EP0280886B1 - Procédé de fabrication de revêtements décoratifs sur métaux - Google Patents

Procédé de fabrication de revêtements décoratifs sur métaux Download PDF

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Publication number
EP0280886B1
EP0280886B1 EP88101400A EP88101400A EP0280886B1 EP 0280886 B1 EP0280886 B1 EP 0280886B1 EP 88101400 A EP88101400 A EP 88101400A EP 88101400 A EP88101400 A EP 88101400A EP 0280886 B1 EP0280886 B1 EP 0280886B1
Authority
EP
European Patent Office
Prior art keywords
von
pulse
matt
layer
und
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.)
Expired - Lifetime
Application number
EP88101400A
Other languages
German (de)
English (en)
Other versions
EP0280886A1 (fr
Inventor
Waldemar Dr. Rer. Nat. Krysmann
Peter Dr. Sc. Nat. Kurze
Maria Chem -Ing. Berger
Klaus Dr.Rer.Nat. Rabending
Joachim Dipl.-Chem. Schreckenbach
Thomas Dipl.-Ing. Schwarz
Karl-Heinz Dipl.-Ing. Hartmann
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.)
Aalberts Surface Technologies GmbH Kerpen
Original Assignee
Ahc-Oberflachentechnik Friebe & Reininghaus 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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25748112&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0280886(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from DD29961887A external-priority patent/DD257274B1/de
Priority claimed from DD29962087A external-priority patent/DD257275A1/de
Application filed by Ahc-Oberflachentechnik Friebe & Reininghaus GmbH filed Critical Ahc-Oberflachentechnik Friebe & Reininghaus GmbH
Priority to AT88101400T priority Critical patent/ATE76117T1/de
Publication of EP0280886A1 publication Critical patent/EP0280886A1/fr
Application granted granted Critical
Publication of EP0280886B1 publication Critical patent/EP0280886B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/024—Anodisation under pulsed or modulated current or potential
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge

Definitions

  • the invention relates to a process for the production of decorative coatings on metals, in particular on aluminum, titanium, niobium, zirconium, tantalum and their alloys, preferably for the jewelry industry, the arts and crafts, equipment manufacturing, cladding and coins, metal plastics and badges.
  • this carrier layer is produced by anodizing using direct or alternating current in electrolytes containing sulfur, phosphorus, maleic or salicylic oxalate. Such surfaces always show a "cold” shine. Also is in these relatively expensive multi-stage processes a homogeneous surface decoration on, for example, plastics, plaques, hollow bodies, delicate structures, eros, etc. not, or only realizable with high technical effort. Furthermore, transparent layers of aluminum oxide produced by anodic oxidation of aluminum are known, which can then be colored with various dyes (US Pat. No. 3,031,387). Since these layers are transparent, the metallic gloss of the surface is always retained.
  • the organic compounds used to color the layers are also influenced by environmental influences such as radiation, temperature and air humidity and change their color.
  • Various decorative metal surfaces are also known in the jewelry industry.
  • DD-WP 204845 describes the use of electronic parts as jewelry.
  • DE-A-1446289 presents a special enamelling process for decorative coatings on jewelry. Colored, anodized aluminum parts are also used as decorative elements.
  • the invention is based on the object of developing a process by means of which aluminum, titanium, niobium, zirconium, tantalum and their alloys on optically shaped surfaces of the metals are optically attractive, decorative-acting matt, white, black or colored layers on all sides with high dimensional accuracy, Adhesion strength and color homogeneity are generated.
  • Pulse mode also enables colored layers of high quality and depth of color to be formed even in electrolytes with a high concentration (up to 20%) of transition metal ions.
  • copper ions in the electrolyte produce the same concentrations from 1% to 20% light yellow to ocher, manganese ions pink to umber-colored, chrome ions green to black, iron ions light gray to deep black, molybdenum ions light gray to dark gray layers.
  • the layers produced by the process according to the invention have an average surface roughness of 4 ⁇ m to 20 ⁇ m and consist of two different layer areas.
  • the layer area adjacent to the metal surface is transparent or white and has a thickness of 0.1 ⁇ m to 1.5 ⁇ m.
  • the cover layer area following this transparent or white layer area is white, black, colored, matt and opaque and has a thickness of 3 ⁇ m to 25 ⁇ m. With a maximum achievable layer thickness of 30 ⁇ m according to the invention, a transition zone occurs between the transparent or white layer region and the top layer region.
  • the transparent or white layer area contains no coloring transition metal ions and acts as an adhesion promoter to the top layer area.
  • the lattice parameter deviations of the metal from the transparent layer area are small because of the field crystallization effect, so that no mechanical stresses occur at the metal-metal oxide interface areas of transparent or white layer areas. Since the transparent or white layer area and the top layer area also consist of the same base metal oxide, a high bond stability between the two oxide layers is ensured despite the lattice expansion of the oxides in the top layer area, also due to built-in transition metal ions. The color in the top layer area is due to the incorporation of transition metal ions. With these inorganic color bodies there is a risk of bleaching not given. Lightfast spinels or mixed oxides are formed.
  • a multiple anodic treatment according to the invention in different electrolytes can form several differently colored cover layer regions, so that homogeneous and / or heterogeneous color distributions arise.
  • the matt appearance of these decorative covers is characterized by their very low gloss. Gloss measurements according to RICHTER showed gloss numbers from 0.5 to 1.5 regardless of the angle of reflection. That means a completely matt surface.
  • Different concentrations of the transition metal ions in the top layer area, the mass fraction of which ranges up to 20% gave color shades combined with a homogeneous or marbled or speckled or flamed or mosaic-like appearance. All or part of the metal surfaces can be provided with the anodic oxide layer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Adornments (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Claims (5)

