EP2376663B1 - Verfahren zur herstellung einer gasatmosphäre zur behandlung von metallen - Google Patents

Verfahren zur herstellung einer gasatmosphäre zur behandlung von metallen Download PDF

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Publication number
EP2376663B1
EP2376663B1 EP09797083.4A EP09797083A EP2376663B1 EP 2376663 B1 EP2376663 B1 EP 2376663B1 EP 09797083 A EP09797083 A EP 09797083A EP 2376663 B1 EP2376663 B1 EP 2376663B1
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EP
European Patent Office
Prior art keywords
atmosphere
furnace
ethanol
nitrogen
mixture
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.)
Active
Application number
EP09797083.4A
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English (en)
French (fr)
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EP2376663A1 (de
Inventor
Florent Chaffotte
Didier Domergue
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.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Publication date
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Priority to PL09797083T priority Critical patent/PL2376663T3/pl
Publication of EP2376663A1 publication Critical patent/EP2376663A1/de
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Publication of EP2376663B1 publication Critical patent/EP2376663B1/de
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Classifications

    • 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
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/76—Adjusting the composition of the atmosphere
    • 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
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • 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
    • C23C8/20—Carburising
    • 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
    • C23C8/20—Carburising
    • C23C8/22—Carburising 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
    • C23C8/28—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
    • 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 present invention relates to the field of heat treatment of metal parts.
  • One of the objectives of the present invention is to propose a novel method of providing an atmosphere to be injected in furnaces intended for the heat or thermochemical treatment of metal parts.
  • the atmospheres targeted by the present invention must make it possible on the one hand to avoid decarburization and oxidation of the parts, but on the other hand to be able to enrich the carbon parts (carburizing and carbonitriding processes). Finally, this atmosphere must be produced in economic conditions, safe, and easy to handle.
  • the heat treatment atmospheres meeting the above criteria generally contain, as major components of nitrogen, which has a neutral role with respect to the treatments mentioned above, hydrogen which protects against oxidation, and carbon monoxide. carbon that both protects against oxidation and decarburization and allows if necessary to achieve a carbon enrichment (cementation). These atmospheres also contain minor components such as CO 2 and water or CH 4 .
  • the atmosphere can also be enriched with hydrocarbons (natural gas, propane, etc.) in order to influence the chemical equilibrium.
  • these atmospheres can be produced by so-called "endothermic generators". These generators produce the atmosphere from a reaction between air and a fuel (usually natural gas), a reaction occurring in a catalytic reactor heated to a temperature of the order of 1000 ° C. This type of atmosphere typically contains as major components 40% nitrogen (N2), 40% hydrogen (H2), and 20% carbon monoxide (CO). Atmospheres produced by an endothermic generator are known and used for many years, but have the disadvantage of requiring for the user the investment of a dedicated production machine. In addition, the use of an endothermic generator is often not very flexible. The production capacity generally adapts with difficulty to the real need and it is then necessary to continuously produce a flow rate higher than the required flow.
  • the contents of the various constituents of the mixture are fixed by the reaction occurring in the catalytic reactor: if it remains possible to reduce the contents of H 2 and CO by dilution with nitrogen (process commonly known as “endo diluted "), it is however not industrially feasible to increase the contents of CO and H 2 beyond 20% and 40% respectively. Indeed, to increase the majority contents it is necessary to increase the oxygen content at the expense of nitrogen, which poses problems of safety and holding materials.
  • the mixture thus formed contains twice as much hydrogen as CO.
  • Atmospheres formed from nitrogen and methanol thus allow in particular to synthesize an atmosphere identical to that produced by an endothermic generator. It is also possible, according to the ratio of nitrogen and methanol, to obtain an atmosphere richer in H 2 and CO. These atmospheres will allow in particular to achieve faster cementation treatments.
  • the inconvenients The main reasons for this solution are, firstly, its cost, which is mainly related to the prices of methanol, and secondly the toxicity of the latter, but also concerns the fact that this process is nowadays limited in speed. treatment compared to technological breakthrough processes such as low pressure carburizing.
  • the cracking reaction of methanol is highly endothermic which results in a significant energy consumption and the formation of cold zones in the furnaces.
  • the carbon potential is therefore characteristic of the equilibrium that can be made between the part and the atmosphere, and the coefficient ⁇ characterizes the speed with which this equilibrium can be reached.
  • An atmosphere containing 50% CO and 50% H2 especially makes it possible to maximize the ⁇ carbon transfer coefficient.
  • EP0953654 A1 proposes a method of generating a carburizing atmosphere with a mixture comprising gaseous CO and ethanol injected at high temperature but does not disclose the atmosphere used at temperatures up to 800oC.
  • the present invention proposes a new process for producing an atmosphere of the type referred to above (to avoid decarburization and oxidation of the parts while being able to enrich the carbon parts), this in direct injection into the furnace of a mixture comprising carbon dioxide and ethanol, optionally supplemented with nitrogen, while injecting CO 2 alone or optionally mixed with nitrogen in the or the phases of the treatment cycle or the zone or zones of the oven whose temperature is below 750oC.
  • This mixture can possibly be enriched with additional species to control the chemical equilibrium in the atmosphere (hydrocarbons, air ).
  • the atmosphere can optionally be enriched with ammonia for the carbonitriding processes.
  • One of the advantageous characteristics of the invention lies, however, in the possibility of using only CO 2 and ethanol to control these chemical equilibria, where the conventional generator or synthesis atmospheres require additions of air and fuel. hydrocarbon. Depending on the CO 2 / ethanol ratio, the residual CO 2 content will be higher or lower, which directly conditions the carbon potential of the atmosphere.
  • the components intended for the synthesis of the atmosphere can for example be injected using injection equipment already known for the implementation of nitrogen-methanol atmospheres.
  • Ethanol can also be vaporized upstream of the injection of the furnace in order to be injected in gaseous form in a mixture with the other gaseous species.
  • ethanol can be introduced directly into the liquid phase in the oven chamber (for example deposited in a cup) so that it vaporizes under the effect of the oven temperature and can thus react with the gaseous species introduced separately into the furnace enclosure.
  • the injection is carried out during a treatment phase or in an oven zone at a temperature greater than 750 ° C, and even more preferably whose temperature is in the range of 850 ° C to 1000 ° C.
  • the present invention thus relates to a method for generating an atmosphere for the heat treatment of metal parts in an oven, according to which the introduction, in at least one phase of the treatment cycle or at least one zone of the furnace of heat treatment of a mixture comprising gaseous CO 2 and ethanol in the form of fine droplets or of steam, so as to carry out inside the furnace the reaction between the CO 2 and the ethanol to form a mixture of hydrogen and CO according to the reaction: CO 2 + C 2 H 5 OH ⁇ 3 CO + 3 H 2 .
  • the injection is carried out in a phase of the treatment cycle or an area of the heat treatment furnace whose temperature is greater than 750 ° C, and even more preferably in the range of 850 ° C to 1000 ° C, while injecting into the phase or phases of the treatment cycle or the zone or zones of the oven whose temperature is below 750 ° C, CO 2 alone or optionally mixed with nitrogen.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Furnace Details (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (4)

