CN115305546A - Internal and external different oxidation process for aluminum alloy special-shaped cavity - Google Patents
Internal and external different oxidation process for aluminum alloy special-shaped cavity Download PDFInfo
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- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
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- 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
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Abstract
The invention relates to different oxidation processes inside and outside an aluminum alloy special-shaped cavity, belonging to the technical field of surface treatment of metal materials. The process comprises the steps of deoiling, alkali washing, polishing, sand blasting and secondary polishing of an aluminum alloy special-shaped cavity, carrying out anodic oxidation of a specific process, then protecting the outer surface, removing a film on the inner surface, carrying out chemical conductive oxidation, and finally removing a protective layer on the outer surface to finish different oxidation processes inside and outside. According to the invention, the anodic oxidation treatment of a specific process is carried out on the outer surface of the aluminum alloy special-shaped cavity, the initial voltage, the termination voltage and the voltage rising rate are optimized, the formed film is more compact, and the hardness and the corrosion resistance of the film are improved; and carrying out chemical conductive oxidation on the inner surface of the aluminum alloy special-shaped cavity, wherein cerium nitrate and lanthanum sulfate in the chemical oxidation treatment liquid synergistically improve the corrosion inhibition effect on the surface of the aluminum alloy, and the rare earth elements cerium and lanthanum participate in the formation of the film layer and fill the gaps of the film layer so as to improve the compactness of the film layer and improve the hardness and corrosion resistance of the film layer.
Description
Technical Field
The invention belongs to the technical field of metal material surface treatment, and relates to an internal and external different oxidation process of an aluminum alloy special-shaped cavity.
Background
The aluminum alloy has the advantages of light weight, strong electric and thermal conductivity, high mechanical strength, good casting performance and plastic processing performance, and wide application in the fields of aerospace, transportation and the like. However, aluminum alloys have the disadvantage of being chemically reactive and susceptible to corrosion, and therefore are generally subjected to oxidation treatment prior to being put into production to improve their corrosion resistance. Aluminum alloy cavity parts are widely applied to microwave receiving modules, and the aluminum alloy cavity is used as a functional part in the microwave receiving module, and the inner wall and the outer wall of the aluminum alloy cavity are required to have excellent corrosion resistance, flatness, low contact resistance and gold-tin weldability. The currently common aluminum alloy chemical oxidation treatment methods include anodic oxidation and chemical oxidation. The chemical oxidation method is that at a certain temperature, the surface of aluminum and solution are chemically reacted, so that a layer of compact oxide film is formed on the surface of the aluminum alloy. The chemical oxidation method can be divided into a hexavalent chromium method, a trivalent chromium method and a chromium-free method according to the components of the chemical oxidation liquid, wherein the hexavalent chromium chemical oxidation film has good corrosion resistance, good adhesiveness and self-repairing capability, and is the aluminum alloy chemical oxidation technology with the best comprehensive performance at present. The anodic oxidation refers to an electrolytic oxidation process of maintaining electrochemical oxidation reaction of aluminum and aluminum alloy through current under the conditions of corresponding electrolyte, specific process conditions and applied voltage, and an oxide film generated on the surface has the characteristics of high porosity, strong adsorbability, easy dyeing and the like. However, in the prior art, both the chemical oxidation treatment process and the anodic oxidation treatment process, the wear resistance and the corrosion resistance of the generated oxide film are required to be further improved.
Patent publication No. CN114318316A discloses a colorless chemical oxidation treatment solution and a process for aluminum alloy, which solve the problems of low efficiency and unsatisfactory corrosion resistance and bonding force of the obtained film in the existing chemical oxidation treatment method. The oxidation treatment solution consisted of the following components: the concentration of phosphoric acid is 30-50g/L, the concentration of chromic anhydride is 2-10g/L, the concentration of sodium fluoride is 3-6g/L, the concentration of potassium citrate is 8-12g/L, and the concentration of cerium nitrate is 0.2-0.5g/L. The treatment process comprises oil removal, photochemical treatment, colorless chemical oxidation treatment, hydrophobic treatment, polymerization hardening and drying. The oxide film layer prepared by the invention is more compact and has high corrosion resistance, but the chemical oxidation treatment liquid contains chromium.
Patent publication No. CN111074257A discloses a chemical oxidation treatment process for a cast aluminum workpiece, comprising the following steps; the method comprises the steps of firstly, shot blasting pretreatment, secondly, shot blasting treatment, thirdly, activation treatment, fourthly, chemical oxidation film forming, and fifthly, after the cast aluminum workpiece is chemically oxidized, cleaning, blow-drying and drying, quality inspection is needed. Although the film layer of the invention has fine crystallization and is complete, continuous and non-missing, the chemical oxidation process of the invention uses potassium dichromate.
Patent publication No. CN114574926A discloses an aluminum alloy anodic oxidation process, an aluminum alloy product and an aluminum alloy anodic oxidation liquid. The aluminum alloy anodic oxidation process comprises the following steps: providing a first oxidation solution, wherein the first oxidation solution comprises oxalic acid, sulfuric acid, glycolic acid, citric acid and water; providing a second oxidizing solution, wherein the second oxidizing solution comprises sulfuric acid, glycolic acid, adipic acid and water; and sequentially placing the aluminum alloy workpiece in the first oxidizing solution and the second oxidizing solution for anodic oxidation. The anodic oxidation process can form a compact oxide film on the surface of the aluminum alloy workpiece, and has little influence on the brightness and luster of a high-brightness surface on the aluminum alloy workpiece. The invention does not disclose the technical scheme that the voltage gradually rises in the anodic oxidation process.
Disclosure of Invention
The invention aims to provide an internal and external different oxidation process of an aluminum alloy special-shaped cavity, belonging to the technical field of metal material surface treatment. The process of the invention comprises the steps of degreasing, alkali washing, polishing, sand blasting and secondary polishing of the aluminum alloy special-shaped cavity, then carrying out anodic oxidation of a specific process, then protecting the outer surface, removing the film of the inner surface, then carrying out chemical conductive oxidation, and finally removing the protective layer of the outer surface to complete different oxidation processes inside and outside. According to the invention, the anodic oxidation treatment of a specific process is carried out on the outer surface of the aluminum alloy special-shaped cavity, and the initial voltage, the termination voltage and the voltage rising rate are optimized, so that the formed film is more compact, and the hardness and the corrosion resistance of the film are improved; and carrying out chemical conductive oxidation treatment on the inner surface of the aluminum alloy special-shaped cavity, wherein cerium nitrate and lanthanum sulfate in the chemical oxidation treatment liquid synergistically improve the corrosion inhibition effect on the surface of the aluminum alloy, and the rare earth element cerium and lanthanum participate in the formation of the film layer and fill gaps of the film layer so as to improve the compactness of the film layer and improve the hardness and corrosion resistance of the film layer.
