EP0257671B1 - Process for removing niobium-containing coatings from a substrate - Google Patents

Process for removing niobium-containing coatings from a substrate Download PDF

Info

Publication number
EP0257671B1
EP0257671B1 EP87201347A EP87201347A EP0257671B1 EP 0257671 B1 EP0257671 B1 EP 0257671B1 EP 87201347 A EP87201347 A EP 87201347A EP 87201347 A EP87201347 A EP 87201347A EP 0257671 B1 EP0257671 B1 EP 0257671B1
Authority
EP
European Patent Office
Prior art keywords
coating
niobium
substrate
bath
process according
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
Application number
EP87201347A
Other languages
German (de)
French (fr)
Other versions
EP0257671A1 (en
Inventor
Lucien Clerbois
Gérard Parissis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay SA
Original Assignee
Solvay SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Solvay SA filed Critical Solvay SA
Priority to AT87201347T priority Critical patent/ATE74971T1/en
Publication of EP0257671A1 publication Critical patent/EP0257671A1/en
Application granted granted Critical
Publication of EP0257671B1 publication Critical patent/EP0257671B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00Etching metallic material by chemical means
    • C23F1/44Compositions for etching metallic material from a metallic material substrate of different composition
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00Etching metallic material by chemical means
    • C23F1/10Etching compositions
    • C23F1/14Aqueous compositions
    • C23F1/32Alkaline compositions
    • C23F1/38Alkaline compositions for etching refractory metals

Definitions

  • the present invention relates to a method for removing a coating comprising niobium on a substrate.
  • Niobium and niobium alloys are known for their interesting chemical and electrical properties, in particular their resistance to corrosion vis-à-vis most corrosive substances at room temperature and especially their qualities of excellent conductor of heat and electricity.
  • niobium and its alloys are frequently used for the construction of chemical engineering apparatus and installations and also as a superconductive coating of electrodes.
  • the electrical resistivity of niobium and its alloys becomes almost zero below 8.3 ° K (Revue de la cios Royale Belge des In conurs et des Industriels -n ° 8/9 - 1969: R WINAND, "Properties and uses of refractory metals", pages 381 to 415).
  • the high price of niobium frequently encourages its use in the form of a coating on a substrate (R. Lescarts - Dictionary of non-ferrous metals - 1972 - p. 107).
  • the invention therefore aims to provide a method for quickly and effectively removing a coating comprising niobium on a substrate without giving rise to polluting and toxic discharges and, above all, without damaging the substrate, in particular when the latter is in copper.
  • the invention relates to a method for removing a coating comprising niobium on a substrate, according to which the coating is treated with a pickling bath consisting of an aqueous solution of alkali metal hydroxide and hydrogen peroxide; according to the invention, the bath according to the process should contain, per liter, at least 0.4 mole of alkali metal hydroxide and at least 7.5 ml of 100% hydrogen peroxide and at most 4 moles of alkali metal hydroxide and 155 ml of 100% hydrogen peroxide.
  • the alkali metal hydroxide can for example be sodium hydroxide or potassium hydroxide.
  • Sodium hydroxide is preferred.
  • alkali metal hydroxide and hydrogen peroxide in the process according to the invention depend on various parameters, in particular the temperature at which they are used, the desired attack speed, the thickness of the coating to be remove and material from the substrate.
  • baths which can be used in the process according to the invention are those containing, per liter, between 0.5 and 4 moles of alkali metal hydroxide and between 10 and 155 ml of 100% hydrogen peroxide.
  • the preferred baths are those containing, per liter, between 0.5 and 2 moles of alkali metal hydroxide and between 13 and 75 ml of 100% hydrogen peroxide.
  • the aqueous solution of the baths according to the process according to the invention may advantageously contain, in usual proportions, a stabilizer of hydrogen peroxide such as a derivative of gluconic acid or of a phosphonic acid, for example one of the products known under the brand name "DEQUEST" (Monsanto) which are derivatives of phosphonic acid. It may optionally contain additives commonly present in metal pickling baths, such as surfactants and corrosion inhibitors, for example.
  • the pickling baths according to the process according to the invention are suitable for removing a coating containing niobium on all types of substrates which are not likely to undergo local corrosion in contact with said baths. They are specially adapted for removing a coating comprising niobium on a copper or copper-based alloy substrate.
  • the coating can be pure niobium or a niobium alloy, for example an Nb-C-N alloy or an Nb-Al-Ge alloy, or else an Nb-Ti alloy.
  • the treatment of the coating with the bath can be carried out by any suitable technique, for example by immersion of the substrate with its coating in the bath, by coating or by spraying the bath on the coating.
  • the amount of bath used must be sufficient to dissolve the niobium coating. It depends in particular on the mass of the coating to be removed, its constitution, the composition of the bath and the temperature. It must be determined in each case.
  • the process according to the invention should be carried out at a temperature at which there is no risk of untimely decomposition of the bath.
  • the term of the reaction of the bath with the coating is detected, by a measurement of the electrochemical potential of the substrate in the bath.
  • the method according to the invention finds an application in particular in the construction and maintenance of particle accelerators such as cyclotrons for example, where it can be used to remove a superconductive coating of niobium or of niobium alloy from the wall.
  • particle accelerators such as cyclotrons for example
  • copper cavities forming the electrodes supplied with high frequency current for example an alloy of niobium and titanium as suggested in the document Research and Development - January 1986 - pages 49 and 50: "Physics - Magnet design brings breath of reality to SSC ").
  • a wafer was immersed in the bath at room temperature and the niobium removal process was followed by a measurement of the electrochemical potential of the wafer relative to a reference electrode of calomel saturated with KCl.
  • the weight of niobium removed was determined by measuring the weight of the wafer, before and after treatment, respectively; knowing the area of the wafer, the thickness of the eliminated niobium film has been deduced therefrom.
  • Table II Test No Duration of treatment (min) Potential of the brochure Nb film removed Initial (mV) Final (mV) Thickness ( ⁇ m) 1 10 -210 + 25 1.6 2 18 -250 - 3 0.46 3 51 -380 - 8 0.74
  • the platelets collected at the end of the tests were found to be completely stripped of their niobium coating. They had a uniformly polished surface, free of corrosion zones.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • ing And Chemical Polishing (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Materials For Medical Uses (AREA)
  • Chemically Coating (AREA)

