EP1743952A1 - Verfahren zur Behandlung von Teilen aus Titan oder Titanlegierungen - Google Patents

Verfahren zur Behandlung von Teilen aus Titan oder Titanlegierungen Download PDF

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Publication number
EP1743952A1
EP1743952A1 EP20060290963 EP06290963A EP1743952A1 EP 1743952 A1 EP1743952 A1 EP 1743952A1 EP 20060290963 EP20060290963 EP 20060290963 EP 06290963 A EP06290963 A EP 06290963A EP 1743952 A1 EP1743952 A1 EP 1743952A1
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EP
European Patent Office
Prior art keywords
treatment
parts
container
nitrogen
species
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EP20060290963
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English (en)
French (fr)
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EP1743952B1 (de
Inventor
Jean Paul Lebrun
Laurent Poirier
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Nitruvid SA
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Nitruvid SA
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Priority to PL06290963T priority Critical patent/PL1743952T3/pl
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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
    • C23C8/36—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 using ionised gases, e.g. ionitriding

Definitions

  • the present invention relates to a method of surface treatment of a titanium or titanium alloy part.
  • Titanium or titanium alloy parts intended to harden the surface of these parts in order to improve their service behavior, in particular their resistance to wear or their resistance to galling or any other property related to the contact of the surface with other media or other parts, are well known. These treatments consist in particular of ionic nitriding treatments of the parts.
  • the purpose of the ionic nitriding treatments is to form on the surface of titanium or titanium-based alloy parts, a layer highly enriched in nitrogen whose properties of use are adapted to the intended uses.
  • the titanium part or parts are arranged in a chamber containing a nitrogen-rich gas which is excited, for example by an electric discharge, so as to form a plasma containing nitrogen ions which react with the surface of the room and enrich it with nitrogen.
  • a nitrogen-rich gas which is excited, for example by an electric discharge, so as to form a plasma containing nitrogen ions which react with the surface of the room and enrich it with nitrogen.
  • Each piece is maintained at a temperature adapted so that the nitrogen can penetrate by diffusion inside thereof to a depth depending on the time during which it is subjected to contact with the plasma.
  • the nitriding treatment of titanium or titanium alloy parts leads to a coloration of these, depending on the chemical nature of the layer at the extreme surface. But this coloration is irregular, especially near any discontinuity of the surface of the pieces. Irregularities result in halo or edge effects that prohibit the use of this technique for appearance parts.
  • defects can be generated by a phenomenon called “hollow cathode”. This phenomenon results from the formation in the hollow parts of secondary electrons generated by ion bombardment, which generates new species. The result is a chain reaction that converts kinetic energy into caloric energy and can lead to melting of the part.
  • European EP 1 274 873 a process for treating a part, in particular a titanium or titanium-based alloy part, according to which the part or a set of parts is placed in a container closed by a lid leaving a small gap, which is itself disposed within a reaction chamber containing a gas in which reactive species are generated via, for example, a plasma or an electric discharge.
  • the container has a slot of sufficiently small thickness to prevent ignition of the plasma inside the container, but sufficiently wide to allow the diffusion through this slot of activated species.
  • the gases are specifically chosen so that the activated species formed deliver to the surface of the parts to be treated, two distinct elements selected from nitrogen, carbon, oxygen and boron.
  • an enriched hardened layer is obtained in two distinct interstitial elements taken from nitrogen, carbon, oxygen and boron.
  • hardened surfaces are produced by simultaneous enrichment of nitrogen and carbon.
  • This method has the advantage of making it possible to treat parts taken in bulk while having a very uniform treatment of the entire surface of the parts.
  • it has the disadvantage of not making it possible to obtain surface layers having hardnesses as high as those obtainable by a nitriding treatment of titanium or of a titanium alloy.
  • the object of the present invention is to remedy these drawbacks by proposing a means of hardening the surface of titanium or titanium-based alloy parts, in particular alloy of the Ti6Al4V, Ti6Al7Nb type, or alloy containing mainly niobium and a high proportion of titanium such as the Nb30Ti20W type alloy, or made of any other alloy of the same type, which allows to obtain surface hardnesses as good as those obtained by conventional ionic nitriding treatments, without the disadvantages of these treatments, while allowing uniform treatments to be obtained on the surfaces of the parts, and possibly making it possible to treat a set of loose parts without there being irregularities in the treatment of the parts, particularly in the contact zones of the parts which are in bulk.
