EP0801142B1 - Procédé de traitement de surface d'une pièce métallique, pièce métallique obtenue et ses applications - Google Patents
Procédé de traitement de surface d'une pièce métallique, pièce métallique obtenue et ses applications Download PDFInfo
- Publication number
- EP0801142B1 EP0801142B1 EP19970400816 EP97400816A EP0801142B1 EP 0801142 B1 EP0801142 B1 EP 0801142B1 EP 19970400816 EP19970400816 EP 19970400816 EP 97400816 A EP97400816 A EP 97400816A EP 0801142 B1 EP0801142 B1 EP 0801142B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- metal part
- surface layer
- metal
- gaseous
- 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
Links
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
- C23C8/36—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
- C23C8/38—Treatment 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
- C23C8/36—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 for processing surface of a metal part, and more particularly, a method of surface hardening by enriching carbon or boron with surface layer located near a surface of the part.
- a surface treatment of a metal part has been described in which a gas atmosphere containing an element is brought into contact with a surface of the part brought to a temperature between 270 and 550 ° C. interstitial such as carbon or nitrogen, in the ionized state, at a pressure below 1.33.10 -2 mbar (10 mtorr). Due to the low pressure of the gaseous atmosphere, the interstitial content of the surface layer remains low even for treatment times of several hours.
- these compounds In the case of surface treatment of a steel part stainless, these compounds contain chromium which is taken up in the surface layer of the stainless steel part. This results in a degradation of the part's resistance to corrosion.
- An object of the present invention is to remedy this drawback by proposing a method for hardening the surface of a part metallic which does not deteriorate its resistance to corrosion.
- Another object of the present invention is to provide a treatment of the surface of a metal part which can be used industrially, under favorable conditions with regard to costs and duration of treatment.
- the gaseous compound can consist of a hydrocarbon aliphatic or aromatic or by a cyclan.
- the gaseous compound can also consist of methane and in this case, the gaseous atmosphere can contain from 5 to 30% in methane volume.
- the gaseous compound can also consist of a derivative boron gas, for example, a diborane.
- the gaseous atmosphere may also contain nitrogen or a gaseous derivative of nitrogen such as ammonia.
- the process applies, in particular, to alloy parts metallic whose structure is face centered cubic, centered cubic or tetragonal, more particularly, to stainless steel parts austenitic or martensitic, with nickel-based alloy parts and to cobalt-based alloy parts.
- the process can also be applied to alloy parts metallic based on aluminum or based on titanium.
- the metal part obtained has a surface layer hardened by an interstitial element consisting of at least one of the carbon and boron elements, and optionally, additionally, with nitrogen; the surface layer consists of a homogeneous solid solution free of precipitates containing 5 and 50 atom% and preferably between 10% and 30% interstitial.
- the part is placed in the enclosure of a treatment furnace surface by plasma.
- the enclosure is placed under vacuum and then introduced into the enclosure a mixture of gases, the pressure of which is lower than the pressure atmospheric can be between 0.5 and 200 mbar.
- the mixture of gas consists of a reactive gas on the one hand, and dilution gas on the other parts which are, for example, hydrogen and argon.
- the reactive gas is a gaseous compound either of carbon or of boron; for example, a aliphatic hydrocarbon, an aromatic hydrocarbon or a cyclane, and, in particular methane, or, for example, a diborane.
- the mixture gas may also contain a small proportion of a compound nitrogen gas.
- the gas mixture creating a cold plasma.
- ionization of the gas mixture creates ions which, by bombarding the surface of the part, can passivate it to make it reactive and heat, and, on the other hand, creates very reactive species of carbon or of boron, which are atoms of which certain electron layers are excited. Highly reactive carbon or boron species react with the surface and penetrate inside by diffusion to form a interstitial solid solution free of precipitates.
- the surface temperature must be sufficient, and preferably above 300 ° C. But to avoid the formation of precipitated the surface temperature must remain below 460 ° C. So that the penetration of the active elements in the metal takes place satisfactorily it is also necessary that the production of element active on the surface of the part is not too important. Indeed, with the carbon, for example, if the production of active carbon is too fast, it a harmful carbon black deposit forms on the surface of the part for the treatment. To avoid this, the active gas content of the product is limited. gas mixture in order to balance the kinetics of production of active element on the surface of the part, and the kinetics of penetration of the active element in the room.
