EP0622478B1 - Process for electroplating a zinc alloy coating on a steel substrate and steel substrate thus obtained - Google Patents
Process for electroplating a zinc alloy coating on a steel substrate and steel substrate thus obtained Download PDFInfo
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- EP0622478B1 EP0622478B1 EP94400625A EP94400625A EP0622478B1 EP 0622478 B1 EP0622478 B1 EP 0622478B1 EP 94400625 A EP94400625 A EP 94400625A EP 94400625 A EP94400625 A EP 94400625A EP 0622478 B1 EP0622478 B1 EP 0622478B1
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- alloy
- potential
- release
- hydrogen
- layer
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- 239000000758 substrate Substances 0.000 title claims abstract description 70
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 59
- 239000010959 steel Substances 0.000 title claims abstract description 59
- 239000011248 coating agent Substances 0.000 title claims abstract description 33
- 238000000576 coating method Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910001297 Zn alloy Inorganic materials 0.000 title claims description 51
- 238000009713 electroplating Methods 0.000 title abstract description 5
- 239000010410 layer Substances 0.000 claims abstract description 117
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000011701 zinc Substances 0.000 claims abstract description 79
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 69
- 239000000956 alloy Substances 0.000 claims abstract description 69
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 65
- 239000001257 hydrogen Substances 0.000 claims abstract description 65
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 31
- 239000011247 coating layer Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 19
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 92
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 51
- 229910052759 nickel Inorganic materials 0.000 claims description 46
- 238000004070 electrodeposition Methods 0.000 claims description 14
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000009498 subcoating Methods 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 17
- 229940075397 calomel Drugs 0.000 abstract 1
- 230000008021 deposition Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000002390 adhesive tape Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000016571 aggressive behavior Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
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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)
- Physical Vapour Deposition (AREA)
- Coating With Molten Metal (AREA)
Abstract
Description
La présente invention a pour objet un procédé d'électrodéposition sur une surface d'un substrat en acier d'un revêtement d'un alliage métallique à base de zinc.The present invention relates to a method of electrodeposition on a surface of a steel substrate of a coating of a zinc-based metal alloy.
La présente invention a également pour objet un matériau d'acier revêtu comprenant un substrat en acier et une couche de revêtement d'un alliage métallique à base de zinc.The present invention also relates to a coated steel material comprising a steel substrate and a coating layer of a zinc-based metal alloy.
On sait qu'une couche d'un alliage à base de zinc comme par exemple du type zinc/nickel, zinc/aluminium, ou zinc/cobalt déposée sur un substrat en acier a une excellente activité de protection pour ledit substrat contre la corrosion.It is known that a layer of a zinc-based alloy such as for example of the zinc / nickel, zinc / aluminum, or zinc / cobalt type deposited on a steel substrate has an excellent protective activity for said substrate against corrosion.
Ainsi, les matériaux d'acier revêtus d'un alliage zinc/nickel sont largement utiles comme matériaux résistants à la corrosion dans le domaine des véhicules automobiles, des appareils électroménagers et des matériaux de construction, en particulier pour le bâtiment.Thus, steel materials coated with a zinc / nickel alloy are widely useful as corrosion resistant materials in the field of motor vehicles, household appliances and building materials, in particular for building.
A titre d'exemple dans le domaine automobile, les tôles d'acier revêtues d'une couche de zinc sur une face et d'une couche de revêtement d'un alliage de zincnickel sur l'autre face sont couramment utilisées.For example in the automotive field, steel sheets coated with a layer of zinc on one side and a coating layer of a zinc-nickel alloy on the other side are commonly used.
L'intérêt de ce type de tôles à revêtement différentiel est particulièrement visible dans la fabrication des pièces de carrosseries automobiles, comme par exemple les portières ou les ailes.The advantage of this type of plate with differential coating is particularly visible in the manufacture of auto body parts, such as doors or fenders.
En effet, ces éléments sont soumis à deux types de corrosion.Indeed, these elements are subjected to two types of corrosion.
La première corrosion dite cosmétique initiée principalement par une agression mécanique du type rayures ou gravillonnages peut mettre l'acier à nu en contact avec l'atmosphère extérieure.The first so-called cosmetic corrosion, initiated mainly by mechanical aggression of the scratching or gravel type, can bring the bare steel into contact with the external atmosphere.
La seconde corrosion dite perforante apparaît le plus souvent au niveau des corps creux et progresse de l'intérieur vers l'extérieur de la carrosserie.The second so-called perforating corrosion most often occurs in the hollow bodies and progresses from the inside to the outside of the body.
Alors que la corrosion cosmétique fait appel préférentiellement au pouvoir sacrificiel du revêtement vis à vis de l'acier, la résistance à la perforation est liée à l'effet barrière du revêtement.While cosmetic corrosion preferentially calls upon the sacrificial power of the coating with respect to steel, the resistance to perforation is linked to the barrier effect of the coating.
L'utilisation d'une tôle à revêtement différentiel du type zinc sur une face et zinc/nickel sur l'autre face, permet d'utiliser le pouvoir sacrificiel du revêtement de zinc sur la face extérieure de l'élément de carrosserie et l'effet barrière du revêtement d'alliage zinc/nickel sur la face intérieure de cet élément de carrosserie.The use of a zinc coated sheet of the zinc type on one side and zinc / nickel on the other side allows the sacrificial power of the zinc coating to be used on the outside of the bodywork element and the barrier effect of the zinc / nickel alloy coating on the inside of this bodywork element.
