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EP1144733B1 - Procede pour produire une surface ultraphobe a base d'aluminium structure - Google Patents

Procede pour produire une surface ultraphobe a base d'aluminium structure Download PDF

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Publication number
EP1144733B1
EP1144733B1 EP99968371A EP99968371A EP1144733B1 EP 1144733 B1 EP1144733 B1 EP 1144733B1 EP 99968371 A EP99968371 A EP 99968371A EP 99968371 A EP99968371 A EP 99968371A EP 1144733 B1 EP1144733 B1 EP 1144733B1
Authority
EP
European Patent Office
Prior art keywords
grooves
ultrahydrophobic
aluminium
process according
produced
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
EP99968371A
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German (de)
English (en)
Other versions
EP1144733A1 (fr
Inventor
Karsten Reihs
Daniel-Gordon Duff
Georg Wiessmeier
Burkhard KÖHLER
Eckard Wenz
Juan Gonzalez-Blanco
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.)
Sunyx Surface Nanotechnologies GmbH
Original Assignee
Sunyx Surface Nanotechnologies 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 Sunyx Surface Nanotechnologies GmbH filed Critical Sunyx Surface Nanotechnologies GmbH
Publication of EP1144733A1 publication Critical patent/EP1144733A1/fr
Application granted granted Critical
Publication of EP1144733B1 publication Critical patent/EP1144733B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • 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
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/16—Pretreatment, e.g. desmutting
    • 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
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • 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
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C25D11/246—Chemical after-treatment for sealing layers

