EP0725846B1 - Procede de fabrication d'un revetement refractaire sur un substrat metallique - Google Patents
Procede de fabrication d'un revetement refractaire sur un substrat metallique Download PDFInfo
- Publication number
- EP0725846B1 EP0725846B1 EP94931064A EP94931064A EP0725846B1 EP 0725846 B1 EP0725846 B1 EP 0725846B1 EP 94931064 A EP94931064 A EP 94931064A EP 94931064 A EP94931064 A EP 94931064A EP 0725846 B1 EP0725846 B1 EP 0725846B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- substrate
- porous layer
- process according
- oxides
- bath
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
- C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel
Definitions
- the invention relates to a method of fabrication of a refractory coating on a substrate metallic in order to create a protective layer of said high hardness substrate capable of withstanding high temperatures. It aims in particular to take on steel or nickel-based superalloy substrates or of cobalt to allow them to endure without alteration of the upper temperatures by a few hundreds of degrees at their temperature commonly eligible.
- superalloy is meant so usual alloys based on nickel or cobalt, capable of withstanding high temperatures, generally greater than 1000 ° C.
- the invention extends to metal substrates protected by the use of above-mentioned process.
- the invention proposes to provide a new refractory lining manufacturing process on a metal substrate in order to create on the latter a high hardness protective layer capable of supporting high temperatures. Its main objective ensure good adhesion of the refractory lining on the substrate and a continuity of the expansion coefficient between substrate and coating so as to avoid detachments or flaking during thermal cycles at high temperature.
- Another object of the invention is to significantly reduce the time and temperature of heat treatments required compared to those who are used in known methods.
- the tests carried out made it possible to find that the heat treatment (c) of the process could be performed at a temperature and for a much shorter duration than in the case of processes known.
- a gradual rise in temperature up to a value between 600 ° C and 1000 ° C and maintaining this temperature for a few minutes (at least 5 minutes and generally between 5 and 45 minutes) allow to obtain in the best conditions the above properties.
- This heat treatment can be carried out immediately after the deposition of the oxide and / or hydroxide refractory; given its short duration and the values moderate temperatures required it can also be made during the use of the substrate during the first warming up of it. He is in permissible effect that, on first use, the coating present for a few minutes reduced adhesion characteristics.
- the porous layer is produced by placing the substrate in an aqueous bath containing a mineral acid and sulfur in the form of thiosulfate at a temperature between 40 ° C and 90 ° C, and leaving said substrate in the bath until a layer is obtained porous thickness between 0.1 and 1 micrometer.
- This implementation optimizes the characteristics of the porous layer while allowing it to be obtained at a low cost ; this layer lends itself perfectly to receiving then the refractory layer due to its strong porosity; moreover, its attachment to the substrate is excellent due to the existing composition gradient at proximity to the substrate / porous layer interface.
- an inhibitor can be added to the acid bath acetylenic, in particular an acetylenic alcohol, which optimizes the migration of atoms during the formation of the porous layer, while limiting the phenomenon of dissolution of the substrate.
- the substrate can be used without prior preparation (with the exception of course of a degreasing to possibly get rid of bodies which it could present). However, it is sometimes interesting to subject said substrate to operations prerequisites (intended to expose the metal by rid of any surface oxides).
- This prior preparation may in particular consist of activate the substrate surface beforehand so that give its natural corrosion potential in the bath acid a value lower than its potential for primary passivation: this activation can be carried out by mechanical or chemical pickling operations and / or abrasion ...; it can also be carried out by electrolytic pathway (cathodic activation) by diving an anode in the acid bath and passing a current between said anode and the substrate playing the role of cathode.
- operation (b) of depositing the refractory oxide and / or hydroxide on the above-mentioned porous layer can be carried out by subjecting the substrate coated with said layer to electrolysis in a solution.
- the thickness of the refractory oxide and / or hydroxide layer will be provided in the high range of these values (several micrometers) in the case where it is desired, not only to protect the substrate against any alteration at high temperature, but also create a thermal barrier reducing the temperature to which the substrate is brought, especially in applications involving very high temperatures (turbine engines ).
- the electrolysis described above is advantageously carried out by placing a reference electrode in the electrolytic bath and adjusting the potential difference between the cathode formed by the substrate and this reference electrode to a set value, this setpoint corresponding to a potential between - 2 Volts and - 6 Volts relative to the hydrogen electrode. It is possible, in particular, to use as an electrolytic bath an aqueous solution containing one or more salts of the element (s) (M 2 ) in a concentration of between 0.75.S and S, where S is the saturation threshold of the solution with respect to to said salts. In addition, it is advantageous in certain applications to add to the electrolytic bath a minority proportion of a doping compound, in particular composed of yttrium, rare earth or precious metal, in order to increase the thermal stability of the electrolytic deposition.
