CN112522760A - Method for removing nickel from anodic aluminum oxide alloy - Google Patents
Method for removing nickel from anodic aluminum oxide alloy Download PDFInfo
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- CN112522760A CN112522760A CN202011499693.5A CN202011499693A CN112522760A CN 112522760 A CN112522760 A CN 112522760A CN 202011499693 A CN202011499693 A CN 202011499693A CN 112522760 A CN112522760 A CN 112522760A
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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
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/12—Anodising more than once, e.g. in different baths
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
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- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
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- 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
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- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
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- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
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Abstract
The invention relates to the technical field of metal surface treatment, in particular to a nickel removing method for anodic aluminum oxide alloy, which comprises the following steps: 1) preamble processing: cleaning and physically polishing the aluminum alloy workpiece, and removing no degreasing liquid on the surface of the aluminum alloy workpiece; 2) carrying out first anodic oxidation treatment on the aluminum alloy workpiece in the step 1); 3) sealing holes on the aluminum alloy workpiece treated in the step; 4) putting the aluminum alloy workpiece subjected to hole sealing treatment in the step 3) into the mixed solution for dipping and washing; 5) carrying out secondary anodic oxidation nickel removal on the aluminum alloy workpiece treated in the step 4); 6) and (5) taking out the aluminum alloy workpiece subjected to the second anodic oxidation nickel removal in the step 5), washing with water, and drying to obtain the product. The method has the characteristics of simplicity, good nickel removal effect, short nickel removal time and good hole sealing effect, wherein the nickel-sealed hole is sealed after the first anodic oxidation is adopted, and then the second anodic oxidation is carried out to achieve the nickel removal effect.
Description
Technical Field
The invention relates to the technical field of metal surface treatment, in particular to a nickel removing method for anodic aluminum oxide alloy.
Background
At present, 3C anode oxidation products have requirements on nickel release, and mainly when the products are used, skin can be contacted for a long time; when the nickel-containing oxide layer is used, nickel brought by the oxide layer hole sealing is released, and the skin of part of people is allergic to the nickel, so that the nickel-containing oxide layer can be damaged to different degrees. Solution to nickel release: 1, adopting a nickel-free hole sealing method, wherein the hole sealing method does not contain nickel; and 2, adopting a nickel sealing hole and auxiliary nickel removal process to prevent the nickel in the sealing hole layer from releasing. After hole sealing with nickel is adopted, secondary anode oxidation is carried out to remove nickel, and nickel release is prevented; and introducing a nickel-free sealing agent.
The hole sealing effect of the nickel-free hole sealing agent at the present stage is poor, the color is easy to fade, and the product is not suitable for products with high appearance requirements; the existing nickel removal method has a complex process, greatly influences the capacity of the built production line and greatly increases the equipment cost.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the method for removing the nickel from the anodized aluminum alloy, which has the characteristics of simplicity, good nickel removal effect, short nickel removal time and good hole sealing effect, wherein after the first anodic oxidation is adopted, the hole sealing with the nickel is carried out, and then the second anodic oxidation is carried out, so that the nickel removal effect is achieved.
The purpose of the invention is realized by the following technical scheme: an anode oxidized aluminum alloy nickel removal method is prepared by the following steps:
1) preamble processing: placing an aluminum alloy workpiece in soap water for cleaning, then placing the cleaned aluminum alloy workpiece in an ultrasonic cleaning machine for cleaning, after cleaning, physically polishing the workpiece, then placing the workpiece in a degreasing agent at 65-75 ℃ for soaking for 10-20min, after soaking, cleaning the workpiece with warm water at 70-80 ℃, and then washing the workpiece with clear water until no degreasing liquid exists on the surface of the workpiece for later use;
2) first oxidation: carrying out first anodic oxidation treatment on the aluminum alloy workpiece subjected to the preorder treatment in the step 1) for later use;
3) hole sealing treatment: washing and dyeing the aluminum alloy workpiece obtained in the step 2), and then carrying out nickel hole sealing, wherein the nickel hole sealing agent is heated to 80-100 ℃ during hole sealing, the anodic aluminum oxide alloy is put into the nickel hole sealing agent for heating for 20-40min, and the hole sealing is reserved;
4) and (3) hole sealing post-treatment: placing the aluminum alloy workpiece subjected to hole sealing treatment in the step 3) into a mixed solution consisting of deionized water, nitric acid and a flocculating agent for soaking for 5-15min, and then washing for 1-3 times by using clear water for later use;
5) and (3) second oxidation: carrying out secondary anodic oxidation nickel removal on the aluminum alloy workpiece treated in the step 4) for later use;
6) post-treatment: and (5) taking out the aluminum alloy workpiece subjected to the second anodic oxidation nickel removal in the step 5), washing with water, and drying to obtain the product.