Généralement, pour réaliser le dépôt d'une couche de revêtement d'un alliage à base de zinc sur la surface d'un substrat en acier, on utilise un procédé d'électrodéposition consistant à faire passer ledit substrat dans un bain d'électrolyte contenant des ions zinc et des ions nickel en milieu chlorure ou en milieu sulfate.Generally, in order to deposit a coating layer of a zinc-based alloy on the surface of a steel substrate, an electrodeposition process is used which consists in passing said substrate through an electrolyte bath containing zinc ions and nickel ions in chloride medium or in sulphate medium.
A titre d'exemple, le bain peut avoir la composition suivante :
- ZnCl2 : 2 à 3 moles par litre
- NiCl2 : 0,2 à 1 mole par litre
- Le reste étant de l'eau déminéralisée ou non,
Température du bain 50 à 70°C, - pH : 4 à 5.
- ZnCl 2 : 2 to 3 moles per liter
- NiCl 2 : 0.2 to 1 mole per liter
- The rest being demineralized water or not,
Bath temperature 50 to 70 ° C, - pH: 4 to 5.
La densité de courant est ajustée pour obtenir le pourcentage de nickel désiré dans l'alliage zinc/nickel (habituellement de l'ordre de 12% de nickel).The current density is adjusted to obtain the desired percentage of nickel in the zinc / nickel alloy (usually of the order of 12% nickel).
Or, on constate que le revêtement d'alliage zinc/nickel ainsi électrodéposé a une propriété d'adhérence relativement déplorable.However, it can be seen that the zinc / nickel alloy coating thus electrodeposited has a relatively deplorable adhesion property.
En effet, lors d'un test d'adhérence simple consistant à utiliser une pastille en acier revêtue et recouverte d'un ruban adhésif normalisé, qui est pliée à 90° avant de retirer le ruban adhésif, on constate que la totalité du revêtement s'est détachée du substrat en acier.Indeed, during a simple adhesion test consisting in using a coated steel pellet covered with a standard adhesive tape, which is folded at 90 ° before removing the adhesive tape, it is found that the entire coating has come off the steel substrate.
Pour améliorer l'adhérence du revêtement d'alliage zinc/nickel sur la surface du substrat en acier sur laquelle ledit revêtement a été déposé, une solution consiste à déposer une première couche de revêtement de nickel par dépôt chimique au trempé sans courant électrique, puis à déposer par électrodéposition une couche d'alliage zinc/nickel sur la première couche de nickel préalablement déposée.To improve the adhesion of the zinc / nickel alloy coating on the surface of the steel substrate on which said coating has been deposited, one solution consists in depositing a first layer of nickel coating by chemical deposition by dipping without electric current, then depositing a layer of zinc / nickel alloy by electrodeposition on the first previously deposited nickel layer.
Dans ce cas, l'adhérence du revêtement est meilleure que dans le cas d'un dépôt par électrodéposition directe, mais il n'est pas totalement satisfaisant.In this case, the adhesion of the coating is better than in the case of a deposit by direct electrodeposition, but it is not completely satisfactory.
Le test dit du "ruban adhésif" permet de constater que le revêtement est partiellement arraché de la pastille d'essai revêtue.The so-called "adhesive tape" test shows that the coating is partially torn off from the coated test patch.
On connaît dans le documente JP-A-62 044 594, un procédé d'électrodéposition sur une surface d'un substrat en acier d'une couche d'un revêtement d'un alliage métallique à base de zinc-nickel. Dans ce procédé, on dépose, entre la surface du substrat et la couche de revêtement dudit alliage, une couche de sous revêtement dudit alliage avec un pourcentage de nickel compris entre 20 et 16%.Document JP-A-62 044 594 discloses a method of electrodeposition on a surface of a steel substrate of a layer of a coating of a metal alloy based on zinc-nickel. In this process, between the surface of the substrate and the coating layer of said alloy, a layer of undercoating of said alloy with a percentage of nickel of between 20 and 16% is deposited.
L'invention a donc pour but d'éviter les inconvénients précédemment mentionnés en proposant un procédé d'électrodéposition sur une surface d'un substrat en acier d'une couche d'un revêtement d'un alliage métallique à base de zinc, du type ZnX, dont X est le second élément de cet alliage, qui assure une bonne adhérence du revêtement sur ledit substrat en acier, sans réaliser de couche de revêtement par dépôt chimique au trempé.The object of the invention is therefore to avoid the drawbacks mentioned above by proposing a method of electrodeposition on a surface of a steel substrate of a layer of a coating of a zinc-based metal alloy, of the type ZnX, of which X is the second element of this alloy, which ensures good adhesion of the coating to said steel substrate, without make a coating layer by chemical dip coating.
L'invention a donc pour objet un procédé d'électrodéposition sur une surface d'un substrat en acier d'une couche en revêtement d'un alliage métallique à base de zinc, du type ZnX, X étant le second élément de cet alliage, caractérisé en ce que l'on dépose entre la surface du substrat et la couche de revêtement dudit alliage, une couche de sous revêtement dudit alliage avec un pourcentage dudit élément X tel que le potentiel de réduction dudit alliage de ladite couche de sous revêtement par rapport à une électrode au calomel saturé est supérieur ou égal ou sensiblement inférieur au potentiel de dégagement de l'hydrogène sur l'acier du substrat, pour obtenir le pourcentage du second élément X désiré.The subject of the invention is therefore a method of electrodeposition on a surface of a steel substrate of a coating layer of a zinc-based metal alloy, of the ZnX type, X being the second element of this alloy, characterized in that an undercoat layer of said alloy is deposited between the surface of the substrate and the coating layer of said alloy with a percentage of said element X such that the reduction potential of said alloy of said undercoating layer with respect to at a saturated calomel electrode is greater than or equal to or substantially less than the potential for evolution of hydrogen on the steel of the substrate, to obtain the percentage of the second element X desired.
