EP0084752B1 - Process for chromium plating the inner surface of tubes, anode used in this process - Google Patents

Process for chromium plating the inner surface of tubes, anode used in this process Download PDF

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Publication number
EP0084752B1
EP0084752B1 EP19820402398 EP82402398A EP0084752B1 EP 0084752 B1 EP0084752 B1 EP 0084752B1 EP 19820402398 EP19820402398 EP 19820402398 EP 82402398 A EP82402398 A EP 82402398A EP 0084752 B1 EP0084752 B1 EP 0084752B1
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Prior art keywords
anode
fact
per
different
chromium
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EP19820402398
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German (de)
French (fr)
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EP0084752A1 (en
Inventor
Bernard Marliac
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Direction General pour lArmement DGA
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Direction General pour lArmement DGA
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/04Tubes; Rings; Hollow bodies

Definitions

  • the invention relates to a process for chroming the interior surface of a tubular element, such as for example a weapon tube, by electrolytic deposition as well as to an anode allowing the implementation of this process.
  • One solution is to make the two thicknesses separately by doing two successive chrome plating.
  • Another solution consists in carrying out the chromium plating of the two parts in the same bath by setting up a cover coming to mask the part of the deposit of small thickness at the end of the time necessary for its chromium plating.
  • the first solution is obviously long since it requires two successive chromium plating operations.
  • the second solution is difficult to implement and in any case requires intervention during the electrolytic treatment.
  • US-A-3,706,651 describes a device for minimizing the irregularities of an electrolytic deposit on a curved surface, comprising a rotary anode the active part of which comprises conductive rings separated by insulating rings, each conductive ring being supplied separately with electricity .
  • the present invention therefore proposes to remedy the drawbacks indicated above and to provide a method of chromium plating of the interior surface of a tubular element which makes it possible, in a single operation, to chromium plating several zones intended to have deposits of different thicknesses and which simultaneously allows a gradual and regular transition between deposits of different thicknesses.
  • Yet another objective of the invention is to provide such a method which is easy to implement and of an economic cost price while not requiring more time than is necessary to ensure the establishment of the deposit. the thickest.
  • Yet another objective of the invention is to provide anodes which make it possible to implement such a method.
  • the subject of the invention is a method for producing chromium deposits of different thicknesses on successive sections of the inner wall of a tubular element by electrolytic means in which one places, inside the tubular element , an anode centered on the axis of the tubular element and an electrolytic liquid is introduced allowing, during the passage of the electric current, to deposit a deposit of chromium on the tubular wall forming cathode of the tubular element, characterized in that the anode is made up of several parts of different electrical conductivities, namely one part per section of tubular element to be coated, the value of the conductivity and the diameter of the corresponding part of anode being chosen as a function of the thickness of the deposit to be made on the corresponding section of the wall of the tubular element.
  • the anode provided may consist of several consecutive strands of different conductivities or, if appropriate, of a central part coated with tubular sleeves of different conductivities.
  • the electrolysis liquid is circulated inside the tube in order to constantly ensure its renewal and its homogenization.
  • the subject of the invention is also, as new industrial products, the anodes used in this process and characterized in that they comprise at least two successive effective parts of different conductivities.
  • a tubular element 1 comprising two sections, namely a fairly elongated section 2, followed by a shorter section 3.
  • the section 2 has a constant diameter over most of its length, then a first conical widening of slight slope 2a, followed of a cylindrical part 2b.
  • the section 3 has a cylindrical part 3a of large diameter while a conical connection zone 4 joins the cylindrical parts 2b and 3a, the zone 4 belonging half to the section 2 and half to the section 3.
  • a spacer 8 surrounding the emerging end of the anode 5 is supported on the part 6 and ends with a part 9 forming both a suspension and contact hook for the anode.
  • a part 10 also acting as a "current thief", this part supporting a centering part 11.
  • a nut 12 On the threaded end of the anode 5, is screwed a nut 12 with a washer 13 on which comes to bear a tubular spacer 14 with the interposition of a number of Belleville washers 15 which, taking support on the other hand on the part 11, serve to put the anode 5 in tension and to keep it strictly in a coaxial position.
  • the anode 5 has, inside the tubular element 1, a first part 5a formed of a brass-lead rod which is followed, in section 3, by a strand 5b of platinum titanium. Outside the tube, the strand 5b is continued by a brass-lead rod 5c. It can be seen that the strands 5a and 5b have different diameters, the diameter of the strand 5a being greater than that of the strand 5b.
  • a usual bath of chromic acid is circulated in the tubular element, around the anode 5, entering via the conduit 16 and leaving via the conduit 17, means for circulation and regeneration of the bath (not shown ) being arranged outside.
  • the length of the transition zone 4 is approximately 10 mm.

