EP0227518B1 - Hydrazine bath for the chemical deposition of nickel and/or cobalt, and process for preparing the same - Google Patents

Hydrazine bath for the chemical deposition of nickel and/or cobalt, and process for preparing the same Download PDF

Info

Publication number
EP0227518B1
EP0227518B1 EP86402528A EP86402528A EP0227518B1 EP 0227518 B1 EP0227518 B1 EP 0227518B1 EP 86402528 A EP86402528 A EP 86402528A EP 86402528 A EP86402528 A EP 86402528A EP 0227518 B1 EP0227518 B1 EP 0227518B1
Authority
EP
European Patent Office
Prior art keywords
bath according
bath
nickel
hydroxide
cobalt
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
EP86402528A
Other languages
German (de)
French (fr)
Other versions
EP0227518A1 (en
Inventor
Pierre Josso
Isabelle Gossart
Claude Duret-Thual
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.)
Office National dEtudes et de Recherches Aerospatiales ONERA
Original Assignee
Office National dEtudes et de Recherches Aerospatiales ONERA
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 Office National dEtudes et de Recherches Aerospatiales ONERA filed Critical Office National dEtudes et de Recherches Aerospatiales ONERA
Publication of EP0227518A1 publication Critical patent/EP0227518A1/en
Application granted granted Critical
Publication of EP0227518B1 publication Critical patent/EP0227518B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents

Definitions

  • the invention relates to the chemical deposition of nickel and / or cobalt by autocatalytic reduction.
  • the nickel and / or cobalt deposits obtained from these baths are not pure. They indeed contain phosphorus or boron from the reducing agent, as well as elements from stabilizers: sulfur and / or heavy metals, for example thallium.
  • Patent No. 2,531,103 of the Applicant proposes baths making it possible to obtain deposits free of impurities from the stabilizers, and intended in particular for the treatment of turbine blades for aeronautical applications, these impurities being very troublesome for these applications and cannot be removed by further processing.
  • the deposits obtained still contain phosphorus or boron coming from phosphorus or boron reducers and these impurities are troublesome for the applications considered; it is therefore necessary to remove them after the deposition operation.
  • Hydrazine meets these conditions, its oxidation by nickel or cobalt ions exclusively leading to the formation of hydrogen and nitrogen, which are released in the gaseous state.
  • An object of the invention is to provide baths for the chemical deposition of nickel and / or cobalt which can be used industrially and which make it possible to obtain very pure deposits of considerable thickness.
  • Another object is to provide hydrazine baths for the chemical deposition of nickel and / or cobalt which can be used industrially and which leads to deposits of considerable thickness.
  • the inventors studied the equilibria and the chemical reactions taking place in hydrazine baths and led to the formulation of the hypotheses set out below.
  • the nickel and / or cobalt ions are complexed concurrently by the hydrazine and by the complexing agent proper of the bath, the partition coefficient between the hydrazine and the complexing agent being determined by the dissociation constants of the two complexing reactions.
  • the subject of the invention is a bath for the chemical deposition of nickel and / or cobalt, comprising a compound of the metal (or metals) to be deposited, a reducing agent consisting of hydrazine, a metal complexing agent, and at least one stabilizer, characterized in that said compound is nickel-II-tri (ethylenediamine) hydroxide and / or cobalt-II-tri (ethylenediamine) hydroxide of formula M (NH2CZH4-NH2) 3 (OH) z, in which M represents nickel and / or cobalt, ethylenediamine playing the role of the complexing agent.
  • Nickel (or cobalt) II-tri (ethylenediamine) hydroxide is perfectly compatible with hydrazine and their joint use allows the bath to operate for a practically unlimited period by continuous addition of the metallic compound and the reducing agent, the ethylenediamine concentration does not not intervening in the deposition mechanism as long as this body is in excess, which results in the possibility of obtaining very pure and thick deposits.
  • the bath according to the invention is preferably brought to a pH greater than 11 by an basifying agent which can be sodium hydroxide.
  • the bath according to the invention allows the inclusion in the deposit of particles, for example of alumina AI 2 0 3 or of yttrin Y 2 0 3 , contained in the bath. Thanks to the regularity over time of the characteristics of the bath, a uniform distribution of the particles is obtained in the thickness of the deposit.
  • the invention also relates to a process for manufacturing a bath as described above, in which an alkaline solution of M (NH 2 C 2 H 4 ⁇ NH 2 ) 3 (OH) 2 , called a stock solution, and then add stabilizers and hydrazine.
  • FIGS. 1 to 6 are micrographic sections of chemical deposition obtained by the use of the 'invention.
  • the initial metal salt is a pure salt for electroplating.
  • the choice of the anion (designated by A-) associated with the cation is indifferent and left to the choice of a person skilled in the art (chloride, sulfate or the like).
  • the starting salt is the basic carbonate of M, commonly used in the art for the correction of the pH of electrolytic baths with nickel and / or cobalt sulfamate.
  • the advantage presented by the use of such a salt lies in its intrinsic purity, due to its method of preparation. It is treated directly with anhydrous ethylenediamine in an amount 10% greater than the stoichiometric amount required and the reaction takes place:
  • the solution obtained is diluted to half.
  • the anion of the initial salt is indifferent; the MA 2 solution is prepared in the same way. To this solution is added a large excess of oxalic acid which causes precipitation of M oxalate according to the reaction:
  • the temperature of the bath is maintained between 88 and 92 ° C.
  • the deposition rate is then between 10 and 15 ⁇ m.h -1 .
  • Figure 1 is a photograph of a deposit obtained on a brass substrate, magnified 500 times.
  • the deposit of pure nickel obtained is light gray, of regular thickness and of a hardness of approximately 450 HK (or Knoop hardness) under load of 50 g.
  • the temperature is maintained between 88 and 92 ° C.
  • the deposition reaction starts spontaneously, even on copper alloy substrates.
  • the weight gain is approximately 115 mg.cm -2 .h -1 , which corresponds to a growth rate of the deposit of approximately 130 ⁇ m.h -1 .
  • the deposit obtained is black and does not reflect light. metallographic observation of a section of this deposit shows that it is porous (see FIG. 2 which represents a photograph magnified 100 times of a deposit obtained on a brass substrate).
  • the hardness measured on the gross bath deposit amounts to approximately 400 HK (or 450 HV, Vickers hardness), under a load of 50 g.
  • This bath contains thallium ions and consequently leads to the presence of traces of thallium in the deposit.
  • these thallium baths are not suitable for the aeronautical applications mentioned above. However, they can be of great interest in other applications, because of their longevity, regularity, thickness, physical and mechanical characteristics of the deposits which they make it possible, and the possibility of include in them evenly distributed particles.
  • a bath comprising, as stabilizer, thallium sulfate.
  • This bath differs from the previous one in that the nickel-II-tri (ethylenediamine) hydroxide is replaced by an equivalent amount of cobalt-II-tri (ethylenediamine) hydroxide, and in that 1.7 mol.1 -1 are added. ethylenediamine.
  • the temperature of the bath is maintained between 78 and 82 ° C.
  • the deposition rate is between 25 and 30 ⁇ m.h -1 .
  • FIG. 3 The photograph in FIG. 3, magnified 500 times, illustrates the deposit of cobalt obtained on a brass substrate.
  • This deposit is semi-gloss, dense and regular, with a hardness of approximately 350 HK, under a load of 50 g.
  • This example illustrates a nickel deposition bath containing alumina particles.
  • the temperature is maintained between 88 and 92 ° C.
  • the deposition rate is around 35 ⁇ m.h -1 .
  • the deposit is black.
  • An examination on a metallographic section shows alumina particles included in the nickel deposit (see FIG. 4 which represents a photograph magnified 700 times of a deposit obtained on a brass substrate, the alumina having been added after 20 minutes of deposit).
  • the hardness of this deposit is approximately 400 HV, under a load of 50 g, comparable to that obtained for the deposit without alumina; and as in Example 5, the deposit is porous.
  • the temperature is maintained between 88 and 92 ° C.
  • the deposition reaction starts spontaneously, even on substrates made of copper alloys.
  • the deposition rate is approximately 20 ⁇ m.h. -1 .
  • the deposit is dark gray, dense and regular (see Figure 5 which represents a photograph 750 times magnified by two successive deposits obtained on a brass substrate, without any surface preparation between them).
  • Example 8 The bath of Example 8 is resumed, to which 20 grams per liter of yttrin particles with a particle size of between 0.5 and 1.5 microns are added.
  • the temperature is maintained between 88 and 92 ° C and the bath is stirred by means of a rotary agitator at about 800 revolutions per minute.
  • the deposition rate is between 10 and 15 ⁇ m.h -1 .
  • the deposit obtained is dark gray, dense and regular: a metallographic examination shows the yttrin particles enclosed in a nickel matrix (see FIG. 6 which represents a photograph 950 times magnified of a deposit obtained on a mild steel substrate) .
  • the temperature is maintained between 78 and 82 ° C.
  • the deposition rate is 18.1 ⁇ m.h -1
  • a 13.2 ⁇ m thick deposit of a nickel-cobalt alloy was produced, as shown by the qualitative analysis by energy dispersive spectroscopy of the scanning electron microscope.
  • the content of occluded gas in the various deposits obtained is relatively low, which causes little tension in the metal layers.
  • the oxygen, nitrogen and hydrogen contents of the deposit of Example 6 are respectively 429, 542 and 9 ppm, significantly lower than the minimum values cited in the aforementioned article by Dini and Coronado, namely 900 , 2410 and 150 ppm.
  • the nickel deposition rate which is around 15 ⁇ m.h -1 for dense deposits, can be increased by adding thallium. Deposition rates of 130 ⁇ m.h -1 were thus obtained. In this case, the deposits are porous and black.