Selon d'autres caractéristiques de l'invention :
- on dépose, entre la couche de sous revêtement et la couche de revêtement dudit alliage, au moins une couche intermédiaire de sous revêtement avec un pourcentage du second élément X tel que le potentiel de réduction dudit alliage de la couche intermédiaire n de sous revêtement est supérieur ou égal ou sensiblement inférieur au potentiel de dégagement d'hydrogène sur ledit alliage de la couche intermdiaire n - 1 de sous revêtement précédemment déposée,
- on dépose, entre la couche de sous revêtement et la couche de revêtement dudit alliage, une couche intermédiaire de sous revêtement avec un pourcentage du second élément X tel que le potentiel de réduction dudit alliage de la couche intermédiaire de sous revêtement est supérieur ou égal ou sensiblement inférieur au potentiel de dégagement d'hydrogène sur ledit alliage de la couche de sous revêtement précédemment déposée.
- at least one intermediate undercoating layer is deposited between the undercoating layer and the coating layer of said alloy with a percentage of the second element X such that the reduction potential of said alloy of the intermediate layer n of undercoating is greater or equal to or substantially less than the hydrogen release potential on said alloy of the intermediate layer n - 1 of previously deposited undercoating,
- an intermediate undercoating layer is deposited between the undercoating layer and the coating layer of said alloy with a percentage of the second element X such that the reduction potential of said alloy of the intermediate undercoating layer is greater than or equal to or significantly lower than the hydrogen release potential on said alloy of the previously deposited undercoating layer.
L'invention a également pour objet un matériau d'acier revêtu comprenant un substrat en acier et une couche de revêtement d'un alliage métallique à base de zinc du type ZnX, X étant le second élément de cet alliage, ladite couche de revêtement étant déposée par électrodéposition sur une surface dudit substrat, caractérisé en ce qu'il comporte entre la surface du substrat et la couche de revêtement, une couche de sous revêtement dudit alliage avec un pourcentage du second élément X tel que le potentiel de réduction dudit alliage de la couche de sous revêtement par rapport à une électrode au calomel saturé est compris entre le potentiel de dégagement de l'hydrogène sur l'acier du substrat et ledit potentiel de dégagement d'hydrogène moins 10%, et il comporte entre la couche de sous revêtement et la couche de revêtement, au moins une couche intermédiaire de sous revêtement avec un pourcentage du second élément X tel que le potentiel de réduction dudit alliage de la couche intermédiaire de sous revêtement est compris entre le potentiel de dégagement d'hydrogène sur la couche de sous revêtement précédemment déposée et ledit potentiel de dégagement d'hydrogène moins 15%.The invention also relates to a coated steel material comprising a steel substrate and a coating layer of a zinc-based metal alloy of the ZnX type, X being the second element of this alloy, said coating layer being deposited by electrodeposition on a surface of said substrate, characterized in that it comprises between the surface of the substrate and the coating layer, an undercoating layer of said alloy with a percentage of the second element X such that the reduction potential of said alloy the undercoating layer with respect to a saturated calomel electrode is between the hydrogen release potential on the steel of the substrate and said hydrogen release potential minus 10%, and it comprises between the underlay coating and the coating layer, at least one intermediate layer of undercoating with a percentage of the second element X such as the reduction potential of said alloy of the intermediate undercoating layer is between the hydrogen release potential on the previously deposited undercoat layer and said hydrogen release potential minus 15%.
L'invention a encore pour objet un matériau d'acier revêtu comprenant un substrat en acier et une couche de revêtement d'un alliage zinc/nickel à 12% de nickel, ladite couche de revêtement étant déposée par électrodéposition sur une surface dudit substrat, caractérisé en ce qu'il comporte entre la surface du substrat et la couche de revêtement, une couche de sous revêtement d'alliage zinc/nickel à 24% de nickel et, sur ladite couche de sous revêtement, une couche intermédiaire de sous revêtement d'alliage zinc/nickel à 18% de nickel.The subject of the invention is also a coated steel material comprising a steel substrate and a coating layer of a zinc / nickel alloy with 12% nickel, said coating layer being deposited by electrodeposition on a surface of said substrate, characterized in that it comprises between the surface of the substrate and the coating layer, an undercoating layer of zinc / nickel alloy with 24% nickel and, on said undercoating layer, an intermediate layer undercoating of zinc / nickel alloy with 18% nickel.
Les caractéristiques et avantages de l'invention apparaîtront au cours de la description qui va suivre, donnée uniquement à titre d'exemple.The characteristics and advantages of the invention will become apparent during the description which follows, given solely by way of example.
Dans ce qui suit, l'invention sera décrite pour un alliage métallique à base de zinc du type ZnX, le second élément X de cet alliage étant du nickel, mais pouvant être également par exemple du fer, du cobalt ou du chrome.In what follows, the invention will be described for a zinc-based metal alloy of the ZnX type, the second element X of this alloy being nickel, but which can also be, for example, iron, cobalt or chromium.
Pour déposer un alliage métallique par électrodéposition sur une surface d'un substrat en acier, par exemple un alliage zinc/nickel à 12% de nickel, on polarise le substrat métallique pour l'amener au potentiel de réduction de l'alliage à déposer, c'est à dire que l'on polarise ledit substrat au potentiel de -0,95 V/Ecs dans le cas de l'alliage zinc/nickel à 12% de nickel.To deposit a metal alloy by electrodeposition on a surface of a steel substrate, for example a zinc / nickel alloy with 12% nickel, the metal substrate is polarized to bring it to the reduction potential of the alloy to be deposited, that is to say that said substrate is polarized at the potential of -0.95 V / Ecs in the case of the zinc / nickel alloy with 12% nickel.
