EP0099793B1 - Electrolytic bath based on trivalent chromium - Google Patents
Electrolytic bath based on trivalent chromium Download PDFInfo
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- EP0099793B1 EP0099793B1 EP83401350A EP83401350A EP0099793B1 EP 0099793 B1 EP0099793 B1 EP 0099793B1 EP 83401350 A EP83401350 A EP 83401350A EP 83401350 A EP83401350 A EP 83401350A EP 0099793 B1 EP0099793 B1 EP 0099793B1
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- Prior art keywords
- chromium
- trivalent chromium
- bath
- ions
- trivalent
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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
- C25D3/04—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 and its use for chromium plating of conductive surfaces.
- 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.
- electrolysis bath based on trivalent chromium consisting of an aqueous solution of trivalent chromium halide
- this bath consists of an aqueous solution of trivalent chromium halide, containing at least Cr 3 + ions.
- H +, and halide ions and containing no complex between trivalent chromium and OH- ions or between trivalent chromium and organic molecules and it has a concentration of 0.1 to 1 gram ion per liter of trivalent chromium, a lower pH 1.5 and it is obtained by careful reduction of chromium trioxide, in a hydrohalogenated medium, using a reducing agent chosen from alcohols, hydrogen peroxide, hyposulfites, sulfur dioxide.
- the trivalent chromium salt obtained can be used directly for a chromium plating operation, at the end of the reduction of chromium trioxide, without the essential addition of additional products, in particular complexing agent of trivalent chromium or organic solvent so that it can start the chromium plating operation, and the proper functioning of this bath is only linked to the presence of Cr 3+ ions, halide ions, water molecules and H + ions.
- the chromium trioxide solution may possibly contain sulfuric or hydrobromic ions, but no additional additive is essential for the proper functioning of the bath.
- 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 entrainment 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, even exceeding one 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 NaCi, KCI, NH 4 CI tolerates the products commonly used in chromium plating 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 chromium 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 ⁇ m (Example 4).
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- 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)
Description
La présente invention concerne un bain d'électrolyse à base de chrome trivalent et son utilisation pour le chromage de surfaces conductrices.The present invention relates to an electrolysis bath based on trivalent chromium and its use for chromium plating of conductive surfaces.
Pour réaliser un dépôt électrolytique 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, 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 for reducing hexavalent chromium to trivalent chromium, using organic or inorganic reducing agents, which have been known for a very long time, constitute one of the interesting manufacturing means 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 applies in particular to GB patents No. 1,144,913 and 2,086,939, FR 2,254,657, 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-organic semi-aqueous electrolysis bath.
Ainsi en est-il du brevet FR-A-2 213 991. Celui-ci décrit un procédé de préparation d'une solution utilisable en chromage électrolytique, contenant des ions chromiques, halogénures et des ions H+, l'halogénure chromique pouvant avoir une basicité nulle. Cependant un dépôt de chrome avec un tel bain n'est obtenu que si celui-ci est utilisé dans les conditions décrites dans le brevet britannique N° 1 144 913, c'est-à-dire en complexant obligatoirement le chrome trois: pour le brevet FR-A-2 213 991 c'est de la DIMETHYLFORMAMIDE qui est choisie comme agent complexant.This is the case with patent FR-A-2 213 991. This describes a process for the preparation of a solution which can be used in electrolytic chromium plating, containing chromic ions, halides and H + ions, the chromic halide may have zero basicity. However, a deposit of chromium with such a bath is only obtained if it is used under the conditions described in British Patent No. 1,144,913, that is to say by obligatorily complexing chromium three: for the patent FR-A-2 213 991 it is DIMETHYLFORMAMIDE which is chosen as complexing agent.
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.
- - decorative chrome plating with a deposit color identical to that of hexavalent chrome,
- - hard chromium plating with sufficient thickness to lend itself to comparison with the hard chromium plating produced with hexavalent chromium 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 2441003, FR 2 460 344, FR 2 474 538 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.
- - 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 particulières 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.
- 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 paragraphe 2°) ci-dessus, d'étendre le domaine d'application à des bains utilisant un halogénure de chrome trivalent et, par le choix judicieux des constituants de ces bains, d'améliorer les performances obtenues.
- 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.
- 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 de bain d'électrolyse à base de chrome trivalent constitué par une solution aqueuse d'halogénure de chrome trivalent, est caractérisé en ce que ce bain est constitué par une solution aqueuse d'halogénure de chrome trivalent, contenant au moins des ions Cr3+. H+, et des ions halogénures et ne contenant pas de complexe entre chrome trivalent et ions OH- ou entre chrome trivalent et molécules organiques, et il a une concentration de 0,1 à 1 ion-gramme par litre de chrome trivalent, un pH inférieur à 1,5 et il est obtenu par réduction ménagée de trioxyde de chrome, en milieu hydrohalogèné, au moyen d'un agent réducteur choisi parmi les alcools, l'eau oxygénée, les hyposulfites, l'anhydride sulfureux.According to the invention of electrolysis bath based on trivalent chromium consisting of an aqueous solution of trivalent chromium halide, is characterized in that this bath consists of an aqueous solution of trivalent chromium halide, containing at least Cr 3 + ions. H +, and halide ions and containing no complex between trivalent chromium and OH- ions or between trivalent chromium and organic molecules, and it has a concentration of 0.1 to 1 gram ion per liter of trivalent chromium, a lower pH 1.5 and it is obtained by careful reduction of chromium trioxide, in a hydrohalogenated medium, using a reducing agent chosen from alcohols, hydrogen peroxide, hyposulfites, sulfur dioxide.
