WO2017114292A1 - 铝合金壳体及其制备方法 - Google Patents

铝合金壳体及其制备方法 Download PDF

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Publication number
WO2017114292A1
WO2017114292A1 PCT/CN2016/111568 CN2016111568W WO2017114292A1 WO 2017114292 A1 WO2017114292 A1 WO 2017114292A1 CN 2016111568 W CN2016111568 W CN 2016111568W WO 2017114292 A1 WO2017114292 A1 WO 2017114292A1
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WIPO (PCT)
Prior art keywords
aluminum alloy
electrophoresis
weight
alloy casing
concave
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PCT/CN2016/111568
Other languages
English (en)
French (fr)
Inventor
熊雄
廖重重
陈梁
钟志文
Original Assignee
比亚迪股份有限公司
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Filing date
Publication date
Application filed by 比亚迪股份有限公司 filed Critical 比亚迪股份有限公司
Priority to EP16881081.0A priority Critical patent/EP3399851A4/en
Publication of WO2017114292A1 publication Critical patent/WO2017114292A1/zh
Priority to US16/020,416 priority patent/US20180305838A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/22—Removing surface-material, e.g. by engraving, by etching
    • B44C1/222—Removing surface-material, e.g. by engraving, by etching using machine-driven mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/22—Removing surface-material, e.g. by engraving, by etching
    • B44C1/228—Removing surface-material, e.g. by engraving, by etching by laser radiation
    • 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
    • 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
    • C25D11/12—Anodising more than once, e.g. in different baths
    • 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
    • C25D11/20—Electrolytic after-treatment
    • 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
    • C25D11/20—Electrolytic after-treatment
    • C25D11/22—Electrolytic after-treatment for colouring layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/04—Electrophoretic coating characterised by the process with organic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • 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
    • C25D11/14—Producing integrally coloured layers

Definitions

  • the invention belongs to the technical field of electronic products, and in particular, to an aluminum alloy casing and a preparation method thereof.
  • the main purpose of surface treatment of the metal casing of electronic products is to decorate and protect the two aspects.
  • anodizing, micro-arc oxidation and hard anodizing of the surface of the metal casing Both of them can achieve the above two effects, but in terms of decoration, the treated metal casing has a single decorative appearance and a single texture.
  • the metal casing obtained by the above surface treatment technology has a single decorative appearance and a single texture. It is necessary to develop an aluminum alloy casing having a good decorative appearance and a three-dimensional texture and a preparation method thereof.
  • the invention solves the problems of single appearance and single texture of the appearance of the mobile phone casing in the prior art, and aims to provide an aluminum alloy casing and a preparation method thereof, the aluminum alloy casing having a convex and concave three-dimensional texture and having high light Convex and non-high gloss concave.
  • an outer surface of the aluminum alloy case has a convex portion and a concave portion, and a convex portion oxide film and a convex portion electrophoretic decorative layer are sequentially formed on the convex portion, the concave portion having a concave oxide film or a recessed electrophoretic decorative layer, the surface of the convex electrophoretic decorative layer having a gloss of 90-105, the surface of the concave oxide film having a gloss of 5-25 or the surface of the concave electrophoretic decorative layer having a thickness of 0.5-5 Gloss
  • the difference in height between the convex portion and the concave portion is 0.05-0.2 mm.
  • the convex oxide film and the concave oxide film have different colors.
  • the invention also provides a preparation method of an aluminum alloy shell, wherein the preparation method comprises:
  • Step a performing first anodization on the surface of the aluminum alloy shell substrate
  • Step b forming an electrophoretic decorative layer on the surface of the first anodized aluminum alloy shell substrate by the first electrophoresis;
  • Step c performing mechanical polishing on the surface of the aluminum alloy shell substrate after the first electrophoresis treatment
  • Step d engraving a textured pattern having a convex and concave effect on the surface of the mechanically polished aluminum alloy casing by laser engraving;
  • Step e performing second electrophoresis or second anodization or hard anodization or micro-arc oxidation on the textured portion on the surface of the aluminum alloy shell substrate.
  • the first anodizing and/or the second anodizing comprises pretreating the surface of the aluminum alloy casing substrate to form an anode film by anodization.
  • the pretreatment comprises: performing alkali etching for 3-20 s at 50-70 ° C using 50-60 g/L sodium hydroxide, and neutralizing at 15-25 ° C using 200-300 ml/L nitric acid 10 -20s, chemical polishing with 650-750ml/L phosphoric acid and 350-250ml/L sulfuric acid at 90 ° C for 5-20s.
  • the anodizing comprises oxidizing the surface of the aluminum alloy shell substrate at an anode voltage of 13-17 V, 10-21 ° C for 15-50 min using 190-200 g/L of sulfuric acid.
  • the first electrophoresis and/or the second electrophoresis comprises electrophoresis using an electrophoresis liquid having a pH of 7-9 at a temperature of 28-32 ° C and a voltage of 140-200 V for 1-3 min.
  • the hard anodization comprises oxidation at 5-12 ° C for 25-50 min using a hard anodizing solution.
  • the hard anodizing solution contains 170-270 g/L of sulfuric acid and 8-20 g/L of oxalic acid.
  • the micro-arc oxidation comprises oxidizing at 40-30 ° C for 40-100 min using a micro-arc oxidation electrolyte.
  • the micro-arc oxidation electrolyte contains 0.02-0.05 mol/L of sodium silicate and 0.03-0.07 mol/L of sodium hydroxide.
  • the present invention also provides an aluminum alloy casing which is produced by the method for producing an aluminum alloy casing of the present invention.
  • the first anodizing treatment is first performed on the surface of the aluminum alloy shell substrate, and then the electrophoretic decorative layer is formed by the first electrophoresis, and then the surface of the aluminum alloy shell substrate after the first electrophoresis is mechanically polished, and then the radium is used.
  • the carving engraves a texture pattern on the surface of the aluminum alloy shell substrate to form a convex and concave effect by performing second electrophoresis or second anodization or hard anodization or micro-arc oxidation on the texture pattern portion on the surface of the aluminum alloy shell substrate.
  • an aluminum alloy casing having a convex and concave three-dimensional texture and having a high-gloss convex surface and a non-high-gloss concave surface is produced.
  • An aluminum alloy casing wherein an outer surface of the aluminum alloy casing has a convex portion and a concave portion,
  • the convex portion is sequentially formed with a convex portion oxide film and a convex portion electrophoretic decorative layer, wherein the concave portion has a concave oxide film or a concave portion electrophoretic decorative layer, and the surface of the convex portion electrophoretic decorative layer has a gloss of 90-105.
  • the surface of the recessed oxide film has a gloss of 5 to 25 or the surface of the recessed electrophoretic decorative layer has a gloss of 0.5 to 5.
  • the inventors have found that by forming the convex portion and the concave portion on the outer surface of the aluminum alloy casing, the aluminum alloy casing can have a convex and concave three-dimensional texture, and in addition, by polishing the convex oxide film formed on the surface of the convex portion, The surface of the convex oxide film exhibits a high light effect.
  • the gloss is such that the surface of the oxide film is close to the mirror surface, and can be measured by a method known in the art, and can be measured, for example, using a gloss meter.
  • a method of forming a convex portion and a concave portion on an outer surface of an aluminum alloy case and a method of forming a convex portion oxide film on the convex portion and forming a concave portion oxide film on the concave portion are as described in an aluminum alloy case preparing method described later. description.
  • the method of producing an aluminum alloy casing in a preferred case, different colors may be formed in the convex oxide film and the concave oxide film.
  • the aluminum alloy casing can have different color film layers by forming different colors in the convex oxide film and the concave oxide film.
  • a method of preparing an aluminum alloy casing according to the present invention comprising:
  • Step a performing first anodization on the surface of the aluminum alloy shell substrate
  • Step b forming an electrophoretic decorative layer on the surface of the first anodized aluminum alloy shell substrate by the first electrophoresis;
  • Step c performing mechanical polishing on the surface of the aluminum alloy shell substrate after the first electrophoresis treatment
  • Step d engraving a textured pattern having a convex and concave effect on the surface of the mechanically polished aluminum alloy casing by laser engraving;
  • Step e performing second electrophoresis or second anodization or hard anodization or micro-arc oxidation on the textured portion on the surface of the aluminum alloy shell substrate.
  • the surface of the aluminum alloy casing base after the first electrophoresis is mechanically polished after the first electrophoresis forms the electrophoretic decorative layer.
  • the anodized film layer on the surface of the aluminum alloy shell substrate is polished by a mechanical polishing machine, so that the thickness of the anodized film layer is reduced by about 2 ⁇ m as a whole, so that the surface of the anodized film exhibits a bright reflective effect, forming a high gloss surface with high gloss.
  • the laser engraving is carried out, and the surface of the surface is made to have a convex-concave difference of 0.05-0.2 mm by the laser engraving, thereby producing the effect of the three-dimensional texture of the concavity.
  • the aluminum alloy casing base used in the present invention is not particularly limited, and various aluminum alloy casing bodies of industrial standard 1000-7000 series, die-cast aluminum alloy or die-cast aluminum alloy may be used; the aluminum alloy described in the present invention
  • the housing base is an aluminum alloy housing body of various shapes and structures commonly used by those skilled in the art, and the invention is not particularly limited.
  • the various shapes and structures of the aluminum alloy casing base can be completed by machining.
  • the aluminum alloy casing of the present invention can be used for a casing of a mobile phone, a tablet computer, an electron beam or the like.
  • the surface of the aluminum alloy casing base may be sandblasted or brushed before the first anodization of the surface of the aluminum alloy casing base.
  • the blasting can be carried out by a method known in the art.
  • the surface of the aluminum alloy shell substrate can be polished by a sander, and the surface of the aluminum alloy shell substrate can be made with a ceramic sand of 80-400 mesh at 0.1-0.24 MPa.
  • Sandblasting treatment makes the surface of the aluminum alloy shell substrate feel sandy.
  • the wire drawing treatment can be carried out by a method known in the art.
  • the surface of the base material of the aluminum alloy casing can be pulled out from coarse to fine with a wire drawing machine of 400-1200 by a wire drawing machine.
  • the first anodizing and/or the second anodizing may include pre-treating the surface of the aluminum alloy casing substrate to form an anode film by anodization.
  • the thickness of the formed anode film is usually 6 to 10 ⁇ m.
  • the purpose of the pretreatment is to clean the surface of the aluminum alloy casing base to ensure a uniform anode is formed on the surface of the aluminum alloy casing base by anodization.