Selon les résultats des recherches effectuées par la Demanderesse, on suppose que l'adhérence du revêtement ainsi électrodéposé dépend directement du dégagement d'hydrogène.According to the results of the research carried out by the Applicant, it is assumed that the adhesion of the coating thus electrodeposited depends directly on the evolution of hydrogen.
En effet, l'électrodéposition se faisant en milieu acide aqueux par exemple dans un bain contenant ZnCl2, KCl, NiCl2 et H20 le pH de la solution est très acide et on compte un nombre important d'ions H+ en solution.Indeed, since the electrodeposition takes place in an aqueous acid medium, for example in a bath containing ZnCl 2 , KCl, NiCl 2 and H 2 0, the pH of the solution is very acidic and there is a large number of H + ions in solution. .
Au cours de la réaction de dépôt électrolytique, l'hydrogène dégaze sous forme de bulles et souvent ces bulles d'hydrogène se forment en dessous de la couche de revêtement empêchant celui-ci d'adhérer sur la surface du substrat métallique.During the electroplating reaction, the hydrogen degassed in the form of bubbles and often these bubbles of hydrogen are formed below the coating layer preventing it from adhering to the surface of the metal substrate.
On a constaté que plus l'hydrogène se dégage au cours de la réaction d'électrodéposition, plus l'adhérence du revêtement sur la surface du substrat métallique est moins bonne.It has been found that the more hydrogen is released during the electroplating reaction, the more the adhesion of the coating to the surface of the metal substrate. is less good.
Une série d'essais a été réalisé pour tenter de comprendre ce phénomène de dégazage de l'hydrogène au cours de la réaction d'électrodéposition pour trouver une solution afin de minimiser ce dégazage et d'éviter au maximum la formation d'hydrogène dans la solution.A series of tests has been carried out in an attempt to understand this phenomenon of degassing of hydrogen during the electroplating reaction in order to find a solution in order to minimize this degassing and to avoid as much as possible the formation of hydrogen in the solution.
Des éprouvettes ont été revêtues d'une couche de revêtement d'un alliage zinc/nickel à 12% de nickel et d'une épaisseur de 6µm.Test pieces were coated with a coating layer of a zinc / nickel alloy with 12% nickel and a thickness of 6 μm.
Certaines éprouvettes ont fait l'objet du dépôt électrodéposé, entre la surface du substrat et la couche de revêtement d'alliage zinc/nickel, d'une couche de sous revêtement d'alliage zinc/nickel d'une épaisseur de 0,04µm avec un pourcentage de nickel différent selon les éprouvettes.Some test pieces were electrodeposited, between the surface of the substrate and the coating layer of zinc / nickel alloy, of a layer of under coating of zinc / nickel alloy with a thickness of 0.04 μm with a different percentage of nickel depending on the test pieces.
D'autres éprouvettes ont fait l'objet du dépôt électrodéposé, entre la couche de sous revêtement d'alliage zinc/nickel et la couche de revêtement d'alliage zinc/nickel, d'une couche intermédiaire de sous revêtement d'un alliage zinc/nickel d'une épaisseur de 0,04µm, avec un pourcentage de nickel différent.Other test pieces have been electrodeposited, between the layer of undercoating of zinc / nickel alloy and the layer of coating of zinc / nickel alloy, of an intermediate layer of undercoating of a zinc alloy / nickel with a thickness of 0.04µm, with a different percentage of nickel.
Ces éprouvettes ont alors subi le test d'adhérence dit "test du ruban adhésif".These test pieces then underwent the adhesion test called "adhesive tape test".
Selon le degré d'arrachement du revêtement, l'adhérence a été classée dans une fourchette de 1 à 5, le coefficient 1 étant réservé à l'arrachement total du revêtement, le coefficient 5 a aucun arrachement et les coefficients 2 à 4 selon le degré d'arrachement.According to the degree of tearing of the coating, the adhesion was classified in a range of 1 to 5, the coefficient 1 being reserved for the total tearing of the coating, the coefficient 5 has no tearing and the coefficients 2 to 4 according to the degree of tearing.
Le tableau ci-dessous donne les résultats de ces différents essais.
En examinant les résultats de ces essais, on constate que plus le pourcentage de nickel de la couche de sous-revêtement augmente, meilleure est l'adhérence du revêtement.By examining the results of these tests, it can be seen that the more the percentage of nickel in the undercoat layer increases, the better the adhesion of the coating.
L'explication de ce phénomène est liée au potentiel de dégagement de l'hydrogène.The explanation for this phenomenon is linked to the potential for hydrogen release.
Dans l'essai n° 1, on a directement électrodéposé une couche de revêtement d'alliage zinc/nickel à 12% de nickel sur la surface du substrat en acier.In test 1, a coating layer of zinc / nickel alloy with 12% nickel was directly electrodeposited on the surface of the steel substrate.
Pour cela, on a polarisé le substrat pour l'amener à - 0,95V/Ecs, potentiel de réduction de l'alliage zinc/nickel à 12% de nickel par rapport à une électrode au calomel saturé.For this, the substrate was polarized to bring it to - 0.95V / DHW, potential for reduction of the zinc / nickel alloy to 12% nickel compared to a saturated calomel electrode.
Or, pour arriver à -0,95V/Ecs, le substrat en acier a d'abord été amené à -0,78V/Ecs, potentiel de dégagement de l'hydrogène sur l'acier.However, to reach -0.95V / DHW, the steel substrate was first brought to -0.78V / DHW, potential for release of hydrogen on steel.
Ainsi, dès que le substrat a été porté à -0,78V/Ecs, la réaction de dégagement de l'hydrogène a débuté et s'est poursuivie jusqu'à ce que le potentiel du substrat atteigne -0,95V/Ecs.Thus, as soon as the substrate was brought to -0.78V / Ecs, the hydrogen evolution reaction started and continued until the potential of the substrate reached -0.95V / Ecs.
