EP1122331B1 - Verfahren zum Nitrieren und/oder Nitrocarburieren von höher legierten Stählen - Google Patents
Verfahren zum Nitrieren und/oder Nitrocarburieren von höher legierten Stählen Download PDFInfo
- Publication number
- EP1122331B1 EP1122331B1 EP00102359A EP00102359A EP1122331B1 EP 1122331 B1 EP1122331 B1 EP 1122331B1 EP 00102359 A EP00102359 A EP 00102359A EP 00102359 A EP00102359 A EP 00102359A EP 1122331 B1 EP1122331 B1 EP 1122331B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- workpieces
- gas atmosphere
- ammonia
- temperature
- nitriding
- 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
- C23C8/08—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 only one element being applied
- C23C8/24—Nitriding
- C23C8/26—Nitriding of ferrous surfaces
-
- 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 heat treatment of metallic Workpieces, in particular for nitriding or nitrocarburizing alloyed Ferrous materials, such as higher alloy steels.
- the invention also relates on 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 above 500 ° C under the catalytic effect of the surface of the workpieces to be nitrided decays into nitrogen (N) and hydrogen (H).
- the ammonia molecule is adsorbed and gradually degraded on the workpiece surface, whereby the required nitrogen is released in atomic form and is 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.
- the surface layer which, in addition to hexagonal ⁇ -nitride (Fe 2-3 N), also face-centered cubic ⁇ '-nitride (Fe 4 N) and also nitrides of nitride-forming alloy elements, such as chromium, molybdenum, manganese, titanium, niobium, tungsten, vanadium or aluminum nitride.
- the invention has for its object a method for To create heat treatment of metallic workpieces, which also includes Workpieces made of higher alloyed iron materials are largely uniform nitriding layer can be achieved.
- Such a procedure embraces the surprising finding that a largely uniform nitriding layer can be achieved if the Workpieces before the actual heat treatment in process step d, for example, nitriding or nitrocarburizing, initially only in one ammonia-containing gas atmosphere warmed and then in an additional one Gas atmosphere containing oxidizing agent to the treatment temperature, for example, the nitriding temperature, heated and then for a certain Duration may be kept at this temperature with the result that possibly in the case of high-alloy materials, existing passive layers are eliminated or something that be converted into a uniform diffusion of nitrogen into the Material is favored.
- the temperature at which in each Process steps is heated, and the length of time for which the workpieces in the respective gas atmospheres are based on the Composition of the reaction gas and the material to be treated Workpieces and the desired treatment success.
- the ratio of the amounts of ammonia and the oxidizing agent in the gas atmosphere is expediently between 1: 1 and 5: 1 when air is used as the oxidizing agent, and between 1: 0.1 and 1: 1 when carbon dioxide, water vapor or nitrous oxide is used Oxidizing agents are used.
- a particularly advantageous procedure is also given when the Time period when the workpieces are kept in an ammonia or Ammonia and the carbon-donating gas atmosphere in Dependence on the desired thickness of the surface layer to be enriched is chosen.
- Procedural management may also be useful as carbon donor substance carbon dioxide, carbon monoxide or Hydrocarbons can be used individually or as a mixture.
- the workpieces in one reducing or neutral gas atmosphere for example from an endogas or nitrogen, or in a liquid quenching medium Room temperature can be cooled to an economically beneficial Ensure procedure.
- the first workpiece sample shown in FIG. 1 was preheated to a temperature of approximately 450 ° C. in an endogas-containing gas atmosphere and then in a reaction gas consisting of 50 vol.% Ammonia (NH 3 ) and 50 vol.% Endogas the nitriding temperature of approx. 580 ° C warmed. After approximately 240 minutes, during which the workpiece sample was exposed to the gas atmosphere at this temperature, the workpiece sample was cooled to room temperature in an endogenous gas atmosphere.
- a reaction gas consisting of 50 vol.% Ammonia (NH 3 ) and 50 vol.% Endogas the nitriding temperature of approx. 580 ° C warmed.
- the second workpiece sample shown in FIG. 2 was first preheated in an ammonia-containing gas atmosphere to a temperature of approximately 450 ° C. and then in an ammonia-containing reaction gas, the air as the oxidizing agent in a ratio of 3.5 (ammonia): 1 (air ) was added, heated to the nitriding temperature of approx. 580 ° C. The workpiece sample was then held at this temperature and in this gas atmosphere for a period of about 1.5 hours. The gas atmosphere was then exchanged and the workpiece sample was exposed at 580 ° C. to a reaction gas with the composition 50% by volume ammonia (NH 3 ) and 50% by volume endogas for approx. 4 h, in order to achieve the desired nitriding depth of approx. 80 ⁇ m to reach. Finally, the second workpiece sample was then cooled to room temperature in an endogas-containing gas atmosphere.
