EP1122330A1 - Procédé et utilisation d' un dispositif pour la carbonitruration de pièces métalliques - Google Patents

Procédé et utilisation d' un dispositif pour la carbonitruration de pièces métalliques Download PDF

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Publication number
EP1122330A1
EP1122330A1 EP00102360A EP00102360A EP1122330A1 EP 1122330 A1 EP1122330 A1 EP 1122330A1 EP 00102360 A EP00102360 A EP 00102360A EP 00102360 A EP00102360 A EP 00102360A EP 1122330 A1 EP1122330 A1 EP 1122330A1
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EP
European Patent Office
Prior art keywords
hydrocarbons
added
reaction gas
nitrocarburizing
ammonia
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
EP00102360A
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German (de)
English (en)
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EP1122330B1 (fr
Inventor
Wolfgang Lerche
Bernd Edenhofer
Michael Lohrmann
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Ipsen International GmbH
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Ipsen International GmbH
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Publication date
Application filed by Ipsen International GmbH filed Critical Ipsen International GmbH
Priority to EP20000102360 priority Critical patent/EP1122330B1/fr
Priority to DE50008409T priority patent/DE50008409D1/de
Priority to AT00102360T priority patent/ATE280847T1/de
Priority to US09/562,698 priority patent/US6406560B1/en
Publication of EP1122330A1 publication Critical patent/EP1122330A1/fr
Application granted granted Critical
Publication of EP1122330B1 publication Critical patent/EP1122330B1/fr
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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
    • 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
    • C23C8/28—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 one step
    • C23C8/30—Carbo-nitriding
    • C23C8/32—Carbo-nitriding of ferrous surfaces