  • the membrane may include: alkali etching with 50-60 g/L sodium hydroxide at 50-70 ° C for 3-20 s, using 200-300 ml/L nitric acid for neutralization at 15-25 ° C for 10-20 s, using The chemical polishing liquid containing 650-750 ml/L of phosphoric acid and 350-250 ml/L of sulfuric acid was chemically polished at 90-95 ° C for 5-20 s.
  • the method of anodizing may use an anodizing method well known in the art, and preferably, the anodizing may include using aluminum at 190-200 g/L of sulfuric acid.
  • the surface of the alloy casing substrate was oxidized for 15-50 minutes at an anode voltage of 13-17 V at 10-21 °C.
  • an electrophoretic decorative layer is formed on the surface of the aluminum alloy casing base by the first electrophoresis and/or the second electrophoresis, so that the aluminum alloy casing can be effectively protected and decorated.
  • the first electrophoresis and/or the second electrophoresis may include performing electrophoresis for 1-3 min at a temperature of 28-32 ° C and a voltage of 140-200 V using an electrophoresis liquid having a pH of 7-9.
  • the electrophoresis liquid can use an electrophoretic liquid used in the art as long as it can form an electrophoretic decorative layer on the surface of the aluminum alloy casing base.
  • matte lacquer (WNO-1) from Japan Kiyomizu Co., Ltd. and Japan Shimizu Co., Ltd. can be used.
  • the varnish (NNO-4) of the club is a mixture of 7:3 by weight (the solid content of the electrophoresis liquid is 8-14% by weight).
  • the varnish (NNO-4) in the electrophoretic solvent contains: 50% by weight of acrylic resin, 6% by weight of ethylene glycol monobutyl ether, 20% by weight of ethylene glycol monoisobutyl ether, 18% by weight of diethylene glycol butyraldehyde, and 6% by weight of other components; matt paint (WNO -1) contains: 50% by weight of an acrylic resin, 10% by weight of ethylene glycol monobutyl ether, and 40% by weight of other components.
  • various conventional laser engravings in the art can be used to engrave a texture pattern having a convex-concave effect on the surface of the mechanically polished aluminum alloy casing base by a laser engraving method.
  • the method is, for example, engraving using a laser laser engraving machine to expose the surface of the aluminum alloy casing base to the aluminum alloy substrate to form a texture pattern having a depth of 0.1 mm.
  • the hard anodization may include oxidation at 5-12 ° C for 25-50 min using a hard anodizing solution. More preferably, the hard anodizing solution may contain 170-270 g/L of sulfuric acid and 8-20 g/L of oxalic acid.
  • the electrical parameters of the hard anodization include: a pulse wave type is a forward square wave pulse, a duty ratio of 60-80%, a frequency of 500-1000 Hz, and a current density of 3-7 A/dm 2 .
  • the micro-arc oxidation may include oxidation at 40-30 ° C for 40-100 min using a micro-arc oxidation electrolyte. More preferably, the micro-arc oxidation electrolyte may contain 0.02-0.05 mol/L of sodium silicate and 0.03-0.07 mol/L of sodium hydroxide.
  • the oxidation forward voltage of micro-arc oxidation can be 400-600V.
  • a die-cast aluminum alloy back shell substrate (purchased from BYD Co., Ltd.) for a P8 type mobile phone was used as the aluminum alloy case base material of this example.
  • the aluminum alloy shell substrate was subjected to alkali etching for 10 s at a concentration of 55 g/L sodium hydroxide solution at 50 ° C, and then washed twice with deionized water; then, at 15 ° C, at a concentration of 250 ml/L.
  • An anodic film is formed on the surface of the aluminum alloy casing substrate after the above cleaning and drying by anodization.
  • the conditions were as follows: sulfuric acid having a concentration of 190 g/L was used as a bath, the anode voltage was 15 V, the temperature was 19 ° C, and the oxidation time was 5 min.
  • An electrophoretic decorative layer is formed on the surface of the anodized aluminum alloy shell substrate by electrophoresis, the electrophoresis conditions are: a temperature of 30 ° C, a voltage of 160 V, a time of 2 min, a pH of 7.8; and an electrophoresis liquid for the Japanese water purification system
  • the electrophoresis liquid (the solid content of the electrophoresis liquid is 13% by weight) in which the matte paint (WNO-1) of the club and the varnish (NNO-4) of Japan Shimizu Corporation are mixed at a weight ratio of 7:3.
  • the varnish (NNO-4) in a liquid solvent contains 50% by weight of an acrylic resin, 6% by weight of ethylene glycol monobutyl ether, 20% by weight of ethylene glycol monoisobutyl ether, and 18% by weight of diethylene glycol butyraldehyde. And other components of 6% by weight; matte lacquer (WNO-1) contains: 50% by weight of acrylic resin, 10% by weight of ethylene glycol monobutyl ether, and 40% by weight of other components.
  • the film layer on the surface of the aluminum alloy shell substrate after electrophoresis treatment is polished by a mechanical polishing machine, so that the thickness of the film layer is reduced by about 2 ⁇ m as a whole, so that the surface of the film exhibits a bright reflective effect.
  • the laser engraving machine is used to engrave the surface of the mechanically polished aluminum alloy casing base, so that the surface of the aluminum alloy casing base is exposed to the aluminum alloy substrate to form a texture pattern having a concave-concave effect with a depth of 0.05 mm.
  • the engraved aluminum alloy shell substrate was subjected to alkali etching at a concentration of 55 g/L sodium hydroxide solution at 50 °C. After 10 s, it was washed twice with deionized water; then, after neutralizing for 4 min at 15 ° C in a concentration of 250 ml/L of nitric acid, it was washed twice with deionized water.
  • An electrophoretic decorative layer was formed on the surface of the cleaned aluminum alloy casing substrate by electrophoresis under the conditions of a temperature of 30 ° C, a voltage of 160 V, a time of 2 min, and a pH of 7.8; and the electrophoresis liquid was supplied by Japan Shimizu Corporation
  • the electrophoretic liquid (the solid content of the electrophoresis liquid is 13% by weight) in which the matte paint (WNO-1) and the varnish (NNO-4) of Japan Shimizu Co., Ltd. are mixed at a weight ratio of 7:3.
  • the solvent varnish (NNO-4) contains: 50% by weight of an acrylic resin, 6% by weight of ethylene glycol monobutyl ether, 20% by weight of ethylene glycol monoisobutyl ether, 18% by weight of diethylene glycol butyraldehyde, and The other component was 6% by weight; the matt lacquer (WNO-1) contained 50% by weight of an acrylic resin, 10% by weight of ethylene glycol monobutyl ether, and 40% by weight of other components.
  • the aluminum alloy casing of the present invention is obtained.
  • a die-cast aluminum alloy back shell substrate (purchased from BYD Co., Ltd.) for a P8 type mobile phone was used as the aluminum alloy case base material of this example.
  • the aluminum alloy shell substrate was alkali-etched at 70 ° C for 20 s in a 60 g/L sodium hydroxide aqueous solution, and then washed twice with deionized water; then, at 20 ° C, at a concentration of 300 ml/L.
  • An anodic film is formed on the surface of the aluminum alloy casing substrate after the above cleaning and drying by anodization.
  • the conditions were as follows: sulfuric acid having a concentration of 195 g/L was used as a bath, the anode voltage was 17 V, the temperature was 10 ° C, and the oxidation time was 50 min.
  • An electrophoretic decorative layer is formed on the surface of the anodized aluminum alloy shell substrate by electrophoresis, the electrophoresis conditions are: a temperature of 32 ° C, a voltage of 200 V, a time of 1 min, a pH of 7; the electrophoresis liquid is a Japanese water purification system
  • the electrophoresis liquid (the solid content of the electrophoresis liquid is 13% by weight) in which the matte paint (WNO-1) of the club and the varnish (NNO-4) of Japan Shimizu Corporation are mixed at a weight ratio of 7:3.
  • the varnish (NNO-4) in a liquid solvent contains 50% by weight of an acrylic resin, 6% by weight of ethylene glycol monobutyl ether, 20% by weight of ethylene glycol monoisobutyl ether, and 18% by weight of diethylene glycol butyraldehyde. And other components of 6% by weight; matte lacquer (WNO-1) contains: 50% by weight of acrylic resin, 10% by weight of ethylene glycol monobutyl ether, and 40% by weight of other components.
  • the film layer on the surface of the aluminum alloy shell substrate after electrophoresis treatment is polished by a mechanical polishing machine, so that the thickness of the film layer is reduced by about 2 ⁇ m as a whole, so that the surface of the film exhibits a bright reflective effect.
  • the laser engraving machine is used to engrave the surface of the mechanically polished aluminum alloy casing base, so that the surface of the aluminum alloy casing base is exposed to the aluminum alloy substrate to form a texture pattern having a concave-concave effect with a depth of 0.2 mm.
  • the engraved aluminum alloy shell substrate was subjected to alkali etching for 20 s at a concentration of 60 g/L sodium hydroxide aqueous solution at 70 ° C, and then washed twice with deionized water; then, at 25 ° C, at a concentration of After neutralizing for 4 min in 300 ml/L of nitric acid, it was washed twice with deionized water.
  • An electrophoretic decorative layer is formed on the surface of the cleaned aluminum alloy casing substrate by electrophoresis under the conditions of a temperature of 32 ° C, a voltage of 200 V, a time of 1 min, and a pH of 7; the electrophoresis liquid is from Japan Shimizu Corporation
  • the electrophoretic liquid (the solid content of the electrophoresis liquid is 13% by weight) in which the matte paint (WNO-1) and the varnish (NNO-4) of Japan Shimizu Co., Ltd. are mixed at a weight ratio of 7:3.
  • the solvent varnish (NNO-4) contains: 50% by weight of an acrylic resin, 6% by weight of ethylene glycol monobutyl ether, 20% by weight of ethylene glycol monoisobutyl ether, 18% by weight of diethylene glycol butyraldehyde, and The other component was 6% by weight; the matt lacquer (WNO-1) contained 50% by weight of an acrylic resin, 10% by weight of ethylene glycol monobutyl ether, and 40% by weight of other components.
  • the aluminum alloy casing of the present invention is obtained.
  • a die-cast aluminum alloy back shell substrate (purchased from BYD Co., Ltd.) for a P8 type mobile phone was used as the aluminum alloy case base material of this example.
  • the aluminum alloy shell substrate was subjected to alkali etching for 10 s at a concentration of 55 g/L sodium hydroxide aqueous solution at 50 ° C, and then washed twice with deionized water; then, at 25 ° C, at a concentration of 250 ml/L.
  • An anodic film is formed on the surface of the aluminum alloy casing substrate after the above cleaning and drying by anodization.
  • the conditions were as follows: sulfuric acid having a concentration of 190 g/L was used as a bath, the anode voltage was 15 V, the temperature was 19 ° C, and the oxidation time was 5 min.
