WO2002059391A1 - Couches de couverture ultrafines sur substrats metalliques, leur procede de fabrication et leur utilisation - Google Patents

Couches de couverture ultrafines sur substrats metalliques, leur procede de fabrication et leur utilisation Download PDF

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Publication number
WO2002059391A1
WO2002059391A1 PCT/EP2002/000799 EP0200799W WO02059391A1 WO 2002059391 A1 WO2002059391 A1 WO 2002059391A1 EP 0200799 W EP0200799 W EP 0200799W WO 02059391 A1 WO02059391 A1 WO 02059391A1
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WO
WIPO (PCT)
Prior art keywords
layer
substrate
plasma
metal
zinc
Prior art date
Application number
PCT/EP2002/000799
Other languages
German (de)
English (en)
Inventor
Martin Stratmann
Neil Shirtcliffe
Guido Grundmeier
Matthias Brettmann
Original Assignee
Friedrich-Alexander-Universität Erlangen-Nürnberg
Thyssen Krupp Stahl Ag
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 Friedrich-Alexander-Universität Erlangen-Nürnberg, Thyssen Krupp Stahl Ag filed Critical Friedrich-Alexander-Universität Erlangen-Nürnberg
Publication of WO2002059391A1 publication Critical patent/WO2002059391A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
    • C23C8/38—Treatment of ferrous surfaces