  1. Verfahren zur Erzeugung einer Atmosphäre, die für die Wärmebehandlung von Metallteilen in einem Ofen bestimmt ist, bei dem das Einbringen eines Gemisches, das gasförmiges CO2 und Ethanol in Form von feinen Tröpfchen oder Dampf beinhaltet, in mindestens eine Phase des Behandlungszyklus oder mindestens eine Zone des Wärmebehandlungsofens vorgenommen wird, so dass die Reaktion zwischen CO2 und Ethanol innerhalb des Ofens durchgeführt wird, um ein Gemisch aus Wasserstoff und CO gemäß der Reaktion zu bilden:

            CO2 + C2H5OH → 3 CO + 3 H2

    und dadurch gekennzeichnet, dass das Einspritzen in eine Phase des Behandlungszyklus oder eine Zone des Wärmebehandlungsofens durchgeführt wird, deren Temperatur höher als 750 °C ist, während in die Phase(n) des Behandlungszyklus oder in die Zone(n) des Ofens, deren Temperatur niedriger als 750 °C ist, CO2 allein oder gegebenenfalls mit Stickstoff gemischt eingespritzt wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das in eine Phase des Behandlungszyklus oder eine Zone des Wärmebehandlungsofens, deren Temperatur höher als 750 °C ist, eingespritzte Gemisch auch gasförmigen Stickstoff beinhaltet.
  3. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Ethanol vor dem Einspritzen in den Ofen erwärmt und/oder verdampft wird.
  4. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Einspritzen des Gemisches, das gasförmiges CO2 und Ethanol in Form von feinen Tröpfchen oder Dampf beinhaltet, in eine Phase des Behandlungszyklus oder eine Zone des Wärmebehandlungsofens durchgeführt wird, deren Temperatur im Bereich von 850 °C bis 1000 °C liegt.
EP09797083.4A 2008-12-09 2009-11-25 Verfahren zur herstellung einer gasatmosphäre zur behandlung von metallen Active EP2376663B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL09797083T PL2376663T3 (pl) 2008-12-09 2009-11-25 Sposób wytwarzania atmosfery gazowej do obróbki metali