The invention adopts physical polishing technology, abandons the chemical polishing technology commonly used in the prior art, avoids neutralization and water washing after chemical polishing, reduces operation steps, also improves working efficiency, and in addition, the process comprises the steps of sealing holes with nickel after the first anodic oxidation, then carrying out the second anodic oxidation and the first anodic oxidation, an oxide film is formed on the surface of the aluminum alloy, micropores are formed on the surface of the oxide film, the second anodic oxidation forms a layer of the same oxide film on the surface of the original oxide film, the nickel in the micropores is wrapped by the outer oxide film formed by the second anodic oxidation, the nickel cannot be released from the micropores, the harm of the nickel to human bodies and the environment is reduced, meanwhile, the product is not easy to fade, various machining performance indexes can meet the requirements of customers, and finally the residual nickel on the surface of the alloy workpiece body is removed, so that good nickel removing and hole sealing effects are achieved.
Preferably, the temperature for the first oxidation treatment in the step 2) is 22-26 ℃, the time is 20-60min, the voltage is 15-25V, and the first anodic oxidation solution is 190-210g/L sulfuric acid solution; the temperature for the second anodization in the step 5) is 22-26 ℃, the time is 15-30min, the voltage is 8-12V, and the second anodization solution is 180-200g/L sulfuric acid solution.
In the invention, each process parameter in the first oxidation treatment in the step 2) needs to be strictly controlled, so that an oxide film is well ensured to be formed on the surface of the aluminum alloy, the forming speed of the film hole layer is moderate, nano-scale holes can be formed, the holes with the size cannot cause adverse effects on the structural strength of the aluminum alloy body, and then micropores are formed on the surface of the oxide film.
Preferably, the oil removing agent in the step 1) is a mixture consisting of 15-25 parts by weight of ammonium phosphate, 4-12 parts by weight of OP-10, 10-15 parts by weight of sodium carbonate and 400-600 parts by weight of deionized water.
The degreasing agent adopted in the invention obtains the degreasing agent with excellent degreasing effect through ammonium phosphate complex, emulsifier OP-10, sodium carbonate and water, and grease on the surface of the aluminum alloy workpiece can be thoroughly removed when the aluminum alloy workpiece is preorded, thereby being beneficial to the subsequent secondary oxidation treatment and hole sealing operation of the aluminum alloy workpiece, and improving the nickel removal effect and the hole sealing effect.
Preferably, the mixed solution in the step 4) is prepared from deionized water, nitric acid and a flocculating agent according to the weight part ratio of 30-60: 4-8: 1-5.
Preferably, the flocculant comprises the following raw materials in parts by weight:
NaClO30.1 to 0.5 portion
1-3 parts of additive
0.5 to 1.5 portions of ferrous sulfate
0.1 to 0.5 portion of permanganate
8-14 parts of acidic solvent
10-15 parts of sodium gluconate.
The flocculant is prepared from the raw materials, the flocculant prepared from the raw materials has mild operation conditions after hole sealing, is safe in nickel removal, can achieve the nickel removal rate of more than 90% in wastewater, obviously improves the turbidity removal and COD removal effects, shortens the coagulation time by more than 10%, is suitable for sewage treatment of various processes, and has high treatment efficiency and low comprehensive cost.
Preferably, each part of the additive is at least one of ethylene diamine tetraacetic acid, glycerol, isostearic acid, isopropanol, benzotriazole and benzotriazole-5-carboxylic acid; more preferably, each part of the additive is a mixture of disodium ethylene diamine tetraacetate, isostearic acid and benzotriazole-5-carboxylic acid according to the weight ratio of 0.4-0.8:0.6-1.0: 0.8-1.2.
The additive adopted by the raw material of the flocculant is used for carrying out complexation reaction with a material for forming a membrane pore layer, such as alumina, so that pores are expanded and closed, and the further hole sealing is facilitated.
