0 (en) * 1983-04-14 1983-05-18 Lucas Ind Plc Corrosion resistant steel components
DE3419638C2 (de) * 1984-05-25 1987-02-26 MAN Technologie GmbH, 8000 München Verfahren zur oxidativen Erzeugung von Schutzschichten auf einer Legierung
DD278365A1 (de) * 1988-12-22 1990-05-02 Thaelmann Schwermaschbau Veb Verfahren zur gasoxynitrierung von bauteilen aus eisenwerkstoffen

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Publication number Publication date
ES2149835T3 (es) 2000-11-16
DE59409455D1 (de) 2000-08-24
EP0655512A1 (fr) 1995-05-31
DE4339404A1 (de) 1995-05-24
ATE194855T1 (de) 2000-08-15

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