Description

L'invention concerne le dépôt chimique de nickel et/ou de cobalt par réduction autocatalytique.The invention relates to the chemical deposition of nickel and / or cobalt by autocatalytic reduction.

Tous les bains utilisés industriellement jusqu'à maintenant pour ce type de dépôt, qu'il s'agisse de bains acides ou de bains alcalins, utilisent un réducteur contenant du phosphore ou du bore sous forme d'un hypophosphite alcalin ou de dérivés hydrogénés du bore. En plus de ce réducteur, ils contiennent au moins un composé du métal ou des métaux à déposer, au moins un complexant de ce métal et au moins un stabilisant.All the baths used industrially until now for this type of deposit, whether acid baths or alkaline baths, use a reducing agent containing phosphorus or boron in the form of an alkaline hypophosphite or of hydrogenated derivatives of boron. In addition to this reducing agent, they contain at least one compound of the metal or metals to be deposited, at least one complexing agent for this metal and at least one stabilizer.

Les dépôts de nickel et/ou de cobalt obtenus à partir de ces bains ne sont pas purs. Ils contiennent en effet du phosphore ou du bore provenant du réducteur, ainsi que des éléments issus des stabilisants: soufre et/ou métaux lourds, par exemple thallium.The nickel and / or cobalt deposits obtained from these baths are not pure. They indeed contain phosphorus or boron from the reducing agent, as well as elements from stabilizers: sulfur and / or heavy metals, for example thallium.

Le brevet N° 2 531 103 du Demandeur propose des bains permettant d'obtenir des dépôts exempts d'impuretés issues des stabilisants, et destinés notamment au traitement d'aubes de turbines pour les applications aéronautiques, ces impuretés étant très gênantes pour ces applications et ne pouvant être éliminées par un traitement ultérieur.Patent No. 2,531,103 of the Applicant proposes baths making it possible to obtain deposits free of impurities from the stabilizers, and intended in particular for the treatment of turbine blades for aeronautical applications, these impurities being very troublesome for these applications and cannot be removed by further processing.

Mais les dépôts obtenus contiennent encore du phosphore ou du bore provenant des réducteurs au phosphore ou au bore et ces impuretés sont gênantes pour les applications considérées; il est donc nécessaire de les éliminer après l'opération de dépôt.However, the deposits obtained still contain phosphorus or boron coming from phosphorus or boron reducers and these impurities are troublesome for the applications considered; it is therefore necessary to remove them after the deposition operation.

Or, l'élimination du phosphore est très difficile et est même impossible dans certains cas. Quant au bore, il peut être enlevé, mais d'une façon incomplète, par un procédé décrit dans le brevet N° 2 278 794 du Demandeur.However, the removal of phosphorus is very difficult and is even impossible in some cases. As for boron, it can be removed, but in an incomplete manner, by a process described in patent No. 2,278,794 of the Applicant.

Il existe donc besoin de bains de dépôt chimique dont le réducteur ne contient ni phosphore ni bore, et conduisant à des dépôts exempts de ces impuretés.There is therefore a need for chemical deposition baths, the reducing agent of which contains neither phosphorus nor boron, and leading to deposits free of these impurities.

L'hydrazine répond à ces conditions, son oxydation par les ions nickel ou cobalt conduisant exclusivement à la formation d'hydrogène et d'azote, qui se dégagent à l'état gazeux.Hydrazine meets these conditions, its oxidation by nickel or cobalt ions exclusively leading to the formation of hydrogen and nitrogen, which are released in the gaseous state.