- the active gas when the active gas is methane, its content in the gas mixture, is between 5 and 30% and, from preferably around 10%.
- the gaseous atmosphere in contact with the surface of the part is maintained at a pressure which must be higher at 0.5 and which can go up to 200 mbar.
- the plasma can be a so-called “discharge plasma", that is to say a plasma generated by an electric discharge between an anode and a cathode, the part to be treated being brought to a cathodic potential and which can itself be the cathode.
- discharge plasma that is to say a plasma generated by an electric discharge between an anode and a cathode, the part to be treated being brought to a cathodic potential and which can itself be the cathode.
- the ions are accelerated, they bombard the surface of the part which heats it up enough so that there is no need to provide a means of additional heating.
- the plasma can also be a plasma generated by a electromagnetic wave generator, or microwave generator, or a "post-discharge" plasma, that is to say a plasma transferred from a plasma generator to the enclosure in which it is located the room.
- a plasma generated by a electromagnetic wave generator, or microwave generator or a "post-discharge" plasma, that is to say a plasma transferred from a plasma generator to the enclosure in which it is located the room.
- bombardment of the workpiece surface may be insufficient to cause the necessary heating.
- we heats the surface of the room for example, by radiation.
- the duration of the treatment depends on the thickness of the layer treated we want to obtain, this duration can vary between 1 hour and a few tens of hours.
- the solid solution contains a high proportion of element interstitial, between 5 and 50 atom% and, generally between between 10 and 30 atom%. According to the conditions of implementation of the treatment and in particular, depending on the duration of treatment, it is possible to obtain a hardened surface layer with a thickness of 1 to 60 ⁇ m.
- the surface layer of the part may present after the treatment of a Vickers Hv hardness greater than 800.
- This treatment which is applicable to a very wide variety of metal alloys and, in particular, to alloys with a structure face centered cubic, centered cubic or tetragonal (for example, austenitic, ferritic or martensitic stainless steels), allows to obtain a layer 1 to 60 ⁇ m thick, of a solid solution saturated, or even supersaturated, with carbon or boron, homogeneous, that is to say free of carbide or boride precipitates, the hardness of which can be greater than 800 Vickers or even 1000 Vickers and that is very resistant to corrosion. Carbon can be combined with nitrogen to form the layer of solid solution.
- the alloy is an austenitic steel, the carburetted layer cannot be attacked by chemical reagents commonly used in metallography and has a resistance to attack by salt spray greater than 1000 hours.
- a second phase we submit the parts to an atmosphere containing carbon in activated form at a temperature generally lower than the treatment temperature during the first phase and for example, between 300 and 350 ° C.
- the surface layer of the parts is loaded with carbon, so so that a solid solution of carbon in the steel of the nitrogen-laden part, during the first phase.
- the martensitic steel parts then have both a high wear resistance and very good corrosion resistance.
- This treatment in two successive phases applies in particular highly stressed martensitic steel mechanical parts such as than parts used in the field of oil drilling or tools or cutting blades.
- the treatment according to the invention which allows obtain very hard, wear-resistant surface layers and very resistant to corrosion, can be performed on all kinds of parts, and in particular, on any mechanical part subject to wear in corrosive environment (for example: food industry, chemical industry, nuclear industry, marine environment, biomedical applications); mostly austenitic steel container to resist scratching, for example austenitic stainless steel dishes that can be coated before forming; on the blades of sharp stainless steel objects martensitics such as knives and scalpels; on implants orthopedic; on valves; on turbine parts or condensers subject to pitting corrosion.
- the treatment can, also, be made on a strip or on a metal blank, set work after treatment.
- the treatment applies in particular, in the case of panels in decorative austenitic stainless steel, for example, with polished panels and / or colored by a process such as anodization.
- the hardening of the surface of the panels by formation of a solution homogeneous solid of carbon in a surface layer of panels avoids the risk of scratches and degradation of the aesthetic appearance of the panels.
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)
- Heat Treatment Of Articles (AREA)
Description
- on porte la pièce, au moins dans sa zone superficielle, à une température comprise entre 300 et 460°C, et
- on maintient une atmosphère gazeuse renfermant l'élément interstitiel activé au contact de la surface de la pièce, à une pression comprise entre 0,5 et 200 mbars;
De préférence :
- la pression de l'atmosphère gazeuse au contact de la surface de la pièce pendant le traitement est comprise entre 0,5 et 20 m bars;
- l'atmosphère gazeuse est renferme au moins un composé gazeux comportant l'élément interstitiel, dans un plasma froid.