Abstract

Baths consisting of an aqueous solution of hydrogen peroxide and alkali metal hydroxide. The coating is treated with the bath in order to remove the substrate by dissolution.

Description

La présente invention concerne un procédé pour éliminer un revêtement comprenant du niobium sur un substrat.The present invention relates to a method for removing a coating comprising niobium on a substrate.

Le niobium et les alliages de niobium sont connus pour leurs propriétés chimiques et électriques intéressantes, notamment leur résistance à la corrosion vis-à-vis de la plupart des substances corrosives à température ambiante et surtout leurs qualités d'excellent conducteur de la chaleur et de l'électricité. Il en résulte que le niobium et ses alliages sont fréquemment utilisés pour la construction d'appareils et d'installations de génie chimique et aussi comme revêtement supraconducteur d'électrodes. On sait, en effet, que la résistivité électrique du niobium et de ses alliages devient quasi nulle au-dessous de 8,3°K (Revue de la Société Royale Belge des Ingénieurs et des Industriels -n° 8/9 - 1969 : R. WINAND, "Propriétés et usages des métaux réfractaires", pages 381 à 415). Toutefois, le prix élevé du niobium incite fréquemment à l'utiliser sous la forme de revêtement sur un substrat (R. Lescarts - Dictionnaire des métaux non ferreux - 1972 - p. 107).Niobium and niobium alloys are known for their interesting chemical and electrical properties, in particular their resistance to corrosion vis-à-vis most corrosive substances at room temperature and especially their qualities of excellent conductor of heat and electricity. As a result, niobium and its alloys are frequently used for the construction of chemical engineering apparatus and installations and also as a superconductive coating of electrodes. We know, in fact, that the electrical resistivity of niobium and its alloys becomes almost zero below 8.3 ° K (Revue de la Société Royale Belge des Ingénieurs et des Industriels -n ° 8/9 - 1969: R WINAND, "Properties and uses of refractory metals", pages 381 to 415). However, the high price of niobium frequently encourages its use in the form of a coating on a substrate (R. Lescarts - Dictionary of non-ferrous metals - 1972 - p. 107).

Dans la construction ou l'entretien d'électrodes ou d'autres organes portant un revêtement comprenant du niobium, on peut être amené à devoir procéder à la dissolution ou au décapage du revêtement afin de libérer le substrat totalement ou en partie.In the construction or maintenance of electrodes or other bodies carrying a coating comprising niobium, it may be necessary to dissolve or pickle the coating in order to release the substrate completely or in part.