  • the dilution gas is, for example, composed of hydrogen or argon or a mixture of hydrogen and argon.
  • the nitrogen-containing gas is, for example, molecular nitrogen or a gaseous derivative of nitrogen.
  • the gas contains activated species taken in particular from the ionized species N + and N 2 + and the neutral excited species, N, N 2 , NH and H.
  • the treatment temperature is adapted to allow diffusion of the nitrogen into the room and may be between 400 ° C and 1000 ° C, and preferably between 550 ° C and 850 ° C.
  • the temperature and nitrogen content of the treatment atmosphere can be adjusted so that the surface of the parts is constituted only a diffusion layer whose gray color is metallic close to that of the untreated alloy.
  • the temperature and nitrogen content of the process atmosphere can also be adjusted so that the surface of the parts is a diffusion layer and a gold-yellow combination layer.
  • the cooling of the part or parts, at the end of treatment is preferably carried out under vacuum.
  • the pressure of the gaseous medium is less than 100 mbar.
  • the container comprises at least one opening closed by means providing with the edge of the opening a clearance large enough to pass at least one active species, but low enough to prevent a plasma from entering the interior of the container .
  • the container is for example constituted by a box comprising a wall having at least one opening closed in a non-sealed manner by one of the following means: lid placed on the upper part of the wall forming the turn of the opening, plug engaged with play in the opening and support on which the returned box rests, according to the edge of the opening.
  • the container may itself be pierced with numerous interstices allowing the passage of activated species but prohibiting the ignition of the plasma inside thereof.
  • a plurality of pieces which are arranged in at least one container can be processed simultaneously.
  • At least one part may comprise at least one cavity having an opening dimension of between 0.01 mm and 1 mm, the surface of which comprises a layer hardened with nitrogen.
  • At least one part may consist of one of the following objects: screw, nut, ancillary, orthopedic implant, valve, connecting rod, motor segment, shaft, eyewear element, golf club, turbine parts, servo parts such as a bearing, tube, gear, watch elements, valve elements, plug, metal shutter, valve, piston, cylinder, pump part (centrifugal, paddle, gear, lobe), flow regulator part, piece of pressure regulator, solenoid valve part, pressurized nuclear reactor control cluster pencil, coil, blank.
  • the invention also relates to a titanium or titanium alloy piece obtainable by the method according to the invention, which comprises at least one surface hardened by nitrogen, said hardened surface having a golden yellow color or a metallic gray color similar to that of the untreated alloy, uniform without edge effects.
  • the part may comprise at least one cavity having an opening dimension of between 0.01 mm and 1 mm, the internal surface of the cavity being hardened with nitrogen.
  • the piece is, for example, for biomedical use.
  • the treatment method according to the invention is a method in which a part or a set of parts is placed in a closed container so as to leave small gaps allowing the passage of the activated species while preventing the ignition of a plasma through these interstices that are arranged in an atmosphere constituted a gas or a mixture of gases comprising the following elements, nitrogen and one or more elements selected from hydrogen and neutral elements such as argon or more generally noble gases. It should be noted that, especially when they are relatively large, the interstices can be lit but the plasma can not extend inside the container.
  • excited chemical species are created in the gas located outside the container, for example, by means of an electric discharge or by means of plasma generation processes. using microwaves or more generally electromagnetic waves.
  • the parts are heated to maintain them at a temperature which is a treatment temperature
  • the assembly is left for a time sufficient for the excited species to penetrate inside the container and react with the surface of the parts arranged at inside the container and form on the surface of these parts a cured layer having the desired thickness.
  • the gaseous atmosphere in which the active species are generated which are on the one hand ionized species such as N + and N 2 + ions and excited neutral species such as N, N 2 , NH and / or H, is constituted preferably a mixture of the nitrogen and dilution gas type, the dilution gas being either hydrogen or argon, or more generally a neutral gas or a mixture of all these gases.
  • the proportions of dilution gas are between 1% and 99%.
  • a nitriding treatment is obtained on the surface of titanium or titanium alloy parts having both hardnesses equivalent to those obtained by conventional ionic nitriding and the uniformity qualities of surface that is obtained by the treatments of the carbonitruration type made in containers.
  • the parts are heated either indirectly via the surface of the container which is itself heated, for example by means of the plasma, the surface of the container then heats the pieces by radiation, or by any means.
  • another auxiliary heating means disposed in the enclosure and / or the container.
  • cured layers of different natures are obtained.