The purpose of the invention can be realized by the following technical scheme:
an internal and external different oxidation process of an aluminum alloy special-shaped cavity comprises the following steps:
(1) Soaking the aluminum alloy special-shaped cavity in degreasing liquid at the temperature of 50-60 ℃ for 5-10 min to degrease the inner surface and the outer surface, then washing with clean water at normal temperature for 1-2 min for 2 times;
(2) Placing the aluminum alloy special-shaped cavity washed in the step (1) into a sodium hydroxide aqueous solution with the temperature of 30-40 ℃ for soaking for 3-5 min to carry out alkali washing on the inner surface and the outer surface, and then washing with clear water at normal temperature for 1-2 min for 2 times;
(3) Polishing the surfaces of the inner surface and the outer surface of the aluminum alloy special-shaped cavity washed in the step (2) by using a diatomite polishing agent to mirror surface light to ensure that the surface roughness Ra is 0.1-0.12 um, then washing for 1-2 min at normal temperature by using clean water, washing for 2 times, and drying for 3-5 min at the temperature of 100-120 ℃;
(4) Carrying out sand blasting treatment on the inner surface and the outer surface of the aluminum alloy special-shaped cavity dried in the step (3) by using glass beads under the pressure of 600-800 kPa, and controlling the surface roughness Ra of the aluminum alloy special-shaped cavity to be 1.2-1.5 um;
(5) Soaking the polished aluminum alloy special-shaped cavity in the step (4) in polishing solution at 30-40 ℃ for 3-5 min to perform chemical polishing treatment on the inner surface and the outer surface, and then washing the aluminum alloy special-shaped cavity with clean water at normal temperature for 1-2 min for 2 times;
(6) Taking the aluminum alloy special-shaped cavity washed in the step (5) as an anode, putting the aluminum alloy special-shaped cavity into an oxidation tank containing anodic oxidation electrolyte, taking a lead plate as a cathode, controlling the temperature to be 5-10 ℃, switching on a power supply to start oxidation, switching off the power supply after the control voltage gradually rises from the initial voltage to the final voltage in the oxidation process, finishing oxidation to obtain an aluminum alloy special-shaped cavity with anodic oxidation films on the inner and outer surfaces, and then washing the aluminum alloy special-shaped cavity for 1-2 min at normal temperature by using clean water for 2 times;
(7) Putting the washed aluminum alloy special-shaped cavity in the step (6) into a coloring tank filled with coloring liquid with the pH value of 5.5-6.0, stirring for 10-20 min to perform coloring treatment on the inner surface and the outer surface, then washing for 1-2 min with clear water, washing for 2 times, and drying at the temperature of 100-120 ℃ for 3-5 min;
(8) Protecting the outer surface of the aluminum alloy special-shaped cavity dried in the step (7) by using a peelable adhesive to form an outer surface protection layer, and controlling the thickness of the protection layer to be 100-300 mu m;
(9) Soaking the aluminum alloy special-shaped cavity subjected to the outer surface protection in the step (8) in an acidic film removing solution for 10-15 min, then placing the aluminum alloy special-shaped cavity in an alkaline film removing solution for neutralization for 25-35 s to perform inner surface film removing treatment, and then washing the aluminum alloy special-shaped cavity for 2 times at normal temperature for 1-2 min by using clean water;
(10) Putting the aluminum alloy special-shaped cavity washed in the step (9) into chemical oxidation treatment liquid at the temperature of 60-80 ℃ for treatment for 8-15 min, and then washing the aluminum alloy special-shaped cavity for 1-2 min at normal temperature for 2 times;
(11) And (3) putting the aluminum alloy special-shaped cavity washed in the step (10) into hot water at the temperature of 90-110 ℃ for washing for 20-30 s, then putting the aluminum alloy special-shaped cavity into the hot water at the temperature of 100-120 ℃ for drying for 3-5 min, and finally removing the outer surface protective layer to obtain the aluminum alloy special-shaped cavity with oxidized inner and outer surfaces.
As a preferred technical scheme of the invention, the degreasing fluid formula in the step (1) is as follows: the sodium phosphate sodium sulfate sodium salt comprises sodium phosphate, sodium carbonate, sodium dodecyl benzene sulfonate and solvent water, wherein the concentration of the sodium phosphate is 10-20 g/L, the concentration of the sodium carbonate is 1-5 g/L, and the concentration of the sodium dodecyl sulfonate is 2-8 g/L.
As a preferable embodiment of the present invention, the concentration of the aqueous sodium hydroxide solution in the step (2) is 30 to 50g/L.
As a preferable technical scheme of the invention, the polishing solution in the step (5) is a nitric acid aqueous solution with the concentration of 100-150 g/L.
As a preferable technical scheme of the invention, the initial voltage in the step (6) is 8-10V, the termination voltage is 20-24V, and the voltage rising rate is 0.8-1.5V/min.
According to a preferable technical scheme of the invention, the anode oxidation electrolyte formula in the step (6) is lactic acid, oxalic acid, glycolic acid and solvent water, wherein the concentration of the lactic acid is 5-6 g/L, the concentration of the oxalic acid is 8-10 g/L, and the concentration of the glycolic acid is 10-20 g/L.
As a preferable technical scheme of the invention, the formula of the coloring liquid in the step (7) is as follows: the composition comprises bisabolol, solanum nigrum alcohol, camphorwood lignan, ammonium sulfide, sodium sulfide, cobalt acetate, copper sulfate, potassium permanganate, acetic acid and solvent water, wherein the concentration of the bisabolol is 0.5-0.8 g/L, the concentration of the solanum nigrum alcohol is 0.2-0.5g/L, the concentration of the camphorwood lignan is 0.1-0.2 g/L, the concentration of the ammonium sulfide is 0.5-0.8 g/L, the concentration of sodium sulfide with prime number is 1-1.5 g/L, the concentration of the cobalt acetate is 0.2-0.6 g/L, the concentration of the copper sulfate is 0.6-0.8 g/L, the concentration of the potassium permanganate is 0.8-1.2 g/L, and the concentration of the acetic acid is 0.1-0.2 g/L.
As a preferable technical scheme of the invention, the acidic stripping solution in the step (9) is a nitric acid aqueous solution with the concentration of 100-120 g/L.
As a preferable technical scheme of the invention, the alkaline stripping solution in the step (9) is a sodium hydroxide aqueous solution with the concentration of 5-8 g/L.
As a preferable technical solution of the present invention, the chemical oxidation treatment liquid in the step (10) has a formula of: the potassium nitrate-potassium permanganate-potassium citrate composite material comprises cerium nitrate, lanthanum sulfate, hydrochloric acid, potassium permanganate, potassium citrate and solvent water, wherein the concentration of the cerium nitrate is 0.4-0.9 g/L, the concentration of the lanthanum sulfate is 0.5-0.8 g/L, the concentration of the hydrochloric acid is 1.5-2.0 g/L, the concentration of the potassium permanganate is 0.2-0.5g/L, and the concentration of the potassium citrate is 1.5-1.8 g/L.
The invention has the beneficial effects that:
(1) The invention adds the sand blasting and drying processes and simultaneously adjusts the important process parameters in each process step, so that the aluminum alloy product not only has metallic appearance, but also can meet the requirement of electromagnetic shielding performance;
(2) In the anodic oxidation process, the specific ranges of the initial voltage, the final voltage and the voltage rising rate are controlled, and a specific anodic oxidation electrolyte formula is matched, so that the obtained outer surface anodic oxidation film has higher compactness and further has higher hardness and corrosion resistance;
(3) In the chemical oxidation process, cerium nitrate and lanthanum sulfate synergistically improve the corrosion inhibition effect on the surface of the aluminum alloy, and the rare earth elements cerium and lanthanum participate in the formation of the film and fill gaps of the film so as to improve the compactness of the film and improve the hardness and corrosion resistance of the film;
(4) In order to guarantee the anticorrosion/conductive requirements of different surfaces of a part, the traditional method in the industry is to perform anodic oxidation treatment on the whole part, and then remove an oxide film on the surface needing conductive by laser etching or other material reducing processing technologies, the traditional technology can cause the conductive surface to lack protection, so that the corrosion of the part is accelerated, and the method performs different oxidation treatments on different positions of the surface of the same part, and simultaneously guarantees the anticorrosion/conductive requirements of different surfaces of the part.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, characteristics and effects according to the present invention is provided in conjunction with the embodiments.