- l'atmosphère gazeuse renferme un diluant du composé gazeux constitué par l'un au moins des gaz suivants : hydrogène, argon, mélange d'hydrogène et d'argon.
- les pièces pour robinets et vannes utilisés dans un milieu corrosif telles que les clapets, les boisseaux, les sièges et les opercules.
- des éléments d'assemblage vissés tels que les écrous, les vis et les boulons en acier inoxydable austénitique.
- des raccords rapides en acier inoxydable austénitique pour les fluides corrosifs.
- des rouleaux de transport de tôles dans une installation de décapage de tôles, avant revêtement électrolytique.
- des pièces mobiles de pompes utilisées dans l'industrie chimique ou l'industrie alimentaire, telles que les pistons, les chemises de cylindres, les rotors, les cages, les guides ou les mélangeurs.
Claims (28)
- Procédé de traitement de surface d'un pièce métallique, dans lequel on introduit au moins un élément interstitiel constitué par l'un au moins des éléments carbone et bore dans une couche superficielle de la pièce voisine d'une surface de la pièce en mettant en contact avec la surface de la pièce l'élément interstitiel à l'état activé et en faisant diffuser l'élément interstitiel dans la couche superficielle de la pièce, caractérisé en ce que :on porte la pièce, au moins dans sa zone superficielle, à une température comprise entre 300 et 460°C, eton maintient une atmosphère gazeuse renfermant l'élément interstitiel activé au contact de la surface de la pièce, à une pression comprise entre 0,5 et 200 mbars,
- Procédé suivant la revendication 1, caractérisé en ce que la pression de l'atmosphère gazeuse est comprise entre 0,5 et 20 mbars.
- Procédé suivant l'une quelconque des revendications 1 et 2, caractérisé en ce que l'atmosphère gazeuse renferme au moins un composé gazeux comportant l'élément interstitiel activé, dans un plasma froid.
- Procédé suivant la revendication 3, caractérisé en ce que l'atmosphère gazeuse renferme un diluant du composé gazeux constitué par l'un au moins des gaz suivants : hydrogène, argon, un mélange d'hydrogène et d'argon.
- Procédé suivant l'une quelconque des revendications 3 et 4, caractérisé en ce que le composé gazeux est constitué par un hydrocarbure aliphatique ou aromatique ou un cyclane.
- Procédé suivant l'une quelconque des revendications 3 et 4, caractérisé en ce que le composé gazeux est constitué par du méthane et que l'atmosphère renferme de 5 à 30 % en volume de méthane.
- Procédé suivant l'une quelconque des revendications 3 et 4, caractérisé en ce que le composé gazeux est un dérivé gazeux du bore tel qu'un diborane.
- Procédé suivant l'une quelconque des revendications 3 à 7, caractérisé en ce que l'atmosphère gazeuse renferme en outre de l'azote ou un dérivé gazeux de l'azote, tel que l'ammoniac.
- Procédé suivant l'une quelconque des revendications 3 à 8, caractérisé en ce que le plasma est généré par une décharge électrique entre une anode et une cathode qui peut être la pièce métallique.
- Procédé suivant l'une quelconque des revendications 3 à 8, caractérisé en ce que le plasma est généré par un générateur de micro-ondes ou un générateur d'ondes électromagnétiques et éventuellement transféré pour être mis en contact avec la surface de la pièce.
- Procédé suivant l'une quelconque des revendications 1 à 10, caractérisé en ce que la surface de la pièce est chauffée par rayonnement.
- Procédé suivant l'une quelconque des revendications 1 à 9, caractérisé en ce que la pièce est un alliage métallique dont la structure est cubique à face centrée, cubique centrée ou tétragonale.
- Procédé suivant la revendication 12, caractérisé en ce que l'alliage métallique est l'un des alliages suivants : acier inoxydable austénitique, acier inoxydable martensitique, alliage à base de nickel, alliage à base de cobalt.
- Procédé suivant la revendication 12, caractérisé en ce que l'alliage métallique est un alliage à base d'aluminium ou un alliage à base de titane.
