CN108611672B - Aluminum alloy hard anodic oxidation electrolyte, preparation method and application - Google Patents
Aluminum alloy hard anodic oxidation electrolyte, preparation method and application Download PDFInfo
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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
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Abstract
The invention discloses an aluminum alloy hard anodic oxidation electrolyte. The formula of the aluminum alloy hard anodic oxidation electrolyte is as follows: 10-20 parts of sulfuric acid, 2-5 parts of organic acid, 0.1-0.3 part of polyhydric alcohol, 0.05-0.5 part of boron nitride and 90-110 parts of water. The invention also discloses a preparation method of the aluminum alloy hard anodic oxidation electrolyte and application of the aluminum alloy hard anodic oxidation electrolyte in corrosion-resistant aluminum alloy sections. The aluminum alloy hard anodic oxidation electrolyte prepared by the invention is applied to the processing of corrosion-resistant aluminum alloy sections, and a compact oxide film is formed on an aluminum alloy matrix through anodic oxidation, so that the obtained corrosion-resistant aluminum alloy sections have good microhardness, wear resistance and corrosion resistance, and can be applied to various fields of electronics, electric power, aviation, chemical industry, building materials, traffic and the like.
Description
Technical Field
The invention relates to an aluminum alloy anodic oxidation electrolyte, and belongs to the field of surface treatment of aluminum alloys.
Background
Aluminum is a silver-white metal with a density of 2.70 and a melting point of 657 ℃. Aluminum and its alloy materials are widely used in many industrial sectors such as electronics, electric power, aviation, chemical engineering, building materials, traffic and daily life due to their high strength/weight ratio, easy molding and processing, and excellent physical and chemical properties.
Because of the defects of soft surface quality, poor wear resistance, high friction coefficient and the like of the aluminum alloy material, tribological surface modification treatment of aluminum and aluminum alloy is needed when the aluminum alloy material is used, namely, hard anodic oxidation is firstly carried out on the surface of the aluminum alloy, and then various lubricating substances are deposited on the surface and the interior of an aluminum alloy film to form a lubricating coating, so that the friction coefficient of the surface of the aluminum alloy is reduced.
Surface treatment methods of aluminum alloys can be basically classified into oxidation, plating, coating, and the like. Anodic oxidation and chemical oxidation are the most common surface treatment methods at present. After anodic oxidation of aluminum or aluminum alloy, a large number of nano-scale holes are distributed on the surface, higher free energy exists, but the surface free energy of the system cannot be reduced by the method of reducing the surface area of the solid surface like liquid, and only the free energy of the system can be reduced by adsorbing an external medium. However, the microhardness of an anodic oxide film prepared from aluminum alloy in single electrolyte such as sulfuric acid, phosphoric acid and oxalic acid is generally low, the wear resistance and corrosion resistance are poor, the comprehensive mechanical property is not high, and the requirement of industrial production cannot be met. Therefore, the aluminum alloy hard anodic oxidation electrolyte is developed and applied to the processing of corrosion-resistant aluminum alloy, and the preparation method of the corrosion-resistant aluminum alloy improves the microhardness, the wear resistance and the corrosion resistance of the aluminum alloy.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the aluminum alloy hard anodic oxidation electrolyte and the preparation method thereof.
The specific technical scheme is as follows:
an aluminum alloy hard anodizing electrolyte comprises the following components: 10-20 parts of sulfuric acid, 2-5 parts of organic acid, 0.1-0.3 part of polyhydric alcohol and 90-110 parts of water.
Specifically, the polyhydric alcohol is one of glycerol, isopropanol and pentaerythritol.
Further preferably, the polyol is pentaerythritol.
Specifically, the organic acid is modified salicylic acid and/or gallic acid.
The other technical scheme of the invention is as follows:
an aluminum alloy hard anodizing electrolyte consists of the following components: 10-20 parts of sulfuric acid, 2-5 parts of organic acid, 0.1-0.3 part of polyhydric alcohol, 0.05-0.5 part of boron nitride and 90-110 parts of water.
Preferably, the polyol is one of glycerol, isopropanol and pentaerythritol.