- ammonia ammonia
- the comparison of the micrographs shown in the drawing shows that the 1, structure of the first produced by conventional nitriding Workpiece sample in the range from 0 ⁇ m to 40 ⁇ m from the edge uneven nitriding layer, while that after the last Methodically generated nitriding layer of the second workpiece sample is evenly formed.
- Iron materials such as stainless steels
- their high corrosion resistance is inextricably linked to surface passivation, on proportionate achieve better treatment results in a simple way.
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)
Description
- Fig. 1
- ein das Gefüge einer Werkstückprobe nach einer konventionellen Nitrierbehandlung zeigendes Schliffbild und
- Fig. 2
- ein Fig. 1 entsprechendes Schliffbild einer nach dem erfindungsgemäßen Verfahren behandelten Werkstückprobe.
Claims (7)
- Verfahren zur Wärmebehandlung metallischer Werkstücke, insbesondere zum Nitrieren oder Nitrocarburieren von legierten Eisenwerkstoffen, bestehend aus folgenden Verfahrensschritten:a) Erwärmen der Werkstücke in einem Nitrierofen auf eine Temperatur zwischen 400 °C und 500 °C in einer ammoniakhaltigen Gasatmosphäre;b) fortgesetztes Erwärmen der Werkstücke auf eine Temperatur zwischen 500 °C und 700 °C in einer Ammoniak und ein zugesetztes Oxidationsmittel enthaltenden Gasatmosphäre;c) Halten der Werkstücke bei dieser Temperatur und in dieser Gasatmosphäre für eine Zeitdauer zwischen 0,1 h und 5 h;d) fortgesetztes Halten der Werkstücke bei dieser Temperatur für eine Zeitdauer zwischen 1 h und 100 h in einer Ammoniak oder Ammoniak und einen kohlenstoffabgebenden Stoff enthaltenden Gasatmosphäre unde) Abkühlen der Werkstücke auf Raumtemperatur.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass als Oxidationsmittel Luft, Kohlendioxid (CO2), Wasserdampf (H2O)D oder Distickstoffoxid (N2O) zugesetzt werden.
- Verfahren nach Anspruch 2, gekennzeichnet durch ein Verhältnis der Mengen von Ammoniak und dem Oxidationsmittel in der Gasatmosphäre zwischen 1 : 1 und 5 : 1, wenn Luft als Oxidationsmittel eingesetzt wird, und zwischen 1 : 0,1 und 1 : 1, wenn Kohlendioxid, Wasserdampf oder Distickstoffoxid als Oxidationsmittel eingesetzt werden.
- Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Zeitdauer beim fortgesetzten Halten der Werkstücke in einer Ammoniak bzw. Ammoniak und den kohlenstoffabgebenden Stoff enthaltenden Gasatmosphäre in Abhängigkeit von der angestrebten Dicke der anzureichernden Randschicht gewählt wird.
- Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass als kohlenstoffabgebender Stoff Kohlendioxid, Kohlenmonooxid oder Kohlenwasserstoffe einzeln oder als Gemisch eingesetzt werden.
- Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Werkstücke in einer reduzierenden oder neutralen Gasatmosphäre, beispielsweise aus einem Endogas oder Stickstoff bestehend, oder in einem flüssigen Abschreckmedium auf Raumtemperatur abgekühlt werden.
