EP0655512A1 - 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
EP0655512A1
EP0655512A1 EP94116881A EP94116881A EP0655512A1 EP 0655512 A1 EP0655512 A1 EP 0655512A1 EP 94116881 A EP94116881 A EP 94116881A EP 94116881 A EP94116881 A EP 94116881A EP 0655512 A1 EP0655512 A1 EP 0655512A1
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EP
European Patent Office
Prior art keywords
oxidation
target value
atmosphere
reducing agent
gas supply
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
EP94116881A
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German (de)
English (en)
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EP0655512B1 (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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Publication of EP0655512A1 publication Critical patent/EP0655512A1/fr
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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 process for producing uniform oxidation layers on metallic workpieces following a nitriding or nitrocarburizing process, the workpieces being exposed to an oxidizing atmosphere for a predetermined time after the nitriding or nitrocarburizing at a given temperature.
  • the generic methods are used to improve the wear and 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, CO2, laughing gas 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. Ideally, an iron oxide layer of the form Fe3O4 is sought, the so-called magnetite. Desired oxidation layer thicknesses are between 0.5 and 2 ⁇ m predominantly corrosive stress, or between 1 and 3 ⁇ m in the case of predominant wear stress.
  • 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 Fe2O3 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. The generation of thick Fe3O4 layers can be harmful, especially 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 generic method 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 setpoint is determined so that the oxygen potential in the oxidation atmosphere at the given oxidation temperature is always just above the formation limit of Fe3O4 oxide, but below the formation limit of the other iron oxides.
  • a range between 1100 mV and 800 mV at temperatures from 450 ° C to 650 ° C has proven to be suitable for setting the setpoint of the oxygen potential.
  • Air, water, CO2, N2O 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.
  • H2, NH3, CH4 or CO is proposed in an advantageous manner. These components can also be used individually or as a gas mixture.
  • a device for post-oxidation after nitrocarburizing or nitriding comprises an atmosphere furnace which has a heating device and at least one gas supply line.
  • Known atmosphere furnaces usually have circulation devices which lead the gas forming the atmosphere out of a batch space and back into the batch space along heating devices or heat exchangers.
  • the device according to the invention for carrying out the method for producing uniform oxidation layers on metallic workpieces has been further developed in that an oxygen probe is arranged in the area of the batch space of the oxidation atmosphere.
  • this oxygen probe can be used to determine the oxygen potential at any time and depending on the time, evaluate the temperature and the like.
  • the device according to the invention advantageously has a control device which regulates the gas supply to the atmosphere furnace as a function of the measured value and the predetermined target value.
  • the control device acts on valves located in the area of gas supply lines.
  • a particularly advantageous device-side solution for regulating the oxygen potential during post-oxidation is characterized by the use of an Endexo retort.
  • Such retorts are already known for generating carrier gas in nitrocarburizing furnaces. Endogas are usually produced using the Endexo retort during nitrocarburization.
  • the nitrating agent for example ammonia, needs to be switched off.
  • the Endexo retort is then carried out in such a way that the natural gas supply is cut off when the setpoint of the oxygen potential falls below the setpoint, or the natural gas supply is switched on again when the setpoint is exceeded while the air supply to the retort remains constant.
  • an atmosphere oven 1 known per se, consisting of an oven housing 2 which is arranged on a frame 3. Inside the furnace 1 has a furnace chamber 4 which comprises a batch space 5.
  • 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 control valve 9a NH3 the control valve 9b, the endogas or exogas, the control valve 9c nitrogen and the control valve 9d air, water or another oxidizing agent.
  • an oxygen probe 10 is provided, with which the oxygen potential is measured. The measured value is compared with a desired value by a control device, not shown. If a deviation is found, the respective valves 9a, 9b and 9d can be actuated by the control device 13 in order 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 of a so-called endexo retort.
  • the oxygen probe 10 shown it is also possible to discharge a so-called sample gas by means of a gas discharge line 12 and to measure outside the atmosphere furnace 1 by means of an oxygen probe ( ⁇ probe), not shown.
  • ⁇ probe oxygen probe
  • ammonia can be introduced into the furnace via the control valve 9a via a separate feed line 8. This valve remains closed during post-oxidation.
  • Natural gas is supplied via the control valve 9b. If the measured oxygen potential value exceeds the target value, the valve 9b is opened. The natural gas supply is switched off when the value falls below the target value. Only oxidizing agent is supplied to the furnace chamber 4 via the oxygen source 11 and the valve 9c.
  • 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 Fe3O4 oxide, but regularly below the formation limit of the other iron oxides, can, as shown in Fig. 3, for example in the temperature range of specify approx. 450 ° C to approx. 650 ° C with an oxygen probe voltage between approx. 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)
  • Analysing Materials By The Use Of Radiation (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Manufacture And Refinement Of Metals (AREA)
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 true EP0655512A1 (fr) 1995-05-31
EP0655512B1 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)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1122331A1 (fr) * 2000-02-04 2001-08-08 Ipsen International GmbH Procédé pour la nitruration et/ou carbonitruration d' acier fortement allié
WO2003052158A1 (fr) * 2001-12-18 2003-06-26 Messer Griesheim Gmbh Procede de fabrication d'une couche d'oxyde sur des pieces metalliques
US7160576B2 (en) 2002-08-01 2007-01-09 Ipsen International Gmbh Method and device for blacking components
WO2007009521A1 (fr) * 2005-07-22 2007-01-25 Iwis Motorsysteme Gmbh & Co. Kg Chaîne articulée à surface d'appui nitrurée comportant une couche d'oxydation
ITMI20110366A1 (it) * 2011-03-10 2012-09-11 Sol Spa Procedimento per il trattamento di acciai.
WO2023104385A1 (fr) * 2021-12-07 2023-06-15 Robert Bosch Gmbh Procédé et dispositif de nitruration ou nitrocarburation localisée de la surface d'un composant

