CN109537018B - Anodic oxidation method for welded structure and application thereof - Google Patents

Anodic oxidation method for welded structure and application thereof Download PDF

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Publication number
CN109537018B
CN109537018B CN201811493109.8A CN201811493109A CN109537018B CN 109537018 B CN109537018 B CN 109537018B CN 201811493109 A CN201811493109 A CN 201811493109A CN 109537018 B CN109537018 B CN 109537018B
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welding
welded structure
aluminum layer
aluminum
forming
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CN109537018A (en
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肖华
李剑锋
夏丰滨
谭亚新
王瑾
高云峰
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Han s Laser Technology Industry Group Co Ltd
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Han s Laser Technology Industry Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids

Abstract

The invention relates to an anodic oxidation method of a welding structure and application thereof. The anodic oxidation method of the welded structure comprises the following steps: providing a welding structure, wherein the welding structure is provided with a welding surface, and a welding seam is formed on the welding surface; forming an aluminum layer on the welding surface, wherein the aluminum layer completely covers the welding surface; and carrying out anodic oxidation treatment on the welding structure with the aluminum layer. The anodic oxidation method of the welding structure can obtain the oxide layer with uniform thickness and uniform color.

Description

Anodic oxidation method for welded structure and application thereof
Technical Field
The invention relates to the technical field of metal materials, in particular to an anodic oxidation method of a welding structure and application thereof.
Background
Because the aluminum alloy structural part can strengthen the characteristics of the aluminum alloy structural part such as wear resistance, corrosion resistance, electrical insulation, thermal insulation and the like after being subjected to anodic oxidation treatment, meanwhile, dyes with different colors can be directly colored on the anodic oxidation layer and have strong binding force with the anodic oxidation layer, and more anodized aluminum alloy structural parts are applied to parts such as a rear cover, a frame and the like of an electronic product. However, the aluminum alloy structural member inevitably needs to be welded during use to form structures of different shapes to meet different product requirements. For an aluminum alloy welded structure, under the influence of welding heat, the material structure and components of the peripheral area of a welding seam change, so that an anodic oxidation layer with uniform thickness and color cannot be obtained after anodic oxidation. Some studies have obtained an anodized layer with uniform thickness and color by modifying the thickness of the material, but this operation severely limits the structural design of the product.
Disclosure of Invention
In view of the above, it is necessary to provide an anodizing method capable of obtaining a welded structure of an oxide layer having a uniform thickness and a uniform color.
In addition, the application of the anodic oxidation method of the welded structure is also provided.
A method of anodizing a welded structure comprising the steps of:
providing a welding structure, wherein the welding structure is provided with a welding surface, and a welding seam is formed on the welding surface;
forming an aluminum layer on the welding surface, wherein the aluminum layer completely covers the welding surface; and
and carrying out anodic oxidation treatment on the welding structure forming the aluminum layer.
According to the anodic oxidation method for the welding structure, the aluminum layer is formed on the welding surface of the welding structure, the aluminum layer completely covers the welding surface, and the anodic oxidation treatment is carried out on the welding structure with the aluminum layer, so that the oxide layer with uniform thickness and uniform color can be obtained. Tests prove that the thickness of the oxide layer obtained by adopting the anodic oxidation method of the welding structure is 5-50 mu m, and the oxide layer is uniform in thickness and color.
In one embodiment, before the step of forming the aluminum layer on the welding surface, the step of polishing the welding seam is further included.
In one embodiment, the step of polishing the weld seam specifically includes: and grinding the surface of the welding seam by adopting a CNC device.
In one embodiment, the aluminum layer is made of aluminum or an aluminum alloy; the welding structure is made of 5 series aluminum alloy, 6 series aluminum alloy or 7 series aluminum alloy.
In one embodiment, the manner of forming the aluminum layer on the welding surface is a surface additive technology.
In one embodiment, the manner of forming the aluminum layer on the welding surface is spray deposition or 3D printing.
