EP1230415B1 - Verfahren für die nitrocarburierung metallischer werkstücke - Google Patents

Verfahren für die nitrocarburierung metallischer werkstücke Download PDF

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Publication number
EP1230415B1
EP1230415B1 EP00962293A EP00962293A EP1230415B1 EP 1230415 B1 EP1230415 B1 EP 1230415B1 EP 00962293 A EP00962293 A EP 00962293A EP 00962293 A EP00962293 A EP 00962293A EP 1230415 B1 EP1230415 B1 EP 1230415B1
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EP
European Patent Office
Prior art keywords
treatment
carbon
gas
temperature
carbon dioxide
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.)
Expired - Lifetime
Application number
EP00962293A
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German (de)
English (en)
French (fr)
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EP1230415A1 (de
Inventor
Hans-Peter Schmidt
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.)
Messer Group GmbH
Original Assignee
Messer Griesheim GmbH
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Publication date
Application filed by Messer Griesheim GmbH filed Critical Messer Griesheim GmbH
Publication of EP1230415A1 publication Critical patent/EP1230415A1/de
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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

Definitions

  • the invention relates to a method for nitrocarburizing metallic workpieces, by placing the work pieces in a nitrogen, carbon monoxide and hydrogen containing treatment atmosphere at a treatment temperature in one Treatment room are treated, being used to generate the Treatment atmosphere carbon dioxide is used as a carbon donor.
  • the nitrogen donor is basically ammonia (NH 3 ), while various gas mixtures such as air-hydrocarbon mixtures (endogas and exogas) and carbon dioxide are used as carbon donors. In the nitriding furnace, these gases react with the hydrogen present, with stationary carbon, nitrogen and oxygen activity depending on the thermal and chemical conditions.
  • the atomic nitrogen produced during ammonia splitting reacts particularly easily with the metal to form nitrides upon contact with metal surfaces (hereinafter referred to as (N) ad ).
  • Different nitride phases can form in connection with iron.
  • nitride phases in the form of so-called ⁇ -nitride (Fe 2-3 N) and ⁇ '-nitride (Fe 4 N) or mixtures of these nitrides are preferred with regard to high hardness and wear resistance.
  • the carbon dissolved in the nitride affects morphology, compactness, Pore hem and adhesion of the connection layer and its corrosion and Wear resistance.
  • the carbon activity in turn depends on the one used Carbon donor. It falls in the order of propane, endogas, and exogas Carbon dioxide. Because the composition of the gas phase in the nitriding furnace has a significant influence on the result of nitrocarburization, it is beneficial if this is adjustable in the widest possible range.
  • the carbon dioxide contents are usually between 4 and 10% by volume.
  • K B denotes the constant of the Boudouard equilibrium.
  • the maximum carbon activity is 1, which corresponds to the activity of pure graphite.
  • K N nitriding index
  • DE-C1 197 19 225 from which a method for controlling the nitriding index of a nitriding or nitrocarburizing atmosphere in a furnace system when using NH 3 as a nitrogen source is known.
  • the known method is characterized in that the NH 3 gas throughput is kept constant and only the operating point of the prespattern in which the NH 3 split gas is generated is regulated.
  • a high nitriding index requires a high ammonia content in the nitriding furnace, which in turn results in a high residual ammonia content in the furnace exhaust gas, which leaves the furnace unused.
  • methanol does not cleave stoichiometrically, but undesirable cleavage products such as CH 4 and other higher hydrocarbons, CO 2 , aldehydes, ketones etc. are formed, some of which are toxic and corrosive when condensed.
  • cleavage of the methanol strongly depends on the conditions of the boiler room and on the surface of the batch, so that the desired furnace gas composition cannot be reproduced. This has the further consequence that soot deposits on the batch material and the boiler room surface due to uncontrolled cracking reactions or that undesired carbides are formed.
  • the invention is therefore based on the object, the known method for Nitrocarburizing metallic workpieces using carbon dioxide as Modify carbon donors so that the type and extent of nitride formation in are widely adjustable.
  • This object is achieved in that a carbon dioxide-containing Gas flow introduced into a reactor upstream of the treatment room and therein by reaction with a hydrogen donor at a reaction temperature above the treatment temperature is modified to a carburizing gas that a higher carbon activity compared to the gas stream containing carbon dioxide at the treatment temperature.
  • the carbon dioxide-containing cas stream is fed to a reactor modified in the direction of a higher carbon activity and then as Carbonization gas introduced into the treatment room.
  • the process for nitrocarburizing metallic workpieces by the workpieces in a nitrogen, carbon monoxide and hydrogen containing Treatment atmosphere at one treatment temperature in one Treatment room are treated, being used to generate the Treatment atmosphere carbon dioxide is used as a carbon donor characterized in that a carbon dioxide-containing gas stream 1, 21 in a Treatment room 6, 27 upstream reactor 4, 24 initiated and therein Reaction with a hydrogen donor 2, 22 at a reaction temperature is modified to a carburizing gas 5, 25 above the treatment temperature, the one compared to the gas stream containing carbon dioxide 1, 21 higher Has carbon activity at the treatment temperature.
  • a hydrocarbon-containing fluid is used as the hydrogen donor 2 used, in particular natural gas, propane or is used as a hydrogen donor Methane 2 used.
  • Another method is called a hydrogen donor Ammonia 22 used.
  • a splitting device 24 for ammonia is used in particular as a reactor.
  • the carburizing gas 5, 25 is introduced into the Treatment room 6.27 moisture removed.
  • the method there is preferably a regulation 9, 30 for the carbon activity provided in the treatment room 6, 27, in which the supply rate of a serves the hydrogen donor 2, 22 partial stream.
  • the regulation 9.30 for the carbon activity includes a measurement of the oxygen activity 8, 29 and / or the carbon monoxide concentration in the treatment room 8.27.
  • the Carbon dioxide-containing gas stream 1, 21, the carbonization gas 5.25 and / or the Partial stream for the hydrogen donor 2.22 becomes in particular a diluent gas 3, 23 added.
  • the carburizing gas 25 is preferably introduced into the Treatment room 27 to a temperature in the range of the treatment temperature cooled.
  • the carburizing gas 5 preferably has the introduction into the Treatment room 6 a temperature in the range of the reaction temperature.
  • the treatment temperature is preferably in the range between 500 ° C and 700 ° C.
  • the reaction temperature is preferably in the range between 800 and 1150 ° C.

