EP0099793A1 - Electrolytic bath based on trivalent chromium - Google Patents

Electrolytic bath based on trivalent chromium Download PDF

Info

Publication number
EP0099793A1
EP0099793A1 EP83401350A EP83401350A EP0099793A1 EP 0099793 A1 EP0099793 A1 EP 0099793A1 EP 83401350 A EP83401350 A EP 83401350A EP 83401350 A EP83401350 A EP 83401350A EP 0099793 A1 EP0099793 A1 EP 0099793A1
Authority
EP
European Patent Office
Prior art keywords
chromium
trivalent chromium
electrolysis
ions
trivalent
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.)
Granted
Application number
EP83401350A
Other languages
German (de)
French (fr)
Other versions
EP0099793B1 (en
Inventor
Patrick c/o René Tardy Benaben
René Tardy
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.)
Association pour la Recherche et le Developpement des Methodes et Processus Industriels
Original Assignee
Association pour la Recherche et le Developpement des Methodes et Processus Industriels
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 Association pour la Recherche et le Developpement des Methodes et Processus Industriels filed Critical Association pour la Recherche et le Developpement des Methodes et Processus Industriels
Publication of EP0099793A1 publication Critical patent/EP0099793A1/en
Application granted granted Critical
Publication of EP0099793B1 publication Critical patent/EP0099793B1/en
Expired legal-status Critical Current

Links

Classifications

    • 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
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium

Definitions

  • the present invention relates to an electrolysis bath based on trivalent chromium.
  • an aqueous solution of concentrated chromic acid (hexavalent chromium) is commonly used in the presence of catalyst ions (of the sulphate or fluoride type), or alternatively an organic or semi-aqueous mi solution.
  • catalyst ions of the sulphate or fluoride type
  • organic or semi-aqueous mi solution e.g., -organic trivalent chromium.
  • the use of an electrolysis bath based on trivalent chromium is preferable because it has many advantages.
  • this electrolysis bath based on trivalent chromium consists of a solution obtained by gentle reduction, with a reducing agent such as alcohol, hydrogen peroxide, hyposulfite, sulfur dioxide, chromium trioxide in hydrochloric medium.
  • a reducing agent such as alcohol, hydrogen peroxide, hyposulfite, sulfur dioxide, chromium trioxide in hydrochloric medium.
  • the chromium trioxide solution may optionally contain sulfuric or hydrobromic ions, but no additional additive is essential for the proper functioning of the bath.
  • the electrolysis bath according to the invention can be used without separation of the anode and cathode compartments.
  • the anode used for the chromium plating operation is made of a material which can resist the release of chlorine and which allows the formation of hexavalent chromium by anodic oxidation as little as possible.
  • carbon anodes which allow to obtain excellent results.
  • the use of an electrolysis bath according to the invention offers numerous advantages.
  • the bath is very simple to make and its cost price is reduced.
  • concentration of chromium in the bath being low, the losses of chromium by mechanical drive are limited.
  • the absence of separation of the anode and cathode compartments allows chromium plating of complex parts. Because trivalent chromium is used the problems of toxicity and effluent treatment are reduced.
  • the electrolysis bath tolerates the interruption of electric current and it can be applied to different materials.
  • This electrolysis bath makes it possible to deposit on conductive substances a deposit of decorative chromium of color identical to that obtained by chromium plating processes with hexavalent chromium, with a concentration of the solution of trivalent chromium which is between 0.1 and 1 ion-g / 1 (5.2 to 51.99 g / 1 of Cr 3+ ).
  • the bath makes it possible to deposit on conductive substances a coating of chromium with a thickness greater than several tens of microns and even exceeding the hundred microns, deposit, dense, adherent and shiny, of hardness greater than a thousand Vickers.
  • the bath according to the invention in addition to the possible addition of conductive salts, such as NaCl, KC1, NH 4 Cl tolerates the products commonly used in chroming for improving the performance of baths.
  • Appearance of the deposit adherent, shiny, color identical to that of the chrome deposited from the hexavalent chromium baths.
  • Appearance of the deposit adherent, dense, slightly matt, color identical to that of the chrome deposited from the hexavalent chromium baths.
  • Appearance of the deposit adherent, rough, color identical to that of the chromium deposited from the hexavalent chromium baths.
  • the electrolysis bath makes it possible to use a potential difference of the order of 5 volts (example 2) and the deposits obtained are always of excellent quality, even when the he average thickness of the deposit obtained is much greater than 100 microns (Example 4).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