Example 1
An internal and external different oxidation process of an aluminum alloy special-shaped cavity, which comprises the following steps:
(1) Soaking the aluminum alloy special-shaped cavity in deoiling liquid at the temperature of 55 ℃ for 8min to remove oil on the inner surface and the outer surface, and then washing with clean water at normal temperature for 1min and 2 times;
(2) Soaking the aluminum alloy special-shaped cavity washed in the step (1) in a sodium hydroxide aqueous solution at 33 ℃ for 3min for alkali washing of the inner surface and the outer surface, and then washing with clear water at normal temperature for 2min for 2 times;
(3) Polishing the surfaces of the inner surface and the outer surface of the aluminum alloy special-shaped cavity washed in the step (2) by using a diatomite polishing agent to mirror surface light to enable the surface roughness Ra of the aluminum alloy special-shaped cavity to be 0.11um, then washing the aluminum alloy special-shaped cavity for 2 times at normal temperature for 1.5min, and drying the aluminum alloy special-shaped cavity at the temperature of 110 ℃ for 5min;
(4) Carrying out sand blasting treatment on the inner surface and the outer surface of the aluminum alloy special-shaped cavity dried in the step (3) by using glass beads under the condition that the pressure is 650kPa, and controlling the surface roughness Ra of the aluminum alloy special-shaped cavity to be 1.3um;
(5) Soaking the polished aluminum alloy special-shaped cavity in the step (4) in polishing solution at 35 ℃ for 3min to perform chemical polishing treatment on the inner surface and the outer surface, and then washing the aluminum alloy special-shaped cavity with clean water at normal temperature for 1min for 2 times;
(6) Taking the aluminum alloy special-shaped cavity washed in the step (5) as an anode, putting the aluminum alloy special-shaped cavity into an oxidation tank containing anodic oxidation electrolyte, taking a lead plate as a cathode, controlling the temperature to be 10 ℃, switching on a power supply to start oxidation, switching off the power supply after the control voltage gradually rises from the initial voltage to the final voltage in the oxidation process, finishing oxidation to obtain an aluminum alloy special-shaped cavity with anodic oxidation films on the inner and outer surfaces, and then washing the aluminum alloy special-shaped cavity for 2 times at normal temperature by using clean water;
(7) Putting the washed aluminum alloy special-shaped cavity in the step (6) into a coloring tank filled with coloring liquid with the pH value of 5.5-6.0, stirring for 18min to perform coloring treatment on the inner surface and the outer surface, then washing for 1.6min with clear water, washing for 2 times, and drying at 120 ℃ for 3min;
(8) Protecting the outer surface of the aluminum alloy special-shaped cavity dried in the step (7) by using a peelable glue to form an outer surface protection layer, and controlling the thickness of the protection layer to be 200 mu m;
(9) Soaking the aluminum alloy special-shaped cavity subjected to the outer surface protection in the step (8) in an acidic membrane removing solution for 12min, then placing the aluminum alloy special-shaped cavity in an alkaline membrane removing solution for neutralization for 30s to perform inner surface membrane removing treatment, and then washing the aluminum alloy special-shaped cavity for 2 times at normal temperature for 1min by using clean water;
(10) Placing the aluminum alloy special-shaped cavity washed in the step (9) into chemical oxidation treatment liquid at the temperature of 60 ℃ for treatment for 10min, then washing with clean water at normal temperature for 2min, and washing for 2 times;
(11) And (3) putting the aluminum alloy special-shaped cavity washed in the step (10) into hot water at the temperature of 95 ℃ for washing for 28s, then putting the aluminum alloy special-shaped cavity at the temperature of 110 ℃ for drying for 3min, and finally removing the outer surface protective layer to obtain the aluminum alloy special-shaped cavity with oxidized inner and outer surfaces.
The degreasing fluid formula in the step (1) is as follows: sodium phosphate, sodium carbonate, sodium dodecyl benzene sulfonate and solvent water, the concentration of the sodium phosphate is 18g/L, the concentration of the sodium carbonate is 2g/L, and the concentration of the sodium dodecyl sulfate is 5g/L.
The concentration of the sodium hydroxide aqueous solution in the step (2) is 42g/L.
And (5) the polishing solution is a nitric acid aqueous solution with the concentration of 120 g/L.
And (6) setting the initial voltage to be 10V, the final voltage to be 22V and the voltage rising rate to be 0.8V/min.
The anode oxidation electrolyte in the step (6) comprises lactic acid, oxalic acid, glycolic acid and solvent water, wherein the concentration of the lactic acid is 5g/L, the concentration of the oxalic acid is 8g/L, and the concentration of the glycolic acid is 15g/L.
The formula of the coloring liquid in the step (7) is as follows: bisabolol, solanum nigrum alcohol, camphorwood lignan, ammonium sulfide, sodium sulfide, cobalt acetate, copper sulfate, potassium permanganate, acetic acid and solvent water, wherein the concentration of bisabolol is 0.5g/L, the concentration of solanum nigrum alcohol is 0.2g/L, the concentration of camphorwood lignan is 0.1g/L, the concentration of ammonium sulfide is 0.7g/L, the concentration of sodium sulfide with prime number is 1.2g/L, the concentration of cobalt acetate is 0.5g/L, the concentration of copper sulfate is 0.6g/L, the concentration of potassium permanganate is 1.1g/L, and the concentration of acetic acid is 0.12g/L.
And (5) the acidic film removing solution in the step (9) is a nitric acid aqueous solution with the concentration of 110 g/L.
And (9) the alkaline film stripping solution is a sodium hydroxide aqueous solution with the concentration of 6g/L.
The formula of the chemical oxidation treatment liquid in the step (10) is as follows: the cerium nitrate solution comprises cerium nitrate, lanthanum sulfate, hydrochloric acid, potassium permanganate, potassium citrate and solvent water, wherein the concentration of the cerium nitrate is 0.6g/L, the concentration of the lanthanum sulfate is 0.6g/L, the concentration of the hydrochloric acid is 1.8g/L, the concentration of the potassium permanganate is 0.2g/L, and the concentration of the potassium citrate is 1.6g/L.
Example 2
An internal and external different oxidation process of an aluminum alloy special-shaped cavity, which comprises the following steps:
(1) Soaking the aluminum alloy special-shaped cavity in degreasing liquid at 50 ℃ for 10min to remove oil on the inner surface and the outer surface, and then washing with clean water at normal temperature for 1.2min and 2 times;
(2) Soaking the aluminum alloy special-shaped cavity washed in the step (1) in a sodium hydroxide aqueous solution at 35 ℃ for 5min for alkali washing of the inner surface and the outer surface, and then washing with clear water at normal temperature for 2min for 2 times;
(3) Polishing the surfaces of the inner surface and the outer surface of the aluminum alloy special-shaped cavity washed in the step (2) by using a diatomite polishing agent until the surfaces are polished to be mirror surface, enabling the surface roughness Ra of the aluminum alloy special-shaped cavity to be 0.12 mu m, then washing for 2 times at normal temperature for 1.5min by using clean water, and drying for 3min at the temperature of 120 ℃;
(4) Carrying out sand blasting treatment on the inner surface and the outer surface of the aluminum alloy special-shaped cavity dried in the step (3) by using glass beads under the condition that the pressure is 800kPa, and controlling the surface roughness Ra to be 1.2um;
(5) Soaking the polished aluminum alloy special-shaped cavity in the step (4) in polishing solution at 35 ℃ for 5min to perform chemical polishing treatment on the inner surface and the outer surface, and then washing the aluminum alloy special-shaped cavity with clean water at normal temperature for 1min for 2 times;
(6) Taking the aluminum alloy special-shaped cavity washed in the step (5) as an anode, putting the aluminum alloy special-shaped cavity into an oxidation tank containing anodic oxidation electrolyte, taking a lead plate as a cathode, controlling the temperature to be 8 ℃, switching on a power supply to start oxidation, switching off the power supply after the control voltage gradually rises from the initial voltage to the final voltage in the oxidation process, finishing oxidation to obtain an aluminum alloy special-shaped cavity with anodic oxidation films on the inner and outer surfaces, then washing the aluminum alloy special-shaped cavity for 1.5min at normal temperature by using clean water, and washing the aluminum alloy special-shaped cavity for 2 times;
(7) Putting the washed aluminum alloy special-shaped cavity in the step (6) into a coloring tank filled with coloring liquid with the pH value of 5.5-6.0, stirring for 15min to perform coloring treatment on the inner surface and the outer surface, then washing for 1.2min with clear water, washing for 2 times, and drying at the temperature of 100 ℃ for 3min;
(8) Protecting the outer surface of the aluminum alloy special-shaped cavity dried in the step (7) by using a peelable adhesive to form an outer surface protection layer, and controlling the thickness of the protection layer to be 100 mu m;
(9) Soaking the aluminum alloy special-shaped cavity subjected to the outer surface protection in the step (8) in an acidic membrane removing solution for 15min, then placing the aluminum alloy special-shaped cavity in an alkaline membrane removing solution for neutralization for 32s to perform inner surface membrane removing treatment, and then washing the aluminum alloy special-shaped cavity for 2 times at normal temperature for 1min by using clean water;
(10) Placing the aluminum alloy special-shaped cavity washed in the step (9) into a chemical oxidation treatment liquid at the temperature of 80 ℃ for treatment for 12min, then washing with clean water at normal temperature for 1min, and washing for 2 times;
(11) And (4) putting the aluminum alloy special-shaped cavity washed in the step (10) into hot water at the temperature of 90 ℃ for washing for 25s, then placing the aluminum alloy special-shaped cavity at the temperature of 110 ℃ for drying for 3min, and finally removing the outer surface protective layer to obtain the aluminum alloy special-shaped cavity with oxidized inner and outer surfaces.