Pour effectuer le décapage du niobium, on a proposé d'utiliser, à une température inférieure à 50°C, une solution décapante contenant 45 à 65 parties en volume d'eau, 30 à 50 parties en volume d'acide sulfurique concentré, 0,2 à 3,0 parties en volume d'une solution aqueuse concentrée de peroxyde d'hydrogène et 1,0 à 5,0 parties en volume d'acide fluorhydrique concentré (Central Patents Index, Basic Abstracts Journal, Section L, Week D.19, Derwent Publications Ltd., Londres, abrégé 33525D-L : demande de brevet JP-A-56029324 (Tokyo Shibaura Elec. Ltd)). Le décapage ainsi réalisé est généralement rapide et efficace, mais la présence d'acide fluorhydrique rend ces bains connus, toxiques et dangereux pour les utilisateurs et donne lieu, par conséquent, à des rejets polluants. Ces bains sont par ailleurs contre-indiqués dans le cas d'un substrat en cuivre, qu'ils risquent de corroder.To carry out the pickling of niobium, it has been proposed to use, at a temperature below 50 ° C., a pickling solution containing 45 to 65 parts by volume of water, 30 to 50 parts by volume of concentrated sulfuric acid, 0 , 2 to 3.0 parts by volume of a concentrated aqueous solution of hydrogen peroxide and 1.0 to 5.0 parts by volume of concentrated hydrofluoric acid (Central Patents Index, Basic Abstracts Journal, Section L, Week D .19, Derwent Publications Ltd., London, abstract 33525D-L: Patent Application JP-A-56029324 (Tokyo Shibaura Elec. Ltd)). The pickling thus carried out is generally rapid and effective, but the presence of hydrofluoric acid makes these baths known, toxic and dangerous for the users and gives rise, consequently, to polluting discharges. These baths are also contraindicated in the case of a copper substrate, which they risk corroding.

L'invention vise dès lors à fournir un procédé permettant d'éliminer rapidement et efficacement un revêtement comprenant du niobium sur un substrat sans donner naissance à des rejets polluants et toxiques et, surtout, sans endommager le substrat, notamment lorsque celui-ci est en cuivre.The invention therefore aims to provide a method for quickly and effectively removing a coating comprising niobium on a substrate without giving rise to polluting and toxic discharges and, above all, without damaging the substrate, in particular when the latter is in copper.

En conséquence, l'invention concerne un procédé pour éliminer un revêtement comprenant du niobium sur un substrat, selon lequel on traite le revêtement avec un bain décapant consistant en une solution aqueuse d'hydroxyde de métal alcalin et de peroxyde d'hydrogène ; selon l'invention, il convient que le bain conforme au procédé contienne, par litre, au moins 0,4 mole d'hydroxyde de métal alcalin et au moins 7,5 ml de peroxyde d'hydrogène à 100 % et au plus 4 moles d'hydroxyde de métal alcalin et 155 ml de peroxyde d'hydrogène à 100 %.Accordingly, the invention relates to a method for removing a coating comprising niobium on a substrate, according to which the coating is treated with a pickling bath consisting of an aqueous solution of alkali metal hydroxide and hydrogen peroxide; according to the invention, the bath according to the process should contain, per liter, at least 0.4 mole of alkali metal hydroxide and at least 7.5 ml of 100% hydrogen peroxide and at most 4 moles of alkali metal hydroxide and 155 ml of 100% hydrogen peroxide.

Dans le procédé selon l'invention, l'hydroxyde de métal alcalin peut par exemple être de l'hydroxyde de sodium ou de l'hydroxyde de potassium. L'hydroxyde de sodium est préféré.In the process according to the invention, the alkali metal hydroxide can for example be sodium hydroxide or potassium hydroxide. Sodium hydroxide is preferred.