La présente invention concerne un bain d'électrolyse à base de chrome trivalent. Ce bain est caractérisé en ce qu'il contient un halogénure de chrome trivalent qui n'est ni complexé par un produit complexant du chrome ni accompagné par un solvant organique particulier. Grâce à des caractéristiques simples de fonctionnement ce bain permet d'obtenir des résultats commercialement intéressants car vis à vis de la couleur, de l'épaisseur et de la dureté des dépôts obtenus très proches de ceux des bains usuels à base de chrome hexavalent et cela avec l'avantage, par rapport à ces derniers, d'avoir une vitesse et un rendement de déposition très supérieurs et des conditions d'utilisation moins toxiques et moins polluantes.The present invention relates to an electrolysis bath based on trivalent chromium. This bath is characterized in that it contains a trivalent chromium halide which is neither complexed by a chromium complexing product nor accompanied by a particular organic solvent. Thanks to simple operating characteristics, this bath makes it possible to obtain commercially interesting results because with respect to the color, thickness and hardness of the deposits obtained very close to those of the usual baths based on hexavalent chromium and this with the advantage, compared to the latter, of having a very high speed and yield of deposition and less toxic and less polluting conditions of use.

Description

La présente invention concerne un bain d'électrolyse à base de chrome trivalent.The present invention relates to an electrolysis bath based on trivalent chromium.

Pour réaliser un dépôt élctrolytique de chrome ou chromage, on utilise couramment une solution aqueuse d'acide chromique concentré (chrome hexavalent) en présence d'ions catalyseurs (du type sulfates ou fluorures), ou bien encore une solution organique ou mi-aqueuse mi-organique de chrome trivalent. L'utilisation d'un bain d'électrolyse à base de chrome trivalent est préférable car elle présente de nombreux avantages.To carry out an electrolytic deposition of chromium or chromium plating, an aqueous solution of concentrated chromic acid (hexavalent chromium) is commonly used in the presence of catalyst ions (of the sulphate or fluoride type), or alternatively an organic or semi-aqueous mi solution. -organic trivalent chromium. The use of an electrolysis bath based on trivalent chromium is preferable because it has many advantages.

En effet, pour les bains au chrome hexavalent le rendement en courant obtenu est moyen, les pertes en élément chrome sont très élevées et la haute toxicité de l'acide chromique pose un certain nombre de problèmes. Au cours des dernières années, de nombreux procédés ont tenté de remplacer le chrome hexavalent par du chrome trivalent. Le sel de chrome trivalent employé est de nature très variable, et beaucoup de procédés précisent sa méthode particulière de fabrication. Les méthodes de réduction du chrome hexavalent -en chrome trivalent, par des agents réducteurs organiques ou inorganiques, connues depuis fort longtemps constituent un des moyens de fabrication intéressant des sels de chrome trivalent. Cependant jusqu'à présent les sels de chrome trivalent obtenus à partir de ces différentes réductions ne peuvent être utilisés directement pour un chromage par électrodéposition : il est indispensable de transformer le sel de chrome trivalent issu de la réduction en un nouveau composé (en particulier en un complexe organique ou inorganique le plus souvent) ,et, pour que le chromage soit possible, d'accompagner le nouveau composé de chrome trivalent de produits jugés indispensables. Ainsi en est-il en particulier des brevets GB N° 1 144 913 et 2 086 939,FR 2 254 657, 657, 2 305 510, 2 319 721, 2 322 217, 2 335 624, 2 362 948, 2 382 521 et 2 441 003. Ceux-ci imposent la complexation du sel de chrome trivalent, l'adjonction de divers produits ou l'utilisation de bain d'électrolyse mi-aqueux mi-organiques.Indeed, for hexavalent chromium baths the current yield obtained is average, the losses of chromium element are very high and the high toxicity of chromic acid poses a certain number of problems. In recent years, many processes have attempted to replace hexavalent chromium with trivalent chromium. The trivalent chromium salt used is very variable in nature, and many processes specify its particular method of manufacture. The methods of reduction of hexavalent chromium - to trivalent chromium, by organic or inorganic reducing agents, known for a very long time constitute one of the interesting means of manufacture of trivalent chromium salts. However, until now the trivalent chromium salts obtained from these various reductions cannot be used directly for chromium plating by electrodeposition: it is essential to transform the trivalent chromium salt resulting from the reduction into a new compound (in particular in an organic or inorganic complex more often), and, to make chromium plating possible, to accompany the new trivalent chromium compound with products deemed essential. This is particularly the case with GB patents No. 1,144,913 and 2,086,939, FR 2,254,657, 657, 2,305,510, 2,319,721, 2,322,217, 2,335,624, 2,362,948, 2,382,521 and 2,441,003. These impose the complexation of the trivalent chromium salt, the addition of various products or the use of semi-aqueous, semi-organic electrolysis bath.

Par ailleurs, pour que, industriellement, un bain à base de chrome trivalent puisse, avec profit, se substituer aux bains habituels, à base de chrome hexavalent, il lui faudrait pouvoir permettre d'effectuer :

  • - un chromage décoratif avec une couleur de dépôt identique à celle d'un chrome hexavalent,
  • - un chromage dur avec une épaisseur suffisante pour se prêter à une comparaison avec le chromage dur produit avec les bains au chrome hexavalent.
Furthermore, so that, industrially, a bath based on trivalent chromium can, with profit, replace the usual baths, based on hexavalent chromium, it should be able to allow:
  • - decorative chrome plating with a deposit color identical to that of hexavalent chrome,
  • - hard chrome plating with sufficient thickness to lend itself to comparison with the hard chrome plating produced with hexavalent chrome baths.