Preferably, the polyol is pentaerythritol.
Preferably, the organic acid is modified salicylic acid and/or gallic acid.
Preferably, the modified salicylic acid is prepared by the following method, wherein the parts are all parts by weight:
(1) mixing 1-3 parts of chitosan oligosaccharide and 80-120 parts of water to obtain a chitosan oligosaccharide aqueous solution, adjusting the pH value of the chitosan oligosaccharide aqueous solution to 7.5-8.5 by using a sodium hydroxide aqueous solution with the mass fraction of 10%, then adding 1-2 parts of salicylic acid, and stirring at the temperature of 60-70 ℃ at 100-300 r/m for 80-120 minutes to obtain a reaction product;
(2) setting the rotation speed of a rotary evaporator to be 100 rpm, and carrying out rotary evaporation on a reaction product at the vacuum degree of 0.05-0.2MPa and the temperature of 60-70 ℃ until no moisture exists to obtain a solid;
(3) mixing the solid and ethanol according to a mass ratio of 1: (80-100), stirring at 15-25 ℃ for 10-20 minutes at 100-300 r/min, centrifuging at 3000-5000 r/min for 8-12 minutes, and drying the obtained precipitate at 60-70 ℃ to constant weight to obtain the modified salicylic acid.
The invention also provides application of the aluminum alloy hard anodic oxidation electrolyte in corrosion-resistant aluminum alloy. The specific technical scheme is as follows:
the preparation method of the corrosion-resistant aluminum alloy profile comprises the following steps:
(1) removing oil;
(2) performing alkaline etching;
(3) neutralizing;
(4) anodizing;
(5) and (6) sealing the holes.
Preferably, the preparation method of the corrosion-resistant aluminum alloy profile comprises the following steps:
(1) oil removal: soaking the aluminum alloy matrix in 100-140g/L sulfuric acid solution at 15-20 deg.C for 3-5 min, taking out, and washing with water;
(2) alkaline etching: dipping the aluminum alloy matrix treated in the step (1) in a sodium hydroxide solution with the temperature of 35-45 ℃ and the concentration of 30-50g/L for 3-5 minutes, taking out, and washing with water;
(3) neutralizing: dipping the aluminum alloy matrix treated in the step (2) in a sulfuric acid solution with the temperature of 15-20 ℃ and the concentration of 100-140g/L for 2-4 minutes, taking out, and washing with water;
(4) anodic oxidation: anodizing the aluminum alloy substrate treated in the step (3) in electrolyte, wherein the aluminum alloy is used as an anode, the aluminum plate is used as a cathode, the oxidation voltage is 15-20V, and the current density is 1-2A/dm2The temperature of the electrolyte is 15-20 ℃, and the oxidation time is 20-40 minutes;
(5) hole sealing: and (3) dipping the aluminum alloy matrix treated in the step (4) in hole sealing liquid at 85-95 ℃ for 15-30 minutes, taking out, draining the surface moisture, and drying at 80-90 ℃ for 2-4 hours to obtain the corrosion-resistant aluminum alloy section.
Preferably, the electrolyte is prepared by the following method, wherein the parts are all parts by weight: adding 10-20 parts of sulfuric acid, 2-5 parts of organic acid and 0.1-0.3 part of polyalcohol into 100 parts of water, and stirring for 5-10 minutes at 100-300 r/min to obtain the electrolyte.
Preferably, the electrolyte is prepared by the following method, wherein the parts are all parts by weight: adding 10-20 parts of sulfuric acid, 2-5 parts of organic acid and 0.1-0.3 part of polyalcohol into 90-110 parts of water, stirring for 5-10 minutes at 100-300 r/min, adding 0.05-0.5 part of boron nitride, and stirring for 20-30 minutes at 100-300 r/min to obtain the electrolyte.
Preferably, the hole sealing liquid is prepared by the following method, and the parts are all parts by weight: mixing 1-2 parts of cerium nitrate and 100 parts of water, and stirring for 10-20 minutes at the speed of 100-300 revolutions per minute to obtain the hole sealing liquid.