The degreasing liquid formula in the step (1) is as follows: the sodium phosphate-sodium dodecyl benzene sulfonate composite material comprises sodium phosphate, sodium carbonate, sodium dodecyl benzene sulfonate and solvent water, wherein the concentration of the sodium phosphate is 12g/L, the concentration of the sodium carbonate is 3g/L, and the concentration of the sodium dodecyl sulfonate is 6g/L.
The concentration of the sodium hydroxide aqueous solution in the step (2) is 40g/L.
And (5) the polishing solution is a nitric acid aqueous solution with the concentration of 140 g/L.
And (6) the initial voltage is 9V, the final voltage is 20V, and the voltage rising rate is 1.2V/min.
The anode oxidation electrolyte in the step (6) comprises lactic acid, oxalic acid, glycolic acid and solvent water, wherein the concentration of the lactic acid is 6g/L, the concentration of the oxalic acid is 9g/L, and the concentration of the glycolic acid is 18g/L.
The formula of the coloring liquid in the step (7) is as follows: bisabolol, solanum nigrum alcohol, camphorwood lignan, ammonium sulfide, sodium sulfide, cobalt acetate, copper sulfate, potassium permanganate, acetic acid and solvent water, wherein the concentration of bisabolol is 0.6g/L, the concentration of solanum nigrum alcohol is 0.4g/L, the concentration of camphorwood lignan is 0.2g/L, the concentration of ammonium sulfide is 0.6g/L, the concentration of sodium sulfide with prime number is 1.5g/L, the concentration of cobalt acetate is 0.3/L, the concentration of copper sulfate is 0.6g/L, the concentration of potassium permanganate is 1.0g/L, and the concentration of acetic acid is 0.15g/L.
And (9) the acidic film removing solution is nitric acid water solution with the concentration of 120 g/L.
And (4) the alkaline film stripping solution in the step (9) is a sodium hydroxide aqueous solution with the concentration of 5g/L.
The formula of the chemical oxidation treatment liquid in the step (10) is as follows: the cerium nitrate-potassium sulfate-potassium permanganate-potassium nitrate compound comprises cerium nitrate, lanthanum sulfate, hydrochloric acid, potassium permanganate, potassium citrate and solvent water, wherein the concentration of the cerium nitrate is 0.5g/L, the concentration of the lanthanum sulfate is 0.6g/L, the concentration of the hydrochloric acid is 1.6g/L, the concentration of the potassium permanganate is 0.3g/L, and the concentration of the potassium citrate is 1.5g/L.
Comparative example 1
An internal and external different oxidation process of an aluminum alloy special-shaped cavity comprises the following steps:
(1) Soaking the aluminum alloy special-shaped cavity in deoiling liquid at the temperature of 55 ℃ for 8min to remove oil on the inner surface and the outer surface, and then washing the aluminum alloy special-shaped cavity for 1min at normal temperature by using clean water for 2 times;
(2) Soaking the aluminum alloy special-shaped cavity washed in the step (1) in a sodium hydroxide aqueous solution at 33 ℃ for 3min for alkali washing the inner surface and the outer surface, and then washing the aluminum alloy special-shaped cavity with clean water at normal temperature for 2min for 2 times;
(3) Polishing the surfaces of the inner surface and the outer surface of the aluminum alloy special-shaped cavity washed in the step (2) by using a diatomite polishing agent to mirror surface light to enable the surface roughness Ra of the aluminum alloy special-shaped cavity to be 0.11um, then washing the aluminum alloy special-shaped cavity for 2 times at normal temperature for 1.5min, and drying the aluminum alloy special-shaped cavity at the temperature of 110 ℃ for 5min;
(4) Carrying out sand blasting treatment on the inner surface and the outer surface of the aluminum alloy special-shaped cavity dried in the step (3) by using glass beads under the condition that the pressure is 650kPa, and controlling the surface roughness Ra to be 1.3um;
(5) Soaking the polished aluminum alloy special-shaped cavity in the step (4) in polishing solution at 35 ℃ for 3min to perform chemical polishing treatment on the inner surface and the outer surface, and then washing the aluminum alloy special-shaped cavity with clean water at normal temperature for 1min for 2 times;
(6) Taking the aluminum alloy special-shaped cavity washed in the step (5) as an anode, putting the aluminum alloy special-shaped cavity into an oxidation tank containing anodic oxidation electrolyte, taking a lead plate as a cathode, controlling the temperature to be 10 ℃, switching on a power supply to start oxidation, switching off the power supply after the control voltage gradually rises from the initial voltage to the final voltage in the oxidation process, finishing oxidation to obtain an aluminum alloy special-shaped cavity with anodic oxidation films on the inner and outer surfaces, and then washing the aluminum alloy special-shaped cavity for 2 times at normal temperature by using clean water;
(7) Putting the washed aluminum alloy special-shaped cavity in the step (6) into a coloring tank filled with coloring liquid with the pH value of 5.5-6.0, stirring for 18min to perform coloring treatment on the inner surface and the outer surface, then washing for 1.6min with clear water, washing for 2 times, and drying at 120 ℃ for 3min;
(8) Protecting the outer surface of the aluminum alloy special-shaped cavity dried in the step (7) by using a peelable glue to form an outer surface protection layer, and controlling the thickness of the protection layer to be 200 mu m;
(9) Soaking the aluminum alloy special-shaped cavity subjected to outer surface protection in the step (8) in an acidic film removing solution for 12min, then placing the aluminum alloy special-shaped cavity in an alkaline film removing solution for neutralization for 30s to perform inner surface film removing treatment, and then washing the aluminum alloy special-shaped cavity for 1min at normal temperature for 2 times by using clean water;
(10) Placing the aluminum alloy special-shaped cavity washed in the step (9) into chemical oxidation treatment liquid at the temperature of 60 ℃ for treatment for 10min, then washing with clear water at normal temperature for 2min, and washing for 2 times;
(11) And (4) putting the aluminum alloy special-shaped cavity washed in the step (10) into hot water at the temperature of 95 ℃ for washing for 28s, then placing the aluminum alloy special-shaped cavity at the temperature of 110 ℃ for drying for 3min, and finally removing the outer surface protective layer to obtain the aluminum alloy special-shaped cavity with oxidized inner and outer surfaces.
The degreasing fluid formula in the step (1) is as follows: the sodium phosphate-sodium dodecyl benzene sulfonate composite material comprises sodium phosphate, sodium carbonate, sodium dodecyl benzene sulfonate and solvent water, wherein the concentration of the sodium phosphate is 18g/L, the concentration of the sodium carbonate is 2g/L, and the concentration of the sodium dodecyl sulfonate is 5g/L.
The concentration of the sodium hydroxide aqueous solution in the step (2) is 42g/L.
And (5) the polishing solution is a nitric acid aqueous solution with the concentration of 120 g/L.
And (6) setting the initial voltage to be 10V, the final voltage to be 22V and the voltage rising rate to be 0.6V/min.
The anode oxidation electrolyte in the step (6) comprises lactic acid, oxalic acid, glycolic acid and solvent water, wherein the concentration of the lactic acid is 5g/L, the concentration of the oxalic acid is 8g/L, and the concentration of the glycolic acid is 15g/L.
The formula of the coloring liquid in the step (7) is as follows: bisabolol, solanum nigrum alcohol, camphorwood lignan, ammonium sulfide, sodium sulfide, cobalt acetate, copper sulfate, potassium permanganate, acetic acid and solvent water, wherein the concentration of the bisabolol is 0.5g/L, the concentration of the solanum nigrum alcohol is 0.2g/L, the concentration of the camphorwood lignan is 0.1g/L, the concentration of the ammonium sulfide is 0.7g/L, the concentration of the sodium sulfide is 1.2g/L, the concentration of the cobalt acetate is 0.5g/L, the concentration of the copper sulfate is 0.6g/L, the concentration of the potassium permanganate is 1.1g/L, and the concentration of the acetic acid is 0.12g/L.
And (4) the acidic film stripping solution in the step (9) is a nitric acid aqueous solution with the concentration of 110 g/L.
And (9) the alkaline film stripping solution is a sodium hydroxide aqueous solution with the concentration of 6g/L.