In one embodiment, the step of forming the aluminum layer on the welding surface specifically includes: atomizing a spray liquid by using 0.7-0.75 MPa inert gas and spraying the spray liquid on the welding surface to form the aluminum layer, wherein the spray liquid comprises 9-12% of Zn, 2.5-3.2% of Mg, 1.5-2.5% of Cu and 0.1-0.2% of Zr by mass percentage, and the thickness of the aluminum layer is more than 20 mu m.
In one embodiment, the step of anodizing the welded structure forming the aluminum layer includes:
anodizing the welding structure forming the aluminum layer by using electrolyte to form an oxide layer on the surface of the welding structure forming the aluminum layer, wherein the electrolyte comprises 150-200 g/L sulfuric acid, 20-40 g/L oxalic acid, 3-5 g/L malic acid, 5-10 mg/L lactic acid, 10-15 g/L triethanolamine and 5-20 g/L aluminum sulfate; and
and sequentially performing coloring treatment and sealing treatment on the oxide layer.
In one embodiment, in the step of anodizing the welded structure on which the aluminum layer is formed using the electrolyte, the temperature of the oxidation is 20 to 40 ℃, the voltage is 14 to 18V, and the current density is 2.0A/dm2～3.0A/dm2The oxidation time is 40-60 min.
Use of the method of anodising a solder structure as described in any one of the preceding embodiments in the manufacture of an electronic product.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. The following is a preferred embodiment of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
An anodizing method of a welded structure according to an embodiment includes operations S110 to S130 of:
and S110, providing a welding structure, wherein the welding structure is provided with a welding surface, and a welding seam is formed on the welding surface.
In one embodiment, the welding surface is one or more. The welding seam is one or more. It should be noted that, when there are a plurality of welding seams and one welding surface, the welding seams are distributed at intervals on the welding surface.
In one embodiment, the welded structure is made of 5 series aluminum alloy, 6 series aluminum alloy or 7 series aluminum alloy. Further, the material of the welded structure is 5052 aluminum alloy, 6063 aluminum alloy, 7k02 aluminum alloy or 6061 aluminum alloy. It should be noted that the welded structure is not limited to the aluminum alloy indicated above, and other types of aluminum alloys may be used to fabricate the welded structure.
And S120, forming an aluminum layer on the welding surface, wherein the aluminum layer completely covers the welding surface.
In one embodiment, the aluminum layer is made of aluminum or aluminum alloy.
In one embodiment, when the aluminum layer is an aluminum alloy, the aluminum layer is 5052 aluminum alloy, 6063 aluminum alloy, or 7K02 aluminum alloy. It should be noted that the aluminum layer is not limited to the aluminum alloy mentioned above, and other types of aluminum alloys can be used to form the aluminum layer. It should be noted that, when the material of the welded structure and the aluminum layer are both aluminum alloys, the welded structure and the aluminum layer may be the same aluminum alloy or different aluminum alloys.
In one of the embodiments, the thickness of the aluminum layer is greater than 20 μm. Further, the thickness of the aluminum layer is 20 μm to 100 μm.
In one embodiment, the aluminum layer is formed on the bonding surface by a surface additive technology.
In one embodiment, the aluminum layer is formed on the bonding surface by spray deposition or 3D printing. The method of forming the aluminum layer on the bonding surface is not limited to the above-described method, and other methods such as magnetron sputtering or plasma chemical vapor deposition may be used. The aluminum layer may be formed on the bonding surface as long as it is practically possible.
In one embodiment, the step of forming the aluminum layer on the bonding surface specifically includes: and atomizing the spray liquid by using 0.7 MPa-0.75 MPa of inert gas to spray the spray liquid on the welding surface to form an aluminum layer. Wherein the spraying liquid comprises, by mass, 9-12% of Zn, 2.5-3.2% of Mg, 1.5-2.5% of Cu, and 0.1-0.2% of Zr.
Further, the inert gas is selected from at least one of nitrogen and helium.
In one embodiment, before S120, polishing the welding seam is further performed to remove an oxide film on a surface of the welding seam and make the surface of the welded structure more uniform. If the surface of the welded structure has no oxide film, this step may be omitted.
Further, the step of polishing the welding seam specifically comprises: and grinding the surface of the welding seam by adopting a CNC device. The method of polishing the welded joint is not limited to the above-mentioned method, and other methods may be used, for example, a method of polishing with sandpaper or a method of polishing with a chemical agent.