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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 Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Description

L'invention a trait à un procédé de chromage de la surface intérieure d'un élément tubulaire, tel que par exemple un tube d'arme, par dépôt électrolytique ainsi qu'à une anode permettant la mise en oeuvre de ce procédé.The invention relates to a process for chroming the interior surface of a tubular element, such as for example a weapon tube, by electrolytic deposition as well as to an anode allowing the implementation of this process.

Le problème du chromage intérieur d'un élément tubulaire métallique par voie électrolytique est relativement délicat. En effet, lorsque l'on désire obtenir un dépôt de chrome de forte épaisseur sur une grande longueur, il est difficile d'obtenir un aspect suffisamment lisse et homogène pour permettre un rodage après le chromage.The problem of interior chromium plating of a metallic tubular element by electrolytic means is relatively delicate. Indeed, when it is desired to obtain a thick chromium deposit over a long length, it is difficult to obtain a sufficiently smooth and homogeneous appearance to allow running in after chromium plating.

Si l'on cherche à obtenir des épaisseurs différentes dans des zones différentes de la longueur de l'élément tubulaire, par exemple un dépôt de forte épaisseur suivi d'un dépôt de faible épaisseur, le problème se complique encore.If one seeks to obtain different thicknesses in different zones of the length of the tubular element, for example a deposit of great thickness followed by a deposit of thinness, the problem becomes even more complicated.

Une solution consiste à réaliser les deux épaisseurs séparément en faisant deux chromages successifs. Une autre solution consiste à effectuer le chromage des deux parties dans le même bain en mettant en place un cache venant masquer la partie du dépôt de faible épaisseur au bout du temps nécessaire à son chromage. La première solution est évidemment longue car elle nécessite deux opérations de chromage successives. La seconde solution est délicate à mettre en oeuvre et demande de toute façon une intervention pendant le traitement électrolytique.One solution is to make the two thicknesses separately by doing two successive chrome plating. Another solution consists in carrying out the chromium plating of the two parts in the same bath by setting up a cover coming to mask the part of the deposit of small thickness at the end of the time necessary for its chromium plating. The first solution is obviously long since it requires two successive chromium plating operations. The second solution is difficult to implement and in any case requires intervention during the electrolytic treatment.

Dans les deux cas, il n'est pas possible d'obtenir une zone de transition régulière satisfaisante entre les deux dépôts d'épaisseurs différentes. En particulier, il existe un risque d'écaillage dû au recouvrement des deux plages de chromes et/ou un passage brutal de la partie de faible épaisseur à la partie de grande épaisseur.In both cases, it is not possible to obtain a satisfactory regular transition zone between the two deposits of different thicknesses. In particular, there is a risk of chipping due to the overlapping of the two chromatic ranges and / or a sudden passage from the thin part to the very thick part.

US-A-3 706 651 décrit un dispositif pour minimiser les irrégularités d'un dépôt électrolytique sur une surface courbe, comprenant une anode rotative dont la partie active comporte des anneaux conducteurs séparés par des anneaux isolants, chaque anneau conducteur étant alimenté séparément en électricité.US-A-3,706,651 describes a device for minimizing the irregularities of an electrolytic deposit on a curved surface, comprising a rotary anode the active part of which comprises conductive rings separated by insulating rings, each conductive ring being supplied separately with electricity .

