EP3109339B1 - Behandlungsverfahren eines werkstücks aus tantal oder einer tantallegierung - Google Patents

Behandlungsverfahren eines werkstücks aus tantal oder einer tantallegierung Download PDF

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Publication number
EP3109339B1
EP3109339B1 EP16175631.7A EP16175631A EP3109339B1 EP 3109339 B1 EP3109339 B1 EP 3109339B1 EP 16175631 A EP16175631 A EP 16175631A EP 3109339 B1 EP3109339 B1 EP 3109339B1
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EP
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Prior art keywords
carbon
piece
tantalum
furnace
layer
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English (en)
French (fr)
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EP3109339A1 (de
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Dominique COTTON
Sébastien FAURE
Philippe Jacquet
Vincent VIGNAL
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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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
    • C23C8/08—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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02—Alloys based on vanadium, niobium, or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • 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
    • 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
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • 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
    • C23C8/02—Pretreatment of the material to be coated
    • 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
    • C23C8/80—After-treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D19/00—Arrangements of controlling devices
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D7/00—Forming, maintaining, or circulating atmospheres in heating chambers
    • F27D7/06—Forming or maintaining special atmospheres or vacuum within heating chambers
    • F27D2007/066—Vacuum
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D9/00—Cooling of furnaces or of charges therein
    • F27D2009/007—Cooling of charges therein
    • F27D2009/0081—Cooling of charges therein the cooling medium being a fluid (other than a gas in direct or indirect contact with the charge)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D19/00—Arrangements of controlling devices
    • F27D2019/0028—Regulation
    • F27D2019/0031—Regulation through control of the flow of the exhaust gases
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D19/00—Arrangements of controlling devices
    • F27D2019/0028—Regulation
    • F27D2019/0056—Regulation involving cooling
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D19/00—Arrangements of controlling devices
    • F27D2019/0028—Regulation
    • F27D2019/0075—Regulation of the charge quantity

