EP2157213B1 - Couche de protection contre la corrosion dotée de deux couches de zinc - Google Patents

Couche de protection contre la corrosion dotée de deux couches de zinc Download PDF

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Publication number
EP2157213B1
EP2157213B1 EP08014206A EP08014206A EP2157213B1 EP 2157213 B1 EP2157213 B1 EP 2157213B1 EP 08014206 A EP08014206 A EP 08014206A EP 08014206 A EP08014206 A EP 08014206A EP 2157213 B1 EP2157213 B1 EP 2157213B1
Authority
EP
European Patent Office
Prior art keywords
zinc
bath
zinc layer
minimum
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP08014206A
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German (de)
English (en)
Other versions
EP2157213A1 (fr
Inventor
Wolf-Dieter Franz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
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Individual
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Filing date
Publication date
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Priority to EP08014206A priority Critical patent/EP2157213B1/fr
Publication of EP2157213A1 publication Critical patent/EP2157213A1/fr
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Publication of EP2157213B1 publication Critical patent/EP2157213B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/625—Discontinuous layers, e.g. microcracked layers
    • 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
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers

Definitions

  • the invention relates to a corrosion protection coating with zinc.
  • Zinc layers as corrosion protection of metallic objects are well known in the art, as well as methods for depositing such a zinc layer from a galvanic bath.
  • the DE 31 29 129 A1 discloses a method for the two-stage galvanic deposition of high gloss, adhesive coatings for screws. For this purpose, a first zinc layer is deposited from an acidic bath, a second zinc layer from an alkaline bath.
  • the DE 198 37 431 A1 also describes a two-stage coating process wherein the first layer is deposited as a zinc, zinc-nickel alloy or zinc-cobalt alloy from an acidic electrolyte.
  • the second layer is deposited as a zinc-nickel alloy from an alkaline electrolyte.
  • the DE 197 16 375 A1 also relates to a two-stage coating process in which a first zinc layer is deposited from an acidic electrolyte and has a thickness of 0.5 ⁇ m to 3 ⁇ m.
  • the second zinc layer is deposited from an alkaline electrolyte.
  • the JP 61 183491 A describes a multi-stage coating process, wherein as a first layer, a zinc-nickel alloy is provided and the second layer is designed either as a zinc layer or turn as a zinc-nickel alloy.
  • the invention is based on the problem of specifying an improved corrosion protection coating.
  • the invention solves the problem with a method for anticorrosive coating of a metallic surface article wherein a first layer of zinc in an acid plating bath and immediately on the first a second layer of zinc Zinc layer is deposited with a thickness of at least 5 microns in an alkaline galvanic bath, wherein the first zinc layer has a thickness of at least 4 microns and the object is designed as from below the vehicle freely accessible component, in particular as part of a suspension of a motor vehicle ,
  • the invention is based on the idea to improve the corrosion protection with a well-adhering and durable zinc coating by directly two successive zinc layers of an acidic and an alkaline galvanic bath each of at least a certain thickness are deposited.
  • the anticorrosion coating according to the invention has two directly successive zinc layers, of which the first zinc layer is deposited from an aqueous acidic and the second zinc layer from an aqueous alkaline galvanic bath.
  • These two galvanic bath types for the deposition of zinc layers are known in principle from the prior art, the invention being significantly in the specified combination and thickness of the layers deposited from each different baths.
