WO2022063230A1 - 一种制造彩色制品及手机壳的方法 - Google Patents

一种制造彩色制品及手机壳的方法 Download PDF

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Publication number
WO2022063230A1
WO2022063230A1 PCT/CN2021/120331 CN2021120331W WO2022063230A1 WO 2022063230 A1 WO2022063230 A1 WO 2022063230A1 CN 2021120331 W CN2021120331 W CN 2021120331W WO 2022063230 A1 WO2022063230 A1 WO 2022063230A1
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Prior art keywords
mobile phone
tantalum
phone case
niobium
titanium
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PCT/CN2021/120331
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English (en)
French (fr)
Inventor
刘寓中
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北京华宇创新钽铌科技有限公司
北京华宇创新科贸有限责任公司
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Priority to JP2023519319A priority Critical patent/JP2023543279A/ja
Priority to EP21871599.3A priority patent/EP4219798A1/en
Priority to US18/246,638 priority patent/US20230366118A1/en
Priority to CN202180007232.8A priority patent/CN116261609B/zh
Priority to KR1020237013623A priority patent/KR20230107795A/ko
Publication of WO2022063230A1 publication Critical patent/WO2022063230A1/zh

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • 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
    • 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
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/66—Electroplating: Baths therefor from melts
    • C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses

Definitions

  • the present invention relates to a method of manufacturing colored products, in particular to a method of manufacturing colored mobile phone cases, and colored products, especially colored mobile phone cases, manufactured by the method.
  • CN106067911A describes a preparation method of a plastic mobile phone case, comprising the following steps: (1) mixing plastic base material, fluorescent powder and dye in proportion, putting it into an injection molding machine and extruding it into a mobile phone case mold; (2) spraying primer in sequence 2. Carry out vacuum coating after color paint; (3) remove the vacuum coating on the vacuum coating layer in the area where the color paint layer needs to be displayed by laser laser engraving; (4) after vacuum coating, form a middle paint layer and UV on the coating surface in turn topcoat layer.
  • the method described in this patent has complicated processing steps, and the plastic mobile phone case has no radiation protection function.
  • CN105970270A describes a process for processing two kinds of aluminum anodizing colors on aluminum metal mobile phone case, which is characterized in that: it includes the following steps:
  • Step 1 processing the aluminum casing: use CNC cutting to process the aluminum casing;
  • Step 2 injection molding PPS plastic: injection molding PPS plastic at the corresponding position of the aluminum casing obtained in step 1;
  • Step 3 the first aluminum anodic oxidation coloring: after completing the injection molding of PPS plastic in step 2, the first aluminum anodic oxidation coloring is performed on the entire aluminum casing;
  • Step 4 processing high-brightness edges: after completing the first aluminum anodizing coloring in step 3, use CNC to cut and process high-brightness edges of equal width at the edge of the aluminum casing;
  • Step 5 Use photosensitive protection ink to cover part of the high-brightness edge: apply photosensitive protection ink on the surface of part of the high-brightness edge, and then bake it at a certain temperature for a certain period of time before exposing;
  • Step 6 the second aluminum anodic oxidation coloring: the second aluminum anodic oxidation coloring is performed on the part of the high-brightness edge that is not covered by the photosensitive protection ink; wherein, the color of the second aluminum anodic oxidation coloring is the same as that of the first aluminum anodic oxidation coloring. Oxidative coloring is the same color;
  • Step 7 cleaning the photosensitive protection ink: the photosensitive protection ink after exposure in step 5 is cleaned with a cleaning solution to leak high-brightness edges;
  • Step 8 the third aluminum anodic oxidation coloring: carry out the third aluminum anodic oxidation coloring on the high-bright edges exposed after cleaning the exposed photosensitive protection ink in step 7, wherein the color of the third aluminum anodic oxidation coloring is different from The color of the first aluminum anodizing color, that is, the process of processing two aluminum anodizing colors on the aluminum metal mobile phone case.
  • CN107567217A describes a method for preparing a casing, the method comprising: (1) providing a metal base material, and performing hard anodizing treatment on the metal base material to obtain a metal base body having a metal hard anodic oxide shell; ( 2) forming a resin film layer on one surface of the metal substrate obtained in step (1); (3) performing alkaline etching on the substrate obtained in step (2) to remove the metal on the surface where the resin film layer is not formed in the substrate Hard anodic oxide shell; (4) acid etching the base obtained in step (3) to remove the remaining metal in the base.
  • the present invention provides a method for manufacturing colored products, which comprises the following steps:
  • the product base is made of a material selected from tantalum, niobium, tantalum-niobium alloy, titanium and titanium alloy
  • the product base is made of a material selected from tantalum, niobium, tantalum-niobium alloy and titanium, more preferably all
  • the article substrate is made of a material selected from the group consisting of tantalum, niobium, and tantalum-niobium alloys.
  • the present invention also provides a method for manufacturing a colored shell, which comprises the following steps:
  • the shell base is made of a material selected from tantalum, niobium, tantalum-niobium alloy, titanium and titanium alloy, preferably the shell base is made of a material selected from tantalum, niobium, tantalum-niobium alloy and titanium, more preferably all The shell base is made of a material selected from tantalum, niobium and tantalum-niobium alloys.
  • the present invention further provides a method for manufacturing a colored mobile phone case, comprising the following steps:
  • the mobile phone case base is made of a material selected from tantalum, niobium, tantalum-niobium alloy, titanium and titanium alloy, preferably the mobile phone case base is made of a material selected from tantalum, niobium, tantalum-niobium alloy and titanium, more Preferably, the mobile phone case base is made of a material selected from the group consisting of tantalum, niobium and tantalum-niobium alloys.
  • the present invention also provides a color product manufactured by the above method, comprising:
  • the product base is made of a material selected from tantalum, niobium, tantalum-niobium alloy, titanium and titanium alloy
  • the product base is made of a material selected from tantalum, niobium, tantalum-niobium alloy and titanium, more preferably all
  • the article substrate is made of a material selected from the group consisting of tantalum, niobium, and tantalum-niobium alloys.
  • the present invention also provides a color housing manufactured by the above method, which comprises:
  • the shell base is made of a material selected from tantalum, niobium, tantalum-niobium alloy, titanium and titanium alloy, preferably the shell base is made of a material selected from tantalum, niobium, tantalum-niobium alloy and titanium, more preferably all The shell base is made of a material selected from tantalum, niobium and tantalum-niobium alloys.
  • the present invention also provides a color mobile phone case manufactured by the above method, which comprises:
  • the mobile phone case base is made of a material selected from tantalum, niobium, tantalum-niobium alloy, titanium and titanium alloy, preferably the mobile phone case base is made of a material selected from tantalum, niobium, tantalum-niobium alloy and titanium, more Preferably, the mobile phone case base is made of a material selected from the group consisting of tantalum, niobium and tantalum-niobium alloys.
  • the method for manufacturing colored products, especially mobile phone cases, according to the present invention has one or more of the following beneficial effects: (1) products with rich colors, especially mobile phone cases, can be obtained; (2) the prepared color mobile phone case has the advantages of reducing mobile phone radiation (3) the manufacturing process is simple, and (4) the color is easy to repair and change.
  • Figure 1 shows colored tantalum foils prepared under different process conditions according to embodiments of the present invention.
  • FIG. 2 is a colored tantalum mobile phone case prepared under different process conditions according to an embodiment of the present invention.
  • Figure 3 shows colored niobium foils prepared under different process conditions according to embodiments of the present invention.
  • Figure 4 shows colored tantalum-niobium alloy foils prepared under different process conditions according to embodiments of the present invention.
  • Figure 5 shows colored titanium foils prepared under different process conditions according to embodiments of the present invention.
  • 6 is a colored titanium phone case prepared in molten lithium nitrate under different process conditions according to one embodiment of the present invention.
  • FIG. 7 is a colored titanium phone case prepared in molten lithium nitrate under different process conditions according to another embodiment of the present invention.
  • FIG. 9 is a titanium mobile phone case with colorful patterns prepared according to an embodiment of the present invention.
  • FIG. 10 is a tantalum cell phone case with colorful patterns prepared in a 0.05 wt % H 3 PO 4 aqueous solution according to an embodiment of the present invention.
  • FIG. 11 is a niobium cell phone case with colorful patterns prepared in a 0.05 wt % H 3 PO 4 aqueous solution according to an embodiment of the present invention.
  • 12 is a colored tantalum, niobium, and tantalum-niobium alloy foil prepared in lithium nitrate: potassium nitrate (weight ratio 1:1) according to an embodiment of the present invention.
  • the method of the present invention for manufacturing a colored product may adopt an anodizing method and/or a molten salt electrochemical method.
  • anodizing can be used alone, or a combination of anodizing and molten salt electrochemical methods can be used to prepare colored products, including colored mobile phone cases, while for titanium and titanium alloys, preferred Color products are prepared by anodizing, and more preferably, colored products, including colored mobile phone cases, are prepared by molten salt anodizing.
  • anode In an oxygen-containing electrolyte solution, at an appropriate temperature, tantalum, niobium, tantalum-niobium alloy, titanium and titanium alloy products such as mobile phone cases are used as the anode, and nickel or stainless steel or other metals stable to the oxygen-containing electrolyte solution are used as the cathode, Anodizing is performed by applying a suitable anode voltage and constant voltage for a suitable time.
  • the method of the present invention for making a colored article comprises the steps of:
  • the article base is made of material selected from tantalum, niobium, tantalum-niobium alloy, titanium and titanium alloy, preferably the article base is made of material selected from tantalum, niobium, tantalum-niobium alloy and titanium, more preferably all
  • the article base is made of a material selected from tantalum, niobium and tantalum-niobium alloys, and it is also preferred that the article base is made of a material selected from titanium and titanium alloys.
  • the method of the present invention for making a colored housing comprises the steps of:
  • the shell base is made of a material selected from tantalum, niobium, tantalum-niobium alloys, titanium and titanium alloys, preferably the shell base is made of a material selected from tantalum, niobium, tantalum-niobium alloys and titanium, more preferably all
  • the shell base is made of a material selected from tantalum, niobium and tantalum-niobium alloys, and it is also preferred that the shell base is made of a material selected from titanium and titanium alloys.
  • the method of manufacturing a colored mobile phone case of the present invention comprises the following steps:
  • the mobile phone case base is made of a material selected from tantalum, niobium, tantalum-niobium alloy, titanium and titanium alloy
  • the mobile phone case base is made of a material selected from tantalum, niobium, tantalum-niobium alloy and titanium
  • the base of the mobile phone case is made of a material selected from tantalum, niobium and tantalum-niobium alloy
  • it is also preferred that the base of the mobile phone case is made of a material selected from titanium and titanium alloy.
  • the substrates such as case substrates and cell phone case substrates are made of tantalum.
  • the substrates such as case substrates and mobile phone case substrates are made of niobium.
  • the substrates such as case substrates and cell phone case substrates are made of a tantalum niobium alloy.
  • the substrates such as case substrates and cell phone case substrates are made of titanium.
  • the bases such as case bases and cell phone case bases are made of titanium alloys.
  • the anodic oxidation method is carried out under the following conditions: the temperature of the electrolyte solution is 20°C-600°C, the anode voltage is 1V-800V, the constant voltage time is 0.01-2 hours, and the boost current density is 1-200mA/ cm 2 to form an amorphous metal oxide layer on the surface of substrates such as case substrates and cell phone case substrates.
  • the electrolyte solution includes an aqueous solution, a mixture of an aqueous solution and an organic compound, and a non-aqueous solution.
  • the aqueous solution comprises an aqueous acid, base or salt solution, preferably an aqueous phosphoric acid solution.
  • concentration of the phosphoric acid aqueous solution is 0.01-1% by weight, preferably 0.01-0.1% by weight, more preferably 0.01-0.05% by weight.
  • the aqueous solution in a mixture of an aqueous solution and an organic compound, includes an aqueous solution of an acid, a base or a salt, and the organic compound includes an alcoholic organic compound such as ethanol, ethylene glycol, n-butanol, or the like. random combination.
  • the mixture of the aqueous solution and the organic compound comprises an aqueous phosphoric acid solution with a concentration of 0.01-0.05% by weight and an alcohol, such as ethylene glycol, in a volume ratio of 1:1 to 1:3, preferably 1:1 to 2:1, more preferably a 2:1 mixture.
  • the mixture of the aqueous solution and the organic compound comprises a mixture of aqueous phosphoric acid with a concentration of 0.05% by weight and ethylene glycol in a weight ratio of 2:1.
  • the non-aqueous solution includes anhydrous concentrated sulfuric acid, molten salt, and a mixture of molten salt and alkali.
  • the molten salt includes molten lithium nitrate, molten sodium nitrate, molten potassium nitrate and any combination thereof.
  • the alkaline substances include lithium hydroxide, sodium hydroxide, potassium hydroxide and any combination thereof.
  • the anodizing method may be performed by placing a substrate such as a case substrate or a mobile phone case substrate in an aqueous electrolyte solution or a mixed solution of an aqueous electrolyte solution and an organic compound.
  • a substrate such as a case substrate or a mobile phone case substrate
  • the solution temperature is 1-99°C, preferably 10-95°C, more preferably room temperature to 90°C
  • the anode voltage is 5-300V
  • the constant voltage time is 0.5-1.5 hours
  • the boost current density is 5-25mA/ cm 2 .
  • the solution temperature is preferably controlled at room temperature to 95°C. If the temperature is too high, the water volatilization rate is too fast. Higher solution temperature, higher anode voltage, and longer constant voltage time easily lead to the crystallization of amorphous metal oxide layer, and the metal oxide layer after crystallization does not refract and transmit light, so There is no color change (generally gray or off-white) with changes in film thickness.
  • the method of manufacturing a colored phone case comprises the steps of:
  • the base body of the mobile phone case is made of tantalum.
  • the aqueous solution is preferably an aqueous phosphoric acid solution, more preferably an aqueous phosphoric acid solution having a concentration of 0.01-0.05% by weight.