Les teneurs en hydroxyde de métal alcalin et en peroxyde d'hydrogène dans le procédé selon l'invention dépendent de divers paramètres, notamment de la température à laquelle on les utilise, de la vitesse d'attaque souhaitée, de l'épaisseur du revêtement à éliminer et du matériau du substrat. Des exemples de bains utilisables dans le procédé selon l'invention sont ceux contenant, par litre, entre 0,5 et 4 moles d'hydroxyde de métal alcalin et entre 10 et 155 ml de peroxyde d'hydrogène à 100 %. Les bains préférés sont ceux contenant, par litre, entre 0,5 et 2 moles d'hydroxyde de métal alcalin et entre 13 et 75 ml de peroxyde d'hydrogène à 100 %.The contents of alkali metal hydroxide and hydrogen peroxide in the process according to the invention depend on various parameters, in particular the temperature at which they are used, the desired attack speed, the thickness of the coating to be remove and material from the substrate. Examples of baths which can be used in the process according to the invention are those containing, per liter, between 0.5 and 4 moles of alkali metal hydroxide and between 10 and 155 ml of 100% hydrogen peroxide. The preferred baths are those containing, per liter, between 0.5 and 2 moles of alkali metal hydroxide and between 13 and 75 ml of 100% hydrogen peroxide.

La solution aqueuse des bains conformes au procédé selon l'invention peut avantageusement contenir, en des proportions usuelles, un stabilisant du peroxyde d'hydrogène tel qu'un dérivé de l'acide gluconique ou d'un acide phosphonique, par exemple un des produits connus sous la marque "DEQUEST" (Monsanto) qui sont des dérivés d'acide phosphonique. Elle peut éventuellement contenir des additifs communément présents dans les bains de décapage des métaux, tels que des agents tensioactifs et des inhibiteurs de corrosion, par exemple.The aqueous solution of the baths according to the process according to the invention may advantageously contain, in usual proportions, a stabilizer of hydrogen peroxide such as a derivative of gluconic acid or of a phosphonic acid, for example one of the products known under the brand name "DEQUEST" (Monsanto) which are derivatives of phosphonic acid. It may optionally contain additives commonly present in metal pickling baths, such as surfactants and corrosion inhibitors, for example.

Les bains décapants conformes au procédé selon l'invention conviennent pour éliminer un revêtement contenant du niobium sur tous types de substrats qui ne risquent pas de subir des corrosions locales au contact desdits bains. Ils sont spécialement adaptés à l'élimination d'un revêtement comprenant du niobium sur un substrat en cuivre ou en alliage à base de cuivre. Le revêtement peut être du niobium pur ou un alliage de niobium, par exemple un alliage Nb-C-N ou un alliage Nb-Al-Ge, ou encore un alliage Nb-Ti.The pickling baths according to the process according to the invention are suitable for removing a coating containing niobium on all types of substrates which are not likely to undergo local corrosion in contact with said baths. They are specially adapted for removing a coating comprising niobium on a copper or copper-based alloy substrate. The coating can be pure niobium or a niobium alloy, for example an Nb-C-N alloy or an Nb-Al-Ge alloy, or else an Nb-Ti alloy.

Dans le procédé selon l'invention, le traitement du revêtement avec le bain peut être exécuté par toute technique adéquate, par exemple par immersion du substrat avec son revêtement dans le bain, par enduction ou par pulvérisation du bain sur le revêtement.In the method according to the invention, the treatment of the coating with the bath can be carried out by any suitable technique, for example by immersion of the substrate with its coating in the bath, by coating or by spraying the bath on the coating.

La quantité de bain mis en oeuvre doit être suffisante pour dissoudre le revêtement de niobium. Elle dépend notamment de la masse du revêtement à éliminer, de sa constitution, de la composition du bain et de la température. Elle doit être déterminée dans chaque cas.The amount of bath used must be sufficient to dissolve the niobium coating. It depends in particular on the mass of the coating to be removed, its constitution, the composition of the bath and the temperature. It must be determined in each case.

Il convient d'exécuter le procédé selon l'invention à une température à laquelle on ne risque pas une décomposition intempestive du bain. A cet effet, il est généralement opportun de mettre le bain en oeuvre à une température n'excédant pas 50°C, la température ambiante, comprise entre 15 et 25°C, étant la plus adéquate dans la plupart des cas.The process according to the invention should be carried out at a temperature at which there is no risk of untimely decomposition of the bath. For this purpose, it is generally advisable to carry out the bath at a temperature not exceeding 50 ° C., the ambient temperature, between 15 and 25 ° C., being the most adequate in most cases.