  • the zinc layer deposited from an aqueous acidic bath has a very good surface adhesion, in particular also on steel, at least in comparison with the layer deposited from an alkaline bath, but may show a cracked, columnar surface.
  • a zinc layer deposited from an alkaline bath has a quasi-amorphous closed surface of comparatively high hardness but lower ductility, which can be torn comparatively easily under mechanical stress or else detached from the coated material. Only through the combination according to the invention of the first zinc layer with the immediately following second zinc layer can a significantly improved corrosion protection be achieved in the layer thicknesses according to the invention.
  • the first (ductile) zinc layer in particular ensures a very good adhesion to the coated article, can absorb mechanical compression or strain and serves as a primer for the second zinc layer, which has a closed surface of the entire coating of larger Hardship creates.
  • the thickness of the first zinc layer is at least 4 .mu.m, 5 .mu.m or 6 .mu.m and the thickness of the second zinc layer in this order is increasingly preferably at least 5 .mu.m, 7 .mu.m, 9 .mu.m or 10 .mu.m.
  • the layer thickness of the first zinc layer can be increasingly preferred in this order at most 15 microns, 12 microns, 10 microns or 8 microns and the thickness of the second zinc layer in this order increasingly preferably be at most 25 microns, 22 microns, 20 microns or 18 microns.
  • the aqueous acid plating bath preferably has a pH of in these orders increasingly preferably at least 4.5, 4.8 or 4.9 and at most 5.8, 5.5 or 5.3.
  • the aqueous alkaline galvanic bath preferably has a pH of at least 12 and at most 14, with a pH above 13 being particularly preferred here.
  • the galvanic treatment time for depositing the first zinc layer may be in these sequences increasingly preferably at least 4 min, 6 min, 8 min or 10 min and at most 30 min, 27 min, 24 min or 20 min.
  • a bath temperature of at least 12 ° C or 20 ° C and at most 35 ° C or 30 ° C is preferred.
  • the treatment time for depositing the second zinc layer from the alkaline bath may be increasingly preferably at least 15 minutes, 18 minutes or 20 minutes and at most 45 minutes, 42 minutes or 40 minutes in these orders.
  • the alkaline bath preferably has a temperature of at least 15 ° C or 20 ° C and at most 40 ° C or 30 ° C.
  • the current density in the electrodeposition of the first zinc layer in the acid bath is preferably at least 0.3 A / dm 2 and at most 2.5 A / dm 2 , preferably at a voltage between 1.5 V and 5 V.
  • the current density in the alkaline bath is preferably at least 0.5 A / dm 2 and at most 5 A / dm 2 , preferably at a voltage of at least 3 V and at most 8 V.
  • the acid plating bath is preferably increasingly preferred in these orders at least 10 g / l, 20 g / l, 25 g / l or 30 g / l and at most 60 g / l, 45 g / l or 40 g / l zinc, at least 80 g / l, 100 g / l or 120 g / l and not more than 200 g / l, 180 g / l or 160 g / l chloride and at least 10 g / l, 15 g / l, 20 g / l or 25 g / l and at most 40 g / l or 35 g / l boric acid.
  • the acid plating bath may additionally be increasingly preferred in the respective orders at least 0.5 ml / l or 0.8 ml / l and not more than 2 ml / l or 1.5 ml / l organic brightener additive and / or at least 30 ml / l and not more than 80 ml / l or 50 ml / l of organic surfactants.
  • the acidic bath may be an aqueous solution which, with particular preference to all possible impurities, has exclusively the abovementioned components.
  • the alkaline plating bath may be increasingly preferred in these orders at least 5 g / l or 10 g / l and not more than 20 g / l or 14 g / l zinc, at least 50 g / l or 100 g / l and at most 200 g / l or 140 g / l of an alkaline additive, wherein the alkaline additive may be, for example, NaOH.
  • the alkaline bath in these orders may be increasingly preferred in addition at least 8 ml / l or 10 ml / l and not more than 20 ml / l or 15 ml / l of an organic luster carrier and / or at least 0.5 ml / l and at most 3 ml / l or 2 ml / l of an organic gloss enhancer.