A ce moment, le dépôt de l'alliage zinc/nickel sur la surface du substrat en acier débute et en ce qui concerne le dégagement de l'hydrogène ce n'est plus le potentiel de son dégagement sur l'acier qu'il faut prendre en compte, mais son potentiel de dégagement sur l'alliage que l'on a déposé.At this time, the deposition of the zinc / nickel alloy on the surface of the steel substrate begins and as far as the release of hydrogen is concerned, it is no longer the potential for its release on the steel that is required. take into account, but its release potential on the alloy that has been deposited.
En effet, dès que le dépôt commence et que l'on a déposé une mince couche d'alliage sur la surface du substrat en acier, la suite du dépôt de cet alliage s'effectue sur la couche dudit alliage précédemment déposée.In fact, as soon as the deposition begins and a thin layer of alloy has been deposited on the surface of the steel substrate, the rest of the deposition of this alloy takes place on the layer of said alloy previously deposited.
Dans l'essai n° 2, on a d'abord déposé une couche de sous revêtement d'alliage zinc/nickel à 15% de nickel avant de déposer la couche de revêtement à 12% de nickel.In test 2, a layer of undercoating of zinc / nickel alloy with 15% nickel was first deposited before depositing the coating layer with 12% nickel.
Le potentiel de réduction de la couche d'alliage zinc/nickel à 15% de nickel étant égal à -0,90V/Ecs, la réaction de dégagement d'hydrogène a été plus courte que dans le premier essai avant le début du dépôt de l'alliage, ce qui explique que l'adhérence soit légèrement meilleure.The reduction potential of the zinc / nickel alloy layer to 15% nickel being equal to -0.90V / DHW, the hydrogen evolution reaction was shorter than in the first test before the deposition of the alloy, which explains why the grip is slightly better.
L'essai n°4 par exemple, donne un bon résultat en adhérence du fait du potentiel de réduction de l'alliage zinc/nickel à 21% de nickel qui est égal à -0,85V/Ecs, c'est à dire assez proche de -0,78V/Ecs.Test No. 4 for example, gives a good adhesion result due to the potential for reduction of the zinc / nickel alloy to 21% nickel which is equal to -0.85V / DHW, that is to say quite close to -0.78V / DHW.
Ces essais montrent déjà que dans le cas où l'on réalise une couche de sous revêtement avec un alliage zinc/nickel dont le pourcentage de nickel est tel que le potentiel dudit alliage est proche du potentiel de dégagement de l'hydrogène sur le substrat en acier, on augmente de manière significative l'adhérence du revêtement.These tests already show that in the case where an undercoating layer is produced with a zinc / nickel alloy whose percentage of nickel is such that the potential of said alloy is close to the potential for evolution of hydrogen on the substrate. steel, the adhesion of the coating.
Les essais 5 à 9 montrent qu'il est possible d'améliorer encore la qualité de l'adhérence du revêtement en déposant une couche intermédiaire de sous revêtement entre la couche de sous revêtement et la couche de revêtement.Tests 5 to 9 show that it is possible to further improve the quality of the adhesion of the coating by depositing an intermediate layer of undercoating between the undercoating layer and the coating layer.
La couche intermédiaire de sous revêtement d'alliage zinc/nickel a un pourcentage de nickel tel que le potentiel de réduction dudit alliage soit proche du potentiel de dégagement de l'hydrogène sur l'alliage zinc/nickel précédemment déposé dans la couche de sous revêtement.The intermediate layer of zinc / nickel alloy undercoat has a percentage of nickel such that the reduction potential of said alloy is close to the potential for release of hydrogen on the zinc / nickel alloy previously deposited in the undercoat layer .
Le meilleur résultat est d'ailleurs obtenu lors de l'essai n° 9, dans lequel on a d'abord déposé une couche de sous revêtement de 0,04µm d'alliage zinc/nickel à 24% de nickel et une couche intermédiaire de sous revêtement de 0,04µm d'alliage zinc/nickel à 18% de nickel avant de déposer la couche de revêtement final d'alliage zinc/nickel à 12% de nickel.The best result is moreover obtained during test No. 9, in which a layer of undercoating of 0.04 μm of zinc / nickel alloy with 24% nickel was first deposited and an intermediate layer of under coating of 0.04µm of zinc / nickel alloy with 18% nickel before depositing the final coating layer of zinc / nickel alloy with 12% nickel.
De tels dépôts successifs, sont réalisés de manière connue par exemple sur une ligne d'électrodéposition de type CAROSEL, dans laquelle on règle le courant de diffusion dans le bain, d'un premier rouleau conducteur pour assurer un dépôt d'alliage zinc/nickel à 24% de nickel et dans le bain, d'un second rouleau conducteur pour assurer un dépôt d'alliage zinc/nickel à 18% de nickel.Such successive depositions are carried out in a known manner, for example on a plating line of the CAROSEL type, in which the diffusion current in the bath is adjusted, of a first conducting roller to ensure a deposit of zinc / nickel alloy at 24% nickel and in the bath, a second conductive roller to ensure a deposit of zinc / nickel alloy with 18% nickel.
La vitesse de défilement de la bande d'acier formant le substrat est calculée pour obtenir l'épaisseur désirée de revêtement, c'est à dire 0,04 µm.The running speed of the steel strip forming the substrate is calculated to obtain the desired coating thickness, ie 0.04 μm.
Afin de pouvoir régler différemment la densité de courant au niveau de chaque rouleau il suffit par exemple de les équiper au moins les deux premiers, de ponts d'anodes afin de pouvoir brider ces ponts pour obtenir de très faibles densités de courant et donc des dépôts d'alliage zinc/nickel à pourcentage de nickel élevé.In order to be able to adjust the current density differently at each roller, it is sufficient for example to equip them at least the first two, with anode bridges in order to be able to clamp these bridges to obtain very low current densities and therefore zinc / nickel alloy deposits with a high nickel percentage.