Des procédés décrivent l'obtention de chrome épais à partir de composés de chrome trivalent, mais, en règle générale ils imposent la séparation rigoureuse des compartiments anodique et cathodique, ce qui impose de difficiles contraintes techniques d'exploitation.Methods describe obtaining thick chromium from trivalent chromium compounds, but, as a general rule, they impose rigorous separation of the anode and cathode compartments, which imposes difficult technical operating constraints.

A première vue, seuls les brevets de chromage à base de chrome trivalent FR 2 441 003, FR 2 460 344, FR 2474 538 paraissent apporter une réponse valable, le premier pour obtenir un chrome décoratif, le deuxième un chrome épais et le troisième à la fois un chrome décoratif et un chrome -épais. Cependant, dans les deux premiers brevets, le chrome libéré dans le chromage provient d'un complexe de chrome trivalent et :

  • - dans le brevet FR 2 441 003 la concentration en chrome dans la solution d'électrodéposition doit être inférieure à 0,03 M
  • - dans le deuxième brevet FR 2 460 344 il est nécessaire d'effectuer un chromage en plusieurs étapes pour arriver à avoir un chrome d'une épaisseur de cinq microns.
At first glance, only the chromium-trivalent chromium patents FR 2 441 003, FR 2 460 344, FR 2 474 538 seem to provide a valid answer, the first to obtain a decorative chromium, the second a thick chromium and the third to both decorative chrome and thick chrome. However, in the first two patents, the chromium released in the chromium plating comes from a trivalent chromium complex and:
  • - in patent FR 2 441 003 the chromium concentration in the electroplating solution must be less than 0.03 M
  • - In the second patent FR 2 460 344 it is necessary to carry out a chromium plating in several stages to arrive at having a chromium with a thickness of five microns.

Seul le brevet FR 2 474 538 apporte une réponse simple et complète aux problèmes soulevés ci-dessus.Only patent FR 2 474 538 provides a simple and complete answer to the problems raised above.

Pour l'essentiel il porte :

  • 1°) Sur l'utilisation d'un sulfate de chrome trivalent, non introduit dans un complexe, dans un milieu réactionnel simple, en particulier dépourvu de la présence indispensable de solvant particulier, organique ou inorganique.
  • 2°) Sur des caractéristiques particlières de fonctionnement du bain, réalisé avec ce sel de chrome trivalent, permettant d'obtenir, simplement, des résultats commercialement intéressants, car, vis-à-vis de la couleur et de l'épaisseur du chrome déposé, très proches de ceux obtenus avec les bains habituels, au chrome hexavalent.
Essentially it carries:
  • 1) On the use of a trivalent chromium sulfate, not introduced into a complex, in a simple reaction medium, in particular devoid of the essential presence of a particular solvent, organic or inorganic.
  • 2 °) On particular operating characteristics of the bath, produced with this trivalent chromium salt, making it possible to obtain, simply, commercially interesting results, because, with respect to the color and the thickness of the deposited chromium , very close to those obtained with the usual baths, with hexavalent chromium.

Si un tel procédé s'est révélé donner des résultats satisfaisants, on a constaté qu'il était possible, tout en conservant l'intérêt commercial décrit au paragrpahe 2°) ci-dessus, d'étendre le domaine d'aplication à des bains utilisant un halogénure de chrome trivalent et, par le choix judicieux des constituants de ces bains, d'améliorer les performances obtenues.If such a process has been found to give satisfactory results, it has been found that it is possible, while retaining the commercial advantage described in paragraph 2 °) above, to extend the field of application to baths. using a trivalent chromium halide and, by the judicious choice of the constituents of these baths, of improving the performances obtained.

Suivant l'invention ce bain d'électrolyse à base de chrome trivalent est constitué par une solution obtenue par réduction ménagée, par un agent réducteur tel qu'alcool, eau oxygénée, hyposulfite, anhydride sulfureux, de trioxyde de chrome en milieu chlorhydrique.According to the invention, this electrolysis bath based on trivalent chromium consists of a solution obtained by gentle reduction, with a reducing agent such as alcohol, hydrogen peroxide, hyposulfite, sulfur dioxide, chromium trioxide in hydrochloric medium.