Preferably, each part of the acidic solvent is at least one of hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid and acetic acid; more preferably, each part of the acidic solvent is a mixture of hydrofluoric acid, sulfuric acid, phosphoric acid and acetic acid according to the weight ratio of 0.6-1.0:0.4-0.8:0.8-1.2: 0.1-0.5; the concentration of each part of the acid solvent is 20-60 g/L.
The acid solvent adopted by the raw material of the flocculating agent is used for removing the residual nickel, the acid solution enables the nano pores formed on the surface of the pore layer of the membrane to be uniformly distributed during anodic oxidation, and the acid has wide sources and low cost, so that the nickel removal and the further hole sealing are completed in the same step, and the nickel removal operation is simple.
The invention has the beneficial effects that: the invention adopts physical polishing technology, abandons the chemical polishing technology commonly used in the prior art, avoids neutralization and water washing after chemical polishing, reduces operation steps, also improves working efficiency, and in addition, the process comprises the steps of sealing holes with nickel after the first anodic oxidation, then carrying out the second anodic oxidation and the first anodic oxidation, an oxide film is formed on the surface of the aluminum alloy, micropores are formed on the surface of the oxide film, the second anodic oxidation forms a layer of the same oxide film on the surface of the original oxide film, the nickel in the micropores is wrapped by the outer oxide film formed by the second anodic oxidation, the nickel cannot be released from the micropores, the harm of the nickel to human bodies and the environment is reduced, meanwhile, the product is not easy to fade, various machining performance indexes can meet the requirements of customers, and finally the residual nickel on the surface of the alloy workpiece body is removed, so that good nickel removing and hole sealing effects are achieved.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
An anode oxidized aluminum alloy nickel removal method is prepared by the following steps:
1) preamble processing: placing an aluminum alloy workpiece in soap water for cleaning, then placing the cleaned aluminum alloy workpiece in an ultrasonic cleaning machine for cleaning, after cleaning, physically polishing the workpiece, then placing the workpiece in a degreasing agent at 65 ℃ for soaking for 10min, after soaking, cleaning the workpiece with warm water at 70 ℃, and then washing the workpiece with clean water until no degreasing liquid exists on the surface of the workpiece for later use;
2) first oxidation: carrying out first anodic oxidation treatment on the aluminum alloy workpiece subjected to the preorder treatment in the step 1) for later use;
3) hole sealing treatment: washing and dyeing the aluminum alloy workpiece obtained in the step 2), then carrying out nickel hole sealing, heating the nickel hole sealing agent to 80 ℃ during hole sealing, putting the anodic aluminum oxide alloy into the nickel hole sealing agent, heating for 20min, and sealing holes for later use;
4) and (3) hole sealing post-treatment: placing the aluminum alloy workpiece subjected to hole sealing treatment in the step 3) into a mixed solution consisting of deionized water, nitric acid and a flocculating agent for soaking for 5min, and then washing for 1 time by using clear water for later use;
5) and (3) second oxidation: carrying out secondary anodic oxidation nickel removal on the aluminum alloy workpiece treated in the step 4) for later use;
6) post-treatment: and (5) taking out the aluminum alloy workpiece subjected to the second anodic oxidation nickel removal in the step 5), washing with water, and drying to obtain the product.
The temperature for the first oxidation treatment in the step 2) is 22 ℃, the time is 20min, the voltage is 15V, and the first anodic oxidation solution is 190g/L sulfuric acid solution;
the temperature for the second anodizing in the step 5) is 22 ℃, the time is 15min, the voltage is 8V, and the second anodizing solution is 180g/L sulfuric acid solution.
The oil removing agent in the step 1) is a mixture consisting of 15 parts by weight of ammonium phosphate, 4 parts by weight of OP-10, 10 parts by weight of sodium carbonate and 400 parts by weight of deionized water.
The mixed solution in the step 4) is prepared from deionized water, nitric acid and a flocculating agent according to the weight part ratio of 30: 4: 1 is prepared from (1).
The flocculant comprises the following raw materials in parts by weight:
NaClO3 0.1 part
Additive 1 part
Ferrous sulfate 0.5 part
0.1 part of permanganate
Acid solvent 8 parts
10 parts of sodium gluconate.
Each part of the additive is a mixture of ethylene diamine tetraacetic acid, isostearic acid and benzotriazole-5-carboxylic acid according to the weight ratio of 0.4:0.6: 0.8.