Des bains de dépôt chimique de nickel et/ou de cobalt contenant comme réducteur l'hydrozine sont décrits dans un article de Dini et Coronado publié dans Plating Vo. 54, p. 385 (1967), et dans le brevet des Etats-Unis N° 3 198 659.Baths of chemical deposition of nickel and / or cobalt containing as a reducing agent hydrozine are described in an article by Dini and Coronado published in Plating Vo. 54, p. 385 (1967), and in U.S. Patent No. 3,198,659.

Les bains décrits dans l'article nécessitent l'utilisation de produits de départ de très grande pureté et leur maintenance est extrêmement délicate, ce qui conduit à un coût trop élevé pour que puisse être envisagé un développement industriel du procédé.The baths described in the article require the use of very high purity starting materials and their maintenance is extremely delicate, which leads to a cost that is too high for industrial development of the process to be considered.

Les bains décrits dans le brevet Etats-Unis N° 3 198 659, comme l'indique l'article qui s'y réfère, ne permettent que des dépôts extrêmement minces, d'une épaisseur de de l'ordre du micron.The baths described in United States Patent No. 3,198,659, as indicated in the article referring to it, allow only extremely thin deposits, with a thickness of the order of a micron.

Un but de l'invention est de procurer des bains de dépôt chimique de nickel et/ou de cobalt utilisables industriellement et permettant d'obtenir des dépôts très purs et d'épaisseur importante.An object of the invention is to provide baths for the chemical deposition of nickel and / or cobalt which can be used industrially and which make it possible to obtain very pure deposits of considerable thickness.

un autre but est de procurer des bains à l'hydrazine pour le dépôt chimique de nickel et/ou de cobalt utilisables industriellement et conduisant à des dépôts d'épaisseur importante.another object is to provide hydrazine baths for the chemical deposition of nickel and / or cobalt which can be used industrially and which leads to deposits of considerable thickness.

Pour résoudre ce problème, les inventeurs ont étudié les équilibres et les réactions chimiques intervenant dans les bains à l'hydrazine et ont abouti à la formulation des hypothèses exposées ci-après.To solve this problem, the inventors studied the equilibria and the chemical reactions taking place in hydrazine baths and led to the formulation of the hypotheses set out below.

Les ions nickel et/ou cobalt sont complexés concurrement par l'hydrazine et par le complexant proprement dit du bain, le coefficient de partage entre l'hydrazine et le-complexant étant déterminé par les constantes de dissociation des deux réactions de complexation.The nickel and / or cobalt ions are complexed concurrently by the hydrazine and by the complexing agent proper of the bath, the partition coefficient between the hydrazine and the complexing agent being determined by the dissociation constants of the two complexing reactions.

Le dépôt du nickel ou du cobalt se fait uniquement par décharge du complexe hydrazine-cation métallique.The deposition of nickel or cobalt takes place only by discharge of the hydrazine-metal cation complex.

De nombreux ions, et en particulier les ions chlorure, sulfate et nitrate, ont un effet perturbateur sur la formation du complexe hydrazine-cation métallique et/ou sur l'activité catalytique du dépôt.Many ions, and in particular chloride, sulphate and nitrate ions, have a disturbing effect on the formation of the hydrazine-metal cation complex and / or on the catalytic activity of the deposit.

Ces considérations ont conduit les inventeurs sur la voie de la solution.These considerations led the inventors to the path of the solution.

L'invention a pour objet un bain pour le dépôt chimique de nickel et/ou de cobalt, comprenant un composé du métal (ou des métaux) à déposer, un réducteur constitué par l'hydrazine, un complexant du métal, et au moins un stabilisant, caractérisé en ce que ledit composé est le nickel-II-tri(éthylènediamine) hydroxyde et/ou le cobalt-II-tri(éthylènediamine) hydroxide de formule M(NH2CZH4-NH2)3(OH)z, dans laquelle M représente le nickel et/ou le cobalt, l'éthylènediamine jouant le rôle du complexant.The subject of the invention is a bath for the chemical deposition of nickel and / or cobalt, comprising a compound of the metal (or metals) to be deposited, a reducing agent consisting of hydrazine, a metal complexing agent, and at least one stabilizer, characterized in that said compound is nickel-II-tri (ethylenediamine) hydroxide and / or cobalt-II-tri (ethylenediamine) hydroxide of formula M (NH2CZH4-NH2) 3 (OH) z, in which M represents nickel and / or cobalt, ethylenediamine playing the role of the complexing agent.

Le nickel (ou cobalt) II-tri(éthylènediamine) hydroxyde est parfaitement compatible avec l'hydrazine et leur utilisation conjointe permet un fonctionnement du bain pendant une durée pratiquement illimitée par addition continue du composé métallique et du réducteur, la concentration en éthylènediamine n'intervenant pas dans le mécanisme de dépôt tant que ce corps est en excès, d'où il résulte la possibilité d'obtenir des dépôts très purs et épais.Nickel (or cobalt) II-tri (ethylenediamine) hydroxide is perfectly compatible with hydrazine and their joint use allows the bath to operate for a practically unlimited period by continuous addition of the metallic compound and the reducing agent, the ethylenediamine concentration does not not intervening in the deposition mechanism as long as this body is in excess, which results in the possibility of obtaining very pure and thick deposits.

Le bain selon l'invention est de préférence porté à un pH supérieur à 11 par un agent alcalinisant qui peut être l'hydroxyde de sodium.The bath according to the invention is preferably brought to a pH greater than 11 by an basifying agent which can be sodium hydroxide.

Le bain selon l'invention permet l'inclusion dans le dépôt de particules, par exemple d'alumine AI203 ou d'yttrine Y203, contenues dans le bain. Grâce à la régularité dans le temps des caractéristiques du bain, on obtient une répartition uniforme des particules dans l'épaisseur du dépôt.The bath according to the invention allows the inclusion in the deposit of particles, for example of alumina AI 2 0 3 or of yttrin Y 2 0 3 , contained in the bath. Thanks to the regularity over time of the characteristics of the bath, a uniform distribution of the particles is obtained in the thickness of the deposit.

L'invention a également pour objet un procédé de fabrication d'un bain tel que décrit ci-dessus, dans lequel on- prépare une solution alcaline de M(NH2C2H4―NH2)3(OH)2, dite solution-mère, et on y ajoute ensuite les stabilisants et l'hydrazine.The invention also relates to a process for manufacturing a bath as described above, in which an alkaline solution of M (NH 2 C 2 H 4 ―NH 2 ) 3 (OH) 2 , called a stock solution, and then add stabilizers and hydrazine.

Une telle solution-mère, d'une stabilité parfaite, permet de réaliser des bains convenant à différentes applications par addition de stabilisants et éventuellement de particules appropriés.Such a mother solution, with perfect stability, makes it possible to produce baths suitable for different applications by adding stabilizers and possibly suitable particles.

