EP0552097A1 - Process and apparatus for nickel electroplating - Google Patents
Process and apparatus for nickel electroplating Download PDFInfo
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- EP0552097A1 EP0552097A1 EP93400070A EP93400070A EP0552097A1 EP 0552097 A1 EP0552097 A1 EP 0552097A1 EP 93400070 A EP93400070 A EP 93400070A EP 93400070 A EP93400070 A EP 93400070A EP 0552097 A1 EP0552097 A1 EP 0552097A1
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- nickel
- anode
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- bath
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/002—Cell separation, e.g. membranes, diaphragms
Definitions
- the present invention relates to an improved apparatus and method for electrolytically coating nickel. It concerns the field of nickel plating by electrolytic coating of metallic or non-metallic parts, using nickel plating baths using nickel sulfamate as the nickel supply.
- Electrolytic Nickel Coating (REDN) inside the tubes such as tubes of steam generators, pressurizer sleeves or tank cover adapters of pressurized water nuclear power plants, or any other nuclear or non-nuclear tube.
- Another important application relates to the nickel plating of electrical connector elements and more generally to any nickel plating operation using a nickel sulfamate bath either by a static process (bath in a tank with fixed electrodes), or by a dynamic process ( bath circulation or circulation of the parts to be nickelled).
- a third important application relates to the purification of the nickel-plating baths used during said coatings.
- complex compounds is understood to mean compounds originating from the modification of the sulfamate ligand such as for example azodisulfonate.
- Nickel electroplating cell page 500, collar. 2 of Chemical Abstracts, vol. 102, No. 18, May 1985, also discloses an electrolytic nickel coating apparatus in accordance with the preamble of claim 1.
- the invention provides a device in accordance with the characterizing part of claim 1.
- the semi-permeable wall made of inert sintered material or polymer prevents the passage of oxidized compounds formed at the anode, from the anode compartment to the cathode compartment.
- the invention also aims to provide a process making it possible to prevent or prevent the degradation of nickel-plating baths and to use these baths until their nickel content has been used up, without risking incidents due to the early passivation of the nickel.
- 'anode in the case where it consists of soluble nickel, namely nickel depolarized with sulfur, such as for example the products sold by the company INCO (pellets, beads, etc.).
- the invention provides a method of electroplating a part in accordance with claim 5.
- the cathode may consist of the part to be coated, this part being in contact with the bath of the cathode compartment.
- the method may include a step preliminary to the nickel-plating operation in which the cathode consists of a simple electrode allowing the electrolysis of the nickel-plating baths, in order to prevent and prevent their degradation and thus allow their use until exhaustion of their nickel content.
- FIG. 1 and FIG. 2 represent particular modes of implementation of the invention, given by way of nonlimiting examples.
- FIG. 3 represents the evolution of the electrochemical parameters during an electrolysis as carried out in the prior art.
- FIG. 4 represents the evolution of the electrochemical parameters during an electrolysis carried out according to the invention.
- the schematic representation of Figure 1 includes a container 1 formed of two vertical tanks communicating through a transverse channel, intended to receive the bath 2 to be electrolyzed.
- a cathode 3 is immersed in one of the vertical tanks and an anode 4 is immersed in the other vertical tank.
- a semi-permeable wall 5 closes the transverse channel which connects the two vertical tanks and thus separates the anode compartment from the cathode compartment.
- FIG. 2 schematically represents a tank 6 intended to receive the bath 7 to be purified.
- a cathode 8 and an anode 9 isolated from the rest of the bath by a semi-permeable wall 10 thus delimiting, around the anode, a compartment inside the nickel-plating bath itself.
- the semi-permeable wall can be a sinter or a polymer membrane.
- the electrolysis carried out is itself known both for the connection of the electrodes and for the control of different parameters.
- the anode and the cathode could be connected, via a rheostat, to the terminals of a direct current source making it possible to supply a voltage U of a few volts at an intensity I of a few amperes.
- a voltage measuring device can be mounted between the anode and a reference electrode and will provide the potential (Ea) of the anode relative to the reference electrode.
- the three electrodes cathode, anode and reference electrode, are placed in the non-compartmentalized tank.
- FIG. 3 shows that, until time T1, the three parameters I, U, Ea are constant and the electrolysis process takes place normally, beyond T1 we have represented the passivation phenomenon of the anode which generates no only an increase in the potential of the anode relative to the reference electrode Ea, but above all which causes a sudden drop in the nickel-plating current I with rapid degradation of the bath by oxidation and formation of a non-homogeneous nickel deposit.
- This passivation of the anode also produces a deterioration of the bath by acidification with, consequently, the formation of a fragile nickel deposit.
- the cathode is placed in one of the two vertical tanks of a device of the type schematically shown in FIG. 1, the anode and the reference electrode are placed in the other vertical tank, the semi-permeable wall being placed between the two tanks in the transverse channel.
- FIG. 4 shows that, until time T1, the electrolysis evolves in the same way as in the previous case represented in FIG. 3.
- the phenomenon of passivation of the anode causes an elevation of the potential Ea.