Definitions

  • the present invention relates to the treatment by cementation of a metal piece made of tantalum or tantalum alloy, in order to make it more mechanically and chemically resistant.
  • the process according to the invention makes it possible to form on the surface of a tantalum or tantalum alloy part one or more layers of tantalum carbide, by controlling their structures and their thicknesses.
  • Tantalum is a material that is extremely resistant to corrosion and has a very high melting point (melting point ⁇ 3000 ° C).
  • the tantalum or tantalum alloy parts are therefore used in many fields and in particular for the manufacture of crucibles for use in pyrochemistry.
  • thermochemical treatment which consists in increasing the surface carbon content of the part.
  • Subsequent treatment (chemical, mechanical or thermal) can then be implemented to obtain a particular surface microstructure.
  • cementation the part to be cemented is put directly in contact with solid carbon. Once sublimed, the carbon becomes gaseous solid will be adsorbed on the surface of the room, then spread in the room to react with tantalum.
  • This case cementation method requires a sufficiently high carbon vapor pressure for the tantalum to be cemented properly, which requires very high carburization temperatures (> 2000 ° C) and a long heating time (for example 10h at 1700 ° C in the document [1] ).
  • this method requires pressing carbon powder on the surface of the part to be cemented and is therefore not applicable to parts having a complex geometry.
  • the carbon contribution on the surface is heterogeneous.
  • Controlled atmosphere carburizing consists in placing the part to be cemented in a controlled atmosphere furnace, heating the furnace to a carburising temperature (> 1200 ° C for tantalum), then injecting under a pressure of approximately 1 bar a mixture of inert gas (argon) and fuel gas (in general, a hydrocarbon such as methane, acetylene, propane, etc.). In some applications, an air / methanol or nitrogen / methanol mixture may also be employed. The fuel molecules then come to crack on the surface of the part to be cementized and release their carbon, which diffuses then reacts with surface tantalum.
  • This method of carburizing however, has the disadvantage of generating oxides when an oxygenated compound is injected.
  • a hydrocarbon it is common that soot form inside the enclosure of the furnace, polluting it and disrupting the cementation of the room.
  • Cementation under reduced pressure involves placing the part to be cemented in a thermochemical treatment furnace and then evacuating the furnace chamber. The chamber is then heated until the carburising temperature is reached, and then a gaseous hydrocarbon (methane, acetylene, propane, etc.) is injected under a low pressure (that is to say a pressure of less than 100 mbar). from a few millibars to a few tens millibars).
  • a gaseous hydrocarbon methane, acetylene, propane, etc.
  • plasma-assisted cementation is very close to carburizing under reduced pressure.
  • the main interest of this technique lies in the creation of a plasma around the room to be cementer. This plasma activates the surface of the material and thus facilitates the diffusion of carbon in the room.
  • This method is useful for the cementation of very complex geometry parts.
  • it remains undeveloped compared to carburizing under reduced pressure because it requires the use of very specific equipment.
  • One of these main drawbacks is that it does not make it possible to treat parts having singularities such as holes of small diameters, these singularities being able to generate a hollow cathode phenomenon (local melting inside the hole).
  • the bearing face of the parts on the basket of the treatment furnace is never treated, since it is never in direct contact with the plasma.
  • chemical surface treatment can be carried out by acid etching.
  • a surface chemical treatment is described in document [1] .
  • the disadvantage of surface chemical treatments is that they modify the surface condition of the parts and are difficult to implement because of the properties of high hardness and high chemical inertness of carbides vis-à-vis acids. It is therefore necessary to use very powerful acid mixtures (the most common being a mixture of nitric, hydrofluoric and lactic acids), which are generally toxic and very dangerous to use.
  • the etching will attack all of the carbide layers (TaC layer and underlying Ta 2 C layer) and not only the TaC surface layer, leaving only the layer having a saturated tantalum structure. carbon with Ta 2 C at the grain boundaries.
  • the invention aims to at least partially solve the problems encountered in the solutions of the prior art.