D'autres caractéristiques et avantages de l'invention ressortiront de la description donnée ci-après de quelques exemples de réalisation, et des illustrations annexées dans lesquelles les figures 1 à 6 sont des coupes micrographiques de dépôt chimiques obtenus par la mise en oeuvre de l'invention.Other characteristics and advantages of the invention will emerge from the description given below of a few exemplary embodiments, and from the appended illustrations in which FIGS. 1 to 6 are micrographic sections of chemical deposition obtained by the use of the 'invention.

Exemples 1 à 3Examples 1 to 3

Ces exemples sont relatifs à la préparation d'une solution-mère propre à fournir un bain selon l'invention. Ils utilisent respectivement l'hydroxyde, le carbonate basique et l'oxalate du métal à déposer en tant que précurseur insoluble du composé métallique.These examples relate to the preparation of a stock solution capable of providing a bath according to the invention. They respectively use the hydroxide, basic carbonate and oxalate of the metal to be deposited as an insoluble precursor of the metal compound.

Exemple 1Example 1

On désigne par M2- le cation métallique avec M = Ni et/ou Co. Le sel métallique initial est un sel pur pour galvanoplastie. Le choix de l'anion (désigné par A-) associé au cation est indifférent et laissé au choix de l'homme de métier (chlorure, sulfate ou autre).M 2 denotes the metal cation with M = Ni and / or Co. The initial metal salt is a pure salt for electroplating. The choice of the anion (designated by A-) associated with the cation is indifferent and left to the choice of a person skilled in the art (chloride, sulfate or the like).

On procède d'abord aux opérations classiques suivantes:

  • - mis en solution de MA2 et traitement pendant une heure au permanganate de potassium;
  • - traitement de la solution ainsi obtenue au charbon végétal activé pendant une heure et filtration dans l'heure suivante.
    on obtient ainsi une solution de MA2 nettoyée et filtrée comme il est d'usage dans la technique. On opère alors comme suit:
  • - ajout d'hydroxyde de sodium en excès par rapport à la quantité stoechiométrique nécessaire à la précipitation de l'hydroxyde de M selon:
    Figure imgb0001
  • - décantation ou filtration pour récupérer le précipité,
  • - après lavage, traitement du précipité par l'éthylènediamine (symbolisée par ED) anhydre en quantité supérieure de 10% à la quantité stoechiométrique:
    Figure imgb0002
  • - reglage du pH au-dessus de 11 par addition d'hydroxyde de sodium.
The following conventional operations are first carried out:
  • - dissolved in MA 2 and treatment for one hour with potassium permanganate;
  • - treatment of the solution thus obtained with activated vegetable charcoal for one hour and filtration in the following hour.
    an MA 2 solution is thus obtained, cleaned and filtered as is customary in the art. We then operate as follows:
  • addition of sodium hydroxide in excess relative to the stoichiometric quantity necessary for the precipitation of the hydroxide of M according to:
    Figure imgb0001
  • - decantation or filtration to recover the precipitate,
  • - after washing, treatment of the precipitate with anhydrous ethylenediamine (symbolized by ED) in an amount 10% greater than the stoichiometric amount:
    Figure imgb0002
  • - adjustment of the pH above 11 by addition of sodium hydroxide.

La solution-mère est alors prête.The stock solution is then ready.

Exemple 2Example 2

Le sel de départ est le carbonate basique de M, couramment utilisé dans la technique pour la correction du pH des bains électrolytiques au sulfamate de nickel et/ou de cobalt. L'avantage présenté par l'utilisation d'un tel sel réside dans sa pureté intrinsèque, due son mode d'élaboration. On le traite directement par l'éthylènediamine anhydre en quantité supérieure de 10% à la quantité stoechiométrique nécessaire et il se produit la réaction:

Figure imgb0003
The starting salt is the basic carbonate of M, commonly used in the art for the correction of the pH of electrolytic baths with nickel and / or cobalt sulfamate. The advantage presented by the use of such a salt lies in its intrinsic purity, due to its method of preparation. It is treated directly with anhydrous ethylenediamine in an amount 10% greater than the stoichiometric amount required and the reaction takes place:
Figure imgb0003

La solution obtenue est diluée au demi.The solution obtained is diluted to half.

La majorité des ions carbonates présents en solution est ensuite éliminée par ajout d'hydroxyde de baryum en excès par rapport à la quantité stoechiométrique nécessaire selon la réaction:

Figure imgb0004
The majority of the carbonate ions present in solution is then eliminated by adding barium hydroxide in excess relative to the stoichiometric quantity necessary according to the reaction:
Figure imgb0004

Après filtration et réglage du pH à l'hydroxyde de sodium (>11), la solution-mère est prête.After filtration and adjustment of the pH with sodium hydroxide (> 11), the stock solution is ready.

Exemple 3Example 3

Comme dans l'Exemple 1, l'anion du sel initial est indifférent; la solution de MA2 est préparée de la même manière. A cette solution est ajouté un large excès d'acide oxalique qui entraîne la précipitation d'oxalate de M selon la réaction:

Figure imgb0005
As in Example 1, the anion of the initial salt is indifferent; the MA 2 solution is prepared in the same way. To this solution is added a large excess of oxalic acid which causes precipitation of M oxalate according to the reaction:
Figure imgb0005

Après lavage, le précipité est traité par l'éthylènediamine anhydre en quantité supérieure de 10% à la quantité stoechiométrique nécessaire selon la réaction:

Figure imgb0006
After washing, the precipitate is treated with anhydrous ethylenediamine in an amount 10% greater than the stoichiometric amount necessary according to the reaction:
Figure imgb0006

Après dilution au demi, il suffit d'alcaliniser la solution à l'aide d'hydroxyde de sodium en excès pour obtenir le composé désiré selon la réaction:

Figure imgb0007
filtration et réglage du pH à l'hydroxyde de sodium (>11), la solution-mère est prête.After half the dilution, it is sufficient to alkalinize the solution with excess sodium hydroxide to obtain the desired compound according to the reaction:
Figure imgb0007
 filtration and pH adjustment with sodium hydroxide (> 11), the stock solution is ready.

Ce procédé est plus simple à mettre en oeuvre et moins coûteux que les deux précédents.This process is simpler to implement and less expensive than the previous two.

Exemples 4 à 10Examples 4 to 10

Ces exemples permettent d'aboutir à des bains de dépôt de nickel et/ou cobalt indifféremment à partir d'une solution-mère préparée selon l'un des Exemples 1 à 3.These examples make it possible to result in nickel and / or cobalt deposition baths indifferently from a stock solution prepared according to one of Examples 1 to 3.

Exemple 4Example 4

II s'agit d'un bain pour le dépôt de nickel contenant de l'imidazole comme stabilisant.It is a bath for the deposition of nickel containing imidazole as stabilizer.