Lors du passage du substrat d'acier sur le premier rouleau de la ligne d'électrodéposition, celui-ci est polarisé jusqu'au potentiel de réduction de l'alliage zinc/nickel à 24% de nickel, soit -0,80V/Ecs.During the passage of the steel substrate on the first roller of the plating line, this is polarized until the potential for reduction of the zinc / nickel alloy to 24% nickel, i.e. -0.80V / DHW .
Le dégagement d'hydrogène commence dès que le substrat en acier atteint -0,78V/Ecs et le dépôt de l'alliage zinc/nickel commence lorsque le substrat atteint - 0,80V/Ecs, soit pratiquement immédiatement après le dégagement d'hydrogène qui est très limité.The release of hydrogen begins as soon as the steel substrate reaches -0.78V / DHW and the deposition of the zinc / nickel alloy begins when the substrate reaches - 0.80V / DHW, that is to say almost immediately after the release of hydrogen which is very limited.
Ensuite, lorsque le substrat en acier revêtu de la couche de sous revêtement d'alliage zinc/nickel à 24% de nickel passe au niveau du second rouleau conducteur, sa polarité est amenée au potentiel de réduction de l'alliage zinc/nickel à 18% du nickel, soit -0,90V/ Ecs.Then, when the steel substrate coated with the 24% nickel / zinc alloy undercoat layer passes through the second conductive roller, its polarity is brought to the reduction potential of the zinc / nickel alloy to 18 % of nickel, i.e. -0.90V / DHW.
Le dégagement d'hydrogène redevient actif lorsque le substrat en acier atteint le potentiel de dégagement d'hydrogène sur l'alliage zinc/nickel à 24% de nickel et le dépôt de l'alliage zinc/nickel à 18% de nickel débute lorsque le potentiel dudit substrat atteint -0,90V/Ecs.The evolution of hydrogen becomes active again when the steel substrate reaches the potential of evolution of hydrogen on the zinc / nickel alloy with 24% nickel and the deposition of the zinc / nickel alloy with 18% nickel begins when the potential of said substrate reached -0.90V / DHW.
Au niveau des rouleaux conducteurs suivants, le substrat en acier est polarisé à -0,95V/Ecs, potentiel de réduction de l'alliage zinc/nickel à 12% de nickel permettant son dépôt sur le substrat en acier.At the level of the following conductive rollers, the steel substrate is polarized at -0.95V / DHW, potential for reduction of the zinc / nickel alloy to 12% nickel allowing its deposition on the steel substrate.
Ainsi, afin de limiter le dégagement d'hydrogène et d'assurer une bonne adhérence du revêtement, le procédé selon l'invention consiste à déposer, entre la surface du substrat en acier et la couche de revêtement d'alliage zinc/nickel, une couche de sous revêtement d'alliage zinc/nickel avec un pourcentage de nickel tel que le potentiel de réduction dudit alliage de ladite couche de sous revêtement par rapport à une électrode au calomel saturée est supérieur ou égal ou sensiblement inférieur au potentiel de dégagement de l'hydrogène sur l'acier du substrat, puis à déposer, entre la couche de sous revêtement et la couche de revêtement d'alliage zinc/nickel, au moins une couche intermédiaire de sous revêtement avec un pourcentage de nickel tel que le potentiel de réduction de l'alliage zinc/nickel de la couche intermédiaire n de sous revêtement est supérieur ou égal ou sensiblement inférieur au potentiel de dégagement d'hydrogène sur ledit alliage de la couche intermédiaire n-1 de sous revêtement précédemment déposée, jusqu'à déposer une couche d'alliage zinc/nickel.Thus, in order to limit the evolution of hydrogen and to ensure good adhesion of the coating, the method according to the invention consists in depositing, between the surface of the steel substrate and the coating layer of zinc / nickel alloy, a undercoat layer of zinc / nickel alloy with a percentage of nickel such that the reduction potential of said alloy of said undercoat layer with respect to an electrode at saturated calomel is greater than or equal to or substantially less than the potential for evolution of hydrogen on the steel of the substrate, then to deposit, between the undercoating layer and the coating layer of zinc / nickel alloy, at least one layer intermediate undercoating with a percentage of nickel such that the reduction potential of the zinc / nickel alloy of the intermediate layer n of undercoating is greater than or equal to or substantially less than the potential for release of hydrogen on said alloy of the layer n-1 intermediate undercoat previously deposited, until depositing a layer of zinc / nickel alloy.
De manière satisfaisante, on peut également déposer directement la couche intermédiaire de sous revêtement d'alliage zinc/nickel avec le pourcentage de nickel désiré sur la couche de sous revêtement précédemment déposée.In a satisfactory manner, the intermediate layer of zinc / nickel alloy undercoating can also be directly deposited with the desired percentage of nickel on the previously deposited undercoating layer.
Le potentiel de réduction de l'alliage zinc-nickel de la couche de sous revêtement par rapport à une électrode au calomel saturé est compris entre le potentiel de dégagement d'hydrogène sur l'acier du substrat et ledit potentiel de dégagement d'hydrogène moins 10%, ou de préférence moins 5% ou encore moins 2%.The reduction potential of the zinc-nickel alloy of the undercoat layer with respect to a saturated calomel electrode is between the potential for hydrogen release on the steel of the substrate and said potential for hydrogen release minus 10%, or preferably minus 5% or even less 2%.