  • the diffusion in step e) causes the decomposition of all or some of the carbides present in the layer C1.
  • the tantalum carbide TaC of the layer C1 will be decomposed mainly tantalum carbide Ta 2 C, then tantalum tantalum carbon having Ta 2 C grain boundaries.
  • the surface of the part (the so-called “surface layer” below) is free of tantalum carbide of the TaC type, but, as the decomposition begins near the surface, the thickness of this superficial layer can correspond to the thickness of the layer C1 of the carbonaceous multilayer or to an upper part of the layer C1.
  • the layer Ta sat. C + Ta 2 C can also be a Ta sat layer. C, if the degree of carbon saturation of the tantalum layer is lower.
  • the process described does not make it possible to obtain complex multilayer structures of the "low carbon / high carbon layer / low carbon layer" type on a tantalum or tantalum alloy core, as for example those illustrated in FIG. in the figures 5b and 6b hereinafter (that is Ta 2 C / TaC / Ta 2 C / Ta sat C + Ta 2 C / core and Ta sat C + Ta 2 C / Ta 2 C / Ta sat C + Ta 2 C / heart).
  • a tantalum alloy corresponds to an alloy comprising at least 90% by weight of tantalum. Furthermore, it it is a metal alloy, that is to say a mixture of tantalum with another metal. It may for example be a TaW alloy.
  • step b) comprises injecting, preferably continuously, the carbonaceous gas source into the furnace at a flow rate of between 1 and 100 Lh -1 and, preferably, at a lower injection pressure. or equal to 10 mbar.
  • the duration of the injection is a function of the amount of carbon that it is desired to introduce into the peripheral part of the tantalum or tantalum alloy part. This time depends on the injection parameters of the carbon source, the surface of the part, as well as the thickness and type of carbon multilayer that is desired.
  • the injection of the gaseous carbon source in step b) is carried out at an injection pressure of 5 mbar for a flow rate of 20 Lh -1 and in a furnace heated to a temperature of 1600 ° C.
  • the gaseous carbon source used in step b) is ethylene.
  • ethylene has the advantage of allowing a low carbon input and limiting the formation of any soot occurring during the use of higher carbon gases, such as acetylene for example.
  • Step c) is intended to stop the formation of the carbonaceous multilayer; in other words, we seek by this step to stop the carbon contribution in the room.
  • step c) comprises an injection of nitrogen gas into the oven at a pressure of 1 bar, which makes it possible to obtain rapid cooling of the part.
  • Step e) comprises heating the room to a temperature sufficient to allow the diffusion of the carbon present in the layer C1 of the carbonaceous multilayer in the direction of the layers C2 and C3.
  • step e) comprises heating the oven to a temperature of 1600 ° C and a pressure of 10 -2 mbar.
  • step f) the cooling is carried out under vacuum in order to protect the tantalum or tantalum alloy part from any traces of residual pollution of the furnace which could be drawn towards the part if a refurbishment was carried out. high temperature oven pressure.
  • the carbon input in the peripheral part of the part is controlled and mastered, since it comes solely from the gaseous carbon source used during step b) of the process which is the subject of the invention the carbon supply is then prevented by steps c) and d) of the process.
  • the carbon supply is then prevented by steps c) and d) of the process.
  • steps a) and b) of the process makes it possible to work at a lower temperature than with other known cementation methods, and the control of the carbon input. allows optimize processing times, which ultimately saves time, energy and consumables.
  • Hard-to-use chemicals are not used to remove TaC-type tantalum carbide from the surface layer of the part and there is no oxygen and nitrogen pollution in the treated part .
  • the method which is the subject of the invention can be used to process parts having complex geometries and / or having singularities (holes of small diameters, etc.).
  • the method which is the subject of the invention makes it possible to control the cementation of a tantalum or tantalum alloy part, while choosing the nature and the crystallographic structure of the surface layer of the part. It makes it possible to obtain, at the surface of the part, a surface layer of tantalum carbide of Ta 2 C type with an underlying layer of tantalum carbide of the TaC type or of carbon-saturated tantalum with Ta 2 C at the grain boundaries, a mixed surface layer of tantalum saturated with carbon with Ta 2 C at grain boundaries, or even a superficial layer of carbon-saturated tantalum with an underlying Ta 2 C-type tantalum carbide layer, while controlling the thickness of this superficial layer.