Sa composition est la suivante:

  • composé métallique: nickel-II-/tri(éthylènediamine) hydroxyde
    Figure imgb0008
  • agent de pH: hydroxyde de sodium NaOH: 0,5 mol.1-1
  • stabilisants: primaire: imidazole C3H4N2: 0,3 mol.1-1 secondaire: pentoxyde d'arsenic AS2O5: 6,5.10-4 Mol.1-1
  • réducteur: hydrazine hydratée N2H4,H2O: 2,06 mol.1-1
Its composition is as follows:
  • metallic compound: nickel-II- / tri (ethylenediamine) hydroxide
    Figure imgb0008
  • pH agent: sodium hydroxide NaOH: 0.5 mol.1 -1
  • stabilizers: primary: imidazole C 3 H 4 N 2 : 0.3 mol.1 -1 secondary: arsenic pentoxide AS 2 O 5 : 6.5.10 -4 Mol.1 -1
  • reducing agent: hydrated hydrazine N 2 H 4 , H 2 O: 2.06 mol.1 -1

La température du bain est maintenue entre 88 et 92°C. La vitesse de dépôt est alors comprise entre 10 et 15 µm.h-1.The temperature of the bath is maintained between 88 and 92 ° C. The deposition rate is then between 10 and 15 µm.h -1 .

La figure 1 est une photographie d'un dépôt obtenu sur un substrat en laiton, grossie 500 fois. Le dépôt de nickel pur obtenu est gris clair, d'une épaisseur régulière et d'une dureté d'environ 450 HK (ou dureté Knoop) sous charge de 50 g.Figure 1 is a photograph of a deposit obtained on a brass substrate, magnified 500 times. The deposit of pure nickel obtained is light gray, of regular thickness and of a hardness of approximately 450 HK (or Knoop hardness) under load of 50 g.

- Exemple- Example

On prépare un bain de dépôt de nickel comportant comme stabilisant du sulfate de thallium, ayant la composition suivante:

  • composé métallique: nickel-II-tri(éthylènediamine)hydroxyde
    Figure imgb0009
  • agent de pH: hydroxyde de sodium NaOH: 0,5 mol.1-1
  • Stabilisants: primaire: sulfate thalleux TI2SO4: 1,6.10-4 mol.1-1 secondaire: pentoxyde d'arsenic As2O5: 6,5.10-4 mol.1-1
  • réducteur: hydrazine hydratée N2H4,H20: 2,06 mol.1-1
A nickel deposition bath is prepared comprising, as stabilizer, thallium sulphate, having the following composition:
  • metallic compound: nickel-II-tri (ethylenediamine) hydroxide
    Figure imgb0009
  • pH agent: sodium hydroxide NaOH: 0.5 mol.1 -1
  • Stabilizers: primary: thallous sulfate TI 2 SO 4 : 1.6.10 -4 mol.1 -1 secondary: arsenic pentoxide As 2 O 5 : 6.5.10 -4 mol.1 -1
  • reducing agent: hydrated hydrazine N 2 H 4 , H 2 0: 2.06 mol.1 -1

La température est maintenue entre 88 et 92°C.The temperature is maintained between 88 and 92 ° C.

La réaction de dépôt démarre spontanément, même sur substrats en alliage cuivreux. La prise de poids est d'environ 115 mg.cm-2.h-1, ce qui correspond à une vitesse de croissance du dépôt d'environ 130 µm.h-1.The deposition reaction starts spontaneously, even on copper alloy substrates. The weight gain is approximately 115 mg.cm -2 .h -1 , which corresponds to a growth rate of the deposit of approximately 130 µm.h -1 .

La stabilité de cette solution est remarquable et sa durée de vie semble illimitée. On a ainsi déposé 28,4 g de nickel métallique, avec un bain d'un litre contenant initialement l'équivalent de 8,2 g de nickel métallique. On a donc renouvelé 3,5 fois la concentration initiale, après quoi le bain fonctionnait toujours de façon satisfaisante.The stability of this solution is remarkable and its lifespan seems unlimited. 28.4 g of metallic nickel were thus deposited, with a liter bath initially containing the equivalent of 8.2 g of metallic nickel. The initial concentration was therefore renewed 3.5 times, after which the bath still worked satisfactorily.

Le dépôt obtenu est noir et ne réfléchit pas la lumière. l'observation métallographique d'une coupe de ce dépôt montre qu'il est poreux (voir la figure 2 qui représente une photographie grossie 100 fois d'un dépôt obtenu sur un substrat en laiton).The deposit obtained is black and does not reflect light. metallographic observation of a section of this deposit shows that it is porous (see FIG. 2 which represents a photograph magnified 100 times of a deposit obtained on a brass substrate).

La dureté mesurée sur le dépôt brut de bain s'élève à 400 HK environ (ou 450 HV, dureté Vickers), sous charge de 50 g.The hardness measured on the gross bath deposit amounts to approximately 400 HK (or 450 HV, Vickers hardness), under a load of 50 g.

L'analyse des gaz occlus donne 9 ppm d'hydrogène, 542 ppm d'azote et 429 ppm d'oxygène.Analysis of the occluded gases gives 9 ppm of hydrogen, 542 ppm of nitrogen and 429 ppm of oxygen.

Ce bain, ainsi que certains bains des exemples suivants, contient des ions thallium et conduit par conséquent à la présence de traces de thallium dans le dépôt. Comme exposé dans le brevet N° 2 531 103 précité, ces bains au thallium ne conviennent pas pour les applications aéronautiques mentionnées plus haut. Cependant, ils peuvent présenter un grand intérêt dans d'autres applications, en raison de leur longévité, de la régularité, de l'épaisseur, des caractéristiques physiques et mécaniques des dépôts qu'ils permettent d'obtenir, et de la possibilité d'inclure dans ceux-ci des particules réparties uniformément.This bath, as well as certain baths of the following examples, contains thallium ions and consequently leads to the presence of traces of thallium in the deposit. As explained in the aforementioned patent No. 2,531,103, these thallium baths are not suitable for the aeronautical applications mentioned above. However, they can be of great interest in other applications, because of their longevity, regularity, thickness, physical and mechanical characteristics of the deposits which they make it possible, and the possibility of include in them evenly distributed particles.

Exemple 6Example 6

On prépare un bain comportant comme stabilisant du sulfate de thallium. Ce bain diffère du précédent en ce que le nickel-II-tri(éthylènediamine) hydroxyde est remplacé par une quantité equivalente de cobalt-II-tri(éthylènediamine) hydroxyde, et en ce qu'on ajoute 1,7 mol.1-1 d'éthylènediamine.A bath is prepared comprising, as stabilizer, thallium sulfate. This bath differs from the previous one in that the nickel-II-tri (ethylenediamine) hydroxide is replaced by an equivalent amount of cobalt-II-tri (ethylenediamine) hydroxide, and in that 1.7 mol.1 -1 are added. ethylenediamine.