Preferably, the organic acid is modified salicylic acid and/or gallic acid.
More preferably, the organic acid is a mixture of modified salicylic acid and gallic acid, and the mass ratio of the modified salicylic acid to the gallic acid is 1: (3-5).
Preferably, the polyol is one of glycerol, isopropanol and pentaerythritol.
Preferably, the polyol is pentaerythritol.
Preferably, the modified salicylic acid is prepared by the following method, wherein the parts are all parts by weight:
(1) mixing 1-3 parts of chitosan oligosaccharide and 80-120 parts of water to obtain a chitosan oligosaccharide aqueous solution, adjusting the pH value of the chitosan oligosaccharide aqueous solution to 7.5-8.5 by using a sodium hydroxide aqueous solution with the mass fraction of 10%, then adding 1-2 parts of salicylic acid, and stirring at the temperature of 60-70 ℃ at 100-300 r/m for 80-120 minutes to obtain a reaction product;
(2) setting the rotation speed of a rotary evaporator to be 100 rpm, and enabling a reaction product to have a vacuum degree of
Rotary evaporating at 60-70 deg.C under 0.05-0.2MPa to anhydrous to obtain solid;
(3) mixing the solid and ethanol according to a mass ratio of 1: (80-100), stirring at 15-25 ℃ for 10-20 minutes at 100-300 r/min, centrifuging at 3000-5000 r/min for 8-12 minutes, and drying the obtained precipitate at 60-70 ℃ to constant weight to obtain the modified salicylic acid.
The aluminum alloy hard anodic oxidation electrolyte forms a compact oxide film on an aluminum alloy matrix through anodic oxidation in the preparation of the corrosion-resistant aluminum alloy section, and the obtained corrosion-resistant aluminum alloy section has good microhardness, wear resistance and corrosion resistance, and can be applied to various fields of electronics, electric power, aviation, chemical industry, building materials, traffic and the like.
Detailed Description
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Microhardness test of oxide film: the Vickers hardness of the oxide film is tested by a Fischer HM2000 microhardness tester (produced by Germany Feichell test instruments Co., Ltd.), the load is 500mN, the loading time is 20s, the number of parallel samples is 3, each parallel sample selects 10 different test points which are uniformly distributed for measurement, and the average value is taken as the microhardness of the sample.
The abrasion resistance of the oxide film was investigated by a frictional abrasion tester (model THT07-135, manufactured by CSEM corporation, Switzerland) at a temperature of 25 ℃ with a frictional ball of ZrO 6mm in diameter2The ceramic wear-resistant ball has the friction speed of 4cm/s, the load of 5N and the friction length of 8mm, and is used for avoiding that the single friction revolution is too much to cause the anode oxide film to wear through and the total friction revolution is too little to cause the wearing and tearing volume too little to be measured, all samples are rubbed for 2 times for 350 turns, recording the quality before and after the friction test, and calculating the quality loss rate according to the following formula: [ (m)1-m2)/m1]X 100% where m1Mass m of the aluminum alloy section before the Friction test2The quality of the aluminum alloy section after the friction test.
And (3) corrosion resistance testing: the test is carried out according to methods in section 2006.27(2) and section 2.4 of corrosion and protection, which are 'corrosion resistance research on aluminum alloy anodic oxide film nickel acetate sealing method' of Tianlianpene, Yu, and the like, and specifically comprises the following steps: a three-electrode system is adopted, a saturated calomel electrode is used as a reference electrode, a platinum electrode is used as an auxiliary electrode, and the corrosion resistance of the oxide film is evaluated by testing the alternating current impedance spectrum (a test signal is a sine wave with the amplitude of 10mV, the measured frequency is 100 kHz-0.01 Hz, and the test software is Powersine) of the oxide film in a 1mol/LNaCl acidic (pH is 3.0) solution. The pH was adjusted by adding hydrochloric acid to the NaCl solution, the test temperature being 20 ℃. Specifically, the corrosion resistance of the oxide film was evaluated by the impedance value at a frequency of 100 Hz.