Each part of the acidic solvent is a mixture of hydrofluoric acid, sulfuric acid, phosphoric acid and acetic acid according to the weight ratio of 0.6:0.4:0.8: 0.1; the concentration of the acidic solvent is 20 g/L.
Example 2
An anode oxidized aluminum alloy nickel removal method is prepared by the following steps:
1) preamble processing: placing an aluminum alloy workpiece in soap water for cleaning, then placing the cleaned aluminum alloy workpiece in an ultrasonic cleaning machine for cleaning, after cleaning, physically polishing the workpiece, then placing the workpiece in a degreasing agent at 68 ℃ for soaking for 13min, after soaking, cleaning the workpiece with warm water at 73 ℃, and then washing the workpiece with clean water until no degreasing liquid exists on the surface of the workpiece for later use;
2) first oxidation: carrying out first anodic oxidation treatment on the aluminum alloy workpiece subjected to the preorder treatment in the step 1) for later use;
3) hole sealing treatment: washing and dyeing the aluminum alloy workpiece obtained in the step 2), then carrying out nickel hole sealing, heating the nickel hole sealing agent to 85 ℃ during hole sealing, putting the anodic aluminum oxide alloy into the nickel hole sealing agent, heating for 25min, and sealing holes for later use;
4) and (3) hole sealing post-treatment: placing the aluminum alloy workpiece subjected to hole sealing treatment in the step 3) into a mixed solution consisting of deionized water, nitric acid and a flocculating agent for soaking for 8min, and then washing for 1 time by using clear water for later use;
5) and (3) second oxidation: carrying out secondary anodic oxidation nickel removal on the aluminum alloy workpiece treated in the step 4) for later use;
6) post-treatment: and (5) taking out the aluminum alloy workpiece subjected to the second anodic oxidation nickel removal in the step 5), washing with water, and drying to obtain the product.
The temperature for the first oxidation treatment in the step 2) is 23 ℃, the time is 30min, the voltage is 18V, and the first anodic oxidation solution is 1950g/L sulfuric acid solution;
the temperature for the second anodizing in the step 5) is 23 ℃, the time is 18min, the voltage is 9V, and the second anodizing solution is 185g/L sulfuric acid solution.
The oil removing agent in the step 1) is a mixture consisting of 18 parts of ammonium phosphate, 6 parts of OP-10, 12 parts of sodium carbonate and 450 parts of deionized water in parts by weight.
The mixed solution in the step 4) is prepared from deionized water, nitric acid and a flocculating agent according to the weight part ratio of 380: 5: 2 is prepared from (1).
The flocculant comprises the following raw materials in parts by weight:
NaClO3 0.2 part
Additive 1.5 parts
Ferrous sulfate 0.8 part
0.2 part of permanganate
9 portions of acidic solvent
12 parts of sodium gluconate.
Each part of the additive is a mixture of ethylene diamine tetraacetic acid, isostearic acid and benzotriazole-5-carboxylic acid according to the weight ratio of 0.5:0.7: 0.9.
Each part of the acidic solvent is a mixture of hydrofluoric acid, sulfuric acid, phosphoric acid and acetic acid according to the weight ratio of 0.7:0.5:0.9: 0.2; the concentration of the acidic solvent is 30 g/L.
Example 3
An anode oxidized aluminum alloy nickel removal method is prepared by the following steps:
1) preamble processing: placing an aluminum alloy workpiece in soap water for cleaning, then placing the cleaned aluminum alloy workpiece in an ultrasonic cleaning machine for cleaning, after cleaning, physically polishing the workpiece, then placing the workpiece in a degreasing agent at 70 ℃ for soaking for 15min, after soaking, cleaning the workpiece with warm water at 75 ℃, and then washing the workpiece with clean water until no degreasing liquid exists on the surface of the workpiece for later use;
2) first oxidation: carrying out first anodic oxidation treatment on the aluminum alloy workpiece subjected to the preorder treatment in the step 1) for later use;
3) hole sealing treatment: washing and dyeing the aluminum alloy workpiece obtained in the step 2), and then carrying out nickel hole sealing, wherein the nickel hole sealing agent is heated to 90 ℃ during hole sealing, the anodic aluminum oxide alloy is put into the nickel hole sealing agent for heating for 30min, and the hole sealing is carried out for later use;
4) and (3) hole sealing post-treatment: placing the aluminum alloy workpiece subjected to hole sealing treatment in the step 3) into a mixed solution consisting of deionized water, nitric acid and a flocculating agent for soaking for 10min, and then washing for 2 times by using clear water for later use;
5) and (3) second oxidation: carrying out secondary anodic oxidation nickel removal on the aluminum alloy workpiece treated in the step 4) for later use;
6) post-treatment: and (5) taking out the aluminum alloy workpiece subjected to the second anodic oxidation nickel removal in the step 5), washing with water, and drying to obtain the product.