Le sel de chrome trivalent obtenu :

  • - n'est pas inclus dans un complexe (en particulier dans tout complexe entre chrome trivalent et ions à base OH- ou chrome hexavalent et molécule organique).
  • - est utilisable directement pour une opération de chromage,dès la fin de la réduction du trioxyde de chrome, sans adjonction indispensable de produits supplémentaires, en particulier d'agent complexant du chrome trivalent ou de solvant organique pour que puisse démarrer l'opération de chromage ; et que le bon fonctionnement de ce bain n'est lié qu'à la présence d'ions Cr3+, d'ions halogénures, de molécules d'eau et d'ions H+.
The trivalent chromium salt obtained:
  • - is not included in a complex (in particular in any complex between trivalent chromium and ions based on OH- or hexavalent chromium and organic molecule).
  • - can be used directly for a chromium plating operation, at the end of the reduction of chromium trioxide, without essential addition of additional products, in particular trivalent chromium complexing agent or organic solvent so that the chromium plating operation can start ; and that the proper functioning of this bath is only linked to the presence of Cr 3+ ions, halide ions, water molecules and H + ions.

La solution de trioxyde de chrome peut contenir éventuellement des ions sulfuriques ou bromhydriques mais aucun adjuvant supplémentaire n'est indispensable à la bonne marche du bain.The chromium trioxide solution may optionally contain sulfuric or hydrobromic ions, but no additional additive is essential for the proper functioning of the bath.

Le bain d'électrolyse suivant l'invention peut être utilisé sans séparation des compartiments anodique et catho- dioue.The electrolysis bath according to the invention can be used without separation of the anode and cathode compartments.

L'anode utilisée pour l'opération de chromage est constituée en un matériau pouvant résister à un dégagement de chlore et permettant le moins possible la formation de chrome hexavalent par oxydation anodique. De préférence on utilise avec le bain, suivant l'invention, des anodes en carbone qui permettent d'obtenir d'excellents résultats.The anode used for the chromium plating operation is made of a material which can resist the release of chlorine and which allows the formation of hexavalent chromium by anodic oxidation as little as possible. Preferably used with the bath, according to the invention, carbon anodes which allow to obtain excellent results.

Les conditions générales d'utilisation du bain sont les suivantes :

Figure imgb0001
The general conditions of use of the bath are as follows:
Figure imgb0001

L'utilisation d'un bain d'électrolyse suivant l'invention offre de nombreux avantages. Le bain est très simple à réaliser et son prix de revient est réduit. La concentration du bain en chrome étant faible, les pertes en chrome par entrainement mécanique sont limitées. L'absence de séparation des compartiments anodique et cathodique permet le chromage de pièces complexes. Du fait que l'on utilise du chrome trivalent les problèmes de toxicité et de traitement des effluents sont réduits. Le bain d'électrolyse tolère l'interruption de courant électrique et il peut s'appliquer à différents matériaux.The use of an electrolysis bath according to the invention offers numerous advantages. The bath is very simple to make and its cost price is reduced. The concentration of chromium in the bath being low, the losses of chromium by mechanical drive are limited. The absence of separation of the anode and cathode compartments allows chromium plating of complex parts. Because trivalent chromium is used the problems of toxicity and effluent treatment are reduced. The electrolysis bath tolerates the interruption of electric current and it can be applied to different materials.

Ce bain d'électrolyse permet de déposer sur des substances conductrices un dépôt de chrome décoratif de couleur identique à celle obtenue par les procédés de chromage avec du chrome hexavalent, avec une concentration de la solution en chrome trivalent qui est comprise entre 0,1 et 1 ion-g/1 (5,2 à 51,99 g/1 de Cr3+).This electrolysis bath makes it possible to deposit on conductive substances a deposit of decorative chromium of color identical to that obtained by chromium plating processes with hexavalent chromium, with a concentration of the solution of trivalent chromium which is between 0.1 and 1 ion-g / 1 (5.2 to 51.99 g / 1 of Cr 3+ ).

De même, en ce qui concerne le chrome épais, le bain, selon l'invention, permet de déposer sur des substances conductrices un revêtement de chrome d'épaisseur supérieure à plusieurs dizaines de microns et même dépassant la centaine de microns, dépôt, dense, adhérent et brillant, de dureté supérieure à mille Vickers.Similarly, with regard to thick chromium, the bath, according to the invention, makes it possible to deposit on conductive substances a coating of chromium with a thickness greater than several tens of microns and even exceeding the hundred microns, deposit, dense, adherent and shiny, of hardness greater than a thousand Vickers.

Ces dépôts de chrome épais sont réalisés en une seule opération d'électrolyse sans avoir, comme indiqué ci-dessus, à séparer les compartiments anodique et cathodique, et sanss avoir à changer la composition du bain au cours du chromage.These thick chromium deposits are produced in a single electrolysis operation without having, as indicated above, to separate the anode and cathode compartments, and without having to change the composition of the bath during chromium plating.

Le bain selon l'invention outre l'adjonction possible de sels conducteurs, tels que NaCl, KC1, NH4Cl tolère les produits utilisés couramment en chromage pour l'amélioration des performances des bains.The bath according to the invention, in addition to the possible addition of conductive salts, such as NaCl, KC1, NH 4 Cl tolerates the products commonly used in chroming for improving the performance of baths.