Le potentiel de réduction de l'alliage zinc/nickel de la couche intermédiaire de sous revêtement est compris entre le potentiel de dégagement d'hydrogène sur la couche de sous revêtement précédemment déposée et ledit potentiel de dégagement d'hydrogène moins 15%, ou de préférence moins 10%, ou moins 5% ou encore moins 2%.The reduction potential of the zinc / nickel alloy of the undercoat intermediate layer is between the hydrogen release potential on the previously deposited undercoat layer and said hydrogen release potential minus 15%, or preferably minus 10%, or minus 5% or even minus 2%.
La couche de sous revêtement a une épaisseur supérieure à 0,01µm et de préférence supérieure à 0,02µm.The undercoating layer has a thickness greater than 0.01 μm and preferably greater than 0.02 μm.
La ou les couches intermédiaires de sous revêtement ont une épaisseur supérieure à 0,01µm.The intermediate undercoating layer or layers have a thickness greater than 0.01 μm.
Le procédé selon l'invention n'est pas limité au dépôt d'un alliage zinc/nickel, mais peut très bien être appliqué au dépôt d'autres alliages à base de zinc, du type zinc/fer, zing/chrome ou encore zinc/cobalt.The method according to the invention is not limited to the deposition of a zinc / nickel alloy, but can very well be applied to the deposit of other zinc-based alloys, of the zinc / iron, zinc / chromium or zinc / cobalt type.
Claims (31)
- Process for electrodeposition, on a surface of a steel substrate, of a layer of a coating of a zinc-based metal alloy of the ZnX type, X being the second element in the alloy, characterised in that, between the surface of the substrate and the coating layer of said alloy, a sub-coating layer of said alloy is deposited containing a percentage of the second element X such that the reduction potential of said alloy of said undercoating layer relative to a saturated calomel electrode is greater than or equal to or substantially less than the potential for release of hydrogen on the steel of the substrate, in order to obtain the desired percentage of the second element X.
- Process according to claim 1, characterised in that, between the undercoating layer and the coating layer of said alloy, at least one intermediate layer of the undercoating is deposited containing a percentage of the second element X such that the reduction potential of said alloy of the intermediate undercoating layer n is greater than or equal to or substantially less than the potential for the release of hydrogen on said alloy of the intermediate undercoating layer n-1 deposited previously.
- Process according to claim 1, characterised in that, between the undercoating layer and the coating layer of said alloy, an intermediate undercoating layer is deposited containing a percentage of the second element X such that the reduction potential of said alloy in the intermediate undercoating layer is greater than or equal to or substantially less than the potential for release of hydrogen onto said alloy in the undercoating layer deposited previously.
- Process according to claim 1, characterised in that the reduction potential of the alloy in the undercoating layer relative to a saturated calomel electrode is between the potential for release of hydrogen on the steel of the substrate and the potential for the release of hydrogen minus 15%.
- Process according to claim 1, characterised in that the reduction potential of the alloy of the undercoating layer relative to a saturated calomel electrode is between the potential for release of the hydrogen on the steel of the substrate and the potential for the release of hydrogen minus 10%.
- Process according to claim 1, characterised in that the reduction potential of the alloy of the undercoating layer relative to a saturated calomel electrode is between the potential for release of the hydrogen on the steel of the substrate and the potential for the release of hydrogen minus 5%.
- Process according to claim 1, characterised in that the reduction potential of the alloy of the undercoating layer relative to a saturated calomel electrode is between the potential for release of the hydrogen on the steel of the substrate and the potential for the release of hydrogen minus 2%.
- Process according to claim 2 or 3, characterised in that the reduction potential of the alloy of the intermediate undercoating layer is between the potential for release of hydrogen on the undercoating layer deposited previously and said potential for release of hydrogen minus 15%.
- Process according to claim 2 or 3, characterised in that the reduction potential of the alloy of the intermediate undercoating layer is between the potential for release of hydrogen on the undercoating layer deposited previously and said potential for release of hydrogen minus 10%.
- Process according to claim 2 or 3, characterised in that the reduction potential of the alloy of the intermediate undercoating layer is between the potential for release of hydrogen on the undercoating layer deposited previously and said potential for release of hydrogen minus 5%.
- Process according to claim 2 or 3, characterised in that the reduction potential of the alloy of the intermediate undercoating layer is between the potential for release of hydrogen on the undercoating layer deposited previously and said potential for release of hydrogen minus 2%.
- Process according to claim 1, characterised in that the undercoating layer has a thickness of more than 0.01 µm.
- Process according to claim 12, characterised in that the undercoating layer has a thickness of more than 0.02 µm.
- Process according to claim 2 or 3, characterised in that the intermediate undercoating layer or layers have a thickness of more than 0.01 µm.
- Process according to one of the preceding claims, characterised in that the second element X of the zinc based alloy is nickel.
- Process according to one of claims 1 to 14, characterised in that the second element X of the zinc based alloy is iron.
- Process according to one of claims 1 to 14, characterised in that the second element X of the zinc based alloy is cobalt.
- Process according to one of claims 1 to 14, characterised in that the second element X of the zinc based alloy is chromium.
- Coated steel material comprising a steel substrate and a covering layer of zinc based metal alloy of the ZnX type, X being the second element of this alloy, said covering layer being deposited by electrodeposition on a surface of said substrate, characterised in that it comprises, between the surface of the substrate and the covering layer, a layer for undercoating said alloy containing a percentage of the second element X such that the reduction potential of said alloy of said undercoating layer relative to a saturated calomel electrode is between the potential for release of hydrogen on the steel of the substrate and said potential for release of hydrogen minus 10%, and it comprises, between the undercoating layer and the covering layer, at least one intermediate undercoating layer containing a percentage of the second element X such that the reduction potential of said alloy in the intermediate undercoating layer is between the potential for release of hydrogen on the undercoating layer deposited previously and said potential for release of hydrogen minus 15%.