  • a surface layer of nitrogen diffusion in titanium or in the titanium alloy is obtained, and in this case the surface of the pieces takes a nice gray uniform color.
  • a more complex layer is obtained comprising an outer layer, called a combination layer, consisting of a mixture of titanium nitride TiN-Ti 2 N, under which a nitrogen diffusion layer in titanium or titanium alloy.
  • the piece takes on a very characteristic yellow-gold color which, in the case of the process used, is evenly distributed over the surface of the part.
  • the temperature at which the parts must be maintained is a temperature which must be sufficient to allow the diffusion of nitrogen inside the titanium alloys and this temperature is preferably between 400 ° and 1000 °, and more preferably between 550 ° and 850 °. Indeed, beyond 850 ° the parts are likely to deform by creep and below 550 °, the diffusion may be insufficient. More precisely, the temperatures must be adapted on the one hand as a function of the nature of the layer that is to be obtained on the surface and, on the other hand, according to the nature of the alloy.
  • the gaseous atmosphere of the apparatus in which the treatment is carried out is maintained at a low pressure which makes it possible to ignite the plasma outside the container, this pressure is generally less than 100 mbar.
  • the parts when the treatment is complete, the parts must be cooled.
  • the atmosphere in which the treatment is carried out contains hydrogen, it is desirable to degas the hydrogen that could have been absorbed by the titanium parts during cooling, to prevent hydrogen reacts with titanium and forms titanium hydrides.
  • the parts are cooled after treatment under vacuum.
  • FIGS. 1 and 2 schematically represent equipment in which the treatment of parts is carried out.
  • the treatment plant is constituted by an oven enclosure 1, for example made in two parts 1a and 1b, separable from one another to carry out the loading of the oven and assembled in the oven. one to another with interposition of seals, so that the chamber 2 of the oven is substantially gastight, so as to prevent the entry of air into the oven, during the treatment.
  • the enclosure of the furnace can be evacuated and filled with a gaseous mixture such as N 2 + H 2 + Ar, for example via a discharge nozzle 3 'and a filling nozzle 3.
  • a gaseous mixture such as N 2 + H 2 + Ar
  • the enclosure 1 of the treatment furnace contains a support 4 on which parts can be arranged to be treated 5.
  • the support 4 is connected to a cathode terminal of an electrical generator 6 whose second anode terminal is electrically connected to the furnace enclosure 1.
  • the support 4 and the parts or containers 5 disposed on the support 4 are thus brought to a cathodic potential with respect to the enclosure 1 which is at an anode potential.
  • the generator 6 After carrying out the evacuation of the chamber 2 of the furnace 1 and its filling gas mixture N 2 + H 2 + Ar at a pressure less than 100 mbar, the generator 6 is put into operation so as to create a glow discharge abnormal between the cathode formed by the tray 4 and the containers 5 and the wall 1 of the treatment furnace.
  • Plasma is generated around the containers 5 in the glow discharge.
  • the discharge is controlled so as to produce activated species in the gaseous mixture and in particular the N, N 2 , NH excited neutral species characteristic of the implementation of the process of the invention in a gaseous mixture containing nitrogen.
  • the parts are further heated and their temperature is controlled throughout the duration of treatment, as will be described later.
  • the gases contained in the chamber 2 are also continuously renewed in order to regulate the pressure inside the chamber 2 and to constantly supply the nitrogen necessary to generate the activated species used during the treatment. treatment.
  • a plasma can not propagate through a gap whose opening dimension is smaller than a length called Debye length which depends in particular on the nature and pressure of the medium. gaseous plasma.
  • the Debye length is of the order of a few tenths of a millimeter.
  • the inventors have observed that, extremely surprisingly, in the case of a plasma obtained from a gaseous mixture containing nitrogen and hydrogen or neutral elements, the surface treatment of parts made of titanium or titanium alloy on surfaces not exposed to plasma and separated from the plasma area by a gap having an opening of a size not allowing the ignition of a plasma.
  • the inventors have been able to show that this effect was due to the reactivity with respect to the titanium or the titanium alloy which is quite exceptional and durable for the activated species comprising nitrogen and, in particular, neutral species excited with nitrogen. , N 2 , NH.
  • the nitrogen supply is carried out by the neutral excited species N, N 2 , NH.
  • the inventors have also been able to observe that an effect of increase in plasma activity is also obtained in the case of plasmas produced by microwaves or radiofrequency, in a gaseous medium containing nitrogen.
  • FIG. 2 there is shown a container 5 which comprises a body 5a, for example of cylindrical shape closed by a bottom, at one end, and open at a second end, and a cover 5b constituted by a simple metal plate placed on the open end of the cylindrical body 5a of the container 5.
  • the container 5 is constituted in the form of a simple cylindrical box having a flat lid attached and placed on the end edge of the cylindrical body 5a.