Sulfuric acid, concentrated sulfuric acid with a purity of 98 wt% produced by Dibo chemical company, Tianjin, is used.
Sodium hydroxide, manufactured by Yonghua chemical technology (Jiangsu) Co.Ltd.
Boron nitride, which is NO-N-003-1DE boron nitride manufactured by Bohai diamond metallic material Co.Ltd in Qinghe county, and has an average particle size of 100 nm.
Cerium nitrate, CAS number: 13093-17-9, available from Shanghai commander Son industries, Inc.
Salicylic acid, available from Shanghai Merlin Biotechnology Ltd, product number: and S817529.
Gallic acid, CAS No.: 149-91-7, Zhang Ji Jiu Biotech Co.
Pentaerythritol, available from Shanghai Michelin Biochemical technology, Inc., product number: p815603.
Glycerol, provided by Shanghai Michelin Biochemical technology, Inc., product number: G6201.
isopropyl alcohol, available from Shanghai Michelin Biochemical technology, Inc., product number: I811924.
chitosan oligosaccharide, produced by Shaanxi Senan Biochemical engineering Co., Ltd., molecular weight 2000, degree of deacetylation 90.5%.
The ethanol is anhydrous ethanol produced by Yonghua chemical technology (Jiangsu) limited.
The aluminum alloy substrate, 2024 aluminum alloy in the example, has a volume of 50mm × 50mm × 1mm, and the chemical composition of the 2024 aluminum alloy is shown in the following table 1:
table 1: chemical composition table for 2024 aluminium alloy
| Element(s) | Si | Fe | Cu | Mn | Mg | Zn | Ni | Cr | Al |
| Mass fraction of% | 0.5 | 0.5 | 4.5 | 0.53 | 1.4 | 0.3 | 0.1 | 0 | Balance of |
Example 1
The preparation method of the corrosion-resistant aluminum alloy profile comprises the following steps:
(1) oil removal: immersing the aluminum alloy matrix in a sulfuric acid solution with the concentration of 120g/L at the temperature of 18 ℃ for 4 minutes, taking out the aluminum alloy matrix, and washing the aluminum alloy matrix with water;
(2) alkaline etching: immersing the aluminum alloy matrix treated in the step (1) in a sodium hydroxide solution with the temperature of 40 ℃ and the concentration of 40g/L for 4 minutes, taking out, and washing with water;
(3) neutralizing: dipping the aluminum alloy matrix treated in the step (2) in a sulfuric acid solution with the temperature of 18 ℃ and the concentration of 120g/L for 3 minutes, taking out, and washing with water;
(4) anodic oxidation: anodizing the aluminum alloy substrate treated in the step (3) in electrolyte, wherein the aluminum alloy is used as an anode, the aluminum plate is used as a cathode, the oxidation voltage is 18V, and the current density is 1.5A/dm2The temperature of the electrolyte is 18 ℃, and the oxidation time is 30 minutes;
(5) hole sealing: and (3) soaking the aluminum alloy matrix treated in the step (4) in hole sealing liquid at 90 ℃ for 20 minutes, taking out the aluminum alloy matrix, draining surface moisture, and drying the aluminum alloy matrix at 85 ℃ for 3 hours to obtain the corrosion-resistant aluminum alloy section.
The electrolyte is prepared by the following method, wherein the parts are all by weight: 15 parts of sulfuric acid, 3 parts of organic acid and 0.2 part of polyhydric alcohol are added to 100 parts of water, and stirred at 200 rpm for 8 minutes to obtain an electrolyte.
The hole sealing liquid is prepared by the following method, wherein the parts are all by weight: 1.5 parts of cerium nitrate and 100 parts of water are mixed and stirred for 15 minutes at 200 revolutions per minute to obtain the hole sealing liquid.
The polyol is glycerol.