- two nickel-plating operations are carried out, one according to the prior art, the other in compartments separated by a semi-permeable wall, in two nickel-plating baths of composition of identical departure.
- the three electrodes: cathode, anode and reference electrode for mercury sulfamate are placed in a non-compartmentalized tank; in the case of an apparatus according to the invention, the cathode is placed in one of the two vertical tanks of a device of the type schematically shown in FIG. 1, the anode and the reference electrode are placed in the other vertical tank, the semi-permeable wall being a 3 mm thick pyrex sinter n ° 4, sold by the company SOVIREL placed between the two tanks in the transverse channel.
- FIG. 3 represents the evolution of the electrochemical parameters.
- the passivation demonstrated by the rise in potential of the anode, occurred after 40 minutes of nickel plating.
- the current density I having remained stable, nickel plating continued for 8 hours 30 minutes with voluntary stopping of the test;
- FIG. 4 represents the evolution of the electrochemical parameters.
- the initial nickel-plating bath has been greatly enriched with complex compounds such as, for example, azidosulfonate in one of the compartments making any electrolysis impossible, while the bath contained in the other compartment remains capable of ensuring a effective nickel plating after 9 hours of using the original bath.
- complex compounds such as, for example, azidosulfonate
- Maintaining the oxidized compound in a specific compartment so as not to pollute the bath makes it possible to purify the sulfamate baths by electrolysis (extraction of traces of cobalt for example) without pollution of the baths by azodisulfonate.
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- Electrolytic Production Of Metals (AREA)
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Abstract
Description
La présente invention concerne un appareil perfectionné et un procédé de revêtement électrolytique de nickel. Elle intéresse le domaine du nickelage par revêtement électrolytique de pièces métalliques ou non, à l'aide de bains de nickelage utilisant du sulfamate de nickel comme apport de nickel.The present invention relates to an improved apparatus and method for electrolytically coating nickel. It concerns the field of nickel plating by electrolytic coating of metallic or non-metallic parts, using nickel plating baths using nickel sulfamate as the nickel supply.
Elle trouve une application importante dans le Revêtement Electrolytique De Nickel (REDN) à l'intérieur des tubes tels que des tubes de générateurs de vapeur, des manchettes de pressuriseur ou des adaptateurs de couvercle de cuve des centrales nucléaires à eau sous pression, ou tout autre tube du domaine nucléaire ou non nucléaire.It finds an important application in the Electrolytic Nickel Coating (REDN) inside the tubes such as tubes of steam generators, pressurizer sleeves or tank cover adapters of pressurized water nuclear power plants, or any other nuclear or non-nuclear tube.
Une autre application importante concerne le nickelage d'éléments de connecteurs électriques et plus généralement à toute opération de nickelage utilisant un bain de sulfamate de nickel soit par un procédé statique (bain dans une cuve avec des électrodes fixes), soit par un procédé dynamique (circulation du bain ou circulation des pièces à nickeler).Another important application relates to the nickel plating of electrical connector elements and more generally to any nickel plating operation using a nickel sulfamate bath either by a static process (bath in a tank with fixed electrodes), or by a dynamic process ( bath circulation or circulation of the parts to be nickelled).
Une troisième application importante concerne la purification des bains de nickelage utilisés au cours desdits revêtements.A third important application relates to the purification of the nickel-plating baths used during said coatings.
On sait que le nickelage interne des zones des tubes en U de générateur de vapeur, soumises à des contraintes particulièrement élevées, permet d'obturer des microfissures ou de prévenir ces fissurations. A titre d'exemple de procédé de réparation par nickelage connu, on pourra se reporter au document EP-A-O 167 513.It is known that the internal nickel plating of the zones of the U-shaped tubes of a steam generator, subjected to particularly high stresses, makes it possible to close up microcracks or to prevent these cracks. As an example of a known nickel-plating repair process, reference may be made to document EP-A-0 167 513.
Les appareils classiquement utilisés dans le domaine du nickelage par revêtement électrolytique sont constitués:
- d'un récipient contenant le bain de nickelage agité ou non, une anode souvent constituée d'un panier grillagé (par exemple en titane) et rempli de billes de nickel soluble (par exemple celles commercialisées par la Société INCO), et une cathode constituée de la pièce à revêtir de nickel, ou
- des mêmes récipient, bain de nickelage et anode que ci-dessus, mais avec une cathode constituée d'une plaque métallique quelconque (par exemple en acier inoxydable)l'ensemble du dispositif étant, dans ce cas, destiné à préparer le bain de nickelage avant utilisation en le purifiant par élimination, par électrolyse contrôlée, des impuretés métalliques non désirées (par exemple du cobalt dans le cas des installations nucléaires), ou
- d'une anode cylindrique creuse revêtue de nickel soluble et placée au centre du tube à réparer par nickelage constituant la cathode, le bain de nickelage circulant dans un sens entre la cathode et l'anode puis dans le sens opposé à l'intérieur de l'anode.