On donnera ci-dessous, à titre d'exemples non limitatifs, les résultats d'essais qui ont été effectués avec divers bains d'électrolyse suivant l'invention.

  • 1)- Concentration en CrIII: 0,2 ion g/1
    Figure imgb0002
  • 2)- Concentration en CrIII: 0,3 ion g/1, avec addition de KC1: 70 g/1
    Figure imgb0003
The results of tests which have been carried out with various electrolysis baths according to the invention will be given below, by way of nonlimiting examples.
  • 1) - Cr III concentration: 0.2 ion g / 1
    Figure imgb0002
  • 2) - Cr III concentration: 0.3 ion g / 1, with addition of KC1: 70 g / 1
    Figure imgb0003

Aspect du dépôt: adhérent, brillant, couleur identique à celle du chrome déposé à partir des bains au chrome hexavalent.Appearance of the deposit: adherent, shiny, color identical to that of the chrome deposited from the hexavalent chromium baths.

3)- Concentration en CrIII: 0,35 ion g/1

Figure imgb0004
3) - Cr III concentration: 0.35 ion g / 1
Figure imgb0004

Aspect du dépôt: adhérent, dense, légèrement mat, couleur identique à celle du chrome déposé à partir des bains au chrome hexavalent.Appearance of the deposit: adherent, dense, slightly matt, color identical to that of the chrome deposited from the hexavalent chromium baths.

4)- Concentration en CrIII: 0,4 ion g/1

Figure imgb0005
4) - Cr III concentration: 0.4 ion g / 1
Figure imgb0005

Aspect du dépôt: adhérent, rugueux, couleur identique à celle du chrome déposé à partir des bains au chrome hexavalent.Appearance of the deposit: adherent, rough, color identical to that of the chromium deposited from the hexavalent chromium baths.

Comme on peut le voir d'après les exemples précités, le bain d'électrolyse permet d'utiliser une différence de potentiel de l'ordre de 5 volts (exemple 2) et les dépôts obtenus sont toujours d'excellente qualité, même lorsque l'épaisseur moyenne du dépôt obtenu est bien supérieure à 100 micron (exemple 4).As can be seen from the above examples, the electrolysis bath makes it possible to use a potential difference of the order of 5 volts (example 2) and the deposits obtained are always of excellent quality, even when the he average thickness of the deposit obtained is much greater than 100 microns (Example 4).

Claims (6)

1.- 3ain d'électrolyse à base de chrome trivalent constitué par une solution aqueuse d'halogénure de chrome trivalent ,caractérisé en ce que le chrome trivalent n'est pas inclus dans un complexe (en particulier dans tout complexe entre chrome trivalent et ions à base de OH-, ou chrome trivalent et molécules organiques), et que le bon fonctionnement de ce bain n'est lié qu'à la présence d'ions Cr3+, d'ions halogénures, de molécules d'eau et d'ions H+.1.- 3ain of electrolysis based on trivalent chromium constituted by an aqueous solution of trivalent chromium halide, characterized in that the trivalent chromium is not included in a complex (in particular in any complex between trivalent chromium and ions based on OH-, or trivalent chromium and organic molecules), and that the proper functioning of this bath is only linked to the presence of Cr 3+ ions, halide ions, water molecules and d 'H + ions. 2.- Bain d'électrolyse suivant la revendication 1, obtenu par la réduction du trioxyde de chrome (Cr03) par un agent réducteur tel que l'alcool, eau oxygénée, hyposulfite, anhydride sulfureux, en milieu chlorhydrique pouvant contenir éventuellement des ions bromhydriques ou sulfuriques, caractérisé en ce qu'il permet de réaliser l'électrolyse et le dépôt de chrome immédiatement après la réduction du trioxyde de chrome, sans adjonction indispensable de produits supplémentaires en particulier d'agent complexant.2.- electrolysis bath according to claim 1, obtained by the reduction of chromium trioxide (Cr0 3 ) by a reducing agent such as alcohol, hydrogen peroxide, hyposulfite, sulfur dioxide, in a hydrochloric medium which may optionally contain ions hydrobromic or sulfuric, characterized in that it makes it possible to carry out the electrolysis and the deposition of chromium immediately after the reduction of chromium trioxide, without essential addition of additional products in particular of complexing agent. 3.- Bain d'électrolyse suivant la revendication 1 , permettant de déposer sur des substances conductrices, un revêtement de chrome d'épaisseur supérieure à plusieurs dizaines de microns, caractérisé en ce qu'on peut réaliser directement un dépôt de chrome dense et adhérent en une seule opération d'électrolyse, sans avoir à séparer les compartiments anodique et cathodique et sans avoir à changer la composition du bain en cours de revêtement.3.- electrolysis bath according to claim 1, allowing to deposit on conductive substances, a chromium coating of thickness greater than several tens of microns, characterized in that one can directly deposit a dense and adherent chromium in a single electrolysis operation, without having to separate the anode and cathode compartments and without having to change the composition of the bath during coating. 4.- Bain d'électrolyse selon la revendication 1 permettant d'obtenir une vitesse de déposition supérieure à 1 µm.mn-1 avec des densités de courant de 25 et 30 A.dm-2 caractérisé en ce que la densité de courant cathodique pour obtenir un dépôt adhérent et brillant est supérieure à 10 A.dm-2.4.- electrolysis bath according to claim 1 making it possible to obtain a deposition rate greater than 1 µm.mn -1 with current densities of 25 and 30 A.dm- 2 characterized in that the cathode current density to obtain an adherent and shiny deposit is greater than 10 A.dm -2 . 5.- Bain d'électrolyse selon la revendication 1, destiné à réaliser un dépôt de chrome décoratif de couleur identique à celle obtenue par les procédés de chromage avec du chrome hexavalent, caractérisé en ce que la concentration en chrome trivalent de la solution est comprise entre D,1 et 1 ion-g/1.5.- electrolysis bath according to claim 1, intended to produce a deposit of decorative chromium of identical color to that obtained by the chromium plating processes with hexavalent chromium, characterized in that the concentration of trivalent chromium in the solution is included between D, 1 and 1 ion-g / 1. 6.- Bain d'électrolyse selon la revendication 1 caractérisé en ce qu'il peut comporter en outre des quantités quelconques d'au moins un produit (sels conducteurs par exemple, ...) utilisé couramment en chromage pour l'amélioration des performances des bains.6.- electrolysis bath according to claim 1 characterized in that it can also comprise any quantities of at least one product (conductive salts for example, etc.) commonly used in chroming for improving performance baths.
EP83401350A 1982-06-30 1983-06-30 Electrolytic bath based on trivalent chromium Expired EP0099793B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8211488A FR2529581A1 (en) 1982-06-30 1982-06-30 ELECTROLYSIS BATH BASED ON TRIVALENT CHROME
FR8211488 1982-06-30