The temperature for the first oxidation treatment in the step 2) is 24 ℃, the time is 40min, the voltage is 20V, and the first anodic oxidation solution is 200g/L sulfuric acid solution;
the temperature for the second anodizing in the step 5) is 24 ℃, the time is 23min, the voltage is 10V, and the second anodizing solution is 190g/L sulfuric acid solution.
The oil removing agent in the step 1) is a mixture consisting of 20 parts by weight of ammonium phosphate, 8 parts by weight of OP-10, 13 parts by weight of sodium carbonate and 500 parts by weight of deionized water.
The mixed solution in the step 4) is prepared from deionized water, nitric acid and a flocculating agent according to the weight part ratio of 45: 6: 3 is prepared from the following raw materials.
The flocculant comprises the following raw materials in parts by weight:
NaClO3 0.3 part
Additive 2 parts
Ferrous sulfate 1.0 part
0.3 part of permanganate
11 portions of acid solvent
13 parts of sodium gluconate.
Each part of the additive is a mixture of ethylene diamine tetraacetic acid, isostearic acid and benzotriazole-5-carboxylic acid according to the weight ratio of 0.6:0.8: 1.0.
Each part of the acidic solvent is a mixture of hydrofluoric acid, sulfuric acid, phosphoric acid and acetic acid according to the weight ratio of 0.8:0.6:1.02: 0.3; the concentration of the acidic solvent is 40 g/L.
Example 4
An anode oxidized aluminum alloy nickel removal method is prepared by the following steps:
1) preamble processing: placing an aluminum alloy workpiece in soap water for cleaning, then placing the cleaned aluminum alloy workpiece in an ultrasonic cleaning machine for cleaning, after cleaning, physically polishing the workpiece, then placing the workpiece in a degreasing agent at 73 ℃ for soaking for 18min, after soaking, cleaning the workpiece with warm water at 78 ℃, and then washing the workpiece with clean water until no degreasing liquid exists on the surface of the workpiece for later use;
2) first oxidation: carrying out first anodic oxidation treatment on the aluminum alloy workpiece subjected to the preorder treatment in the step 1) for later use;
3) hole sealing treatment: washing and dyeing the aluminum alloy workpiece obtained in the step 2), then carrying out nickel hole sealing, heating the nickel hole sealing agent to 95 ℃ during hole sealing, putting the anodic aluminum oxide alloy into the nickel hole sealing agent, heating for 35min, and sealing holes for later use;
4) and (3) hole sealing post-treatment: placing the aluminum alloy workpiece subjected to hole sealing treatment in the step 3) into a mixed solution consisting of deionized water, nitric acid and a flocculating agent for dipping for 13min, and then washing for 3 times by using clear water for later use;
5) and (3) second oxidation: carrying out secondary anodic oxidation nickel removal on the aluminum alloy workpiece treated in the step 4) for later use;
6) post-treatment: and (5) taking out the aluminum alloy workpiece subjected to the second anodic oxidation nickel removal in the step 5), washing with water, and drying to obtain the product.
The temperature for the first oxidation treatment in the step 2) is 25 ℃, the time is 50min, the voltage is 23V, and the first anodic oxidation solution is a sulfuric acid solution of 205 g/L;
the temperature for the second anodizing in the step 5) is 25 ℃, the time is 26min, the voltage is 11V, and the second anodizing solution is a sulfuric acid solution of 195 g/L.
The oil removing agent in the step 1) is a mixture consisting of 23 parts by weight of ammonium phosphate, 10 parts by weight of OP-10, 14 parts by weight of sodium carbonate and 550 parts by weight of deionized water.
The mixed solution in the step 4) is prepared from deionized water, nitric acid and a flocculating agent according to the weight part ratio of 52: 7: 4, and (b).
The flocculant comprises the following raw materials in parts by weight:
NaClO3 0.4 portion of
2.5 parts of additive
Ferrous sulfate 1.3 parts
0.4 part of permanganate
12 portions of acidic solvent
14 parts of sodium gluconate.