- Procédé suivant la revendication 1, dans le cas d'une pièce en acier inoxydable martensitique, caractérisé en ce que :dans une première phase, on soumet la pièce à une atmosphère renfermant de l'azote, à une température comprise entre 340 et 450°C et de préférence, entre 350 et 380°C, de manière à charger une couche superficielle de la pièce en azote, etdans une seconde phase, on soumet la pièce chargée en azote, à une atmosphère renfermant du carbone à l'état activé, à une température généralement inférieure à la température du traitement au cours de la première phase et comprise de préférence entre 300 et 380°C.
- Pièce métallique comportant une couche superficielle durcie par un élément interstitiel constitué par l'un au moins des éléments carbone et bore et éventuellement de manière additionnelle par de l'azote, caractérisée en ce que la couche superficielle est constituée par une solution solide homogène exempte de précipités renfermant de 5 à 50 atomes % d'élément interstitiel.
- Pièce métallique suivant la revendication 16, caractérisée en ce que la couche superficielle renferme de 10 à 30 atomes % d'interstitiel.
- Pièce métallique suivant l'une quelconque des revendications 16 et 17, caractérisée en ce que la couche superficielle a une épaisseur comprise entre 1 et 60 µm.
- Pièce métallique suivant l'une quelconque des revendications 16 à 18, caractérisée en ce que la couche superficielle a une dureté Vickers Hv supérieure à 800.
- Utilisation d'une pièce métallique suivant l'une quelconque des revendications 16 à 19 comme pièce de frottement en ambiance corrosive et en particulier comme clapet, boisseau, siège ou opercule d'un robinet ou d'une vanne utilisée dans un milieu corrosif.
- Utilisation d'une pièce métallique en acier inoxydable austénitique suivant l'une quelconque des revendications 16 à 19 comme élément d'un assemblage vissé tel qu'un écrou, une vis ou un boulon utilisable dans un milieu corrosif.
- Utilisation d'une pièce métallique en acier inoxydable austénitique suivant l'une quelconque des revendications 16 à 19 comme raccord pour le transport de fluides spéciaux.
- Utilisation d'une pièce métallique suivant l'une quelconque des revendications 16 à 19 comme rouleau de transport de tôle dans une installation de décapage.
- Utilisation d'une pièce métallique suivant l'une quelconque des revendications 16 à 19 comme pièce mobile d'une pompe utilisée dans l'industrie chimique ou dans l'industrie alimentaire, telle qu'un piston, une chemise de cylindre, un rotor, une cage, un guide ou un mélangeur.
- Utilisation d'une pièce métallique suivant l'une quelconque des revendications 16 à 19 comme implant orthopédique.
- Utilisation d'une pièce métallique suivant l'une quelconque des revendications 16 à 19 comme panneau décoratif poli et/ou coloré.
- Pièce métallique suivant l'une quelconque des revendications 16 à 19, caractérisée en ce qu'elle est constituée par un produit plat en acier inoxydable austénitique destiné à subir un formage.
- Pièce métallique suivant l'une quelconque des revendications 16 à 19, caractérisée en ce qu'elle est constituée par un objet coupant en acier inoxydable martensitique, tel qu'un couteau ou un bistouri.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9604561 | 1996-04-12 | ||
FR9604561A FR2747398B1 (fr) | 1996-04-12 | 1996-04-12 | Procede de traitement de surface d'une piece metallique |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0801142A2 EP0801142A2 (fr) | 1997-10-15 |
EP0801142A3 EP0801142A3 (fr) | 1998-09-16 |
EP0801142B1 true EP0801142B1 (fr) | 2002-07-03 |
Family
ID=9491129
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19970400816 Expired - Lifetime EP0801142B1 (fr) | 1996-04-12 | 1997-04-09 | Procédé de traitement de surface d'une pièce métallique, pièce métallique obtenue et ses applications |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0801142B1 (fr) |