Definitions

  • the present invention relates to a method for producing an ultrahydrophobic Surface on aluminum as a carrier material and the use of this surface.
  • the surface of an aluminum substrate is covered with a periodic microstructure provided with a depth of 1 to 1000 pm, the surface then anodized, in particular by anodic oxidation, if appropriate treated in hot water, at a temperature of 400 to 500 ° C calcined, optionally coated with an adhesion promoter layer and then provided with a hydrophobic coating.
  • Ultrahydrophobic surfaces are characterized in that the contact angle of a Drop of liquid, usually water, on the surface clearly is more than 90 ° and that the roll angle does not exceed 10 °.
  • Ultrahydrophobic surfaces with a contact angle> 150 ° and the above Roll-off angles have a very high technical benefit because they e.g. with water but are also not wettable with oil, only dirt particles on these surfaces adhere very poorly and these surfaces are self-cleaning. Taking self-cleaning is understood here the ability of the surface to adhere to the surface Dirt or dust particles easily emitted to liquids covering the surface overflow.
  • EP 476 510 A1 describes a method for producing a Ultraphobic surface reveals a metal oxide film on a glass surface is applied and then etched using an Ar plasma. With Surfaces produced by this process, however, have the disadvantage that the Contact angle of a drop lying on the surface is less than 150 °.
  • US Pat. No. 5,693,236 also describes several processes for the production of ultraphobic Surfaces are taught where zinc oxide microneedles with a binder placed on a surface and then in different ways (e.g. partially exposed by plasma treatment). The surface structured in this way is then coated with a water repellent. To this Wise structured surfaces also only have contact angles of up to 150 ° on.
  • From US-A-5 633 115 is a method for producing an image receiving element known in which an aluminum foil is roughened, anodized and then with a treated aqueous liquid, which is an organic compound with at least one has cationic group.
  • the task is therefore to deliver ultrahydrophobic surfaces and a process of their manufacture available for a 10 ⁇ l drop of water is deposited on the surface, a contact angle ⁇ 150 °, as well preferably have a roll angle 10 10 °.
  • the angle of inclination of a basically planar is used as the roll angle structured surface understood against the horizontal, in which a standing Water droplets of 10 ⁇ l volume are moved due to gravity when the Surface is inclined.
  • the object is achieved by providing a method for Manufacture of an ultrahydrophobic surface on aluminum as a carrier material characterized in that the surface of an aluminum substrate with a periodic Microstructure with a roughness depth of 1 to 1000 microns, preferably from 60 to 600 ⁇ m, the surface is then anodized, at one temperature calcined from 400 to 500 ° C, and then with a hydrophobic Coating is provided.
  • the aluminum substrate is preferably coated after the anodizing and before the calcining treated with hot water.
  • the molded body that is to be provided with the surface according to the invention exists either made entirely of aluminum or has a surface made of this material.
  • Aluminum in the sense of the invention does not only mean pure aluminum but also alloys in which the aluminum content is> 80% by weight, preferably > 90% by weight and very particularly preferably ⁇ 97%.
  • This aluminum surface is first made with an artificial microstructure Mistake.
  • An artificial microstructure in the sense of the invention has depressions and / or surveys, their depth or height and possibly their distance from each other in a range of 1 to 1000 microns.
  • To this desired To create surface structure already during the production of a shaped body, can be made from the outset in molds that the Negative of the desired surface structures.
  • the artificial microstructures can also be made by mechanical processing or be branded.
  • the microstructures preferably have grooves, one can have any cross-sectional shape. These grooves are also preferred approximately parallel, thus forming a group of grooves and preferably have a distance between 50 ⁇ m and 900 ⁇ m.
  • the grooves are 60 to 600 ⁇ m, particularly preferably 100 to 300 ⁇ m deep.
  • a microstructure with two is also preferred in the aluminum surface or more intersecting sets of grooves, the grooves being one respective coulter are arranged substantially parallel to each other, which in at least two directions and at any angle to each other could be.
  • the one provided with the artificial surface structure Surface is anodized.
  • Anodizing takes place e.g. through a common, anodic oxidation familiar to the person skilled in the art, e.g. by Georg W clevermeier "Monolithic microstructure reactors with microflow channels and regular Mesopore systems for selective, heterogeneous catalyzed gas phase reactions ", Shaker Verlag, Aachen, 1997, pp. 181-186.
  • This Literature is hereby introduced as a reference and is therefore part of the Epiphany.
  • the aluminum surface may be hot Water or steam treated (sealed).
  • the surface gets hotter Exposed to water or water vapor.
  • the water or Water vapor has a temperature of 90 to 100 ° C.
  • The is also preferred Surface 300 to 1000 seconds, most preferably 500 to 800 seconds sealed with hot water.
  • the sample is preferably at a preferred temperature range of 70 to 90 ° C preferably dried for 40 to 80 minutes.
  • the expert knows that the hot water treatment with a Water / solvent mixture can be carried out, the surface then preferably exposed to the steam mixture.
  • the anodized aluminum surface is calcined after the anodizing.
  • the calcination is preferably carried out at 400 to 500 ° C in the presence of air.
  • the calcining time is preferably 4 to 8 hours.
  • the surfaces thus obtained are provided with a hydrophobic or, in particular, oleophobic coating.
  • a hydrophobic material in the sense of the invention is a material that has a contact angle with respect to water of greater than 90 ° on a flat, non-structured surface.
  • the ultrahydrophobic surface preferably has a coating with a hydrophobic Phobicization aid, especially an anionic, cationic, amphoteric or nonionic, surfactant compound.
  • Surfactant compounds with any desired are used as phobicization aids Molar mass to look at. These compounds are preferably cationic, anionic, amophotere or non-ionic surface-active compounds, such as in the directory "Surfactants Europe, A Dictionary of Surface Active Agents available in Europe, Edited by Gordon L. Hollis, Royal Socity of Chemistry, Cambridge, 1995.