  • An electrophoretic decorative layer is formed on the surface of the anodized aluminum alloy shell substrate by electrophoresis, the electrophoresis conditions are: a temperature of 30 ° C, a voltage of 160 V, a time of 2 min, a pH of 7.8; and an electrophoresis liquid for the Japanese water purification system
  • the electrophoresis liquid (the solid content of the electrophoresis liquid is 13% by weight) in which the matte paint (WNO-1) of the club and the varnish (NNO-4) of Japan Shimizu Corporation are mixed at a weight ratio of 7:3.
  • the varnish (NNO-4) in a liquid solvent contains 50% by weight of an acrylic resin, 6% by weight of ethylene glycol monobutyl ether, 20% by weight of ethylene glycol monoisobutyl ether, and 18% by weight of diethylene glycol butyraldehyde. And other components of 6% by weight; matte lacquer (WNO-1) contains: 50% by weight of acrylic resin, 10% by weight of ethylene glycol monobutyl ether, and 40% by weight of other components.
  • the film layer on the surface of the aluminum alloy shell substrate after electrophoresis treatment is polished by a mechanical polishing machine, so that the thickness of the film layer is reduced by about 2 ⁇ m as a whole, so that the surface of the film exhibits a bright reflective effect.
  • the surface of the mechanically polished aluminum alloy shell substrate is engraved using a laser laser engraving machine to make the aluminum alloy shell substrate
  • the surface of the aluminum alloy substrate was exposed to form a textured pattern having a convex-concave effect with a depth of 0.1 mm.
  • the engraved aluminum alloy shell substrate was subjected to alkali etching for 10 s at a concentration of 55 g/L sodium hydroxide solution at 50 ° C, and then washed twice with deionized water; then, at 25 ° C, at a concentration of After neutralizing for 4 min in 250 ml/L of nitric acid, it was washed twice with deionized water.
  • An anodic film is formed on the surface of the cleaned aluminum alloy casing substrate by anodization.
  • the conditions were as follows: sulfuric acid having a concentration of 190 g/L was used as a bath, the anode voltage was 15 V, the temperature was 19 ° C, and the oxidation time was 5 min.
  • the aluminum alloy casing of the present invention is obtained.
  • a die-cast aluminum alloy back shell substrate (purchased from BYD Co., Ltd.) for a P8 type mobile phone was used as the aluminum alloy case base material of this example.
  • the aluminum alloy shell substrate was subjected to alkali etching for 10 s at a concentration of 55 g/L sodium hydroxide aqueous solution at 50 ° C, and then washed twice with deionized water; then, at 25 ° C, at a concentration of 250 ml/L.
  • An anodic film is formed on the surface of the aluminum alloy casing substrate after the above cleaning and drying by anodization.
  • the conditions were as follows: sulfuric acid having a concentration of 190 g/L was used as a bath, the anode voltage was 15 V, the temperature was 19 ° C, and the oxidation time was 5 min.
  • An electrophoretic decorative layer is formed on the surface of the anodized aluminum alloy shell substrate by electrophoresis, the electrophoresis conditions are: a temperature of 30 ° C, a voltage of 160 V, a time of 2 min, a pH of 7.8; and an electrophoresis liquid for the Japanese water purification system
  • the electrophoresis liquid (the solid content of the electrophoresis liquid is 13% by weight) in which the matte paint (WNO-1) of the club and the varnish (NNO-4) of Japan Shimizu Corporation are mixed at a weight ratio of 7:3.
  • the varnish (NNO-4) in a liquid solvent contains 50% by weight of an acrylic resin, 6% by weight of ethylene glycol monobutyl ether, 20% by weight of ethylene glycol monoisobutyl ether, and 18% by weight of diethylene glycol butyraldehyde. And other components of 6% by weight; matte lacquer (WNO-1) contains: 50% by weight of acrylic resin, 10% by weight of ethylene glycol monobutyl ether, and 40% by weight of other components.
  • the film layer on the surface of the aluminum alloy shell substrate after electrophoresis treatment is polished by a mechanical polishing machine, so that the thickness of the film layer is reduced by about 2 ⁇ m as a whole, so that the surface of the film exhibits a bright reflective effect.
  • the laser engraving machine is used to engrave the surface of the mechanically polished aluminum alloy casing base, so that the surface of the aluminum alloy casing base is exposed to the aluminum alloy substrate to form a texture pattern having a convex-concave effect with a depth of 0.1 mm.
  • the engraved aluminum alloy shell substrate was subjected to alkali etching for 10 s at a concentration of 55 g/L sodium hydroxide solution at 50 ° C, and then washed twice with deionized water; then, at 25 ° C, at a concentration of Neutralization in 250 ml/L nitric acid for 4 min After that, it was washed twice with deionized water.
  • the cleaned aluminum alloy casing substrate was oxidized at 10 ° C for 25 min using a hard anodizing solution containing 200 g/L of sulfuric acid and 15 g/L of oxalic acid.
  • the electrical parameters of hard anodization include: the pulse wave pattern is a forward square wave pulse, the duty ratio is 70%, the frequency is 800 Hz, and the current density is 5 A/dm 2 .
  • the aluminum alloy casing of the present invention is obtained.
  • a die-cast aluminum alloy back shell substrate (purchased from BYD Co., Ltd.) for a P8 type mobile phone was used as the aluminum alloy case base material of this example.
  • the aluminum alloy shell substrate was subjected to alkali etching for 10 s at a concentration of 55 g/L sodium hydroxide aqueous solution at 50 ° C, and then washed twice with deionized water; then, at 25 ° C, at a concentration of 250 ml/L.
  • An anodic film is formed on the surface of the aluminum alloy casing substrate after the above cleaning and drying by anodization.
  • the conditions were as follows: sulfuric acid having a concentration of 190 g/L was used as a bath, the anode voltage was 15 V, the temperature was 19 ° C, and the oxidation time was 5 min.
  • An electrophoretic decorative layer is formed on the surface of the anodized aluminum alloy shell substrate by electrophoresis, the electrophoresis conditions are: a temperature of 30 ° C, a voltage of 160 V, a time of 2 min, a pH of 7.8; and an electrophoresis liquid for the Japanese water purification system
  • the electrophoresis liquid (the solid content of the electrophoresis liquid is 13% by weight) in which the matte paint (WNO-1) of the club and the varnish (NNO-4) of Japan Shimizu Corporation are mixed at a weight ratio of 7:3.
  • the varnish (NNO-4) in a liquid solvent contains 50% by weight of an acrylic resin, 6% by weight of ethylene glycol monobutyl ether, 20% by weight of ethylene glycol monoisobutyl ether, and 18% by weight of diethylene glycol butyraldehyde. And other components of 6% by weight; matte lacquer (WNO-1) contains: 50% by weight of acrylic resin, 10% by weight of ethylene glycol monobutyl ether, and 40% by weight of other components.
  • the film layer on the surface of the aluminum alloy shell substrate after electrophoresis treatment is polished by a mechanical polishing machine, so that the thickness of the film layer is reduced by about 2 ⁇ m as a whole, so that the surface of the film exhibits a bright reflective effect.
  • the laser engraving machine is used to engrave the surface of the mechanically polished aluminum alloy casing base, so that the surface of the aluminum alloy casing base is exposed to the aluminum alloy substrate to form a texture pattern having a convex-concave effect with a depth of 0.1 mm.
  • the engraved aluminum alloy shell substrate was subjected to alkali etching for 10 s at a concentration of 55 g/L sodium hydroxide solution at 50 ° C, and then washed twice with deionized water; then, at 25 ° C, at a concentration of After neutralizing for 4 min in 250 ml/L of nitric acid, it was washed twice with deionized water.
  • the cleaned aluminum alloy casing substrate was oxidized at 5 ° C for 30 min using a hard anodizing solution containing 170 g/L of sulfuric acid and 20 g/L of oxalic acid.
  • the electrical parameters of hard anodization include: the pulse wave pattern is a positive square wave pulse, the duty ratio is 80%, the frequency is 500 Hz, and the current density is 3 A/dm 2 .
  • the aluminum alloy casing of the present invention is obtained.
  • a die-cast aluminum alloy back shell substrate (purchased from BYD Co., Ltd.) for a P8 type mobile phone was used as the aluminum alloy case base material of this example.
  • the aluminum alloy shell substrate was subjected to alkali etching for 10 s at a concentration of 55 g/L sodium hydroxide aqueous solution at 50 ° C, and then washed twice with deionized water; then, at 25 ° C, at a concentration of 250 ml/L.
  • An anodic film is formed on the surface of the aluminum alloy casing substrate after the above cleaning and drying by anodization.
  • the conditions were as follows: sulfuric acid having a concentration of 190 g/L was used as a bath, the anode voltage was 15 V, the temperature was 19 ° C, and the oxidation time was 5 min.
  • An electrophoretic decorative layer is formed on the surface of the anodized aluminum alloy shell substrate by electrophoresis, the electrophoresis conditions are: a temperature of 30 ° C, a voltage of 160 V, a time of 2 min, a pH of 7.8; and an electrophoresis liquid for the Japanese water purification system
  • the electrophoresis liquid (the solid content of the electrophoresis liquid is 13% by weight) in which the matte paint (WNO-1) of the club and the varnish (NNO-4) of Japan Shimizu Corporation are mixed at a weight ratio of 7:3.
  • the varnish (NNO-4) in a liquid solvent contains 50% by weight of an acrylic resin, 6% by weight of ethylene glycol monobutyl ether, 20% by weight of ethylene glycol monoisobutyl ether, and 18% by weight of diethylene glycol butyraldehyde. And other components of 6% by weight; matte lacquer (WNO-1) contains: 50% by weight of acrylic resin, 10% by weight of ethylene glycol monobutyl ether, and 40% by weight of other components.
  • the film layer on the surface of the aluminum alloy shell substrate after electrophoresis treatment is polished by a mechanical polishing machine, so that the thickness of the film layer is reduced by about 2 ⁇ m as a whole, so that the surface of the film exhibits a bright reflective effect.
  • the laser engraving machine is used to engrave the surface of the mechanically polished aluminum alloy casing base, so that the surface of the aluminum alloy casing base is exposed to the aluminum alloy substrate to form a texture pattern having a convex-concave effect with a depth of 0.1 mm.
  • the engraved aluminum alloy shell substrate was subjected to alkali etching for 10 s at a concentration of 55 g/L sodium hydroxide solution at 50 ° C, and then washed twice with deionized water; then, at 25 ° C, at a concentration of After neutralizing for 4 min in 250 ml/L of nitric acid, it was washed twice with deionized water.
  • the cleaned aluminum alloy casing substrate was oxidized at 12 ° C for 25 min using a hard anodizing solution containing 270 g/L of sulfuric acid and 20 g/L of oxalic acid.