Families Citing this family (2)

* 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
DE102015204656A1 (de) * 2015-03-16 2016-09-22 Aktiebolaget Skf Schichtbildung für Wälzlagerkomponenten

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2114603A (en) * 1982-02-02 1983-08-24 Cabot Corp Method of heat treating nicraly alloys for use as ceramic kiln and furnace hardware
EP0122762A1 (fr) * 1983-04-14 1984-10-24 LUCAS INDUSTRIES public limited company Pièces en acier résistant à la corrosion et procédé de fabrication desdites pièces
GB2159542A (en) * 1984-05-25 1985-12-04 Maschf Augsburg Nuernberg Ag Method for producing protective oxidic layers on metallic surfaces
DE3935469A1 (de) * 1988-12-22 1990-06-28 Thaelmann Schwermaschbau Veb Verfahren zur gasoxynitrierung von bauteilen aus eisenwerkstoffen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2114603A (en) * 1982-02-02 1983-08-24 Cabot Corp Method of heat treating nicraly alloys for use as ceramic kiln and furnace hardware
EP0122762A1 (fr) * 1983-04-14 1984-10-24 LUCAS INDUSTRIES public limited company Pièces en acier résistant à la corrosion et procédé de fabrication desdites pièces
GB2159542A (en) * 1984-05-25 1985-12-04 Maschf Augsburg Nuernberg Ag Method for producing protective oxidic layers on metallic surfaces
DE3935469A1 (de) * 1988-12-22 1990-06-28 Thaelmann Schwermaschbau Veb Verfahren zur gasoxynitrierung von bauteilen aus eisenwerkstoffen

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1122331A1 (fr) * 2000-02-04 2001-08-08 Ipsen International GmbH Procédé pour la nitruration et/ou carbonitruration d' acier fortement allié
WO2003052158A1 (fr) * 2001-12-18 2003-06-26 Messer Griesheim Gmbh Procede de fabrication d'une couche d'oxyde sur des pieces metalliques
CN1322161C (zh) * 2001-12-18 2007-06-20 梅塞尔集团有限公司 用来在金属部件上制备氧化层的方法
US7160576B2 (en) 2002-08-01 2007-01-09 Ipsen International Gmbh Method and device for blacking components
WO2007009521A1 (fr) * 2005-07-22 2007-01-25 Iwis Motorsysteme Gmbh & Co. Kg Chaîne articulée à surface d'appui nitrurée comportant une couche d'oxydation
ITMI20110366A1 (it) * 2011-03-10 2012-09-11 Sol Spa Procedimento per il trattamento di acciai.
EP2497839A1 (fr) * 2011-03-10 2012-09-12 SOL S.p.A. Procédé pour le traitement des aciers
WO2023104385A1 (fr) * 2021-12-07 2023-06-15 Robert Bosch Gmbh Procédé et dispositif de nitruration ou nitrocarburation localisée de la surface d'un composant

Also Published As

Publication number Publication date
ATE194855T1 (de) 2000-08-15
DE4339404A1 (de) 1995-05-24
DE59409455D1 (de) 2000-08-24
EP0655512B1 (fr) 2000-07-19
ES2149835T3 (es) 2000-11-16

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