  • the duration of the heating in step b) of the method that is the subject of the invention depends on the amount of carbon that it is desired to bring to the part.
  • the duration of the heating in step e) is, in turn, depending on the nature of the layer that is desired to obtain on the surface, as well as the thickness that it is desired that it has.
  • a tantalum piece for example a crucible having a diameter of 100 mm, is used for a thickness of 1.5 mm and a height of 150 mm.
  • the part to be treated is installed in the enclosure of an oven, for example a furnace of mark BMI bearing the reference BMICRO.
  • the oven chamber is evacuated until a pressure of 10 -2 ⁇ 0.01 mbar is reached.
  • the enclosure After stabilization of the pressure, the enclosure is heated with a ramp of 30 ° C / min, until reaching 1600 ° C ⁇ 1%.
  • the work is then cemented by injecting into the chamber a fuel gas under a low pressure (pressure less than about ten millibars) for a predetermined period.
  • ethylene is injected (C 2 H 6) in the enclosure under a pressure of 5 ⁇ 1 mbar and at a controlled flow rate of 20 L / h for 1 hour.
  • the part is then cooled, for example by means of nitrogen injected into the chamber of the oven at a pressure of 1 bar for a period of 90 minutes.
  • a carbon-based multilayer 1 comprising a surface layer C1 of tantalum carbide of the TaC type, an underlying layer C2 of tantalum carbide of Ta 2 C type and a layer under C3 in carbon-saturated tantalum with precipitates of Ta 2 C at the grain boundaries ( Figures 1a and 1b ).
  • tantalum is a very hot reactive element vis-à-vis atoms such as carbon, oxygen and nitrogen and these elements can for example be in molecules adsorbed on the walls of the oven enclosure.
  • the piece is placed in a cavity (for example formed by depositing a bell on a support, the bell and the support being both in tantalum) which is placed in the oven enclosure.
  • a cavity for example formed by depositing a bell on a support, the bell and the support being both in tantalum
  • polluting elements O, N 2 , etc.
  • any carbon atoms present on the walls of the furnace enclosure before they come into contact with the room.
  • This also makes it possible to slow gas exchange between the furnace chamber and the workpiece, which is favorable for the carbon diffusion process.
  • a double pumping of the furnace enclosure may optionally be carried out by performing an intermediate purge with nitrogen (pressure of 10 -2 +/- 0.01 mbar) in order to evacuate any pollutant.
  • step e will allow the carbon present in the layer C1 of the carbonaceous multilayer 1 to diffuse to the layers C2 and C3 of the multilayer.
  • the assembly formed by the part and the protective device (cavity) is heated at 30 ° C / minute until the desired treatment temperature.
  • the tantalum piece had on the surface a carbonaceous multilayer 1 having a surface layer C1 in TaC, an underlying layer C2 in Ta 2 C and an underlying layer C3 in carbon saturated tantalum with precipitates of Ta 2 C at the grain boundaries.
  • the carbon diffuses from the surface layer C1 to TaC (the layer richest in carbon) towards the layer C2 in Ta 2 C, and from the layer C2 in Ta 2 C to the layer C3 in your sat. C + Ta 2 C. This cascade carbon diffusion causes the reduction in thickness of the layer of TaC the benefit of the Ta layer 2 C.
  • step b) Different structures that can be obtained by varying the duration of the heating in step b) and / or step e) are illustrated in the following figures.
  • a carbonaceous multilayer 1 having a layer C1 in TaC, a layer C2 in Ta 2 C and a layer is obtained.
  • C3 in Ta sat. C + Ta 2 C ( Figures 1a and 1b ).
  • a surface layer 2 is obtained in Ta 2 C on an underlying layer 3 in Ta sat. C + Ta 2 C ( Figures 3a and 3b ).
  • the part provided with the carbonaceous multilayer is subjected to vacuum heating for 6 h at 1600 ° C. in step e), a carbon-saturated tantalum layer 2 with Ta 2 C precipitates is obtained. at the grain boundaries ( Figures 4a, 4b and 4c , the precipitates being visible in black on the figure 4c ).
  • the carbon diffusion is such that the layers C1, C2 and C3 of the carbonaceous multilayer are transformed into the surface layer 2.
  • step b) if the piece is subjected to carburization by heating under vacuum at 1600 ° C. for 2 hours in step b) and heating under vacuum at 1600 ° C. for 30 minutes in step e) a part having a surface layer 2 in Ta 2 C, a first sub-layer 3 in TaC, a second sub-layer 4 in Ta 2 C and a third sub-layer 5 in Ta sat are obtained.
  • C + Ta 2 C Figures 5a and 5b ).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Chemical Vapour Deposition (AREA)