The organic acid is modified salicylic acid, and the modified salicylic acid is prepared by the following method, wherein the parts are in parts by weight:
(1) mixing 2 parts of chitosan oligosaccharide and 100 parts of water to obtain a chitosan oligosaccharide aqueous solution, adjusting the pH value of the chitosan oligosaccharide aqueous solution to 8.0 by using a sodium hydroxide aqueous solution with the mass fraction of 10%, then adding 1.5 parts of salicylic acid, and stirring at 65 ℃ at 200 rpm for 100 minutes to obtain a reaction product;
(2) setting the rotating speed of a rotary evaporator to be 100 rpm, and carrying out rotary evaporation on a reaction product at the vacuum degree of 0.1MPa and the temperature of 65 ℃ until no moisture exists to obtain a solid;
(3) mixing the solid and ethanol according to a mass ratio of 1: 90, stirring at 20 ℃ for 15 minutes at 200 rpm, centrifuging at 4000 rpm for 10 minutes, and drying the obtained precipitate at 65 ℃ to constant weight to obtain the modified salicylic acid.
Example 2
The preparation method of the corrosion-resistant aluminum alloy profile comprises the following steps:
(1) oil removal: immersing the aluminum alloy matrix in a sulfuric acid solution with the concentration of 120g/L at the temperature of 18 ℃ for 4 minutes, taking out the aluminum alloy matrix, and washing the aluminum alloy matrix with water;
(2) alkaline etching: immersing the aluminum alloy matrix treated in the step (1) in a sodium hydroxide solution with the temperature of 40 ℃ and the concentration of 40g/L for 4 minutes, taking out, and washing with water;
(3) neutralizing: dipping the aluminum alloy matrix treated in the step (2) in a sulfuric acid solution with the temperature of 18 ℃ and the concentration of 120g/L for 3 minutes, taking out, and washing with water;
(4) anodic oxidation: anodizing the aluminum alloy substrate treated in the step (3) in electrolyte, wherein the aluminum alloy is used as an anode, the aluminum plate is used as a cathode, the oxidation voltage is 18V, and the current density is 1.5A/dm2The temperature of the electrolyte is 18 ℃, and the oxidation time is 30 minutes;
(5) hole sealing: and (3) soaking the aluminum alloy matrix treated in the step (4) in hole sealing liquid at 90 ℃ for 20 minutes, taking out the aluminum alloy matrix, draining surface moisture, and drying the aluminum alloy matrix at 85 ℃ for 3 hours to obtain the corrosion-resistant aluminum alloy section.
The electrolyte is prepared by the following method, wherein the parts are all by weight: adding 15 parts of sulfuric acid, 3 parts of organic acid and 0.2 part of polyalcohol into 100 parts of water, stirring for 8 minutes at 200 revolutions per minute, adding 0.1 part of boron nitride, and stirring for 25 minutes at 200 revolutions per minute to obtain the electrolyte.
The hole sealing liquid is prepared by the following method, wherein the parts are all by weight: 1.5 parts of cerium nitrate and 100 parts of water are mixed and stirred for 15 minutes at 200 revolutions per minute to obtain the hole sealing liquid.
The polyol is glycerol.
The organic acid is modified salicylic acid, and the modified salicylic acid is prepared by the following method, wherein the parts are in parts by weight:
(1) mixing 2 parts of chitosan oligosaccharide and 100 parts of water to obtain a chitosan oligosaccharide aqueous solution, adjusting the pH value of the chitosan oligosaccharide aqueous solution to 8.0 by using a sodium hydroxide aqueous solution with the mass fraction of 10%, then adding 1.5 parts of salicylic acid, and stirring at 65 ℃ at 200 rpm for 100 minutes to obtain a reaction product;
(2) setting the rotating speed of a rotary evaporator to be 100 rpm, and carrying out rotary evaporation on a reaction product at the vacuum degree of 0.1MPa and the temperature of 65 ℃ until no moisture exists to obtain a solid;
(3) mixing the solid and ethanol according to a mass ratio of 1: 90, stirring at 20 ℃ for 15 minutes at 200 rpm, centrifuging at 4000 rpm for 10 minutes, and drying the obtained precipitate at 65 ℃ to constant weight to obtain the modified salicylic acid.
Example 3
Essentially the same as example 2 except that the polyol was isopropanol.
Example 4
Essentially the same as example 2, except that: the polyol is pentaerythritol.