The formula of the chemical oxidation treatment liquid in the step (10) is as follows: the cerium nitrate-potassium sulfate-potassium permanganate-potassium nitrate compound comprises cerium nitrate, lanthanum sulfate, hydrochloric acid, potassium permanganate, potassium citrate and solvent water, wherein the concentration of the cerium nitrate is 0.6g/L, the concentration of the lanthanum sulfate is 0.6g/L, the concentration of the hydrochloric acid is 1.8g/L, the concentration of the potassium permanganate is 0.2g/L, and the concentration of the potassium citrate is 1.6g/L.
Comparative example 2
An internal and external different oxidation process of an aluminum alloy special-shaped cavity, which comprises the following steps:
(1) Soaking the aluminum alloy special-shaped cavity in deoiling liquid at the temperature of 55 ℃ for 8min to remove oil on the inner surface and the outer surface, and then washing the aluminum alloy special-shaped cavity for 1min at normal temperature by using clean water for 2 times;
(2) Soaking the aluminum alloy special-shaped cavity washed in the step (1) in a sodium hydroxide aqueous solution at 33 ℃ for 3min for alkali washing the inner surface and the outer surface, and then washing the aluminum alloy special-shaped cavity with clean water at normal temperature for 2min for 2 times;
(3) Polishing the surfaces of the inner surface and the outer surface of the aluminum alloy special-shaped cavity washed in the step (2) by using a diatomite polishing agent to mirror surface light to enable the surface roughness Ra of the aluminum alloy special-shaped cavity to be 0.11um, then washing the aluminum alloy special-shaped cavity for 2 times at normal temperature for 1.5min, and drying the aluminum alloy special-shaped cavity at the temperature of 110 ℃ for 5min;
(4) Carrying out sand blasting treatment on the inner surface and the outer surface of the aluminum alloy special-shaped cavity dried in the step (3) by using glass beads under the condition that the pressure is 650kPa, and controlling the surface roughness Ra to be 1.3um;
(5) Soaking the aluminum alloy special-shaped cavity polished in the step (4) in polishing solution at 35 ℃ for 3min to perform chemical polishing treatment on the inner surface and the outer surface, and then washing the aluminum alloy special-shaped cavity with clear water at normal temperature for 1min and 2 times;
(6) Taking the aluminum alloy special-shaped cavity washed in the step (5) as an anode, putting the aluminum alloy special-shaped cavity into an oxidation tank containing anodic oxidation electrolyte, taking a lead plate as a cathode, controlling the temperature to be 10 ℃, switching on a power supply to start oxidation, switching off the power supply after the control voltage gradually rises from the initial voltage to the final voltage in the oxidation process, finishing oxidation to obtain an aluminum alloy special-shaped cavity with anodic oxidation films on the inner and outer surfaces, then washing the aluminum alloy special-shaped cavity for 2min at normal temperature by using clean water, and washing the aluminum alloy special-shaped cavity for 2 times;
(7) Putting the aluminum alloy special-shaped cavity washed in the step (6) into a coloring tank filled with coloring liquid with the pH value of 5.5-6.0, stirring for 18min to perform coloring treatment on the inner surface and the outer surface, then washing for 1.6min by clear water, washing for 2 times, and drying at 120 ℃ for 3min;
(8) Protecting the outer surface of the aluminum alloy special-shaped cavity dried in the step (7) by using a peelable glue to form an outer surface protection layer, and controlling the thickness of the protection layer to be 200 mu m;
(9) Soaking the aluminum alloy special-shaped cavity subjected to outer surface protection in the step (8) in an acidic film removing solution for 12min, then placing the aluminum alloy special-shaped cavity in an alkaline film removing solution for neutralization for 30s to perform inner surface film removing treatment, and then washing the aluminum alloy special-shaped cavity for 1min at normal temperature for 2 times by using clean water;
(10) Placing the aluminum alloy special-shaped cavity washed in the step (9) into chemical oxidation treatment liquid at the temperature of 60 ℃ for treatment for 10min, then washing with clean water at normal temperature for 2min, and washing for 2 times;
(11) And (4) putting the aluminum alloy special-shaped cavity washed in the step (10) into hot water at the temperature of 95 ℃ for washing for 28s, then placing the aluminum alloy special-shaped cavity at the temperature of 110 ℃ for drying for 3min, and finally removing the outer surface protective layer to obtain the aluminum alloy special-shaped cavity with oxidized inner and outer surfaces.
The degreasing liquid formula in the step (1) is as follows: the sodium phosphate-sodium dodecyl benzene sulfonate composite material comprises sodium phosphate, sodium carbonate, sodium dodecyl benzene sulfonate and solvent water, wherein the concentration of the sodium phosphate is 18g/L, the concentration of the sodium carbonate is 2g/L, and the concentration of the sodium dodecyl sulfonate is 5g/L.
The concentration of the sodium hydroxide aqueous solution in the step (2) is 42g/L.
And (5) the polishing solution is a nitric acid aqueous solution with the concentration of 120 g/L.
And (6) setting the initial voltage to be 10V, the final voltage to be 22V and the voltage rising rate to be 1.8V/min.
The anode oxidation electrolyte in the step (6) is prepared from lactic acid, oxalic acid, glycolic acid and solvent water, wherein the concentration of the lactic acid is 5g/L, the concentration of the oxalic acid is 8g/L, and the concentration of the glycolic acid is 15g/L.
The formula of the coloring liquid in the step (7) is as follows: bisabolol, solanum nigrum alcohol, camphorwood lignan, ammonium sulfide, sodium sulfide, cobalt acetate, copper sulfate, potassium permanganate, acetic acid and solvent water, wherein the concentration of bisabolol is 0.5g/L, the concentration of solanum nigrum alcohol is 0.2g/L, the concentration of camphorwood lignan is 0.1g/L, the concentration of ammonium sulfide is 0.7g/L, the concentration of sodium sulfide with prime number is 1.2g/L, the concentration of cobalt acetate is 0.5g/L, the concentration of copper sulfate is 0.6g/L, the concentration of potassium permanganate is 1.1g/L, and the concentration of acetic acid is 0.12g/L.
And (4) the acidic film stripping solution in the step (9) is a nitric acid aqueous solution with the concentration of 110 g/L.
And (4) the alkaline film stripping solution in the step (9) is a sodium hydroxide aqueous solution with the concentration of 6g/L.
The formula of the chemical oxidation treatment liquid in the step (10) is as follows: the cerium nitrate solution comprises cerium nitrate, lanthanum sulfate, hydrochloric acid, potassium permanganate, potassium citrate and solvent water, wherein the concentration of the cerium nitrate is 0.6g/L, the concentration of the lanthanum sulfate is 0.6g/L, the concentration of the hydrochloric acid is 1.8g/L, the concentration of the potassium permanganate is 0.2g/L, and the concentration of the potassium citrate is 1.6g/L.