In one embodiment, after polishing the welding seam, before S120, cleaning the polished welding structure. And cleaning to remove oil stain, dust and other dirt on the surface of the polished welded structure. Further, the operation of cleaning the welded structure after the polishing treatment specifically includes: and sequentially carrying out degreasing treatment and alkali washing on the polished welding structure.
Specifically, the operation of performing degreasing treatment on the polished welded structure specifically includes: and (3) degreasing the polished welding structure at 40-60 ℃ by adopting a sulfuric acid aqueous solution with the mass percentage of 10-20%. The treatment mode is soaking or spraying. The treatment time is 3min to 5 min.
The operation of carrying out alkaline washing on the degreased welding structure specifically comprises the following steps: and cleaning the degreased welding structure for 3-5 min at 40-60 ℃ by using alkali liquor. The alkali liquor is 30-50% sodium hydroxide aqueous solution. The alkali washing mode is soaking or spraying.
In one embodiment, after the degreasing treatment is performed on the polished welded structure, before the alkali cleaning is performed on the degreased welded structure, the water cleaning is further performed on the degreased welded structure. The water washing temperature is 30-40 ℃, and the water washing time is 5-10 min. The water is deionized water or pure water. The water washing mode is spraying or soaking.
In one embodiment, after the step of performing alkali washing on the degreased welded structure, before S120, the step of performing water washing on the welded structure after the alkali washing is further included. The water washing temperature is 30-40 ℃, and the water washing time is 5-10 min. The water is deionized water or pure water. The water washing mode is spraying or soaking.
It should be noted that if the surface of the welded structure after the polishing process is free from stains such as oil stains and dust, the operation of cleaning the welded structure after the polishing process can be omitted.
And S130, carrying out anodic oxidation treatment on the welding structure with the aluminum layer.
Specifically, S130 includes operations S131 to S132 as follows:
and S131, anodizing the welding structure forming the aluminum layer by using the electrolyte so as to form an oxide layer on the surface of the welding structure forming the aluminum layer. The electrolyte comprises 150 g/L-200 g/L sulfuric acid, 20 g/L-40 g/L oxalic acid, 3 g/L-5 g/L malic acid, 5 mg/L-10 mg/L lactic acid, 10 g/L-15 g/L triethanolamine and 5 g/L-20 g/L aluminum sulfate. The electrolyte solution further includes a solvent. The solvent in the electrolyte can be deionized water or pure water.
In one embodiment, the concentration ratio of sulfuric acid to aluminum sulfate in the electrolyte is 10-20. At this concentration, the oxide layer can be made more uniform.
In one embodiment, the temperature of the oxidation is 20-40 ℃, the voltage is 14-18V, and the current density is 2.0A/dm2～3.0A/dm2The oxidation time is 40-60 min. Wherein the voltage is a direct current voltage. The temperature of the oxidation is 22-28 ℃. The oxidation time is 50 min-60 min.
The method of anodizing the welded structure on which the aluminum layer is formed is not limited to the above-described method, and other anodizing methods commonly used in the art may be used, and may be provided according to actual circumstances.
And S132, sequentially performing coloring treatment and sealing treatment on the oxide layer.
The way of sequentially performing coloring treatment and sealing treatment on the oxide layer is a common way in the field, and can be set according to actual conditions.
In one embodiment, the oxide layer has a thickness of 5 μm to 50 μm. Further, the thickness of the oxide layer was 15 μm.
In one embodiment, after S120 and before S130, the method further includes performing degreasing, alkali cleaning and chemical polishing on the welded structure forming the aluminum layer in sequence. Through the treatment, oil stain, dust and other dirt on the welding structure forming the aluminum layer are removed, and the thickness uniformity and the color uniformity of the oxidized layer after anodic oxidation are ensured.
Specifically, the step of performing degreasing treatment on the welded structure for forming the aluminum layer specifically includes: and (3) treating the welding structure for forming the aluminum layer by using a sulfuric acid aqueous solution with the mass percentage of 10-20%. The treatment time is 3min to 5 min. The treatment mode is soaking or spraying.