- a doping compound in particular composed of yttrium, rare earth or precious metal
- the pH of the electrolytic solution is adjusted to a value between 1.5 and 5, and the temperature is maintained said electrolytic solution at a value between 10 ° C and 30 ° C.
- patent 2,608,459 and its addition certificate 2.632.875 describe the realization of a porous catalytic layer by attack of the substrate in an acid medium in the presence of chalcogen; the addition certificate evokes the deposition on this layer of a precious metal by electrolysis (platinum or rhodium) in sight improve the catalytic effect of the first layer.
- this is a completely different from that of the invention, aimed at obtaining totally different properties (catalytic properties on one side and high temperature thermal protection of the other).
- the process of the invention can in particular be applied to coat steel substrates.
- an essentially porous layer is produced composed of iron oxides and / or iron hydroxides and (b) on deposits an oxide and / or hydroxide on this porous layer one or more of the following: aluminum, zirconium, magnesium, silicon.
- the process can also be applied for coating nickel-based superalloy substrates or cobalt.
- a layer is made porous essentially composed of oxides and / or hydroxides base metal of the superalloy and (b) is deposited on this porous layer an oxide and / or hydroxide of one or more following elements: aluminum, zirconium, magnesium, silicon.
- metal substrate is meant both a solid homogeneous material and a material composed of several layers, the surface layer being metallic and containing the metal or metals (M 1 ).
- the invention extends to the new product consisting of a metal substrate protected by a refractory coating obtained by implementing the method defined above; this coating comprises a porous layer of oxides of the metal or metals (M 1 ) of the substrate, and a thickness of at least one refractory oxide of one or of elements (M 2 ) different from the metal or metals (M 1 ) , the interface between the porous layer and the thickness mentioned above comprising one or more mixed oxides of the elements present (M 1 , M 2 ).
- the treatment bath is an aqueous solution of sulfuric acid at 9% by weight of acid, added with 0.32 gram of sulfur per liter in the form of sodium thiosulfate Na 2 S 2 O 3 , 5 H 2 O and 3 g per liter of propargyl alcohol.
- the bath temperature is maintained at 55 ° C.
- the natural corrosion potential of steel in such a bath is measured by means of a connected voltmeter electrically to steel, on the one hand, and to an electrode of reference to calomel, on the other hand, arranged in the bath.
- the sheet has previously undergone a degreasing with ethyl alcohol; the potential of corrosion measured is equal to - 0.52 Volt. This value being lower than the primary passivation potential (- 0.10 V) measured beforehand by plotting the polarization curve of the steel in the bath using a potentiostat, the treatment could be performed directly, without activation prior.
- the treatment consisted in maintaining the steel immersed in the bath for 25 minutes at 55 ° C.
- the sheet After treatment, the sheet is washed with water then dried; we get a layer of black color, porous and about 0.4 ⁇ m thick.
- the sheet After treatment the sheet is removed from the bath then dried; it is covered with a layer of light gray color.
- the thickness of the hydroxide layer added is 0.6 micron.
- the sheet thus coated is placed in a oven at 950 ° C for 30 minutes.
- the profiles of distribution of the elements according to the depth, obtained by micro-analysis with the ionic probe, are given in figure 1. It is noted that the coating contains not only the compounds of the metallic elements coming from steel (iron and chromium) but also from deposited aluminum. On the surface, only aluminum oxide is present; deeper, when you get closer to the substrate, the composition of the layer gradually changes, the content of aluminum compound decreasing in favor of that of metal oxides (iron and chromium).
- the mixed oxides present are binary and ternary oxides of iron, chromium and aluminum, the content and composition of which vary progressively in the coating and over a shallow depth of the substrate.
- the X-ray diffractogram line indexing table is as follows:
- Oxidation tests were carried out in subjecting samples to a gradual rise in temperature, in an oven open to the atmosphere. In these tests, we measure the weight of the sample as a function of the temperature ; the beginning of oxidation results in a increase in sample weight.
- Figure 2 shows that the uncoated steel oxidizes from 750 ° C (curve A); the steel coated in this example 1 does not undergo any oxidation up to 1000 ° C (curve B).
- the hardness of the materials was measured with a VICKERS microduremeter under a load of 50 g.