  1. Procédé de fabrication de revêtements décoratifs sur métaux formant une couche de barrage, que sont l'aluminium, le titane, le zirconium, le niobium, le tantale ou leurs alliages, au moyen d'une réaction anodique électrochimique ou plasmachimique provoquée par une tension d'impulsion, dans des électrolytes aqueux, caractérisé en ce qu'on effectue la réaction avec :
    - des pointes de tension de 250 V à 750 V
    - des durées d'impulsion de 20 µs à 2 ms
    - des fréquences d'impulsion de 35 Hz à 300 Hz
    - des courants d'impulsion de 10 A à 120 A
    - des densités de courant moyennes de 0,1 A/cm² à 1 A/cm2 et
    - des températures d'électrolytes allant de 318 °K à 360°K
    en réalisant des couches mattes, épousant un contour, décoratives, d'une épaisseur de 3 µm à 30 µm.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on produit des couches mattes, colorées ou noires, par utilisation d'électrolytes aqueux contenant des ions métalliques de transition, pour une concentration de 1 % à 20 %.
  3. Procédé selon les revendications 1 et 2, caractérisé en ce que l'on produit des structures de couche homogènes à plusieurs couches et/ou hétérogènes multicolores par utilisation répétée d'un procédé mettant en oeuvre différents électrolytes.
  4. Procédé selon les revendications 1 à 3, caractérisé en ce que l'on utilise comme base des objets décorés ou des objets portant des gravures.
  5. Procédé selon les revendications 1 à 3, caractérisé en ce que l'on utilise comme base des éléments plans de grande surface.
EP88101400A 1987-02-02 1988-02-01 Procédé de fabrication de revêtements décoratifs sur métaux Expired - Lifetime EP0280886B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88101400T ATE76117T1 (de) 1987-02-02 1988-02-01 Verfahren zur herstellung dekorativer ueberzuege auf metallen.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DD29961887A DD257274B1 (de) 1987-02-02 1987-02-02 Verfahren zur herstellung dekorativer oberflaechen auf metallen
DD29962087A DD257275A1 (de) 1987-02-02 1987-02-02 Dekorativer ueberzug auf metallen
DD299620 1987-02-02
DD299618 1987-02-02

Publications (2)

Publication Number Publication Date
EP0280886A1 EP0280886A1 (fr) 1988-09-07
EP0280886B1 true EP0280886B1 (fr) 1992-05-13

Family

ID=25748112

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88101400A Expired - Lifetime EP0280886B1 (fr) 1987-02-02 1988-02-01 Procédé de fabrication de revêtements décoratifs sur métaux

Country Status (3)

Country Link
US (1) US4869789A (fr)
EP (1) EP0280886B1 (fr)
DE (1) DE3870925D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007046775A1 (de) * 2007-09-27 2009-04-02 Friedrich-Schiller-Universität Jena Verfahren zur Generierung von nanokristallinen oder nanokristallinhaltigen Metalloxid- und Metallmischoxidschichten auf sperrschichtbildenden Metallen