  • the container such as 5 has been used to produce, within the treatment chamber 2 of the furnace 1, the surface treatment of pieces 7 arranged loose within the container.
  • the parts 7 are for example nuts or screws made of titanium alloy such as Ti6Al4V.
  • the body 5a and the lid 5b of the cylindrical box may preferably be made of titanium alloy.
  • the inner surface of the body 5a of the box and possibly the lid 5b may be coated with an insulating material such as a ceramic.
  • a container 5 having a solid wall or body 5a closed by a cover 5b placed on one end of the wall
  • a container 5 comprising a wall pierced with a plurality of openings inside which one engages shutter elements with a weak clearance not allowing the ignition of a plasma through the openings of the wall.
  • the container 5 made under the shape of a box, for example cylindrical, in a disposition turned so that it rests along the edge of its opening on a support ensuring a non-sealed closure of the box.
  • the container may itself be pierced with numerous interstices allowing the passage of activated species but prohibiting the ignition of the plasma inside thereof.
  • the container has at least one opening closed by a closing means forming with the edge of the opening a non-zero play in the mechanical sense but important enough to let the activated species or species and low enough to prevent a plasma to penetrate inside the container.
  • one or more housings 5 are arranged on the support 4 and brought to a cathodic potential inside the treatment enclosure. It was ensured that the residual clearance between the lid 5b and the body 5a of the containers 5 is less than the Debye length. In fact, various experiments have been carried out with a variable clearance, comprised between one hundredth and ten tenths of a millimeter, between the lid 5b and the body 5a of the containers due to the roughness of the surfaces and to a bearing or clamping force. variable applied on the lid 5b.
  • ignition of the plasma inside the container 5 does not occur when an electrical discharge is produced between the containers 5 and the wall 1 of the oven.
  • the excited neutral species such as N, N 2 , NH can be found at the active state inside the containers, because of their lifetime sufficient.
  • These excited species having a very high reactivity vis-a-vis titanium or titanium alloys, can achieve the supply of nitrogen to the pieces 7.
  • a gap of a few tenths of a millimeter allows for example to prohibit the ignition of the plasma or inside the container while ensuring the passage of active neutral excited species.
  • a gap size gap gap allowing the treatment without contact with the plasma for example between 0.01 and 1 mm, is not an absolute condition, some values greater than 1 mm for example to prohibit the ignition of the plasma while ensuring the passage of neutral excited species.
  • the pressure of the gas is a factor to take into account.
  • FIG 2 there is shown a nozzle 8 of a container 5 which can be connected to a means for discharging the gas mixture to the outside of the treatment chamber 2 of the furnace. This promotes the introduction of the gaseous mixture containing neutral species activated inside the containers 5, when such a mode of evacuation through the containers is used.
  • the treatment of the parts 7 inside the container 5 is carried out at a temperature which makes it possible to obtain a diffusion of nitrogen inside the part and the formation of a layer of nitrogen diffusion in the alloy of titanium and possibly at the extreme surface of the piece a so-called combination layer consisting of titanium nitride.
  • the treatment is carried out at a temperature which is preferably between 400 ° C and 1000 ° C, and preferably between 550 ° C and 850 ° C, with a treatment time which is adapted to obtain a diffusion of nitrogen to a sufficient depth.
  • This treatment time may be for example between 1 hour and 24 hours, or more depending on the nature of the parts and the thickness of the layer that is desired.
  • the treatment temperature is preferably greater than 550 ° C, so as to obtain a sufficiently rapid diffusion of nitrogen. It is preferably less than 850 ° C, because beyond 850 ° C, the parts are likely to flow under their own weight, because of the high temperature.
  • the temperature and the gaseous mixture may be adjusted according to whether it is desired to obtain a surface having no combination layer or, conversely, comprising a combination layer.
  • an extreme layer is formed at the extreme surface. consisting of a TiN-Ti mixture 2 N, consisting of extremely hard titanium nitride over a small thickness. Such a layer is extended inside the room by a diffusion layer.
  • the piece takes on a beautiful golden yellow color.
  • the temperatures of 550 ° C. and 750 ° C. as well as the gas nitrogen contents are given for information only and may also depend on the exact nature of the alloy.
  • the hardened layers that can be obtained are layers whose thickness may be between 1 micron and 200 microns, depending on both the duration of the treatment and the temperature of the treatment.
  • the hardness of the layer obtained at the extreme surface is of the order of 600 Vickers, more generally is between 500 and 700 Vickers (HV01) measured under a load of 100 grams. The hardness decreases regularly when the depth below the surface increases to reach the normal hardness of the alloy considered.