  • a tantalum mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the tantalum mobile phone case is applied with 28- Anode voltage of 32V and constant voltage for 0.5-1.5 hours to obtain a blue mobile phone case.
  • a tantalum mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the tantalum mobile phone case is applied by anodizing method, preferably at room temperature (25° C.), in a 0.01-0.05 wt% H 3 PO 4 aqueous solution for 72- Anode voltage of 84V and constant voltage for 0.5-1.5 hours to obtain a golden mobile phone case.
  • a tantalum mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the tantalum mobile phone case is applied 91- Anode voltage of 103V and constant voltage for 0.5-1.5 hours to obtain a blue-purple mobile phone case.
  • a tantalum mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the tantalum mobile phone case is applied, preferably at room temperature (25° C.), in a 0.01-0.05 wt % H 3 PO 4 aqueous solution for 150- 160V anode voltage and constant voltage for 0.5-1.5 hours to get a pink mobile phone case.
  • a tantalum mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the tantalum mobile phone case is applied 203- Anode voltage of 210V and constant voltage for 0.5-1.5 hours to obtain a green mobile phone case.
  • the method of making a colored phone case includes the steps of:
  • the base of the mobile phone case is made of niobium.
  • the aqueous solution is preferably an aqueous phosphoric acid solution, more preferably an aqueous phosphoric acid solution having a concentration of 0.01-0.05% by weight.
  • a niobium mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the niobium mobile phone case is applied by anodizing method, preferably at room temperature (25° C.), in a 0.01-0.05 wt % H 3 PO 4 aqueous solution for 21- Anode voltage of 29V and constant voltage for 0.5-1.5 hours to obtain a blue mobile phone case.
  • a niobium mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the niobium mobile phone case is applied by anodizing method, preferably at room temperature (25° C.), in a 0.01-0.05 wt% H 3 PO 4 aqueous solution for 31-
  • the anode voltage is 38V and the constant voltage is maintained for 0.5-1.5 hours to obtain a silver-white mobile phone case.
  • a niobium mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the niobium mobile phone case is applied by anodizing method, preferably at room temperature (25° C.), in a 0.01-0.05 wt % H 3 PO 4 aqueous solution for 40- Anode voltage of 48V and constant voltage for 0.5-1.5 hours to obtain a golden mobile phone case.
  • a niobium mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the niobium mobile phone case is applied by anodizing method, preferably at room temperature (25° C.), in a 0.01-0.05 wt% H 3 PO 4 aqueous solution for 71- Anode voltage of 78V and constant voltage for 0.5-1.5 hours to obtain a green mobile phone case.
  • a niobium mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the niobium mobile phone case is applied by anodizing method, preferably at room temperature (25° C.), in a 0.01-0.05 wt % H 3 PO 4 aqueous solution for 105- Anode voltage of 113V and constant voltage for 0.5-1.5 hours to obtain a purple-red mobile phone case.
  • the method of manufacturing a colored mobile phone case comprises the steps of:
  • the base body of the mobile phone case is made of tantalum-niobium alloy.
  • the aqueous solution is preferably an aqueous phosphoric acid solution, more preferably an aqueous phosphoric acid solution having a concentration of 0.01-0.05% by weight.
  • a tantalum-niobium alloy mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the tantalum-niobium alloy mobile phone case is prepared by anodizing method, preferably at room temperature (25° C.) in a 0.01-0.05 wt% H 3 PO 4 aqueous solution
  • the anode voltage of 8-18V is applied in the medium and the constant voltage is maintained for 0.5-1.5 hours to obtain a chocolate-colored mobile phone case.
  • a tantalum-niobium alloy mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the tantalum-niobium alloy mobile phone case is prepared by anodizing method, preferably at room temperature (25° C.) in a 0.01-0.05 wt% H 3 PO 4 aqueous solution
  • the anode voltage of 27-28V is applied and the constant voltage is maintained for 0.5-1.5 hours to obtain a sky blue mobile phone case.
  • a tantalum-niobium alloy mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the tantalum-niobium alloy mobile phone case is prepared by anodizing method, preferably at room temperature (25° C.) in a 0.01-0.05 wt% H 3 PO 4 aqueous solution
  • the anode voltage of 38-46V is applied and the constant voltage is maintained for 0.5-1.5 hours to obtain a silver-gray mobile phone case.
  • a tantalum-niobium alloy mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the tantalum-niobium alloy mobile phone case is prepared by anodizing method, preferably at room temperature (25° C.) in a 0.01-0.05 wt% H 3 PO 4 aqueous solution
  • the anode voltage of 97-102V is applied in the middle and constant voltage is applied for 0.5-1.5 hours to obtain a marine green mobile phone case.
  • a tantalum-niobium alloy mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the tantalum-niobium alloy mobile phone case is prepared by anodizing method, preferably at room temperature (25° C.) in a 0.01-0.05 wt% H 3 PO 4 aqueous solution
  • the anode voltage of 138-145V is applied and the constant voltage is maintained for 0.5-1.5 hours to obtain a violet-colored mobile phone case.
  • a tantalum-niobium alloy mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the tantalum-niobium alloy mobile phone case is prepared by anodizing method, preferably at room temperature (25° C.) in a 0.01-0.05 wt% H 3 PO 4 aqueous solution
  • the anode voltage of 246-251V is applied and constant voltage is applied for 0.5-1.5 hours to obtain a dark brown mobile phone case.
  • the method of manufacturing a colored phone case comprises the steps of:
  • the base of the mobile phone case is made of titanium.
  • the aqueous solution is preferably an aqueous phosphoric acid solution, more preferably an aqueous phosphoric acid solution having a concentration of 0.01-0.05% by weight.
  • a titanium mobile phone case with a thickness of 0.01-0.3 mm is prepared, and 44-54 V is applied to the titanium mobile phone case, preferably at room temperature (25° C.), in a 0.01-0.05 wt% H 3 PO 4 aqueous solution by anodizing method.
  • the anode voltage is kept constant for 0.5-1.5 hours to obtain a white-green mobile phone case.
  • a titanium mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the titanium mobile phone case is applied by anodizing method, preferably at room temperature (25° C.), in a 0.01-0.05 wt% H 3 PO 4 aqueous solution for 72- Anode voltage of 84V and constant voltage for 0.5-1.5 hours to obtain a golden mobile phone case.
  • a titanium mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the titanium mobile phone case is applied in a 0.01-0.05 wt % H 3 PO 4 aqueous solution for 92- Anode voltage of 109V and constant voltage for 0.5-1.5 hours to obtain a purple-red mobile phone case.
  • a titanium mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the titanium mobile phone case is applied 121- Anode voltage of 133V and constant voltage for 0.5-1.5 hours to obtain a green mobile phone case.
  • a titanium mobile phone case with a thickness of 0.01-0.3 mm is prepared, and the titanium mobile phone case is applied 159- Anode voltage of 180V and constant voltage for 0.5-1.5 hours to obtain a brown-gray mobile phone case.
  • the anodization method can also be carried out by placing the shell substrate in a non-aqueous electrolyte solution.
  • the electrolyte solution temperature is from the melting point of the electrolyte solution substance to 500°C, the anode voltage is 3V-66V, and the constant voltage time is 0.1-80 minutes.
  • the electrolyte solution temperature is 250-380°C, the anode voltage is 10-40V, and the constant voltage time is 3 seconds-40 minutes.
  • the method of manufacturing a colored case, especially a mobile phone case comprises the following steps:
  • the shell base is made of a material selected from the group consisting of tantalum, niobium, tantalum-niobium alloys, titanium and titanium alloys.
  • the oxide film formed in the non-aqueous solution is porous, and its thickness, that is, the color, is not only related to the temperature and anode voltage, but also to the constant voltage time during the formation of the oxide film. It has nothing to do with the constant pressure time.
  • the non-aqueous solution includes anhydrous concentrated sulfuric acid, molten salt, and a mixture of molten salt and alkaline substances.
  • the molten salt includes molten lithium nitrate, molten sodium nitrate, molten potassium nitrate and any combination thereof.
  • the alkaline substances include lithium hydroxide, sodium hydroxide, potassium hydroxide and any combination thereof.
  • the non-aqueous solution is preferably molten salt, including molten potassium nitrate, molten sodium nitrate, molten lithium nitrate and any combination thereof.
  • the molten salt is molten lithium nitrate.
  • the method of manufacturing a colored case, especially a mobile phone case comprises the following steps:
  • the housing base is made of titanium.
  • the shell matrix made of titanium is anodized in lithium nitrate at 460°C for 5 minutes at a voltage of 10V to obtain a golden shell .
  • the shell matrix made of titanium is anodized in lithium nitrate at 482°C for 10 minutes at a voltage of 12V, resulting in a purple shell.
  • the shell matrix made of titanium is anodized in lithium nitrate at 460° C. for 60 minutes at a voltage of 10 V to obtain a royal blue shell.
  • the shell matrix made of titanium is subjected to anodization treatment in lithium nitrate at 300-350° C. at a voltage of 10 V for 2 minutes to obtain a sky blue shell.
  • the shell matrix made of titanium is anodized in lithium nitrate at 482°C for 10 minutes at a voltage of 12V, resulting in a purple shell.
  • the present invention provides a method for preparing a colored article with multiple color patterns, especially a colored mobile phone case, comprising the steps of:
  • a part of the mobile phone case can be protected with an adhesive tape with a specific pattern first, and then the mobile phone case is subjected to anodizing treatment to obtain a One color pattern is formed, then the tape is peeled off and the color pattern formed on the phone case is protected with another tape, and the phone case is further anodized to obtain another color pattern.
  • a plurality of adhesive tapes can be used to protect the mobile phone case during anodizing to obtain a mobile phone case with multiple colors, for example, three or more colors.
  • the tapes used are usually waterproof tapes, while being resistant to the anodizing conditions used.
  • the method for preparing colored articles with multiple color patterns, especially colored mobile phone cases comprises:
  • the waterproof tape should also meet the tolerance of the anodizing conditions used, such as temperature, acid resistance, etc.
  • the method of manufacturing a colored case, especially a mobile phone case comprises the following steps:
  • the shell base is made of a material selected from tantalum, niobium and tantalum-niobium alloys.
  • the molten salt electrochemical method is a molten lithium salt electrochemical method.
  • the molten salt electrochemical method includes placing the shell matrix in an oxygen-containing inorganic lithium salt at 200°C-650°C, a mixed melt of an oxygen-containing inorganic lithium salt and lithium hydroxide, and a mixed melt of the salt and lithium hydroxide.
  • liquid, or a mixed molten solution of lithium salt and oxygen-containing salt apply an anode voltage of 1-66V, constant voltage for 3 seconds-60 hours, such as 0.1-90 minutes, wherein the boost current density is 1-1000mA/cm 2 , Get a white or off-white shell.
  • an ultrasonic generator is provided in the mixed melt or the mixed melt.
  • the temperature of the mixed melt or the mixed melt is 250°C-520°C
  • the applied anode voltage is 5-25V
  • the boost current density is 5-20 mA/cm 2 .
  • the oxygen-containing inorganic lithium salt is LiNO3 .
  • the mixed melt of lithium salt and oxygen-containing salt is a mixed melt of LiNO 3 and KNO 3 .
  • the mixed melt of lithium salt and oxygen-containing salt is a mixed melt of LiNO 3 and KNO 3 in a weight ratio of 1:2 to 2:1, preferably 1:1.
  • the thickness of the amorphous metal oxide films (layers) formed at higher temperatures varies with the time of anodization Increase and increase, after reaching a certain thickness, the amorphous metal oxide film will electrochemically react with nitrate to form white or off-white lithium tantalate film, lithium niobate film, lithium tantalate and lithium niobate mixture film, , especially at higher temperatures and higher anode voltages.
  • the method of manufacturing a colored case, especially a mobile phone case comprises the following steps:
  • the housing base is made of tantalum.
  • a shell substrate made of tantalum is subjected to a constant voltage of 5-50V in lithium nitrate at 440°C-650°C for 3 seconds-5 hours, resulting in a white shell.
  • the shell matrix made of tantalum is subjected to constant voltage at a voltage of 8-50V in lithium nitrate at 570°C-585°C for 2 minutes to 5 hours to obtain a white shell.
  • lithium nitrate:potassium nitrate (weight ratio 1:2 to 2:1, preferably 1:1 by weight) at 380°C-550°C in 5- Under the voltage of 48V, the constant voltage was maintained for 2 seconds to 2 hours, and a white shell was obtained.
  • lithium nitrate:potassium nitrate (weight ratio 1:2 to 2:1, preferably 1:1 by weight) at 450°C-480°C for the shell matrix made of niobium Under the constant voltage of 5-28V for 2-30 minutes, a white shell is obtained.
  • the method of manufacturing a colored case, especially a mobile phone case comprises the following steps:
  • the shell base is made of a material selected from tantalum, niobium and tantalum-niobium alloys.
  • the shell matrix made of tantalum-niobium alloy is subjected to constant pressure at 135-145V for 1-2 hours in a 0.01-0.05 wt% H3PO4 aqueous solution, followed by nitric acid at 460-585 °C Lithium: potassium nitrate (weight ratio is 1:2 to 2:1, preferably weight ratio is 1:1) under constant voltage of 25-32V for 1-3 hours to obtain a white shell.
  • a molten oxygen-containing lithium salt such as lithium nitrate, or a mixture of lithium nitrate and potassium nitrate or sodium nitrate
  • a suitable anode voltage is added to the molten solution for electrochemical reaction to form a corresponding white lithium tantalate film, or a lithium niobate film, or a mixture film of lithium tantalate and lithium niobate.
  • the designed color anodic oxide film is formed by anodizing in dilute aqueous solution or anodizing in molten salt.