  • the electrical parameters of hard anodization include: the pulse wave pattern is a positive square wave pulse, the duty ratio is 60%, the frequency is 1000 Hz, and the current density is 7 A/dm 2 .
  • the aluminum alloy casing of the present invention is obtained.
  • a die-cast aluminum alloy back shell substrate (purchased from BYD Co., Ltd.) for a P8 type mobile phone was used as the aluminum alloy case base material of this example.
  • the aluminum alloy shell substrate was subjected to alkali etching for 10 s at a concentration of 55 g/L sodium hydroxide aqueous solution at 50 ° C, and then washed twice with deionized water; then, at 25 ° C, at a concentration of 250 ml/L.
  • An anodic film is formed on the surface of the aluminum alloy casing substrate after the above cleaning and drying by anodization.
  • the conditions were as follows: sulfuric acid having a concentration of 190 g/L was used as a bath, the anode voltage was 15 V, the temperature was 19 ° C, and the oxidation time was 5 min.
  • An electrophoretic decorative layer is formed on the surface of the anodized aluminum alloy shell substrate by electrophoresis, the electrophoresis conditions are: a temperature of 30 ° C, a voltage of 160 V, a time of 2 min, a pH of 7.8; and an electrophoresis liquid for the Japanese water purification system
  • the electrophoresis liquid (the solid content of the electrophoresis liquid is 13% by weight) in which the matte paint (WNO-1) of the club and the varnish (NNO-4) of Japan Shimizu Corporation are mixed at a weight ratio of 7:3.
  • the varnish (NNO-4) in a liquid solvent contains 50% by weight of an acrylic resin, 6% by weight of ethylene glycol monobutyl ether, 20% by weight of ethylene glycol monoisobutyl ether, and 18% by weight of diethylene glycol butyraldehyde. And other components of 6% by weight; matte lacquer (WNO-1) contains: 50% by weight of acrylic resin, 10% by weight of ethylene glycol monobutyl ether, and 40% by weight of other components.
  • the film layer on the surface of the aluminum alloy shell substrate after electrophoresis treatment is polished by a mechanical polishing machine, so that the thickness of the film layer is reduced by about 2 ⁇ m as a whole, so that the surface of the film exhibits a bright reflective effect.
  • the laser engraving machine is used to engrave the surface of the mechanically polished aluminum alloy casing base, so that the surface of the aluminum alloy casing base is exposed to the aluminum alloy substrate to form a texture pattern having a convex-concave effect with a depth of 0.1 mm.
  • the engraved aluminum alloy shell substrate was subjected to alkali etching for 10 s at a concentration of 55 g/L sodium hydroxide solution at 50 ° C, and then washed twice with deionized water; then, at 25 ° C, at a concentration of After neutralizing for 4 min in 250 ml/L of nitric acid, it was washed twice with deionized water.
  • the cleaned aluminum alloy casing substrate was oxidized for 40 min at 25 ° C and an oxidation forward voltage of 500 V using a micro-arc oxidation electrolyte containing 0.03 mol/L sodium silicate and 0.05 mol/L sodium hydroxide.
  • the aluminum alloy casing of the present invention is obtained.
  • a die-cast aluminum alloy back shell substrate (purchased from BYD Co., Ltd.) for a P8 type mobile phone was used as the aluminum alloy case base material of this example.
  • the aluminum alloy shell substrate was subjected to alkali etching for 10 s at a concentration of 55 g/L sodium hydroxide aqueous solution at 50 ° C, and then washed twice with deionized water; then, at 25 ° C, at a concentration of 250 ml/L.
  • An anodic film is formed on the surface of the aluminum alloy casing substrate after the above cleaning and drying by anodization.
  • the conditions were as follows: sulfuric acid having a concentration of 190 g/L was used as a bath, the anode voltage was 15 V, the temperature was 19 ° C, and the oxidation time was 5 min.
  • An electrophoretic decorative layer is formed on the surface of the anodized aluminum alloy shell substrate by electrophoresis, the electrophoresis conditions are: a temperature of 30 ° C, a voltage of 160 V, a time of 2 min, a pH of 7.8; and an electrophoresis liquid for the Japanese water purification system
  • the electrophoresis liquid (the solid content of the electrophoresis liquid is 13% by weight) in which the matte paint (WNO-1) of the club and the varnish (NNO-4) of Japan Shimizu Corporation are mixed at a weight ratio of 7:3.
  • the varnish (NNO-4) in a liquid solvent contains 50% by weight of an acrylic resin, 6% by weight of ethylene glycol monobutyl ether, 20% by weight of ethylene glycol monoisobutyl ether, and 18% by weight of diethylene glycol butyraldehyde. And other components of 6% by weight; matte lacquer (WNO-1) contains: 50% by weight of acrylic resin, 10% by weight of ethylene glycol monobutyl ether, and 40% by weight of other components.
  • the film layer on the surface of the aluminum alloy shell substrate after electrophoresis treatment is polished by a mechanical polishing machine, so that the thickness of the film layer is reduced by about 2 ⁇ m as a whole, so that the surface of the film exhibits a bright reflective effect.
  • the laser engraving machine is used to engrave the surface of the mechanically polished aluminum alloy casing base, so that the surface of the aluminum alloy casing base is exposed to the aluminum alloy substrate to form a texture pattern having a convex-concave effect with a depth of 0.1 mm.
  • the engraved aluminum alloy shell substrate was subjected to alkali etching for 10 s at a concentration of 55 g/L sodium hydroxide solution at 50 ° C, and then washed twice with deionized water; then, at 25 ° C, at a concentration of After neutralizing for 4 min in 250 ml/L of nitric acid, it was washed twice with deionized water.
  • the cleaned aluminum alloy casing substrate was oxidized at 30 ° C for 30 min at an oxidation forward voltage of 400 V using a micro-arc oxidation electrolyte containing 0.02 mol/L sodium silicate and 0.07 mol/L sodium hydroxide.
  • the aluminum alloy casing of the present invention is obtained.
  • a die-cast aluminum alloy back shell substrate (purchased from BYD Co., Ltd.) for a P8 type mobile phone was used as the aluminum alloy case base material of this example.
  • the aluminum alloy shell substrate was subjected to alkali etching for 10 s at a concentration of 55 g/L sodium hydroxide aqueous solution at 50 ° C, and then washed twice with deionized water; then, at 25 ° C, at a concentration of 250 ml/L.
  • An anodic film is formed on the surface of the aluminum alloy casing substrate after the above cleaning and drying by anodization.
  • the conditions were as follows: sulfuric acid having a concentration of 190 g/L was used as a bath, the anode voltage was 15 V, the temperature was 19 ° C, and the oxidation time was 5 min.
  • An electrophoretic decorative layer is formed on the surface of the anodized aluminum alloy shell substrate by electrophoresis, the electrophoresis conditions are: a temperature of 30 ° C, a voltage of 160 V, a time of 2 min, a pH of 7.8; and an electrophoresis liquid for the Japanese water purification system
  • the electrophoresis liquid (the solid content of the electrophoresis liquid is 13% by weight) in which the matte paint (WNO-1) of the club and the varnish (NNO-4) of Japan Shimizu Corporation are mixed at a weight ratio of 7:3.
  • the varnish (NNO-4) in a liquid solvent contains 50% by weight of an acrylic resin, 6% by weight of ethylene glycol monobutyl ether, 20% by weight of ethylene glycol monoisobutyl ether, and 18% by weight of diethylene glycol butyraldehyde. And other components of 6% by weight; matte lacquer (WNO-1) contains: 50% by weight of acrylic resin, 10% by weight of ethylene glycol monobutyl ether, and 40% by weight of other components.
  • the film layer on the surface of the aluminum alloy shell substrate after electrophoresis treatment is polished by a mechanical polishing machine, so that the thickness of the film layer is reduced by about 2 ⁇ m as a whole, so that the surface of the film exhibits a bright reflective effect.
  • the laser engraving machine is used to engrave the surface of the mechanically polished aluminum alloy casing base, so that the surface of the aluminum alloy casing base is exposed to the aluminum alloy substrate to form a texture pattern having a convex-concave effect with a depth of 0.1 mm.
  • the engraved aluminum alloy shell substrate was subjected to alkali etching for 10 s at a concentration of 55 g/L sodium hydroxide solution at 50 ° C, and then washed twice with deionized water; then, at 25 ° C, at a concentration of After neutralizing for 4 min in 250 ml/L of nitric acid, it was washed twice with deionized water.
  • the cleaned aluminum alloy casing substrate was oxidized for 60 min at 20 ° C and an oxidation forward voltage of 600 V using a micro-arc oxidation electrolyte containing 0.05 mol/L sodium silicate and 0.03 mol/L sodium hydroxide.
  • the aluminum alloy casing of the present invention is obtained.
  • Example 1-9 The gloss of the surface of the aluminum alloy casing obtained in Example 1-9 was tested using a gloss meter (BKY Micro Gloss Meter A-4460, Germany), and the results are shown in Table 1.
  • the sample was placed in a precision high temperature test chamber (Hongling HRHL45), heated at 85 ° C for 240 hours, and then placed at room temperature for 2 hours to observe whether the sample was peeled off, deformed, cracked and changed in color, such as no shedding, Deformations, cracks, and color changes indicate that the sample is acceptable.
  • Hongling HRHL45 precision high temperature test chamber
  • the sample was placed in a constant temperature and humidity tester (Taiwan Qingsheng, THS-2001), placed at -40 ° C for 240 hours, and then placed at room temperature for 2 hours to observe whether the sample was peeled off, deformed, cracked and colored. Changes, such as no shedding, deformation, cracks, and color changes, indicate that the sample is acceptable.
  • the sample was placed in a constant temperature and humidity tester (Taiwan Qingsheng, HTS-400) with a humidity of 90% and a temperature of 60 ° C for 96 hours, and then left at room temperature for 2 hours to observe whether the sample was peeled off or deformed. Cracks and color changes, such as no shedding, deformation, cracks, and color changes, indicate that the sample is acceptable.
  • a constant temperature and humidity tester Teaiwan Qingsheng, HTS-400
  • the sample was placed in a thermal shock tester (Hongling HTS-400), placed at -40 ° C for 1 hour, then the temperature was converted to 85 ° C, placed for 1 hour, and the conversion time was 15 seconds. 12 cycles (24 hours). Observe the appearance of the sample for peeling, deformation, cracks and color changes. If there is no shedding, deformation, cracks and color changes, the sample is qualified.
  • Table 1 shows the performance test results of the aluminum alloy shells obtained in Examples 1 to 9.
  • the surface of the aluminum alloy casing provided by the invention is not easy to wear, the surface layer is not easy to fall off, and the aluminum is improved.