Comparative example 1
The preparation method of the corrosion-resistant aluminum alloy profile comprises the following steps:
(1) oil removal: immersing the aluminum alloy matrix in a sulfuric acid solution with the concentration of 120g/L at the temperature of 18 ℃ for 4 minutes, taking out the aluminum alloy matrix, and washing the aluminum alloy matrix with water;
(2) alkaline etching: immersing the aluminum alloy matrix treated in the step (1) in a sodium hydroxide solution with the temperature of 40 ℃ and the concentration of 40g/L for 4 minutes, taking out, and washing with water;
(3) neutralizing: dipping the aluminum alloy matrix treated in the step (2) in a sulfuric acid solution with the temperature of 18 ℃ and the concentration of 120g/L for 3 minutes, taking out, and washing with water;
(4) anodic oxidation: anodizing the aluminum alloy substrate treated in the step (3) in electrolyte, wherein the aluminum alloy is used as an anode, the aluminum plate is used as a cathode, the oxidation voltage is 18V, and the current density is 1.5A/dm2The temperature of the electrolyte is 18 ℃, and the oxidation time is 30 minutes;
(5) hole sealing: and (3) soaking the aluminum alloy matrix treated in the step (4) in hole sealing liquid at 90 ℃ for 20 minutes, taking out the aluminum alloy matrix, draining surface moisture, and drying the aluminum alloy matrix at 85 ℃ for 3 hours to obtain the corrosion-resistant aluminum alloy section.
The electrolyte is prepared by the following method, wherein the parts are all by weight: adding 15 parts of sulfuric acid, 3 parts of organic acid and 0.2 part of polyalcohol into 100 parts of water, stirring for 8 minutes at 200 revolutions per minute, adding 0.1 part of boron nitride, and stirring for 25 minutes at 200 revolutions per minute to obtain the electrolyte.
The hole sealing liquid is prepared by the following method, wherein the parts are all by weight: 1.5 parts of cerium nitrate and 100 parts of water are mixed and stirred for 15 minutes at 200 revolutions per minute to obtain the hole sealing liquid.
The polyol is pentaerythritol.
The organic acid is salicylic acid.
Example 5
The preparation method of the corrosion-resistant aluminum alloy profile comprises the following steps:
(1) oil removal: immersing the aluminum alloy matrix in a sulfuric acid solution with the concentration of 120g/L at the temperature of 18 ℃ for 4 minutes, taking out the aluminum alloy matrix, and washing the aluminum alloy matrix with water;
(2) alkaline etching: immersing the aluminum alloy matrix treated in the step (1) in a sodium hydroxide solution with the temperature of 40 ℃ and the concentration of 40g/L for 4 minutes, taking out, and washing with water;
(3) neutralizing: dipping the aluminum alloy matrix treated in the step (2) in a sulfuric acid solution with the temperature of 18 ℃ and the concentration of 120g/L for 3 minutes, taking out, and washing with water;
(4) anodic oxidation: anodizing the aluminum alloy substrate treated in the step (3) in electrolyte, wherein the aluminum alloy is used as an anode, the aluminum plate is used as a cathode, the oxidation voltage is 18V, and the current density is 1.5A/dm2The temperature of the electrolyte is 18 ℃, and the oxidation time is 30 minutes;
(5) hole sealing: and (3) soaking the aluminum alloy matrix treated in the step (4) in hole sealing liquid at 90 ℃ for 20 minutes, taking out the aluminum alloy matrix, draining surface moisture, and drying the aluminum alloy matrix at 85 ℃ for 3 hours to obtain the corrosion-resistant aluminum alloy section.
The electrolyte is prepared by the following method, wherein the parts are all by weight: adding 15 parts of sulfuric acid, 3 parts of organic acid and 0.2 part of polyalcohol into 100 parts of water, stirring for 8 minutes at 200 revolutions per minute, adding 0.1 part of boron nitride, and stirring for 25 minutes at 200 revolutions per minute to obtain the electrolyte.