Comparative example 3
An internal and external different oxidation process of an aluminum alloy special-shaped cavity comprises the following steps:
(1) Soaking the aluminum alloy special-shaped cavity in deoiling liquid at the temperature of 55 ℃ for 8min to remove oil on the inner surface and the outer surface, and then washing with clean water at normal temperature for 1min and 2 times;
(2) Soaking the aluminum alloy special-shaped cavity washed in the step (1) in a sodium hydroxide aqueous solution at 33 ℃ for 3min for alkali washing of the inner surface and the outer surface, and then washing with clear water at normal temperature for 2min for 2 times;
(3) Polishing the surfaces of the inner surface and the outer surface of the aluminum alloy special-shaped cavity washed in the step (2) by using a diatomite polishing agent until the surfaces are polished to be mirror surface, so that the surface roughness Ra of the aluminum alloy special-shaped cavity is 0.11 mu m, then washing for 2 times at normal temperature for 1.5min by using clean water, and drying for 5min at the temperature of 110 ℃;
(4) Carrying out sand blasting treatment on the inner surface and the outer surface of the aluminum alloy special-shaped cavity dried in the step (3) by using glass beads under the condition that the pressure is 650kPa, and controlling the surface roughness Ra to be 1.3um;
(5) Soaking the aluminum alloy special-shaped cavity polished in the step (4) in polishing solution at 35 ℃ for 3min to perform chemical polishing treatment on the inner surface and the outer surface, and then washing the aluminum alloy special-shaped cavity with clear water at normal temperature for 1min and 2 times;
(6) Taking the aluminum alloy special-shaped cavity washed in the step (5) as an anode, putting the aluminum alloy special-shaped cavity into an oxidation tank containing anodic oxidation electrolyte, taking a lead plate as a cathode, controlling the temperature to be 10 ℃, switching on a power supply to start oxidation, switching off the power supply after the control voltage gradually rises from the initial voltage to the final voltage in the oxidation process, finishing oxidation to obtain an aluminum alloy special-shaped cavity with anodic oxidation films on the inner and outer surfaces, and then washing the aluminum alloy special-shaped cavity for 2 times at normal temperature by using clean water;
(7) Putting the washed aluminum alloy special-shaped cavity in the step (6) into a coloring tank filled with coloring liquid with the pH value of 5.5-6.0, stirring for 18min to perform coloring treatment on the inner surface and the outer surface, then washing for 1.6min with clear water, washing for 2 times, and drying at 120 ℃ for 3min;
(8) Protecting the outer surface of the aluminum alloy special-shaped cavity dried in the step (7) by using a peelable adhesive to form an outer surface protection layer, and controlling the thickness of the protection layer to be 200 mu m;
(9) Soaking the aluminum alloy special-shaped cavity subjected to outer surface protection in the step (8) in an acidic film removing solution for 12min, then placing the aluminum alloy special-shaped cavity in an alkaline film removing solution for neutralization for 30s to perform inner surface film removing treatment, and then washing the aluminum alloy special-shaped cavity for 1min at normal temperature for 2 times by using clean water;
(10) Placing the aluminum alloy special-shaped cavity washed in the step (9) into chemical oxidation treatment liquid at the temperature of 60 ℃ for treatment for 10min, then washing with clean water at normal temperature for 2min, and washing for 2 times;
(11) And (4) putting the aluminum alloy special-shaped cavity washed in the step (10) into hot water at the temperature of 95 ℃ for washing for 28s, then placing the aluminum alloy special-shaped cavity at the temperature of 110 ℃ for drying for 3min, and finally removing the outer surface protective layer to obtain the aluminum alloy special-shaped cavity with oxidized inner and outer surfaces.
The degreasing liquid formula in the step (1) is as follows: the sodium phosphate-sodium dodecyl benzene sulfonate composite material comprises sodium phosphate, sodium carbonate, sodium dodecyl benzene sulfonate and solvent water, wherein the concentration of the sodium phosphate is 18g/L, the concentration of the sodium carbonate is 2g/L, and the concentration of the sodium dodecyl sulfonate is 5g/L.
The concentration of the sodium hydroxide aqueous solution in the step (2) is 42g/L.
And (5) the polishing solution is a nitric acid aqueous solution with the concentration of 120 g/L.
And (6) setting the initial voltage to be 10V, the final voltage to be 22V and the voltage rising rate to be 0.8V/min.
The anode oxidation electrolyte in the step (6) is prepared from lactic acid, oxalic acid, glycolic acid and solvent water, wherein the concentration of the lactic acid is 5g/L, the concentration of the oxalic acid is 8g/L, and the concentration of the glycolic acid is 15g/L.
The formula of the coloring liquid in the step (7) is as follows: bisabolol, solanum nigrum alcohol, camphorwood lignan, ammonium sulfide, sodium sulfide, cobalt acetate, copper sulfate, potassium permanganate, acetic acid and solvent water, wherein the concentration of bisabolol is 0.5g/L, the concentration of solanum nigrum alcohol is 0.2g/L, the concentration of camphorwood lignan is 0.1g/L, the concentration of ammonium sulfide is 0.7g/L, the concentration of sodium sulfide with prime number is 1.2g/L, the concentration of cobalt acetate is 0.5g/L, the concentration of copper sulfate is 0.6g/L, the concentration of potassium permanganate is 1.1g/L, and the concentration of acetic acid is 0.12g/L.
And (4) the acidic film stripping solution in the step (9) is a nitric acid aqueous solution with the concentration of 110 g/L.
And (9) the alkaline film stripping solution is a sodium hydroxide aqueous solution with the concentration of 6g/L.
The formula of the chemical oxidation treatment liquid in the step (10) is as follows: the cerium nitrate-potassium permanganate-potassium nitrate compound comprises cerium nitrate, hydrochloric acid, potassium permanganate, potassium citrate and solvent water, wherein the concentration of the cerium nitrate is 1.2g/L, the concentration of the hydrochloric acid is 1.8g/L, the concentration of the potassium permanganate is 0.2g/L, and the concentration of the potassium citrate is 1.6g/L.
Comparative example 4
An internal and external different oxidation process of an aluminum alloy special-shaped cavity comprises the following steps:
(1) Soaking the aluminum alloy special-shaped cavity in deoiling liquid at the temperature of 55 ℃ for 8min to remove oil on the inner surface and the outer surface, and then washing with clean water at normal temperature for 1min and 2 times;
(2) Soaking the aluminum alloy special-shaped cavity washed in the step (1) in a sodium hydroxide aqueous solution at 33 ℃ for 3min for alkali washing the inner surface and the outer surface, and then washing the aluminum alloy special-shaped cavity with clean water at normal temperature for 2min for 2 times;
(3) Polishing the surfaces of the inner surface and the outer surface of the aluminum alloy special-shaped cavity washed in the step (2) by using a diatomite polishing agent to mirror surface light to enable the surface roughness Ra of the aluminum alloy special-shaped cavity to be 0.11um, then washing the aluminum alloy special-shaped cavity for 2 times at normal temperature for 1.5min, and drying the aluminum alloy special-shaped cavity at the temperature of 110 ℃ for 5min;
(4) Carrying out sand blasting treatment on the inner surface and the outer surface of the aluminum alloy special-shaped cavity dried in the step (3) by using glass beads under the condition that the pressure is 650kPa, and controlling the surface roughness Ra to be 1.3um;
(5) Soaking the aluminum alloy special-shaped cavity polished in the step (4) in polishing solution at 35 ℃ for 3min to perform chemical polishing treatment on the inner surface and the outer surface, and then washing the aluminum alloy special-shaped cavity with clear water at normal temperature for 1min and 2 times;
(6) Taking the aluminum alloy special-shaped cavity washed in the step (5) as an anode, putting the aluminum alloy special-shaped cavity into an oxidation tank containing anodic oxidation electrolyte, taking a lead plate as a cathode, controlling the temperature to be 10 ℃, switching on a power supply to start oxidation, switching off the power supply after the control voltage gradually rises from the initial voltage to the final voltage in the oxidation process, finishing oxidation to obtain an aluminum alloy special-shaped cavity with anodic oxidation films on the inner and outer surfaces, and then washing the aluminum alloy special-shaped cavity for 2 times at normal temperature by using clean water;
(7) Putting the washed aluminum alloy special-shaped cavity in the step (6) into a coloring tank filled with coloring liquid with the pH value of 5.5-6.0, stirring for 18min to perform coloring treatment on the inner surface and the outer surface, then washing for 1.6min with clear water, washing for 2 times, and drying at 120 ℃ for 3min;
(8) Protecting the outer surface of the aluminum alloy special-shaped cavity dried in the step (7) by using a peelable adhesive to form an outer surface protection layer, and controlling the thickness of the protection layer to be 200 mu m;
(9) Soaking the aluminum alloy special-shaped cavity subjected to outer surface protection in the step (8) in an acidic film removing solution for 12min, then placing the aluminum alloy special-shaped cavity in an alkaline film removing solution for neutralization for 30s to perform inner surface film removing treatment, and then washing the aluminum alloy special-shaped cavity for 1min at normal temperature for 2 times by using clean water;
(10) Placing the aluminum alloy special-shaped cavity washed in the step (9) into chemical oxidation treatment liquid at the temperature of 60 ℃ for treatment for 10min, then washing with clean water at normal temperature for 2min, and washing for 2 times;
(11) And (4) putting the aluminum alloy special-shaped cavity washed in the step (10) into hot water at the temperature of 95 ℃ for washing for 28s, then placing the aluminum alloy special-shaped cavity at the temperature of 110 ℃ for drying for 3min, and finally removing the outer surface protective layer to obtain the aluminum alloy special-shaped cavity with oxidized inner and outer surfaces.