Landscapes

  • 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)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
EP00962293A 1999-08-25 2000-08-04 Verfahren für die nitrocarburierung metallischer werkstücke Expired - Lifetime EP1230415B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19940370A DE19940370C2 (de) 1999-08-25 1999-08-25 Verfahren für die Nitrocarburierung metallischer Werkstücke
DE19940370 1999-08-25
PCT/EP2000/007576 WO2001014611A1 (de) 1999-08-25 2000-08-04 Verfahren für die nitrocarburierung metallischer werkstücke

Publications (2)

Publication Number Publication Date
EP1230415A1 EP1230415A1 (de) 2002-08-14
EP1230415B1 true EP1230415B1 (de) 2004-01-14

Family

ID=7919599

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00962293A Expired - Lifetime EP1230415B1 (de) 1999-08-25 2000-08-04 Verfahren für die nitrocarburierung metallischer werkstücke

Country Status (7)

Country Link
EP (1) EP1230415B1 (cs)
AT (1) ATE257865T1 (cs)
CZ (1) CZ298996B6 (cs)
DE (2) DE19940370C2 (cs)
ES (1) ES2214316T3 (cs)
PL (1) PL195105B1 (cs)
WO (1) WO2001014611A1 (cs)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6801111B2 (en) 2002-08-21 2004-10-05 Square D Company Latch for an electrical device
US7621201B2 (en) * 2008-03-05 2009-11-24 Gm Global Technology Operations, Inc. Hot forming tools for aluminum and magnesium sheets

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0024106B1 (en) * 1979-07-09 1986-01-02 Ford Motor Company Limited Method of heat treating ferrous workpieces
JPH01129957A (ja) * 1987-11-13 1989-05-23 Toyota Motor Corp マルエージング鋼の表面処理方法
DE3937699A1 (de) * 1989-11-13 1991-05-16 Thaelmann Schwermaschbau Veb Verfahren zum herstellen von (epsilon)-karbonitridschichten definierter zusammensetzung
DE4229803A1 (de) * 1992-09-11 1994-03-17 Iva Industrieoefen Verfahren A Kontrolle und Steuerung von Nitrier- bzw. Nitrocarburieratmosphären
DE19514932A1 (de) * 1995-04-22 1996-10-24 Ipsen Ind Int Gmbh Verfahren und Vorrichtung zur Regelung des CO-Gehaltes einer Ofenatmosphäre zum Aufkohlen und Carbonitrieren metallischer Werkstücke
DE19652125C1 (de) * 1996-12-14 1998-04-30 Volker Dipl Ing Leverkus Verfahren zur Regelung einer Nitrier- bzw. Nitrocarburier-Atmosphäre sowie Vorrichtung zur Durchführung des Verfahrens
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

Also Published As

Publication number Publication date
PL353217A1 (en) 2003-11-03
ATE257865T1 (de) 2004-01-15
PL195105B1 (pl) 2007-08-31
EP1230415A1 (de) 2002-08-14
CZ2002645A3 (cs) 2003-02-12
WO2001014611A1 (de) 2001-03-01
DE19940370C2 (de) 2001-07-12
DE50005043D1 (de) 2004-02-19
DE19940370A1 (de) 2001-03-01
ES2214316T3 (es) 2004-09-16
CZ298996B6 (cs) 2008-04-02

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