In one embodiment, the step of performing alkaline cleaning on the degreased welded structure specifically comprises: and (3) treating the degreased welding structure by using 30-50% of sodium hydroxide aqueous solution by mass. The treatment time is 3 min-5 min. The treatment mode is soaking or spraying.
In one embodiment, the step of chemically polishing the welded structure after the alkali cleaning specifically comprises: and polishing the welded structure subjected to alkali washing by using polishing liquid. The treatment time is 1-3 min. The treatment mode is soaking or spraying. The polishing solution comprises 25g/L of sodium phosphate, 40g/L of sodium carbonate, 3g/L of sodium hydroxide and 8g/L of OP emulsifier. Further, the OP emulsifier is OP-10 emulsifier.
After the step of alkali-washing the degreased welded structure and before the step of chemically polishing the alkali-washed welded structure, the method further includes washing the alkali-washed welded structure with water. Further, the step of washing the welded structure after the alkali washing with water specifically includes: and cleaning the welded structure after the alkali cleaning for 5-10 min at 35-45 ℃ by adopting water. Wherein the water is deionized water or pure water. The cleaning mode is spraying or soaking.
After the chemical polishing process is performed on the welded structure after the alkali cleaning, before S130, the method further includes washing the welded structure after the chemical polishing process with water. Further, the step of washing the chemically polished welded structure with water specifically comprises: and cleaning the chemically polished welding structure for 5-10 min at 35-45 ℃ by adopting water. Wherein the water is deionized water or pure water. The cleaning mode is spraying or soaking.
In one embodiment, after S131 and before S132, cleaning the anodized welded structure is further included. Further, the step of cleaning the anodized welded structure specifically comprises: and cleaning the welded structure after anodic oxidation by adopting water at the temperature of 35-45 ℃ for 5-10 min. Wherein the water is deionized water or pure water. The cleaning mode is spraying or soaking.
According to the anodic oxidation method for the welding structure, the aluminum layer is formed on the welding surface of the welding structure, the aluminum layer completely covers the welding surface, the anodic oxidation treatment is carried out on the welding structure with the aluminum layer, the oxide layer with uniform thickness and uniform color can be obtained, and the anodic oxidation method can be applied to the preparation of electronic products. Tests prove that the thickness of the oxide layer obtained by adopting the anodic oxidation method of the welding structure is 5-50 mu m, and the oxide layer is uniform in thickness and uniform in color.
The following are specific examples:
in the following examples, the welded structure was a 6063 aluminum alloy welded part, and the welded structure had a length of 100mm, a width of 50mm and a thickness of 1.5mm, and had a weld face with a weld line width of 0.8 mm. The OP emulsifier is OP-10 emulsifier.
Example 1
(1) And grinding the surface of the welding seam of the welded structure by adopting a CNC device.
(2) Degreasing treatment: and (2) putting the welded structure treated in the step (1) into an aqueous solution of sulfuric acid with the mass percentage of 15% for degreasing treatment, wherein the degreasing temperature is 50 ℃, and the degreasing time is 4 min.
(3) Washing with water: and washing the degreased welding structure with water. The water washing temperature is 35 ℃, and the water washing time is 7 min.
(4) Alkali washing: and (4) placing the welded structure washed by water in the step (3) into a sodium hydroxide solution with the mass percentage of 40% for alkali washing, wherein the alkali washing temperature is 50 ℃, and the alkali washing time is 4 min.
(5) And (3) water washing treatment: and (4) washing the welded structure after alkali washing by using water. The water washing temperature was 35 ℃ and the water washing time was 7min, so that the pH of the washing waste liquid was 5.5.
(6) Anodic oxidation: and (4) anodizing the welded structure subjected to water washing in the step (5) by using an electrolyte so as to form an oxide layer on the surface of the welded structure forming the aluminum layer. The temperature of oxidation is 30 ℃, the voltage is 16V, and the time of oxidation is 50 min. The electrolyte comprises 180g/L sulfuric acid, 25g/L oxalic acid, 4g/L malic acid, 8mg/L lactic acid, 10g/L triethanolamine and 10g/L aluminum sulfate.