The hole sealing liquid is prepared by the following method, wherein the parts are all by weight: 1.5 parts of cerium nitrate and 100 parts of water are mixed and stirred for 15 minutes at 200 revolutions per minute to obtain the hole sealing liquid.
The polyol is pentaerythritol.
The organic acid is gallic acid.
The obtained corrosion-resistant aluminum alloy section has the microhardness of 517Hv, the mass loss rate of 4.13 percent and the impedance value of 1.74 multiplied by 106Ω/cm2。
Example 6
The preparation method of the corrosion-resistant aluminum alloy profile comprises the following steps:
(1) oil removal: immersing the aluminum alloy matrix in a sulfuric acid solution with the concentration of 120g/L at the temperature of 18 ℃ for 4 minutes, taking out the aluminum alloy matrix, and washing the aluminum alloy matrix with water;
(2) alkaline etching: immersing the aluminum alloy matrix treated in the step (1) in a sodium hydroxide solution with the temperature of 40 ℃ and the concentration of 40g/L for 4 minutes, taking out, and washing with water;
(3) neutralizing: dipping the aluminum alloy matrix treated in the step (2) in a sulfuric acid solution with the temperature of 18 ℃ and the concentration of 120g/L for 3 minutes, taking out, and washing with water;
(4) anodic oxidation: anodizing the aluminum alloy substrate treated in the step (3) in electrolyte, wherein the aluminum alloy is used as an anode, the aluminum plate is used as a cathode, the oxidation voltage is 18V, and the current density is 1.5A/dm2The temperature of the electrolyte is 18 ℃, and the oxidation time is 30 minutes;
(5) hole sealing: and (3) soaking the aluminum alloy matrix treated in the step (4) in hole sealing liquid at 90 ℃ for 20 minutes, taking out the aluminum alloy matrix, draining surface moisture, and drying the aluminum alloy matrix at 85 ℃ for 3 hours to obtain the corrosion-resistant aluminum alloy section.
The electrolyte is prepared by the following method, wherein the parts are all by weight: adding 15 parts of sulfuric acid, 3 parts of organic acid and 0.2 part of polyalcohol into 100 parts of water, stirring for 8 minutes at 200 revolutions per minute, adding 0.1 part of boron nitride, and stirring for 25 minutes at 200 revolutions per minute to obtain the electrolyte.
The hole sealing liquid is prepared by the following method, wherein the parts are all by weight: 1.5 parts of cerium nitrate and 100 parts of water are mixed and stirred for 15 minutes at 200 revolutions per minute to obtain the hole sealing liquid.
The organic acid is a mixture of modified salicylic acid and gallic acid, and the mass ratio of the modified salicylic acid to the gallic acid is 1: 4.
the polyol is pentaerythritol.
The modified salicylic acid is prepared by the following method, wherein the parts are all by weight:
(1) mixing 2 parts of chitosan oligosaccharide and 100 parts of water to obtain a chitosan oligosaccharide aqueous solution, adjusting the pH value of the chitosan oligosaccharide aqueous solution to 8.0 by using a sodium hydroxide aqueous solution with the mass fraction of 10%, then adding 1.5 parts of salicylic acid, and stirring at 65 ℃ at 200 rpm for 100 minutes to obtain a reaction product;
(2) setting the rotating speed of a rotary evaporator to be 100 rpm, and carrying out rotary evaporation on a reaction product at the vacuum degree of 0.1MPa and the temperature of 65 ℃ until no moisture exists to obtain a solid;
(3) mixing the solid and ethanol according to a mass ratio of 1: 90, stirring at 20 ℃ for 15 minutes at 200 rpm, centrifuging at 4000 rpm for 10 minutes, and drying the obtained precipitate at 65 ℃ to constant weight to obtain the modified salicylic acid.
The microhardness 601Hv, the mass loss rate of 3.46 percent and the impedance value of 2.41 multiplied by 10 of the corrosion-resistant aluminum alloy section are obtained6Ω/cm2。
Test example 1
Aluminum alloy (grade 7150, 50mm × 50mm × 1mm) is subjected to conventional chemical degreasing, cleaning and neutralization, then is put into electrolyte for hard anodic oxidation, and is cleaned and sealed to obtain the film. Wherein the technological parameters of the hard anodic oxidation are as follows: the temperature is 2 ℃, the anode current density is 1A/dm2And the time is 50min, and the cathode material is a lead plate to obtain the corrosion-resistant aluminum alloy. The electrolytes were prepared in examples 1 to 6 and comparative example 1, respectively.