  • anionic phobing aids alkyl sulfates, Ether sulfates, ethetcarboxylates, phosphate esters, sulfosucinates, sulfosuccinatamides, Paraffin sulfonates, olefin sulfonates, sarcosinates, isothionates, taurates and Lingnine Links.
  • Quaternary alkylammonium compounds are examples of cationic phobicization aids and to call Imidazole
  • Amphoteric phobicization aids are, for example, betaines, glycinates, propionates and imidazole.
  • Nonionic phobicization aids are, for example: alkoxylates, alkyloamides, Esters, amine oxides and alkypolyglycosides.
  • alkylatable compounds such as. B. fatty alcohols, Fatty amines, fatty acids, phenols, alkylphenols, arylalkylphenols, such as Styrene-phenol condensates, carboxamides and resin acids.
  • Phobicization auxiliaries are particularly preferred in which 1 to 100%, in particular preferably 60 to 95% of the hydrogen atoms are substituted by fluorine atoms.
  • Examples include perfluorinated alkyl sulfate, perfluorinated alkyl sulfonates, and perfluorinated Alkyl phosphonates, perfluorinated alkyl phosphinates and perfluorinated Called carboxylic acids.
  • polymeric phobicization aids for hydrophobic coating or as polymeric hydrophobic material for the surface.
  • These polymeric phobicization aids can be nonionic, anionic, cationic or amphoteric compounds.
  • these polymeric phobicization aids can be homopolymers and copolymers, graft and graft copolymers and random block polymers.
  • Particularly preferred polymerizing auxiliaries are those of the AB-, BAB and ABC block polymers.
  • the AB or BAB block polymers is the A segment a hydrophilic homopolymer or copolymer, and the B block is a hydrophobic Homopolymer or copolymer or a salt thereof.
  • Anionic, polymeric phobicizing aids are also particularly preferred, in particular Condensation products of aromatic sulfonic acids with formaldehyde and alkylnaphthalenesulfonic acids or from formaldehyde, naphthalenesulfonic acids and / or benzenesulfonic acids, condensation products from optionally substituted Phenol with formaldehyde and sodium bisulfite.
  • condensation products which are obtained by reacting Naphthols with alkanols, additions of alkylene oxide and at least partially Conversion of the terminal hydroxyl groups into sulfo groups or half esters the maleic acid and phthalic acid or succinic acid are available.
  • the phobicization aid is from the group of the sulfosuccinic acid esters and alkylbenzenesulfonates.
  • Sulfated, alkoxylated fatty acids or their salts are also preferred.
  • Alkoxylated fatty acid alcohols are understood to mean in particular those with 5 to 120, with 6 to 60, very particularly preferably with 7 to 30 ethylene oxide units, C 6 -C 22 fatty acid alcohols which are saturated or unsaturated, in particular stearyl alcohol.
  • the sulfated alkoxylated fatty acid alcohols are preferably in the form of a salt, especially as alkali or amine salts, preferably as diethylamine salt.
  • an adhesion promoter layer is therefore optionally applied between the surface and the hydrophobic coating.
  • any substance familiar to the person skilled in the art which increases the bond between the surface and the respective hydrophobic coating can be used as an adhesion promoter.
  • Preferred adhesion promoters for example for thiols as a hydrophobic coating, are noble metal layers, for example made of Au, Pt or Ag, or layers of GaAs, in particular of gold.
  • the layer thickness of the adhesion promoter layer is preferably from 10 to 100 nm.
  • ultrahydrophobic surfaces are self-cleaning, the self-cleaning can be done in that the Surface is exposed to rain or moving water from time to time.
  • the ultrmychophobic surface rolls the water drops on the surface and Dirt particles that adhere very poorly to the surface attach to the Surface of the rolling pots and are thus from the Ultrohydrophobe Surface removed.
  • This self-cleaning does not only work when it comes into contact with water but also with oil.
  • ultrahydrophobic surface produced by the method according to the invention ship hulls can be coated in order to reduce their frictional resistance.
  • Another application of the ultrahydrophobic surface is the treatment of surfaces on which no water should adhere in order to avoid icing. Examples include the surfaces of heat exchangers, for example in refrigerators, or the surfaces of aircraft.
  • the surfaces produced using the method according to the invention are suitable also for attachment to house facades, roofs, monuments, around them to make self-cleaning.
  • the invention also relates to a material or building material having an ultrahydrophobic surface according to the invention.
  • Another object of the invention is the use of the ultrahydrophobic surface according to the invention for the friction-reducing lining of vehicle bodies, aircraft or ship hulls.
  • the invention also relates to the use of the invention ultrahydrophobic surface as self-cleaning coating or planking of Buildings, roofs, windows, ceramic building materials, e.g. for sanitary facilities, Domestic appliances.
  • the invention also relates to the use of the invention ultra-hydrophobic surface as a rust-protecting coating of metal objects.
  • the gold layer of the sample was placed in a solution of n-decanethiol for 24 hours in ethanol (1 g / l) at room temperature in a closed vessel coated, then rinsed with ethanol and dried.
  • the surface has a static contact angle of ⁇ 160 °. at If the surface is inclined by ⁇ 3 °, a water drop with a volume of 10 ⁇ l rolls from.
  • the surface has a static contact angle of> 160 °. at If the surface is inclined by ⁇ 3 °, a water drop with a volume of 10 ⁇ l rolls from.
  • the film thus produced was anodized in an apparatus or in a frame Oxidized (anodized), the Georg W clevermeier "monolithic microstructure reactors with micro flow channels and regular mesopore systems for selective, heterogeneous catalyzed gas phase reactions ", Shaker Verlag, Aachen, 1997 on pages 181-184.
  • the film was first degreased with tetrachlorethylene and then rinsed with deionized water.
  • the anodic oxidation was carried out in 1.5% by weight oxalic acid, which was kept at a constant temperature of 285 K.
  • the anodizing voltage was 50 V and the andizing time was 3 hours.
  • the film was calcined at 450 ° C in the presence of air for 6 hours.
  • the sheet treated in this way was coated with an approximately 50 nm thick gold layer Atomization coated.
  • This coating corresponds to the process that too usual for preparation in electron microscopy and with Klaus Wetzig, Dietrich Schulze, "In situ Scanning Electron Microscopy in Material Research", 36-40, Akademie Verlag, Berlin 1995 is described.