Definitions

  • the present invention relates to new ultra-thin cover layers on metallic substrates.
  • the present invention relates to a new method for producing ultra-thin cover layers on metallic substrates.
  • the present invention relates to the use of the new ultra-thin cover layers as corrosion protection layers and adhesive layers.
  • Reactive consumer metals such as steel, zinc, aluminum, magnesium, titanium, copper and the alloys of at least two of these metals are characterized by the thinnest oxide skin or cover layer formed in the air.
  • B. significantly affects the corrosion behavior of the metal both in the uncoated and in the coated state.
  • the object of the present invention is to provide a new ultra-thin cover layer on a metallic substrate, which is matched to the reactive metal used in each case, so that the anti-corrosion properties and the adhesion both to the respective metal surfaces and to one on the new ultra-thin cover layer located plasma polymer layer, adhesive layer, paint, film or foam layer can be further improved.
  • the substrates, which are coated with the new ultra-thin top layer are said to be particularly suitable for the production of molded parts that are used in such technically demanding areas as the manufacture of automobiles, airplanes, ships, furniture, doors, windows, cladding for buildings in indoor and outdoor use, components and enclosures for machines per ° the nature or containers and packaging containers may be used.
  • the new ultra-thin cover layer for a metallic substrate has been found, which can be produced by treating the metallic surface of the substrate or at least one layer on the metallic surface of the substrate from at least one metal oxide with a plasma containing water and / or carbon dioxide.
  • top layer The following is the new ultra-thin top layer referred to a substrate as "top layer according to the invention”.
  • Substrate found by plasma treatment and / or plasma polymerization in which at least one metallic surface of a substrate or a layer of at least one metal oxide on at least one metallic surface of a substrate is treated with a plasma containing water and / or carbon dioxide.
  • the cover layer according to the invention is located on a substrate.
  • the substrate can consist of a wide variety of metals or of metallized materials.
  • It preferably consists of reactive metals or materials metallized with reactive metals.
  • Suitable reactive metals are iron, steel, zinc, aluminum, magnesium, titanium and the alloys of at least two of these metals.
  • Zinc is particularly well suited as such or in the form of a galvanized steel surface.
  • suitable materials which have a metallized surface are naturally occurring or synthetic, organic and inorganic materials such as plastics, glass, ceramic, wood, paper, leather and composites of these materials.
  • the substrates can represent a wide variety of three-dimensional molded parts, such as automobile bodies or parts thereof, ship hulls, aircraft parts, furniture, doors, windows, cladding for structures, components and housings for machines, containers
  • DJ Tl. DJ: DJ tr ⁇ os; ⁇ J Hi DJ ⁇ co ⁇ ⁇ ! p.
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  • ⁇ ⁇ - P.! J ⁇ - O 3 ⁇ p ⁇ ⁇ ⁇ - et DJ ⁇ c ⁇ ⁇ - o O O ⁇ ⁇ ⁇ 3 s: * Hi P,
  • Suitable adhesive layers can be produced, for example, from the customary and known one- or multi-component adhesives.
  • Suitable coatings can be made, for example, from customary and known, pigmented and unpigmented, physically curable, thermally self-crosslinking curable, thermally externally crosslinking curable, radiation-curable or thermally and radiation-curable (dual-cure) electrocoat materials, conventional or aqueous one- or multi-component lacquers, essentially or completely water- and solvent-free liquid single- or multi-component powder coatings (100% systems), essentially or completely water- and solvent-free solid single- or multi-component powder coatings or aqueous dispersions of solid single- or multi-component powder coatings (powder slurries).
  • suitable films are from the German patent applications DE 195 35 934 AI, DE 195 17 069 AI, DE 195 17 067 AI or DE 195 17 068 AI or the European patent applications EP 0 352 298 AI, EP 0 285 071 AI or EP 0 266 109 AI known.
  • Suitable foam layers consist of foams i. S. from DIN 7726: 198205. These are materials with open and / or closed cells distributed over their entire mass and a bulk density that is lower than that of the framework substance.
  • foams i. S. of DIN 53580 see also Rö pp Lexikon Chemie, CD-ROM: Version 2.0, Geora, Thieme Verlag, Stuttgart, New York, 1999, "Foams").
  • the laminates according to the invention are deformable without being mechanically damaged and their excellent corrosion resistance and interlayer adhesion being reduced.
  • the laminates according to the invention are therefore high
  • Fig. 1 shows an FTIR spectrum of a plasma-induced hydroxide formation on zinc in H 2 0 Plas a;
  • Fig. 3 shows an FTIR spectrum of a plasma-induced carbonate formation on zinc in the C0 2 plasma
  • Fig. 4 shows the plasma-induced carbonate formation on zinc in the C0 2 plasma by means of photoelectrode spectroscopy (ESCA);
  • FIG. 5 shows an FTIR spectrum of a plasma-induced oxide formation on zinc in the 0-plasma.
  • a zinc surface cleaned with an argon plasma was exposed to a microwave glow discharge generated using a linear source in a pure water atmosphere.
  • the result was a zinc hydroxide-containing layer with a thickness of 5 nm.
  • the presence of the hydroxide groups could be determined using the FTIR spectroscopy can be detected on the basis of the characteristic signals of the HO groups and the Zn (OH) 2 groups in addition to the signal of the ZnO groups (FIG. 1)
  • a zinc surface cleaned with an argon plasma was exposed to a microwave glow discharge generated using a linear source in a carbon dioxide atmosphere.
  • the result was a zinc carbonate-containing layer with a thickness of 5 nm.
  • the presence of the carbonate groups could be detected by FTIR spectroscopy using the characteristic signal of the ZnC0 3 groups in addition to the signals of the Zn (OH) 2 groups and the ZnO groups be (Fig. 3).
  • Cover layer 2 showed the characteristic signal of carbon in carbonate (C0 2 ⁇ ), corresponding to a binding energy of 290.5 eV (Fig. 4).
  • a zinc surface cleaned with an argon plasma was exposed to a microwave glow discharge generated with the aid of a linear source in a pure oxygen atmosphere.
  • the result was a zinc oxide layer with a thickness of 5 nm.
  • the oxidic nature of the layer could be demonstrated by FTIR spectroscopy on the basis of the characteristic signal of the ZnO groups. No signals from HO groups and Zn (OH) 2 groups were observed (FIG. 5).
  • the substrate with the cover layer 1 according to the invention from example 1 was used.
  • the substrate with the top layer 2 according to the invention from example 2 was used.
  • the substrate with the cover layer of the comparison test V 1 not according to the invention was used.
  • top layers of Examples 1 and 2 and of Comparative Experiment V1 were partially covered with an adhesive tape immediately after their production, after which the adhesive tape and the free surface of the top layers were coated with a two-component clearcoat based on epoxy-amine. After the layers of paint had hardened, the adhesive tapes were removed. As the paintwork did not adhere to the adhesive tapes, defined defects resulted when the tape was peeled off at the boundary between the top layer and the lacquer. k réelle. After the defects had been filled with 0.5 M saline solution, the delamination of the paintwork was determined by means of spatially resolved measurements of the respective infiltration speed with the aid of the scanning Kelvin probe. The lower the rate of infiltration, the higher the corrosion protection effect and the interlayer adhesion.
  • Examples 3 and 4 could be shaped by deep drawing without mechanical damage.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