- a container containing the nickel bath, stirred or not, an anode often consisting of a mesh basket (for example made of titanium) and filled with nickel beads soluble (for example those sold by the company INCO), and a cathode made up of the part to be coated with nickel, or
- of the same container, nickel plating bath and anode as above, but with a cathode made up of any metal plate (for example made of stainless steel) the whole device being, in this case, intended to prepare the nickel plating bath before use by purifying it by elimination, by controlled electrolysis, of unwanted metallic impurities (for example cobalt in the case of nuclear installations), or
- a hollow cylindrical anode coated with soluble nickel and placed in the center of the tube to be repaired by nickel-plating constituting the cathode, the nickel-plating bath circulating in a direction between the cathode and the anode and then in the opposite direction inside the 'anode.
Or, avec les dispositifs décrits ci-dessus, lors de l'électrolyse, il se forme, tant au niveau de la cathode qu'au niveau de l'anode, des composés complexes qui, de plus, peuvent se recombiner librement entre eux.However, with the devices described above, during electrolysis, complex compounds are formed both at the cathode and at the anode which, moreover, can freely recombine with one another.
On entend par composés complexes des composés provenant de la modification du ligand sulfamate tel que par exemple l'azodisulfonate.The term “complex compounds” is understood to mean compounds originating from the modification of the sulfamate ligand such as for example azodisulfonate.
Ces composés complexes posent des problèmes lors de l'opération de nickelage qui se manifestent le plus souvent par la passivation de l'anode de nickel du fait notamment de la réduction sur la cathode de composés oxydés formés à l'anode qui déséquilibrent le système électrochimique vers un potentiel où l'anode se passive, et/ou par une augmentation de la résistance électrochimique de la cellule de nickelage du fait notamment de la présence de composés peu ionisés, ce qui conduit à ne plus travailler dans les conditions d'intensité ou de potentiel voulues pour le nickelage, à obtenir des dépôts n'ayant plus la qualité requise et/ou à dégrader rapidement les bains de nickelage.These complex compounds pose problems during the nickel-plating operation which are most often manifested by the passivation of the nickel anode, in particular due to the reduction on the cathode of oxidized compounds formed at the anode which unbalance the electrochemical system. towards a potential where the anode becomes passive, and / or by an increase in the electrochemical resistance of the nickel-plating cell due in particular to the presence of poorly ionized compounds, which leads to no longer working under the conditions of intensity or potential desired for nickel plating, obtaining deposits which no longer have the required quality and / or rapidly degrading the nickel plating baths.
L'article "Nickel electroplating cell" page 500, col. 2 de Chemical Abstracts, vol. 102, n° 18, Mai 1985, fait par ailleurs connaître un appareil de revêtement électrolytique de nickel conforme au préambule de la revendication 1. L'invention propose en revanche un dispositif conforme à la partie caractérisante de la revendication 1.The article "Nickel electroplating cell" page 500, collar. 2 of Chemical Abstracts, vol. 102, No. 18, May 1985, also discloses an electrolytic nickel coating apparatus in accordance with the preamble of claim 1. The invention, however, provides a device in accordance with the characterizing part of claim 1.
La paroi semi-perméable en matériau fritté inerte ou polymère empêche le passage de composés oxydés formés à l'anode, du compartiment anodique au compartiment cathodique.The semi-permeable wall made of inert sintered material or polymer prevents the passage of oxidized compounds formed at the anode, from the anode compartment to the cathode compartment.
L'invention vise également à fournir un procédé permettant de prévenir ou d'empêcher la dégradation des bains de nickelage et d'utiliser ces bains jusqu'à épuisement de leur teneur en nickel, sans risquer d'incidents dus à la passivation précoce de l'anode dans le cas où elle est constituée de nickel soluble, à savoir du nickel dépolarisé au soufre, tel que par exemple les produits commercialisés par la Société INCO (pellets, billes, etc.).The invention also aims to provide a process making it possible to prevent or prevent the degradation of nickel-plating baths and to use these baths until their nickel content has been used up, without risking incidents due to the early passivation of the nickel. 'anode in the case where it consists of soluble nickel, namely nickel depolarized with sulfur, such as for example the products sold by the company INCO (pellets, beads, etc.).
Pour cela, l'invention propose un procédé de revêtement électrolytique d'une pièce conforme à la revendication 5.For this, the invention provides a method of electroplating a part in accordance with
La cathode peut être constituée de la pièce à revêtir, cette pièce étant en contact avec le bain du compartiment cathodique.The cathode may consist of the part to be coated, this part being in contact with the bath of the cathode compartment.
Par ailleurs, le procédé peut comprendre une étape préliminaire à l'opération de nickelage dans laquelle la cathode est constituée d'une simple électrode permettant l'électrolyse des bains de nickelage, afin d'empêcher et de prévenir leur dégradation et permettre ainsi leur utilisation jusqu'à épuisement de leur teneur en nickel.Furthermore, the method may include a step preliminary to the nickel-plating operation in which the cathode consists of a simple electrode allowing the electrolysis of the nickel-plating baths, in order to prevent and prevent their degradation and thus allow their use until exhaustion of their nickel content.
Pour mieux comprendre l'invention on va décrire maintenant plus en détails l'appareil de revêtement électrolytique de nickel conforme à l'invention.To better understand the invention we will now describe in more detail the electrolytic nickel coating apparatus according to the invention.