La présente invention se propose donc de remédier aux inconvénients indiqués ci-dessus et de fournir un procédé de chromage de la surface intérieure d'un élément tubulaire qui permette, en une seule opération, d'assurer le chromage de plusieurs zones destinées à avoir des dépôts d'épaisseurs différentes et qui permette simultanément d'obtenir une transition progressive et régulière entre les dépôts d'épaisseurs différentes.The present invention therefore proposes to remedy the drawbacks indicated above and to provide a method of chromium plating of the interior surface of a tubular element which makes it possible, in a single operation, to chromium plating several zones intended to have deposits of different thicknesses and which simultaneously allows a gradual and regular transition between deposits of different thicknesses.

Un autre objectif encore de l'invention est de fournir un tel procédé qui soit facile à mettre en oeuvre et d'un prix de revient économique tout en ne demandant pas plus de temps qu'il est nécessaire pour assurer la mise en place du dépôt le plus épais.Yet another objective of the invention is to provide such a method which is easy to implement and of an economic cost price while not requiring more time than is necessary to ensure the establishment of the deposit. the thickest.

Un autre objectif encore de l'invention est de fournir des anodes permettant de mettre en oeuvre un tel procédé.Yet another objective of the invention is to provide anodes which make it possible to implement such a method.

L'invention a pour objet un procédé de réalisation de dépôts de chrome d'épaisseurs différentes sur des tronçons successifs de la paroi intérieure d'un élément tubulaire par voie électrolytique dans lequel on met en place, à l'intérieur de l'élément tubulaire, une anode centrée sur l'axe de l'élément tubulaire et on introduit un liquide électrolytique permettant, lors du passage du courant électrique, de déposer un dépôt de chrome sur la paroi tubulaire formant cathode de l'élément tubulaire, caractérisé en ce qu'on constitue l'anode en plusieurs parties de conductibilités électriques différentes, à savoir une partie par tronçon d'élément tubulaire à revêtir, la valeur de la conductibilité et le diamètre de la partie correspondante d'anode étant choisis en fonction de l'épaisseur du dépôt à réaliser sur le tronçon correspondant de la paroi de l'élément tubulaire.The subject of the invention is a method for producing chromium deposits of different thicknesses on successive sections of the inner wall of a tubular element by electrolytic means in which one places, inside the tubular element , an anode centered on the axis of the tubular element and an electrolytic liquid is introduced allowing, during the passage of the electric current, to deposit a deposit of chromium on the tubular wall forming cathode of the tubular element, characterized in that the anode is made up of several parts of different electrical conductivities, namely one part per section of tubular element to be coated, the value of the conductivity and the diameter of the corresponding part of anode being chosen as a function of the thickness of the deposit to be made on the corresponding section of the wall of the tubular element.

On constate que, grâce à l'invention, il est possible ainsi non seulement d'obtenir, dans une même phase de dépôt électrolytique, des épaisseurs de dépôt différentes suivant les tronçons de paroi intérieure prévus, mais encore de réaliser entre deux dépôts consécutifs une zone de transition progressive et régulière.It can be seen that, thanks to the invention, it is thus possible not only to obtain, in the same phase of electrolytic deposition, different thicknesses of deposition according to the sections of inner wall provided, but also to achieve between two consecutive deposition a progressive and regular transition zone.

Dans le cas cependant où l'on souhaiterait obtenir des zones de transition progressives et régulières ayant elles-mêmes une grande longueur, on peut avantageusement prévoir, au niveau correspondant de l'anode, plusieurs parties successives relativement courtes de conductibilités électriques différentes, par exemple décroissantes, si l'on veut une diminution régulière de l'épaisseur.However, in the case where it is desired to obtain progressive and regular transition zones which themselves are very long, it is advantageous to provide, at the corresponding level of the anode, several successive relatively short parts of different electrical conductivities, for example decreasing, if we want a regular decrease in thickness.

De façon avantageuse, l'anode prévue peut être constituée de plusieurs brins consécutifs de conductibilités différentes ou bien, le cas échéant, d'une partie centrale revêtue de manchons tubulaires de conductibilités différentes.Advantageously, the anode provided may consist of several consecutive strands of different conductivities or, if appropriate, of a central part coated with tubular sleeves of different conductivities.