(7) And sequentially performing coloring treatment and sealing treatment on the oxide layer.
Example 2
(1) And grinding the surface of the welding seam of the welded structure by adopting a CNC device.
(2) Degreasing treatment: and (2) putting the welded structure treated in the step (1) into an aqueous solution of sulfuric acid with the mass percentage of 15% for degreasing treatment, wherein the degreasing temperature is 50 ℃, and the degreasing time is 4 min.
(3) Washing with water: and washing the degreased welding structure with water. The water washing temperature is 35 ℃, and the water washing time is 7 min.
(4) Alkali washing: and (4) placing the welded structure washed by water in the step (3) into a sodium hydroxide solution with the mass percentage of 40% for alkali washing, wherein the alkali washing temperature is 50 ℃, and the alkali washing time is 4 min.
(5) And (3) water washing treatment: and (4) washing the welded structure after alkali washing by using water. The water washing temperature was 35 ℃ and the water washing time was 7min, so that the pH of the washing waste liquid was 5.5.
(6) And (5) atomizing the spraying liquid by using 0.7MPa inert gas, and spraying the atomized spraying liquid on the welding surface of the welded structure after water washing in the step (5) to form an aluminum layer, so as to obtain the welded structure with the aluminum layer. The inert gas is nitrogen. The spraying liquid comprises 11% of Zn, 2.8% of Mg, 2% of Cu and 0.15% of Zr in percentage by mass. The thickness of the aluminum layer was 15 μm.
(7) Degreasing treatment: and (3) processing the welding structure for forming the aluminum layer by using a 15 mass percent sulfuric acid aqueous solution. The treatment time was 4 min. The treatment method is soaking.
(8) Alkali washing: and (3) treating the degreased welding structure by using an aqueous solution of sodium hydroxide with the mass percentage of 40%. The treatment time was 4 min. The treatment method is soaking.
(9) Washing with water: and cleaning the welded structure after the alkali cleaning for 7min at 40 ℃ by adopting water. Wherein the water is deionized water. The cleaning mode is soaking.
(10) And (4) polishing the welded structure washed by the water in the step (9) by using polishing liquid. The treatment time was 2 min. The treatment method is soaking. The polishing solution comprises 25g/L of sodium phosphate, 40g/L of sodium carbonate, 3g/L of sodium hydroxide and 8g/L of OP emulsifier.
(11) Washing with water: and cleaning the chemically polished welding structure for 7min at 40 ℃ by adopting water. Wherein the water is deionized water. The cleaning mode is soaking.
(12) Anodic oxidation: and (4) anodizing the welded structure after washing in the step (11) by using an electrolyte so as to form an oxide layer on the surface of the welded structure forming the aluminum layer. The temperature of oxidation is 30 ℃, the voltage is 16V, and the time of oxidation is 50 min. The electrolyte comprises 180g/L sulfuric acid, 25g/L oxalic acid, 4g/L malic acid, 8mg/L lactic acid, 10g/L triethanolamine and 10g/L aluminum sulfate.
(13) And sequentially performing coloring treatment and sealing treatment on the oxide layer.
Example 3
(1) Degreasing treatment: and (3) putting the welded structure into a 15 mass percent sulfuric acid aqueous solution for degreasing treatment, wherein the degreasing temperature is 50 ℃, and the degreasing time is 4 min.
(2) Washing with water: and washing the degreased welding structure with water. The water washing temperature is 35 ℃, and the water washing time is 7 min.
(3) Alkali washing: and (3) placing the welded structure washed by water in the step (2) into a sodium hydroxide solution with the mass percentage of 40% for alkali washing, wherein the alkali washing temperature is 50 ℃, and the alkali washing time is 4 min.
(4) And (3) water washing treatment: and (4) washing the welded structure after alkali washing by using water. The water washing temperature was 35 ℃ and the water washing time was 7min, so that the pH of the washing waste liquid was 5.5.