- the hardness of coated steel is 550 kg / mm 2
- that of bare steel is only 200 kg / mm 2 .
- This increase in hardness is remarkable all the more since the value thus obtained is the average value between the hardness of the steel which is low and that of the coating itself which cannot be measured because of the too small thickness of the deposit.
- the intrinsic hardness of the coating is therefore even higher than 550 kg / mm 2 .
- the steel thus coated was subjected to a gradual rise in temperature in an oven up to 1050 ° C, then kept at that temperature with a view to simulate a possible use at high temperature. In this case, the heat treatment is therefore carried out during of the temperature rise when using the material.
- the coating is consisting of zirconia (refractory oxide) and mixed oxide of iron, chromium and aluminum from the reaction to high temperature of the compounds of the porous layer and of the deposit made by electrolysis.
- Figure 3 illustrates the distribution of elements in the repository.
- the surface zone consists only of aluminum and zirconium compounds (Al 2 O 3 , Zr O 2 ); while in the deeper zone these compounds coexist with mixed oxides of iron, chromium, aluminum and zirconium (as shown by an X-ray analysis carried out as in Example 1).
- Figure 2 illustrates the good resistance to oxidation of the coating up to 1100 ° C (curve C).
- Example 1 The hardness test carried out as in Example 1 gives the hardness of the coated steel 600 kg / mm 2 , this hardness is three times higher than that of the starting steel.
- the composition of the treatment bath is an aqueous solution of sulfuric acid at 9% by weight acid with 0.64 g of sulfur per liter under form of sodium thiosulfate and 2.3 g per liter propargyl alcohol.
- the temperature is maintained at 55 ° C.
- the corrosion potential being of the order of - 0.55 Volt, the treatment could be carried out without prior activation.
- the duration of treatment is 25 minutes and leads to a thick porous layer equal to 0.5 micron.
- the layer added has a thickness of 1 micron.
- the steel thus coated was subjected to a gradual rise in temperature in an oven up to 700 ° C, then maintained at this temperature for 30 minutes.
- X-ray and probe analysis ionic shows, as before, the presence of oxides mixed iron, aluminum and silica with gradients gradually varying concentration and composition in the coating from the substrate / layer interface porous.
- the high temperature resistance test is then carried out by heating the material for 5 hours at 700 ° C.
- the uncoated steel oxidizes quickly, its weight gain then being equal to 20 mg / cm 2 , with the appearance of blistering and flaking.
- the weight gain is only 8 mg / cm 2 and there is no flaking phenomenon, proof that the coating considerably improves the high temperature resistance of mild steel (which resists badly to the phenomenon of oxidation).
- the hardness of the coated steel measured as in Example 1 is 550 kg / mm 2 , or almost 3 times higher than that of bare steel.
- the treatment bath is a solution aqueous sulfuric acid at 27% by weight of acid, supplemented with, 32 grams of sulfur per liter in the form hydrated sodium thiosulfate and 3 g per liter propargyl alcohol.
- the bath temperature is maintained at 85 ° C.
- the natural corrosion potential of the superalloy being positive and greater than the value of the potential of primary passivation, treatment was required prior activation by placing an anode in the bath and by passing a current between the anode and the part (cathode) so as to bring it to a potential of - 1.2 volts for 5 minutes. After this activation treatment, the piece is kept in the bath for 20 minutes to form a porous layer 0.3 microns thick.
- the thickness of the overlay is 0.5 micron.
- the material was subjected to a heating of 8 hours at 1100 ° C. No degradation by oxidation has been noted.
- the surface hardness of the coated superalloy is 600 kg / mm 2 , a value almost 3 times higher than that of the starting superalloy.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Chemical Treatment Of Metals (AREA)
Description
- la figure 1 est un diagramme donnant une image de la composition du revêtement obtenu à l'exemple 1,
- la figure 2 est un diagramme comparatif illustrant la résistance à l'oxydation à chaud des revêtements obtenus aux exemples 1 et 2 par rapport à un substrat non revêtu,
- la figure 3 est un diagramme donnant une image de la composition du revêtement obtenu à l'exemple 2.
- pH de la solution : 2
- température de la solution : 15° C,
- potentiel de traitement : - 4 V (par rapport à l'électrode au calomel),
- durée du traitement : 20 minutes.
- d'alumine α Al2O3 de structure cristalline rhombohédrique (maille hexagonale correspondante : a = 0,4758 nm c = 1,2991 nm)
- de composé mixte Fe(Al,Cr)2O4 de structure cubique (F d 3 m a = 0,828 nm).