  • Colored articles made according to the method of the present invention include:
  • the article base is made of a material selected from tantalum, niobium, tantalum-niobium alloy, titanium and titanium alloys, preferably the article base is made of a material selected from tantalum, niobium, tantalum-niobium alloy and titanium, preferably the
  • the article substrate is made of a material selected from the group consisting of tantalum, niobium, and tantalum-niobium alloys.
  • the colored casing manufactured according to the method of the present invention comprises:
  • the shell base is made of a material selected from tantalum, niobium, tantalum-niobium alloys, titanium and titanium alloys, preferably the shell base is made of a material selected from tantalum, niobium, tantalum-niobium alloys and titanium, more preferably all
  • the shell base is made of a material selected from tantalum, niobium and tantalum-niobium alloys.
  • the colored mobile phone case manufactured according to the method of the present invention comprises:
  • the mobile phone case base is made of a material selected from tantalum, niobium, tantalum-niobium alloy, titanium and titanium alloy, preferably the mobile phone case base is made of a material selected from tantalum, niobium, tantalum-niobium alloy and titanium, more Preferably, the mobile phone case base is made of a material selected from the group consisting of tantalum, niobium and tantalum-niobium alloys.
  • the amorphous metal oxide includes amorphous tantalum pentoxide, amorphous niobium pentoxide, amorphous titanium dioxide, and mixtures thereof.
  • the lithium-containing compound includes lithium tantalate, lithium niobate, and mixtures thereof.
  • the shell base has a thickness of 0.01-0.5 mm, preferably 0.02-0.3 mm.
  • the shell base of the present invention can be fabricated by techniques known in the art, such as cutting, casting, calendering, etc., without particular limitation.
  • the mobile phone case includes a mobile phone body casing, a mobile phone decorative casing, a mobile phone protective casing, and the like.
  • colored products include casings such as mobile phone casings and computer casings; accessories such as rings, bracelets, necklaces and watch straps; pendants such as Buddha statues, human figures and animal figures.
  • a transparent plastic casing can be added outside the mobile phone case of the present invention to protect the mobile phone from being damaged when accidentally bumped.
  • the purpose of anti-scratch and anti-deformation can be achieved by embedding the mobile phone case of the present invention in the transparent plastic case, and at the same time, the transparent plastic case enables the bright colors of the colored mobile phone case to be viewed.
  • the mobile phone decorative case or mobile phone protective case embedded in the transparent plastic case can be easily replaced with another color.
  • the mobile phone case of the present invention such as a mobile phone decorative case or a mobile phone protective case
  • a plastic transparent case for example, the metal mobile phone case of the present invention is placed in a transparent plastic case, so as to better ensure It will not cause possible scratches, abrasions or deformations to the metal phone case due to careless operation and other reasons when taking off the plastic case of the phone.
  • colored should be understood to include, but not be limited to, red, green, blue, yellow, violet, gold, white, silver, gray, and the like.
  • a method of manufacturing a colored product comprising the steps of:
  • the article substrate is made of a material selected from the group consisting of tantalum, niobium, tantalum-niobium alloys, titanium and titanium alloys.
  • the shell base is made of a material selected from the group consisting of tantalum, niobium, tantalum-niobium alloys, titanium and titanium alloys.
  • the base body of the mobile phone case is made of a material selected from tantalum, niobium, tantalum-niobium alloy, titanium and titanium alloy.
  • step (2) comprises:
  • the anodizing method is carried out under the following conditions: the temperature of the electrolyte solution is 20°C-600°C, the anode voltage is 1V-800V, and the constant voltage time is 3 seconds to 5 hours, preferably 30 seconds to 1.5 hours, and a boost current density of 1 to 200 mA/cm 2 to form an amorphous metal oxide layer/or a lithium-containing compound layer on the surface of the substrate.
  • the electrolyte solution comprises an aqueous solution, a mixture of an aqueous solution and an organic compound, and a non-aqueous solution.
  • the aqueous solution comprises an aqueous solution of an acid, a base or a salt, preferably an aqueous phosphoric acid solution, the concentration of the aqueous phosphoric acid solution being 0.01-1 wt%, preferably 0.01-0.05 wt%.
  • the aqueous solution comprises an aqueous solution of an acid, a base or a salt
  • the organic compound comprises an alcohol such as ethanol, ethylene glycol, n-butanol or any combination thereof.
  • non-aqueous solution comprises anhydrous concentrated sulfuric acid, molten salt, and a mixture of molten salt and alkali.
  • the molten salt comprises molten lithium nitrate, molten sodium nitrate, molten potassium nitrate, and any combination thereof.
  • the anodizing method is performed under the following conditions: the temperature of the electrolyte solution is 1-99°C, and the anode voltage is 5V -600V, and the constant voltage time is within 90 minutes; preferably, the electrolyte solution temperature is from room temperature to 95°C, the anode voltage is 10-200V, and the constant voltage time is 30-60 minutes.
  • niobium mobile phone case having a thickness of 0.01-0.3 mm is prepared, and the niobium mobile phone case is preferably 0.01-0.05 wt % H 3 PO 4 aqueous solution at room temperature (25° C.) by anodizing method.
  • the anode voltage of 40-48V is applied and the constant voltage is maintained for 0.5-1.5 hours to obtain a golden yellow mobile phone case.
  • a titanium mobile phone case having a thickness of 0.01-0.3 mm is prepared, and the titanium mobile phone case is preferably 0.01-0.05 wt % H 3 PO 4 at room temperature (25° C.) by anodizing method.
  • the anode voltage of 72-84V is applied to the aqueous solution and the constant voltage is applied for 0.5-1.5 hours to obtain a golden mobile phone case.
  • the anodization method is performed under the following conditions: the temperature of the electrolyte solution is from the melting point of the electrolyte solution substance to 500°C, and the anode voltage is 3V-66V , and the constant pressure time is within 60 minutes; preferably, the electrolyte solution temperature is 250-350° C., the anode voltage is 5-40V, and the constant pressure time is 3-30 minutes.
  • the molten salt electrochemical method comprises placing the substrate at 250°C-650°C of an oxygen-containing inorganic lithium salt, a mixture of an oxygen-containing inorganic lithium salt and lithium hydroxide.
  • Mixed melt, mixed melt of salt and lithium hydroxide, or mixed melt of lithium salt and oxygen-containing salt apply anode voltage of 1-66V, constant voltage for 0.01-60 hours, wherein the boost current density is 1- 1000mA/cm 2 to get a white or off-white mobile phone case.
  • the shell base is made of a material selected from tantalum, niobium and tantalum-niobium alloys.
  • the article base is made of material selected from tantalum, niobium, tantalum-niobium alloy, titanium and titanium alloy, preferably the article base is made of material selected from tantalum, niobium, tantalum-niobium alloy and titanium, more preferably all
  • the article substrate is made of a material selected from the group consisting of tantalum, niobium, and tantalum-niobium alloys.
  • amorphous metal oxide comprises amorphous tantalum pentoxide, amorphous niobium pentoxide, amorphous titanium dioxide, and mixtures thereof.
  • the colored article of embodiment 27 or 28, wherein the colored article includes housings, such as cell phone cases and computer cases; accessories, such as rings, bracelets, necklaces, and watch straps; pendants such as statues of Buddhas, figures, and animals picture.
  • the cell phone case comprises a cell phone body case, a cell phone decorative case, and a cell phone protective case.
  • a tantalum mobile phone case with a thickness of 0.28 mm was prepared, and an anode voltage of 1-286 V was applied to the tantalum mobile phone case in a 0.05 wt% H 3 PO 4 aqueous solution at room temperature by anodizing method, and a constant voltage was applied for 40 minutes to obtain a colored tantalum mobile phone.
  • a tantalum mobile phone case with a thickness of 0.03 mm is prepared, and an anode voltage of 30V is applied to the tantalum mobile phone case preferably in a 0.05 wt% H 3 PO 4 aqueous solution at room temperature (25° C.) by anodizing method and constant voltage is applied for 40 minutes to obtain blue color.
  • tantalum phone case as shown in Figure 2.
  • a tantalum mobile phone case with a thickness of 0.03 mm is prepared, and an anode voltage of 75V is applied to the tantalum mobile phone case preferably at room temperature (25° C.) in a 0.05 wt % H 3 PO 4 aqueous solution and constant pressure is applied for 40 minutes by anodizing method to obtain golden yellow color.
  • tantalum phone case as shown in Figure 2.
  • a tantalum mobile phone case with a thickness of 0.02 mm is prepared, and an anode voltage of 100V is applied to the tantalum mobile phone case preferably in a 0.05 wt% H 3 PO 4 aqueous solution at room temperature (25° C.) by anodizing method and constant pressure is applied for 40 minutes to obtain a blue-violet color.
  • tantalum phone case as shown in Figure 2.
  • a tantalum mobile phone case with a thickness of 0.075 mm is prepared, and an anode voltage of 110V is applied to the tantalum mobile phone case in a 0.05 wt% H 3 PO 4 aqueous solution at room temperature (25° C.) by anodizing method and constant pressure is applied for 40 minutes to obtain a turquoise color.
  • tantalum phone case as shown in Figure 2.
  • a tantalum mobile phone case with a thickness of 0.03 mm is prepared, and an anode voltage of 120V is applied to the tantalum mobile phone case preferably at room temperature (25° C.) in a 0.05 wt % H 3 PO 4 aqueous solution and constant pressure is applied for 40 minutes to obtain a light green color by anodizing method.
  • tantalum phone case as shown in Figure 2.
  • a tantalum mobile phone case with a thickness of 0.05 mm is prepared, and an anode voltage of 154V is applied to the tantalum mobile phone case preferably in a 0.05 wt% H 3 PO 4 aqueous solution at room temperature (25° C.) by anodizing method and constant pressure is applied for 40 minutes to obtain light pink.
  • color tantalum phone case as shown in Figure 2.
  • a tantalum mobile phone case with a thickness of 0.1 mm is prepared, and an anode voltage of 160V is applied to the tantalum mobile phone case preferably at room temperature (25° C.) in a 0.05 wt% H 3 PO 4 aqueous solution and constant pressure is applied for 40 minutes by anodizing method to obtain a pink color tantalum phone case, as shown in Figure 2.
  • a tantalum mobile phone case with a thickness of 0.03 mm was prepared, and an anode voltage of 178V was applied to the tantalum mobile phone case preferably at room temperature (25° C.) in a 0.05 wt% H 3 PO 4 aqueous solution for 40 minutes at a constant voltage for 40 minutes to obtain a purple mobile phone case with a thickness of 0.03 mm. Tantalum phone case, as shown in Figure 2.
  • a tantalum mobile phone case with a thickness of 0.03 mm is prepared, and an anode voltage of 205V is applied to the tantalum mobile phone case preferably in a 0.05 wt% H 3 PO 4 aqueous solution at room temperature (25° C.) by anodizing method and constant pressure is applied for 40 minutes to obtain a green Tantalum phone case, as shown in Figure 2.
  • a niobium mobile phone case with a thickness of 0.03 mm was prepared, and an anode voltage of 1-210V was applied to the niobium mobile phone case in a 0.05 wt% H 3 PO 4 aqueous solution at room temperature by anodizing method, and the voltage was constant for 40 minutes to obtain a colored niobium mobile phone.
  • Shells of which a blue niobium phone case was obtained at 25V, a silvery white niobium phone case was obtained at 36V, a golden yellow niobium phone case was obtained at 44V, and a sapphire green niobium phone case was obtained at 73V, and at 108V A purple-red niobium phone case is obtained, as shown in Figure 3.
  • a tantalum-niobium alloy (weight ratio of 6:4) mobile phone case with a thickness of 0.1 mm or 0.28 mm is prepared, and the tantalum-niobium alloy mobile phone case is preferably 0.05 wt% H 3 PO 4 aqueous solution at room temperature (25° C.) by anodizing method.
  • the anode voltage of 1-260V was respectively applied in 1-260V and constant voltage was applied for 40 minutes to obtain a colored tantalum-niobium alloy mobile phone case, in which a sky blue tantalum-niobium alloy mobile phone case was obtained at 0.1mm and 28V, and a gray one was obtained at 0.1mm and 43V.
  • Tantalum niobium alloy mobile phone case get marine green tantalum niobium alloy mobile phone case at 0.28mm and 100V, get violet tantalum niobium alloy mobile phone case at 0.1mm and 141V, get dark brown tantalum niobium alloy at 0.28mm and 249V Alloy phone case, as shown in Figure 4.
  • a titanium mobile phone case with a thickness of 0.02 mm was prepared, and an anode voltage of 1-197 V was respectively applied to the titanium mobile phone case in a 0.05 wt% H 3 PO 4 aqueous solution at room temperature (25° C.) by anodizing method and constant pressure was applied for 40 minutes,
  • the colored titanium mobile phone case is obtained, wherein the silver-gray niobium mobile phone case is obtained under 16V, the silver-white niobium mobile phone case is obtained under 24V, the golden yellow niobium mobile phone case is obtained under 82V, and the rose-red niobium mobile phone is obtained under 98V. shell to get a rose-brown niobium phone case at 175V, as shown in Figure 5.
  • a titanium mobile phone case with a thickness of 0.02 mm was prepared, and then an anode voltage of 10 V was applied to the titanium mobile phone case in a molten lithium nitrate solution at 300 °C for 2 minutes to obtain a blue titanium mobile phone case, as shown in Figure 6.
  • a titanium mobile phone case with a thickness of 0.02 mm was prepared, and then a 10V anode voltage was applied to the titanium mobile phone case in a molten lithium nitrate solution at 350 °C and the pressure was constant for 2 minutes to obtain a sky blue titanium mobile phone case, as shown in Figure 6.
  • a titanium mobile phone case with a thickness of 0.02 mm was prepared, and then a 12V anode voltage was applied to the titanium mobile phone case in a molten lithium nitrate solution at 482 °C for 0.5 minutes to obtain a rose-red titanium mobile phone case, as shown in Figure 6.
  • a titanium mobile phone case with a thickness of 0.02 mm was prepared, and then a 12V anode voltage was applied to the titanium mobile phone case in a molten lithium nitrate solution at 482 °C for 10 minutes to obtain a purple titanium mobile phone case, as shown in Figure 6.