DE (1) | DE69713662T2 (fr) |
FR (1) | FR2747398B1 (fr) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9715180D0 (en) | 1997-07-19 | 1997-09-24 | Univ Birmingham | Process for the treatment of austenitic stainless steel articles |
FR2807956B1 (fr) * | 2000-04-19 | 2003-10-24 | Nitruvid | Procede de traitement de surface d'une piece et piece obtenue |
GB0209797D0 (en) * | 2002-04-29 | 2002-06-05 | Univ Birmingham | Method of surface hardening cobalt-chromium based alloy articles |
LU90986B1 (en) * | 2002-11-07 | 2004-05-10 | Plasma Metal S A | Process for nitriding articles in bulk. |
FR2888586B1 (fr) * | 2005-07-13 | 2008-01-11 | Nitruvid Snc | Procede de traitement d'une piece en titane ou alliage de titane et piece obtenue |
FR2980804B1 (fr) | 2011-09-30 | 2014-06-27 | Areva Np | Procede de realisation a partir d'une ebauche en acier inoxydable austenitique a faible teneur en carbone d'une gaine resistant a l'usure et a la corrosion pour reacteur nucleaire, gaine et grappe de commande correspondantes |
FR2980803B1 (fr) | 2011-09-30 | 2013-10-25 | Areva Np | Procede de realisation d'une piece en acier inoxydable resistant a l'usure et a la corrosion pour reacteur nucleaire, piece et grappe de commande correspondantes. |
DE102012216117A1 (de) * | 2012-09-12 | 2014-03-13 | Hilti Aktiengesellschaft | Verfahren zum Herstellen einer selbstschneidenden Schraube |
CN104769148B (zh) | 2012-11-07 | 2016-11-23 | 阿海珐核能公司 | 用于在遮掩部分的同时热化学处理部件的方法及相应掩模 |
CN108486525A (zh) * | 2017-02-22 | 2018-09-04 | 学校法人丰田学园 | 金属制品的制造方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RO74414A2 (fr) * | 1974-03-23 | 1981-09-24 | Institutul De Cercetari Si Proiectari Tehnologice Pentru Sectoare Calde,Ro | Procede de nitruration ionique |
DD159350A1 (de) * | 1981-06-02 | 1983-03-02 | Bernd Buecken | Verfahren zur haertung von eisenwerkstoffen in einer stromstarken gasentladung |
FI63783C (fi) * | 1981-09-30 | 1983-08-10 | Kymin Oy Kymmene Ab | Foerfarande foer nitrering vid laogt tryck med hjaelp av glimurladdning |
JPS60211061A (ja) * | 1984-04-05 | 1985-10-23 | Toyota Central Res & Dev Lab Inc | アルミニウム材のイオン窒化方法 |
FR2587729B1 (fr) * | 1985-09-24 | 1988-12-23 | Centre Nat Rech Scient | Procede et dispositif de traitement chimique, notamment de traitement thermochimique et de depot chimique dans un plasma homogene de grand volume |
JPH01176066A (ja) * | 1987-12-28 | 1989-07-12 | Hamamatsu Netsushiyori Kogyo Kk | イオン窒化処理済サーメットチップ及びその製造方法 |
JPH01261213A (ja) * | 1988-04-12 | 1989-10-18 | Idemitsu Petrochem Co Ltd | 4a,Va,6a族金属の炭化方法 |
FR2630133B1 (fr) * | 1988-04-18 | 1993-09-24 | Siderurgie Fse Inst Rech | Procede pour l'amelioration de la resistance a la corrosion de materiaux metalliques |
FR2652591B1 (fr) * | 1989-10-03 | 1993-10-08 | Framatome | Procede d'oxydation superficielle d'une piece en metal passivable, et elements d'assemblage combustible en alliage metallique revetus d'une couche d'oxyde protectrice. |
FR2653137B1 (fr) * | 1989-10-17 | 1993-06-11 | Siderurgie Fse Inst Rech | Procede de traitement de surface de produits siderurgiques par action d'un plasma. |
GB2261227B (en) * | 1991-11-08 | 1995-01-11 | Univ Hull | Surface treatment of metals |
JP2917810B2 (ja) * | 1994-04-28 | 1999-07-12 | 住友金属工業株式会社 | 表面の耐剥離特性に優れた炭窒化処理鋼 |
-
1996
- 1996-04-12 FR FR9604561A patent/FR2747398B1/fr not_active Expired - Lifetime
-
1997
- 1997-04-09 DE DE1997613662 patent/DE69713662T2/de not_active Expired - Lifetime
- 1997-04-09 EP EP19970400816 patent/EP0801142B1/fr not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0801142A3 (fr) | 1998-09-16 |
DE69713662T2 (de) | 2002-12-05 |
FR2747398A1 (fr) | 1997-10-17 |
DE69713662D1 (de) | 2002-08-08 |
EP0801142A2 (fr) | 1997-10-15 |
FR2747398B1 (fr) | 1998-05-15 |
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