La figure 1 et la figure 2 représentent des modes particuliers de mise en oeuvre de l'invention, donnés à titre d'exemples non limitatifs.FIG. 1 and FIG. 2 represent particular modes of implementation of the invention, given by way of nonlimiting examples.
La figure 3 représente l'évolution des paramètres électrochimiques au cours d'une électrolyse telle que réalisée dans l'art antérieur.FIG. 3 represents the evolution of the electrochemical parameters during an electrolysis as carried out in the prior art.
La figure 4 représente l'évolution des paramètres électrochimiques au cours d'une électrolyse réalisée selon l'invention.FIG. 4 represents the evolution of the electrochemical parameters during an electrolysis carried out according to the invention.
La représentation schématique de la figure 1 comporte un récipient 1 formé de deux cuves verticales communiquant par un canal transversal, destiné à recevoir le bain 2 à électrolyser. Une cathode 3 est immergée dans l'une des cuves verticales et une anode 4 est immergée dans l'autre cuve verticale. Une paroi semi-perméable 5 obture le canal transversal qui relie les deux cuves verticales et sépare ainsi le compartiment anodique du compartiment cathodique.The schematic representation of Figure 1 includes a container 1 formed of two vertical tanks communicating through a transverse channel, intended to receive the bath 2 to be electrolyzed. A
La figure 2 représente schématiquement une cuve 6 destinée à recevoir le bain 7 à purifier. Dans le bain sont immergées une cathode 8 et une anode 9 isolée du reste du bain par une paroi semi-perméable 10 délimitant ainsi, autour de l'anode, un compartiment à l'intérieur même du bain de nickelage. Dans un tel dispositif la paroi semi-perméable peut être un fritté ou une membrane de polymère.FIG. 2 schematically represents a
L'agencement de la figure 2 peut être inversé, c'est-à-dire que c'est alors la cathode qui est isolée du reste du bain par une paroi semi-perméable.The arrangement of Figure 2 can be reversed, that is to say that it is then the cathode which is isolated from the rest of the bath by a semi-permeable wall.
L'électrolyse réalisée est en elle-même connue tant pour la liaison des électrodes que pour le contrôle des différents paramètres.The electrolysis carried out is itself known both for the connection of the electrodes and for the control of different parameters.
Par exemple, l'anode et la cathode pourront être reliées, par l'intermédiaire d'un rhéostat, aux bornes d'une source de courant continu permettant de fournir une tension U de quelques volts sous une intensité I de quelques ampères . Un organe de mesure de tension pourra être monté entre l'anode et une électrode de référence et fournira le potentiel (Ea) de l'anode par rapport à l'électrode de référence.For example, the anode and the cathode could be connected, via a rheostat, to the terminals of a direct current source making it possible to supply a voltage U of a few volts at an intensity I of a few amperes. A voltage measuring device can be mounted between the anode and a reference electrode and will provide the potential (Ea) of the anode relative to the reference electrode.
Dans le cas d'appareil de nickelage par revêtement électrolytique de l'art antérieur, les trois électrodes : cathode, anode et électrode de référence, sont placées dans la cuve non compartimentée.In the case of electrolytic coating nickel-plating apparatus of the prior art, the three electrodes: cathode, anode and reference electrode, are placed in the non-compartmentalized tank.
La figure 3 montre que, jusqu'au temps T₁, les trois paramètres I, U, Ea sont constants et le processus d'électrolyse se déroule normalement, au delà de T₁ on a représenté le phénomène de passivation de l'anode qui engendre non seulement une élévation du potentiel de l'anode par rapport à l'électrode de référence Ea, mais surtout qui provoque une chute brutale du courant I de nickelage avec dégradation rapide du bain par oxydation et formation d'un dépôt de nickel non homogène. Cette passivation de l'anode produit également une détérioration du bain par acidification avec, en conséquence, la formation d'un dépôt de nickel fragile.FIG. 3 shows that, until time T₁, the three parameters I, U, Ea are constant and the electrolysis process takes place normally, beyond T₁ we have represented the passivation phenomenon of the anode which generates no only an increase in the potential of the anode relative to the reference electrode Ea, but above all which causes a sudden drop in the nickel-plating current I with rapid degradation of the bath by oxidation and formation of a non-homogeneous nickel deposit. This passivation of the anode also produces a deterioration of the bath by acidification with, consequently, the formation of a fragile nickel deposit.
Cette description basée sur une électrolyse à potentiel U imposé pourrait être également appliquée au cas d'une électrolyse à intensité I imposée. Au lieu d'une chute brutale du courant I on noterait une montée brutale de la tension U, mais les conséquences sur le bain et la qualité du dépôt seraient les mêmes.This description based on an electrolysis with imposed U potential could also be applied in the case of an electrolysis with imposed intensity I. Instead of a sudden drop in current I, there would be a sharp rise in voltage U, but the consequences on the bath and the quality of the deposit would be the same.