  • a titanium mobile phone case with a thickness of 0.02 mm was prepared, and then an anode voltage of 10 V was applied to the titanium mobile phone case in a molten lithium nitrate solution at 460 °C and a constant voltage was applied for 1 minute to obtain a light yellow titanium mobile phone case, as shown in Figure 7.
  • a titanium mobile phone case with a thickness of 0.02 mm was prepared, and then a 10V anode voltage was applied to the titanium mobile phone case in a molten lithium nitrate solution at 460° C. for 2 minutes to obtain a light yellow titanium mobile phone case, as shown in Figure 7.
  • a titanium mobile phone case with a thickness of 0.02 mm was prepared, and then a 10V anode voltage was applied to the titanium mobile phone case in a molten lithium nitrate solution at 460° C. and a constant voltage was applied for 5 minutes to obtain a golden yellow titanium mobile phone case, as shown in Figure 7.
  • a titanium mobile phone case with a thickness of 0.02 mm was prepared, and then a 10V anode voltage was applied to the titanium mobile phone case in a molten lithium nitrate solution at 460° C. for 15 minutes to obtain a purple-colored titanium mobile phone case, as shown in Figure 7.
  • a titanium mobile phone case with a thickness of 0.02 mm was prepared, and then a 10V anode voltage was applied to the titanium mobile phone case in a molten lithium nitrate solution at 460° C. for 20 minutes to obtain a lavender titanium mobile phone case, as shown in Figure 7.
  • a titanium mobile phone case with a thickness of 0.02 mm was prepared, and then a 10V anode voltage was applied to the titanium mobile phone case in a molten lithium nitrate solution at 460 °C for 30 minutes to obtain a purple titanium mobile phone case, as shown in Figure 7.
  • a titanium mobile phone case with a thickness of 0.02 mm was prepared, and then a 10V anode voltage was applied to the titanium mobile phone case in a molten lithium nitrate solution at 460° C. and the constant voltage was maintained for 35 minutes to obtain a titanium mobile phone case with purple sauce, as shown in Figure 7.
  • a titanium mobile phone case with a thickness of 0.02 mm was prepared, and then a 10V anode voltage was applied to the titanium mobile phone case in a molten lithium nitrate solution at 460° C. for 60 minutes to obtain a sapphire blue titanium mobile phone case, as shown in Figure 7.
  • a tantalum mobile phone case with a thickness of 0.05 mm was prepared, and a 10V anode voltage was applied to the tantalum mobile phone case in molten lithium nitrate at 580 ° C and the constant voltage reaction was performed for 3s and 60s to obtain a gray-white tantalum mobile phone case, as shown in Figure 8.
  • a mobile phone case with a thickness of 0.28 mm was prepared, and a 10V anode voltage was applied to the tantalum mobile phone case in molten lithium nitrate at 580° C. and a constant voltage reaction was performed for 3 s to 10 minutes to obtain a gray or white tantalum mobile phone case, as shown in Figure 8.
  • the tantalum - niobium alloy mobile phone case was first placed in a 90 °C aqueous solution of 0.05 wt% H3PO4 at a constant pressure of 143V for 1.5 hours, and then in a molten lithium nitrate:potassium nitrate (482 °C) solution. 1:1 weight ratio) to the tantalum-niobium alloy mobile phone case by applying a voltage of 28V and performing a constant voltage electrochemical reaction for 3 hours to obtain a white tantalum-niobium alloy mobile phone case, as shown in Figure 8.
  • the tantalum - niobium alloy mobile phone case was first placed in a 90 °C aqueous solution of 0.05 wt% H3PO4 at a constant pressure of 143V for 1.5 hours, and then in a molten lithium nitrate:potassium nitrate (482 °C) solution. 1:1 weight ratio) to the tantalum-niobium alloy mobile phone case by applying a voltage of 28V and performing a constant voltage electrochemical reaction for 3 hours to obtain a white tantalum-niobium alloy mobile phone case, as shown in Figure 8.
  • a niobium mobile phone case with a thickness of 0.05 mm was prepared, and a voltage of 10V was applied to the niobium mobile phone case in a molten lithium nitrate: potassium nitrate (1:1 weight ratio) at 460 ° C and a constant voltage was applied for 20 minutes to obtain a white niobium mobile phone case, as shown in the figure. 8 shown.
  • a niobium mobile phone case with a thickness of 0.28 mm was prepared, and a voltage of 10V was applied to the niobium mobile phone case in a molten lithium nitrate: potassium nitrate (1:1 weight ratio) at 460 ° C for 20 minutes to obtain a white niobium mobile phone case, as shown in the figure. 8 shown.
  • a titanium foil with a thickness of 0.03 mm was prepared. Under the protection of tape, a voltage of 15V was applied to the titanium foil in molten lithium nitrate at 268 ° C and the pressure was constant for 5 minutes to obtain a blue background pattern. The striped pattern was protected with tape. Then, a voltage of 10 V was applied to the titanium foil in molten lithium nitrate at 268 °C and a constant voltage was applied for 5 minutes to obtain a purple stripe pattern, as shown in sample 1 in Fig. 9 .
  • a titanium foil with a thickness of 0.03 mm was prepared. Under the protection of tape, a voltage of 10 V was applied to the titanium foil in molten lithium nitrate at 268 °C and a constant voltage was applied for 5 minutes to obtain a purple background pattern. The striped pattern was protected with tape, and then A voltage of 5V was applied to the titanium foil in molten lithium nitrate at 268°C and a constant voltage was applied for 5 minutes to obtain a golden-yellow stripe pattern, as shown in sample 2 in Fig. 9 .
  • a titanium foil with a thickness of 0.03 mm was prepared, and under the protection of tape, a voltage of 15V was applied to the titanium foil in molten lithium nitrate at 268 ° C and a constant voltage was applied for 5 minutes to obtain a blue background pattern.
  • the Taurus pattern was protected with tape. Then, a voltage of 5V was applied to the titanium foil in molten lithium nitrate at 268° C. and a constant voltage was applied for 5 minutes to obtain a Taurus pattern, as shown in sample 3 in FIG. 9 .
  • Tantalum foils each including multiple color patterns are obtained, as shown in Figure 10, in which the background 1 in sample one is purple, the stripe 2 is blue, and the stripe 3 is golden yellow; the five-pointed star and the Chinese pattern in sample two are golden yellow, The background is purple; the five-pointed star and China patterns in sample three are golden yellow and the background is blue-purple; the cow pattern in sample four is golden yellow and the background is blue; the cow pattern in sample five is golden yellow and the background is purple.
  • a niobium foil with a thickness of 0.05 mm was prepared, and under the protection of a tape, in a 0.05 wt% H 3 PO 4 aqueous solution in accordance with the order of the serial numbers in the figure, the corresponding voltage was applied to each color for 20 minutes.