Dans le procédé selon l'invention, il est important de pouvoir suivre l'évolution du processus d'élimination du revêtement du substrat, de manière à déceler avec précision l'instant opportun pour cesser le traitement avec le bain. A cet effet, dans une forme d'exécution avantageuse du procédé selon l'invention, on décèle le terme de la réaction du bain avec le revêtement, par une mesure du potentiel électrochimique du substrat dans le bain. Dans la mise en oeuvre de cette forme d'exécution du procédé, il suffit dès lors de coupler une cellule de mesure de potentiel entre le substrat muni de son revêtement et une électrode de référence, immergée dans le bain.In the method according to the invention, it is important to be able to follow the progress of the process of removing the coating from the substrate, so as to accurately detect the opportune moment to stop the treatment with the bath. To this end, in a advantageous embodiment of the method according to the invention, the term of the reaction of the bath with the coating is detected, by a measurement of the electrochemical potential of the substrate in the bath. In the implementation of this embodiment of the method, it therefore suffices to couple a potential measurement cell between the substrate provided with its coating and a reference electrode, immersed in the bath.

Le procédé selon l'invention trouve notamment une application dans la construction et l'entretien des accélérateurs de particules tels que les cyclotrons par exemple, où il peut être utilisé pour éliminer un revêtement supraconducteur de niobium ou d'alliage de niobium de la paroi en cuivre des cavités formant les électrodes alimentées en courant à haute fréquence (par exemple un alliage de niobium et de titane comme suggéré dans le document Research and Development - January 1986 - pages 49 et 50 : "Physics - Magnet design brings breath of reality to SSC").The method according to the invention finds an application in particular in the construction and maintenance of particle accelerators such as cyclotrons for example, where it can be used to remove a superconductive coating of niobium or of niobium alloy from the wall. copper cavities forming the electrodes supplied with high frequency current (for example an alloy of niobium and titanium as suggested in the document Research and Development - January 1986 - pages 49 and 50: "Physics - Magnet design brings breath of reality to SSC ").

L'intérêt de l'invention va ressortir des exemples dont la description suit.The advantage of the invention will emerge from the examples, the description of which follows.

Ces exemples concernent des essais dans lesquels des plaquettes en cuivre portant un revêtement de niobium ont été traitées conformément au procédé selon l'invention, pour éliminer le revêtement de niobium.These examples relate to tests in which copper plates carrying a niobium coating were treated in accordance with the method according to the invention, in order to remove the niobium coating.

On a procédé à trois essais avec des bains conformes au procédé selon l'invention, dont la composition est donnée au tableau I. Tableau I Essai No Composition du bain NaOH (mole/l) H₂O₂ (100 %) (ml/l) Stabilisant : DTPMP à 50 % (*) (ml/l) 1 1 76 2,5 2 1 38 0 3 0,5 25 2,5 (*) Diethylenetriaminepenta(methylenephosphonic acid) Three tests were carried out with baths in accordance with the process according to the invention, the composition of which is given in Table I. Table I Trial No Bath composition NaOH (mole / l) H₂O₂ (100%) (ml / l) Stabilizer: DTPMP at 50% (*) (ml / l) 1 1 76 2.5 2 1 38 0 3 0.5 25 2.5 (*) Diethylenetriaminepenta (methylenephosphonic acid)

Dans chaque essai, on a immergé une plaquette dans le bain à la température ambiante et on a suivi le processus d'élimination du niobium par une mesure du potentiel électrochimique de la plaquette par rapport à une électrode de référence au calomel saturé en KCl. On a déterminé le poids de niobium éliminé au moyen d'une mesure du poids de la plaquette, respectivement avant et après le traitement; connaissant la superficie de la plaquette, on en a déduit l'épaisseur de la pellicule de niobium éliminée.In each test, a wafer was immersed in the bath at room temperature and the niobium removal process was followed by a measurement of the electrochemical potential of the wafer relative to a reference electrode of calomel saturated with KCl. The weight of niobium removed was determined by measuring the weight of the wafer, before and after treatment, respectively; knowing the area of the wafer, the thickness of the eliminated niobium film has been deduced therefrom.