Dans le cas d'un appareil conforme à l'invention, la cathode est placée dans l'une des deux cuves verticales d'un dispositif du genre de celui schématiquement représenté en figure 1, l'anode et l'électrode de référence sont placées dans l'autre cuve verticale, la paroi semi-perméable étant placée entre les deux cuves dans le canal transversal.In the case of an apparatus according to the invention, the cathode is placed in one of the two vertical tanks of a device of the type schematically shown in FIG. 1, the anode and the reference electrode are placed in the other vertical tank, the semi-permeable wall being placed between the two tanks in the transverse channel.
La figure 4 montre que, jusqu'au temps T₁, l'électrolyse évolue de la même façon que dans le cas précédent représenté à la figure 3. De même que dans le cas précédent, le phénomène de passivation de l'anode provoque une élévation du potentiel Ea.FIG. 4 shows that, until time T₁, the electrolysis evolves in the same way as in the previous case represented in FIG. 3. As in the previous case, the phenomenon of passivation of the anode causes an elevation of the potential Ea.
En revanche, les paramètres de l'électrolyse dans le bain de sulfamate de nickel continuent à se maintenir, c'est-à-dire que l'intensité I et le potentiel U restent constants.On the other hand, the parameters of the electrolysis in the nickel sulfamate bath continue to be maintained, that is to say that the intensity I and the potential U remain constant.
Cette description reste valable, que l'électrolyse soit faite à potentiel U imposé ou à intensité I imposée.This description remains valid, whether the electrolysis is carried out at an imposed potential U or at an imposed intensity I.
En conséquence, ni la qualité du bain cathodique ni celle du dépôt ne sont perturbées par l'éventuelle passivation de l'anode.Consequently, neither the quality of the cathode bath nor that of the deposit is disturbed by the possible passivation of the anode.
La description permet de comprendre également que l'on peut désormais, grâce à l'invention, utiliser une anode insoluble dès le début de l'électrolyse, ce qui était impossible dans l'art antérieur compte tenu de la dégradation rapide des paramètres.The description also makes it possible to understand that it is now possible, thanks to the invention, to use an insoluble anode from the start of electrolysis, which was impossible in the prior art given the rapid degradation of the parameters.
Pour permettre d'évaluer les avantages apportés par l'invention, deux opérations de nickelage sont réalisées, l'une selon l'art antérieur, l'autre en compartiments séparés par une paroi semi-perméable, dans deux bains de nickelage de composition de départ identique.To assess the advantages provided by the invention, two nickel-plating operations are carried out, one according to the prior art, the other in compartments separated by a semi-permeable wall, in two nickel-plating baths of composition of identical departure.
Dans chaque opération de nickelage :
- on prépare 120 cm3 d'une solution de nickelage comprenant :
- 93 g/l de nickel sous forme de sulfamate et
- 40 g/l d'acide borique.
- la distance entre les électrodes est de 8 cm,
- les électrodes sont constituées de plaquettes de 1,4 cm x 1,4 cm x 0,1 cm,
- la cathode est en alliage "Inconel 600",
- l'anode est en nickel et recouverte, sur une face, de nickel dépolarisé au soufre,
- avant le nickelage, les électrodes subissent :
- un décapage électrolytique dans l'acide sulfurique à 10 % à 58°C,
- pendant 60 secondes avec une intensité de 32 A/cm2 pour la cathode,
- pendant 25 secondes avec une intensité de 32 A/cm2 pour l'anode,
- un rinçage à l'eau,
- une polarisation en milieu acide sulfamique/ sulfamate de nickel à 58°C pendant 30 secondes avec une intensité de 4,8 A/cm2, la cathode étant polarisée cathodiquement,
- les électrodes décrites ci-dessus et une électrode de référence au sulfamate mercureux sont placées dans le bain de sulfamate de nickel,
- au cours de l'opération de nickelage on électrolyse le bain de sulfamate de nickel avec une différence de potentiel U maintenue constante, après une variation linéaire de 0 à U volts en une minute, de manière à avoir en régime stable une densité de courant I comprise entre 20 et 25 A/dm2; la densité de courant et la tension de l'anode (c'est-à-dire le potentiel Ea de l'anode par rapport à l'électrode de référence) sont enregistrées.
- 120 cm3 of a nickel-plating solution are prepared comprising:
- 93 g / l of nickel in the form of sulfamate and
- 40 g / l boric acid.
- the distance between the electrodes is 8 cm,
- the electrodes consist of plates of 1.4 cm x 1.4 cm x 0.1 cm,
- the cathode is made of an "Inconel 600" alloy,
- the anode is made of nickel and covered, on one side, with sulfur-depolarized nickel,
- before nickel plating, the electrodes undergo:
- electrolytic pickling in 10% sulfuric acid at 58 ° C,
- for 60 seconds with an intensity of 32 A / cm2 for the cathode,
- for 25 seconds with an intensity of 32 A / cm2 for the anode,
- rinsing with water,
- polarization in a sulfamic acid / nickel sulfamate medium at 58 ° C. for 30 seconds with an intensity of 4.8 A / cm 2, the cathode being cathodically polarized,
- the electrodes described above and a mercury sulfamate reference electrode are placed in the nickel sulfamate bath,
- during the nickel-plating operation, the nickel sulfamate bath is electrolyzed with a potential difference U kept constant, after a linear variation from 0 to U volts in one minute, so as to have a steady current density I between 20 and 25 A / dm2; the current density and the voltage of the anode (that is to say the potential Ea of the anode relative to the reference electrode) are recorded.