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0858379A FR2939448B1 (fr) 2008-12-09 2008-12-09 Procede de production d'une atmosphere gazeuse pour le traitement des metaux.
PCT/FR2009/052290 WO2010066979A1 (fr) 2008-12-09 2009-11-25 Procede de production d'une atmosphere gazeuse pour le traitement des metaux

Publications (2)

Publication Number Publication Date
EP2376663A1 EP2376663A1 (de) 2011-10-19
EP2376663B1 true EP2376663B1 (de) 2019-01-02

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EP09797083.4A Active EP2376663B1 (de) 2008-12-09 2009-11-25 Verfahren zur herstellung einer gasatmosphäre zur behandlung von metallen

Country Status (10)

Country Link
US (1) US8679264B2 (de)
EP (1) EP2376663B1 (de)
JP (1) JP5529158B2 (de)
DK (1) DK2376663T3 (de)
ES (1) ES2715925T3 (de)
FR (1) FR2939448B1 (de)
PL (1) PL2376663T3 (de)
PT (1) PT2376663T (de)
TR (1) TR201903521T4 (de)
WO (1) WO2010066979A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2985508B1 (fr) * 2012-01-06 2015-05-01 Air Liquide Procede de generation d'un melange de gaz contenant du monoxyde de carbone et de l'hydrogene en proportions sensiblement egales
EP3243585A1 (de) * 2016-05-13 2017-11-15 Linde Aktiengesellschaft Verfahren und vorrichtung zum kodieren bei der wärmebehandlung eines bauteils sowie ein kodierungsgas zum kodieren von bauteilen bei der wärmebehandlung eines bauteils

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2037816B (en) * 1978-11-30 1982-10-27 Boc Ltd Heat treatment method
US4306919A (en) * 1980-09-04 1981-12-22 Union Carbide Corporation Process for carburizing steel
BR8504616A (pt) * 1985-09-20 1987-04-28 Aichelin Ind E Comercio De For Processo para o enriquecimento da atmosfera de fornos de tratamentos termoquimicos de pecas metalicas
US5221369A (en) * 1991-07-08 1993-06-22 Air Products And Chemicals, Inc. In-situ generation of heat treating atmospheres using non-cryogenically produced nitrogen
DE4340060C1 (de) * 1993-11-24 1995-04-20 Linde Ag Verfahren zum Gasaufkohlen
JP3505690B2 (ja) * 1994-08-18 2004-03-08 関東冶金工業株式会社 金属の加熱処理方法
JP3409236B2 (ja) * 1997-02-18 2003-05-26 同和鉱業株式会社 熱処理炉の雰囲気制御方法
DE19819042A1 (de) * 1998-04-28 1999-11-04 Linde Ag Verfahren und Anlage zum Gasaufkohlen
JP3531736B2 (ja) * 2001-01-19 2004-05-31 オリエンタルエンヂニアリング株式会社 浸炭方法及び浸炭装置

Non-Patent Citations (1)

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Title
None *

Also Published As

Publication number Publication date
FR2939448B1 (fr) 2011-05-06
DK2376663T3 (en) 2019-04-08
PT2376663T (pt) 2019-04-01
TR201903521T4 (tr) 2019-04-22
US20110272637A1 (en) 2011-11-10
PL2376663T3 (pl) 2019-07-31
ES2715925T3 (es) 2019-06-07
US8679264B2 (en) 2014-03-25
EP2376663A1 (de) 2011-10-19
JP2012511633A (ja) 2012-05-24
FR2939448A1 (fr) 2010-06-11
JP5529158B2 (ja) 2014-06-25
WO2010066979A1 (fr) 2010-06-17

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