Dans une forme de réalisation préférée, on procède, pendant l'électrolyse, à une circulation du liquide d'électrolyse à l'intérieur du tube afin d'assurer constamment son renouvellement et son homogénéisation. On peut ainsi obtenir, sur de très grandes longueurs, des dépôts extrêmement réguliers et lisses.In a preferred embodiment, during electrolysis, the electrolysis liquid is circulated inside the tube in order to constantly ensure its renewal and its homogenization. One can thus obtain, over very long lengths, extremely regular and smooth deposits.

L'invention a également pour objet, à titre de produits industriels nouveaux, les anodes utilisées dans ce procédé et se caractérisant par le fait qu'elles comportent au moins deux parties efficaces successives de conductibilités différentes.The subject of the invention is also, as new industrial products, the anodes used in this process and characterized in that they comprise at least two successive effective parts of different conductivities.

D'autres avantages et caractéristiques de l'invention apparaîtront à la lecture de la description suivante faite à titre d'exemple non limitatif et se référant au dessin annexé dans lequel la figure unique représente une vue en coupe transversale d'un élément tubulaire avec son anode.Other advantages and characteristics of the invention will appear on reading the following description given by way of nonlimiting example and referring to the appended drawing in which the single figure represents a cross-sectional view of a tubular element with its anode.

En se référant à la figure, on voit qu'on a représenté un élément tubulaire 1, comprenant deux tronçons, à savoir un tronçon assez allongé 2, suivi d'un tronçon plus court 3. On voit que le tronçon 2 présente un diamètre constant sur la plus grande partie de sa longueur, puis un premier élargissement conique de faible pente 2a, suivi d'une partie cylindrique 2b. Le tronçon 3 possède une partie cylindrique 3a de grand diamètre alors qu'une zone de raccordement conique 4 réunit les parties cylindriques 2b et 3a, la zone 4 appartenant pour moitié au tronçon 2 et pour moitié au tronçon 3.Referring to the figure, we see that there is shown a tubular element 1, comprising two sections, namely a fairly elongated section 2, followed by a shorter section 3. It can be seen that the section 2 has a constant diameter over most of its length, then a first conical widening of slight slope 2a, followed of a cylindrical part 2b. The section 3 has a cylindrical part 3a of large diameter while a conical connection zone 4 joins the cylindrical parts 2b and 3a, the zone 4 belonging half to the section 2 and half to the section 3.

On voit qu'à l'intérieur du tube 1 est montée une anode allongée coaxiale 5 traversant une pièce de centrage 6 qui est réunie à un manchon 7, dit « voleur de courant •, fixé autour et en bout du tronçon 2. Une entretoise 8 entourant l'extrémité émergente de l'anode 5 prend appui sur la pièce 6 et se termine par une pièce 9 formant à la fois crochet de suspension et de contact pour l'anode.We see that inside the tube 1 is mounted an elongated coaxial anode 5 passing through a centering piece 6 which is joined to a sleeve 7, said "current thief •, fixed around and at the end of the section 2. A spacer 8 surrounding the emerging end of the anode 5 is supported on the part 6 and ends with a part 9 forming both a suspension and contact hook for the anode.

A l'autre extrémité du tube, il est prévu une pièce 10 faisant également office de « voleur de courant », cette pièce supportant une pièce de centrage 11. Sur l'extrémité filetée de l'anode 5, est vissé un écrou 12 avec une rondelle 13 sur laquelle vient prendre appui une entretoise tubulaire 14 avec interposition d'un certain nombre de rondelles Belleville 15 qui, prenant d'autre part appui sur la pièce 11, servent à mettre l'anode 5 en traction et à la maintenir strictement dans une position coaxiale.At the other end of the tube, there is provided a part 10 also acting as a "current thief", this part supporting a centering part 11. On the threaded end of the anode 5, is screwed a nut 12 with a washer 13 on which comes to bear a tubular spacer 14 with the interposition of a number of Belleville washers 15 which, taking support on the other hand on the part 11, serve to put the anode 5 in tension and to keep it strictly in a coaxial position.