La température du bain est maintenue entre 78 et 82°C. La vitesse de dépôt est comprise entre 25 et 30 µm.h-1.The temperature of the bath is maintained between 78 and 82 ° C. The deposition rate is between 25 and 30 µm.h -1 .

La photographie de la figure 3, grossie 500 fois, illustre le dépôt de cobalt obtenu sur substrat en laiton. Ce dépôt est semi-brillant, dense et régulier, d'une dureté d'environ 350 HK, sous charge de 50 g.The photograph in FIG. 3, magnified 500 times, illustrates the deposit of cobalt obtained on a brass substrate. This deposit is semi-gloss, dense and regular, with a hardness of approximately 350 HK, under a load of 50 g.

Dans ce bain, il est nécessaire d'introduire de l'éthylènediamine libre pour maintenir en solution les ions cobalt, ceux-ci ayant une affinité pour l'éthylènediamine moindre que les ions nickel.In this bath, it is necessary to introduce free ethylenediamine in order to keep the cobalt ions in solution, the latter having a lesser affinity for ethylenediamine than the nickel ions.

Exemple 7Example 7

Cet exemple illustre un bain de dépôt de nickel contenant des particules d'alumine.This example illustrates a nickel deposition bath containing alumina particles.

Sa composition est la suivante:

  • composé métallique: nickel-II-tri(éthylènediamine) hydroxyde
    Figure imgb0010
  • agent de pH: hydroxyde de sodium NaOH: 0,5 mol.1-1
  • stabilisants: primaire: sulfate thalleux Tl2SO4: 1,6.10-4 mol.1-1 secondaire: pentoxyde d'arsenic AS205 6,5.10-4 mol.1-1
  • charge: alumine A1203 (diamètre moyen = 0,6 pm): 25 g/l-1
  • réducteur: hydrazine hydratée N2H4,H20: 2,06 mol.1-1
Its composition is as follows:
  • metallic compound: nickel-II-tri (ethylenediamine) hydroxide
    Figure imgb0010
  • pH agent: sodium hydroxide NaOH: 0.5 mol.1 -1
  • stabilizers: primary: thallous sulfate Tl 2 SO 4 : 1.6.10 -4 mol.1 -1 secondary: arsenic pentoxide A S2 0 5 6.5.10 -4 mol.1 -1
  • filler: alumina A1 2 0 3 (average diameter = 0.6 pm): 25 g / l -1
  • reducing agent: hydrated hydrazine N 2 H 4 , H 2 0: 2.06 mol.1 -1

La température est maintenue entre 88 et 92°C. La vitesse de dépôt est de l'ordre de 35 µm.h-1.The temperature is maintained between 88 and 92 ° C. The deposition rate is around 35 µm.h -1 .

Le dépôt est de couleur noire. Un examen sur coupe métallographique montre des particules d'alumine englobées dans le dépôt de nickel (voir la figure 4 qui représente une photographie grossie 700 fois d'un dépôt obtenu sur un substrat en laiton, l'alumine ayant été ajoutée après 20 minutes de dépôt). La dureté de ce dépôt est de 400 HV environ, sous charge de 50 g, comparable à celle obtenue pour le dépôt sans alumine; et comme dans l'exemple 5, le dépôt est poreux.The deposit is black. An examination on a metallographic section shows alumina particles included in the nickel deposit (see FIG. 4 which represents a photograph magnified 700 times of a deposit obtained on a brass substrate, the alumina having been added after 20 minutes of deposit). The hardness of this deposit is approximately 400 HV, under a load of 50 g, comparable to that obtained for the deposit without alumina; and as in Example 5, the deposit is porous.

Exemple 8Example 8

On prépare un bain de dépôt de nickel stabilisé à l'acétate de plomb, ayant pour composition:

  • composé métallique: nickel-II-tri(éthylènediamine) hydroxyde
    Figure imgb0011
  • agent de pH: hydroxyde de sodium NaOH: 0,5 mol.1-1
  • stabilisants: primaire: acétate de plomb Pb(O2CCH3)2,3H2O:
    Figure imgb0012
    secondaire: pentoxyde d'arsenic As2O5: 6,5.10-4 mol.1-1
  • réducteur: hydrazine hydratée N2H4,H20: 2,06 mol.1-1
A nickel deposition bath stabilized with lead acetate is prepared, having the composition:
  • metallic compound: nickel-II-tri (ethylenediamine) hydroxide
    Figure imgb0011
  • pH agent: sodium hydroxide NaOH: 0.5 mol.1 -1
  • stabilizers: primary: lead acetate Pb (O 2 CCH 3 ) 2 , 3H 2 O:
    Figure imgb0012
     secondary: arsenic pentoxide As 2 O 5 : 6.5.10 -4 mol.1 -1
  • reducing agent: hydrated hydrazine N 2 H 4 , H 2 0: 2.06 mol.1 -1

La température est maintenue entre 88 et 92°C. La réaction de dépôt démarre spontanément, même sur substrats en alliages cuivreux.The temperature is maintained between 88 and 92 ° C. The deposition reaction starts spontaneously, even on substrates made of copper alloys.

La vitesse de dépôt est d'environ 20 µm.h.-1.The deposition rate is approximately 20 µm.h. -1 .

Le dépôt est de couleur gris sombre, dense et régulier (voir la figure 5 qui représente un photographie grossie 750 fois de deux dépôts successifs obtenus sur un substrat en laiton, sans aucune préparation de surface entre ceux-ci).The deposit is dark gray, dense and regular (see Figure 5 which represents a photograph 750 times magnified by two successive deposits obtained on a brass substrate, without any surface preparation between them).

Exemple 9Example 9

On reprend le bain de l'exemple 8, auquel on ajoute 20 grammes par litre de particules d'yttrine de granulométrie comprise entre 0,5 et 1,5 micron.The bath of Example 8 is resumed, to which 20 grams per liter of yttrin particles with a particle size of between 0.5 and 1.5 microns are added.

On maintient la température entre 88 et 92°C et on agite le bain au moyen d'un agitateur tournant à environ 800 tours par minute.The temperature is maintained between 88 and 92 ° C and the bath is stirred by means of a rotary agitator at about 800 revolutions per minute.

La vitesse de dépôt est comprise entre 10 et 15 µm.h-1.The deposition rate is between 10 and 15 µm.h -1 .

Le dépôt obtenu est gris foncé, dense et régulier: un examen métallographique montre les particules d'yttrine englobées dans une matrice de nickel (voir la figure 6 qui représente une photographie grossie 950 fois d'un dépôt obtenu sur un substrat en acier doux).The deposit obtained is dark gray, dense and regular: a metallographic examination shows the yttrin particles enclosed in a nickel matrix (see FIG. 6 which represents a photograph 950 times magnified of a deposit obtained on a mild steel substrate) .