The degreasing fluid formula in the step (1) is as follows: the sodium phosphate-sodium dodecyl benzene sulfonate composite material comprises sodium phosphate, sodium carbonate, sodium dodecyl benzene sulfonate and solvent water, wherein the concentration of the sodium phosphate is 18g/L, the concentration of the sodium carbonate is 2g/L, and the concentration of the sodium dodecyl sulfonate is 5g/L.
The concentration of the sodium hydroxide aqueous solution in the step (2) is 42g/L.
And (5) the polishing solution is a nitric acid aqueous solution with the concentration of 120 g/L.
And (6) setting the initial voltage to be 10V, the final voltage to be 22V and the voltage rising rate to be 0.8V/min.
The anode oxidation electrolyte in the step (6) is prepared from lactic acid, oxalic acid, glycolic acid and solvent water, wherein the concentration of the lactic acid is 5g/L, the concentration of the oxalic acid is 8g/L, and the concentration of the glycolic acid is 15g/L.
The formula of the coloring liquid in the step (7) is as follows: bisabolol, solanum nigrum alcohol, camphorwood lignan, ammonium sulfide, sodium sulfide, cobalt acetate, copper sulfate, potassium permanganate, acetic acid and solvent water, wherein the concentration of the bisabolol is 0.5g/L, the concentration of the solanum nigrum alcohol is 0.2g/L, the concentration of the camphorwood lignan is 0.1g/L, the concentration of the ammonium sulfide is 0.7g/L, the concentration of the sodium sulfide is 1.2g/L, the concentration of the cobalt acetate is 0.5g/L, the concentration of the copper sulfate is 0.6g/L, the concentration of the potassium permanganate is 1.1g/L, and the concentration of the acetic acid is 0.12g/L.
And (4) the acidic film stripping solution in the step (9) is a nitric acid aqueous solution with the concentration of 110 g/L.
And (9) the alkaline film stripping solution is a sodium hydroxide aqueous solution with the concentration of 6g/L.
The formula of the chemical oxidation treatment solution in the step (10) is as follows: the lanthanum sulfate, hydrochloric acid, potassium permanganate, potassium citrate and solvent water, wherein the concentration of lanthanum sulfate is 1.2g/L, the concentration of hydrochloric acid is 1.8g/L, the concentration of potassium permanganate is 0.2g/L, and the concentration of potassium citrate is 1.6g/L.
Performance testing
The inner and outer surfaces of the aluminum alloy special-shaped cavity with oxidized inner and outer surfaces in the examples 1-2 and the comparative examples 1-4 are tested according to GB/T1730-2007, GB/T1733-1993 and GB6458-86 respectively for hardness, water resistance and neutral salt spray tests, and the test results are shown in the following table;
TABLE 1 test results of performance of aluminum alloy special-shaped cavity with oxidized inner and outer surfaces
From the test results, the comparative example 1 reduces the voltage rising rate to 0.6V/min during anodic oxidation on the basis of the example 1, and the hardness, the water resistance and the neutral salt spray resistance of the outer surface of the obtained aluminum alloy special-shaped cavity with oxidized inner and outer surfaces are obviously reduced; comparative example 2 the voltage rise rate during anodic oxidation was increased to 1.8V/min on the basis of example 1, and the hardness, water resistance and neutral salt spray resistance of the outer surface of the obtained aluminum alloy profiled cavity with oxidized inner and outer surfaces were all significantly reduced; comparative example 3 on the basis of example 1, cerium nitrate in the chemical oxidation treatment liquid replaces the same amount of lanthanum sulfate, and the hardness, water resistance and neutral salt spray resistance of the inner surface and the outer surface of the obtained aluminum alloy special-shaped cavity oxidized are obviously reduced; comparative example 4 on the basis of example 1, the equivalent cerium nitrate was replaced with lanthanum sulfate in the chemical oxidation treatment solution, and the hardness, water resistance and neutral salt spray resistance of the inner and outer surfaces of the obtained aluminum alloy irregular cavity were significantly reduced.
Although the present invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the present invention.
Claims (10)
1. The different oxidation technology inside and outside an aluminum alloy special-shaped cavity is characterized by comprising the following steps:
(1) Putting the aluminum alloy special-shaped cavity into deoiling liquid at the temperature of 50-60 ℃ to be soaked for 5-10 min for deoiling on the inner surface and the outer surface, then washing with clean water at normal temperature for 1-2 min for 2 times;
(2) Placing the aluminum alloy special-shaped cavity washed in the step (1) into a sodium hydroxide aqueous solution with the temperature of 30-40 ℃ for soaking for 3-5 min to carry out alkali washing on the inner surface and the outer surface, and then washing with clear water at normal temperature for 1-2 min for 2 times;
(3) Polishing the surfaces of the inner surface and the outer surface of the aluminum alloy special-shaped cavity washed in the step (2) by using a diatomite polishing agent to mirror surface light to ensure that the surface roughness Ra is 0.1-0.12 um, then washing for 1-2 min at normal temperature by using clean water, washing for 2 times, and drying for 3-5 min at the temperature of 100-120 ℃;
(4) Carrying out sand blasting treatment on the inner surface and the outer surface of the aluminum alloy special-shaped cavity dried in the step (3) by using glass beads under the pressure of 600-800 kPa, and controlling the surface roughness Ra of the aluminum alloy special-shaped cavity to be 1.2-1.5 um;
(5) Soaking the polished aluminum alloy special-shaped cavity in the step (4) in polishing solution at 30-40 ℃ for 3-5 min to perform chemical polishing treatment on the inner surface and the outer surface, and then washing the aluminum alloy special-shaped cavity with clean water at normal temperature for 1-2 min for 2 times;
(6) Taking the aluminum alloy special-shaped cavity washed in the step (5) as an anode, putting the aluminum alloy special-shaped cavity into an oxidation tank containing anodic oxidation electrolyte, taking a lead plate as a cathode, controlling the temperature to be 5-10 ℃, switching on a power supply to start oxidation, switching off the power supply after the control voltage gradually rises from the initial voltage to the final voltage in the oxidation process, finishing oxidation to obtain an aluminum alloy special-shaped cavity with anodic oxidation films on the inner and outer surfaces, and then washing the aluminum alloy special-shaped cavity for 1-2 min at normal temperature by using clean water for 2 times;
(7) Putting the washed aluminum alloy special-shaped cavity in the step (6) into a coloring tank filled with coloring liquid with the pH value of 5.5-6.0, stirring for 10-20 min to perform coloring treatment on the inner surface and the outer surface, then washing for 1-2 min with clear water, washing for 2 times, and drying at the temperature of 100-120 ℃ for 3-5 min;
(8) Protecting the outer surface of the aluminum alloy special-shaped cavity dried in the step (7) by using a peelable adhesive to form an outer surface protection layer, and controlling the thickness of the protection layer to be 100-300 mu m;
(9) Soaking the aluminum alloy special-shaped cavity subjected to outer surface protection in the step (8) in an acidic film removing solution for 10-15 min, then placing the aluminum alloy special-shaped cavity in an alkaline film removing solution for neutralization for 25-35 s to perform inner surface film removing treatment, and then washing the aluminum alloy special-shaped cavity for 2 times at normal temperature for 1-2 min by using clear water;
(10) Putting the aluminum alloy special-shaped cavity washed in the step (9) into chemical oxidation treatment liquid at the temperature of 60-80 ℃ for treatment for 8-15 min, and then washing the aluminum alloy special-shaped cavity for 1-2 min at normal temperature for 2 times;
(11) And (3) putting the aluminum alloy special-shaped cavity washed in the step (10) into hot water at the temperature of 90-110 ℃ for washing for 20-30 s, then putting the aluminum alloy special-shaped cavity into the hot water at the temperature of 100-120 ℃ for drying for 3-5 min, and finally removing the outer surface protective layer to obtain the aluminum alloy special-shaped cavity with oxidized inner and outer surfaces.
2. The different oxidation processes inside and outside the aluminum alloy special-shaped cavity according to claim 1, wherein the degreasing fluid formula in the step (1) is as follows: sodium phosphate, sodium carbonate, sodium dodecyl benzene sulfonate and solvent water, the concentration of the sodium phosphate is 10-20 g/L, the concentration of the sodium carbonate is 1-5 g/L, and the concentration of the sodium dodecyl sulfate is 2-8 g/L.