- 330 g de sulfate d'aluminium hydraté Al2(SO4)3 14 H2O,
- 100 g de chlorure de zirconium Zr Cl4.
- 500 g de sulfate d'aluminium hydraté Al2(SO4)3, 14 H2O,
- 135 g de chlorure de silicium Si Cl4.
- température du bain : 15° C,
- potentiel de traitement : - 3 V,
- durée de traitement : 15 minutes.
- 330 g de sulfate d'aluminium hydraté
- 100 g de chlorure de zirconium
- 20 g de chlorure d'yttrium
- température du bain : 15° C
- potentiel de traitement : - 4,5 volts
- durée de traitement : 4 minutes
Claims (18)
- Procédé de fabrication d'un revêtement réfractaire sur un substrat métallique, comprenant les étapes suivantes :(a) on réalise à la surface du substrat une couche poreuse composée d'oxydes et/ou hydroxydes du ou des métaux (M1) du substrat, en disposant ledit substrat dans un bain acide contenant des atomes d'oxygène et sous forme dissoute au moins un chalcogène,(b) on dépose ensuite sur cette couche poreuse au moins un oxyde et/ou hydroxyde réfractaire d'un ou d'éléments (M2) différents du ou des métaux (M1) du substrat et aptes à former avec ceux-ci un ou des oxydes mixtes,(c) et on chauffe l'ensemble à une température adaptée pour faire réagir à l'interface les oxydes de la couche poreuse et le ou les oxydes réfractaires en vue de former un ou des oxydes mixtes des éléments en présence (M1, M2).
- Procédé selon la revendication 1, en vue de revêtir un substrat en acier, dans lequel (a) on réalise une couche poreuse essentiellement composée d'oxydes de fer et/ou hydroxydes de fer et (b) on dépose sur cette couche poreuse un oxyde et/ou hydroxyde d'un ou des éléments suivants : aluminium, zirconium, magnésium, silicium.
- Procédé selon la revendication 1, en vue de revêtir un substrat en superalliage à base de nickel ou de cobalt, dans lequel (a) on réalise une couche poreuse essentiellement composée d'oxydes et/ou hydroxydes du métal de base du superalliage et (b) on dépose sur cette couche poreuse un oxyde et/ou hydroxyde d'un ou des éléments suivants : aluminium, zirconium, magnésium, silicium.
- Procédé selon l'une des revendications 1, 2 ou 3, dans lequel (a) la couche poreuse est réalisée en disposant le substrat dans un bain aqueux contenant un acide minéral et du soufre sous forme de thiosulfate à une température comprise entre 40° C et 90° C et en laissant ledit substrat dans le bain jusqu'à l'obtention d'une couche poreuse d'épaisseur comprise entre 0,1 et 1 micromètre.
- Procédé selon la revendication 4, dans lequel (a) on ajoute au bain acide un inhibiteur acétylénique, en particulier un alcool acétylénique.
- Procédé selon l'une des revendications 4 ou 5, dans lequel (a) on active préalablement la surface du substrat de façon à donner à son potentiel de corrosion naturelle dans le bain acide une valeur inférieure à celle de son potentiel de passivation primaire.
- Procédé selon l'une des revendications 4 ou 5, dans lequel (a) on fait subir au substrat disposé dans le bain acide une oxydation anodique en vue d'accroítre la vitesse de formation de la couche poreuse.
- Procédé selon l'une des revendications précédentes, dans lequel (b) on dépose l'oxyde et/ou hydroxyde réfractaire sur la couche poreuse en soumettant le substrat revêtu de ladite couche à une électrolyse dans une solution électrolytique contenant un ou des sels du ou des éléments (M2), la cathode étant constituée par le substrat revêtu, et l'anode par un métal inerte, l'électrolyse étant poursuivie jusqu'à l'obtention d'une épaisseur d'oxyde et/ou hydroxyde réfractaire comprise entre 0,1 et 5 micromètres.
- Procédé selon la revendication 8, dans lequel (b) on ajuste le pH de la solution électrolytique à une valeur comprise entre 1,5 et 5.
- Procédé selon l'une des revendications 8 ou 9, dans lequel (b) on maintient la température de la solution électrolytique à une valeur comprise entre 10° C et 30° C.