  • Table 1 below shows the mobile phone radiation measured in different directions of the mobile phone when the mobile phone makes a call after the mobile phone case of the present invention is installed, and is tested by the Electromagnetic Testing Center of Tsinghua University.
  • Table 1 show that the mobile phone case of the present invention has a certain anti-radiation effect. Compared with the mobile phone without the mobile phone case of the present invention, the radiation amount of the mobile phone in all directions of the mobile phone when making a call is reduced.

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Abstract

一种制造彩色制品的方法，包括以下步骤：（1）提供制品基体，（2）采用阳极氧化法和/或熔盐电化学法对所述制品基体进行表面处理，其中所述制品基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成；所述的彩色制品优选为彩色手机壳。

Description

一种制造彩色制品及手机壳的方法 技术领域
本发明涉及一种制造彩色制品的方法，特别是涉及一种制造彩色手机壳的方法，以及由所述方法制造的彩色制品，特别是彩色手机壳。
背景技术
彩色制品往往能够得到人们的青睐，特别是外观颜色漂亮的手机尤其能吸引人的注意。随着手机行业日新月异的发展，手机本身的功能越来越强大。同时，手机的外观也越来越受到重视，特别是手机壳的颜色。此外，由于手机具有一定的辐射，制造具有防辐射功能的手机壳也受到越来越多的关注。
CN106067911A描述了一种塑料手机壳的制备方法，包括以下步骤：(1)将塑胶基材、荧光粉和染料按比例混合，投入注塑机中挤入手机壳模具成型；(2)依次喷涂底漆、色漆后进行真空镀膜；(3)将真空镀膜层上需要显示所述色漆层的区域的真空镀膜通过激光镭雕去除；(4)真空镀膜后在镀膜表面依次形成中漆层和UV面漆层。
该专利描述的方法加工步骤繁琐，且塑料手机壳不具有防辐射的功能。
CN105970270A描述了一种在铝质金属手机壳上加工两种铝阳极氧化颜色的工艺，其特征在于：它包括以下步骤：
步骤一，加工铝质机壳：利用CNC切割加工出铝质机壳；
步骤二，注塑PPS塑料：在步骤一制得的铝质机壳的相应位置注塑PPS塑料；
步骤三，第一次铝阳极氧化着色：完成步骤二注塑PPS塑料后，对铝质机壳整体进行第一次铝阳极氧化着色；
步骤四，加工高光亮边：完成步骤三的第一次铝阳极氧化着色后，利用CNC在铝质机壳的边缘处切割加工出等宽的高光亮边；
步骤五，用感光保护油墨遮蔽部分高光亮边：在部分高光亮边表面涂抹感光保护油墨，然后在一定温度下烘烤一定时间后进行曝光；
步骤六，第二次铝阳极氧化着色：对没有感光保护油墨遮蔽的部分高光亮 边进行第二次铝阳极氧化着色；其中，所述第二次铝阳极氧化着色的颜色与第一次铝阳极氧化着色的颜色一样；
步骤七，清洗感光保护油墨：利用清洗液对步骤五中曝光后的感光保护油墨进行清洗，以漏出高光亮边；
步骤八，第三次铝阳极氧化着色：对步骤七中清洗曝光后的感光保护油墨后露出的高光亮边进行第三次铝阳极氧化着色，其中，第三次铝阳极氧化着色的颜色不同于第一次铝阳极氧化着色的颜色，即完成在铝质金属手机壳上加工两种铝阳极氧化颜色的工艺。
该专利描述的方法同样加工步骤繁琐。
CN107567217A描述了一种壳体的制备方法，该方法包括：(1)提供金属基材，将所述金属基材进行硬质阳极氧化处理，得到具有金属硬质阳极氧化物外壳的金属基体；(2)在步骤(1)得到的金属基体的一个表面上形成树脂膜层；(3)将步骤(2)得到的基体进行碱性蚀刻，以去除基体中未形成树脂膜层的表面上的金属硬质阳极氧化物外壳；(4)将步骤(3)得到的基体进行酸性蚀刻，以去除基体中剩余的金属。
在该专利中，表面形成的孔洞和蚀刻会引起表面颜色变化。另外，该专利描述的方法同样加工步骤繁琐。
因此，仍需要寻找一种制造彩色制品，尤其是彩色手机壳的方法，其不仅工艺简单，能够获得丰富的色彩，而且制得的手机壳还具有防辐射功能。
发明内容
为此，本发明提供一种制造彩色制品的方法，其包括以下步骤：
(1)提供制品基体；和
(2)采用阳极氧化法和/或熔盐电化学法对所述制品基体进行表面处理，
其中所述制品基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成，优选所述制品基体由选自钽、铌、钽铌合金和钛的材料制成,更优选所述制品基体由选自钽、铌和钽铌合金的材料制成。
本发明还提供一种制造彩色壳体的方法，其包括以下步骤：
(1)提供壳基体；和
(2)采用阳极氧化法和/或熔盐电化学法对所述壳基体进行表面处理，
其中所述壳基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成，优选所述壳基体由选自钽、铌、钽铌合金和钛的材料制成,更优选所述壳基体由选自钽、铌和钽铌合金的材料制成。
本发明进一步提供一种制造彩色手机壳的方法，其包括以下步骤：
(1)提供手机壳基体；和
(2)采用阳极氧化法和/或熔盐电化学法对所述手机壳基体进行表面处理，
其中所述手机壳基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成，优选所述手机壳基体由选自钽、铌、钽铌合金和钛的材料制成,更优选所述手机壳基体由选自钽、铌和钽铌合金的材料制成。
本发明还提供一种由上述方法制造的彩色制品，其包括：
(1)制品基体；和
(2)在制品基体的表面上形成的无定型金属氧化物层和/或含锂化合物层，
其中所述制品基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成，优选所述制品基体由选自钽、铌、钽铌合金和钛的材料制成,更优选所述制品基体由选自钽、铌和钽铌合金的材料制成。
本发明还提供一种由上述方法制造的彩色壳体，其包括：
(1)壳基体；和
(2)在壳基体的表面上形成的无定型金属氧化物层和/或含锂化合物层，
其中所述壳基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成，优选所述壳基体由选自钽、铌、钽铌合金和钛的材料制成,更优选所述壳基体由选自钽、铌和钽铌合金的材料制成。
本发明还提供一种由上述方法制造的彩色手机壳，其包括：
(1)手机壳基体；和
(2)在手机壳基体的表面上形成的无定型金属氧化物层和/或含锂化合物层，
其中所述手机壳基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成，优选所述手机壳基体由选自钽、铌、钽铌合金和钛的材料制成,更优选所述手机壳基体由选自钽、铌和钽铌合金的材料制成。
本发明制造彩色制品，尤其是手机壳的方法具有以下一项或多项有益效果：(1)能够得到色彩丰富的制品，尤其是手机壳；(2)制得的彩色手机壳具有减少手机辐射的作用；(3)制作工艺简单，和(4)易于修复颜色及更换颜色。
附图说明
图1为根据本发明实施方案在不同工艺条件下制备的彩色钽箔。
图2为根据本发明实施方案在不同工艺条件下制备的彩色钽手机壳。
图3为根据本发明实施方案在不同工艺条件下制备的彩色铌箔。
图4为根据本发明实施方案在不同工艺条件下制备的彩色钽铌合金箔。
图5为根据本发明实施方案在不同工艺条件下制备的彩色钛箔。
图6为根据本发明一个实施方案在不同工艺条件下在熔融硝酸锂中制备的彩色钛手机壳。
图7为根据本发明另一个实施方案在不同工艺条件下在熔融硝酸锂中制备的彩色钛手机壳。
图8为根据本发明实施方案在熔融硝酸锂中制备的灰白色和白色的钽箔、铌箔和钽铌合金箔。
图9为根据本发明实施方案制备的具有多彩图案的钛手机壳。
图10为根据本发明实施方案在0.05重量％H 3PO 4水溶液中制备的具有多彩图案的钽手机壳。
图11为根据本发明实施方案在0.05重量％H 3PO 4水溶液中制备的具有多彩图案的铌手机壳。
图12为根据本发明实施方案在硝酸锂:硝酸钾(重量比1:1)中制备的彩色钽、铌和钽铌合金箔。
具体实施方式
本发明制造彩色制品(例如手机壳)的方法可以采用阳极氧化法和/或熔盐电化学法。特别地，对于钽、铌和钽铌合金既可以单独采用阳极氧化法，也可以采用阳极氧化法和熔盐电化学法的组合制备彩色制品，包括彩色手机壳，而对于钛和钛合金，优选采用阳极氧化法制备彩色制品，更优选采用熔盐阳极氧化 法制备彩色制品，包括彩色手机壳。
阳极氧化法
在含氧电解质溶液中，在适当的温度下，以钽、铌、钽铌合金、钛和钛合金制品例如手机壳为阳极，以镍或不锈钢或其他对含氧电解质溶液稳定的金属为阴极，施加适合的阳极电压并恒压适当的时间进行阳极氧化。
在一个实施方案中，本发明制造彩色制品的方法包括以下步骤：
(1)提供制品基体；和
(2)采用阳极氧化法对所述制品基体进行表面处理，
其中所述制品基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成，优选所述制品基体由选自钽、铌、钽铌合金和钛的材料制成，更优选所述制品基体由选自钽、铌和钽铌合金的材料制成，还优选所述制品基体由选自钛和钛合金的材料制成。
在一个实施方案中，本发明制造彩色壳体的方法包括以下步骤：
(1)提供壳基体；和
(2)采用阳极氧化法对所述壳基体进行表面处理，
其中所述壳基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成，优选所述壳基体由选自钽、铌、钽铌合金和钛的材料制成，更优选所述壳基体由选自钽、铌和钽铌合金的材料制成，还优选所述壳基体由选自钛和钛合金的材料制成。
在一个实施方案中，本发明制造彩色手机壳的方法包括以下步骤：
(1)提供手机壳基体；和
(2)采用阳极氧化法对所述手机壳基体进行表面处理，
其中所述手机壳基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成，优选所述手机壳基体由选自钽、铌、钽铌合金和钛的材料制成，更优选所述手机壳基体由选自钽、铌和钽铌合金的材料制成，还优选所述手机壳基体由选自钛和钛合金的材料制成。
在一个优选实施方案中，所述基体例如壳基体和手机壳基体由钽制成。
在一个优选实施方案中，所述基体例如壳基体和手机壳基体由铌制成。
在一个优选实施方案中，所述基体例如壳基体和手机壳基体由钽铌合金制 成。
在一个优选实施方案中，所述基体例如壳基体和手机壳基体由钛制成。
在一个优选实施方案中，所述基体例如壳基体和手机壳基体由钛合金制成。
优选地，所述阳极氧化法在以下条件下进行：电解质溶液温度为20℃-600℃,阳极电压为1V-800V，恒压时间为0.01-2小时，和升压电流密度为1-200mA/cm 2，以在基体例如壳基体和手机壳基体的表面上形成无定型金属氧化物层。
所述电解质溶液包括水溶液、水溶液与有机化合物的混合物、和非水溶液。
在一个实施方案中，所述水溶液包括酸、碱或盐的水溶液，优选磷酸水溶液。优选地，所述磷酸水溶液的浓度为0.01-1重量％，优选为0.01-0.1重量％，更优选为0.01-0.05重量％。
在一个实施方案中，在水溶液与有机化合物的混合物中，所述水溶液包括酸、碱或盐的水溶液，且所述有机化合物包括醇类有机化合物，例如乙醇、乙二醇、正丁醇或其任意组合。
在一个优选实施方案中，所述水溶液与有机化合物的混合物包括浓度为0.01-0.05重量％的磷酸水溶液与醇类，例如乙二醇的体积比为1:1至1:3，优选1:1至2:1，更优选2:1的混合物。优选地，所述水溶液与有机化合物的混合物包括浓度为0.05重量％的磷酸水溶液与乙二醇的重量比2:1的混合物。
优选地，所述非水溶液包括无水浓硫酸、熔融盐、和熔融盐与碱类物质的混合物。优选地，所述熔融盐包括熔融硝酸锂、熔融硝酸钠、熔融硝酸钾及其任意组合。优选地，所述碱类物质包括氢氧化锂、氢氧化钠、氢氧化钾及其任意组合。
在一个实施方案中，所述阳极氧化法可以通过将基体例如壳基体或手机壳基体置于电解质水溶液中或电解质水溶液与有机化合物的混合溶液中进行。优选地，溶液温度为1-99℃，优选10-95℃，更优选室温至90℃，阳极电压为5-300V，恒压时间为0.5-1.5小时，和升压电流密度为5-25mA/cm 2。
溶液温度优选控制在室温至95℃。温度过高，水分挥发速度过快。较高的溶液温度，较高的阳极电压，及较长的恒压时间容易导致无定型金属氧化物层的晶化，晶化以后的金属氧化物层对光线不产生折射、透射的作用，因而不会随膜厚度的变化而发生颜色变化(一般呈灰色或灰白色)。
在一个实施方案中，所述制造彩色手机壳的方法包括以下步骤：
(1)提供手机壳基体；和
(2)采用阳极氧化法在水溶液中对所述手机壳基体进行表面处理，
其中所述手机壳基体由钽制成。
所述水溶液优选为磷酸水溶液，更优选浓度为0.01-0.05重量％的磷酸水溶液。
在一个优选实施方案中，制备厚度为0.01-0.3mm的钽手机壳，利用阳极氧化法将钽手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加28-32V的阳极电压并恒压0.5-1.5小时，得到蓝色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的钽手机壳，利用阳极氧化法将钽手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加72-84V的阳极电压并恒压0.5-1.5小时，得到金黄色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的钽手机壳，利用阳极氧化法将钽手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加91-103V的阳极电压并恒压0.5-1.5小时，得到蓝紫色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的钽手机壳，利用阳极氧化法将钽手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加150-160V的阳极电压并恒压0.5-1.5小时，得到粉红色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的钽手机壳，利用阳极氧化法将钽手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加203-210V的阳极电压并恒压0.5-1.5小时，得到绿色的手机壳。
在另一个实施方案中，所述制造彩色手机壳的方法包括以下步骤：
(1)提供手机壳基体；和
(2)采用阳极氧化法在水溶液中对所述手机壳基体进行表面处理，
其中所述手机壳基体由铌制成。
所述水溶液优选为磷酸水溶液，更优选浓度为0.01-0.05重量％的磷酸水溶液。
在一个优选实施方案中，制备厚度为0.01-0.3mm的铌手机壳，利用阳极氧化法将铌手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加 21-29V的阳极电压并恒压0.5-1.5小时，得到蓝色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的铌手机壳，利用阳极氧化法将铌手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加31-38V的阳极电压并恒压0.5-1.5小时，得到银白色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的铌手机壳，利用阳极氧化法将铌手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加40-48V的阳极电压并恒压0.5-1.5小时，得到金黄色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的铌手机壳，利用阳极氧化法将铌手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加71-78V的阳极电压并恒压0.5-1.5小时，得到绿色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的铌手机壳，利用阳极氧化法将铌手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加105-113V的阳极电压并恒压0.5-1.5小时，得到紫红色的手机壳。