Each part of the additive is a mixture of ethylene diamine tetraacetic acid, isostearic acid and benzotriazole-5-carboxylic acid according to the weight ratio of 0.7:0.9: 1.1.
Each part of the acidic solvent is a mixture of hydrofluoric acid, sulfuric acid, phosphoric acid and acetic acid according to the weight ratio of 0.9:0.7:1.1: 0.4; the concentration of the acidic solvent is 50 g/L.
Example 5
An anode oxidized aluminum alloy nickel removal method is prepared by the following steps:
1) preamble processing: placing an aluminum alloy workpiece in soap water for cleaning, then placing the cleaned aluminum alloy workpiece in an ultrasonic cleaning machine for cleaning, after cleaning, physically polishing the workpiece, then placing the workpiece in a degreasing agent at 75 ℃ for soaking for 20min, after soaking, cleaning the workpiece with warm water at 80 ℃, and then washing the workpiece with clean water until no degreasing liquid exists on the surface of the workpiece for later use;
2) first oxidation: carrying out first anodic oxidation treatment on the aluminum alloy workpiece subjected to the preorder treatment in the step 1) for later use;
3) hole sealing treatment: washing and dyeing the aluminum alloy workpiece obtained in the step 2), and then carrying out nickel hole sealing, wherein the nickel hole sealing agent is heated to 100 ℃ during hole sealing, the anodic aluminum oxide alloy is put into the nickel hole sealing agent to be heated for 40min, and the hole sealing is carried out for later use;
4) and (3) hole sealing post-treatment: placing the aluminum alloy workpiece subjected to hole sealing treatment in the step 3) into a mixed solution consisting of deionized water, nitric acid and a flocculating agent for soaking for 15min, and then washing for 3 times by using clear water for later use;
5) and (3) second oxidation: carrying out secondary anodic oxidation nickel removal on the aluminum alloy workpiece treated in the step 4) for later use;
6) post-treatment: and (5) taking out the aluminum alloy workpiece subjected to the second anodic oxidation nickel removal in the step 5), washing with water, and drying to obtain the product.
The temperature for the first oxidation treatment in the step 2) is 26 ℃, the time is 60min, the voltage is 25V, and the first anodic oxidation solution is a sulfuric acid solution of 210 g/L;
the temperature for the second anodizing in the step 5) is 26 ℃, the time is 30min, the voltage is 12V, and the second anodizing solution is 200g/L sulfuric acid solution.
The oil removing agent in the step 1) is a mixture consisting of 25 parts by weight of ammonium phosphate, 12 parts by weight of OP-10, 15 parts by weight of sodium carbonate and 600 parts by weight of deionized water.
The mixed solution in the step 4) is prepared from deionized water, nitric acid and a flocculating agent according to the weight part ratio of 60: 8: 5 is prepared from (A) and (B).
The flocculant comprises the following raw materials in parts by weight:
NaClO3 0.5 portion
Additive 3 parts
Ferrous sulfate 1.5 parts
0.5 part of permanganate
14 parts of acidic solvent
15 parts of sodium gluconate.
Each part of the additive is a mixture of ethylene diamine tetraacetic acid, isostearic acid and benzotriazole-5-carboxylic acid according to the weight ratio of 0.8:1.0: 1.2.
Each part of the acidic solvent is a mixture of hydrofluoric acid, sulfuric acid, phosphoric acid and acetic acid according to the weight ratio of 1.0:0.8:1.2: 0.5; the concentration of the acidic solvent is 60 g/L.
Comparative example 1
This comparative example differs from example 1 above in that: the second oxidation treatment was not performed in this comparative example, and the rest of the comparative example is the same as example 1, and is not described again here.
Comparative example 2
This comparative example differs from example 3 above in that: in the comparative example, aluminum ferric sulfate is used to replace the flocculant, and the rest of the comparative example is the same as example 3, and is not described again.