- Material according to claim 19, characterised in that the reduction potential of the alloy in the undercoating layer relative to a saturated calomel electrode is between the potential for release of hydrogen on the steel of the substrate and said potential for release of hydrogen minus 5%.
- Material according to claim 19, characterised in that the reduction potential of the alloy in the undercoating layer relative to a saturated calomel electrode is between the potential for release of hydrogen on the steel of the substrate and said potential for release of hydrogen minus 2%.
- Material according to claim 19, characterised in that the reduction potential of the alloy of the intermediate undercoating layer is between the potential for release of hydrogen on the undercoating layer deposited previously and said potential for release of hydrogen minus 10%.
- Material according to claim 19, characterised in that the reduction potential of the alloy of the intermediate undercoating layer is between the potential for release of hydrogen on the undercoating layer deposited previously and said potential for release of hydrogen minus 5%.
- Material according to claim 19, characterised in that the reduction potential of the alloy of the intermediate undercoating layer is between the potential for release of hydrogen on the undercoating layer deposited previously and said potential for release of hydrogen minus 2%.
- Material according to claim 19, characterised in that the undercoating layer has a thickness greater than 0.01 µm.
- Material according to claim 30, characterised in that the undercoating layer has a thickness greater than 0.02 µm.
- Material according to claimed, characterised in that the second element X of the zinc based alloy is iron.
- Material according to claim 19, characterised in that the second element X of the zinc based alloy is cobalt.
- Material according to claim 19, characterised in that the second element X of the zinc based alloy is chromium.
- Coated steel material comprising a steel substrate and a covering layer of a zinc/nickel alloy containing 12% nickel, said covering layer being deposited by electrodeposition on a surface of said substrate, characterised in that it comprises, between the surface of the substrate and the covering layer, a first undercoating layer of zinc/nickel alloy containing 24% nickel and, on said undercoating layer, an intermediate undercoating layer of zinc/nickel alloy containing 18% nickel.
- Material according to claim 30, characterised in that the undercoating layers have a thickness greater than 0.04 µm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9305038A FR2704560B1 (en) | 1993-04-28 | 1993-04-28 | METHOD FOR ELECTRODEPOSITION ON A SURFACE OF A STEEL SUBSTRATE OF A LAYER OF A COATING OF A ZINC-BASED ALLOY AND MATERIAL OF STEEL COATED WITH A COATING LAYER OF A ZINC-BASED ALLOY. |
| FR9305038 | 1993-04-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0622478A1 EP0622478A1 (en) | 1994-11-02 |
| EP0622478B1 true EP0622478B1 (en) | 1997-08-06 |
Family
ID=9446542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94400625A Expired - Lifetime EP0622478B1 (en) | 1993-04-28 | 1994-03-23 | Process for electroplating a zinc alloy coating on a steel substrate and steel substrate thus obtained |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0622478B1 (en) |
| JP (1) | JPH06346280A (en) |
| AT (1) | ATE156524T1 (en) |
| CA (1) | CA2122198A1 (en) |
| DE (1) | DE69404730T2 (en) |
| ES (1) | ES2107144T3 (en) |
| FR (1) | FR2704560B1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10205751B4 (en) * | 2002-02-12 | 2004-09-30 | Robert Bosch Gmbh | Ignition device, in particular spark plug for internal combustion engines |
| SI2770088T1 (en) | 2013-02-22 | 2017-08-31 | Dr. Ing. Max Schloetter Gmbh & Co. Kg | Extremely corrosion-resistant steel parts and method for their production |
| DE202013001731U1 (en) | 2013-02-22 | 2013-03-11 | Dr.-Ing. Max Schlötter Gmbh & Co. Kg | High corrosion resistant steel parts |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58130299A (en) * | 1982-01-26 | 1983-08-03 | Nisshin Steel Co Ltd | Production of zn-ni alloy electroplated steel plate having high corrosion resistance in worked part |
| DE3414048A1 (en) * | 1984-04-13 | 1985-10-17 | Nisshin Steel Co., Ltd., Tokio/Tokyo | METHOD FOR PRODUCING STEEL PARTS GALVANIZED WITH A ZINC-NICKEL ALLOY |
| JPS6244594A (en) * | 1985-08-21 | 1987-02-26 | Sumitomo Metal Ind Ltd | Highly corrosion-resistant surface-treated steel sheets for automobiles |
| JPS62294198A (en) * | 1986-06-12 | 1987-12-21 | Sumitomo Metal Ind Ltd | Rustproof steel sheet for automobile and its production |
-
1993
- 1993-04-28 FR FR9305038A patent/FR2704560B1/en not_active Expired - Fee Related
-
1994
- 1994-03-23 EP EP94400625A patent/EP0622478B1/en not_active Expired - Lifetime
- 1994-03-23 AT AT94400625T patent/ATE156524T1/en not_active IP Right Cessation
- 1994-03-23 ES ES94400625T patent/ES2107144T3/en not_active Expired - Lifetime
- 1994-03-23 DE DE69404730T patent/DE69404730T2/en not_active Expired - Fee Related
- 1994-04-26 CA CA002122198A patent/CA2122198A1/en not_active Abandoned
- 1994-04-28 JP JP6090797A patent/JPH06346280A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE69404730T2 (en) | 1998-02-05 |
| JPH06346280A (en) | 1994-12-20 |
| CA2122198A1 (en) | 1994-10-29 |
| DE69404730D1 (en) | 1997-09-11 |
| FR2704560B1 (en) | 1995-08-11 |
| ATE156524T1 (en) | 1997-08-15 |
| EP0622478A1 (en) | 1994-11-02 |
| ES2107144T3 (en) | 1997-11-16 |
| FR2704560A1 (en) | 1994-11-04 |
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