Dans le cas d'un appareil de nickelage par revêtement électrolytique de l'art antérieur, les trois électrodes : cathode, anode et électrode de référence au sulfamate mercureux, sont placées dans une cuve non compartimentée; dans le cas d'un appareil conforme à l'invention, la cathode est placée dans l'une des deux cuves verticales d'un dispositif du genre de celui schématiquement représenté en figure 1, l'anode et l'électrode de référence sont placées dans l'autre cuve verticale, la paroi semi-perméable étant un fritté en pyrex n° 4 d'épaisseur 3 mm, commercialisé par la Société SOVIREL placé entre les deux cuves dans le canal transversal.In the case of an electrolytic coating nickel-plating apparatus of the prior art, the three electrodes: cathode, anode and reference electrode for mercury sulfamate, are placed in a non-compartmentalized tank; in the case of an apparatus according to the invention, the cathode is placed in one of the two vertical tanks of a device of the type schematically shown in FIG. 1, the anode and the reference electrode are placed in the other vertical tank, the semi-permeable wall being a 3 mm thick pyrex sinter n ° 4, sold by the company SOVIREL placed between the two tanks in the transverse channel.
Dans les deux cas, la durée totale de l'électrolyse a été volontairement fixée à 8 heures 30.In both cases, the total duration of the electrolysis was intentionally set at 8:30 a.m.
Dans le cas de la cuve non compartimentée, la passivation de l'anode est intervenue au bout de 30 minutes environ et a été mise en évidence par la montée de son potentiel de surface d'une valeur Ea égale à environ 300 mV jusqu'à une valeur dépassant 1000 mV.In the case of the non-compartmentalized tank, the passivation of the anode took place after approximately 30 minutes and was highlighted by the increase in its surface potential with a value Ea equal to approximately 300 mV up to a value exceeding 1000 mV.
Dans ce premier cas, pour un volume de 60 cm3 de solution dans le compartiment cathodique, ou pour 5,6 grammes de nickel présents dans la solution de départ, 0,86 grammes de nickel ont été déposés sur la cathode, soit 15% du nickel disponible dans la solution, pendant les 8 heures 30 de nickelage; la figure 3 représente l'évolution des paramètres électrochimiques.In this first case, for a volume of 60 cm3 of solution in the cathode compartment, or for 5.6 grams of nickel present in the starting solution, 0.86 grams of nickel were deposited on the cathode, or 15% of the nickel available in the solution, during the 8 hours 30 minutes of nickel plating; FIG. 3 represents the evolution of the electrochemical parameters.
Dans le cas de l'appareil conforme à l'invention, la passivation, mise en évidence par la montée de potentiel de l'anode, s'est produite après 40 minutes de nickelage. Par contre, la densité de courant I étant restée stable, le nickelage s'est poursuivi pendant 8 heures 30 avec arrêt volontaire de l'essai; la figure 4 représente l'évolution des paramètres électrochimiques.In the case of the apparatus according to the invention, the passivation, demonstrated by the rise in potential of the anode, occurred after 40 minutes of nickel plating. On the other hand, the current density I having remained stable, nickel plating continued for 8 hours 30 minutes with voluntary stopping of the test; FIG. 4 represents the evolution of the electrochemical parameters.
Dans ce dernier cas, pour un volume de 60 cm3 de solution dans le compartiment cathodique, ou pour 5,6 grammes de nickel présents dans la solution de départ, 4,4 grammes de nickel ont été déposés sur la cathode, soit 78 % du nickel disponible dans la solution, pendant les 8 heures 30 de nickelage.In the latter case, for a volume of 60 cm3 of solution in the cathode compartment, or for 5.6 grams of nickel present in the starting solution, 4.4 grams of nickel were deposited on the cathode, or 78% of the nickel available in the solution, during the 8 hours 30 minutes of nickel plating.
Nous allons maintenant illustrer l'intérêt de l'invention lorsque l'appareil conforme à l'invention est utilisé pour la purification ou la régénération de bain de nickelage.We will now illustrate the advantage of the invention when the apparatus according to the invention is used for the purification or the regeneration of nickel-plating bath.
L'expérience précédente a été prolongée par les essais suivants :
- I - Après les 8 heures 30 d'électrolyse de l'expérience précédente, le compartiment cathodique a été vidangé et remplacé par du bain neuf et une cathode neuve y a été placée à la place de la cathode d'origine. Dans le compartiment anodique d'origine, on a plongé une cathode neuve à la place de l'anode d'origine. On a donc inversé les deux compartiments. Dès mise en route de l'électrolyse, l'anode placée dans le bain neuf s'est passivée.