  • the hardness at the extreme surface is between 600 Vickers. and 1000 Vickers (HV01) measured under a load of 100 grams.
  • HV01 Vickers
  • the treatment that is carried out on titanium or titanium alloy parts has the advantage of giving these parts properties of interesting uses.
  • treatment was carried out inside a container of pieces made of Ti6Al4V type alloy screws at a temperature of about 750 ° C. for about 18 hours.
  • the screws thus treated had anti-seizing characteristics quite remarkable.
  • the batch processing of titanium alloy parts has been carried out at a temperature of the order of 750 ° C., for a duration of the order of ten hours.
  • Diffusion layers have thus been obtained on parts with a thickness of between 20 ⁇ m and 100 ⁇ m, having a hardness greater than 600 Vickers (HV01) measured under a load of 100 grams and characteristics in terms of friction and wear very strongly. improved compared to untreated parts.
  • the pieces were in containers such as the container that has been described, placed in a chamber into which a mixture of nitrogen and hydrogen or nitrogen, hydrogen and hydrogen had been introduced.
  • Argon at a pressure less than 100 mbar, and in which active species had been generated by creating a plasma by electric charges.
  • the method which has just been described has the advantage of making it possible to process a set of parts without generating plasma or electric arcs in the vicinity of the surface of the parts. This avoids damaging the surface of the parts.
  • This treatment which has many advantages since it avoids the direct contact of the parts with the plasma, makes it possible to treat parts arranged in a unitary or bulk manner inside the container, parts stacked one on the other, in this case, the surfaces in contact with the parts of the stack are subjected to the treatment in the same way as the apparent surfaces, or coiled coils whose interstice between successive turns allow the passage of the activated species.
  • the treatment also makes it possible to carry out a surface treatment with activated species of nitrogen inside cavities of very small dimensions, and for example internal surfaces of an injection channel of a fuel injector or channels of an injection ramp of a motor vehicle.
  • the method makes it possible to treat, in good conditions, parts having cavities or slots the dimensions of which would make it possible, under the conditions of conventional ionic nitriding treatment, to ignite the plasma.
  • a plasma can not light in the cavities, and therefore there is no risk of damaging the surface of these cavities, unlike the case of classical ionic nitriding.
  • the inner surface of the container may be conductive or otherwise non-electrically conductive so that the parts are either polarized or unpolarized during processing.
  • the treatment of container parts coated internally with an insulating material, for example with a ceramic, can be carried out.
  • the invention can be applied to very diverse parts and in particular to any mechanical part subjected to wear in a corrosive medium.
  • the invention can advantageously be used to produce materials used in the biomedical industry, the aviation industry, the watch industry, the nuclear industry and the automotive industry. the food industry, the leisure and competition sports industry, the chemical industry or parts used in the marine environment.
  • the invention has particularly interesting applications in the context of titanium alloys subjected to frictional stresses, or moderately high contact pressures and having to resist scratching, wear or seizing
  • the invention can be advantageously applied to screws or fasteners, for example used in the biomedical industry or in the aeronautical industry.
  • the invention can be applied to any orthopedic implant element.
  • the invention is applicable to valves, motor vehicle fuel injectors, motor segments that can be stacked or impeller corrosion-prone turbine parts.
  • the invention is applicable to all parts such as valves, plugs, metal shutters, valves, pistons, cylinders, pump parts, (centrifugal, paddle, gear, lobe), flow control parts, regulator part pressure valves, solenoid valve parts, servo parts such as bearings.
  • the treatment can be carried out on a band which can be rolled up or on a metal blank implemented after treatment.
  • the surface treatment according to the invention can be carried out for another purpose than to ensure hardening.
  • any treatment aimed at modifying at least one property of the surface of the part by interactions with the activated species can be envisaged.
  • the surface treatment according to the invention can be carried out even on a passivated surface.
  • the treatment according to the invention is a treatment in which only nitrogen is introduced into the rooms. It is therefore made with a gas mixture whose chemical composition consists exclusively of nitrogen and neutral elements.
  • industrial gases which contain impurities. These impurities, which may especially contain carbon, oxygen and boron, must be in an amount small enough to have no significant effect on the treatment. It is possible in particular to use industrial gases of conventional purity, for example industrial nitrogen with a purity greater than or equal to 99.8% by volume, industrial hydrogen with a purity greater than or equal to 99.8% by volume, industrial argon of purity greater than or equal to at 99.99% by volume.