3. The different oxidation processes inside and outside the aluminum alloy special-shaped cavity according to claim 1, wherein the concentration of the sodium hydroxide aqueous solution in the step (2) is 30-50 g/L.
4. The different oxidation processes inside and outside the aluminum alloy special-shaped cavity according to claim 1, wherein the polishing solution in the step (5) is a nitric acid aqueous solution with a concentration of 100-150 g/L.
5. The different oxidation processes inside and outside the aluminum alloy special-shaped cavity according to claim 1, wherein the starting voltage in the step (6) is 8-10V, the ending voltage is 20-24V, and the voltage rising rate is 0.8-1.5V/min.
6. The different oxidation processes inside and outside an aluminum alloy special-shaped cavity according to claim 1, wherein the anodic oxidation electrolyte formula in the step (6) is lactic acid, oxalic acid, glycolic acid and solvent water, the concentration of the lactic acid is 5-6 g/L, the concentration of the oxalic acid is 8-10 g/L, and the concentration of the glycolic acid is 10-20 g/L.
7. The different oxidation processes inside and outside the aluminum alloy special-shaped cavity according to claim 1, wherein the formula of the coloring liquid in the step (7) is as follows: the composition comprises bisabolol, solanum nigrum alcohol, camphorwood lignan, ammonium sulfide, sodium sulfide, cobalt acetate, copper sulfate, potassium permanganate, acetic acid and solvent water, wherein the concentration of the bisabolol is 0.5-0.8 g/L, the concentration of the solanum nigrum alcohol is 0.2-0.5g/L, the concentration of the camphorwood lignan is 0.1-0.2 g/L, the concentration of the ammonium sulfide is 0.5-0.8 g/L, the concentration of sodium sulfide with prime number is 1-1.5 g/L, the concentration of the cobalt acetate is 0.2-0.6 g/L, the concentration of the copper sulfate is 0.6-0.8 g/L, the concentration of the potassium permanganate is 0.8-1.2 g/L, and the concentration of the acetic acid is 0.1-0.2 g/L.
8. The different internal and external oxidation process of the aluminum alloy special-shaped cavity according to claim 1, wherein the acidic stripping solution in the step (9) is a nitric acid aqueous solution with the concentration of 100-120 g/L.
9. The different oxidation processes inside and outside the aluminum alloy special-shaped cavity according to claim 1, wherein the alkaline stripping solution in the step (9) is a sodium hydroxide aqueous solution with a concentration of 5-8 g/L.
10. The different oxidation processes inside and outside the aluminum alloy special-shaped cavity according to claim 1, wherein the chemical oxidation treatment liquid in the step (10) is prepared from the following formula: the cerium nitrate solution comprises cerium nitrate, lanthanum sulfate, hydrochloric acid, potassium permanganate, potassium citrate and solvent water, wherein the concentration of the cerium nitrate is 0.4-0.9 g/L, the concentration of the lanthanum sulfate is 0.5-0.8 g/L, the concentration of the hydrochloric acid is 1.5-2.0 g/L, the concentration of the potassium permanganate is 0.2-0.5g/L, and the concentration of the potassium citrate is 1.5-1.8 g/L.
Priority Applications (1)
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1920110A (en) * | 2006-07-26 | 2007-02-28 | 台山市金桥铝型材厂有限公司 | Anodic oxidation technology for inner and outer wall of aluminium tube |
| CN101153392A (en) * | 2006-09-28 | 2008-04-02 | 比亚迪股份有限公司 | Composition for surface treatment of light metal and its composite material |
| CN101403117A (en) * | 2008-11-07 | 2009-04-08 | 长沙湘计海盾科技有限公司 | Composite oxidation technology for aluminum or aluminum alloy product surface |
| CN104328420A (en) * | 2013-07-22 | 2015-02-04 | 无锡永发电镀有限公司 | Preparation method for chromium-free passivating solution for aviation aluminium alloy |
| CN104651821A (en) * | 2015-02-11 | 2015-05-27 | 常州君合科技股份有限公司 | Novel aluminum and high-molecular aluminum alloy chromium-free film forming agent |
| CN106191955A (en) * | 2016-08-26 | 2016-12-07 | 广东欧珀移动通信有限公司 | A kind of aluminium alloy anode oxide technique and anodized aluminum alloy |
| CN106191961A (en) * | 2014-05-22 | 2016-12-07 | 江苏理工学院 | Sealing treatment method in aluminum alloy surface treatment |
| CN107937960A (en) * | 2017-12-01 | 2018-04-20 | 佛山市高明高盛铝业有限公司 | A kind of aluminium alloy anode oxide technique |
| CN107964674A (en) * | 2017-12-01 | 2018-04-27 | 佛山市高明高盛铝业有限公司 | A kind of novel aluminum alloy anode oxidation process |
| CN108300987A (en) * | 2018-01-05 | 2018-07-20 | 佛山力邦通信设备科技有限公司 | A kind of aluminium alloy iris electric conductive oxidation technique |
| CN109778279A (en) * | 2018-12-26 | 2019-05-21 | 沈阳富创精密设备有限公司 | A kind of uniform anode oxidation process of cavity |
| CN112064000A (en) * | 2020-08-17 | 2020-12-11 | 尹波 | Passivation process for surface of aluminum alloy material |
| CN112725865A (en) * | 2020-12-23 | 2021-04-30 | 苏州佳世峰精密机械有限公司 | Surface treatment process of high-strength corrosion-resistant aluminum alloy for wheelchair processing |
-
2022
- 2022-08-31 CN CN202211063489.8A patent/CN115305546B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1920110A (en) * | 2006-07-26 | 2007-02-28 | 台山市金桥铝型材厂有限公司 | Anodic oxidation technology for inner and outer wall of aluminium tube |
| CN101153392A (en) * | 2006-09-28 | 2008-04-02 | 比亚迪股份有限公司 | Composition for surface treatment of light metal and its composite material |
| CN101403117A (en) * | 2008-11-07 | 2009-04-08 | 长沙湘计海盾科技有限公司 | Composite oxidation technology for aluminum or aluminum alloy product surface |
| CN104328420A (en) * | 2013-07-22 | 2015-02-04 | 无锡永发电镀有限公司 | Preparation method for chromium-free passivating solution for aviation aluminium alloy |
| CN106191961A (en) * | 2014-05-22 | 2016-12-07 | 江苏理工学院 | Sealing treatment method in aluminum alloy surface treatment |
| CN104651821A (en) * | 2015-02-11 | 2015-05-27 | 常州君合科技股份有限公司 | Novel aluminum and high-molecular aluminum alloy chromium-free film forming agent |
| CN106191955A (en) * | 2016-08-26 | 2016-12-07 | 广东欧珀移动通信有限公司 | A kind of aluminium alloy anode oxide technique and anodized aluminum alloy |
| CN107937960A (en) * | 2017-12-01 | 2018-04-20 | 佛山市高明高盛铝业有限公司 | A kind of aluminium alloy anode oxide technique |
| CN107964674A (en) * | 2017-12-01 | 2018-04-27 | 佛山市高明高盛铝业有限公司 | A kind of novel aluminum alloy anode oxidation process |
| CN108300987A (en) * | 2018-01-05 | 2018-07-20 | 佛山力邦通信设备科技有限公司 | A kind of aluminium alloy iris electric conductive oxidation technique |
| CN109778279A (en) * | 2018-12-26 | 2019-05-21 | 沈阳富创精密设备有限公司 | A kind of uniform anode oxidation process of cavity |
| CN112064000A (en) * | 2020-08-17 | 2020-12-11 | 尹波 | Passivation process for surface of aluminum alloy material |
| CN112725865A (en) * | 2020-12-23 | 2021-04-30 | 苏州佳世峰精密机械有限公司 | Surface treatment process of high-strength corrosion-resistant aluminum alloy for wheelchair processing |
Non-Patent Citations (3)
| Title |
|---|
| 张士林等, 上海科学技术文献出版社 * |
| 甘树坤等: "金属表面耐蚀性稀土转化膜的研究进展", 《吉林化工学院学报》 * |
| 邓型深等: "草酸-柠檬酸中 6061 铝合金的阳极氧化", 《电镀与涂饰》 * |
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