  • the durability of the alloy casing and the convex and concave texture pattern impart an excellent appearance effect to the aluminum alloy casing, and have a hierarchical and convex three-dimensional texture, so that the aluminum alloy casing provided by the invention has both the advantages of appearance and durability.
  • the aluminum alloy casing obtained in Examples 1-9 was mechanically polished to have a high-brightness and non-high-brightness effect on the surface.

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Abstract

一种铝合金壳体，其中，铝合金壳体的外表面具有凸部和凹部，凸部上依次形成有凸部氧化膜和凸部电泳装饰层，凹部具有氧化膜或凹部电泳装饰层，凸部具有电泳装饰层的表面具有90-105的光泽度，凹部氧化膜的表面具有5-25的光泽度或凹部电泳装饰层的表面具有0.5-5的光泽度。还公开了一种铝合金壳体的制备方法。

Description

铝合金壳体及其制备方法 技术领域
本发明属于电子产品技术领域，具体而言，本发明涉及一种铝合金壳体及其制备方法。
背景技术
随着电子科技的发展，越来越多的电子产品出现在我们的生活中，如手机、平板电脑、电子书等等，这些电子产品的外壳大多使用塑料外壳，但随着人们对电子产品品质的要求不断提高，越来越多的电子产品采用金属外壳。金属外壳一方面具有比塑料外壳更好的保护作用，另一方面其具有的独特的金属质感也是金属外壳越来越受到关注的重要原因。
目前，对电子产品金属外壳进行表面处理的主要目的是装饰和防护两个方面，在现有的对金属外壳进行表面处理的方法中，金属外壳表面的阳极氧化、微弧氧化及硬质阳极氧化都能起到上述两个方面的效果，但在装饰性方面，处理后金属外壳的外观装饰性单一，质感单一。
因此，采用上述表面处理技术得到的金属外壳，外观装饰性和质感单一。需要开发一种外观装饰性良好、具有立体质感的铝合金壳体及其制备方法。
发明内容
本发明为了解决现有技术中手机壳体的外观装饰性单一、质感单一的问题，其目的在于提供一种铝合金壳体及其制备方法，该铝合金壳体具有凸凹立体质感、且具有高光凸面和非高光凹面。
为了实现上述目的，本发明提供一种铝合金壳体。根据本发明的实施例，所述铝合金壳体的外表面具有凸部和凹部，在所述凸部上依次形成有凸部氧化膜和凸部电泳装饰层，所述凹部具有凹部氧化膜或凹部电泳装饰层，所述凸部电泳装饰层的表面具有90-105的光泽度，所述凹部氧化膜的表面具有5-25的光泽度或所述凹部电泳装饰层的表面具有0.5-5的光泽度
优选地，所述凸部和所述凹部的高度差为0.05-0.2mm。
优选地，所述凸部氧化膜和所述凹部氧化膜具有不同的颜色。
本发明还提供一种铝合金壳体的制备方法，其中，该制备方法依次包括：
步骤a、对铝合金壳体基体表面进行第一阳极氧化；
步骤b、通过第一电泳在经过第一阳极氧化的铝合金壳体基体表面形成电泳装饰层；
步骤c、对经过第一电泳处理后是铝合金壳体基体表面进行机械抛光；
步骤d、通过镭雕的方法在经过机械抛光的铝合金壳体基体表面上雕刻出具有凸凹效果的纹理图案；
步骤e、对铝合金壳体基体表面上的纹理图案部分进行第二电泳或第二阳极氧化或硬质阳极氧化或微弧氧化。
优选地，所述第一阳极氧化和/或第二阳极氧化包括将铝合金壳体基体表面进行预处理后通过阳极氧化形成阳极膜。
优选地，所述预处理包括：使用50-60g/L的氢氧化钠在50-70℃下进行碱蚀3-20s，使用200-300ml/L的硝酸在15-25℃下进行中和10-20s，使用含有650-750ml/L的磷酸和350-250ml/L的硫酸的化抛液在90℃下进行化学抛光5-20s。
优选地，所述阳极氧化包括使用190-200g/L的硫酸将铝合金壳体基体表面在13-17V的阳极电压、10-21℃下氧化15-50min。
优选地，所述第一电泳和/或第二电泳包括使用pH值为7-9的电泳液在28-32℃的温度、140-200V的电压下进行电泳1-3min。
优选地，所述硬质阳极氧化包括使用硬质阳极氧化液在5-12℃下氧化25-50min。
优选地，所述硬质阳极氧化液含有170-270g/L的硫酸和8-20g/L的草酸。
优选地，所述微弧氧化包括使用微弧氧化电解液在20-30℃下氧化40-100min。
优选地，所述微弧氧化电解液含有0.02-0.05mol/L的硅酸钠和0.03-0.07mol/L的氢氧化钠。
本发明还提供了一种铝合金壳体，该铝合金壳体是通过本发明的铝合金壳体的制备方法制备得到的。
通过上述技术方案，首先对铝合金壳体基体表面先进行第一阳极氧化处理，然后通过第一电泳形成电泳装饰层，进而将第一电泳后铝合金壳体基体表面进行机械抛光，然后利用镭雕在铝合金壳体基体表面上雕刻出纹理图案，形成凸凹的效果，通过对铝合金壳体基体表面上的纹理图案部分进行第二电泳或第二阳极氧化或硬质阳极氧化或微弧氧化，从而制作出一种凸凹立体质感、且具有高光凸面与非高光凹面的铝合金壳体。
本发明的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。
发明详细描述
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
根据本发明实施例的铝合金壳体，其中，该铝合金壳体的外表面具有凸部和凹部，在 所述凸部上依次形成有凸部氧化膜和凸部电泳装饰层，所述凹部具有凹部氧化膜或凹部电泳装饰层，所述凸部电泳装饰层的表面具有90-105的光泽度，所述凹部氧化膜的表面具有5-25的光泽度或所述凹部电泳装饰层的表面具有0.5-5的光泽度。发明人发现，通过在铝合金壳体的外表面形成凸部和凹部能够使得铝合金壳体具有凸凹立体质感，另外，通过对在所述凸部表面上形成的凸部氧化膜进行抛光，使得所述凸部氧化膜的表面呈现高光效果。本发明中，光泽度为氧化膜表面接近镜面的程度，可以通过本领域中公知的方法测定得到，例如可以使用光泽度仪进行测定。
本发明中，铝合金壳体的外表面的凸部和凹部的形成方法、以及在凸部上形成凸部氧化膜、在凹部上形成凹部氧化膜的方法如后述铝合金壳体制备方法中描述。
根据本发明实施例的铝合金壳体的制备方法，在优选的情况下，可以在所述凸部氧化膜和所述凹部氧化膜中形成不同颜色。通过在所述凸部氧化膜和所述凹部氧化膜中形成不同颜色，可以使得铝合金壳体具有不同颜色膜层。
根据本发明的铝合金壳体的制备方法，其中，该制备方法依次包括：
步骤a、对铝合金壳体基体表面进行第一阳极氧化；
步骤b、通过第一电泳在经过第一阳极氧化的铝合金壳体基体表面形成电泳装饰层；
步骤c、对经过第一电泳处理后是铝合金壳体基体表面进行机械抛光；
步骤d、通过镭雕的方法在经过机械抛光的铝合金壳体基体表面上雕刻出具有凸凹效果的纹理图案；
步骤e、对铝合金壳体基体表面上的纹理图案部分进行第二电泳或第二阳极氧化或硬质阳极氧化或微弧氧化。
根据本发明实施例的铝合金壳体的制备方法，为了获得铝合金壳体的高亮效果，在第一电泳形成电泳装饰层后对第一电泳后铝合金壳体基体表面进行机械抛光。通过机械抛光机将铝合金壳体基体表面的阳极氧化膜层进行抛光，使得阳极氧化膜层厚度整体减薄约2μm，使得阳极氧化膜表面呈现光亮反光的效果，形成具有高光泽度的高光面，再进行镭雕，通过镭雕使表面具有0.05-0.2mm的凸凹差，产生凹凸立体质感的效果。
本发明中所使用的铝合金壳体基体没有特别限制，可以使用工业标准1000-7000系列物、模铸铝合金或压铸铝合金的各种铝合金壳体本体；本发明中所述的铝合金壳体基体为本领域技术人员常用的各种形状、结构的铝合金壳体本体，本发明没有特别限制。铝合金壳体基体的各种形状、结构，可通过机械加工完成。本发明的铝合金壳体可以用于手机、平板电脑、电子束等的壳体。
根据本发明实施例的铝合金壳体的制备方法，在步骤a中，在对铝合金壳体基体表面进行第一阳极氧化之前，可以预先对铝合金壳体基体表面进行喷砂或拉丝处理。在本发明中， 所述喷砂可以采用本领域中公知的方法进行，例如可以将铝合金壳体基体表面用打磨机打磨后，使用80-400目的陶瓷砂，以0.1-0.24MPa对铝合金壳体基体表面进行喷砂处理，使铝合金壳体基体表面呈现砂感。所述拉丝处理可以采用本领域中公知的方法进行，例如可以将铝合金壳体基体表面用拉丝机以400-1200号的拉丝轮从粗到细拉出所需拉丝质感。
根据本发明实施例的铝合金壳体的制备方法，优选地，所述第一阳极氧化和/或第二阳极氧化可以包括将铝合金壳体基体表面进行预处理后通过阳极氧化形成阳极膜。对于所形成的阳极膜的厚度没有特别要求，通常为6-10μm。
根据本发明实施例的铝合金壳体的制备方法，优选地，所述预处理的目的在于将铝合金壳体基体表面进行清洁干净，确保通过阳极氧化在铝合金壳体基体表面形成均匀的阳极膜，可以包括：使用50-60g/L的氢氧化钠在50-70℃下进行碱蚀3-20s，使用200-300ml/L的硝酸在15-25℃下进行中和10-20s，使用含有650-750ml/L的磷酸和350-250ml/L的硫酸的化抛液在90-95℃下进行化学抛光5-20s。
根据本发明实施例的铝合金壳体的制备方法，所述阳极氧化的方法可以使用本领域中公知的阳极氧化方法，优选地，所述阳极氧化可以包括使用190-200g/L的硫酸将铝合金壳体基体表面在13-17V的阳极电压、10-21℃下氧化15-50min。