L'anode 5 présente, à l'intérieur de l'élément tubulaire 1, une première partie 5a formée d'une tige de laiton-plomb qui est suivie, dans le tronçon 3, d'un brin 5b en titane platiné. A l'extérieur du tube, le brin 5b se poursuit par une tige de laiton-plomb 5c. On voit que les brins 5a et 5b ont des diamètres différents, le diamètre du brin 5a étant supérieur à celui du brin 5b. Un bain usuel d'acide chromique est mis en circulation dans l'élément tubulaire, autour de l'anode 5, en entrant par le conduit 16 et en sortant par le conduit 17, des moyens de circulation et de régénération de bain (non représenté) étant disposés à l'extérieur.The anode 5 has, inside the tubular element 1, a first part 5a formed of a brass-lead rod which is followed, in section 3, by a strand 5b of platinum titanium. Outside the tube, the strand 5b is continued by a brass-lead rod 5c. It can be seen that the strands 5a and 5b have different diameters, the diameter of the strand 5a being greater than that of the strand 5b. A usual bath of chromic acid is circulated in the tubular element, around the anode 5, entering via the conduit 16 and leaving via the conduit 17, means for circulation and regeneration of the bath (not shown ) being arranged outside.

On constate que, lorsque l'on procède au dépôt électrolytique de chrome, on obtient, dans le tronçon 2, une couche de chrome lisse épaisse et, dans le tronçon 3, une couche mince de chrome également lisse. La transition s'effectue au niveau de la zone 4 sur une longueur de quelques millimètres. A la coupe, on constate que la zone de transition est tout à fait progressive et régulière.It is noted that, when the electrolytic deposition of chromium is carried out, in section 2, a thick smooth layer of chromium is obtained and, in section 3, a thin layer of chromium also smooth. The transition takes place at zone 4 over a length of a few millimeters. When cutting, we see that the transition zone is completely progressive and regular.

A titre d'exemple, on a effectué un dépôt de chrome sur une pièce tubulaire dans les conditions suivantes :

  • Longueur du tronçon 2 : 1 726 mm
  • Longueur du tronçon 3 : 115 mm
  • Diamètre interne du tronçon 2 : 0 23 mm
  • Diamètre interne du tronçon 3 : 0 33 mm
  • Diamètre de la partie 5a : 0 13 à 13,5 mm
  • Diamètre de la partie 5b : 0 8 mm
  • Bain : acide chromique à la concentration de 250 g/I
  • Intensité électrique : 360 ampères
  • Durée du dépôt : 9 h 30 à 10 h.
For example, chromium was deposited on a tubular part under the following conditions:
  • Section 2 length: 1,726 mm
  • Section 3 length: 115 mm
  • Internal diameter of section 2: 0 23 mm
  • Internal diameter of section 3: 0 33 mm
  • Diameter of part 5a: 0 13 to 13.5 mm
  • Diameter of part 5b: 0 8 mm
  • Bath: chromic acid at a concentration of 250 g / I
  • Electric current: 360 amps
  • Duration of the deposit: 9:30 to 10 a.m.

On a obtenu dans le tronçon 2 un dépôt de chrome ayant une épaisseur de l'ordre de 0,22 mm et dans le tronçon 3 un dépôt d'une épaisseur de 0,008 à 0,01 mm.Was obtained in section 2 a deposit of chromium having a thickness of about 0.22 mm and in section 3 a deposit with a thickness of 0.008 to 0.01 mm.

La longueur de la zone de transition 4 est approximativement de 10 mm.The length of the transition zone 4 is approximately 10 mm.

A titre d'exemple de matériaux différents pouvant constituer des parties d'anode et ayant des conductibilités différentes, on pourra prendre :

  • Laiton recouvert de plomb,
  • Cuivre recouvert de plomb,
  • Acier recouvert de plomb,
  • Fer Armco,
  • Titane platiné.
By way of example of different materials which can constitute parts of anode and having different conductivities, we can take:
  • Lead coated brass,
  • Lead coated copper,
  • Lead coated steel,
  • Iron Armco,
  • Platinum titanium.

