WO2009098326A1 - Éloxal sans chrome hexavalent avec des polymères conducteurs et des nanoparticules - Google Patents

Éloxal sans chrome hexavalent avec des polymères conducteurs et des nanoparticules Download PDF

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Publication number
WO2009098326A1
WO2009098326A1 PCT/ES2008/000056 ES2008000056W WO2009098326A1 WO 2009098326 A1 WO2009098326 A1 WO 2009098326A1 ES 2008000056 W ES2008000056 W ES 2008000056W WO 2009098326 A1 WO2009098326 A1 WO 2009098326A1
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WIPO (PCT)
Prior art keywords
nanoparticles
coating
acid
aluminum
anodizing
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.)
Ceased
Application number
PCT/ES2008/000056
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English (en)
Spanish (es)
Inventor
Francisco J. Cano Iranzo
Oihana Zubillaga Alcorta
Gorka IMBULUZQUETA GARCÍA
Iñaki AZCARATE PEÑA
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Fundacion Tecnalia Research and Innovation
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Fundacion Inasmet
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Publication date
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Priority to PCT/ES2008/000056 priority Critical patent/WO2009098326A1/fr
Publication of WO2009098326A1 publication Critical patent/WO2009098326A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used

Definitions

  • the present invention relates to a coating of an aluminum surface, in particular, a corrosion resistant coating, comprising aluminum oxide, metal oxide nanoparticles and a conductive polymer.
  • the invention also relates to a new anodizing process for providing said corrosion resistant coating, as well as an anodizing composition for obtaining said coating.
  • Anodizing is a treatment used to protect aluminum and its alloys against corrosion. Said coating also improves the adhesion of the organic coatings in the event that these are subsequently applied. Similarly, the anodizing layers can be used in various applications to increase wear resistance, abrasion or simply for decorative purposes.
  • the anodizing process can be carried out in a wide variety of electrolytes and different process conditions (time, temperature, current density), imparting to the surface of the alloy the properties required for use in service.
  • the main anodizing processes are carried out in solutions of sulfuric acid and chromic acid.
  • Other less used anodizing processes, for more specific purposes, are carried out in solutions of acids such as oxalic, phosphoric, boric acid, or others.
  • the anodizing layer obtained by these processes is composed of a first oxide barrier layer in contact with the metal, and a second microporous oxide layer. This layer is usually sealed to close the pores and thus improve the resistance to
  • US 6,916,414 discloses an anodizing process for forming surface protective coatings comprising the use of anodizing solutions that may contain phosphate, permanganate, silicate, zirconate, vanadate, titanate, alkali metal fluorides and / or fluoride complexes.
  • US Patent 5,374,347 describes sealed corrosion resistant coatings obtained by immersion of an anodized aluminum substrate in an aqueous solution of trivalent chromium. The corrosion properties of the coating thus obtained can be improved by subjecting the coating obtained to a subsequent treatment with an oxidizing agent such as a peroxide. This procedure has the disadvantage that it introduces a small amount of Cr (VI) into the coating.
  • the electrolytic bath is a solution of ammonium pentaborate with 0.05% oxide nanoparticles (SiO 2 , TiO 2 , SnO doped with Sb).
  • oxide nanoparticles SiO 2 , TiO 2 , SnO doped with Sb.
  • Yu-Guo Guo et al. they start from an anodized aluminum oxide membrane in which acrylamide electropolymerize and then introduce Au and Pt nanoparticles [(3) Yu-Guo Guo et al. Highly Dispersed Metal Nanoparticles in Porous Anodic Alumina Films Prepared by a Breathing Process of Polyacrylamide Hydrogel. Chemical Materials 2003, VoI 15, pp. 4332-4336.). Therefore, the deposition of nanoparticles on previously anodized aluminum substrates, both in successive phases [(1), (3)] and simultaneously (2), is known from the state of the art.
  • conductive polymers such as polyaniline or polypyrrole
  • Said polymers can be used in the form of a continuous coating as described in US 6,762,238, or as corrosion inhibiting pigments (US 6,756,123; US 6,190,780).
  • US 6,328,874 describes an aluminum anodizing process simultaneous to the synthesis of a conductive polymer from the corresponding monomer on aluminum, giving rise to a coating composed of aluminum oxide and conductive polymer. The coating is then sealed in boiling water.
  • US Patent 5,980,723 describes a process in which aluminum oxide and the conductive polymer are formed at the same time. Sealing is done later depositing then another layer composed of conductive polymer.
  • anodizing process that provides an aluminum protective coating against corrosion, in which the anodizing and sealing are carried out in a single stage.
  • Figure 1 shows the results of an in-depth analysis of X-ray Photoelectron Spectrometry (XPS) of the external part of an anodized coating with polyaniline and T ⁇ O2 nanoparticles on 3105 aluminum alloy; in the axis “y” the atomic percentage (%) of the elements C, N, O, Al, and Ti is shown and in "x" the distance in depth from the external surface in nm.
  • XPS X-ray Photoelectron Spectrometry
  • Figure 2 shows an image obtained by SEM-EDS electron microscope showing in section the anodizing coating with polyaniline and T ⁇ O 2 nanoparticles on 3105 aluminum alloy obtained according to Example 1, and where:
  • Figure 3 shows an image of a test tube of the 3105 aluminum alloy with an anodized-polyaniline coating, with titanium oxide nanoparticles obtained according to Example 1, after 1000 hours of exposure in a neutral salt spray chamber.
  • Figure 4 shows the results of an XPS in-depth analysis of the external part of an anodized coating with polyaniline and ZrÜ 2 nanoparticles on 2024T3 aluminum alloy; in the axis "y” the atomic percentage (%) of the elements C, N, O, Al, and Zr is shown and in "x" the distance in depth from the external surface in nm.
  • An object of the present invention relates to a process for forming a coating on an aluminum surface comprising:
  • anodizing composition comprises:
  • Another object of the invention relates to the coating obtained by said method on the aluminum surface comprising oxide of aluminum, nanoparticles of a metal oxide and a conductive polymer.
  • Another additional object of the invention relates to an anodizing composition
  • an anodizing composition comprising water, a precursor monomer of a conductive polymer, nanoparticles of a metal oxide and an acid.
  • Another additional object of the invention relates to an aluminum surface coated with the coating of the invention.
  • one more object of the invention refers to an object, which comprises at least one aluminum surface, which comprises the coating of the present invention.
  • the present invention relates in a first aspect to a method of anodizing an aluminum surface that confers a protective coating against corrosion.
  • Said anodizing process hereinafter the method of the invention, comprises the following steps: (i) contacting the aluminum surface with an anodizing composition;
  • anodizing composition comprises:
  • composition in the present description refers to an aqueous solution in which each component thereof can be completely or partially dissolved or dispersed.
  • the process of the invention is performed on aluminum.
  • aluminum is understood as pure aluminum and its alloys. In principle, all alloys are treatable by the method of the invention.
  • the aluminum surface can be a surface of any piece, and present any shape and dimensions, such as a test tube, or an iron, panel etc.
  • the process of the invention comprises contacting the aluminum surface with an anodizing composition described below. Said surface is cleaned and preconditioned according to any conventional method for aluminum and its alloys.
  • the anodizing composition is placed in a suitable container and equipped with at least one entrance for the cathode and one entrance for the anode.
  • the aluminum surface to be coated acts as an anode and occupies said position.
  • As a cathode a conventional electrical conductive material is used.
  • an electrical potential is applied by means of a power supply of electricity typically between 0.5 and 50 V for a time generally between 1 and 350 min.
  • the temperature at which the process takes place can be between 5 and 5O 0 C.
  • the anodizing composition is stirred during the process of the invention.
  • the nanoparticles have a negative charge so that under the influence of the current they are directed towards the anode on which they are deposited.
  • the anodizing composition that is used to carry out the process of the invention constitutes an additional object of the invention, and comprises:
  • the precursor monomer of a conductive polymer can be any monomer conventionally used to prepare a conductive polymer as any of those described in US Patent 6,328,874 B1. It should be noted only for illustrative purposes, among others, substituted or unsubstituted monomers of, aniline, aromatic heterocycles such as pyrrole, thiophene etc.
  • a conductive polymer can be a homopolymer or a conductive copolymer, such as polyaniline, polypyrrole and polythiophene.
  • the substituted monomers useful for the present invention are those polymerizable capable of producing an intrinsically conductive polymer.
  • a substituted monomer can be, among others, a monomer with one or more of the following substituents such as a hydrocarbon chain, a carboxyl group, carbonyl group, amino group, hydroxyl group and mixtures thereof, said substituents can be said or attached heteroatom like any of the different carbons in the monomer ring.
  • the precursor monomer is aniline.
  • the monomer concentration is typically between 0.05 and 5 M.
  • the anodizing composition comprises an acid.
  • an acid With personality For illustrative purposes, oxalic acid, sulfuric acid, citric acid, hydrochloric acid, perchloric acid, nitric acid, sulfonic acids and their mixtures are among others.
  • the acid is oxalic acid, and according to another particular embodiment it is sulfuric acid.
  • the acid concentration is generally between
  • the anodizing composition has a pH between 0.5 and 5.
  • the anodizing composition also comprises nanoparticles of a metal oxide.
  • the invention can be selected from a wide group of metal oxides, among which we can mention, titanium oxide, zirconium oxide, aluminum oxide, silicon oxide and mixtures thereof.
  • the nanoparticles are made of zirconium oxide.
  • the nanoparticles are made of titanium oxide.
  • the concentration of nanoparticles is generally between 0.1 and
  • the process of the invention has advantages over other procedures of the prior art. For example, the use of hexavalent chromium with the associated toxicological and environmental problems inherent is avoided, and nevertheless an effective coating with high protective properties against corrosion is obtained. In addition, the coating process is carried out in a single stage, unlike other prior art procedures, without the need for subsequent sealing.
  • the invention provides a coating, obtainable according to the process of the invention, on an aluminum surface comprising aluminum oxide, nanoparticles of a metal oxide and a conductive polymer.
  • the coating of the invention is characterized in that the The presence of nanoparticles and conductive polymer is greater in the part furthest from the aluminum surface, and they act as a sealant of the microporous structure of the aluminum oxide.
  • Figure 1 The depth composition (expressed in% of each of the elements) of two examples of coating is represented in Figure 1 and Figure 4.
  • Figure 1 shows an XPS spectrum (Photoelectron Spectrometry of X-rays; X-ray photoelectron spectroscopy) of the external part of said anodizing layer, and reveals a greater presence of titanium oxide (O, Ti) and polymer (C, N) near the external surface of the coating, which is It combines at lower levels closer to the aluminum surface, with the aluminum oxide.
  • Figure 4 (corresponding to example 2) shows the composition of the outer part of a layer containing zirconium oxide (O, Zr) instead of titanium oxide, the presence of this oxide and the polymer (C,
  • N also greater in the outer part of the layer, to be combined with the aluminum oxide as it approaches the aluminum surface.
  • the thickness of the anodizing coating layer is in the range of 0.5-50 microns, and that of the external part thereof, composed of polymer and nanoparticles in the range of 20-500 nm.
  • the nanoparticle / polymer ratio is between 1 to 10, while in the external part thereof, the nanoparticle / polymer ratio can be between 0.1-100. That the nanoparticles and the polymer are concentrated in the outermost part of the coating does not rule out their presence throughout the entire section of the layer.
  • Figure 2 shows an SEM-EDS (Scanning Electron Microscopy - Energy Dispersive X-ray Spectroscopy) image in section of a coating obtained according to Example 1 for the 3105 aluminum alloy in an anodizing composition of sulfuric acid, aniline and titanium oxide .
  • the invention provides an aluminum surface comprising the coating of the present invention.
  • the surface can have any size and dimensions, and be a surface of any article of any shape and size.
  • said aluminum surface is a test piece, an iron, a panel, among others.
  • FIG. 3 The corrosion protection of aluminum, obtained with a coating of the invention, is illustrated in Figure 3 (corresponding to example 1), where an image of an aluminum alloy 3105 with an anodized-polyaniline nanoparticles coating after 1000 is shown. hours of exposure in neutral salt spray chamber. These tests were carried out in accordance with ASTM B-117. As can be seen from this image, good corrosion protection is observed with the coating that incorporates the nanoparticles, with no presence of white corrosion products or pitting.
  • the invention provides any object, comprising at least one aluminum surface, comprising the coating of the present invention.
  • a test tube of aluminum alloy 3105 was introduced into said dispersion of nanoparticles.
  • a cathode made of titanium was then incorporated into the vessel and an electric current was established between the aluminum and the cathode, so that the aluminum acted as an anode, imposing a potential difference of 6 volts between the two electrodes for 1 hour.
  • a coating layer consisting of aluminum oxide, polyaniline and titanium oxide was obtained.
  • the composition of the layer obtained is shown in Figure 1. This figure shows that the layer of TIO 2 and polyaniline has a thickness of 25 nm, with a TiO 2 / polymer ratio of 1.
  • FIG. 2 A sectional image of the complete coating obtained in the conditions is shown in Figure 2. In this figure it is observed that the entire layer has a thickness of 4 microns.
  • a solution was prepared in a vessel starting from distilled water and adding oxalic acid to a concentration of 0.1 mol / L. To this solution pure aniline was added to a concentration of 0.1mol / L, and stirred until a homogeneous solution was obtained. Then, zirconium oxide nanoparticles were incorporated into the solution until a concentration of 1g / L in the solution of acid and aniline, stirring to keep them dispersed.
  • a titanium cathode was then incorporated into the vessel, and a potential difference of 1OV between the cathode and the aluminum specimen, which functioned as an anode, was imposed by an electrical power source for 1 hour.
  • a coating layer consisting of aluminum oxide, polyaniline and zirconium oxide was obtained.
  • the composition of the external part of the layer obtained is shown in Figure 4.
  • the layer of ZrO 2 and polyaniline has a thickness of 60 nm, with a ZKV polymer ratio of 5.

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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)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un procédé de formation d'un recouvrement sur une surface d'aluminium, consistant: (i) à mettre en contact la surface de l'aluminium avec une composition d'anodisation; (ii) à appliquer un potentiel électrique entre la surface d'aluminium qui agit comme anode et une cathode; et (iii) à obtenir un recouvrement sur l'anode qui comprend de l'oxyde d'aluminium, un polymère conducteur et des nanoparticules d'oxyde métallique. Ladite composition d'anodisation est une composition aqueuse acide qui comprend un monomère précurseur d'un polymère conducteur et des nanoparticules d'oxyde métallique.
PCT/ES2008/000056 2008-02-04 2008-02-04 Éloxal sans chrome hexavalent avec des polymères conducteurs et des nanoparticules Ceased WO2009098326A1 (fr)

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PCT/ES2008/000056 WO2009098326A1 (fr) 2008-02-04 2008-02-04 Éloxal sans chrome hexavalent avec des polymères conducteurs et des nanoparticules

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PCT/ES2008/000056 WO2009098326A1 (fr) 2008-02-04 2008-02-04 Éloxal sans chrome hexavalent avec des polymères conducteurs et des nanoparticules

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6328874B1 (en) * 1998-01-05 2001-12-11 Mcdonnell Douglas Corporation Anodically formed intrinsically conductive polymer-aluminum oxide composite as a coating on aluminum
ES2186217T3 (es) * 1997-08-27 2003-05-01 Jude Runge-Marchese Dispositivo electroquimica de un material compuesto de polimero-oxido..
WO2005093872A1 (fr) * 2004-03-19 2005-10-06 E.I. Dupont De Nemours And Company Composites polymeres/nanoparticules organiques electroconducteurs et procedes d'utilisation associes
WO2006015756A1 (fr) * 2004-08-03 2006-02-16 Chemetall Gmbh Procede de revetement de surfaces metalliques avec une couche de protection contre la corrosion
US20060254922A1 (en) * 2005-03-21 2006-11-16 Science & Technology Corporation @ Unm Method of depositing films on aluminum alloys and films made by the method
EP1832629A1 (fr) * 2006-03-10 2007-09-12 MPG Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Pigment pour inhiber la corrosion comprenant un nanoreservoir d'un inhibiteur de corrosion

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2186217T3 (es) * 1997-08-27 2003-05-01 Jude Runge-Marchese Dispositivo electroquimica de un material compuesto de polimero-oxido..
US6328874B1 (en) * 1998-01-05 2001-12-11 Mcdonnell Douglas Corporation Anodically formed intrinsically conductive polymer-aluminum oxide composite as a coating on aluminum
WO2005093872A1 (fr) * 2004-03-19 2005-10-06 E.I. Dupont De Nemours And Company Composites polymeres/nanoparticules organiques electroconducteurs et procedes d'utilisation associes
WO2006015756A1 (fr) * 2004-08-03 2006-02-16 Chemetall Gmbh Procede de revetement de surfaces metalliques avec une couche de protection contre la corrosion
US20060254922A1 (en) * 2005-03-21 2006-11-16 Science & Technology Corporation @ Unm Method of depositing films on aluminum alloys and films made by the method
EP1832629A1 (fr) * 2006-03-10 2007-09-12 MPG Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Pigment pour inhiber la corrosion comprenant un nanoreservoir d'un inhibiteur de corrosion

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ABDEL AAL.: "Hard and corrosion resistant nanocomposite coating for Al alloy.", MATERIALS SCIENCE AND ENGINEERING A., vol. 474, 2008, pages 181 - 187, XP022411754, DOI: doi:10.1016/j.msea.2007.04.058 *

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