- II - L'expérience inverse a été réalisée : après 8 heures 30 d'électrolyse, le compartiment anodique a été vidangé et remplacé par du bain neuf avec une cathode neuve à la place de l'anode d'origine, la cathode d'origine ayant été remplacée par une anode neuve qui donc est plongée dans le bain cathodique d'origine déjà utilisé pendant 8 heures 30. Dans ce cas, avec l'électrolyse, le nickelage s'est poursuivi pendant 30 minutes sans passivation, l'arrêt du test ayant été volontaire.
- I - After 8 hours 30 minutes of electrolysis of the previous experiment, the cathode compartment was drained and replaced by a new bath and a new cathode was placed there in place of the original cathode. In the compartment original anode, a new cathode was immersed in place of the original anode. We therefore reversed the two compartments. As soon as the electrolysis was started, the anode placed in the new bath became passivated.
- II - The reverse experiment was carried out: after 8 hours 30 minutes of electrolysis, the anode compartment was drained and replaced by a new bath with a new cathode in place of the original anode, the original cathode having been replaced by a new anode which is therefore immersed in the original cathode bath already used for 8 hours 30 minutes. In this case, with electrolysis, nickel plating continued for 30 minutes without passivation, stopping the test having been voluntary.
On constate donc que le bain de nickelage initial s'est largement enrichi de composés complexes tels que par exemple l'azidosulfonate dans l'un des compartiments rendant impossible toute électrolyse, alors que le bain contenu dans l'autre compartiment reste apte à assurer un nickelage efficace après 9 heures d'utilisation du bain d'origine.It can therefore be seen that the initial nickel-plating bath has been greatly enriched with complex compounds such as, for example, azidosulfonate in one of the compartments making any electrolysis impossible, while the bath contained in the other compartment remains capable of ensuring a effective nickel plating after 9 hours of using the original bath.
Le maintien du composé oxydé dans un compartiment spécifique de manière à ne pas polluer le bain permet d'effectuer l'épuration des bains de sulfamate par électrolyse (extraction des traces de cobalt par exemple) sans pollution de bains par l'azodisulfonate.Maintaining the oxidized compound in a specific compartment so as not to pollute the bath makes it possible to purify the sulfamate baths by electrolysis (extraction of traces of cobalt for example) without pollution of the baths by azodisulfonate.
Claims (7)
caractérisé en ce qu'il comprend une paroi semi-perméable en matériau fritté inerte ou en polymère séparant un compartiment cathodique d'un compartiment anodique.Apparatus for electrolytic coating of nickel of a part, from a nickel-plating bath using, as the nickel filler, nickel sulfamate, having a container containing the nickel-plating bath in which an anode and a cathode,
characterized in that it comprises a semi-permeable wall made of inert sintered material or of polymer separating a cathode compartment from an anode compartment.
caractérisé en ce que l'on empêche les libres échanges entre les composés complexes formés à la cathode et ceux formés à l'anode en séparant l'anode de la cathode par une paroi semi-perméable en matériau fritté inerte ou en polymère permettant le passage du courant d'électrolyse.Process for the electrolytic coating of a part according to which an electrolysis current is passed through a nickel-plating bath using nickel sulfamate as the filler compound, between a cathode constituted by the part to be coated and an anode, both immersed in the bath,
characterized in that the free exchanges between the complex compounds formed at the cathode and those formed at the anode are prevented by separating the anode from the cathode by a semi-permeable wall of inert sintered material or of polymer allowing passage of the electrolysis current.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9200407A FR2686352B1 (en) | 1992-01-16 | 1992-01-16 | APPARATUS AND METHOD FOR ELECTROLYTIC COATING OF NICKEL. |
| FR9200407 | 1992-01-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0552097A1 true EP0552097A1 (en) | 1993-07-21 |
| EP0552097B1 EP0552097B1 (en) | 1998-03-11 |
Family
ID=9425680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93400070A Expired - Lifetime EP0552097B1 (en) | 1992-01-16 | 1993-01-13 | Process and apparatus for nickel electroplating |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5403460A (en) |
| EP (1) | EP0552097B1 (en) |
| DE (1) | DE69317315T2 (en) |
| FR (1) | FR2686352B1 (en) |
| ZA (1) | ZA93264B (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19834353C2 (en) | 1998-07-30 | 2000-08-17 | Hillebrand Walter Gmbh & Co Kg | Alkaline zinc-nickel bath |
| DE19848467C5 (en) * | 1998-10-21 | 2006-04-27 | Walter Hillebrand Gmbh & Co. Kg Galvanotechnik | Alkaline zinc-nickel bath |