在又一个实施方案中，所述制造彩色手机壳的方法包括以下步骤：
(1)提供手机壳基体；和
(2)采用阳极氧化法在水溶液中对所述手机壳基体进行表面处理，
其中所述手机壳基体由钽铌合金制成。
所述水溶液优选为磷酸水溶液，更优选浓度为0.01-0.05重量％的磷酸水溶液。
在一个优选实施方案中，制备厚度为0.01-0.3mm的钽铌合金手机壳，利用阳极氧化法将钽铌合金手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加8-18V的阳极电压并恒压0.5-1.5小时，得到巧克力色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的钽铌合金手机壳，利用阳极氧化法将钽铌合金手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加27-28V的阳极电压并恒压0.5-1.5小时，得到天蓝色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的钽铌合金手机壳，利用阳极氧化法将钽铌合金手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加38-46V的阳极电压并恒压0.5-1.5小时，得到银灰色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的钽铌合金手机壳，利用 阳极氧化法将钽铌合金手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加97-102V的阳极电压并恒压0.5-1.5小时，得到海洋绿色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的钽铌合金手机壳，利用阳极氧化法将钽铌合金手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加138-145V的阳极电压并恒压0.5-1.5小时，得到紫罗兰色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的钽铌合金手机壳，利用阳极氧化法将钽铌合金手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加246-251V的阳极电压并恒压0.5-1.5小时，得到深褐色的手机壳。
在一个实施方案中，所述制造彩色手机壳的方法包括以下步骤：
(1)提供手机壳基体；和
(2)采用阳极氧化法在水溶液中对所述手机壳基体进行表面处理，
其中所述手机壳基体由钛制成。
所述水溶液优选为磷酸水溶液，更优选浓度为0.01-0.05重量％的磷酸水溶液。
在一个优选实施方案中，制备厚度为0.01-0.3mm的钛手机壳，利用阳极氧化法将钛手机壳优选在室温(25℃)在0.01-0.05重量％H 3PO 4水溶液中施加44-54V的阳极电压并恒压0.5-1.5小时，得到白绿色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的钛手机壳，利用阳极氧化法将钛手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加72-84V的阳极电压并恒压0.5-1.5小时，得到金黄色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的钛手机壳，利用阳极氧化法将钛手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加92-109V的阳极电压并恒压0.5-1.5小时，得到紫红色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的钛手机壳，利用阳极氧化法将钛手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加121-133V的阳极电压并恒压0.5-1.5小时，得到绿色的手机壳。
在一个优选实施方案中，制备厚度为0.01-0.3mm的钛手机壳，利用阳极氧化法将钛手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加159-180V的阳极电压并恒压0.5-1.5小时，得到棕灰色的手机壳。
所述阳极氧化法还可以通过将壳基体置于非水溶液电解质溶液中进行。电解质溶液温度为电解质溶液物质的熔点至500℃，阳极电压为3V-66V，和恒压时间为0.1-80分钟。优选地，电解质溶液温度为250-380℃，阳极电压为10-40V，和恒压时间为3秒-40分钟。
在一个实施方案中，所述制造彩色壳体，尤其手机壳的方法包括以下步骤：
(1)提供壳基体；和
(2)采用阳极氧化法在非水溶液中对所述壳基体进行表面处理，
其中所述壳基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成。
在非水溶液中形成的氧化膜是多孔的，且在氧化膜形成过程中其厚度，也就是颜色不但与温度、阳极电压有关，而且还与恒压时间有关，而对于在水溶液中的阳极氧化，则与恒压时间无关。
所述非水溶液包括无水浓硫酸、熔融盐、和熔融盐与碱类物质的混合物。优选地，所述熔融盐包括熔融硝酸锂、熔融硝酸钠、熔融硝酸钾及其任意组合。优选地，所述碱类物质包括氢氧化锂、氢氧化钠、氢氧化钾及其任意组合。
所述非水溶液优选为熔融盐，包括熔融硝酸钾、熔融硝酸钠、熔融硝酸锂及其任意组合。优选地，所述熔融盐为熔融硝酸锂。
在一个实施方案中，所述制造彩色壳体，尤其手机壳的方法包括以下步骤：
(1)提供壳基体；和
(2)采用阳极氧化法在非水溶液中对所述壳基体进行表面处理，
其中所述壳基体由钛制成。
如图6和图7所示，在一个优选实施方案中，对由钛制成的壳基体在460℃的硝酸锂中在10V的电压下进行阳极氧化法处理5分钟，得到金黄色的壳体。
在一个优选实施方案中，对由钛制成的壳基体在482℃的硝酸锂中在12V的电压下进行阳极氧化法处理10分钟，得到紫色的壳体。
在一个优选实施方案中，对由钛制成的壳基体在460℃的硝酸锂中在10V的电压下进行阳极氧化法处理60分钟，得到宝蓝色的壳体。
在一个优选实施方案中，对由钛制成的壳基体在300-350℃的硝酸锂中在10V的电压下进行阳极氧化法处理2分钟，得到天蓝色的壳体。
在一个优选实施方案中，对由钛制成的壳基体在482℃的硝酸锂中在12V 的电压下进行阳极氧化法处理10分钟，得到紫色的壳体。
在一个实施方案中，本发明提供了一种制备具有多种色彩图案的彩色制品，尤其是彩色手机壳的方法，其包括以下步骤：
(1)按照预定图案在制品基体上通过阳极氧化法和/或熔盐电化学法形成一种彩色图案；和
(2)对形成的彩色图案进行遮挡，然后通过阳极氧化法和/或熔盐电化学法形成另一种彩色图案。
在一个优选的实施方案中，在制备具有多种色彩图案的彩色制品，尤其是彩色手机壳的方法中，可以先用具有特定图案的胶带保护一部分手机壳，然后对手机壳进行阳极氧化处理而形成一种颜色图案，然后撕掉胶带并对手机壳上形成的颜色图案用另外的胶带进行保护，接着对手机壳进行进一步的阳极氧化得到另一种颜色图案。当然，在阳极氧化时可以采用多个胶带对手机壳进行保护以得到具有多种颜色的手机壳，例如三种或三种以上的颜色。所用胶带通常为防水胶带，同时对使用的阳极氧化条件具有耐受性。
在一个优选的实施方案中，制备具有多种色彩图案的彩色制品，尤其是彩色手机壳的方法包括：
(1)确定在手机壳上的金属材料及特定图案；
(2)确定手机壳上的每一个图案采用的颜色；
(3)确定实现手机外壳每个图案的颜色的表面处理次序，该次序应符合按氧化膜厚度逐渐减少的原则，即先表面处理(或阳极氧化处理)的颜色所对应的图案的膜的厚度应大于其后处理颜色的膜的厚度；和
(4)用防水、防酸的胶带将首先阳极氧化处理的图案以外的部分进行保护，待完成第一次氧化处理后再撕去，再用此胶带保护的方法进行下一个图案的阳极氧化处理，直到最后所有的图案处理完毕。
所述的防水胶带还应满足所用阳极氧化条件的耐受性，如温度，防酸性等。
熔盐电化学法
在一个实施方案中，所述制造彩色壳体，尤其手机壳的方法包括以下步骤：
(1)提供壳基体；和
(2)采用熔盐电化学法对所述壳基体进行表面处理，
其中所述壳基体由选自钽、铌和钽铌合金的材料制成。
优选地，所述熔盐电化学法为熔融锂盐电化学法。
优选地，所述熔盐电化学法包括将壳基体置于200℃-650℃的含氧无机锂盐，含氧无机锂盐与氢氧化锂的混合熔融物，盐与氢氧化锂的混合熔融液，或锂盐与含氧盐的混合熔融液中，施加1-66V的阳极电压，恒压3秒-60小时，例如0.1-90分钟，其中升压电流密度为1-1000mA/cm 2，得到白色或灰白色的壳体。优选地，将超声波发生器设置于所述混合熔融物或所述混合熔融液中。
优选地，所述混合熔融物或所述混合熔融液的温度为250℃-520℃，施加的阳极电压为5-25V，升压电流密度为5-20mA/cm 2。
在一个优选的实施方案中，含氧无机锂盐为LiNO 3。
在一个优选的实施方案中，锂盐与含氧盐的混合熔融液为LiNO 3和KNO 3的混合熔融液。
在一个优选的实施方案中，锂盐与含氧盐的混合熔融液为重量比为1:2至2:1，优选1:1的LiNO 3和KNO 3的混合熔融液。
对于所述混合熔融物或所述混合熔融液，例如硝酸盐如LiNO 3、NaNO 3和KNO 3，在较高温度下所生成的无定型金属氧化物膜(层)的厚度随阳极氧化的时间增加而增加，达到一定厚度后，无定型金属氧化物膜会与硝酸盐发生电化学反应而生成白色或灰白色的钽酸锂膜、铌酸锂膜、钽酸锂和铌酸锂混合物的膜、，尤其是在较高温度和较高阳极电压下。
在一个实施方案中，所述制造彩色壳体，尤其手机壳的方法包括以下步骤：
(1)提供壳基体；和
(2)采用熔盐电化学法对所述壳基体进行表面处理，
其中所述壳基体由钽制成。
在一个实施方案中，对由钽制成的壳基体在440℃-650℃的硝酸锂中在5-50V的电压下恒压3秒-5小时，得到白色的壳体。
在一个优选的实施方案中，对由钽制成的壳基体在570℃-585℃的硝酸锂中在8-50V的电压下恒压2分钟至5小时，得到白色的壳体。
在一个实施方案中，对由铌制成的壳基体在380℃-550℃的硝酸锂:硝酸钾(重量比为1:2至2:1，优选重量比为1:1)中在5-48V的电压下恒压2秒-2小时， 得到白色的壳体。
在一个优选的实施方案中，对由铌制成的壳基体在450℃-480℃的硝酸锂:硝酸钾(重量比为1:2至2:1，优选重量比为1:1)中在5-28V的电压下恒压2-30分钟，得到白色的壳体。
在一个实施方案中，所述制造彩色壳体，尤其手机壳的方法包括以下步骤：
(1)提供壳基体；和
(2)采用阳极氧化法和熔盐电化学法对所述壳基体进行表面处理，
其中所述壳基体由选自钽、铌和钽铌合金的材料制成。
在一个优选的实施方案中，对由钽铌合金制成的壳基体在0.01-0.05重量％H 3PO 4水溶液中在135-145V下恒压1-2小时，然后在460-585℃的硝酸锂:硝酸钾(重量比为1:2至2:1，优选重量比为1:1)中在25-32V的电压下恒压1-3小时，得到白色的壳体。
还可以通过阳极氧化法和熔盐电化学法的组合在手机壳上形成白色或其他彩色的组合图案。例如，可先在钽，铌，或钽鈮合金制成的手机壳上，用电化学反应的方法在熔融的含氧锂盐，如硝酸锂，或硝酸锂与硝酸钾或硝酸钠等的混合熔融液中加适合的阳极电压进行电化学反应生成相对应的白色钽酸锂膜，或铌酸锂膜，或钽酸锂与铌酸锂的混合物膜。如果希望图案是白色的，而对比的底色为彩色的阳极氧化膜，则可用机械抛磨或用HF酸腐蚀的方法将图案以外的白色膜去掉，直至露出金属钽，铌，或钽铌合金为止，然后采用稀水溶液的阳极氧化或熔融盐中阳极氧化生成所设计的彩色阳极氧化物膜。
根据本发明方法制造的彩色制品包括：
(1)制品基体；和
(2)在制品基体的表面上形成的无定型金属氧化物层和/或含锂化合物层，优选无定型金属氧化物层，
其中所述制品基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成，优选所述制品基体由选自钽、铌、钽铌合金和钛的材料制成，优选所述制品基体由选自钽、铌和钽铌合金的材料制成。
根据本发明方法制造的彩色壳体包括：
(1)制品壳基体；和
(2)在壳基体的表面上形成的无定型金属氧化物层和/或含锂化合物层，优选无定型金属氧化物层，
其中所述壳基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成，优选所述壳基体由选自钽、铌、钽铌合金和钛的材料制成，更优选所述壳基体由选自钽、铌和钽铌合金的材料制成。
根据本发明方法制造的彩色手机壳包括：
(1)制品手机壳基体；和
(2)在手机壳基体的表面上形成的无定型金属氧化物层和/或含锂化合物层，优选无定型金属氧化物层，
其中所述手机壳基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成，优选所述手机壳基体由选自钽、铌、钽铌合金和钛的材料制成，更优选所述手机壳基体由选自钽、铌和钽铌合金的材料制成。
在一个实施方案中，所述无定型金属氧化物包括无定型五氧化二钽、无定型五氧化二铌、无定型二氧化钛及其混合物。
在一个优选实施方案中，所述含锂化合物包括钽酸锂、铌酸锂及其混合物。
在一个优选实施方案中，所述壳基体具有0.01-0.5mm，优选0.02-0.3mm的厚度。
本发明所述的壳基体可以通过本领域已知的技术进行制作，例如通过切割、铸塑、压延等，没有特别的限制。
在本发明上下文中，所述手机壳包括手机机身外壳、手机装饰外壳、手机保护外壳等。
在本发明上下文中，彩色制品包括壳体，例如手机壳和电脑壳等；饰品，例如戒指、手镯、项链和表带等；挂件如佛像、人物像和动物像等。
在一个实施方案中，可以在本发明的手机壳外面加一个透明的塑料外壳，以保护手机在不慎磕碰时不至受损。将本发明的手机壳镶嵌在透明塑料壳里可以达到抗划伤、抗变形的目的，同时透明塑料壳使得能够观赏到彩色手机壳的鲜艳颜色。此外，可以方便地将镶嵌在透明塑料壳里的手机装饰外壳或手机保护外壳更换成别的颜色。
在另一个实施方案中，还可以将本发明的手机壳例如手机装饰外壳或手机 保护外壳与塑料透明壳结合为一体，例如将本发明的金属手机壳置于透明塑料壳中，使得更能保证不会在摘下手机塑料外壳时，由于操作不慎等原因，对金属手机壳造成可能的划伤、磨损或变形。
在本发明上下文中，“彩色”应理解为包括但不限于红色、绿色、蓝色、黄色、紫色、金黄色、白色、银白色、灰色等。
除非另外指出，本发明所有的百分数或百分比均以重量计。
根据以下优选实施方案，本领域技术人员能够更容易地理解本发明，但是所述优选实施方案不意图限制本发明的范围。
1.一种制造彩色制品的方法，其包括以下步骤：
(1)提供制品基体；和
(2)采用阳极氧化法和/或熔盐电化学法对所述制品基体进行表面处理，
其中所述制品基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成。
2.根据实施方案1所述的方法，其包括以下步骤：
(1)提供壳基体；和
(2)采用阳极氧化法和/或熔盐电化学法对所述壳基体进行表面处理，
其中所述壳基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成。
3.根据实施方案2所述的方法，其包括以下步骤：
(1)提供手机壳基体；和
(2)采用阳极氧化法和/或熔盐电化学法对所述手机壳基体进行表面处理，
其中所述手机壳基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成。