- Verwendung einer Vorrichtung zur Durchführung des Verfahrens nach einem der Ansprüche 1 bis 6, bestehend aus einem Wärmebehandlungsofen mit einem beheizbaren, gasdichten Innenraum zum Nitrieren oder Nitrocarburieren von metallischen Werkstücken und mit einer Einrichtung zum dosierten Zugeben von Ammoniak, einem kohlenstoffabgebenden Stoff und einem Oxidationsmittel.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT00102359T ATE235581T1 (de) | 2000-02-04 | 2000-02-04 | Verfahren zum nitrieren und/oder nitrocarburieren von höher legierten stählen |
DE50001540T DE50001540D1 (de) | 2000-02-04 | 2000-02-04 | Verfahren zum Nitrieren und/oder Nitrocarburieren von höher legierten Stählen |
EP00102359A EP1122331B1 (de) | 2000-02-04 | 2000-02-04 | Verfahren zum Nitrieren und/oder Nitrocarburieren von höher legierten Stählen |
US09/562,695 US6328819B1 (en) | 2000-02-04 | 2000-04-28 | Method and use of an apparatus for the thermal treatment, in particular nitriding treatment, of metal workpieces |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00102359A EP1122331B1 (de) | 2000-02-04 | 2000-02-04 | Verfahren zum Nitrieren und/oder Nitrocarburieren von höher legierten Stählen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1122331A1 EP1122331A1 (de) | 2001-08-08 |
EP1122331B1 true EP1122331B1 (de) | 2003-03-26 |
Family
ID=8167773
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00102359A Expired - Lifetime EP1122331B1 (de) | 2000-02-04 | 2000-02-04 | Verfahren zum Nitrieren und/oder Nitrocarburieren von höher legierten Stählen |
Country Status (4)
Country | Link |
---|---|
US (1) | US6328819B1 (de) |
EP (1) | EP1122331B1 (de) |
AT (1) | ATE235581T1 (de) |
DE (1) | DE50001540D1 (de) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
DE102016221891A1 (de) | 2016-11-08 | 2018-05-09 | Robert Bosch Gmbh | Verfahren zur Wärmebehandlung eines aus einem hochlegierten Stahl bestehenden Werkstücks |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6929757B2 (en) * | 2003-08-25 | 2005-08-16 | General Motors Corporation | Oxidation-resistant magnetorheological fluid |
US7622197B2 (en) * | 2006-11-20 | 2009-11-24 | Ferroxy-Aled, Llc | Seasoned ferrous cookware |
ITMI20110366A1 (it) * | 2011-03-10 | 2012-09-11 | Sol Spa | Procedimento per il trattamento di acciai. |
RU2519356C2 (ru) * | 2012-05-24 | 2014-06-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский автомобильно-дорожный государственный технический университет (МАДИ)" | Способ циклического газового азотирования штампов из сталей для горячего деформирования |
CN104603319B (zh) * | 2012-06-26 | 2017-10-10 | 弗尔维奥 法布里佐·卡文娜 | 钢制零件的表面抗氧化处理的方法和设备 |
JP6930738B2 (ja) * | 2018-08-03 | 2021-09-01 | 錦見鋳造株式会社 | 調理器具の製造方法 |
WO2021037753A1 (en) | 2019-08-23 | 2021-03-04 | Elos Medtech Pinol A/S | Surface hardening for a dental implant |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1351234A (en) * | 1970-07-21 | 1974-04-24 | Nissan Motor | Process for forming a soft nitride layer in a metal surface |
DD119822A1 (de) * | 1975-06-20 | 1976-05-12 | ||
JPS52138027A (en) * | 1976-04-08 | 1977-11-17 | Nissan Motor | Ferrous member superior in initial fitting and wear resisting property and production process therefor |
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 |
JPS60215756A (ja) * | 1984-01-27 | 1985-10-29 | プロセダイン コ−ポレイシヨン | ステンレス鋼の硬化方法 |
US5037491A (en) * | 1986-02-28 | 1991-08-06 | Fox Patrick L | Shallow case hardening and corrosion inhibition process |
DE3718240C1 (de) * | 1987-05-30 | 1988-01-14 | Ewald Schwing | Verfahren zur Waermebehandlung von metallischen Werkstuecken in einer gasdurchstroemten Wirbelschicht |
DE4339404A1 (de) * | 1993-11-18 | 1995-05-24 | Ipsen Ind Int Gmbh | Verfahren zur Herstellung einheitlicher Oxidationsschichten auf metallischen Werkstücken und Vorrichtung zur Durchführung des Verfahrens |
-
2000
- 2000-02-04 EP EP00102359A patent/EP1122331B1/de not_active Expired - Lifetime
- 2000-02-04 AT AT00102359T patent/ATE235581T1/de active
- 2000-02-04 DE DE50001540T patent/DE50001540D1/de not_active Expired - Lifetime
- 2000-04-28 US US09/562,695 patent/US6328819B1/en not_active Expired - Lifetime
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
US9970093B2 (en) | 2013-12-16 | 2018-05-15 | Robert Bosch Gmbh | Method for gas carbonitriding |
US10281042B2 (en) | 2013-12-16 | 2019-05-07 | Robert Bosch Gmbh | Cylinder drum of a hydrostatic axial piston machine having a wear-resistant layer |
DE102016221891A1 (de) | 2016-11-08 | 2018-05-09 | Robert Bosch Gmbh | Verfahren zur Wärmebehandlung eines aus einem hochlegierten Stahl bestehenden Werkstücks |
WO2018086930A1 (de) | 2016-11-08 | 2018-05-17 | Robert Bosch Gmbh | Verfahren zur wärmebehandlung eines aus einem hochlegierten stahl bestehenden werkstücks |
Also Published As
Publication number | Publication date |
---|---|
ATE235581T1 (de) | 2003-04-15 |
US6328819B1 (en) | 2001-12-11 |
EP1122331A1 (de) | 2001-08-08 |
DE50001540D1 (de) | 2003-04-30 |
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