Definitions

  • the invention relates to a method for heat treatment of metallic Workpieces in a nitrogen-containing gas atmosphere, especially for Nitrocarburizing of ferrous materials.
  • the invention further relates to the Use of a device for performing such a method.
  • thermochemical heat treatment To create defined workpiece properties, such as a high one Wear resistance or sufficient corrosion resistance metallic workpieces are subjected to a thermochemical heat treatment.
  • the result of the heat treatment is, for example, nitriding or nitrocarburizing Enriching the edge layer of the workpieces with nitrogen and / or Carbon in order to achieve the required mechanical and to impart chemical properties on the surface and in the edge area.
  • the surface layer is enriched with nitrogen by the ammonia (NH 3 ) contained in a reaction gas at temperatures of generally over 500 ° C under the catalytic effect of the surface of the workpieces to be nitrided breaks down into nitrogen (N) and hydrogen (H).
  • the ammonia molecule is adsorbed and gradually degraded on the workpiece surface, releasing the required nitrogen in atomic form and making it available for solution in iron and for the formation of iron nitride (Fe x N).
  • the surface layer is simultaneously enriched with carbon.
  • Atomic carbon (C) diffuses in an analogous manner through the workpiece surface into the boundary layer.
  • connection layer which, when nitriding or nitrocarburizing, mainly consists of hexagonal ⁇ -nitride (Fe 2-3 N) and face-centered cubic ⁇ '-nitride (Fe 4 N) exists.
  • connection layer which, when nitriding or nitrocarburizing, mainly consists of hexagonal ⁇ -nitride (Fe 2-3 N) and face-centered cubic ⁇ '-nitride (Fe 4 N) exists.
  • the choice of the process parameters temperature and duration of treatment but above all the composition of the reaction gas used, have a decisive influence on the properties of the connection layer. This is due to the fact that the proportion of the elements diffusing through the surface into the surface layer, such as nitrogen (N), carbon (C) or also oxygen (O) and sulfur (S), the temperature and treatment time given the process gas composition for given process parameters is determined.
  • the carbonization index K C for a reaction gas used for nitrocarburizing with a composition of 50% by volume ammonia (NH 3 ) and 50% by volume endogas with regard to an optimized ⁇ -nitride content has values between 1, 5 and 2.5, if the proportion of ammonia reacted during nitrocarburizing in the gas atmosphere is between 15% by volume and 40% by volume.
  • the carbonization index K C is significantly lower for a reaction gas with a composition of 50% by volume NH 3 , 45% by volume N 2 and 5% by volume CO 2 .
  • nitrocarburizing is carried out with a proportion of carbon dioxide in the gas atmosphere between 0 vol.% And 7 vol.% And a proportion of ammonia between 0 vol.% And 40 vol.%
  • the carbonization index K C values between 0 and 0.5 on. Due to the by the formula: CO + H 2 O CO 2 + H 2 described balance of the components carbon monoxide (CO), water vapor (H 2 O) D, carbon dioxide (CO 2) and hydrogen (H 2) in the gas atmosphere, the nitriding potential K N K C and the carburizing interdependent.
  • the carbonization index K C can only be changed to a limited extent with a predetermined nitriding index K N and can therefore only be used to a limited extent to influence workpiece properties.
  • Another disadvantage is that the carbonization index K C does not have sufficiently high values for the reaction gases usually used, so that the technical properties of metallic workpieces, such as wear resistance or corrosion resistance, which are influenced by the carbon content in the connecting layer, are not to the extent possible can be exploited.
  • the invention is based on the object of developing a method for the heat treatment of metallic workpieces such that an improved wear and corrosion resistance of the treated workpieces can be achieved.
  • This object is achieved in a method of the type mentioned according to the invention in that the surface layer of the treated workpieces is selectively adjusted by a suitable choice of the nitriding potential K N and carburizing K C of an ammonia-containing reaction gas, the present in the compound layer of nitrogen and carbon content, and to generate a relatively high carbon content in the compound layer hydrocarbons are added to the reaction gas.
  • Such a process embraces the surprising finding that the process-related coupling of the coalation index K C to the nitration index K N has been eliminated by the additional carbon supply in the gas atmosphere caused by the addition of hydrocarbons in the reaction gas.
  • the carbon index K C can then be changed independently of the nitriding index K N.
  • the result of this is that comparatively high values for the carbon index K C can be achieved in the gas atmosphere.
  • unsaturated hydrocarbons of the type C n H 2n preferably ethylene (C 2 H 4 ) or propylene (C 2 H 6 ).
  • saturated hydrocarbons of the type C n H 2n + 2 preferably ethane (C 2 H 6 ) or propane (C 3 H 8 ). This is because thermal splitting of the saturated hydrocarbons during the course of the process can result in the formation of unsaturated hydrocarbons.
  • the hydrocarbons can advantageously also be added only while holding at a certain temperature, preferably a nitriding temperature between 500 ° C. and 700 ° C. With regard to a process control optimized with regard to the required workpiece properties, it can also be expedient to add the hydrocarbons only at the end of the holding to the nitriding temperature.
  • hydrocarbons are added discontinuously, for example only at certain times, which enables a process-adapted procedure.
  • hydrocarbons are added in a proportion of 3% by volume to 25% by volume.
  • Such a limitation of the addition of hydrocarbons depending on the composition of the reaction gas offers the advantage that an increased separation of free carbon, which generally leads to undesirable sooting, for example of the interior of heat treatment furnaces, is avoided.
  • a reaction gas with a composition of 95% by volume ammonia (NH 3 ) and 5% by volume propane (C 3 H 8 ) is proposed, which is also economical to produce.
  • 1 and 2 show the content of carbon w C and nitrogen w N of the connecting layer of two nitrocarburized workpiece samples as a function of the edge distance r of the connecting layer.
  • the identical workpiece samples of the steel grade 16 Mn Cr 5 material no. 1.7131 were heated to a nitriding temperature of approx. 580 ° C in an ammonia-containing gas atmosphere of a chamber furnace.
  • the volume flow of the reaction gases G 1 , G 2 flowing through the chamber furnace was in each case approximately 4 m 3 / h. After approximately 180 minutes of nitrocarburizing, the samples were cooled to room temperature in a nitrogen atmosphere. The connection layer determined afterwards was approx. 16 ⁇ m - 18 ⁇ m.
  • the depth profiles of carbon differ considerably from one another.
  • the curve of the carbon content in the workpiece sample treated with the reaction gas G 2 lies well above the carbon content achieved with the reaction gas G 1 up to the middle of the connecting layer and only then takes a course which roughly matches this and is approximately parallel to the drop in the nitrogen content.
  • the course of the carbon content in FIGS. 1 and 2 thus confirms that the addition of propane in the reaction gas G 2 produces a higher carbon content in the connecting layer, which results from a higher carbon index K C of the reaction gas G 2 and not least to one leads to improved wear and corrosion resistance of the workpiece sample.

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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)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP20000102360 2000-02-04 2000-02-04 Procédé et utilisation d' un dispositif pour la carbonitruration de pièces métalliques Expired - Lifetime EP1122330B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP20000102360 EP1122330B1 (fr) 2000-02-04 2000-02-04 Procédé et utilisation d' un dispositif pour la carbonitruration de pièces métalliques
DE50008409T DE50008409D1 (de) 2000-02-04 2000-02-04 Verfahren und Verwendung einer Vorrichtung zum Nitrocarburieren von Eisenwerkstoffen
AT00102360T ATE280847T1 (de) 2000-02-04 2000-02-04 Verfahren und verwendung einer vorrichtung zum nitrocarburieren von eisenwerkstoffen
US09/562,698 US6406560B1 (en) 2000-02-04 2000-04-28 Method for the thermal treatment of metal

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20000102360 EP1122330B1 (fr) 2000-02-04 2000-02-04 Procédé et utilisation d' un dispositif pour la carbonitruration de pièces métalliques

Publications (2)

Publication Number Publication Date
EP1122330A1 true EP1122330A1 (fr) 2001-08-08
EP1122330B1 EP1122330B1 (fr) 2004-10-27

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EP20000102360 Expired - Lifetime EP1122330B1 (fr) 2000-02-04 2000-02-04 Procédé et utilisation d' un dispositif pour la carbonitruration de pièces métalliques