  • the alkaline galvanic bath is preferably in the form of an aqueous solution and, in a particularly preferred embodiment, may contain, in addition to possible impurities, at most the abovementioned components in aqueous solution.
  • the object to be coated is rinsed, conveniently at least with water.
  • rinsing can take place after the deposition of the second galvanic zinc layer.
  • a cleaning of the article to be coated prior to the deposition of the first zinc layer is advantageous, in which case, in particular, depending on the material of the article to be coated, from the prior art, numerous cleaning methods are known.
  • the galvanic bath and / or also the object to be coated can be moved in the bath.
  • a thick-layer passivation can follow (in particular directly) onto the second zinc layer, wherein it can be applied in a further process in a chemical bath in a further bath.
  • Such an additional thick-film passivation can additionally increase the mechanical resistance of the entire coating.
  • an additional protection against chemical influences can be achieved.
  • a lacquer can also be applied directly to the second zinc layer or also directly following the thick-layer passivation.
  • the mechanical resistance and / or the protection against chemical influences can likewise be improved in a known manner.
  • the paint can be applied by electrochemical dip coating, preferably by cathodic dip coating, which is also referred to as KTL coating and is known from the prior art.
  • An article which has at least the two galvanic zinc layers according to the invention can be used as a component of a motor vehicle, particularly preferably as a component that is freely accessible from below the vehicle. It may be a vehicle part made of stainless steel and be protected according to the invention from moisture, corrosive substances such as salt, but also mechanical effects on its surface. Particularly preferred may be a component of a motor vehicle floor, in particular a part of a drive system or a suspension, for example a subframe, have a coating according to the invention.
  • a subframe made of a non-stainless steel sheet is cleaned in a first treatment, in particular degreased and freed from surface oxides. After rinsing in water, it is galvanized in an acid plating bath at 28 ° C with a current of 0.6 A / dm 2 under a voltage of 2.7 V at a treatment time of 15 min.
  • the bath with a pH of 5.0 consists here of an aqueous solution of 35 g / l zinc, 140 g / l chloride, 30 g / l boric acid, 1.2 ml / l organic brightener and 40 ml / l organic surfactants.
  • a first ductile well-adhering zinc layer of surface-cracked structure of about 7 microns is applied and then rinsed the steering column in water.
  • a further galvanic treatment takes place in an alkaline bath with a pH of about 14 and at a temperature of 26 ° C.
  • a second zinc layer is deposited during a treatment period of 30 minutes at a current density of 1 A / dm 2 at an applied voltage of 5.5 V.
  • This second galvanic bath in this case has an aqueous solution of 12 g / l zinc, 120 g / l NaOH, 12 ml / l organic gloss and 1.2 ml / l organic gloss enhancer on.
  • a layer thickness of about 16 microns of a quasi-amorphous zinc structure is deposited here, wherein after the galvanic coating of the subframe is rinsed again with water.
  • a thick film passivation is chemically deposited on a coated subframe in a further bath directly on the second zinc layer, and then the article is rinsed again in a water bath.
  • the subframe produced in this way has a corrosion protection coating with two directly successive zinc layers and an outer thick-film passivation.
  • Another embodiment resides in the anti-corrosion coating of a subframe which differs from that previously described by a cathodic dip-coating rather than the thick-film passivation.
  • a fourth embodiment corresponds to the first, thus has two successive zinc layers according to the invention.
  • a thick-film passivation is applied directly to the second zinc layer and directly to this one KTL coating.
  • This embodiment thus has a corrosion protection coating with these four successive layers.