Claims (7)

1. Electrolytic process for depositing different thicknesses of chromium on the inside wall of successive length of a tube element, inside which is placed one anode (5) centered on the tube elements axis (1) and an electrolytic liquid which, when an electric current is passed through it, deposits chromium on the wall of the tube, which is the cathode of the tube element, characterized by the fact that anode (5) is made up of several parts (5a, 5b) having different electric conductivities, with one part (5a, 5b) per length (2, 3) of tube element to be coated, with the conductivity and diameter of corresponding anode part (5a, 5b) being chosen as a function of the thickness of the deposition to be made on the corresponding length of tube element wall (1).
2. Process as per claim 1, characterized by the fact that a gradual transition zone of chromium deposit is made using an anode that includes several successive parts of different electrical conductivities, at the level of the transition zone.
3. Process as per claim 1, characterized by the fact that an electrolytic bath is circulated between the anode and the inner wall of the tube element.
4. Anode used in the process as per any one claim 1 to 3, characterized by the fact that it has at least two successive effective parts (5a, 5b) with different electrical conductivities.
5. Anode as per claim 4, characterized by the fact that the different parts (5a, 5b) have different diameters.
6. Anode as per either claim 4 or 5, characterized by the fact that it consists of several consecutive strands having different electrical conductivities.
7. Anode as per either claim 4 or 5, characterized by the fact that it consists of a center part covered with a tubular sleeves having different electrical conductivities.
EP19820402398 1982-01-21 1982-12-30 Process for chromium plating the inner surface of tubes, anode used in this process Expired EP0084752B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8200868 1982-01-21
FR8200868A FR2520009A1 (en) 1982-01-21 1982-01-21 PROCESS OF INTERNAL CHROMING OF A TUBULAR ELEMENT, ANODE FOR ITS IMPLEMENTATION AND CHROME ELEMENT OBTAINED ACCORDING TO THIS PROCESS

Publications (2)

Publication Number Publication Date
EP0084752A1 EP0084752A1 (en) 1983-08-03
EP0084752B1 true EP0084752B1 (en) 1986-03-05

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DE (1) DE3269763D1 (en)
FR (1) FR2520009A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4931150A (en) * 1988-03-28 1990-06-05 Sifco Industries, Inc. Selective electroplating apparatus and method of using same
US4853099A (en) * 1988-03-28 1989-08-01 Sifco Industries, Inc. Selective electroplating apparatus
DE4335139A1 (en) * 1993-10-15 1995-04-20 Rheinmetall Ind Gmbh Process for manufacturing a weapon barrel with a wear-resistant inner coating
DE4419864C2 (en) * 1994-06-07 2001-01-11 Rheinmetall W & M Gmbh Electrode for internal electrolytic coating and / or for electropolishing gun barrels
JP2001073198A (en) 1999-07-01 2001-03-21 Sumitomo Special Metals Co Ltd Device for electroplating and electroplating method using this device
SE529744C2 (en) * 2005-12-22 2007-11-13 Abb Technology Ag Device and method of metallic coating and use of the device
CN115976617A (en) * 2022-11-23 2023-04-18 西安空间无线电技术研究所 Silver plating process method for auxiliary anode and aluminum alloy multi-bend waveguide part

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR712505A (en) * 1930-06-14 1931-10-03 Orfevrerie Christofle Method and location of electrolytic deposits of metals
GB712314A (en) * 1951-02-08 1954-07-21 Electro Metal Hardening Co S A Method of and apparatus for a uniform electrolytic internal chromium plating of tubes
US3706651A (en) * 1970-12-30 1972-12-19 Us Navy Apparatus for electroplating a curved surface

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FR2520009A1 (en) 1983-07-22
DE3269763D1 (en) 1986-04-10
FR2520009B1 (en) 1984-03-23
EP0084752A1 (en) 1983-08-03

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