The aluminum alloy workpieces treated in examples 1, 3 and 5 and comparative examples 1 and 2 were subjected to a sealing test and a nickel-containing test, and the test results are shown in the following table 1:
hole sealing test: coating the surfaces of the aluminum alloy workpieces prepared in the examples 1, 3 and 5 and the comparative examples 1 and 2 with a black hole sealing test pen; after resting for 10s, the writing was attempted to be erased with a cotton swab. And observing whether the smearing position is erased completely or not so as to qualitatively test the hole sealing performance. If the hole sealing material can be erased completely, the surface of the aluminum alloy material has no pores, and the handwriting cannot penetrate into the pores, so that the hole sealing effect is good. If the aluminum alloy material cannot be completely erased, pores exist on the surface of the aluminum alloy material, and the hole sealing effect is poor
Nickel containing test: dipping the dimethylglyoxime test liquid medicine by using a cotton swab, wiping the surface of the aluminum alloy sheet, and observing whether the cotton swab turns red or not. The dimethylglyoxime test liquid medicine turns red when meeting nickel ions, if the cotton swab turns red, the nickel ions exist on the surface of the aluminum alloy sheet, and the nickel removal effect is poor; if the color of the aluminum alloy sheet is not changed to red, the surface of the aluminum alloy sheet is free from nickel ions, and the nickel removing effect is good.
TABLE 1
| Item | Hole sealing test results | Nickel containing test results |
| Example 1 | Can be erased and the hole sealing is complete | Does not turn red and does not precipitate nickel |
| Example 3 | Can be erased and the hole sealing is complete | Does not turn red and does not precipitate nickel |
| Example 5 | Can be erased and the hole sealing is complete | Does not turn red and does not precipitate nickel |
| Comparative example 1 | No erasure and poor hole sealing effect | Reddening and nickel precipitation |
| Comparative example 2 | Can be erased and the hole sealing is complete | Reddening and nickel precipitation |
As can be seen from the comparison among the examples 1, 3 and 5, the treatment process of the invention has the characteristics of good nickel removal effect, short nickel removal time and good hole sealing effect.
As can be seen from the comparison between examples 1, 3 and 5 and comparative examples 1 and 2, the effect of removing nickel and sealing holes of the aluminum alloy workpiece is obviously affected by the second oxidation treatment, and the flocculant provided by the invention can further improve the nickel removal effect, so that the flocculant has a wide market prospect and a wide application value.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (9)
1. A nickel removing method for anodic aluminum oxide alloy is characterized by comprising the following steps: is prepared by the following steps:
preamble processing: placing an aluminum alloy workpiece in soap water for cleaning, then placing the cleaned aluminum alloy workpiece in an ultrasonic cleaning machine for cleaning, after cleaning, physically polishing the workpiece, then placing the workpiece in a degreasing agent at 65-75 ℃ for soaking for 10-20min, after soaking, cleaning the workpiece with warm water at 70-80 ℃, and then washing the workpiece with clear water until no degreasing liquid exists on the surface of the workpiece for later use;
first oxidation: carrying out first anodic oxidation treatment on the aluminum alloy workpiece subjected to the preorder treatment in the step 1) for later use;
hole sealing treatment: washing and dyeing the aluminum alloy workpiece obtained in the step 2), and then carrying out nickel hole sealing, wherein the nickel hole sealing agent is heated to 80-100 ℃ during hole sealing, the anodic aluminum oxide alloy is put into the nickel hole sealing agent for heating for 20-40min, and the hole sealing is reserved;
and (3) hole sealing post-treatment: placing the aluminum alloy workpiece subjected to hole sealing treatment in the step 3) into a mixed solution consisting of deionized water, nitric acid and a flocculating agent for soaking for 5-15min, and then washing for 1-3 times by using clear water for later use;
and (3) second oxidation: carrying out secondary anodic oxidation nickel removal on the aluminum alloy workpiece treated in the step 4) for later use;
post-treatment: and (5) taking out the aluminum alloy workpiece subjected to the second anodic oxidation nickel removal in the step 5), washing with water, and drying to obtain the product.
2. The method for removing nickel from an anodized aluminum alloy as defined in claim 1, wherein: the temperature for the first oxidation treatment in the step 2) is 22-26 ℃, the time is 20-60min, the voltage is 15-25V, and the first anodic oxidation solution is a sulfuric acid solution with the concentration of 190-210 g/L.
3. The method for removing nickel from an anodized aluminum alloy as defined in claim 1, wherein: the temperature for the second anodic oxidation in the step 5) is 22-26 ℃, the time is 15-30min, the voltage is 8-12V, and the second anodic oxidation solution is a sulfuric acid solution with the concentration of 180-200 g/L.