L'invention concerne des couches de couverture ultrafines pour substrats métalliques, ces couches étant façonnées par traitement de la surface métallique desdits substrats ou bien au moins d'une couche qui se trouve sur cette surface et qui est composée d'au moins un oxyde métallique avec un plasma contenant de l'eau et/ou du dioxyde de carbone. La présente invention porte également sur leur mode de production par traitement au plasma et/ou polymérisation par plasma, ainsi que sur leur utilisation comme couches de protection anticorrosion et/ou couches adhésives dans des agglomérés.
PCT/EP2002/000799 2001-01-25 2002-01-25 Couches de couverture ultrafines sur substrats metalliques, leur procede de fabrication et leur utilisation WO2002059391A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10103463.6 2001-01-25
DE2001103463 DE10103463B4 (de) 2001-01-25 2001-01-25 Verbundmaterial aus metallischen Substraten und Verfahren zur Herstellung und dessen Verwendung

Publications (1)

Publication Number Publication Date
WO2002059391A1 true WO2002059391A1 (fr) 2002-08-01

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PCT/EP2002/000799 WO2002059391A1 (fr) 2001-01-25 2002-01-25 Couches de couverture ultrafines sur substrats metalliques, leur procede de fabrication et leur utilisation

Country Status (2)

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DE (1) DE10103463B4 (fr)
WO (1) WO2002059391A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2468422A1 (fr) * 2010-12-22 2012-06-27 Dizayn Grup Teknoloji Arastirma ve Gelistirme San. Tic. A.S. Procédé de production d'une structure en alliage de cuivre/zinc revêtu de polymère doté d'une adhérence améliorée
DE102013219337B3 (de) * 2013-09-25 2015-04-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Plasmapolymerer Festkörper, insbesondere plasmapolymere Schicht, deren Herstellung sowie deren Verwendung als Korrosionsschutz

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2920108A2 (fr) 2012-11-19 2015-09-23 Chemetall GmbH Procédé de revêtement de surfaces métalliques avec des couches d'oxyde de zinc nanocristallin, compositions aqueuses correspondantes et utilisation des surfaces ainsi revêtues

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5062900A (en) * 1988-04-18 1991-11-05 Institut De Recherches De La Siderurgie Francaise Process for the improvement of the corrosion resistance of metallic materials
EP0694630A1 (fr) * 1994-07-26 1996-01-31 The Boc Group, Inc. Traitement protecteur de substrats en métal
WO1998054397A1 (fr) * 1997-05-30 1998-12-03 Micell Technologies Traitement de surface
DE19758347A1 (de) * 1997-12-22 1999-06-24 Inst Angewandte Chemie Berlin Verfahren zur plasmagestützten Herstellung von Magnetitschichten
US6083355A (en) * 1997-07-14 2000-07-04 The University Of Tennessee Research Corporation Electrodes for plasma treater systems
EP1132492A2 (fr) * 2000-03-08 2001-09-12 Wolff Walsrode AG Matériaux en forme de bandes traitées par plasma
EP1132195A2 (fr) * 2000-03-08 2001-09-12 Wolff Walsrode AG Traitement de surface ou revêtement de bandes utilisant un plasmatron atmosphérique à arc non transféré

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4980196A (en) * 1990-02-14 1990-12-25 E. I. Du Pont De Nemours And Company Method of coating steel substrate using low temperature plasma processes and priming

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5062900A (en) * 1988-04-18 1991-11-05 Institut De Recherches De La Siderurgie Francaise Process for the improvement of the corrosion resistance of metallic materials
EP0694630A1 (fr) * 1994-07-26 1996-01-31 The Boc Group, Inc. Traitement protecteur de substrats en métal
WO1998054397A1 (fr) * 1997-05-30 1998-12-03 Micell Technologies Traitement de surface
US6083355A (en) * 1997-07-14 2000-07-04 The University Of Tennessee Research Corporation Electrodes for plasma treater systems
DE19758347A1 (de) * 1997-12-22 1999-06-24 Inst Angewandte Chemie Berlin Verfahren zur plasmagestützten Herstellung von Magnetitschichten
EP1132492A2 (fr) * 2000-03-08 2001-09-12 Wolff Walsrode AG Matériaux en forme de bandes traitées par plasma
EP1132195A2 (fr) * 2000-03-08 2001-09-12 Wolff Walsrode AG Traitement de surface ou revêtement de bandes utilisant un plasmatron atmosphérique à arc non transféré

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2468422A1 (fr) * 2010-12-22 2012-06-27 Dizayn Grup Teknoloji Arastirma ve Gelistirme San. Tic. A.S. Procédé de production d'une structure en alliage de cuivre/zinc revêtu de polymère doté d'une adhérence améliorée
DE102013219337B3 (de) * 2013-09-25 2015-04-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Plasmapolymerer Festkörper, insbesondere plasmapolymere Schicht, deren Herstellung sowie deren Verwendung als Korrosionsschutz

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DE10103463B4 (de) 2009-10-08
DE10103463A1 (de) 2002-08-14

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