Exemple 10Example 10

Un bain nickel-cobalt a la composition suivante:

  • composé métallique: Nickel-II-tri(éthylènediamine) hydroxyde: 0.14 mol.1-1 Cobalt-II-tri(éthylènediamine) hydroxyde: 7.10-3 mol.1-3
  • complexant: éthylènediamine: 3.10-3 mol.1-1
  • agent de pH: hydroxyde de sodium: 0,5 mol.1-1
  • stabilisants: primaire: acétate de plomb: 0,5 mol.1-1 secondaire: As20s 6,5.10-4 mol.1-1
  • réducteur: hydrazine hydratée: 2,06 mol.1-1
A nickel-cobalt bath has the following composition:
  • metallic compound: Nickel-II-tri (ethylenediamine) hydroxide: 0.14 mol.1 -1 Cobalt-II-tri (ethylenediamine) hydroxide: 7.10- 3 mol.1 -3
  • complexing agent: ethylenediamine: 3.10 -3 mol.1 -1
  • pH agent: sodium hydroxide: 0.5 mol.1 -1
  • stabilizers: primary: lead acetate: 0.5 mol.1 -1 secondary: As 2 0 s 6.5.10- 4 mol.1 -1
  • reducing agent: hydrated hydrazine: 2.06 mol.1 -1

La température est maintenue entre 78 et 82°C.The temperature is maintained between 78 and 82 ° C.

La vitesse de dépôt est de 18,1 µm.h-1 The deposition rate is 18.1 µm.h -1

On a réalisé un dépôt d'une épaisseur de 13,2 pm d'un alliage nickel-cobalt, comme le montre l'analyse qualitative par spectroscopie dispersive en énergie du microscope électronique à balayage.A 13.2 μm thick deposit of a nickel-cobalt alloy was produced, as shown by the qualitative analysis by energy dispersive spectroscopy of the scanning electron microscope.

La teneur en gaz occlus des différents dépôts obtenus est relativement faible, ce qui entraîne peu de tension dans les couches métalliques. Ainsi, les teneurs en oxygène, en azote et en hydrogène du dépôt de l'exemple 6 sont respectivement de 429, 542 et 9 ppm, sensiblement plus basses que les valeurs minimales citiées dans l'article précité de Dini et Coronado, à savoir 900, 2410 et 150 ppm.The content of occluded gas in the various deposits obtained is relatively low, which causes little tension in the metal layers. Thus, the oxygen, nitrogen and hydrogen contents of the deposit of Example 6 are respectively 429, 542 and 9 ppm, significantly lower than the minimum values cited in the aforementioned article by Dini and Coronado, namely 900 , 2410 and 150 ppm.

Il est possible également d'obtenir des dépôts de cobalt et/ou de nickel semi-brillant.It is also possible to obtain deposits of cobalt and / or semi-bright nickel.

La vitesse de dépôt du nickel, qui est de 15 µm.h-1 environ pour les dépôts denses, peut être augmentée par addition-de thallium. Des vitesses de dépôt de 130 µm.h-1ont ainsi été obtenues. Dans ce cas, les dépôts sont poreux et noirs.The nickel deposition rate, which is around 15 µm.h -1 for dense deposits, can be increased by adding thallium. Deposition rates of 130 µm.h -1 were thus obtained. In this case, the deposits are porous and black.

Les contraintes résiduelles dans ces dépôts sont également faibles, autorisant l'obtention de couches de forte épaisseur. Ainsi, on a réalisé au laboratoire un dépôt d'environ 1 mm.The residual stresses in these deposits are also low, allowing the production of very thick layers. Thus, a deposit of approximately 1 mm was made in the laboratory.

Claims (21)

1. Bath for the chemical deposition of nickel and/or cobalt, comprising a compound of the,metal (or metals) to be deposited, a reducer constituted by hydrazine, a complexant of the metal and at least one stabiliser, characterized in that the said compound is nickel-II-tri(ethylene diamine) hydroxide and/or cobalt II-tri(ethylene diamine) hydroxide of the formula M(NH2―C2H4―NH2)3(OH)2, in which M represents nickel and/or cobalt, with the ethylene diamine playing the part of complexant.
2. Bath according to claim 1, characterized in that it contains an alkalinising agent.
3. Bath according to claim 2, characterized in that the alkalinising agent is sodium hydroxide.
4. Bath according to one of the preceding claims, characterized in that its pH is higher than 11.
5. Bath according to one of the preceding claims, characterized in that it contains imidazole as stabiliser.
6. Bath according to one of claims 1 to 4, characterized in that it contains a thallous salt as stabiliser.
7. Bath according to claim 6, characterized in that the stabilisant is thallous sulphate.
8. Bath according to one of claims 1 to 4, characterized in that it contains a salt of lead as stabiliser.
9. Bath according to claim 8, characterized in that the stabiliser is lead acetate.
10. Bath according to one of the preceding claims, characterized in that it contains arsenic pentoxide as stabiliser.
11. Bath according to one of the preceding claims, characterized in that it contains particles intended to be included in the deposit.
12. Bath according to claim 11, characterized in that it contains particles of alumina.
13. Bath according to claim 11, characterized in that it contains particles of yttrine.
14. Bath according to one of the preceding claims, characterized in that it contains free ethylene diamine.
15. Process for preparing a bath according to one of the preceding claims, characterized in that an alkaline solution of M(NH2-C2H4-NH2)3(OH)2 is prepared, termed the mother solution, and then the stabilisers and the hydrazine are added thereto.
16. Process according to claim 15, characterized in that the mother solution is prepared by using an insoluble compound of the metal and by treating the said compound with ethylene diamine.
17. Process according to claim 16, characterized in that the insoluble comound is the hydroxide M(OH)2 which is precipitated from a solution of a salt of the metal by means of an alkaline hydroxide.
18. Process according to claim 16, characterized in that the insoluble compound is the basic carbonate of the metal and in that the carbonate ions are precipitated by barium hydroxide.
19. Process according to claim 16, characterized in that the insoluble compound is the oxalate M(C02)2 which is precipitated from a solution of a salt of the metal by oxalic acid.
20. Process according to one of claims 16 to 19, characterized in that a slight excess of ethylene diamine is used with respect to the stoichiometric quantity.
21. Mother solution suitable for providing a bath according to one of claims 1 to 14, characterized in that it is composed essentially of M(NH2―C2H4―NH2)3(OH)2 in aqueous alkaline solution.
EP86402528A 1985-11-22 1986-11-13 Hydrazine bath for the chemical deposition of nickel and/or cobalt, and process for preparing the same Expired - Lifetime EP0227518B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8517339 1985-11-22
FR8517339A FR2590595B1 (en) 1985-11-22 1985-11-22 HYDRAZINE BATH FOR THE CHEMICAL DEPOSITION OF NICKEL AND / OR COBALT, AND METHOD FOR MANUFACTURING SUCH A BATH.