Les résultats des essais sont répertoriés au tableau II. Tableau II Essai N° Durée du traitement (min) Potentiel de la plaquette Pellicule de Nb éliminée Initial (mV) Final (mV) Epaisseur (µm) 1 10 -210 + 25 1,6 2 18 -250 - 3 0,46 3 51 -380 - 8 0,74 The results of the tests are listed in Table II. Table II Test No Duration of treatment (min) Potential of the brochure Nb film removed Initial (mV) Final (mV) Thickness (µm) 1 10 -210 + 25 1.6 2 18 -250 - 3 0.46 3 51 -380 - 8 0.74

Les plaquettes recueillies à l'issue des essais se sont avérées entièrement débarrassées de leur revêtement de niobium. Elles présentaient une surface uniformément polie, exempte de zones de corrosion.The platelets collected at the end of the tests were found to be completely stripped of their niobium coating. They had a uniformly polished surface, free of corrosion zones.

Claims (7)

  1. Process for removing a coating containing niobium on a substrate, according to which the coating is treated with a pickling bath consisting of an aqueous solution of 7.5 to 155 ml of hydrogen peroxide and 0.4 to 4 moles of alkali metal hydroxide per litre.
  2. Process according to Claim 1, characterized in that the alkali metal hydroxide is sodium hydroxide.
  3. Process according to Claim 1 or 2, characterized in that the aqueous solution contains, per litre, between 13 and 75 ml of hydrogen peroxide and between 0.5 and 2 moles of alkali metal hydroxide.
  4. Process according to any one of Claims 1 to 3, characterised in that the agueous solution contains a stabiliser for hydrogen peroxide, chosen from the derivatives of gluconic acid and of phosphonic acids.
  5. Process according to any one of Claims 1 to 4, characterised in that the bath is used at a temperature of between 15 and 25°C.
  6. Process according to any one of Claims 1 to 5, characterised in that it is applied to the removal of a coating of niobium or of niobium alloy on a substrate made of copper or copper alloy.
  7. Process according to any one of Claims 1 to 6, characterised in that the end of the reaction of the bath with the coating is detected by a measurement of the electrochemical potential of the substrate in the bath.
EP87201347A 1986-07-25 1987-07-14 Process for removing niobium-containing coatings from a substrate Expired - Lifetime EP0257671B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87201347T ATE74971T1 (en) 1986-07-25 1987-07-14 METHOD OF REMOVING A NIOBIUM CONTAINING COATING FROM A SUBSTRATE.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8611001A FR2601968B1 (en) 1986-07-25 1986-07-25 STRIPPING BATHS AND METHOD FOR REMOVING A COATING COMPRISING NIOBIUM ON A SUBSTRATE.
FR8611001 1986-07-25

Publications (2)

Publication Number Publication Date
EP0257671A1 EP0257671A1 (en) 1988-03-02
EP0257671B1 true EP0257671B1 (en) 1992-04-15

Family

ID=9337854

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87201347A Expired - Lifetime EP0257671B1 (en) 1986-07-25 1987-07-14 Process for removing niobium-containing coatings from a substrate

Country Status (7)

Country Link
US (1) US4950359A (en)
EP (1) EP0257671B1 (en)
JP (1) JPS6335787A (en)
AT (1) ATE74971T1 (en)
BR (1) BR8605611A (en)
DE (1) DE3778246D1 (en)
FR (1) FR2601968B1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5269850A (en) * 1989-12-20 1993-12-14 Hughes Aircraft Company Method of removing organic flux using peroxide composition
US5232619A (en) * 1990-10-19 1993-08-03 Praxair S.T. Technology, Inc. Stripping solution for stripping compounds of titanium from base metals
EP0506928B1 (en) * 1990-10-19 1995-09-13 Praxair S.T. Technology, Inc. Stripping solution and process for stripping compounds of titanium from base metals
US5201997A (en) * 1991-12-31 1993-04-13 United Technologies Corporation Chemical milling of niobium
US6074961A (en) * 1998-06-18 2000-06-13 Taiwan Semiconductor Manufacturing Company Caro's cleaning of SOG control wafer residue
US20110017608A1 (en) * 2009-07-27 2011-01-27 Faraday Technology, Inc. Electrochemical etching and polishing of conductive substrates
US8836120B2 (en) 2011-04-19 2014-09-16 Infineon Technologies Ag Semiconductor device with a layer including niobium, and/or tantalum overlying a contact pad or a metal layer
CN105018934A (en) * 2015-07-15 2015-11-04 安徽多晶涂层科技有限公司 Coating stripping powder for hard coating, prepared coating stripping liquid and coating stripping method
JP7297623B2 (en) * 2019-09-24 2023-06-26 株式会社東芝 Wire processing method