4.根据实施方案1-3中任一项所述的方法，其中步骤(2)包括：
-按照预定图案在基体上通过阳极氧化法和/或熔盐电化学法形成一种彩色图案；和
-对形成的彩色图案进行遮挡，然后通过阳极氧化法和/或熔盐电化学法形成另一种彩色图案。
5.根据实施方案1-3中任一项所述的方法，其中所述阳极氧化法在以下条件下进行：电解质溶液温度为20℃-600℃,阳极电压为1V-800V，恒压时间为小时3秒-5小时，优选小时30秒-1.5小时，和升压电流密度为1-200mA/cm 2，以在基体的表面上形成无定型金属氧化物层/或含锂化合物层。
6.根据实施方案5所述的方法，其中所述电解质溶液包括水溶液、水溶液与有机化合物的混合物、和非水溶液。
7.根据实施方案6所述的方法，其中所述水溶液包括酸、碱或盐的水溶液，优选磷酸水溶液，所述磷酸水溶液的浓度为0.01-1重量％，优选0.01-0.05重量％。
8.根据实施方案6所述的方法，其中在水溶液与有机化合物的混合物中，所述水溶液包括酸、碱或盐的水溶液，和所述有机化合物包括醇例如乙醇、乙二醇、正丁醇或其任意组合。
9.根据实施方案6所述的方法，其中所述水溶液与有机化合物的混合物包括浓度为0.01-0.05重量％H 3PO 4水溶液与乙二醇的重量比为1:1至3:1，优选1:1至2:1的混合物。
10.根据实施方案6所述的方法，其中所述非水溶液包括无水浓硫酸、熔融盐、和熔融盐与碱类物质的混合物。
11.根据实施方案10所述的方法，其中所述熔融盐包括熔融硝酸锂、熔融硝酸钠、熔融硝酸钾及其任意组合。
12.根据实施方案10所述的方法，其中所述碱类物质包括氢氧化锂、氢氧化钠、氢氧化钾及其任意组合。
13.根据实施方案6所述的方法，其中当电解质溶液为水溶液或水溶液与有机化合物的混合物时，所述阳极氧化法在以下条件下进行：电解质溶液温度为1-99℃，阳极电压为5V-600V，和恒压时间为90分钟以内；优选地，电解质溶液温度为室温至95℃，阳极电压为10-200V，和恒压时间为30-60分钟。
14.根据实施方案13所述的方法，其中制备厚度为0.01-0.3mm的钽手机壳，利用阳极氧化法将钽手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加72-84V的阳极电压并恒压0.5-1.5小时，得到金黄色的手机壳。
15根据实施方案13所述的方法，其中制备厚度为0.01-0.3mm的铌手机壳，利用阳极氧化法将铌手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加40-48V的阳极电压并恒压0.5-1.5小时，得到金黄色的手机壳。
16.根据实施方案13所述的方法，其中制备厚度为0.01-0.3mm的钽铌合金手机壳，利用阳极氧化法将钽铌合金手机壳优选在室温(25℃)下在0.01-0.05重 量％H 3PO 4水溶液中施加27-28V的阳极电压并恒压0.5-1.5小时，得到天蓝色的手机壳。
17.根据实施方案13所述的方法，其中制备厚度为0.01-0.3mm的钛手机壳，利用阳极氧化法将钛手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加72-84V的阳极电压并恒压0.5-1.5小时，得到金黄色的手机壳。
18.根据实施方案6所述的方法，其中当电解质溶液为非水溶液时，所述阳极氧化法在以下条件下进行：电解质溶液温度为电解质溶液物质的熔点至500℃，阳极电压为3V-66V，和恒压时间为60分钟以内；优选地，电解质溶液温度为250-350℃，阳极电压为5-40V，和恒压时间为3-30分钟。
19.根据实施方案18所述的方法，其中对由钛制成的壳基体在460℃的硝酸锂中在10V的电压下进行阳极氧化法处理5分钟，得到金黄色的壳体。
20.根据实施方案1-3中任一项所述的方法，其中熔盐电化学法包括将基体置于250℃-650℃的含氧无机锂盐，含氧无机锂盐与氢氧化锂的混合熔融物，盐与氢氧化锂的混合熔融液，或锂盐与含氧盐的混合熔融液中，施加1-66V的阳极电压，恒压0.01-60小时，其中升压电流密度为1-1000mA/cm 2，得到白色或灰白色的手机壳。
21.根据实施方案20所述的方法，其中所述混合熔融物或所述混合熔融液的温度为300℃-520℃，施加的阳极电压为5-25V，和升压电流密度为5-20mA/cm 2。
22.根据实施方案20所述的方法，其中含氧无机锂盐为LiNO 3。
23.根据实施方案20所述的方法，其中对由钽制成的壳基体在440-650℃的硝酸锂中在8-50V的电压下恒压2分钟至5小时，得到白色的壳体。
24.根据实施方案20所述的方法，其中对由铌制成的壳基体在380-550℃的重量比为1:2至2:1，优选重量比为1:1的硝酸锂/硝酸钾混合物中在5-28V的电压下恒压2-30分钟，得到白色的壳体。
25.根据实施方案2或3所述的方法，其包括以下步骤：
(1)提供壳基体；和
(2)采用阳极氧化法和熔盐电化学法对所述壳基体进行表面处理，
其中所述壳基体由选自钽、铌和钽铌合金的材料制成。
26.根据实施方案25所述的方法，其中对由钽铌合金制成的壳基体在0.01-0.05重量％H 3PO 4的水溶液中在135-145V下恒压1-2小时，然后在400-585℃的重量比为1:2至2:1，优选重量比为1:1的硝酸锂/硝酸钾混合物中在25-32V的电压下恒压1-3小时，得到白色的壳体。
27.一种根据实施方案1-26中任一项所述的方法制造的彩色制品，其包括：
(1)制品基体；和
(2)在制品基体的表面上形成的无定型金属氧化物层和/或含锂化合物层，优选无定型金属氧化物层，
其中所述制品基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成，优选所述制品基体由选自钽、铌、钽铌合金和钛的材料制成，更优选所述制品基体由选自钽、铌和钽铌合金的材料制成。
28.根据实施方案27所述的彩色制品，其中所述无定型金属氧化物包括无定型五氧化二钽、无定型五氧化二铌、无定型二氧化钛及其混合物。
29.根据实施方案27或28所述的彩色制品，其中所述含锂化合物包括钽酸锂、铌酸锂及其混合物。
30.根据实施方案27或28所述的彩色制品，其中所述彩色制品包括壳体，例如手机壳和电脑壳；饰品，例如戒指、手镯、项链和表带；挂件如佛像、人物像和动物像。
31.根据实施方案30所述的彩色制品，其中所述手机壳包括手机机身外壳、手机装饰外壳和手机保护外壳。
实施例
在下文中结合附图描述了某些示例性实施例。正如本领域技术人员可认识到的那样，在不脱离本发明的精神或范围的情况下，可通过各种不同方式修改所描述的实施例。因此，附图和描述被认为本质上是示例性的而非限制性的。
实施例1
制备厚度为0.28mm的钽手机壳，利用阳极氧化法将钽手机壳在室温下在0.05重量％H 3PO 4水溶液中分别施加1-286V的阳极电压并恒压40分钟，得到彩色的钽手机壳，其中在30V下得到蓝色的钽手机壳，在78V下得到金黄色的 钽手机壳，在95V下得到紫色的钽手机壳，在125V下得到绿色的钽手机壳，在142V下得到黄色的钽手机壳，在168V下得到玫瑰红色的钽手机壳，如图1所示。
实施例2
制备厚度为0.03mm的钽手机壳，利用阳极氧化法将钽手机壳优选在室温(25℃)下在0.05重量％H 3PO 4水溶液中施加30V的阳极电压并恒压40分钟，得到蓝色的钽手机壳，如图2所示。
实施例3
制备厚度为0.03mm的钽手机壳，利用阳极氧化法将钽手机壳优选在室温(25℃)下在0.05重量％H 3PO 4水溶液中施加75V的阳极电压并恒压40分钟，得到金黄色的钽手机壳，如图2所示。
实施例4
制备厚度为0.02mm的钽手机壳，利用阳极氧化法将钽手机壳优选在室温(25℃)下在0.05重量％H 3PO 4水溶液中施加100V的阳极电压并恒压40分钟，得到蓝紫色的钽手机壳，如图2所示。
实施例5
制备厚度为0.075mm的钽手机壳，利用阳极氧化法将钽手机壳优选在室温(25℃)下在0.05重量％H 3PO 4水溶液中施加110V的阳极电压并恒压40分钟，得到青绿色的钽手机壳，如图2所示。
实施例6
制备厚度为0.03mm的钽手机壳，利用阳极氧化法将钽手机壳优选在室温(25℃)下在0.05重量％H 3PO 4水溶液中施加120V的阳极电压并恒压40分钟，得到浅绿色的钽手机壳，如图2所示。
实施例7
制备厚度为0.05mm的钽手机壳，利用阳极氧化法将钽手机壳优选在室温(25℃)下在0.05重量％H 3PO 4水溶液中施加154V的阳极电压并恒压40分钟，得到浅粉红色的钽手机壳，如图2所示。
实施例8
制备厚度为0.1mm的钽手机壳，利用阳极氧化法将钽手机壳优选在室温 (25℃)下在0.05重量％H 3PO 4水溶液中施加160V的阳极电压并恒压40分钟，得到粉红色的钽手机壳，如图2所示。
实施例9
制备厚度为0.03mm的钽手机壳，利用阳极氧化法将钽手机壳优选在室温(25℃)下在0.05重量％H 3PO 4水溶液中施加178V的阳极电压并恒压40分钟，得到紫色的钽手机壳，如图2所示。
实施例10
制备厚度为0.03mm的钽手机壳，利用阳极氧化法将钽手机壳优选在室温(25℃)下在0.05重量％H 3PO 4水溶液中施加205V的阳极电压并恒压40分钟，得到绿色的钽手机壳，如图2所示。
实施例11
制备厚度为0.03mm的铌手机壳，利用阳极氧化法将铌手机壳在室温下在0.05重量％H 3PO 4水溶液中分别施加1-210V的阳极电压并恒压40分钟，得到彩色的铌手机壳，其中在25V下得到蓝色的铌手机壳，在36V下得到银白色的铌手机壳，在44V下得到金黄色的铌手机壳，在73V下得到宝石绿色的铌手机壳，在108V下得到紫红色的铌手机壳，如图3所示。
实施例12
制备厚度为0.1mm或0.28mm的钽铌合金(重量比为6:4)手机壳，利用阳极氧化法将钽铌合金手机壳优选在室温(25℃)下在0.05重量％H 3PO 4水溶液中分别施加1-260V的阳极电压并恒压40分钟，得到彩色的钽铌合金手机壳，其中在0.1mm和28V下得到天蓝色的钽铌合金手机壳，在0.1mm和43V下得到灰色的钽铌合金手机壳，在0.28mm和100V下得到海洋绿色的钽铌合金手机壳，在0.1mm和141V下得到紫罗兰色的钽铌合金手机壳，在0.28mm和249V下得到深褐色的钽铌合金手机壳，如图4所示。
实施例13
制备厚度为0.02mm的钛手机壳，利用阳极氧化法将钛手机壳优选在室温(25℃)下在0.05重量％H 3PO 4水溶液中分别施加1-197V的阳极电压并恒压40分钟，得到彩色的钛手机壳，其中在16V下得到银灰色的铌手机壳，在24V下得到银白色的铌手机壳，在82V下得到金黄色的铌手机壳，在98V下得到玫瑰 红色的铌手机壳，在175V下得到玫瑰棕色的铌手机壳，如图5所示。
实施例14
制备厚度为0.02mm的钛手机壳，然后在300℃的熔融硝酸锂溶液中对钛手机壳施加10V阳极电压并恒压2分钟，得到蓝色的钛手机壳，如图6所示。
实施例15
制备厚度为0.02mm的钛手机壳，然后在350℃的熔融硝酸锂溶液中对钛手机壳施加10V阳极电压并恒压2分钟，得到天蓝色的钛手机壳，如图6所示。
实施例16
制备厚度为0.02mm的钛手机壳，然后在482℃的熔融硝酸锂溶液中对钛手机壳施加12V阳极电压并恒压0.5分钟，得到玫瑰红色的钛手机壳，如图6所示。
实施例17
制备厚度为0.02mm的钛手机壳，然后在482℃的熔融硝酸锂溶液中对钛手机壳施加12V阳极电压并恒压10分钟，得到紫色的钛手机壳，如图6所示。
实施例18
制备厚度为0.02mm的钛手机壳，然后在460℃的熔融硝酸锂溶液中对钛手机壳施加10V阳极电压并恒压1分钟，得到浅黄色的钛手机壳，如图7所示。
实施例19
制备厚度为0.02mm的钛手机壳，然后在460℃的熔融硝酸锂溶液中对钛手机壳施加10V阳极电压并恒压2分钟，得到淡黄色的钛手机壳，如图7所示。
实施例20
制备厚度为0.02mm的钛手机壳，然后在460℃的熔融硝酸锂溶液中对钛手机壳施加10V阳极电压并恒压5分钟，得到金黄色的钛手机壳，如图7所示。
实施例21
制备厚度为0.02mm的钛手机壳，然后在460℃的熔融硝酸锂溶液中对钛手机壳施加10V阳极电压并恒压15分钟，得到绛紫色的钛手机壳，如图7所示。
实施例22
制备厚度为0.02mm的钛手机壳，然后在460℃的熔融硝酸锂溶液中对钛手机壳施加10V阳极电压并恒压20分钟，得到淡紫色的钛手机壳，如图7所示。
实施例23
制备厚度为0.02mm的钛手机壳，然后在460℃的熔融硝酸锂溶液中对钛手机壳施加10V阳极电压并恒压30分钟，得到紫色的钛手机壳，如图7所示。
实施例24
制备厚度为0.02mm的钛手机壳，然后在460℃的熔融硝酸锂溶液中对钛手机壳施加10V阳极电压并恒压35分钟，得到酱紫色的钛手机壳，如图7所示。
实施例25
制备厚度为0.02mm的钛手机壳，然后在460℃的熔融硝酸锂溶液中对钛手机壳施加10V阳极电压并恒压60分钟，得到宝石蓝色的钛手机壳，如图7所示。
实施例26
制备厚度为0.05mm的钽手机壳，在580℃的熔融硝酸锂中对钽手机壳施加10V阳极电压并恒压反应3s和60s，得到灰白色的钽手机壳，如图8所示。
实施例27
制备厚度为0.28mm的手机壳，在580℃的熔融硝酸锂中对钽手机壳施加10V阳极电压并恒压反应3s至10分钟，得到灰色或白色的钽手机壳，如图8所示。
实施例28
制备厚度为0.05mm的钽铌合金手机壳，先将钽铌合金手机壳在0.05重量％H 3PO 4的90℃水溶液中143V恒压1.5小时，然后在482℃的熔融硝酸锂:硝酸钾(1:1重量比)中对钽铌合金手机壳施加28V电压并恒压电化学反应3小时，得到白色的钽铌合金手机壳，如图8所示。
实施例29
制备厚度为0.28mm的钽铌合金手机壳，先将钽铌合金手机壳在0.05重量％H 3PO 4的90℃水溶液中143V恒压1.5小时，然后在482℃的熔融硝酸锂:硝酸钾(1:1重量比)中对钽铌合金手机壳施加28V电压并恒压电化学反应3小时，得到白色的钽铌合金手机壳，如图8所示。
实施例30
制备厚度为0.05mm的铌手机壳，在460℃的熔融硝酸锂:硝酸钾(1:1重量比)中对铌手机壳施加10V电压并恒压20分钟，得到白色的铌手机壳，如图8 所示。
实施例31
制备厚度为0.28mm的铌手机壳，在460℃的熔融硝酸锂:硝酸钾(1:1重量比)中对铌手机壳施加10V电压并恒压20分钟，得到白色的铌手机壳，如图8所示。
实施例32
制备厚度为0.03mm的钛箔，在胶带保护的情况下在268℃的熔融硝酸锂中对钛箔施加15V电压并恒压5分钟得蓝色背景图案，用胶带对所述条纹图案进行保护，然后在268℃的熔融硝酸锂中对钛箔施加10V电压并恒压5分钟得紫色条纹图案，如图9中的样品一所示。
实施例33
制备厚度为0.03mm的钛箔，在胶带保护的情况下在268℃的熔融硝酸锂中对钛箔施加10V电压并恒压5分钟得紫色背景图案，用胶带对所述条纹图案进行保护，然后在268℃的熔融硝酸锂中对钛箔施加5V电压并恒压5分钟得金黄色条纹图案，如图9中的样品二所示。
实施例34
制备厚度为0.03mm的钛箔，在胶带保护的情况下在268℃的熔融硝酸锂中对钛箔施加15V电压并恒压5分钟得蓝色背景图案，用胶带对所述金牛图案进行保护，然后在268℃的熔融硝酸锂中对钛箔施加5V电压并恒压5分钟得金牛图案，如图9中的样品三所示。
实施例35
制备厚度为0.05mm或0.075mm的钽箔，在胶带保护的情况下在0.05重量％H 3PO 4水溶液中按照图中所标序号的顺序在相应电压下对每种颜色各恒压30分钟，得到各自包括多种颜色图案的钽箔，如图10所示，其中样品一中背景1为紫色，条纹2为蓝色，条纹3为金黄色；样品二中五角星和中国图案为金黄色，背景为紫色；样品三中五角星和China图案为金黄色，背景为蓝紫色；样品四中牛图案为金黄色，背景为蓝色；样品五中牛图案为金黄色，背景为紫色。
实施例36
制备厚度为0.05mm的铌箔，在胶带保护的情况下在0.05重量％H 3PO 4水 溶液中按照图中所标序号的顺序在相应电压下对每种颜色各恒压20分钟，得到各自包括多种颜色图案的铌箔，如图11所示。
下表1中显示了装上本发明手机壳后，在手机拨打电话时在手机的不同方向上测得的手机辐射，由清华大学电磁检测中心测试。
表1
Figure PCTCN2021120331-appb-000001
表1结果表明，本发明手机壳具有一定的防辐射作用。相对于不装本发明手机壳的手机，装上本发明手机壳的手机在拨打电话时在手机各个方向上的辐射量均降低。