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Country Link
US (1) US6406560B1 (fr)
EP (1) EP1122330B1 (fr)
AT (1) ATE280847T1 (fr)
DE (1) DE50008409D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2302081A1 (fr) * 2009-08-26 2011-03-30 Ipsen International GmbH Procédé et dispositif de préparation de gaz de procédé pour des traitements à chaud de matériaux/pièces métalliques dans des fours industriels

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7622197B2 (en) * 2006-11-20 2009-11-24 Ferroxy-Aled, Llc Seasoned ferrous cookware
CN102732820B (zh) * 2011-04-10 2015-01-21 上海上大热处理有限公司 汽车刹车盘的气体氮碳共渗方法
CN103703274B (zh) * 2011-06-30 2016-10-26 罗伯特·博世有限公司 用于无级变速器传动带的柔性环及其制造方法
US9389155B1 (en) * 2013-03-12 2016-07-12 United Technologies Corporation Fatigue test specimen
DE102013226090A1 (de) 2013-12-16 2015-06-18 Robert Bosch Gmbh Verfahren zum Gasnitrocarburieren
DE102013226091A1 (de) * 2013-12-16 2015-06-18 Robert Bosch Gmbh Zylindertrommel einer hydrostatischen Axialkolbenmaschine mit einer Verschleißschutzschicht
WO2019205114A1 (fr) * 2018-04-28 2019-10-31 邢台三厦铸铁有限公司 Ustensile de cuisine en fonte et procédé de traitement de sa surface

Citations (5)

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Publication number Priority date Publication date Assignee Title
DE4033706A1 (de) * 1990-10-24 1991-02-21 Hans Prof Dr Ing Berns Einsatzhaerten mit stickstoff zur verbesserung des korrosionswiderstandes martensitischer nichtrostender staehle
DE3937699A1 (de) * 1989-11-13 1991-05-16 Thaelmann Schwermaschbau Veb Verfahren zum herstellen von (epsilon)-karbonitridschichten definierter zusammensetzung
DE4127063A1 (de) * 1990-08-23 1992-02-27 Joachim Dr Rer Nat Kunze Verschleissfeste (epsilon)-eisenkarbonitridschicht auf kohlenstoffhaltigen staehlen und verfahren zu ihrer herstellung
DE19509614A1 (de) * 1995-03-21 1996-09-26 Hans Ruediger Dr Ing Hoffmann Regelung von Nitrier- und Nitrocarburieratmosphären
DE19719225C1 (de) * 1997-05-07 1998-08-06 Volker Dipl Ing Leverkus Verfahren zur Regelung einer Nitrier- bzw. Nitrocarburier-Atmosphäre sowie Vorrichtung zur Durchführung des Verfahrens

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Publication number Priority date Publication date Assignee Title
US4496401A (en) * 1981-10-15 1985-01-29 Lucas Industries Corrosion resistant steel components and method of manufacture thereof
FR2524006B1 (fr) * 1982-03-23 1985-10-11 Air Liquide Procede de durcissement superficiel de pieces metalliques
US4547228A (en) * 1983-05-26 1985-10-15 Procedyne Corp. Surface treatment of metals
DE3718240C1 (de) * 1987-05-30 1988-01-14 Ewald Schwing Verfahren zur Waermebehandlung von metallischen Werkstuecken in einer gasdurchstroemten Wirbelschicht
RU2048601C1 (ru) * 1993-12-20 1995-11-20 Рыжов Николай Михайлович Способ диагностики процесса химико-термической обработки сталей и сплавов в тлеющем разряде и устройство для его осуществления

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3937699A1 (de) * 1989-11-13 1991-05-16 Thaelmann Schwermaschbau Veb Verfahren zum herstellen von (epsilon)-karbonitridschichten definierter zusammensetzung
DE4127063A1 (de) * 1990-08-23 1992-02-27 Joachim Dr Rer Nat Kunze Verschleissfeste (epsilon)-eisenkarbonitridschicht auf kohlenstoffhaltigen staehlen und verfahren zu ihrer herstellung
DE4033706A1 (de) * 1990-10-24 1991-02-21 Hans Prof Dr Ing Berns Einsatzhaerten mit stickstoff zur verbesserung des korrosionswiderstandes martensitischer nichtrostender staehle
DE19509614A1 (de) * 1995-03-21 1996-09-26 Hans Ruediger Dr Ing Hoffmann Regelung von Nitrier- und Nitrocarburieratmosphären
DE19719225C1 (de) * 1997-05-07 1998-08-06 Volker Dipl Ing Leverkus Verfahren zur Regelung einer Nitrier- bzw. Nitrocarburier-Atmosphäre sowie Vorrichtung zur Durchführung des Verfahrens

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2302081A1 (fr) * 2009-08-26 2011-03-30 Ipsen International GmbH Procédé et dispositif de préparation de gaz de procédé pour des traitements à chaud de matériaux/pièces métalliques dans des fours industriels

Also Published As

Publication number Publication date
EP1122330B1 (fr) 2004-10-27
US6406560B1 (en) 2002-06-18
ATE280847T1 (de) 2004-11-15
DE50008409D1 (de) 2004-12-02

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