EP1230415B1 - Verfahren für die nitrocarburierung metallischer werkstücke - Google Patents
Verfahren für die nitrocarburierung metallischer werkstücke Download PDFInfo
- 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
- Authority
- 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
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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
- 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.
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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)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Description
Claims (13)
- Verfahren zum Nitrocarburieren metallischer Werkstücke, indem die Werkstücke in einer Stickstoff, Kohlenmonoxid und Wasserstoff enthaltenden Behandlungsatmosphäre bei einer Behandlungstemperatur in einem Behandlungsraum behandelt werden, wobei zur Erzeugung der Behandlungsatmosphäre Kohlendioxid als Kohlenstoffspender eingesetzt wird, dadurch gekennzeichnet, daß ein Kohlendioxid-haltiger Gasstrom (1; 21) in einen dem Behandlungsraum (6; 27) vorgeschalteten Reaktor (4; 24) eingeleitet und darin durch Reaktion mit einem Wasserstoffspender (2; 22) bei einer Reaktionstemperatur oberhalb der Behandlungstemperatur zu einem Kohlungsgas (5; 25) modifiziert wird, das eine im Vergleich zum Kohlendioxid-haltigen Gasstrom (1; 21) höhere Kohlenstoffaktivität bei der Behandlungstemperatur aufweist.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Wasserstoffspender ein Kohlenwasserstoff-haltiges Fluid (2) eingesetzt wird.
- Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß als Wasserstoffspender Erdas, Propan oder Methan (2) eingesetzt wird.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Wasserstoffspender Ammoniak (22) eingesetzt wird.
- Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß als Reaktor ein Spaltgerät (24) für Ammoniak eingesetzt wird.
- Verfahren nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß dem Kohlungsgas (5; 25) vor Einleitung in den Behandlungsraum (6; 27) Feuchtigkeit entzogen wird.
- Verfähren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß eine Regelung (9; 30) für die Kohlenstoffaktivität im Behandlungsraum (6; 27) vorgesehen ist, bei der als Stellgröße die Zufuhrrate eines den Wasserstoffspender (2; 22) enthaltenden Teilstromes dient.
- Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß die Regelung (9; 30) für die Kohlenstoffaktivität eine Messung der Sauerstoffaktivität (8; 29) und/oder der Kohlenmonoxidkonzentration im Behandlungsraum (6; 27) umfaßt.
- Verfahren nach einem der Ansprüche 7 oder 8, dadurch gekennzeichnet, daß dem Kohlendioxid-haltigen Gasstrom (1; 21), dem Kohlungsgas (5; 25) und/oder dem Teilstrom für den Wasserstoffspender (2; 22) ein Verdünnungsgas (3; 23) beigemischt wird.
- Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß das Kohlungsgas (25) vor Einleitung in den Behandlungsraum (27) auf eine Temperatur im Bereich der Behandlungstemperatur abgekühlt wird.
- Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß das Kohlungsgas (5) bei Einteitung in den Behandlungsraum (6) eine Temperatur im Bereich der Reaktionstemperatur aufweist.
- Verfahren nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß die Behandlungstemperatur im Bereich zwischen 500°C und 700°C liegt.
- Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß die Reaktionstemperatur im Bereich zwischen 800 und 1150°C liegt.
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 (de) |
AT (1) | ATE257865T1 (de) |
CZ (1) | CZ298996B6 (de) |
DE (2) | DE19940370C2 (de) |
ES (1) | ES2214316T3 (de) |
PL (1) | PL195105B1 (de) |
WO (1) | WO2001014611A1 (de) |
Families Citing this family (3)
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 |
DE102023133600A1 (de) * | 2022-12-01 | 2024-06-06 | Gottfried Pöckl | Verfahren zum Nitrieren von Bauteilen |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0024106B1 (de) * | 1979-07-09 | 1986-01-02 | Ford Motor Company Limited | Verfahren zur Wärmebehandlung von Werkstücken aus Eisen |
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 |
-
1999
- 1999-08-25 DE DE19940370A patent/DE19940370C2/de not_active Expired - Fee Related
-
2000
- 2000-08-04 AT AT00962293T patent/ATE257865T1/de not_active IP Right Cessation
- 2000-08-04 DE DE50005043T patent/DE50005043D1/de not_active Expired - Lifetime
- 2000-08-04 EP EP00962293A patent/EP1230415B1/de not_active Expired - Lifetime
- 2000-08-04 CZ CZ20020645A patent/CZ298996B6/cs not_active IP Right Cessation
- 2000-08-04 WO PCT/EP2000/007576 patent/WO2001014611A1/de active IP Right Grant
- 2000-08-04 ES ES00962293T patent/ES2214316T3/es not_active Expired - Lifetime
- 2000-08-04 PL PL00353217A patent/PL195105B1/pl unknown
Also Published As
Publication number | Publication date |
---|---|
ES2214316T3 (es) | 2004-09-16 |
PL353217A1 (en) | 2003-11-03 |
CZ2002645A3 (cs) | 2003-02-12 |
DE19940370C2 (de) | 2001-07-12 |
EP1230415A1 (de) | 2002-08-14 |
ATE257865T1 (de) | 2004-01-15 |
PL195105B1 (pl) | 2007-08-31 |
DE50005043D1 (de) | 2004-02-19 |
WO2001014611A1 (de) | 2001-03-01 |
DE19940370A1 (de) | 2001-03-01 |
CZ298996B6 (cs) | 2008-04-02 |
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