| US6482298B1 (en) * | 2000-09-27 | 2002-11-19 | International Business Machines Corporation | Apparatus for electroplating alloy films |
| WO2003014421A1 (en) * | 2001-08-01 | 2003-02-20 | Nikko Materials Company, Limited | Method for producing high purity nickel, high purity nickel, sputtering target comprising the high purity nickel, and thin film formed by using said spattering target |
| US7195702B2 (en) * | 2003-06-06 | 2007-03-27 | Taskem, Inc. | Tin alloy electroplating system |
| US7063628B2 (en) * | 2004-03-23 | 2006-06-20 | Callaway Golf Company | Plated magnesium golf club head |
| US7087268B2 (en) * | 2004-03-30 | 2006-08-08 | Callaway Golf Company | Method of plating a golf club head |
| US20060096867A1 (en) * | 2004-11-10 | 2006-05-11 | George Bokisa | Tin alloy electroplating system |
| US7311615B2 (en) * | 2005-07-01 | 2007-12-25 | Charles Hsu | Golf club head with ceramic layer |
| US20110226613A1 (en) | 2010-03-19 | 2011-09-22 | Robert Rash | Electrolyte loop with pressure regulation for separated anode chamber of electroplating system |
| US8980068B2 (en) | 2010-08-18 | 2015-03-17 | Allen R. Hayes | Nickel pH adjustment method and apparatus |
| US9404194B2 (en) | 2010-12-01 | 2016-08-02 | Novellus Systems, Inc. | Electroplating apparatus and process for wafer level packaging |
| US8425751B1 (en) | 2011-02-03 | 2013-04-23 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Systems and methods for the electrodeposition of a nickel-cobalt alloy |
| US9534308B2 (en) | 2012-06-05 | 2017-01-03 | Novellus Systems, Inc. | Protecting anodes from passivation in alloy plating systems |
| EP3377679A4 (en) | 2015-11-19 | 2019-05-01 | Fabric8Labs, Inc. | Three dimensional additive manufacturing of metal objects by stereo-electrochemical deposition |
| KR20230125095A (en) | 2017-11-01 | 2023-08-28 | 램 리써치 코포레이션 | Controlling plating electrolyte concentration on an electrochemical plating apparatus |
| US10914000B1 (en) | 2019-08-23 | 2021-02-09 | Fabric8Labs, Inc. | Method for manufacturing a printhead of an electrochemical additive manufacturing system |
| US11512404B2 (en) | 2019-08-23 | 2022-11-29 | Fabric8Labs, Inc. | Matrix-controlled printhead for an electrochemical additive manufacturing system |
| US11680330B2 (en) | 2021-07-22 | 2023-06-20 | Fabric8Labs, Inc. | Electrochemical-deposition apparatuses and associated methods of electroplating a target electrode |
| US11795561B2 (en) | 2021-08-02 | 2023-10-24 | Fabric8Labs, Inc. | Electrochemical-deposition system, apparatus, and method using optically-controlled deposition electrodes |
| US11920251B2 (en) | 2021-09-04 | 2024-03-05 | Fabric8Labs, Inc. | Systems and methods for electrochemical additive manufacturing of parts using multi-purpose build plate |
| US11970783B2 (en) | 2021-09-23 | 2024-04-30 | Fabric8Labs, Inc. | Systems and methods for manufacturing electrical components using electrochemical deposition |
| US11745432B2 (en) | 2021-12-13 | 2023-09-05 | Fabric8Labs, Inc. | Using target maps for current density control in electrochemical-additive manufacturing systems |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE925264C (en) * | 1952-11-15 | 1955-03-17 | Hesse & Co Dr | Process for nickel plating without nickel anodes |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS563692A (en) * | 1979-06-23 | 1981-01-14 | Kooken:Kk | Method and apparatus for high speed plating |
| US4902388A (en) * | 1989-07-03 | 1990-02-20 | United Technologies Corporation | Method for electroplating nickel onto titanium alloys |
| JPH03120390A (en) * | 1989-09-29 | 1991-05-22 | Toshiba Corp | Low stress nickel plating bath |
| JP2764337B2 (en) * | 1990-05-10 | 1998-06-11 | 新日本製鐵株式会社 | Ni or Ni-Zn alloy or Ni-Zn-Co alloy plating method |
-
1992
- 1992-01-16 FR FR9200407A patent/FR2686352B1/en not_active Expired - Fee Related
-
1993
- 1993-01-13 EP EP93400070A patent/EP0552097B1/en not_active Expired - Lifetime
- 1993-01-13 DE DE69317315T patent/DE69317315T2/en not_active Expired - Fee Related
- 1993-01-15 US US08/005,207 patent/US5403460A/en not_active Expired - Fee Related
- 1993-01-15 ZA ZA93264A patent/ZA93264B/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE925264C (en) * | 1952-11-15 | 1955-03-17 | Hesse & Co Dr | Process for nickel plating without nickel anodes |
Non-Patent Citations (2)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 102, no. 18, Mai 1985, Columbus, Ohio, US; abstract no. 156932r, HITACHI 'nickel electroplating cell' page 500 ;colonne 2 ; * |
| PATENT ABSTRACTS OF JAPAN vol. 5, no. 49 (C-49)(721) 8 Avril 1981 & JP-A-56 003 692 ( KOOKEN KK ) 14 Janvier 1981 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0552097B1 (en) | 1998-03-11 |
| DE69317315T2 (en) | 1998-10-15 |
| FR2686352B1 (en) | 1995-06-16 |
| ZA93264B (en) | 1994-07-15 |
| DE69317315D1 (en) | 1998-04-16 |
| US5403460A (en) | 1995-04-04 |
| FR2686352A1 (en) | 1993-07-23 |
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