Publications (2)

Publication Number Publication Date
EP0227518A1 EP0227518A1 (en) 1987-07-01
EP0227518B1 true EP0227518B1 (en) 1990-07-25

Family

ID=9325098

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86402528A Expired - Lifetime EP0227518B1 (en) 1985-11-22 1986-11-13 Hydrazine bath for the chemical deposition of nickel and/or cobalt, and process for preparing the same

Country Status (5)

Country Link
US (1) US4844739A (en)
EP (1) EP0227518B1 (en)
JP (1) JPS62202080A (en)
DE (1) DE3672977D1 (en)
FR (1) FR2590595B1 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4780342A (en) * 1987-07-20 1988-10-25 General Electric Company Electroless nickel plating composition and method for its preparation and use
JPH06104903B2 (en) * 1988-08-19 1994-12-21 上村工業株式会社 Electroless composite plating bath and plating method
JP2525521B2 (en) * 1991-06-25 1996-08-21 日本リーロナール株式会社 Electroless tin-lead alloy plating bath
US6183546B1 (en) * 1998-11-02 2001-02-06 Mccomas Industries International Coating compositions containing nickel and boron
FR2787472B1 (en) 1998-12-16 2001-03-09 Onera (Off Nat Aerospatiale) PROCESS FOR PRODUCING A METAL ALLOY POWDER OF THE MCRALY TYPE AND COATINGS OBTAINED THEREWITH
WO2001066825A1 (en) * 2000-03-08 2001-09-13 Mccomas, Edward Coating compositions containing nickel and boron
KR100859259B1 (en) * 2005-12-29 2008-09-18 주식회사 엘지화학 Cobalt-base alloy electroless-plating solution and electroless-plating by using the same
US7794530B2 (en) * 2006-12-22 2010-09-14 Lam Research Corporation Electroless deposition of cobalt alloys

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3416955A (en) * 1965-01-13 1968-12-17 Clevite Corp Electroless cobalt plating bath
NL7701589A (en) * 1976-02-17 1977-08-19 Basf Wyandotte Corp CATHOD FOR USE IN A CHLORINE ALKALI ELECTROLYSIS CELL AS WELL AS A METHOD OF FORMING A DENSE, NON-POROUS ADHESIVE NICKEL COATING ON A STEEL SUBSTRATE.
US4265943A (en) * 1978-11-27 1981-05-05 Macdermid Incorporated Method and composition for continuous electroless copper deposition using a hypophosphite reducing agent in the presence of cobalt or nickel ions
DE3049417A1 (en) * 1980-12-30 1982-07-29 Siemens AG, 1000 Berlin und 8000 München "BATH AND METHOD FOR ELECTRICALLY DEPOSITING NICKEL SURFACES"
US4368223A (en) * 1981-06-01 1983-01-11 Asahi Glass Company, Ltd. Process for preparing nickel layer
JPS60248882A (en) * 1984-05-24 1985-12-09 Aisin Seiki Co Ltd Electroless plating bath for plating high-phosphorus nickel alloy

Also Published As

Publication number Publication date
JPH0156144B2 (en) 1989-11-29
US4844739A (en) 1989-07-04
FR2590595A1 (en) 1987-05-29
DE3672977D1 (en) 1990-08-30
FR2590595B1 (en) 1988-02-26
EP0227518A1 (en) 1987-07-01
JPS62202080A (en) 1987-09-05

Similar Documents

Publication Publication Date Title
Schlesinger Electroless and electrodeposition of silver
EP0227518B1 (en) Hydrazine bath for the chemical deposition of nickel and/or cobalt, and process for preparing the same
JP2004018923A (en) Method for producing metal fine powder
CH381493A (en) Bath for the chemical deposition of adherent palladium coatings, and use of said bath
EP0023368A1 (en) Cathode for the electrolytic production of hydrogen
CH622829A5 (en)
EP0423005A1 (en) Hydrazinbath for chemical plating platin and or palladium and process for preparing such a bath
WO2016098789A1 (en) Cyanogen-free gold electroplating liquid and gold electroplating method
FR2807450A1 (en) ELECTROLYTIC BATH INTENDED FOR THE ELECTROCHEMICAL DEPOSIT OF PALLADIUM OR ITS ALLOYS
EP1268347B1 (en) Palladium complex salt and use thereof for adjusting palladium concentration of an electrolytic solution for deposit of palladium or one of its alloys
Okinaka et al. Electroless deposition of gold
JP2009215569A (en) Method for producing alloy powder using molten salt reaction bath
EP2730682B1 (en) Alkaline, cyanide-free solution for electroplating of gold alloys, a method for electroplating and a substrate comprising a bright, corrosion-free deposit of a gold alloy
JP2008174795A (en) Gold plating liquid and gold plating method
JP3288457B2 (en) Gold plating solution and gold plating method
US2702271A (en) Process for the deposition of gold or gold alloys
EP0480876A2 (en) Electrodeposition of a gold alloy containing copper and zinc and its method of production
CA1103204A (en) Electrode for electrolysis
US4309256A (en) Process for the galvanoplastic deposition of a gold alloy
TWI702313B (en) Chrome plating solution, electroplating method and manufacturing method of chrome plating solution
BE1003583A5 (en) Coating composition and method of using a metal.
JP2020143308A (en) Electrolytic gold plating solution and method of producing the same, and gold plating method and gold complex
CA1220611A (en) Electrochemical elimination of nickel, antimony, arsenic and tin from a lead chloride solution
FR2619371A1 (en) AMMONIUM PLUTONATE URANATE, PROCESS FOR PREPARING THE SAME AND USE THEREOF FOR THE PRODUCTION OF MIXED OXIDE (U, PU) O2
JP4463972B2 (en) Method for producing electroless platinum plating solution, electroless platinum plating solution and electroless platinum plating method

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): DE GB IT

17P Request for examination filed

Effective date: 19870727

17Q First examination report despatched

Effective date: 19890313

ITF It: translation for a ep patent filed

Owner name: STUDIO BUSSONE

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE GB IT

REF Corresponds to:

Ref document number: 3672977

Country of ref document: DE

Date of ref document: 19900830

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
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
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19931026

Year of fee payment: 8

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

Ref country code: DE

Payment date: 19940128

Year of fee payment: 8

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

Ref country code: GB

Effective date: 19941113

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19941113

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

Ref country code: DE

Effective date: 19950801

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 NON-PAYMENT OF DUE FEES

Effective date: 20051113