L'invention a également pour objet l'utilisation d'un tel bain d'électrolyse, pour déposer sur des substances conductrices un revêtement de chrome métallique dense et adhérent, sans qu'il soit nécessaire de changer la composition du bain en cours de revêtement, caractérisée par les conditions suivantes:
- densité de courant cathodique supérieure à 10 A/dm2;
- pH inférieur à 1,5 de préférence voisin de 1;
- température ambiante;
- sans séparation des compartiments anodique et cathodique de la cellule d'électrolyse utilisée;
- en maintenant une concentration en chrome de 0.1 à 1 ion-gramme par litre.
- cathodic current density greater than 10 A / dm 2 ;
- pH below 1.5, preferably close to 1;
- ambient temperature;
- without separation of the anode and cathode compartments of the electrolysis cell used;
- maintaining a chromium concentration of 0.1 to 1 gram ion per liter.
Le sel de chrome trivalent obtenu 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 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 can be used directly for a chromium plating operation, at the end of the reduction of chromium trioxide, without the essential addition of additional products, in particular complexing agent of trivalent chromium or organic solvent so that it can start the chromium plating operation, and 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 possibly contain sulfuric or hydrobromic ions, but no additional additive is essential for the proper functioning of the bath.
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 d'utilisation du bain sont les suivantes:
- - densité de courant cathodique supérieure à 10 A/dm2;
- - concentration en chrome: de 0,1 à 1 ion-gramme par litre en chrome trivalent soit 5,2 à 51,99 g/I de Cr3+;
- - pH inférieur à 1,5 de préférence voisin de 1;
- - température ambiante;
- - cathode current density greater than 10 A / d m 2 ;
- - chromium concentration: from 0.1 to 1 gram ion per liter of trivalent chromium, ie 5.2 to 51.99 g / I of Cr 3+ ;
- - pH below 1.5, preferably close to 1;
- - ambient temperature;
le rendement en courant (calculé suivant la loi de Faraday) étant supérieur à 30%.the current yield (calculated according to Faraday's law) being greater than 30%.
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 entraînement 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 rnatérieux.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 entrainment 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 de 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, even exceeding one 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 sans 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 NaCi, KCI, NH4CI 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 NaCi, KCI, NH 4 CI tolerates the products commonly used in chromium plating 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.
Aspect du dépôt: adhérent, brillant, couleur identique à celle du chrome déposé à partir des bains au chrome hexavalent.
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, 1e 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 µm (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 μm (Example 4).
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8211488 | 1982-06-30 | ||
| FR8211488A FR2529581A1 (en) | 1982-06-30 | 1982-06-30 | ELECTROLYSIS BATH BASED ON TRIVALENT CHROME |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0099793A1 EP0099793A1 (en) | 1984-02-01 |
| EP0099793B1 true 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) |
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| 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 |
| FR2726289B1 (en) * | 1994-10-28 | 1997-03-28 | Floquet Monopole | PROCESS FOR ELECTRODEPOSITION OF A CHROME COATING COMPRISING SOLID INCLUSIONS AND BATH IMPLEMENTED IN THIS PROCESS |
| 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 |
| CN101410556B (en) * | 2006-03-31 | 2010-12-29 | 爱托特奇德国股份有限公司 | Crystalline chromium deposit |
| CA2700147C (en) | 2007-10-02 | 2015-12-29 | Atotech Deutschland Gmbh | Crystalline chromium 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 |
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| CA1084441A (en) * | 1975-07-03 | 1980-08-26 | Stanley Renton | Chromium electroplating |
| 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 |
| FR2474538A1 (en) * | 1980-01-28 | 1981-07-31 | Tardy Rene | METHOD FOR ELECTROLYTIC DEPOSITION OF CHROME USING A TRIVALENT CHROME BATH |
| US4392922A (en) * | 1980-11-10 | 1983-07-12 | Occidental Chemical Corporation | Trivalent chromium electrolyte and process employing vanadium reducing agent |
-
1982
- 1982-06-30 FR FR8211488A patent/FR2529581A1/en not_active Withdrawn
-
1983
- 1983-06-30 EP EP83401350A patent/EP0099793B1/en not_active Expired
- 1983-06-30 DE DE8383401350T patent/DE3370661D1/en not_active Expired
-
1985
- 1985-03-18 US US06/712,476 patent/US4612091A/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| Gmelins Handbuch der Anorganischen Chemie, Vol. 52, A1(1962), Seiten 480-482 * |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2529581A1 (en) | 1984-01-06 |
| DE3370661D1 (en) | 1987-05-07 |
| EP0099793A1 (en) | 1984-02-01 |
| US4612091A (en) | 1986-09-16 |
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