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1999807A (en) * 1934-06-25 1935-04-30 Harold L Gibbs Extraction of values from ores
US3394063A (en) * 1965-10-22 1968-07-23 Matthew C. Blume Electrolytic stripping of copper, zinc and tin based coatings from a ferrous base using an alkaline pyrophosphate electrolyte
US3492210A (en) * 1967-10-16 1970-01-27 Hamilton Cosco Inc Electrolytic stripping of nonferrous metals from a ferrous metal base
JPS4829638A (en) * 1971-08-20 1973-04-19
US3802973A (en) * 1972-08-09 1974-04-09 Pennwalt Corp Aluminum etching process
DE2239425C3 (en) * 1972-08-10 1978-04-20 Siemens Ag, 1000 Berlin Und 8000 Muenchen Process for the electrolytic treatment of niobium surfaces for alternating current applications
US4304762A (en) * 1978-09-27 1981-12-08 Lever Brothers Company Stabilization of hydrogen peroxide
US4497725A (en) * 1980-04-01 1985-02-05 Interox Chemicals Ltd. Aqueous bleach compositions
US4495158A (en) * 1984-02-29 1985-01-22 Gte Products Corporation Process for the recovery of tantalum values

Also Published As

Publication number Publication date
DE3778246D1 (en) 1992-05-21
US4950359A (en) 1990-08-21
BR8605611A (en) 1988-03-29
FR2601968B1 (en) 1989-04-14
ATE74971T1 (en) 1992-05-15
JPS6335787A (en) 1988-02-16
FR2601968A1 (en) 1988-01-29
EP0257671A1 (en) 1988-03-02

Similar Documents

Publication Publication Date Title
CA1294238C (en) Selective electrolytic removal of metal coating from base metal with alkanesulfonic acid solution
WO1983000704A1 (en) Copper-containing articles with a corrosion inhibitor coating and methods of producing the coating
EP0257671B1 (en) Process for removing niobium-containing coatings from a substrate
EP0931854A1 (en) Corrosion inhibiting of stainless steel in organic sulphonic acid
TW200949016A (en) Etching solution, etching pre-treating solution and etching process for copper or copper alloy
CN107513716A (en) A kind of raw material of aluminum alloy method for cleaning surface
JPH0480117B2 (en)
FR2571744A1 (en) METHOD AND SOLUTION FOR CHEMICAL ENGRAVING NICKEL
CN104498950B (en) A kind of high selectivity titanium layer etching bath composition
JPS6092487A (en) Gold and palladium quick recovery
EP0574858B1 (en) Inorganic oxidant compositions for removing contaminants
JPS62170484A (en) Method for lubricating stainless steel before cold working
US2408220A (en) Stripping of copper from zinc
WO2000075404A1 (en) Electrolytic removing agent for silver and method for electrolytic removing
JPH0413431B2 (en)
BE740608A (en) Metal cleaning and protection process
EP0143051B1 (en) Process for removing gangue from metallic parts
JPH09302325A (en) Drying pretreatment agent of metal and drying of metal
SU885168A1 (en) Pickling solution
US3262775A (en) Stripping of chromium plate using a solution containing sulfamic acid and a water soluble chloride
FR2562914A1 (en) PROCESS FOR INHIBITING CORROSION OF A METAL MASS IN CONTACT WITH AN ACIDIC BATH CONTAINING AN OXIDANT
JPS5887275A (en) Stripping method for sn layer on cu and cu alloy
CN117577463A (en) Surface passivation technology for red copper busbar of capacitor
JP2022133629A (en) Production method of aluminum wires
JPS64469B2 (en)

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

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19880822

17Q First examination report despatched

Effective date: 19900212

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SOLVAY

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU 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: 19920415

Ref country code: SE

Effective date: 19920415

Ref country code: AT

Effective date: 19920415

Ref country code: GR

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: 19920415

Ref country code: NL

Effective date: 19920415

Ref country code: GB

Effective date: 19920415

REF Corresponds to:

Ref document number: 74971

Country of ref document: AT

Date of ref document: 19920515

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3778246

Country of ref document: DE

Date of ref document: 19920521

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

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: 19920726

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]
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

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19930401

26N No opposition filed
EPTA Lu: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20010706

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20010712

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20010713

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20010918

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020714

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020731

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020731

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020731

BERE Be: lapsed

Owner name: *SOLVAY

Effective date: 20020731

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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: 20030331

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST