EP1760173A2 - Revêtement de zinc mat et procédé de électrodéposition d'un revêtement de zinc mat - Google Patents

Revêtement de zinc mat et procédé de électrodéposition d'un revêtement de zinc mat Download PDF

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Publication number
EP1760173A2
EP1760173A2 EP05023090A EP05023090A EP1760173A2 EP 1760173 A2 EP1760173 A2 EP 1760173A2 EP 05023090 A EP05023090 A EP 05023090A EP 05023090 A EP05023090 A EP 05023090A EP 1760173 A2 EP1760173 A2 EP 1760173A2
Authority
EP
European Patent Office
Prior art keywords
electrolyte
zinc
coating
matt
deposited
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.)
Withdrawn
Application number
EP05023090A
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German (de)
English (en)
Other versions
EP1760173A3 (fr
Inventor
Karl-Heinz Kampschulte
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.)
Dr M Kampschulte & Co KG GmbH
Original Assignee
Dr M Kampschulte & Co KG GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dr M Kampschulte & Co KG GmbH filed Critical Dr M Kampschulte & Co KG GmbH
Publication of EP1760173A2 publication Critical patent/EP1760173A2/fr
Publication of EP1760173A3 publication Critical patent/EP1760173A3/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • 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
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • 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
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • 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
    • C25D5/619—Amorphous layers
    • 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
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

  • the present patent application relates to a matte zinc coating and to a method of depositing such matte zinc layers on substrates.
  • the substrates can either be made of different metals or of plastics themselves.
  • the choice of a suitable metallic coating is made depending on the desired and achievable surface properties of the substrates. These can decorative properties, as they are achieved by shiny layers, or even functional properties, such. As the increase in corrosion resistance or the achievement of a specific conductivity of the surface, be.
  • One type of surface coating is the deposition of zinc layers on substrates.
  • a zinc layer is deposited galvanically on the substrate, as a result of which, inter alia, a changed appearance and / or improved corrosion resistance is achieved.
  • alkaline electrolytes or acid-based electrolytes based on chloride are used.
  • additives for acidic electrolytes a whole series of additives, individually or in mixture, are proposed.
  • additives for alkaline electrolytes a number of other additives are proposed.
  • quaternary polyvinylimidazoles, low and / or high molecular weight polyethyleneimines, imidazoles and imidazole derivatives, 4-methoxybenzaldehyde, 1-benzyl-3-sodium-carboxypyridinium chloride, polymeric quaternary ammonium compounds, cationic polymers and mixtures of these are known.
  • galvanically applied zinc layers are usually subsequently coated with a conversion layer.
  • these layers are often glistening again until the formation of glossy layers.
  • matt paints paints with special matting additives or specially adjusted so-called “top coats” (silicate or waxy coatings) are often applied subsequently.
  • This object is achieved in terms of coating by a zinc coating, which is characterized by an average surface roughness RMS of about 10 nm to about 150 nm.
  • the zinc coatings according to the invention can be electrodeposited from acidic or alkaline, cyanide-free electrolytes.
  • the layers obtained are independent in appearance from the base material used.
  • the object of the present invention is achieved by an electrolyte for depositing a satin-matt zinc coating on a substrate, which is characterized in that the electrolyte contains at least one additive acting as a matting agent in addition to a source of zinc ions.
  • the electrolyte can be used as matting agent polyalkoxylated naphthols of the general formula 1 Sulfopropylated alkoxilates of the general formula 2 Ethersulfonates of the general formula 3 or Quaternary ammonium compounds of the general formula 4 contain.
  • matting agents of the general formulas 1 to 3 have proven to be suitable in particular for acidic electrolytes, whereas matting agents of the general formula 4 can be used according to the invention, in particular in alkaline electrolytes.
  • the electrolyte contains the matting agent in a concentration of about 0.01 g / l to about 10 g / l, preferably between about 0.1 g / l and about 1.0 g / l.
  • the electrolyte may contain other additives.
  • additives may be surfactants, organic acids, inorganic acids, levelers, alkalizing agents or complexing agents.
  • the pretreated surface to be coated is contacted with the electrolyte at a temperature between about 10 ° Celsius and about 60 ° Celsius, preferably between about 15 ° Celsius and about 40 ° Celsius.
  • the contact time is between about 5 minutes and about 120 minutes, preferably between about 30 minutes and about 60 minutes.
  • a current density between about 0.5 A / dm 2 and about 6 A / dm 2 , preferably about 1 A / dm 2 and about 4 A / dm 2 is set.
  • the voltage used in this case can be applied as a DC voltage, pulse voltage or pulse-reverse voltage.
  • polymeric quaternary ammonium compounds of the general formula 4 When using alkaline electrolytes in particular polymeric quaternary ammonium compounds of the general formula 4 have proven to be suitable to achieve surfaces with a hitherto completely zinc-atypical surface characteristics, which have a uniform matt appearance even after subsequent conversion treatment, even if these substances are used without further additives ,
  • the layers were made on sheets, as they are commonly used in so-called "Hull cells".
  • the measuring points are arranged from left to right according to decreasing current density, left is the range of the highest, right the lowest current density.
  • Fig. 1 shows the gloss curves of three different zinc layers, which were determined by a reflection measurement with a reflectometer (Dr. Lange).
  • the three layers are a known from the prior art bright zinc coating (Quasar 3000), as described in the following in Comparative Example A1, and each one of an acidic (ZnG 3) and an alkaline (ZnG 5) Electrolyte deposited zinc layer according to the invention. It can be clearly seen that the known from the prior art bright zinc coating has a significantly higher gloss level compared to the Mattzink füren invention.
  • FIG. 2 shows the layer distribution for the bright zinc coating layer already described for FIG. 1 as well as the two matt zinc layers according to the invention. It can be seen here that the layer distribution of the acid-deposited matt zinc zinc layer according to the invention corresponds excellently to the layer distribution of the acid-deposited bright zinc zinc layer known from the prior art.
  • the alkaline-deposited matt zinc coating according to the invention shows an almost linear layer distribution.
  • FIG. 2A shows the comparison of the layer distribution, once obtained from a conventional alkaline cyan-free bright zinc electrode, on the other hand, of the alkali-deposited matt zinc zinc layer according to the invention, in each case after a previously occurring current passage of 1 A / l of electrolyte. At the same time, an approximately twice as thick layer of zinc was deposited on the specimen with the same amount of current applied.