- Procédé selon l'une des revendications 8, 9 ou 10, dans lequel (b) on dispose dans le bain électrolytique une électrode de référence et on ajuste la différence de potentiel entre la cathode constituée par le substrat et cette électrode de référence à une valeur de consigne, cette valeur de consigne correspondant à un potentiel compris entre - 2 Volts et - 6 Volts par rapport à l'électrode à hydrogène.
- Procédé selon l'une des revendications 8, 9, 10 ou 11, dans lequel (b) on utilise comme bain électrolytique une solution aqueuse contenant un ou des sels du ou des éléments (M2) en concentration comprise entre 0,75.S et S, où S est le seuil de saturation de la solution par rapport auxdits sels.
- Procédé selon l'une des revendications 8, 9, 10, 11 ou 12, dans lequel (b) on ajoute dans le bain électrolytique une proportion minoritaire d'un composé de dopage, en particulier composé d'yttrium, de terre rare ou de métal précieux, en vue d'accroítre la stabilité thermique du dépôt électrolytique.
- Procédé selon l'une des revendications précédentes, dans lequel (c) on chauffe progressivement l'ensemble jusqu'à une température comprise entre 600° C et 1 000° C et on le maintient au moins 5 minutes à cette température.
- Procédé selon la revendication 14, dans lequel (c) le traitement thermique est réalisé immédiatement après le dépôt de l'oxyde et/ou hydroxyde réfractaire pendant une durée comprise entre 5 et 45 minutes.
- Procédé selon la revendication 14, dans lequel (c) le traitement thermique est réalisé lors de l'utilisation du substrat, à l'occasion de la première mise en température de celui-ci.
- Substrat métallique protégé par un revêtement réfractaire comprenant une couche poreuse d'oxydes du ou des métaux (M1) du substrat, et une épaisseur d'au moins un oxyde réfractaire d'un ou d'éléments (M2) différents du ou des métaux (M1), l'interface entre la couche poreuse et l'épaisseur sus-évoquée comportant un ou des oxydes mixtes des éléments en présence (M1, M2).
- Substrat selon la revendication 17, en acier ou en superalliage à base de nickel ou de cobalt, protégé par un revêtement comprenant une couche poreuse essentiellement constituée d'oxydes de fer pour l'acier ou d'oxyde du métal de base, nickel ou cobalt, pour le superalliage.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9312790 | 1993-10-25 | ||
FR9312790A FR2711575B1 (fr) | 1993-10-25 | 1993-10-25 | Procédé de fabrication d'un revêtement réfractaire sur un substrat métallique. |
PCT/FR1994/001191 WO1995012012A1 (fr) | 1993-10-25 | 1994-10-13 | Procede de fabrication d'un revetement refractaire sur un substrat metallique |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0725846A1 EP0725846A1 (fr) | 1996-08-14 |
EP0725846B1 true EP0725846B1 (fr) | 1998-03-04 |
Family
ID=9452246
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94931064A Expired - Lifetime EP0725846B1 (fr) | 1993-10-25 | 1994-10-13 | Procede de fabrication d'un revetement refractaire sur un substrat metallique |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0725846B1 (fr) |
DE (1) | DE69408859T2 (fr) |
FR (1) | FR2711575B1 (fr) |
WO (1) | WO1995012012A1 (fr) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1249049B (fr) * | 1959-03-05 | |||
US3208922A (en) * | 1961-05-09 | 1965-09-28 | Gen Electric | Galvanic process for coating iron alloys with magnesium hydroxide |
SU975832A1 (ru) * | 1981-04-09 | 1982-11-23 | Uralsky Nii Trubnoj Promy | Раствор для подготовки поверхности стали перед нанесением гальванического покрытия 1 |
SU1673648A1 (ru) * | 1989-03-07 | 1991-08-30 | Днепропетровский химико-технологический институт | Раствор дл обработки стали перед электроосаждением цинковых покрытий |
-
1993
- 1993-10-25 FR FR9312790A patent/FR2711575B1/fr not_active Expired - Fee Related
-
1994
- 1994-10-13 WO PCT/FR1994/001191 patent/WO1995012012A1/fr active IP Right Grant
- 1994-10-13 DE DE69408859T patent/DE69408859T2/de not_active Expired - Fee Related
- 1994-10-13 EP EP94931064A patent/EP0725846B1/fr not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
FR2711575B1 (fr) | 1996-01-12 |
FR2711575A1 (fr) | 1995-05-05 |
WO1995012012A1 (fr) | 1995-05-04 |
DE69408859D1 (de) | 1998-04-09 |
DE69408859T2 (de) | 1998-10-29 |
EP0725846A1 (fr) | 1996-08-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR20040108772A (ko) | 반도체 처리 장치에서 사용하기 위한 할로겐-저항양극산화 알루미늄 | |
EP0297982B1 (fr) | Procédé de codéposition électrolytique d'une matrice nickel-cobalt et de particules céramiques et revêtement obtenu | |