4. The method for removing nickel from an anodized aluminum alloy as defined in claim 1, wherein: the oil removing agent in the step 1) is a mixture consisting of 15-25 parts by weight of ammonium phosphate, 4-12 parts by weight of OP-10, 10-15 parts by weight of sodium carbonate and 400 parts by weight of deionized water.
5. The method for removing nickel from an anodized aluminum alloy as defined in claim 1, wherein: the mixed solution in the step 4) is prepared from deionized water, nitric acid and a flocculating agent according to the weight part ratio of 30-60: 4-8: 1-5.
6. The method for removing nickel from an anodized aluminum alloy as defined in claim 1, wherein: the flocculant comprises the following raw materials in parts by weight:
NaClO30.1 to 0.5 portion
1-3 parts of additive
0.5 to 1.5 portions of ferrous sulfate
0.1 to 0.5 portion of permanganate
8-14 parts of acidic solvent
10-15 parts of sodium gluconate.
7. The method for removing nickel from an anodized aluminum alloy as defined in claim 6, wherein: each part of the additive is at least one of ethylene diamine tetraacetic acid, glycerin, isostearic acid, isopropanol, benzotriazole and benzotriazole-5-carboxylic acid.
8. The method for removing nickel from an anodized aluminum alloy as defined in claim 1, wherein: each part of the acidic solvent is at least one of hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid and acetic acid.
9. The method for removing nickel from an anodized aluminum alloy as defined in claim 8, wherein: the concentration of each part of the acid solvent is 20-60 g/L.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102330137A (en) * | 2011-09-03 | 2012-01-25 | 广亚铝业有限公司 | Inorganic colorful electrolysis coloring technology for aluminium profile anodic oxide film |
| CN103880133A (en) * | 2013-09-25 | 2014-06-25 | 上海丰远环保科技有限公司 | Strongly acidic high-phosphorus nickel-containing wastewater composite phosphorus and nickel removal coagulant and phosphorus and nickel removal method thereof |
| CN105239129A (en) * | 2015-10-21 | 2016-01-13 | 广东大雅智能厨电股份有限公司 | Surface treatment method of aluminum alloy product |
| CN106702456A (en) * | 2016-12-12 | 2017-05-24 | 惠州市至德精密部件有限公司 | Aluminum and aluminum alloy anodic oxidation nickel removing and hole sealing process |
| CN107587179A (en) * | 2017-09-21 | 2018-01-16 | 东莞市铭通金属科技有限公司 | A kind of anodised aluminium removes nickel method |
| CN108950638A (en) * | 2018-07-27 | 2018-12-07 | 歌尔股份有限公司 | Aluminum alloy materials and preparation method thereof |
| CN111850652A (en) * | 2020-06-03 | 2020-10-30 | 海盐县赛鑫金属制品有限公司 | Aluminum and aluminum alloy anodic oxidation nickel removal hole sealing process and device thereof |
-
2020
- 2020-12-18 CN CN202011499693.5A patent/CN112522760A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102330137A (en) * | 2011-09-03 | 2012-01-25 | 广亚铝业有限公司 | Inorganic colorful electrolysis coloring technology for aluminium profile anodic oxide film |
| CN103880133A (en) * | 2013-09-25 | 2014-06-25 | 上海丰远环保科技有限公司 | Strongly acidic high-phosphorus nickel-containing wastewater composite phosphorus and nickel removal coagulant and phosphorus and nickel removal method thereof |
| CN105239129A (en) * | 2015-10-21 | 2016-01-13 | 广东大雅智能厨电股份有限公司 | Surface treatment method of aluminum alloy product |
| CN106702456A (en) * | 2016-12-12 | 2017-05-24 | 惠州市至德精密部件有限公司 | Aluminum and aluminum alloy anodic oxidation nickel removing and hole sealing process |
| CN107587179A (en) * | 2017-09-21 | 2018-01-16 | 东莞市铭通金属科技有限公司 | A kind of anodised aluminium removes nickel method |
| CN108950638A (en) * | 2018-07-27 | 2018-12-07 | 歌尔股份有限公司 | Aluminum alloy materials and preparation method thereof |
| CN111850652A (en) * | 2020-06-03 | 2020-10-30 | 海盐县赛鑫金属制品有限公司 | Aluminum and aluminum alloy anodic oxidation nickel removal hole sealing process and device thereof |
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Application publication date: 20210319 |