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Claims (13)

  1. Procédé d'application d'un revêtement de protection contre la corrosion sur un objet à surface métallique, dans lequel
    on dépose une première couche de zinc dans un bain galvanique acide et
    on dépose, directement sur la première couche de zinc, une deuxième couche de zinc d'une épaisseur d'au moins 5 µm dans un bain galvanique alcalin,
    caractérisé en ce que la première couche de zinc possède une épaisseur d'au moins 4 µm, et l'objet est conçu sous la forme d'un composant de véhicule motorisé librement accessible depuis la partie inférieure du véhicule, notamment sous la forme d'un composant d'une suspension de roue.
  2. Procédé selon la revendication 1, dans lequel l'épaisseur de la première couche de zinc est au maximum de 15 µm.
  3. Procédé selon la revendication 1 ou 2, dans lequel l'épaisseur de la deuxième couche de zinc est au maximum de 25 µm.
  4. Procédé selon l'une des revendications précédentes, dans lequel la valeur du pH du bain acide est d'au moins 4,5 et au maximum de 5,8.
  5. Procédé selon l'une des revendications précédentes, dans lequel la valeur du pH du bain alcalin est d'au moins 12 et au maximum de 14.
  6. Procédé selon l'une des revendications précédentes, dans lequel la durée de traitement dans le bain galvanique acide est d'au moins 4 min.
  7. Procédé selon l'une des revendications précédentes, dans lequel la durée de traitement dans le bain alcalin est d'au moins 15 min.
  8. Procédé selon l'une des revendications précédentes mettant en oeuvre une intensité de courant d'au moins 0,3 A/dm2 dans le bain acide.
  9. Procédé selon l'une des revendications précédentes, mettant en oeuvre une intensité de courant d'au moins 0,5 A/dm2 dans le bain alcalin.
  10. Procédé selon l'une des revendications précédentes, dans lequel le bain galvanique acide présente :
    au moins 10 g/l et au maximum 60 g/l de zinc,
    au moins 80 g/l et au maximum 200 g/l de chlorure et
    au moins 10 g/l et au maximum 40 g/l d'acide borique.
  11. Procédé selon l'une des revendications précédentes, dans lequel le bain galvanique alcalin présente :
    au moins 5 g/l et au maximum 20 g/l de zinc, et
    au moins 50 g/l et au maximum 200 g/l de NaOH.
  12. Procédé selon l'une des revendications précédentes, dans lequel une couche épaisse de passivation est déposée directement sur la deuxième couche de zinc.
  13. Procédé selon l'une des revendications précédentes, dans lequel un revêtement appliqué selon le processus électrophorétique cathodique est déposé, le cas échéant, directement sur la couche épaisse de passivation ou sur la deuxième couche de zinc.
EP08014206A 2008-08-08 2008-08-08 Couche de protection contre la corrosion dotée de deux couches de zinc Not-in-force EP2157213B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08014206A EP2157213B1 (fr) 2008-08-08 2008-08-08 Couche de protection contre la corrosion dotée de deux couches de zinc

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP08014206A EP2157213B1 (fr) 2008-08-08 2008-08-08 Couche de protection contre la corrosion dotée de deux couches de zinc

Publications (2)

Publication Number Publication Date
EP2157213A1 EP2157213A1 (fr) 2010-02-24
EP2157213B1 true EP2157213B1 (fr) 2012-10-24

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Application Number Title Priority Date Filing Date
EP08014206A Not-in-force EP2157213B1 (fr) 2008-08-08 2008-08-08 Couche de protection contre la corrosion dotée de deux couches de zinc

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Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3129129A1 (de) * 1981-07-20 1983-02-03 Schering Ag, 1000 Berlin Und 4619 Bergkamen Verfahren zur galvanischen abscheidung hochglaenzender, haftfester zinkueberzuege unter verwendung alkalischer cyanidfreier baeder
JPS61183491A (ja) * 1985-02-08 1986-08-16 Usui Internatl Ind Co Ltd 耐食性重合被覆鋼材
DE19716375A1 (de) * 1997-04-18 1998-10-22 Alfred R Franz Fa Verfahren zur galvanischen Abscheidung von haftfesten, gegenüber Zug und Druck unempfindlichen, harten Zink-Schutzschichten mit relativ gleichmäßiger Zing-Verteilung auf Gegenständen aus Stahl und Metallegierungen
DE19837431C2 (de) * 1998-08-18 2001-10-31 Schloetter Fa Dr Ing Max Beschichtung von Bauteilen aus gehärtetem Stahl oder Eisenguß und Verfahren zur Aufbringung derselben

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EP2157213A1 (fr) 2010-02-24

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