根据本发明实施例的铝合金壳体的制备方法，通过第一电泳和/或第二电泳在铝合金壳体基体表面形成电泳装饰层，能够有效地对铝合金壳体进行保护和装饰作用。所述第一电泳和/或第二电泳可以包括使用pH值为7-9的电泳液在28-32℃的温度、140-200V的电压下进行电泳1-3min。所述电泳液只要能够在铝合金壳体基体表面形成电泳装饰层，可以使用本领域中所使用的电泳液，例如可以使用由日本清水株式会社的哑光漆(WNO-1)和日本清水株式会社的亮光漆(NNO-4)以重量比7：3混合而成的电泳液(电泳液的固体成分含量为8-14重量％)，该电泳液溶剂中亮光漆(NNO-4)含有：丙烯酸树脂50重量％、乙二醇一丁醚6重量％、乙二醇单异丁基醚20重量％、二乙二醇丁醛18重量％、以及其它成分6重量％；哑光漆(WNO-1)含有：丙烯酸树脂50重量％、乙二醇一丁醚10重量％、以及其它成分40重量％。
根据本发明实施例的铝合金壳体的制备方法，通过镭雕的方法在经过机械抛光的铝合金壳体基体表面上雕刻出具有凸凹效果的纹理图案可以使用本领域中各种常规的镭雕方法，例如使用激光镭雕机进行雕刻，使铝合金壳体基体表面露出铝合金基材，形成深度为0.1mm的纹理图案。
根据本发明实施例的铝合金壳体的制备方法，优选地，所述硬质阳极氧化可以包括使用硬质阳极氧化液在5-12℃下氧化25-50min。更优选地，所述硬质阳极氧化液可以含有170-270g/L的硫酸和8-20g/L的草酸。所述硬质阳极氧化的电学参数包括：脉冲波型为正向 方波脉冲，占空比为60-80％，频率为500-1000Hz，电流密度为3-7A/dm2。
根据本发明实施例的铝合金壳体的制备方法，优选地，所述微弧氧化可以包括使用微弧氧化电解液在20-30℃下氧化40-100min。更优选地，所述微弧氧化电解液可以含有0.02-0.05mol/L的硅酸钠和0.03-0.07mol/L的氢氧化钠。微弧氧化的氧化正向电压可以为400-600V。
下面通过列举实施例，对本发明的铝合金壳体的制备方法进行进一步说明。但本发明并限定于以下所列举的实施例。
实施例1
本实施例用于说明本发明的铝合金壳体及其制备方法
以P8型手机用压铸铝合金后壳基材(购自比亚迪有限公司)作为本实施例的铝合金壳体基材。
在50℃下，将铝合金壳体基材在浓度为55g/L氢氧化钠水溶液中进行碱蚀10s后，用去离子水清洗2次；然后，在15℃下，在浓度为250ml/L的硝酸中进行中和10s后，用去离子水清洗2次；然后，在90℃下，在含有650ml/L磷酸和350ml/L硫酸的化抛液中抛光10s后，用去离子水清洗2次；然后，在15℃下，在浓度为250ml/L硝酸中进行中和10s后，用去离子水清洗2次；然后，在干燥箱内在80℃下烘干20min，得到清洗烘干后的铝合金壳体基材。
通过阳极氧化在上述清洗烘干后的铝合金壳体基材表面形成阳极膜。条件为：使用浓度为190g/L的硫酸作为槽液，阳极电压为15V，温度为19℃，氧化时间为5min。
通过电泳在经过阳极氧化的铝合金壳体基材表面形成电泳装饰层，所述电泳的条件为：温度为30℃，电压为160V，时间为2min，pH为7.8；电泳液为由日本清水株式会社的哑光漆(WNO-1)和日本清水株式会社的亮光漆(NNO-4)以重量比7：3混合而成的电泳液(电泳液的固体成分含量为13重量％)，该电泳液溶剂中亮光漆(NNO-4)含有：丙烯酸树脂50重量％、乙二醇一丁醚6重量％、乙二醇单异丁基醚20重量％、二乙二醇丁醛18重量％、以及其它成分6重量％；哑光漆(WNO-1)含有：丙烯酸树脂50重量％、乙二醇一丁醚10重量％、以及其它成分40重量％。
利用机械抛光机将经过电泳处理铝合金壳体基体表面的膜层进行抛光，使得膜层厚度整体减薄约2μm，使得膜表面呈现光亮反光的效果。
使用激光镭雕机在经过机械抛光的铝合金壳体基体表面进行雕刻，使铝合金壳体基体表面露出铝合金基材，形成深度为0.05mm的具有凸凹效果的纹理图案。
在50℃下，将经过雕刻的铝合金壳体基材在浓度为55g/L氢氧化钠水溶液中进行碱蚀 10s后，用去离子水清洗2次；然后，在15℃下，在浓度为250ml/L的硝酸中进行中和4min后，用去离子水清洗2次。
通过电泳在经过清洗的铝合金壳体基材表面形成电泳装饰层，所述电泳的条件为：温度为30℃，电压为160V，时间为2min，pH为7.8；电泳液为由日本清水株式会社的哑光漆(WNO-1)和日本清水株式会社的亮光漆(NNO-4)以重量比7：3混合而成的电泳液(电泳液的固体成分含量为13重量％)，该电泳液溶剂中亮光漆(NNO-4)含有：丙烯酸树脂50重量％、乙二醇一丁醚6重量％、乙二醇单异丁基醚20重量％、二乙二醇丁醛18重量％、以及其它成分6重量％；哑光漆(WNO-1)含有：丙烯酸树脂50重量％、乙二醇一丁醚10重量％、以及其它成分40重量％。得到本发明的铝合金壳体。
实施例2
本实施例用于说明本发明的铝合金壳体及其制备方法
以P8型手机用压铸铝合金后壳基材(购自比亚迪有限公司)作为本实施例的铝合金壳体基材。
在70℃下，将铝合金壳体基材在浓度为60g/L氢氧化钠水溶液中进行碱蚀20s后，用去离子水清洗2次；然后，在20℃下，在浓度为300ml/L的硝酸中进行中和20s后，用去离子水清洗2次；然后，在93℃下，在含有700ml/L磷酸和300ml/L硫酸的化抛液中抛光10s后，用去离子水清洗2次；然后，在20℃下，在浓度为300ml/L硝酸中进行中和20s后，用去离子水清洗2次；然后，在干燥箱内在80℃下烘干20min，得到清洗烘干后的铝合金壳体基材。
通过阳极氧化在上述清洗烘干后的铝合金壳体基材表面形成阳极膜。条件为：使用浓度为195g/L的硫酸作为槽液，阳极电压为17V，温度为10℃，氧化时间为50min。
通过电泳在经过阳极氧化的铝合金壳体基材表面形成电泳装饰层，所述电泳的条件为：温度为32℃，电压为200V，时间为1min，pH为7；电泳液为由日本清水株式会社的哑光漆(WNO-1)和日本清水株式会社的亮光漆(NNO-4)以重量比7：3混合而成的电泳液(电泳液的固体成分含量为13重量％)，该电泳液溶剂中亮光漆(NNO-4)含有：丙烯酸树脂50重量％、乙二醇一丁醚6重量％、乙二醇单异丁基醚20重量％、二乙二醇丁醛18重量％、以及其它成分6重量％；哑光漆(WNO-1)含有：丙烯酸树脂50重量％、乙二醇一丁醚10重量％、以及其它成分40重量％。
利用机械抛光机将经过电泳处理铝合金壳体基体表面的膜层进行抛光，使得膜层厚度整体减薄约2μm，使得膜表面呈现光亮反光的效果。
使用激光镭雕机在经过机械抛光的铝合金壳体基体表面进行雕刻，使铝合金壳体基体表面露出铝合金基材，形成深度为0.2mm的具有凸凹效果的纹理图案。
在70℃下，将经过雕刻的铝合金壳体基材在浓度为60g/L氢氧化钠水溶液中进行碱蚀20s后，用去离子水清洗2次；然后，在25℃下，在浓度为300ml/L的硝酸中进行中和4min后，用去离子水清洗2次。
通过电泳在经过清洗的铝合金壳体基材表面形成电泳装饰层，所述电泳的条件为：温度为32℃，电压为200V，时间为1min，pH为7；电泳液为由日本清水株式会社的哑光漆(WNO-1)和日本清水株式会社的亮光漆(NNO-4)以重量比7：3混合而成的电泳液(电泳液的固体成分含量为13重量％)，该电泳液溶剂中亮光漆(NNO-4)含有：丙烯酸树脂50重量％、乙二醇一丁醚6重量％、乙二醇单异丁基醚20重量％、二乙二醇丁醛18重量％、以及其它成分6重量％；哑光漆(WNO-1)含有：丙烯酸树脂50重量％、乙二醇一丁醚10重量％、以及其它成分40重量％。得到本发明的铝合金壳体。
实施例3
本实施例用于说明本发明的铝合金壳体及其制备方法
以P8型手机用压铸铝合金后壳基材(购自比亚迪有限公司)作为本实施例的铝合金壳体基材。
在50℃下，将铝合金壳体基材在浓度为55g/L氢氧化钠水溶液中进行碱蚀10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L的硝酸中进行中和10s后，用去离子水清洗2次；然后，在95℃下，在含有650ml/L磷酸和350ml/L硫酸的化抛液中抛光10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L硝酸中进行中和10s后，用去离子水清洗2次；然后，在干燥箱内在80℃下烘干20min，得到清洗烘干后的铝合金壳体基材。
通过阳极氧化在上述清洗烘干后的铝合金壳体基材表面形成阳极膜。条件为：使用浓度为190g/L的硫酸作为槽液，阳极电压为15V，温度为19℃，氧化时间为5min。
通过电泳在经过阳极氧化的铝合金壳体基材表面形成电泳装饰层，所述电泳的条件为：温度为30℃，电压为160V，时间为2min，pH为7.8；电泳液为由日本清水株式会社的哑光漆(WNO-1)和日本清水株式会社的亮光漆(NNO-4)以重量比7：3混合而成的电泳液(电泳液的固体成分含量为13重量％)，该电泳液溶剂中亮光漆(NNO-4)含有：丙烯酸树脂50重量％、乙二醇一丁醚6重量％、乙二醇单异丁基醚20重量％、二乙二醇丁醛18重量％、以及其它成分6重量％；哑光漆(WNO-1)含有：丙烯酸树脂50重量％、乙二醇一丁醚10重量％、以及其它成分40重量％。
利用机械抛光机将经过电泳处理铝合金壳体基体表面的膜层进行抛光，使得膜层厚度整体减薄约2μm，使得膜表面呈现光亮反光的效果。
使用激光镭雕机在经过机械抛光的铝合金壳体基体表面进行雕刻，使铝合金壳体基体 表面露出铝合金基材，形成深度为0.1mm的具有凸凹效果的纹理图案。
在50℃下，将经过雕刻的铝合金壳体基材在浓度为55g/L氢氧化钠水溶液中进行碱蚀10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L的硝酸中进行中和4min后，用去离子水清洗2次。
通过阳极氧化在经过清洗的铝合金壳体基材表面形成阳极膜。条件为：使用浓度为190g/L的硫酸作为槽液，阳极电压为15V，温度为19℃，氧化时间为5min。得到本发明的铝合金壳体。
实施例4
本实施例用于说明本发明的铝合金壳体及其制备方法
以P8型手机用压铸铝合金后壳基材(购自比亚迪有限公司)作为本实施例的铝合金壳体基材。