(5) And (4) atomizing the spraying liquid by using 0.7MPa inert gas, and spraying the atomized spraying liquid on the welding surface of the welded structure washed by water in the step (4) to form an aluminum layer, so as to obtain the welded structure with the aluminum layer. The inert gas is nitrogen. The spraying liquid comprises 11% of Zn, 2.8% of Mg, 2% of Cu and 0.15% of Zr in percentage by mass. The thickness of the aluminum layer was 15 μm.
(6) Degreasing treatment: and (3) processing the welding structure for forming the aluminum layer by using a 15 mass percent sulfuric acid aqueous solution. The treatment time was 4 min. The treatment method is soaking.
(7) Alkali washing: and (3) treating the degreased welding structure by using an aqueous solution of sodium hydroxide with the mass percentage of 40%. The treatment time was 4 min. The treatment method is soaking.
(8) Washing with water: and cleaning the welded structure after the alkali cleaning for 7min at 40 ℃ by adopting water. Wherein the water is deionized water. The cleaning mode is soaking.
(9) And (5) polishing the welded structure washed by the water in the step (8) by using polishing liquid. The treatment time was 2 min. The treatment method is soaking. The polishing solution comprises 25g/L of sodium phosphate, 40g/L of sodium carbonate, 3g/L of sodium hydroxide and 8g/L of OP emulsifier.
(10) Washing with water: and cleaning the chemically polished welding structure for 7min at 40 ℃ by adopting water. Wherein the water is deionized water. The cleaning mode is soaking.
(11) Anodic oxidation: and (4) anodizing the welded structure subjected to water washing in the step (10) by using an electrolyte so as to form an oxide layer on the surface of the welded structure forming the aluminum layer. The temperature of oxidation is 30 ℃, the voltage is 16V, and the time of oxidation is 50 min. The electrolyte comprises 180g/L sulfuric acid, 25g/L oxalic acid, 4g/L malic acid, 8mg/L lactic acid, 10g/L triethanolamine and 10g/L aluminum sulfate.
(12) And sequentially performing coloring treatment and sealing treatment on the oxide layer.
Example 4
(1) And grinding the surface of the welding seam of the welded structure by adopting a CNC device.
(2) And (3) atomizing the spraying liquid by using 0.7MPa inert gas, and spraying the spraying liquid on the welding surface of the welding structure treated in the step (1) to form an aluminum layer, so as to obtain the welding structure forming the aluminum layer. The inert gas is nitrogen. The spraying liquid comprises 11% of Zn, 2.8% of Mg, 2% of Cu and 0.15% of Zr in percentage by mass. The thickness of the aluminum layer was 15 μm.
(3) Degreasing treatment: and (3) processing the welding structure for forming the aluminum layer by using a 15 mass percent sulfuric acid aqueous solution. The treatment time was 4 min. The treatment method is soaking.
(4) Alkali washing: and (3) treating the degreased welding structure by using an aqueous solution of sodium hydroxide with the mass percentage of 40%. The treatment time was 4 min. The treatment method is soaking.
(5) Washing with water: and cleaning the welded structure after the alkali cleaning for 7min at 40 ℃ by adopting water. Wherein the water is deionized water. The cleaning mode is soaking.
(6) And polishing the welded structure subjected to alkali washing by using polishing liquid. The treatment time was 2 min. The treatment method is soaking. The polishing solution comprises 25g/L of sodium phosphate, 40g/L of sodium carbonate, 3g/L of sodium hydroxide and 8g/L of OP emulsifier.
(7) Washing with water: and cleaning the chemically polished welding structure for 7min at 40 ℃ by adopting water. Wherein the water is deionized water. The cleaning mode is soaking.
(8) Anodic oxidation: and (4) anodizing the welded structure subjected to water washing in the step (7) by using an electrolyte so as to form an oxide layer on the surface of the welded structure forming the aluminum layer. The temperature of oxidation is 30 ℃, the voltage is 16V, and the time of oxidation is 50 min. The electrolyte comprises 180g/L sulfuric acid, 25g/L oxalic acid, 4g/L malic acid, 8mg/L lactic acid, 10g/L triethanolamine and 10g/L aluminum sulfate.
(9) And sequentially performing coloring treatment and sealing treatment on the oxide layer.
Example 5
(1) And grinding the surface of the welding seam of the welded structure by adopting a CNC device.