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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)
  • General Chemical & Material Sciences (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Laminated Bodies (AREA)

Claims (11)

  1. Procédé pour la préparation d'une surface ultrahydrophobe sur de l'aluminium comme matériau support, caractérisé en ce que la surface d'un substrat en aluminium est pourvue d'une microstructure périodique avec une profondeur de 1 à 1000 µm, de préférence de 60 à 600 µm, la surface est ensuite anodisée, en particulier par oxydation anodique, le cas échéant traitée dans l'eau chaude, calcinée à une température de 400 à 500°C, le cas échéant revêtue d'une couche de promoteur d'adhérence et ensuite pourvue d'un revêtement ultrahydrophobe et en ce qu'elle présente, dans le cas d'une goutte d'eau de 10 µl, un angle de contact ≥ 150° et un angle de mouillage ≤ 10°.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on réalise dans la surface en aluminium une microstructure avec des rainures qui sont de préférence parallèles les unes aux autres.
  3. Procédé selon la revendication 1, caractérisé en ce qu'on réalise dans la surface en aluminium une microstructure présentant deux réseaux de rainures ou plus qui se croisent, les rainures d'un réseau étant essentiellement parallèles les unes aux autres.
  4. Procédé selon la revendication 2 ou 3, caractérisé en ce qu'on réalise dans la surface en aluminium des rainures présentant une profondeur de 60 à 600 µm, de préférence de 100 à 300 µm.
  5. Procédé selon la revendication 4, caractérisé en ce qu'on réalise dans la surface en aluminium des rainures avec une distance entre deux rainures adjacentes d'un même réseau de 50 à 900 µm.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la surface en aluminium est revêtue après la calcination avec une couche mince en métal précieux comme couche de promoteur d'adhérence, de préférence une couche d'or, en particulier par dépôt d'une couche d'or d'une épaisseur de 10 à 100 nm.
  7. Surface ultrahydrophobe obtenue par un procédé selon l'une quelconque des revendications 1 à 6.
  8. Matériau ou matériau de construction présentant une surface ultrahydrophobe selon la revendication 7.
  9. Utilisation de la surface ultrahydrophobe selon la revendication 7 pour le revêtement diminuant le frottement de carrosseries de véhicules, de coques d'avions ou de navires.
  10. Utilisation de la surface ultrahydrophobe selon la revendication 7 pour le revêtement ou le planchéiage auto-nettoyant de bâtiments, toitures, fenêtres, matériaux de construction céramiques, par exemple pour des installations sanitaires, des appareils domestiques.
  11. Utilisation de la surface ultrahydrophobe selon la revendication 7 comme revêtement de protection contre la corrosion d'objets métalliques.
EP99968371A 1998-12-24 1999-12-22 Procede pour produire une surface ultraphobe a base d'aluminium structure Expired - Lifetime EP1144733B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19860137A DE19860137C2 (de) 1998-12-24 1998-12-24 Verfahren zur Herstellung einer ultraphoben Oberfläche auf Basis von strukturiertem Aluminium und deren Verwendung
DE19860137 1998-12-24
PCT/EP1999/010323 WO2000039369A1 (fr) 1998-12-24 1999-12-22 Procede pour produire une surface ultraphobe a base d'aluminium structure