FR2757181A1 (fr) | Procede de realisation d'un revetement protecteur a haute efficacite contre la corrosion a haute temperature pour superalliages, revetement protecteur obtenu par ce procede et pieces protegees par ce revetement | |
EP2459780B1 (fr) | Piece comportant un substrat portant une couche de revetement ceramique à base d'oxyde de cérium | |
EP0537062A1 (fr) | Procédé de traitement pour déposer une couche de carbone en phase vapeur sur la surface d'une pièce métallique | |
FR2768750A1 (fr) | Procede pour ameliorer la resistance a l'oxydation et a la corrosion d'une piece en superalliage et piece en superalliage obtenue par ce procede | |
FR2877018A1 (fr) | Procede d'oxydation micro arc pour la fabrication d'un revetement sur un substrat metallique, et son utilisation | |
EP1106293B1 (fr) | Electrode pour l'usinage d'une pièce par électroérosion et son procédé de fabrication | |
Wu et al. | Effect of Na2SiO3 concentration on corrosion resistance and wear resistance of MAO ceramic film on the Al‐Mg‐Sc alloy | |
EP0725846B1 (fr) | Procede de fabrication d'un revetement refractaire sur un substrat metallique | |
EP0070069B1 (fr) | Procédé de fabrication d'un absorbeur sélectif de capteur solaire | |
CA2769198C (fr) | Methode de fabrication d'une barriere thermique | |
EP1060818B1 (fr) | Structures tridimensionnelles à haute porosité en alliages contenant du chrome | |
EP1541718A2 (fr) | Procédé de colmatage exempt de chrome hexavalent applicable après anodisation sulfurique d'alliages d'aluminium, solution de colmatage utilisée dans ce procédé et article traité issu d'un tel procédé | |
EP0709496B1 (fr) | Procédé d'électrodéposition d'un revêtement de chrome comportant des inclusions solides et bain mis en oeuvre dans ce procédé | |
JP6254806B2 (ja) | 電解処理用アルミニウム合金圧延板、並びに電解処理アルミニウム合金圧延板及びその製造方法 | |
FR2839729A1 (fr) | Procede de protection d'un substrat en acier ou alliage d'aluminium contre la corrosion permettant de lui conferer des proprietes tribologiques, et substrat obtenu | |
JP5194267B2 (ja) | 緻密表面層をもつサーメット皮膜の形成方法とサーメット皮膜被覆部材 | |
WO2008040761A2 (fr) | Procede d'electroformage et piece ou couche obtenue par ce procede | |
EP0289432A1 (fr) | Procédé pour former à la surface d'un substrat en alliage d'aluminium une zone riche en aluminiure d'au moins un des éléments nickel, fer, cobalt | |
RU2734426C1 (ru) | Способ получения защитных покрытий на магнийсодержащих сплавах алюминия | |
EP0997555B1 (fr) | Procédé de réalisation d'un dépôt de céramique de faible épaisseur sur un substrat métallique | |
EP4237699A1 (fr) | Procédé de fabrication d'une bande de freinage d'un disque de frein en fonte à résistance accrue à l'usure et à la corrosion et bande de freinage ainsi obtenue | |
Usmani et al. | Solar selective coatings with enhanced thermal and corrosion stability: electrochemically deposited black chrome on stainless steel in the presence of graphite encapsulated FeCo nanoparticles | |
Murakami et al. | Application of Ir-base alloys to novel oxidation resistant bond-coatings |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19960404 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE ES FR GB IT NL SE |
|
17Q | First examination report despatched |
Effective date: 19960805 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE ES FR GB IT NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT Effective date: 19980304 Ref country code: ES Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19980304 |
|
REF | Corresponds to: |
Ref document number: 69408859 Country of ref document: DE Date of ref document: 19980409 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19980604 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19980609 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19991013 Year of fee payment: 6 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19991015 Year of fee payment: 6 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19991026 Year of fee payment: 6 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19991029 Year of fee payment: 6 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19991127 Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20001013 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20001031 |
|
BERE | Be: lapsed |
Owner name: INSTITUT NATIONAL POLYTECHNIQUE DE TOULOUSE INPT Effective date: 20001031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010501 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20001013 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010629 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20010501 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010703 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |