EP2857559A1 - Procédé de traitement de surface d'alliage d'aluminium, alliage d'aluminium traité par ce procédé et substrat composite en alliage d'aluminium comprenant l'alliage d'aluminium - Google Patents

Procédé de traitement de surface d'alliage d'aluminium, alliage d'aluminium traité par ce procédé et substrat composite en alliage d'aluminium comprenant l'alliage d'aluminium Download PDF

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Publication number
EP2857559A1
EP2857559A1 EP13187340.8A EP13187340A EP2857559A1 EP 2857559 A1 EP2857559 A1 EP 2857559A1 EP 13187340 A EP13187340 A EP 13187340A EP 2857559 A1 EP2857559 A1 EP 2857559A1
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EP
European Patent Office
Prior art keywords
aluminum alloy
oxide film
electrolyte
surface treatment
porous oxide
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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.)
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EP13187340.8A
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German (de)
English (en)
Inventor
Cheng-I Tu
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Individual
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Priority to EP13187340.8A priority Critical patent/EP2857559A1/fr
Publication of EP2857559A1 publication Critical patent/EP2857559A1/fr
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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
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
    • 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
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • 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 an aluminum alloy surface treatment method, an aluminum alloy processed by the method, and an aluminum alloy composite substrate comprising the aluminum alloy.
  • Plastic layers are generally coated and combined with the housing of metal products such as the housing of 3C products to achieve the effects of heat insulation, collision resistance, and scratch resistance.
  • pores are formed on the surface of the aluminum or aluminum alloy by a surface etching process in order to inject plastic directly, and thus the surface treatment of aluminum or aluminum alloy is an important processing technique of aluminum materials.
  • the surface treatment of aluminum or aluminum alloy mainly includes anodic oxidation or chemical conversion, and the conventional anodic oxidation of aluminum or aluminum alloy has been disclosed in R.O.C. Pat. Publication No. 201325905 entitled "Aluminum or aluminum alloy surface treatment method and product", and this patent discloses an aluminum or aluminum alloy surface treatment method and a product manufactured thereof, wherein the product comprises an aluminum or aluminum alloy substrate, and an anodic oxide film and an electroplated layer sequentially formed on the aluminum or aluminum alloy substrate, and the anodic oxide film includes a barrier layer and a porous layer sequentially formed on a surface of the aluminum or aluminum alloy substrate, and the anodic oxide film further includes a plurality of second pores, and the second pores penetrate through the barrier layer and the porous layer.
  • a chemical conversion solution containing chromate such as potassium dichromate (K 2 Cr 2 O 7 ) is used in the chemical conversion surface treatment process of chromate, and thus resulting in heavy metal pollution during the chemical conversion process of the aluminum alloy.
  • a porous anodic oxide film is formed on the surface of aluminum or aluminum alloy by anodic oxidation, so that the internal surfaces of a large number of pores increase the bonding strength between the surface of aluminum or aluminum alloy and the plastic, but the unsealed pores of the anodic oxide film increase the level of environmental pollution (such as the moisture in air) as the effective surfaces of the aluminum or aluminum alloy exposed in the environment increase, so that the yield rate of a subsequent surface treatment process (such as the surface coating, plastic coating, and plastic injection molding) drops.
  • the aluminum alloy processed by the method and the aluminum alloy composite substrate comprising the aluminum alloy a porous oxide film containing polyaniline is formed on a surface of the aluminum alloy to reduce the influence of the environmental pollution (such as moisture) on the aluminum alloy stored in a general environment.
  • the pores-unsealed porous oxide film containing polyaniline can resist pollutions better than the pores-unsealed conventional anodic oxide film to prevent the pores of the anodic oxide film from being blocked, which may adversely affect the bonding strength between the aluminum alloy and plastic.
  • the polyaniline-containing porous oxide film is conducive to the bonding strength between the aluminum alloy and plastic, so that the aluminum alloy composite substrate formed by plastic molding injection has a high bonding power.
  • the present invention provides an aluminum alloy surface treatment method comprising the following steps:
  • the acidic solution is an aqueous solution selected from the collection of sulfuric acid, phosphoric acid and oxalic acid.
  • the organic acid is one selected from the collection of benzenesulfonic acid, p-toluenesulfonic acid, n-butyl-benzenesulfonamide, dodecyl benzenesulfonic acid and camphorsulfonic acid.
  • the acidic solution of the electrolyte is an aqueous solution of sulfuric acid with a concentration by volume of 100 milliliters to 250 milliliters per liter, and aniline with a concentration of 10 grams to 30 grams per liter and dodecyl benzenesulfonic acid with a concentration of 30 grams to 70 grams per liter are added into the aqueous sulfuric acid solution, and the aluminum alloy is put into the electrolyte and electrically conducted to perform an anodic oxidation treatment at a temperature of 15°C to 25°C for 5 minutes to 60 minutes, and the density of current passing through the aqueous sulfuric acid solution is 0.005 ampere to 0.045 ampere per square centimeter of the aluminum alloy and the voltage is 14 volts to 24 volts.
  • the aluminum alloy has a porous oxide film containing polyaniline, and the porous oxide film containing polyaniline has a plurality of pores formed thereon.
  • the porous oxide film containing polyaniline has a film thickness of 2 microns ( ⁇ m) to 18 microns ( ⁇ m).
  • the pores have an opening diameter of 10 nanometers (nm) to 200 nanometers (nm).
  • the plastic layer is combined with the porous oxide film containing polyaniline and filled up in the pores.
  • the present invention can effectively reduce the influence of the environmental pollution, which may block the pores of the porous oxide film containing polyaniline, on the aluminum alloy stored in a general environment, so as to improve the yield rate of a subsequent surface treatment process (such as surface coating, plastic coating and plastic injection molding).
  • the present invention with the porous oxide film containing polyaniline can improve the bonding strength between the aluminum alloy and plastic, so that the aluminum alloy composite substrate formed by plastic injection molding has a high bonding power.
  • the present invention can extend the service life of the aluminum alloy composite substrate effectively.
  • the present invention provides a simple aluminum alloy surface treatment method without causing any heavy metal pollution.
  • FIG. 1 is a flow chart of a preferred embodiment of the present invention
  • FIG. 2 is a schematic view of the structure of a polyaniline-containing porous oxide film formed on a surface of aluminum alloy in accordance with a preferred embodiment of the present invention
  • FIG. 3 is a first electronic microscopic view of the surface of an aluminum alloy in accordance with a preferred embodiment of the present invention
  • FIG. 4 is a second electronic microscopic view of the surface of an aluminum alloy in accordance with a preferred embodiment of the present invention.
  • FIG. 5 is a graph of the film thickness of a polyaniline-containing porous oxide film versus the time of an anodic oxidation treatment in accordance with a preferred embodiment of the present invention
  • FIG. 6 is a schematic view of the structure of a aluminum alloy composite substrate in accordance with a preferred embodiment of the present invention.
  • FIG. 7 is an infrared spectrogram of a porous oxide film in accordance with a preferred embodiment of the present invention.
  • the aluminum alloy used in this preferred embodiment is aluminum alloy 6061, and the aluminum alloy surface treatment method of this preferred embodiment comprises the following steps:
  • A1 Degrease and clean the surface of an aluminum alloy (1) by a degreasing agent, wherein the aluminum alloy (1) is dipped into the degreasing agent for the degreasing process, and then rinse the aluminum alloy (1) by water after the degreasing process is completed. Make sure that the surface of the aluminum alloy (1) is cleaned.
  • A2 Remove oxide and insoluble substances from the surface of the aluminum alloy (1) by a deoxidizer, wherein the aluminum alloy (1) is dipped into the deoxidizer to perform deoxidization, and then rinse the aluminum alloy (1) by water after the deoxidization is completed. Make sure that the surface of the aluminum alloy (1) is cleaned.
  • the electrolyte is an aqueous sulfuric acid solution with a concentration by volume of 100 to 250ml per liter, and aniline with a concentration of 10 to 30g per liter and dodecyl benzenesulfonic acid with a concentration of 30 to 70g per liter are added into the aqueous sulfuric acid solution.
  • the film thickness (d) is related to the anodic oxidation treatment time and can range from 2 ⁇ m to 18 ⁇ m (as shown in FIG. 5 ).
  • the pores (3) have an opening diameter (t) of 10 to 80 nanometers (nm) (as shown in FIG. 4 ).
  • Rinsing Procedure Rinse the aluminum alloy (1) by water to wash away the electrolyte remained or attached on the surface of the aluminum alloy (1) after the anodic oxidation treatment is completed.
  • the porous oxide film (2) containing polyaniline (21) is formed on a surface of the aluminum alloy (1), and the pores (3) are provided for forming a plastic material (such as Polyvinyl chloride (PVC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), polyether ether keton (PEEK), polyphenylene sulfide (PPS) and high fiberglass etc.) onto the surface of the aluminum alloy (1) by injection molding or plastic coating and tightly coupling the plastic material with the porous oxide film (2) containing polyaniline (21), such that a plastic layer (4) is formed on the porous oxide film (2) containing polyaniline (21) to form the aluminum alloy composite substrate of the present invention as shown in FIG.
  • a plastic material such as Polyvinyl chloride (PVC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), polyether
  • polyaniline (21) on the surface of the porous oxide film (2) is conducive to the attachment of the plastic layer (4) onto the porous oxide film (2) containing polyaniline (21) to improve the bonding strength between the aluminum alloy (1) and the plastic layer (4), so that the aluminum alloy (1) and the plastic layer (4) will not be separated from each other easily by external forces or collisions, and the plastic layer (4) can be securely combined with the aluminum alloy (1).
  • the porous oxide film (2) containing polyaniline (21) formed on the aluminum alloy (1) can reduce the degree of block, resulted from the environmental pollution, of the porous oxide film (2) of the aluminum alloy (1) stored in a general environment before injection molding, plastic coating or coating is performed, so that the bonding strength between the aluminum alloy (1) and the plastic is not affected easily, and the yield rate of a subsequent surface treatment process can be improved.
  • the present invention can extend the service life of the aluminum alloy composite substrate effectively.
  • the analytic result of the infrared spectrogram definitely shows that the porous oxide film contains polyaniline.
  • the testing conditions include a tensile speed of 10mm/min and a testing temperature of 25°C, and the test results of the tensile test show that the aluminum alloy composite substrate comprising the aluminum alloy (1) processed by the aluminum alloy surface treatment method of the present invention has a high bonding power.
  • Maximum Tensile Strength Kgf/cm 2
  • Maximum Deformation mm 1 297.47 2.71 2 306.02 2.78 3 374.50 2.55 4 328.88 2.91 5 321.03 3.24
EP13187340.8A 2013-10-04 2013-10-04 Procédé de traitement de surface d'alliage d'aluminium, alliage d'aluminium traité par ce procédé et substrat composite en alliage d'aluminium comprenant l'alliage d'aluminium Withdrawn EP2857559A1 (fr)

Priority Applications (1)

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EP13187340.8A EP2857559A1 (fr) 2013-10-04 2013-10-04 Procédé de traitement de surface d'alliage d'aluminium, alliage d'aluminium traité par ce procédé et substrat composite en alliage d'aluminium comprenant l'alliage d'aluminium

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EP13187340.8A EP2857559A1 (fr) 2013-10-04 2013-10-04 Procédé de traitement de surface d'alliage d'aluminium, alliage d'aluminium traité par ce procédé et substrat composite en alliage d'aluminium comprenant l'alliage d'aluminium

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105506703A (zh) * 2015-11-25 2016-04-20 广东长盈精密技术有限公司 金属塑胶复合体的制备方法
CN105926018A (zh) * 2016-07-12 2016-09-07 长春奥生汽车零部件有限责任公司 一种铝合金的表面强化处理方法
CN106801242A (zh) * 2016-07-11 2017-06-06 南京理工大学 快速制备大面积高度有序大孔间距多孔阳极氧化铝膜的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW391988B (en) 1998-07-29 2000-06-01 Defence Dept Chung Shan Inst Improved method for surface treatment of aluminum alloy
US20130164555A1 (en) * 2011-12-23 2013-06-27 Fih (Hong Kong) Limited Surface treatment method for alumninum or alumninum alloy and article manufactured by the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW391988B (en) 1998-07-29 2000-06-01 Defence Dept Chung Shan Inst Improved method for surface treatment of aluminum alloy
US20130164555A1 (en) * 2011-12-23 2013-06-27 Fih (Hong Kong) Limited Surface treatment method for alumninum or alumninum alloy and article manufactured by the same
TW201325905A (zh) 2011-12-23 2013-07-01 Fih Hong Kong Ltd 鋁或鋁合金表面處理方法及製品

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DOMINGO HUERTA-VILCA ET AL: "Anodic treatment of aluminum in nitric acid containing aniline, previous to deposition of polyaniline and its role on corrosion", SYNTHETIC METALS, vol. 140, no. 1, 1 January 2004 (2004-01-01), pages 23 - 27, XP055107204, ISSN: 0379-6779, DOI: 10.1016/S0379-6779(02)01314-0 *
ZUBILLAGA O ET AL: "Synthesis of anodic films in the presence of aniline and TiO2 nanoparticles on AA2024-T3 aluminium alloy", THIN SOLID FILMS, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 517, no. 24, 30 October 2009 (2009-10-30), pages 6742 - 6746, XP026735947, ISSN: 0040-6090, [retrieved on 20090529], DOI: 10.1016/J.TSF.2009.05.039 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105506703A (zh) * 2015-11-25 2016-04-20 广东长盈精密技术有限公司 金属塑胶复合体的制备方法
CN106801242A (zh) * 2016-07-11 2017-06-06 南京理工大学 快速制备大面积高度有序大孔间距多孔阳极氧化铝膜的方法
CN106801242B (zh) * 2016-07-11 2019-02-22 南京理工大学 快速制备大面积高度有序大孔间距多孔阳极氧化铝膜的方法
CN105926018A (zh) * 2016-07-12 2016-09-07 长春奥生汽车零部件有限责任公司 一种铝合金的表面强化处理方法

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