在50℃下，将铝合金壳体基材在浓度为55g/L氢氧化钠水溶液中进行碱蚀10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L的硝酸中进行中和10s后，用去离子水清洗2次；然后，在95℃下，在含有650ml/L磷酸和350ml/L硫酸的化抛液中抛光10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L硝酸中进行中和10s后，用去离子水清洗2次；然后，在干燥箱内在80℃下烘干20min，得到清洗烘干后的铝合金壳体基材。
通过阳极氧化在上述清洗烘干后的铝合金壳体基材表面形成阳极膜。条件为：使用浓度为190g/L的硫酸作为槽液，阳极电压为15V，温度为19℃，氧化时间为5min。
通过电泳在经过阳极氧化的铝合金壳体基材表面形成电泳装饰层，所述电泳的条件为：温度为30℃，电压为160V，时间为2min，pH为7.8；电泳液为由日本清水株式会社的哑光漆(WNO-1)和日本清水株式会社的亮光漆(NNO-4)以重量比7：3混合而成的电泳液(电泳液的固体成分含量为13重量％)，该电泳液溶剂中亮光漆(NNO-4)含有：丙烯酸树脂50重量％、乙二醇一丁醚6重量％、乙二醇单异丁基醚20重量％、二乙二醇丁醛18重量％、以及其它成分6重量％；哑光漆(WNO-1)含有：丙烯酸树脂50重量％、乙二醇一丁醚10重量％、以及其它成分40重量％。
利用机械抛光机将经过电泳处理铝合金壳体基体表面的膜层进行抛光，使得膜层厚度整体减薄约2μm，使得膜表面呈现光亮反光的效果。
使用激光镭雕机在经过机械抛光的铝合金壳体基体表面进行雕刻，使铝合金壳体基体表面露出铝合金基材，形成深度为0.1mm的具有凸凹效果的纹理图案。
在50℃下，将经过雕刻的铝合金壳体基材在浓度为55g/L氢氧化钠水溶液中进行碱蚀10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L的硝酸中进行中和4min 后，用去离子水清洗2次。
使用含有200g/L的硫酸和15g/L的草酸的硬质阳极氧化液将经过清洗的铝合金壳体基材在10℃下氧化25min。硬质阳极氧化的电学参数包括：脉冲波型为正向方波脉冲，占空比为70％，频率为800Hz，电流密度为5A/dm2。得到本发明的铝合金壳体。
实施例5
本实施例用于说明本发明的铝合金壳体及其制备方法
以P8型手机用压铸铝合金后壳基材(购自比亚迪有限公司)作为本实施例的铝合金壳体基材。
在50℃下，将铝合金壳体基材在浓度为55g/L氢氧化钠水溶液中进行碱蚀10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L的硝酸中进行中和10s后，用去离子水清洗2次；然后，在95℃下，在含有650ml/L磷酸和350ml/L硫酸的化抛液中抛光10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L硝酸中进行中和10s后，用去离子水清洗2次；然后，在干燥箱内在80℃下烘干20min，得到清洗烘干后的铝合金壳体基材。
通过阳极氧化在上述清洗烘干后的铝合金壳体基材表面形成阳极膜。条件为：使用浓度为190g/L的硫酸作为槽液，阳极电压为15V，温度为19℃，氧化时间为5min。
通过电泳在经过阳极氧化的铝合金壳体基材表面形成电泳装饰层，所述电泳的条件为：温度为30℃，电压为160V，时间为2min，pH为7.8；电泳液为由日本清水株式会社的哑光漆(WNO-1)和日本清水株式会社的亮光漆(NNO-4)以重量比7：3混合而成的电泳液(电泳液的固体成分含量为13重量％)，该电泳液溶剂中亮光漆(NNO-4)含有：丙烯酸树脂50重量％、乙二醇一丁醚6重量％、乙二醇单异丁基醚20重量％、二乙二醇丁醛18重量％、以及其它成分6重量％；哑光漆(WNO-1)含有：丙烯酸树脂50重量％、乙二醇一丁醚10重量％、以及其它成分40重量％。
利用机械抛光机将经过电泳处理铝合金壳体基体表面的膜层进行抛光，使得膜层厚度整体减薄约2μm，使得膜表面呈现光亮反光的效果。
使用激光镭雕机在经过机械抛光的铝合金壳体基体表面进行雕刻，使铝合金壳体基体表面露出铝合金基材，形成深度为0.1mm的具有凸凹效果的纹理图案。
在50℃下，将经过雕刻的铝合金壳体基材在浓度为55g/L氢氧化钠水溶液中进行碱蚀10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L的硝酸中进行中和4min后，用去离子水清洗2次。
使用含有170g/L的硫酸和20g/L的草酸的硬质阳极氧化液将经过清洗的铝合金壳体基材在5℃下氧化30min。硬质阳极氧化的电学参数包括：脉冲波型为正向方波脉冲，占空比 为80％，频率为500Hz，电流密度为3A/dm2。得到本发明的铝合金壳体。
实施例6
本实施例用于说明本发明的铝合金壳体及其制备方法
以P8型手机用压铸铝合金后壳基材(购自比亚迪有限公司)作为本实施例的铝合金壳体基材。
在50℃下，将铝合金壳体基材在浓度为55g/L氢氧化钠水溶液中进行碱蚀10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L的硝酸中进行中和10s后，用去离子水清洗2次；然后，在95℃下，在含有650ml/L磷酸和350ml/L硫酸的化抛液中抛光10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L硝酸中进行中和10s后，用去离子水清洗2次；然后，在干燥箱内在80℃下烘干20min，得到清洗烘干后的铝合金壳体基材。
通过阳极氧化在上述清洗烘干后的铝合金壳体基材表面形成阳极膜。条件为：使用浓度为190g/L的硫酸作为槽液，阳极电压为15V，温度为19℃，氧化时间为5min。
通过电泳在经过阳极氧化的铝合金壳体基材表面形成电泳装饰层，所述电泳的条件为：温度为30℃，电压为160V，时间为2min，pH为7.8；电泳液为由日本清水株式会社的哑光漆(WNO-1)和日本清水株式会社的亮光漆(NNO-4)以重量比7：3混合而成的电泳液(电泳液的固体成分含量为13重量％)，该电泳液溶剂中亮光漆(NNO-4)含有：丙烯酸树脂50重量％、乙二醇一丁醚6重量％、乙二醇单异丁基醚20重量％、二乙二醇丁醛18重量％、以及其它成分6重量％；哑光漆(WNO-1)含有：丙烯酸树脂50重量％、乙二醇一丁醚10重量％、以及其它成分40重量％。
利用机械抛光机将经过电泳处理铝合金壳体基体表面的膜层进行抛光，使得膜层厚度整体减薄约2μm，使得膜表面呈现光亮反光的效果。
使用激光镭雕机在经过机械抛光的铝合金壳体基体表面进行雕刻，使铝合金壳体基体表面露出铝合金基材，形成深度为0.1mm的具有凸凹效果的纹理图案。
在50℃下，将经过雕刻的铝合金壳体基材在浓度为55g/L氢氧化钠水溶液中进行碱蚀10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L的硝酸中进行中和4min后，用去离子水清洗2次。
使用含有270g/L的硫酸和20g/L的草酸的硬质阳极氧化液将经过清洗的铝合金壳体基材在12℃下氧化25min。硬质阳极氧化的电学参数包括：脉冲波型为正向方波脉冲，占空比为60％，频率为1000Hz，电流密度为7A/dm2。得到本发明的铝合金壳体。
实施例7
本实施例用于说明本发明的铝合金壳体及其制备方法
以P8型手机用压铸铝合金后壳基材(购自比亚迪有限公司)作为本实施例的铝合金壳体基材。
在50℃下，将铝合金壳体基材在浓度为55g/L氢氧化钠水溶液中进行碱蚀10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L的硝酸中进行中和10s后，用去离子水清洗2次；然后，在95℃下，在含有650ml/L磷酸和350ml/L硫酸的化抛液中抛光10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L硝酸中进行中和10s后，用去离子水清洗2次；然后，在干燥箱内在80℃下烘干20min，得到清洗烘干后的铝合金壳体基材。
通过阳极氧化在上述清洗烘干后的铝合金壳体基材表面形成阳极膜。条件为：使用浓度为190g/L的硫酸作为槽液，阳极电压为15V，温度为19℃，氧化时间为5min。
通过电泳在经过阳极氧化的铝合金壳体基材表面形成电泳装饰层，所述电泳的条件为：温度为30℃，电压为160V，时间为2min，pH为7.8；电泳液为由日本清水株式会社的哑光漆(WNO-1)和日本清水株式会社的亮光漆(NNO-4)以重量比7：3混合而成的电泳液(电泳液的固体成分含量为13重量％)，该电泳液溶剂中亮光漆(NNO-4)含有：丙烯酸树脂50重量％、乙二醇一丁醚6重量％、乙二醇单异丁基醚20重量％、二乙二醇丁醛18重量％、以及其它成分6重量％；哑光漆(WNO-1)含有：丙烯酸树脂50重量％、乙二醇一丁醚10重量％、以及其它成分40重量％。
利用机械抛光机将经过电泳处理铝合金壳体基体表面的膜层进行抛光，使得膜层厚度整体减薄约2μm，使得膜表面呈现光亮反光的效果。
使用激光镭雕机在经过机械抛光的铝合金壳体基体表面进行雕刻，使铝合金壳体基体表面露出铝合金基材，形成深度为0.1mm的具有凸凹效果的纹理图案。
在50℃下，将经过雕刻的铝合金壳体基材在浓度为55g/L氢氧化钠水溶液中进行碱蚀10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L的硝酸中进行中和4min后，用去离子水清洗2次。
使用含有0.03mol/L的硅酸钠和0.05mol/L的氢氧化钠的微弧氧化电解液将经过清洗的铝合金壳体基材在25℃、氧化正向电压为500V下氧化40min。得到本发明的铝合金壳体。
实施例8
本实施例用于说明本发明的铝合金壳体及其制备方法
以P8型手机用压铸铝合金后壳基材(购自比亚迪有限公司)作为本实施例的铝合金壳体基材。