  • Fig. 3 the scanning electron micrograph of a known from the prior art bright zinc coating at 400-fold, 800-fold and 2000-fold magnification reproduced. It will be appreciated that the bright zinc coating produced according to the prior art has a perfectly flat surface.
  • FIG. 4 shows a scanning electron micrograph of a matt zinc zinc layer of the invention deposited at an acidic electrolyte at 400, 800 and 2000 times magnification. Even at a magnification of 400 times, the clear structuring of the matt zinc layers according to the invention can be seen.
  • the pictures show a uniformly rough sandpaper-like surface.
  • FIG. 5 shows the scanning electron micrograph of a matt zinc zinc layer of the invention deposited at an alkaline electrolyte at 400 ⁇ , 800 ⁇ and 2000 ⁇ magnification.
  • the surface structuring of the layer produced can be clearly seen even at 400 ⁇ magnification.
  • 2000x magnification it can be seen that the surface has a uniformly rough, tissue-like structure.
  • FIG. 6 shows the scanning force micrograph of a bright zinc coating layer deposited according to the prior art.
  • the determined average surface roughness RMS of the bright zinc coating lies in a range of 9.5 to 10 nm.
  • FIG. 7 shows the scanning force micrograph of a matt zinc zinc layer of the invention deposited from an acidic electrolyte. It can be clearly seen the structuring of the surface.
  • the mean surface roughness RMS of the acid-deposited matt-zinc coating according to the invention is in a range between 70 and 90 nm.
  • FIG. 8 shows the scanning force micrograph of a matt zinc zinc layer of the invention deposited from an alkaline electrolyte. Again, the surface structuring of the zinc layer according to the invention can be clearly seen.
  • the mean surface roughness RMS of the alkaline deposited layer according to the invention is in a range between 80 and 136 nm.
  • FIG. 9 shows the juxtaposition of the roughness profiles of a bright zinc coating layer known from the prior art, a matt zinc coating layer of the invention deposited from an acidic electrolyte and a matt zinc zinc layer (Quasar, G3, G5) deposited from an alkaline electrolyte.
  • the differences in the roughness profiles of the matt zinc coatings according to the invention compared with the bright zinc coatings known from the prior art clearly show the uniform strong surface structuring of the layers deposited according to the invention.
  • FIG. 10 shows a receptacle of a matt-galvanized workpiece according to the invention and a workpiece which has been bright-galvanized according to the prior art.
  • the invention matt dipped workpiece is to recognize, including the bright galvanized workpiece is located.
  • the different optical impressions of the workpieces are clearly visible.
  • Fig. 11 shows two comparative illustrations of the present invention galvanized workpieces and the resulting visual impression of the workpieces after subsequent painting, forming a conversion layer or forming a conversion layer and subsequent painting.
  • the first three workpieces seen from the left represent matte zinc layers deposited according to the invention from an acidic electrolyte.
  • the last three workpieces of the left picture represent, according to the invention, zinc layers deposited from an alkaline electrolyte.
  • FIG. 11 shows from left to right a workpiece coated in an acidic matt-zinc electrolyte according to the invention after subsequent painting, a workpiece coated in an alkaline matt zinc electrolyte according to the invention after subsequent formation of a conversion layer, a workpiece coated according to the invention in an acidic electrolyte after subsequent formation of a Conversion layer and subsequent coating, a coated according to the invention in an alkaline matte zinc electroplated workpiece after subsequent painting, an inventively coated in an acidic matte zinc workpiece after subsequent formation of a conversion layer and an invention in an alkaline matte zinc coated workpiece after subsequent formation of a conversion layer and subsequent painting. It can be recognize that the subsequent surface treatments do not lead to a strong Aufglänzen the coatings, respectively the surfaces.
  • a measurement of the layer thickness obtained with the same exposure time and applied amount of current showed no significant differences in the achieved layer thicknesses at the same measuring points.
  • the specimens according to A1 and A6 were subjected to a REM and an RFM examination. It was found that the specimen according to A1) had no microroughness, the specimen according to A6) but considerable, uniformly distributed over the test specimen microroughness with a correspondingly uniform refraction of light.
  • test specimen after B6 was subjected to a REM and an RFM examination. It shows a surface structure, which corresponds to no previously known surface structure of galvanically deposited zinc layers.
  • a measurement of the layer thickness obtained with the same exposure time and applied amount of current showed no significant differences in the achieved layer thicknesses at the same measuring points.
  • test specimens according to A1) (bright zinc, "Quasar") and also according to A6 (matt zinc, "G3") as well as according to B6) (matt zinc, "G5") were subjected to a profile analysis. It was found that the matte zinc layers have a characteristic microroughness, which significantly differentiates them from glossy 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 And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
EP05023090A 2005-08-30 2005-10-22 Revêtement de zinc mat et procédé de électrodéposition d'un revêtement de zinc mat Withdrawn EP1760173A3 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102005040964A DE102005040964A1 (de) 2005-08-30 2005-08-30 Matte Zinkbeschichtung und Verfahren zur Abscheidung matter Zinkschichten