Publications (2)

Publication Number Publication Date
EP0099793A1 true EP0099793A1 (en) 1984-02-01
EP0099793B1 EP0099793B1 (en) 1987-04-01

Family

ID=9275557

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83401350A Expired EP0099793B1 (en) 1982-06-30 1983-06-30 Electrolytic bath based on trivalent chromium

Country Status (4)

Country Link
US (1) US4612091A (en)
EP (1) EP0099793B1 (en)
DE (1) DE3370661D1 (en)
FR (1) FR2529581A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5868917A (en) * 1994-10-28 1999-02-09 Floquet Monopole Process for the electrodeposition of a chromium coating containing solid inclusions and plating solution employed in this process

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5413646A (en) * 1991-02-08 1995-05-09 Blount, Inc. Heat-treatable chromium
US5294326A (en) * 1991-12-30 1994-03-15 Elf Atochem North America, Inc. Functional plating from solutions containing trivalent chromium ion
JP3188361B2 (en) * 1994-06-27 2001-07-16 ペルメレック電極株式会社 Chrome plating method
US6004448A (en) 1995-06-06 1999-12-21 Atotech Usa, Inc. Deposition of chromium oxides from a trivalent chromium solution containing a complexing agent for a buffer
US6248228B1 (en) 1999-03-19 2001-06-19 Technic, Inc. And Specialty Chemical System, Inc. Metal alloy halide electroplating baths
DE10354760A1 (en) * 2003-11-21 2005-06-23 Enthone Inc., West Haven Process for depositing nickel and chromium (VI) free metallic matte layers
US7052592B2 (en) * 2004-06-24 2006-05-30 Gueguine Yedigarian Chromium plating method
US7887930B2 (en) * 2006-03-31 2011-02-15 Atotech Deutschland Gmbh Crystalline chromium deposit
BRPI0817924B1 (en) 2007-10-02 2019-02-12 Atotech Deutschland Gmbh ELECTROPOSED CRYSTALLINE FUNCTIONAL CHROME ALLOY DEPOSIT, ELECTROPOSITION BATH TO DEPOSIT A CRYSTALLINONANOGRAULAR FUNCTIONAL CHROME ALLOY DEPOSIT, AND PROCESS TO ELECTROPOSIT A CRYSTAL CRYSTAL CHRONOUS ALLOY DEPOSIT
US9758884B2 (en) * 2012-02-16 2017-09-12 Stacey Hingley Color control of trivalent chromium deposits
CN104775139A (en) * 2015-04-21 2015-07-15 柳州凡一科技有限公司 Boat deck electroplating method of rice transplanter