在50℃下，将铝合金壳体基材在浓度为55g/L氢氧化钠水溶液中进行碱蚀10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L的硝酸中进行中和10s后，用去 离子水清洗2次；然后，在95℃下，在含有650ml/L磷酸和350ml/L硫酸的化抛液中抛光10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L硝酸中进行中和10s后，用去离子水清洗2次；然后，在干燥箱内在80℃下烘干20min，得到清洗烘干后的铝合金壳体基材。
通过阳极氧化在上述清洗烘干后的铝合金壳体基材表面形成阳极膜。条件为：使用浓度为190g/L的硫酸作为槽液，阳极电压为15V，温度为19℃，氧化时间为5min。
通过电泳在经过阳极氧化的铝合金壳体基材表面形成电泳装饰层，所述电泳的条件为：温度为30℃，电压为160V，时间为2min，pH为7.8；电泳液为由日本清水株式会社的哑光漆(WNO-1)和日本清水株式会社的亮光漆(NNO-4)以重量比7：3混合而成的电泳液(电泳液的固体成分含量为13重量％)，该电泳液溶剂中亮光漆(NNO-4)含有：丙烯酸树脂50重量％、乙二醇一丁醚6重量％、乙二醇单异丁基醚20重量％、二乙二醇丁醛18重量％、以及其它成分6重量％；哑光漆(WNO-1)含有：丙烯酸树脂50重量％、乙二醇一丁醚10重量％、以及其它成分40重量％。
利用机械抛光机将经过电泳处理铝合金壳体基体表面的膜层进行抛光，使得膜层厚度整体减薄约2μm，使得膜表面呈现光亮反光的效果。
使用激光镭雕机在经过机械抛光的铝合金壳体基体表面进行雕刻，使铝合金壳体基体表面露出铝合金基材，形成深度为0.1mm的具有凸凹效果的纹理图案。
在50℃下，将经过雕刻的铝合金壳体基材在浓度为55g/L氢氧化钠水溶液中进行碱蚀10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L的硝酸中进行中和4min后，用去离子水清洗2次。
使用含有0.02mol/L的硅酸钠和0.07mol/L的氢氧化钠的微弧氧化电解液将经过清洗的铝合金壳体基材在30℃、氧化正向电压为400V下氧化100min。得到本发明的铝合金壳体。
实施例9
本实施例用于说明本发明的铝合金壳体及其制备方法
以P8型手机用压铸铝合金后壳基材(购自比亚迪有限公司)作为本实施例的铝合金壳体基材。
在50℃下，将铝合金壳体基材在浓度为55g/L氢氧化钠水溶液中进行碱蚀10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L的硝酸中进行中和10s后，用去离子水清洗2次；然后，在95℃下，在含有650ml/L磷酸和350ml/L硫酸的化抛液中抛光10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L硝酸中进行中和10s后，用去离子水清洗2次；然后，在干燥箱内在80℃下烘干20min，得到清洗烘干后的铝合金壳体基材。
通过阳极氧化在上述清洗烘干后的铝合金壳体基材表面形成阳极膜。条件为：使用浓度为190g/L的硫酸作为槽液，阳极电压为15V，温度为19℃，氧化时间为5min。
通过电泳在经过阳极氧化的铝合金壳体基材表面形成电泳装饰层，所述电泳的条件为：温度为30℃，电压为160V，时间为2min，pH为7.8；电泳液为由日本清水株式会社的哑光漆(WNO-1)和日本清水株式会社的亮光漆(NNO-4)以重量比7：3混合而成的电泳液(电泳液的固体成分含量为13重量％)，该电泳液溶剂中亮光漆(NNO-4)含有：丙烯酸树脂50重量％、乙二醇一丁醚6重量％、乙二醇单异丁基醚20重量％、二乙二醇丁醛18重量％、以及其它成分6重量％；哑光漆(WNO-1)含有：丙烯酸树脂50重量％、乙二醇一丁醚10重量％、以及其它成分40重量％。
利用机械抛光机将经过电泳处理铝合金壳体基体表面的膜层进行抛光，使得膜层厚度整体减薄约2μm，使得膜表面呈现光亮反光的效果。
使用激光镭雕机在经过机械抛光的铝合金壳体基体表面进行雕刻，使铝合金壳体基体表面露出铝合金基材，形成深度为0.1mm的具有凸凹效果的纹理图案。
在50℃下，将经过雕刻的铝合金壳体基材在浓度为55g/L氢氧化钠水溶液中进行碱蚀10s后，用去离子水清洗2次；然后，在25℃下，在浓度为250ml/L的硝酸中进行中和4min后，用去离子水清洗2次。
使用含有0.05mol/L的硅酸钠和0.03mol/L的氢氧化钠的微弧氧化电解液将经过清洗的铝合金壳体基材在20℃、氧化正向电压为600V下氧化60min。得到本发明的铝合金壳体。
性能测试
分别按照下述方法对由实施例1-9制得的具有清晰的凸凹图案的铝合金壳体进行性能检测，测试结果如表1所示。
光泽度测试
使用光泽度仪(德国BKY微型光泽仪A-4460)对实施例1-9制得的铝合金壳体表面的光泽度进行测试，其结果如表1所示。
抗划伤性测试
采用三菱(UNI)硬度为2H的铅笔，在样品上，按45度方向施加800克力，10毫米行程，不同位置划3道，观察样品外观是否有明显划痕，如无明显划痕则说明样品合格。
耐高温性测试
将样品放入精密高温试验箱(宏凌HRHL45)内，在85℃条件下加热240小时，然后在室温下放置2小时，观察样品外观是否有脱落、变形、裂痕和颜色变化，如无脱落、变形、裂痕和颜色变化则说明样品合格。
耐低温性测试
将样品放入恒温恒湿试验机(台湾庆声，THS-2001)内，在-40℃条件下放置240小时，然后在室温下放置2小时，观察样品外观是否有脱落、变形、裂痕和颜色变化，如无脱落、变形、裂痕和颜色变化则说明样品合格。
耐湿性测试
将样品放入湿度为90％，温度为60℃的恒温恒湿试验机(台湾庆声，HTS-400)内放置96小时，然后在室温下放置2小时，观察样品外观是否有脱落、变形、裂痕和颜色变化，如无脱落、变形、裂痕和颜色变化则说明样品合格。
温度冲击测试
将样品放入冷热冲击试验机(宏凌HTS-400)内，先在-40℃环境下，放置1小时，然后将温度转换到85℃，放置1小时，转换时间为15秒，共做12个循环(24小时)。观察样品外观是否有脱落、变形、裂痕和颜色变化，如无脱落、变形、裂痕和颜色变化则说明样品合格。
盐雾试验
将样品放置在温度为30℃，湿度≥85％的试验箱(HOLINK H-SST-90盐水喷雾试验机)内，用pH＝6.8的溶液(溶液成份：50克/升NaCl)，连续喷雾48个小时后取出；用常温清水冲洗5分钟并用吹风机吹干，在室温下放置1小时，观察样品外观是否有脱落、变形、裂痕和颜色变化，如无脱落、变形、裂痕和颜色变化则说明样品合格。
表1实施例1～9所得铝合金壳体进行性能检测结果
Figure PCTCN2016111568-appb-000001
从上表可以看出，本发明提供的铝合金壳体表面不易磨损、表层不易脱落，提高了铝 合金壳体的耐用性，并且具有凸凹纹理图案赋予铝合金壳体优良的外观效果，具有层次分明的凸凹立体质感，使本发明的提供的铝合金壳体同时具备美观和耐用的优点。另外，实施例1-9中得到的铝合金壳体，经过机械抛光，使得表面还具有高亮和非高亮效果。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (12)

  1. 一种铝合金壳体，其特征在于，所述铝合金壳体的外表面具有凸部和凹部，在所述凸部上依次形成有凸部氧化膜和凸部电泳装饰层，所述凹部具有凹部氧化膜或凹部电泳装饰层，所述凸部电泳装饰层的表面具有90-105的光泽度，所述凹部氧化膜的表面具有5-25的光泽度或所述凹部电泳装饰层的表面具有0.5-5的光泽度。
  2. 根据权利要求1所述的铝合金壳体，其特征在于，所述凸部和所述凹部的高度差为0.05-0.2mm。
  3. 根据权利要求1或2所述的铝合金壳体，其特征在于，所述凸部氧化膜和所述凹部氧化膜具有不同的颜色。
  4. 一种铝合金壳体的制备方法，其特征在于，该制备方法依次包括：
    步骤a、对铝合金壳体基体表面进行第一阳极氧化；
    步骤b、通过第一电泳在经过第一阳极氧化的铝合金壳体基体表面形成电泳装饰层；
    步骤c、对经过第一电泳处理后是铝合金壳体基体表面进行机械抛光；
    步骤d、通过镭雕的方法在经过机械抛光的铝合金壳体基体表面上雕刻出具有凸凹效果的纹理图案；
    步骤e、对铝合金壳体基体表面上的纹理图案部分进行第二电泳或第二阳极氧化或硬质阳极氧化或微弧氧化。
  5. 根据权利要求4所述的制备方法，其特征在于，所述第一阳极氧化和/或第二阳极氧化包括将铝合金壳体基体表面进行预处理后通过阳极氧化形成阳极膜。
  6. 根据权利要求4或5所述的制备方法，其特征在于，所述预处理包括：使用50-60g/L的氢氧化钠在50-70℃下进行碱蚀3-20s，使用200-300ml/L的硝酸在15-25℃下进行中和10-20s，以及，使用含有650-750ml/L的磷酸和350-250ml/L的硫酸的化抛液在90-95℃下进行化学抛光5-20s。
  7. 根据权利要求4-6中任一项所述的制备方法，其特征在于，所述阳极氧化包括使用190-200g/L的硫酸将铝合金壳体基体表面在13-17V的阳极电压、10-21℃下氧化5-50min。
  8. 根据权利要求4-7中任一项所述的制备方法，其特征在于，所述第一电泳和/或第二电泳包括使用pH值为7-9的电泳液在28-32℃的温度、140-200V的电压下进行电泳1-3min。
  9. 根据权利要求4-8中任一项所述的制备方法，其特征在于，所述硬质阳极氧化包括使用硬质阳极氧化液在5-12℃下氧化25-50min。
  10. 根据权利要求4-9中任一项所述的制备方法，其特征在于，所述硬质阳极氧化液含有170-270g/L的硫酸和8-20g/L的草酸。
  11. 根据权利要求4-10中任一项所述的制备方法，其特征在于，所述微弧氧化包括使用微弧氧化电解液在20-30℃下氧化40-100min。
  12. 根据权利要求4-11中任一项所述的制备方法，其特征在于，所述微弧氧化电解液含有0.02-0.05mol/L的硅酸钠和0.03-0.07mol/L的氢氧化钠。
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