(2) Degreasing treatment: and (2) putting the welded structure treated in the step (1) into an aqueous solution of sulfuric acid with the mass percentage of 15% for degreasing treatment, wherein the degreasing temperature is 50 ℃, and the degreasing time is 4 min.
(3) Washing with water: and washing the degreased welding structure with water. The water washing temperature is 35 ℃, and the water washing time is 7 min.
(4) Alkali washing: and (4) placing the welded structure washed by water in the step (3) into a sodium hydroxide solution with the mass percentage of 40% for alkali washing, wherein the alkali washing temperature is 50 ℃, and the alkali washing time is 4 min.
(5) And (3) water washing treatment: and (4) washing the welded structure after alkali washing by using water. The water washing temperature was 35 ℃ and the water washing time was 7min, so that the pH of the washing waste liquid was 5.5.
(6) And (5) atomizing the spraying liquid by using 0.7MPa inert gas, and spraying the atomized spraying liquid on the welding surface of the welded structure after water washing in the step (5) to form an aluminum layer, so as to obtain the welded structure with the aluminum layer. The inert gas is nitrogen. The spraying liquid comprises 11% of Zn, 2.8% of Mg, 2% of Cu and 0.15% of Zr in percentage by mass. The thickness of the aluminum layer was 15 μm.
(7) Anodic oxidation: anodizing the welded structure forming the aluminum layer with an electrolyte to form an oxide layer on the surface of the welded structure forming the aluminum layer. The temperature of oxidation is 30 ℃, the voltage is 16V, and the time of oxidation is 50 min. The electrolyte comprises 180g/L sulfuric acid, 25g/L oxalic acid, 4g/L malic acid, 8mg/L lactic acid, 10g/L triethanolamine and 10g/L aluminum sulfate.
(8) And sequentially performing coloring treatment and sealing treatment on the oxide layer.
And (3) testing:
the color difference of the oxide layer on the surface of the weld of the welded structures of examples 1 to 5 and the thickness uniformity of the oxide layer on the surface of the weld were measured. The results are shown in Table 1. Table 1 shows the color difference of the oxide layer on the surface of the weld bead and the thickness of the oxide layer on the surface of the weld bead in the welded structures of examples 1 to 5.
Wherein, the thickness of the aluminum layer is measured by adopting a microscopic measurement method and is repeated three times, and the measurement result is expressed by the average value of the three times;
measuring the color difference of an oxide layer on the surface of a welding seam by using a color difference meter according to GB/T14952.3-1994' method for inspecting the color difference and the appearance quality of the anodized and colored anodic oxide film of aluminum and aluminum alloy;
and measuring the thickness of an oxide layer on the surface of the welding seam by adopting a cross section thickness microscopic measurement method. Specifically, five areas in the oxide layer are uniformly selected, the oxide layer of at least two areas in the five areas is positioned on the welding line, the oxide layer of at least two areas is positioned outside the welding line, the thickness of the oxide layer of the five areas is measured by using a metallographic microscope head, and the average value is taken as the thickness of the oxide layer. The mean and variance of the thickness of the five regions were calculated and the results are expressed as mean ± variance.
TABLE 1
Thickness of oxide layer (μm) Color difference of oxide layer (DE)
Example 1 15±3 Color > 5DE
Example 2 15±1 Color is less than or equal to 5DE
Example 3 15±2.5 Color is less than or equal to 5DE
Example 4 15±2 Color is less than or equal to 5DE
Example 5 15±3 Color > 5DE
As can be seen from table 1, the color difference values of the oxide layers of the welded structures obtained in examples 2 to 4 are not more than 5 and less than the color difference value (> 5) of the oxide layer of the welded structure obtained in example 1, which indicates that the color difference of the oxide layers can be reduced by forming an aluminum layer on the welded structure and then anodizing the aluminum layer. The thickness of the oxide layer of the solder structure obtained in example 2 was 15 μm + -1 μm, while the thickness of the oxide layer of the solder structure obtained in example 1 was 15 μm + -3 μm, indicating that the thickness of the oxide layer of the solder structure obtained in example 2 was more uniform.