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DD295198B5 (de) * 1990-06-14 1996-06-27 Physikalisch Tech Studien Gmbh Elektrolyt zur erzeugung duenner schwarzer konversionsschichten auf leichtmetallen
DE4104847A1 (de) * 1991-02-16 1992-08-20 Friebe & Reininghaus Ahc Verfahren zur keramisierung von metalloberflaechen
DE4116910A1 (de) * 1991-05-21 1992-11-26 Jenoptik Jena Gmbh Verfahren zur erzeugung oxidkeramischer oberflaechenschichten auf leichtmetall-gusslegierungen
DE4239391C2 (de) * 1991-11-27 1996-11-21 Electro Chem Eng Gmbh Gegenstände aus Aluminium, Magnesium oder Titan mit einer mit Fluorpolymeren gefüllten Oxidkeramikschicht und Verfahren zu ihrer Herstellung
DE4139006C3 (de) * 1991-11-27 2003-07-10 Electro Chem Eng Gmbh Verfahren zur Erzeugung von Oxidkeramikschichten auf sperrschichtbildenden Metallen und auf diese Weise erzeugte Gegenstände aus Aluminium, Magnesium, Titan oder deren Legierungen mit einer Oxidkeramikschicht
DE4209733A1 (de) * 1992-03-25 1993-09-30 Hauzer Franciscus Johannes Verfahren zur elektrolytischen Beschichtung von Substraten und dergleichen
US5685970A (en) * 1992-07-01 1997-11-11 Gould Electronics Inc. Method and apparatus for sequentially metalized polymeric films and products made thereby
ES2052455B1 (es) * 1992-12-31 1994-12-01 Novamax Tech Holdings Procedimiento para la obtencion por via electrolitica sobre aluminio anodizado de una gama de colores del espectro visible.
CN1034522C (zh) * 1995-04-18 1997-04-09 哈尔滨环亚微弧技术有限公司 等离子体增强电化学表面陶瓷化方法及其制得的产品
US5720866A (en) * 1996-06-14 1998-02-24 Ara Coating, Inc. Method for forming coatings by electrolyte discharge and coatings formed thereby
DE19721730C2 (de) * 1997-05-24 2001-02-22 Anatoli J Vassiliev Verfahren zum Erzeugen harter Oxidschichten an der Oberfläche eines Substrats auf Basis von Leichtmetallen sowie Verwendung eines solchen Substrats
RU2149929C1 (ru) * 1999-04-02 2000-05-27 Закрытое акционерное общество "Техно-ТМ" Способ микроплазменной электролитической обработки поверхности электропроводящих материалов
US6342145B1 (en) 1999-07-14 2002-01-29 Nielsen & Bainbridge Llc Process for manufacturing multi-colored picture frames
US6290834B1 (en) 2000-04-12 2001-09-18 Ceramic Coatings Technologies, Inc. Ceramic coated liquid transfer rolls and methods of making them
DE10022074A1 (de) * 2000-05-06 2001-11-08 Henkel Kgaa Elektrochemisch erzeugte Schichten zum Korrosionsschutz oder als Haftgrund
US7452454B2 (en) 2001-10-02 2008-11-18 Henkel Kgaa Anodized coating over aluminum and aluminum alloy coated substrates
US6916414B2 (en) 2001-10-02 2005-07-12 Henkel Kommanditgesellschaft Auf Aktien Light metal anodization
US7569132B2 (en) * 2001-10-02 2009-08-04 Henkel Kgaa Process for anodically coating an aluminum substrate with ceramic oxides prior to polytetrafluoroethylene or silicone coating
US7820300B2 (en) * 2001-10-02 2010-10-26 Henkel Ag & Co. Kgaa Article of manufacture and process for anodically coating an aluminum substrate with ceramic oxides prior to organic or inorganic coating
US7578921B2 (en) * 2001-10-02 2009-08-25 Henkel Kgaa Process for anodically coating aluminum and/or titanium with ceramic oxides
RU2263163C1 (ru) * 2004-07-30 2005-10-27 Институт химии Дальневосточного отделения Российской академии наук (статус государственного учреждения) (Институт химии ДВО РАН) Способ плазменно-электролитического оксидирования вентильных металлов и их сплавов
US20060207884A1 (en) * 2005-03-17 2006-09-21 Volodymyr Shpakovsky Method of producing corundum layer on metal parts
US9701177B2 (en) 2009-04-02 2017-07-11 Henkel Ag & Co. Kgaa Ceramic coated automotive heat exchanger components
KR101642832B1 (ko) * 2009-09-14 2016-07-27 삼성전자주식회사 펠리클 프레임, 펠리클, 리소그래피 장치 및 펠리클 프레임의 제조방법
US8516663B2 (en) 2010-05-12 2013-08-27 Hollenwolff, Llc Cufflink technology
RU2457404C2 (ru) * 2010-07-12 2012-07-27 Государственное образовательное учреждение высшего профессионального образования "Сибирский государственный аэрокосмический университет имени академика М.Ф. Решетнева" (СибГАУ) Секционный радиатор отопления
AT514194B1 (de) * 2013-07-05 2014-11-15 Münze Österreich Ag Metallplatte
DE102016106588B4 (de) * 2016-04-11 2023-12-14 Neuman & Esser Process Technology Gmbh Sichter
US9975372B2 (en) 2016-06-21 2018-05-22 Charles White Multi-dimensional art works and methods

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US926084A (en) 1906-04-23 1909-06-22 Gen Electric Process of purifying tungstic anhydrid.
GB979755A (en) 1961-07-03 1965-01-06 Allegheny Ludlum Steel Improvements in or relating to a stainless steel member
US3956080A (en) * 1973-03-01 1976-05-11 D & M Technologies Coated valve metal article formed by spark anodizing
US4144142A (en) * 1975-11-04 1979-03-13 Riken Keikinzoku Kogyo Kabushiki Kaisha Method for producing colored anodic film on aluminum-based material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007046775A1 (de) * 2007-09-27 2009-04-02 Friedrich-Schiller-Universität Jena Verfahren zur Generierung von nanokristallinen oder nanokristallinhaltigen Metalloxid- und Metallmischoxidschichten auf sperrschichtbildenden Metallen

Also Published As

Publication number Publication date
US4869789A (en) 1989-09-26
DE3870925D1 (de) 1992-06-17
EP0280886A1 (fr) 1988-09-07

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