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2524803A (en) * 1947-03-26 1950-10-10 Du Pont Production of a basic chromic chloride
GB1144913A (en) * 1966-10-31 1969-03-12 British Non Ferrous Metals Res Electrodeposition of chromium
US3706642A (en) * 1971-02-19 1972-12-19 Du Pont Preparation of chromium plating bath
FR2213991A1 (en) * 1973-01-16 1974-08-09 British Chrome Chemicals Ltd Basic trivalent chromium hydroxyhalide electroplating cpd. - from hexavalent chromium by redn. with carbohydrate in presence of halohydric acid
FR2474538A1 (en) * 1980-01-28 1981-07-31 Tardy Rene METHOD FOR ELECTROLYTIC DEPOSITION OF CHROME USING A TRIVALENT CHROME BATH

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1706642A (en) * 1923-05-07 1929-03-26 United Shoe Machinery Corp Shoe machine and method of making shoes
GB301478A (en) * 1927-12-01 1929-02-21 Langbein Pfanhauser Werke Ag Process for the electrolytic deposition of chromium
US1922853A (en) * 1927-12-01 1933-08-15 United Chromium Inc Process for the electrolytic deposition of chromium
US1838777A (en) * 1928-03-26 1931-12-29 Ternstedt Mfg Co Chromium plating
US1797357A (en) * 1928-03-29 1931-03-24 Ternstedt Mfg Co Chromium plating
US2928723A (en) * 1956-08-23 1960-03-15 Diamond Alkali Co Process for making basic chromic chlorides
US3414492A (en) * 1965-12-14 1968-12-03 Corillium Corp Chromium plating process
US3419481A (en) * 1966-04-08 1968-12-31 Diamond Shamrock Corp Electrolyte and process for electroplating black chromium and article thereby produced
US3442777A (en) * 1966-06-20 1969-05-06 Corillium Corp Chromium plating process
SU475346A1 (en) * 1972-10-23 1975-06-30 Институт Органического Катализа И Электрохимии Ан Казахской Сср The method of producing chromium chloride
US4054494A (en) * 1973-12-13 1977-10-18 Albright & Wilson Ltd. Compositions for use in chromium plating
GB1455580A (en) * 1973-12-13 1976-11-17 Albright & Wilson Electrodeposition of chromium
SU582205A1 (en) * 1975-03-21 1977-11-30 Институт Органического Катализа И Электрохимии Ан Кахазской Сср Method of preparing chromium chloride
GB1498532A (en) * 1975-03-26 1978-01-18 Bnf Metals Tech Centre Trivalent chromium plating baths
NL183660C (en) * 1975-07-03 1988-12-16 Albright & Wilson METHOD FOR CHROMING ELECTROLYTIC ROADS; METHOD FOR TESTING AN ELECTROLYTIC COATING BATH; TEST SAMPLE.
GB1562188A (en) * 1975-08-27 1980-03-05 Albright & Wilson Chromium electroplating baths
GB1544833A (en) * 1975-12-18 1979-04-25 Albright & Wilson Chromium electroplating
GB1592761A (en) * 1976-08-24 1981-07-08 Albright & Wilson Electroplating baths
GB1552263A (en) * 1977-03-04 1979-09-12 Bnf Metals Tech Centre Trivalent chromium plating baths
US4167460A (en) * 1978-04-03 1979-09-11 Oxy Metal Industries Corporation Trivalent chromium plating bath composition and process
GB2051861B (en) * 1979-06-29 1983-03-09 Ibm Deposition of thick chromium films from trivalent chromium plating solutions
GB2038361B (en) * 1978-11-11 1983-08-17 Ibm Trivalent chromium plating bath
US4392922A (en) * 1980-11-10 1983-07-12 Occidental Chemical Corporation Trivalent chromium electrolyte and process employing vanadium reducing agent

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2524803A (en) * 1947-03-26 1950-10-10 Du Pont Production of a basic chromic chloride
GB1144913A (en) * 1966-10-31 1969-03-12 British Non Ferrous Metals Res Electrodeposition of chromium
US3706642A (en) * 1971-02-19 1972-12-19 Du Pont Preparation of chromium plating bath
FR2213991A1 (en) * 1973-01-16 1974-08-09 British Chrome Chemicals Ltd Basic trivalent chromium hydroxyhalide electroplating cpd. - from hexavalent chromium by redn. with carbohydrate in presence of halohydric acid
FR2474538A1 (en) * 1980-01-28 1981-07-31 Tardy Rene METHOD FOR ELECTROLYTIC DEPOSITION OF CHROME USING A TRIVALENT CHROME BATH

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 95, no. 8, août 1981, page 727, no. 72414x, Columbus, Ohio, USA; R.E. SOWDEN: 'Reduction of a solution of sodium chromate in hydrochloric acid by methanol' & COMMUN. FAC. SCI. UNIV. ANKARA, SER. B 1980, vol. 26, no. 9, pages 61 - 75 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5868917A (en) * 1994-10-28 1999-02-09 Floquet Monopole Process for the electrodeposition of a chromium coating containing solid inclusions and plating solution employed in this process