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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)
EP06290963.5A 2005-07-13 2006-06-13 Verfahren zur Behandlung von Teilen aus Titan oder Titanlegierungen Expired - Lifetime EP1743952B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL06290963T PL1743952T3 (pl) 2005-07-13 2006-06-13 Sposób obróbki tytanu lub elementów ze stopu tytanu

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR0507542A FR2888586B1 (fr) 2005-07-13 2005-07-13 Procede de traitement d'une piece en titane ou alliage de titane et piece obtenue

Publications (2)

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EP1743952A1 true EP1743952A1 (de) 2007-01-17
EP1743952B1 EP1743952B1 (de) 2015-08-26

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EP (1) EP1743952B1 (de)
ES (1) ES2551127T3 (de)
FR (1) FR2888586B1 (de)
PL (1) PL1743952T3 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108866474A (zh) * 2018-06-22 2018-11-23 珠海格力精密模具有限公司 模具处理方法
CN112243464A (zh) * 2018-07-11 2021-01-19 西铁城时计株式会社 金色构件的制造方法及金色构件
WO2024174448A1 (zh) * 2023-02-23 2024-08-29 深圳市尚水智能股份有限公司 一种用于制造新能源电池浆料的叶轮及其制造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0801142A2 (de) * 1996-04-12 1997-10-15 Nitruvid Oberflächenbehandlung eines Metallsubstrates, so hergestelltes Metallsubstrat und seine Anwendungen
EP1274873A1 (de) * 2000-04-19 2003-01-15 Nitruvid Verfahren zur oberflächenbehandlung eines werkstückes und dadurch hergestelltes werkstück
WO2004042106A1 (en) * 2002-11-07 2004-05-21 Plasma Metal S.A. Process for nitriding articles in bulk

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0801142A2 (de) * 1996-04-12 1997-10-15 Nitruvid Oberflächenbehandlung eines Metallsubstrates, so hergestelltes Metallsubstrat und seine Anwendungen
EP1274873A1 (de) * 2000-04-19 2003-01-15 Nitruvid Verfahren zur oberflächenbehandlung eines werkstückes und dadurch hergestelltes werkstück
WO2004042106A1 (en) * 2002-11-07 2004-05-21 Plasma Metal S.A. Process for nitriding articles in bulk

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108866474A (zh) * 2018-06-22 2018-11-23 珠海格力精密模具有限公司 模具处理方法
CN112243464A (zh) * 2018-07-11 2021-01-19 西铁城时计株式会社 金色构件的制造方法及金色构件
CN112243464B (zh) * 2018-07-11 2023-03-17 西铁城时计株式会社 金色构件的制造方法及金色构件
WO2024174448A1 (zh) * 2023-02-23 2024-08-29 深圳市尚水智能股份有限公司 一种用于制造新能源电池浆料的叶轮及其制造方法

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Publication number Publication date
ES2551127T3 (es) 2015-11-16
EP1743952B1 (de) 2015-08-26
PL1743952T3 (pl) 2016-01-29
FR2888586A1 (fr) 2007-01-19
FR2888586B1 (fr) 2008-01-11

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