尽管显示和描述了本发明的具体实施方案，应当理解其它改进、替代和可选方案是本领域技术人员所了解的。这类改进、替代和可选实施方案可不偏离应由所附权利要求书确定的本发明的精神和范围而做出。本发明的各个特征描述于所附权利要求书中

Claims (31)

  1. 一种制造彩色制品的方法，其包括以下步骤：
    (1)提供制品基体；和
    (2)采用阳极氧化法和/或熔盐电化学法对所述制品基体进行表面处理，
    其中所述制品基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成。
  2. 根据权利要求1所述的方法，其包括以下步骤：
    (1)提供壳基体；和
    (2)采用阳极氧化法和/或熔盐电化学法对所述壳基体进行表面处理，
    其中所述壳基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成。
  3. 根据权利要求2所述的方法，其包括以下步骤：
    (1)提供手机壳基体；和
    (2)采用阳极氧化法和/或熔盐电化学法对所述手机壳基体进行表面处理，
    其中所述手机壳基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成。
  4. 根据权利要求1-3中任一项所述的方法，其中步骤(2)包括：
    -按照预定图案在基体上通过阳极氧化法和/或熔盐电化学法形成一种彩色图案；和
    -对形成的彩色图案进行遮挡，然后通过阳极氧化法和/或熔盐电化学法形成另一种彩色图案。
  5. 根据权利要求1-3中任一项所述的方法，其中所述阳极氧化法在以下条件下进行：电解质溶液温度为20℃-600℃,阳极电压为1V-800V，恒压时间为小时3秒-5小时，优选小时30秒-1.5小时，和升压电流密度为1-200mA/cm 2，以在基体的表面上形成无定型金属氧化物层/或含锂化合物层。
  6. 根据权利要求5所述的方法，其中所述电解质溶液包括水溶液、水溶液与有机化合物的混合物、和非水溶液。
  7. 根据权利要求6所述的方法，其中所述水溶液包括酸、碱或盐的水溶液，优选磷酸水溶液，所述磷酸水溶液的浓度为0.01-1重量％，优选0.01-0.05重量％。
  8. 根据权利要求6所述的方法，其中在水溶液与有机化合物的混合物中，所述水溶液包括酸、碱或盐的水溶液，和所述有机化合物包括醇例如乙醇、乙 二醇、正丁醇或其任意组合。
  9. 根据权利要求6所述的方法，其中所述水溶液与有机化合物的混合物包括浓度为0.01-0.05重量％H 3PO 4水溶液与乙二醇的重量比为1:1至3:1，优选1:1至2:1的混合物。
  10. 根据权利要求6所述的方法，其中所述非水溶液包括无水浓硫酸、熔融盐、和熔融盐与碱类物质的混合物。
  11. 根据权利要求10所述的方法，其中所述熔融盐包括熔融硝酸锂、熔融硝酸钠、熔融硝酸钾及其任意组合。
  12. 根据权利要求10所述的方法，其中所述碱类物质包括氢氧化锂、氢氧化钠、氢氧化钾及其任意组合。
  13. 根据权利要求6所述的方法，其中当电解质溶液为水溶液或水溶液与有机化合物的混合物时，所述阳极氧化法在以下条件下进行：电解质溶液温度为1-99℃，阳极电压为5V-600V，和恒压时间为90分钟以内；优选地，电解质溶液温度为室温至95℃，阳极电压为10-200V，和恒压时间为30-60分钟。
  14. 根据权利要求13所述的方法，其中制备厚度为0.01-0.3mm的钽手机壳，利用阳极氧化法将钽手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加72-84V的阳极电压并恒压0.5-1.5小时，得到金黄色的手机壳。
  15. 根据权利要求13所述的方法，其中制备厚度为0.01-0.3mm的铌手机壳，利用阳极氧化法将铌手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加40-48V的阳极电压并恒压0.5-1.5小时，得到金黄色的手机壳。
  16. 根据权利要求13所述的方法，其中制备厚度为0.01-0.3mm的钽铌合金手机壳，利用阳极氧化法将钽铌合金手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加27-28V的阳极电压并恒压0.5-1.5小时，得到天蓝色的手机壳。
  17. 根据权利要求13所述的方法，其中制备厚度为0.01-0.3mm的钛手机壳，利用阳极氧化法将钛手机壳优选在室温(25℃)下在0.01-0.05重量％H 3PO 4水溶液中施加72-84V的阳极电压并恒压0.5-1.5小时，得到金黄色的手机壳。
  18. 根据权利要求6所述的方法，其中当电解质溶液为非水溶液时，所述阳极氧化法在以下条件下进行：电解质溶液温度为电解质溶液物质的熔点至 500℃，阳极电压为3V-66V，和恒压时间为60分钟以内；优选地，电解质溶液温度为250-350℃，阳极电压为5-40V，和恒压时间为3-30分钟。
  19. 根据权利要求18所述的方法，其中对由钛制成的壳基体在460℃的硝酸锂中在10V的电压下进行阳极氧化法处理5分钟，得到金黄色的壳体。
  20. 根据权利要求1-3中任一项所述的方法，其中熔盐电化学法包括将基体置于250℃-650℃的含氧无机锂盐，含氧无机锂盐与氢氧化锂的混合熔融物，盐与氢氧化锂的混合熔融液，或锂盐与含氧盐的混合熔融液中，施加1-66V的阳极电压，恒压0.01-60小时，其中升压电流密度为1-1000mA/cm 2，得到白色或灰白色的手机壳。
  21. 根据权利要求20所述的方法，其中所述混合熔融物或所述混合熔融液的温度为300℃-520℃，施加的阳极电压为5-25V，和升压电流密度为5-20mA/cm 2。
  22. 根据权利要求20所述的方法，其中含氧无机锂盐为LiNO 3。
  23. 根据权利要求20所述的方法，其中对由钽制成的壳基体在440-650℃的硝酸锂中在8-50V的电压下恒压2分钟至5小时，得到白色的壳体。
  24. 根据权利要求20所述的方法，其中对由铌制成的壳基体在380-550℃的重量比为1:2至2:1，优选重量比为1:1的硝酸锂/硝酸钾混合物中在5-28V的电压下恒压2-30分钟，得到白色的壳体。
  25. 根据权利要求2或3所述的方法，其包括以下步骤：
    (1)提供壳基体；和
    (2)采用阳极氧化法和熔盐电化学法对所述壳基体进行表面处理，
    其中所述壳基体由选自钽、铌和钽铌合金的材料制成。
  26. 根据权利要求25所述的方法，其中对由钽铌合金制成的壳基体在0.01-0.05重量％H 3PO 4的水溶液中在135-145V下恒压1-2小时，然后在400-585℃的重量比为1:2至2:1，优选重量比为1:1的硝酸锂/硝酸钾混合物中在25-32V的电压下恒压1-3小时，得到白色的壳体。
  27. 一种根据权利要求1-26中任一项所述的方法制造的彩色制品，其包括：
    (1)制品基体；和
    (2)在制品基体的表面上形成的无定型金属氧化物层和/或含锂化合物层， 优选无定型金属氧化物层，
    其中所述制品基体由选自钽、铌、钽铌合金、钛和钛合金的材料制成，优选所述制品基体由选自钽、铌、钽铌合金和钛的材料制成，更优选所述制品基体由选自钽、铌和钽铌合金的材料制成。
  28. 根据权利要求27所述的彩色制品，其中所述无定型金属氧化物包括无定型五氧化二钽、无定型五氧化二铌、无定型二氧化钛及其混合物。
  29. 根据权利要求27或28所述的彩色制品，其中所述含锂化合物包括钽酸锂、铌酸锂及其混合物。
  30. 根据权利要求27或28所述的彩色制品，其中所述彩色制品包括壳体，例如手机壳和电脑壳；饰品，例如戒指、手镯、项链和表带；挂件如佛像、人物像和动物像。
  31. 根据权利要求30所述的彩色制品，其中所述手机壳包括手机机身外壳、手机装饰外壳和手机保护外壳。
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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85101505A (zh) * 1985-04-01 1986-08-27 华北光电技术研究所 耐磨的带有钽酸锂薄膜的钽制器件及其制备工艺
CN86102269A (zh) * 1986-04-09 1987-10-28 华北光电技术研究所 用于湿法、干湿法纺丝的带有钽酸锂膜的钽喷丝头(板)
CN1006791B (zh) 1984-10-16 1990-02-14 三井东圧化学株式会社 制造新的苯醌衍生物之方法以及作为适用于记录材料的显色剂的应用
CN1844483A (zh) * 2006-03-15 2006-10-11 厦门大学 钛及钛合金表面阳极氧化着色的方法
CN101717982A (zh) * 2009-12-16 2010-06-02 厦门大学 一种无氟环保型钛合金表面阳极氧化着色方法
CN102115902A (zh) * 2009-12-30 2011-07-06 沈阳天贺新材料开发有限公司 一种钛及钛合金表面阳极氧化着色的处理方法
CN102808209A (zh) * 2011-06-03 2012-12-05 上海造币有限公司 铌及铌合金表面氧化着色的方法
CN105970270A (zh) 2016-05-13 2016-09-28 兴科电子(东莞)有限公司 一种在铝质金属手机壳上加工两种铝阳极氧化颜色的工艺
WO2017116291A1 (ru) * 2015-12-28 2017-07-06 Кирилл Сергеевич НАПОЛЬСКИЙ Способ формирования цветного декоративного покрытия с помощью анодирования
CN107201540A (zh) * 2017-04-21 2017-09-26 昆明理工大学 一种用于制备金色钛合金阳极氧化膜的电解液
CN107567217A (zh) 2016-06-30 2018-01-09 比亚迪股份有限公司 一种壳体及其制备方法和应用

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0660436B2 (ja) * 1986-03-28 1994-08-10 ユ ツオン リユ タンタル、ニオブまたはその合金製物品の保護膜およびその製法
TW508231B (en) * 1999-04-12 2002-11-01 Jiin-Huey Chernlin Medical implant
CN100390320C (zh) * 2004-06-23 2008-05-28 中国科学院金属研究所 电化学法在钛或钛合金植入材料表面处理中的应用
US20060229715A1 (en) * 2005-03-29 2006-10-12 Sdgi Holdings, Inc. Implants incorporating nanotubes and methods for producing the same
US8075312B2 (en) * 2005-08-30 2011-12-13 Zimmer Dental, Inc. Dental implant with improved osseointegration features
ES2310129B1 (es) * 2007-06-01 2009-10-02 Juan Carlos Garcia Saban Nueva superficie de implantes metalicos a base de titanio destinados a ser insertado en tejido oseo.
EP2014259A1 (en) * 2007-07-09 2009-01-14 Astra Tech AB A bone tissue implant comprising lithium ions
CN101311329A (zh) * 2008-02-20 2008-11-26 福建师范大学 具有生物活性的氧化钛纳米管阵列骨修复生物材料的制备方法
CH699087A1 (de) * 2008-07-07 2010-01-15 Samuel Steinemann Implantat.
CN103526262A (zh) * 2013-10-17 2014-01-22 赵全明 一种对钽及其合金进行表面改性的方法及其所用的电解液
CN105012030A (zh) * 2014-04-28 2015-11-04 重庆润泽医药有限公司 一种牙种植体
EP3195825B1 (en) * 2014-09-17 2019-07-31 Universidade do Minho Dental implant
CN106693069B (zh) * 2017-02-22 2019-05-07 华中科技大学 医用多孔钛钽人工骨、人工关节的制备方法及其产品
CN109234783A (zh) * 2018-11-21 2019-01-18 中国船舶重工集团公司第七二五研究所 一种对环境友好的彩色钛合金阳极氧化膜制备方法
CN109487323B (zh) * 2018-12-20 2020-12-11 大连理工大学 一种在钛金属表面微弧氧化制备含生物活性元素多孔膜的电解液
CN109758245A (zh) 2019-03-19 2019-05-17 中南大学湘雅口腔医(学)院 一种钽铌合金牙种植体材料及钽铌合金牙种植体
CN109965996A (zh) 2019-03-19 2019-07-05 湖南省紫百合义齿科技有限公司 一种钽钽铌合金牙种植体及其制备方法
CN110610046B (zh) 2019-05-24 2023-05-12 中航迈特粉冶科技（北京）有限公司 医用多孔钽植入物及其制造方法
CN111494035A (zh) * 2020-04-24 2020-08-07 深圳大洲医学科技有限公司 一种骨小梁多孔钽牙种植体及其制备方法

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1006791B (zh) 1984-10-16 1990-02-14 三井东圧化学株式会社 制造新的苯醌衍生物之方法以及作为适用于记录材料的显色剂的应用
CN85101505A (zh) * 1985-04-01 1986-08-27 华北光电技术研究所 耐磨的带有钽酸锂薄膜的钽制器件及其制备工艺
CN86102269A (zh) * 1986-04-09 1987-10-28 华北光电技术研究所 用于湿法、干湿法纺丝的带有钽酸锂膜的钽喷丝头(板)
CN1844483A (zh) * 2006-03-15 2006-10-11 厦门大学 钛及钛合金表面阳极氧化着色的方法
CN101717982A (zh) * 2009-12-16 2010-06-02 厦门大学 一种无氟环保型钛合金表面阳极氧化着色方法
CN102115902A (zh) * 2009-12-30 2011-07-06 沈阳天贺新材料开发有限公司 一种钛及钛合金表面阳极氧化着色的处理方法
CN102808209A (zh) * 2011-06-03 2012-12-05 上海造币有限公司 铌及铌合金表面氧化着色的方法
WO2017116291A1 (ru) * 2015-12-28 2017-07-06 Кирилл Сергеевич НАПОЛЬСКИЙ Способ формирования цветного декоративного покрытия с помощью анодирования
CN105970270A (zh) 2016-05-13 2016-09-28 兴科电子(东莞)有限公司 一种在铝质金属手机壳上加工两种铝阳极氧化颜色的工艺
CN107567217A (zh) 2016-06-30 2018-01-09 比亚迪股份有限公司 一种壳体及其制备方法和应用
CN107201540A (zh) * 2017-04-21 2017-09-26 昆明理工大学 一种用于制备金色钛合金阳极氧化膜的电解液

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