Among them, the thickness of the oxide layer of the welded structure obtained in example 3 was 15 μm ± 2.5 μm, which indicates that the oxide layer of the welded structure obtained in example 3 was not as uniform as the oxide layer of the welded structure obtained in example 2, and further indicates that the uniformity of the oxide layer can be improved by grinding the surface of the weld bead of the welded structure using the CNC apparatus. The thickness of the oxide layer of the welded structure obtained in example 4 was 15 μm ± 2 μm, which indicates that the oxide layer of the welded structure obtained in example 4 was not uniform as the oxide layer of the welded structure obtained in example 2, and further indicates that the degreasing treatment and the alkali washing treatment of the welded structure before the formation of the aluminum layer can improve the uniformity of the oxide layer. The thickness of the oxide layer of the welded structure obtained in example 5 was 15 μm ± 3 μm, which indicates that the oxide layer of the welded structure obtained in example 5 was not uniform as the oxide layer of the welded structure obtained in example 2 and that the color difference value (> 5) of the oxide layer, and further indicates that degreasing, alkali washing and polishing the welded structure before anodizing can improve the uniformity of the oxide layer and reduce the occurrence of defects such as color difference.
In summary, by using the anodic oxidation method for the welding structure of the above embodiment, the oxide layer with uniform thickness and uniform color can be obtained, and meanwhile, the oxide layer has uniform components and a compact structure, so that various designs can be performed on the product structure.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (9)

1. A method of anodizing a welded structure comprising the steps of:
providing a welding structure, wherein the welding structure is provided with a welding surface, and a welding seam is formed on the welding surface;
forming an aluminum layer on the welding surface, wherein the aluminum layer completely covers the welding surface; and
carrying out anodic oxidation treatment on the welding structure forming the aluminum layer;
before the step of forming the aluminum layer on the welding surface, polishing, degreasing and alkali washing are carried out on the welding seam.
2. The anodic oxidation method of a welded structure according to claim 1, characterized in that said step of polishing said weld seam is in particular: and grinding the surface of the welding seam by adopting a CNC device.
3. The anodic oxidation method for a welded structure according to claim 1, wherein the aluminum layer is made of aluminum or an aluminum alloy; the welding structure is made of 5 series aluminum alloy, 6 series aluminum alloy or 7 series aluminum alloy.
4. The method of anodizing a welded structure according to claim 1, wherein a means for forming an aluminum layer on said welding surface is a surface additive technique.
5. The method for anodizing a welded structure according to claim 4, wherein the means for forming the aluminum layer on the welding surface is spray deposition or 3D printing.
6. The anodic oxidation method of a welded structure according to claim 5, characterized in that the step of forming an aluminum layer on the welding surface is in particular: atomizing a spray liquid by using 0.7-0.75 MPa inert gas and spraying the spray liquid on the welding surface to form the aluminum layer, wherein the spray liquid comprises 9-12% of Zn, 2.5-3.2% of Mg, 1.5-2.5% of Cu and 0.1-0.2% of Zr by mass percentage, and the thickness of the aluminum layer is more than 20 mu m.
7. The method of anodizing a welded structure according to claim 1, wherein the step of anodizing the welded structure in which the aluminum layer is formed comprises:
anodizing the welding structure forming the aluminum layer by using electrolyte to form an oxide layer on the surface of the welding structure forming the aluminum layer, wherein the electrolyte comprises 150-200 g/L sulfuric acid, 20-40 g/L oxalic acid, 3-5 g/L malic acid, 5-10 mg/L lactic acid, 10-15 g/L triethanolamine and 5-20 g/L aluminum sulfate; and
and sequentially performing coloring treatment and sealing treatment on the oxide layer.
8. The method for anodizing a welded structure according to claim 7, wherein in the step of anodizing said welded structure forming said aluminum layer with an electrolyte, the temperature of oxidation is 20 ℃ to 40 ℃, the voltage is 14V to 18V, and the current density is 2.0A/dm2～3.0A/dm2The oxidation time is 40-60 min.
9. Use of the anodic oxidation process of a welded structure according to any one of claims 1 to 8 in the manufacture of an electronic product.
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