Also Published As

Publication number Publication date
DE3370661D1 (en) 1987-05-07
EP0099793B1 (en) 1987-04-01
FR2529581A1 (en) 1984-01-06
US4612091A (en) 1986-09-16

Similar Documents

Publication Publication Date Title
EP0099793B1 (en) Electrolytic bath based on trivalent chromium
FR2699556A1 (en) Baths for forming an electrolytic deposit of copper and process for electrolytic deposition using this bath.
CN107326414B (en) Plastic substrate chromium-free metallization method
FR2493880A1 (en) ELECTROLYTES FOR THE DEPOSITION OF TRIVALENT CHROME, EMPLOYING A VANADIUM REDUCER
FR2658536A1 (en) COMPOSITIONS AND METHODS FOR ELECTRODEPOSITION.
FR2649996A1 (en) CYANIDE-FREE COOKING PROCESS
EP1423557B1 (en) Electrolytic solution for electrochemical deposition of gold and its alloys
FR2576609A1 (en) COMPOSITION AND PROCESS FOR FORMING PALLADIUM COATING IN PALLADIUM ALLOYS
LU81724A1 (en) METHOD FOR ELECTROLYTIC COATING AND TREATING AN IRON-BASED WIRE CARRYING AN ELECTROLYTIC COATING
FR2474538A1 (en) METHOD FOR ELECTROLYTIC DEPOSITION OF CHROME USING A TRIVALENT CHROME BATH
US2457059A (en) Method for bonding a nickel electrodeposit to a nickel surface
FR2537164A1 (en) PROCESS FOR THE PURIFICATION OF BATHS FOR THE ELECTROLYTIC COATING OF TRIVALENT CHROME
EP0291416A1 (en) Process for the reduction of a solution containing titanium and iron
FR2460344A1 (en) METHOD FOR ELECTRODEPOSITIONING THICK CHROMED LAYERS USING A TRIVALENT CHROMIUM SOLUTION AND ARTICLES HAVING A COATING OBTAINED THEREBY
EP0709496B1 (en) Process for electroplating a chromium layer containing solid particles and bath used in this process
WO2005014890A1 (en) An electrolyte solution
EP4077773A1 (en) Method for reducing the concentration of iron ions in a trivalent chromium eletroplating bath
EP1070771A1 (en) Aqueous acid bath for zinc plating process and zinc plating process using the bath
EP1591545B1 (en) Eco-friendly stripping of chromium-plated plastic materials and extension to Cr-plated passivatable metallic substrates
US5194100A (en) Heat treatable chromium
FR2656007A1 (en) GALVANIC DEPOSITION BATH WITH GOLD ALLOY.
BE895746A (en) ELECTROLYTIC DEPOSIT OF ZINC-COBALT ALLOYS
BE835580A (en) TRIVALENT CHROME ELECTROLYC DEPOSIT BATH
FR2600676A1 (en) METHOD FOR ELECTRODEPOSITION OF A CHROME-IRON ALLOY
LU85403A1 (en) PROCESS FOR FORMING A GLOSSY DEPOSIT OF METAL OR A METAL CONTAINING ALLOY ON A CONDUCTIVE SUBSTRATE

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

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

17P Request for examination filed

Effective date: 19840402

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

ITF It: translation for a ep patent filed

Owner name: INTERBREVETTI S.R.L.

AK Designated contracting states

Kind code of ref document: B1

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

REF Corresponds to:

Ref document number: 3370661

Country of ref document: DE

Date of ref document: 19870507

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

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

Ref country code: SE

Payment date: 19910626

Year of fee payment: 9

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

Ref country code: LU

Payment date: 19910627

Year of fee payment: 9

Ref country code: GB

Payment date: 19910627

Year of fee payment: 9

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

Ref country code: FR

Payment date: 19910628

Year of fee payment: 9

Ref country code: DE

Payment date: 19910628

Year of fee payment: 9

Ref country code: BE

Payment date: 19910628

Year of fee payment: 9

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

Ref country code: NL

Payment date: 19910630

Year of fee payment: 9

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

Ref country code: CH

Payment date: 19911231

Year of fee payment: 9

EPTA Lu: last paid annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

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

Effective date: 19920630

Ref country code: LI

Effective date: 19920630

Ref country code: GB

Effective date: 19920630

Ref country code: CH

Effective date: 19920630

Ref country code: BE

Effective date: 19920630

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

Ref country code: SE

Effective date: 19920701

BERE Be: lapsed

Owner name: ASSOCIATION POUR LA RECHERCHE ET LE DEVELOPPEMENT

Effective date: 19920630

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

Ref country code: NL

Effective date: 19930101

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19920630

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

Ref country code: FR

Effective date: 19930226

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: DE

Effective date: 19930302

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 83401350.0

Effective date: 19930204