Claims (7)

  1. Verfahren zur Bearbeitung eines Werkstücks aus Tantal oder aus einer Tantallegierung, umfassend die folgenden Schritte:
    a) Platzieren des Werkstücks in einem Ofen und Heizen des Ofens unter Vakuum auf eine Temperatur von wenigstens gleich 1400°C;
    b) Bilden einer Kohlenstoff-Vielfachschicht (1) in dem Umfangsbereich des Werkstücks durch Injizieren einer gasförmigen Kohlenstoffquelle bei einem Druck von höchstens gleich 10 mbar in den geheizten Ofen, wobei die Kohlenstoff-Vielfachschicht wenigstens eine Schicht C1 aus Tantalkarbid umfasst, die an der Oberfläche des Werkstücks gelegen ist, sowie zwei darunter liegende Schichten C2 und C3, die jeweils einen Kohlenstoffgehalt aufweisen, der verschieden von und kleiner als der Kohlenstoffgehalt der Schicht C1 ist;
    c) Anhalten der Bildung der Kohlenstoff-Vielfachschicht (1) durch Kühlen des Werkstücks;
    d) Platzieren, um das Werkstück herum, einer Vorrichtung, die dazu ausgelegt ist, Kohlenstoff, Sauerstoff und Stickstoff einzufangen, um das Werkstück vor dem Kohlenstoff sowie eventuellen Spuren von Sauerstoff und Stickstoff zu schützen, die in dem Ofen vorhanden sind;
    e) Herbeiführen der Diffusion des gesamten oder eines Teils des Kohlenstoffs, der in der Schicht C1 vorhanden ist, in Richtung der Schichten C2 und C3 durch Heizen des Ofens unter Vakuum, wobei das Werkstück in der Schutzvorrichtung gehalten wird; und
    f) Anhalten der Diffusion des Kohlenstoffs in dem Werkstück durch Kühlen des Werkstücks unter Vakuum, bevor der in der Kohlenstoff-Vielfachschicht vorhandene Kohlenstoff den zentralen Bereich des Werkstücks erreicht;
    wodurch man ein Werkstück erhält, dessen Oberfläche frei von Tantal in der Form TaC ist, dessen zentraler Bereich frei von Kohlenstoff ist, und dessen zwischen der Oberfläche und dem zentralen Bereich gelegene Bereich Tantal und Kohlenstoff umfasst.
  2. Verfahren nach Anspruch 1, bei dem der Schritt d) die folgenden Operationen umfasst:
    i) Platzieren des Werkstücks in einem geschlossenen Hohlraum, dessen Wände aus einem Material sind, das Kohlenstoff, Sauerstoff und Stickstoff anzieht, wobei das Material vorzugsweise aus Tantal ist; und
    ii) Säubern des Hohlraums mit Hilfe eines Inertgases derart, dass aus dem Ofen jedes Gas abgeleitet wird, das wenigstens eines der atomaren Elemente enthalten kann, die ausgewählt sind aus Kohlenstoff, Sauerstoff und Stickstoff.
  3. Verfahren nach Anspruch 1 oder Anspruch 2, bei dem der Schritt a) die folgenden Operationen umfasst:
    i) Einsetzen des Werkstücks in den Ofen;
    ii) Evakuieren des Ofens; und
    iii) allmähliches Heizen des Ofens, bis eine Arbeitstemperatur erreicht wird, die zwischen 1500 und 1700°C enthalten ist.
  4. Verfahren nach einem der Ansprüche 1 bis 3, bei dem der Schritt b) das Injizieren der gasförmigen Kohlenstoffquelle in den Ofen mit einer Rate umfasst, die zwischen 1 und 100 L.h-1 enthalten ist und bei einem Injektionsdruck, der kleiner oder gleich 10 mbar ist.
  5. Verfahren nach Anspruch 4, bei dem das Injizieren der gasförmigen Kohlenstoffquelle im Schritt b) bei einem Injektionsdruck von 5 mbar für eine Rate von 20 L.h-1 und in einem Ofen realisiert wird, der auf eine Temperatur von 1600°C geheizt ist.
  6. Verfahren nach einem der Ansprüche 1 bis 5, bei dem der Schritt e) das Heizen des Ofens auf eine Temperatur von 1600°C und bei einem Druck von 10-2 mbar umfasst.
  7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem die gasförmige Kohlenstoffquelle, die im Schritt b) verwendet wird, Ethylen ist.
EP16175631.7A 2015-06-25 2016-06-22 Behandlungsverfahren eines werkstücks aus tantal oder einer tantallegierung Active EP3109339B1 (de)

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CN107164678B (zh) * 2017-04-26 2018-10-02 北京有色金属研究总院 一种高温化学容器用钽材料及其制备方法
CN112159952B (zh) * 2020-10-10 2022-07-12 哈尔滨科友半导体产业装备与技术研究院有限公司 一种能同时碳化多个钽片的装置及方法

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FR3037971B1 (fr) 2017-07-21
JP6803156B2 (ja) 2020-12-23
US10287667B2 (en) 2019-05-14
US20160376692A1 (en) 2016-12-29
EP3109339A1 (de) 2016-12-28
JP2017088998A (ja) 2017-05-25
FR3037971A1 (fr) 2016-12-30
KR20170001636A (ko) 2017-01-04

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