Publications (2)

Publication Number Publication Date
EP1144733A1 EP1144733A1 (fr) 2001-10-17
EP1144733B1 true EP1144733B1 (fr) 2004-10-06

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EP99968371A Expired - Lifetime EP1144733B1 (fr) 1998-12-24 1999-12-22 Procede pour produire une surface ultraphobe a base d'aluminium structure

Country Status (5)

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EP (1) EP1144733B1 (fr)
AT (1) ATE278825T1 (fr)
AU (1) AU2538800A (fr)
DE (2) DE19860137C2 (fr)
WO (1) WO2000039369A1 (fr)

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Publication number Priority date Publication date Assignee Title
US8870839B2 (en) 2008-04-22 2014-10-28 The Procter & Gamble Company Disposable article including a nanostructure forming material

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Publication number Priority date Publication date Assignee Title
US6652669B1 (en) 1998-12-24 2003-11-25 Sunyx Surface Nanotechnologies Gmbh Method for producing an ultraphobic surface on an aluminum base
DE19947788A1 (de) 1999-10-05 2001-04-12 Bayer Ag Verfahren und Vorrichtung zum Bewegen von Flüssigkeiten
DE10009935C2 (de) * 2000-03-02 2003-12-11 Karlsruhe Forschzent Verfahren zum anodischen Oxidieren der Innenflächen eines kapillarähnlichen Hohlraums
DE10162188A1 (de) * 2001-12-17 2003-06-18 Sunyx Surface Nanotechnologies Hydrophobe Oberfläche mit einer Vielzahl von Elektroden
DE10162816A1 (de) * 2001-12-19 2003-07-03 Sunyx Surface Nanotechnologies Optischer Schalter
WO2003071274A1 (fr) 2002-02-22 2003-08-28 Sunyx Surface Nanotechnologies Gmbh Utilisation de surfaces ultraphobes dotees d'une pluralite de zones hydrophiles pour l'analyse d'echantillons
DE10246840A1 (de) * 2002-10-08 2004-04-29 Daimlerchrysler Ag Verfahren zur Herstellung einer transparenten Abdeckung, insbesondere einer Fensterscheibe, mit einer Funktionsschicht sowie transparente Abdeckung
DE102006011769B4 (de) * 2006-03-13 2010-07-29 WKW Erbslöh Automotive GmbH Bauteil und Verfahren zum Herstellen eines Bauteils
DE102007044159A1 (de) * 2007-09-11 2009-03-12 Leibniz-Institut Für Polymerforschung Dresden E.V. Metallwerkstoffe mit hybrid-stabilisierter Oxidschicht, Verfahren zu der Herstellung sowie deren Verwendung
EP2157432A1 (fr) 2008-08-15 2010-02-24 Qiagen GmbH Procédé d'analyse d'un échantillon complexe par spectrométrie de masse
AT12627U1 (de) * 2011-05-11 2012-09-15 Neuhold Hermine Schild
CN102534694B (zh) * 2011-12-31 2014-07-02 浙江工业大学 一种铜基定向超疏水材料的制备方法
DE102014003508A1 (de) * 2014-03-14 2015-09-17 Airbus Defence and Space GmbH Verfahren zur Herstellung sowie Verwendung einer polierten nanostrukturierten metallischen Oberfläche mit wasser- und eisabweisenden Eigenschaften
EP4386114A4 (fr) * 2021-10-12 2025-06-11 Samsung Electronics Co., Ltd. Panneau extérieur pour appareil domestique, appareil domestique le comprenant, et procédé de fabrication de panneau extérieur

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8870839B2 (en) 2008-04-22 2014-10-28 The Procter & Gamble Company Disposable article including a nanostructure forming material
US10071003B2 (en) 2008-04-22 2018-09-11 The Procter & Gamble Company Disposable article including a nanostructure forming material

Also Published As

Publication number Publication date
WO2000039369A1 (fr) 2000-07-06
EP1144733A1 (fr) 2001-10-17
DE19860137A1 (de) 2000-06-29
DE19860137C2 (de) 2002-07-18
ATE278825T1 (de) 2004-10-15
AU2538800A (en) 2000-07-31
DE59910778D1 (de) 2004-11-11

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