Publications (2)

Publication Number Publication Date
EP1760173A2 true EP1760173A2 (fr) 2007-03-07
EP1760173A3 EP1760173A3 (fr) 2008-08-06

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DE (1) DE102005040964A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016188806A1 (fr) 2015-05-22 2016-12-01 Basf Se Sulfonates d'éther de bêta-naphtol, procédés pour leur préparation et leur utilisation comme additifs améliorant la brillance

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202009012622U1 (de) 2009-09-18 2011-02-10 Hqm Sachsenring Gmbh Kugelgelenk

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3121016A1 (de) * 1981-05-27 1982-12-16 Friedr. Blasberg GmbH und Co KG, 5650 Solingen "polymeres zusatzmittel fuer galvanische zinkbaeder auf basis von polyalkyleniminen, verfahren zur herstellung und verwendung desselben sowie waessrig-alkalisches, cyanidfreies zinkbad enthaltend dasselbe"
DE3839824A1 (de) * 1987-11-28 1989-06-08 Lpw Chemie Gmbh Verfahren zur galvanischen abscheidung von zinkschichten und/oder von glanz-zinkschichten
US5656148A (en) * 1995-03-02 1997-08-12 Atotech Usa, Inc. High current density zinc chloride electrogalvanizing process and composition
DE10033433A1 (de) * 2000-07-10 2002-01-24 Basf Ag Verfahren zur elektrolytischen Verzinkung aus alkansulfonsäurehaltigen Elektrolyten
US6585812B2 (en) * 1995-02-15 2003-07-01 Atotech Usa, Inc. High current density zinc sulfate electrogalvanizing process and composition
US20030192785A1 (en) * 2000-07-20 2003-10-16 Herdman Roderick Dennis Zinc and zinc alloy electroplating additives and electroplating methods

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5435898A (en) * 1994-10-25 1995-07-25 Enthone-Omi Inc. Alkaline zinc and zinc alloy electroplating baths and processes
DE19840019C1 (de) * 1998-09-02 2000-03-16 Atotech Deutschland Gmbh Wäßriges alkalisches cyanidfreies Bad zur galvanischen Abscheidung von Zink- oder Zinklegierungsüberzügen sowie Verfahren

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3121016A1 (de) * 1981-05-27 1982-12-16 Friedr. Blasberg GmbH und Co KG, 5650 Solingen "polymeres zusatzmittel fuer galvanische zinkbaeder auf basis von polyalkyleniminen, verfahren zur herstellung und verwendung desselben sowie waessrig-alkalisches, cyanidfreies zinkbad enthaltend dasselbe"
DE3839824A1 (de) * 1987-11-28 1989-06-08 Lpw Chemie Gmbh Verfahren zur galvanischen abscheidung von zinkschichten und/oder von glanz-zinkschichten
US6585812B2 (en) * 1995-02-15 2003-07-01 Atotech Usa, Inc. High current density zinc sulfate electrogalvanizing process and composition
US5656148A (en) * 1995-03-02 1997-08-12 Atotech Usa, Inc. High current density zinc chloride electrogalvanizing process and composition
DE10033433A1 (de) * 2000-07-10 2002-01-24 Basf Ag Verfahren zur elektrolytischen Verzinkung aus alkansulfonsäurehaltigen Elektrolyten
US20030192785A1 (en) * 2000-07-20 2003-10-16 Herdman Roderick Dennis Zinc and zinc alloy electroplating additives and electroplating methods

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016188806A1 (fr) 2015-05-22 2016-12-01 Basf Se Sulfonates d'éther de bêta-naphtol, procédés pour leur préparation et leur utilisation comme additifs améliorant la brillance
US10611725B2 (en) 2015-05-22 2020-04-07 Basf Se Beta-naphthol ether sulfonates, processes for preparing them and use thereof as brightness improvers

Also Published As

Publication number Publication date
DE102005040964A1 (de) 2007-03-01
EP1760173A3 (fr) 2008-08-06

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