And respectively carrying out salt spray tests on the obtained corrosion-resistant aluminum alloy according to the GB/T10125-1997 standard. The test temperature in the salt spray test chamber was 36 ℃, the corrosive medium used was a 5 wt% NaCl solution with a pH of 7, and the angle formed by the test surface of the sample with the vertical direction was 20 °. The surfaces of the test piece except the test surface were sealed and protected by a transparent adhesive tape. The test results are shown in Table 2.
Table 2: corrosion resistance effect table after treatment of aluminum alloy 7150 by electrolyte
| Examples | Time for fading and corrosion points on surface of sample |
| Example 1 | 551h |
| Example 2 | 566h |
| Example 3 | 584h |
| Example 4 | 632h |
| Example 5 | 654h |
| Example 6 | 750h |
| Comparative example 1 | 605h |
Test example 2
The microhardness of the corrosion-resistant aluminum alloy sections obtained in examples 1 to 4 and comparative example 1 was measured, and the specific test results are shown in table 3.
Table 3: micro-hardness test result table for corrosion-resistant aluminum alloy section
| Microhardness, Hv | |
| Example 1 | 395 |
| Example 2 | 459 |
| Example 3 | 467 |
| Example 4 | 528 |
| Comparative example 1 | 482 |
Test example 3
The wear resistance of the corrosion-resistant aluminum alloy sections obtained in examples 1 to 4 and comparative example 1 was tested, and the specific test results are shown in table 4.
Table 4: corrosion-resistant aluminum alloy section bar wear resistance test result table
| Mass loss rate% | |
| Example 1 | 5.24 |
| Example 2 | 4.67 |
| Example 3 | 4.55 |
| Example 4 | 4.03 |
| Comparative example 1 | 4.21 |
Test example 4
The corrosion resistance of the corrosion-resistant aluminum alloy sections obtained in examples 1 to 4 and comparative example 1 was tested, and the specific test results are shown in table 5.
Table 5: corrosion resistance test result table for corrosion-resistant aluminum alloy section
| Impedance value, omega/cm2 | |
| Example 1 | 9.24×105 |
| Example 2 | 1.06×106 |
| Example 3 | 1.18×106 |
| Example 4 | 1.87×106 |
| Comparative example 1 | 1.62×106 |
Example 2 the performance of the oxide film can be significantly improved by adding inorganic powder silicon nitride into the electrolyte.
Examples 2 to 4 were conducted using different polyhydric alcohols, respectively, and it was found that the performance of the oxide film obtained in example 4 using pentaerythritol was good. The polyatomic alcohol can reduce the dissolving speed of electrolyte to the film, improve the allowable temperature range, accelerate the growth speed of the film, increase the density and thickness of the film, and have different influences on anodic oxidation. Example 4 the performance of the oxide film obtained by using the modified salicylic acid is better than that of comparative example 1, and it is possible that the molecular structure of the modified salicylic acid is changed, and the organic functional group grafted on the molecule is more beneficial to improving the performance of the oxide film.
It should be noted that the present invention is not limited to the above embodiments, and any simple modification, equivalent change and modification made to the above embodiments by those skilled in the art based on the technical solution of the present invention fall within the protection scope of the present invention.
Claims (3)
1. The aluminum alloy hard anodic oxidation electrolyte is characterized by comprising the following components: 10-20 parts of sulfuric acid, 2-5 parts of organic acid, 0.1-0.3 part of polyol, 0.05-0.5 part of boron nitride and 90-110 parts of water; the organic acid is a mixture of modified salicylic acid and gallic acid, and the mass ratio of the modified salicylic acid to the gallic acid is 1: (3-5);
the modified salicylic acid is prepared by the following method, wherein the parts are all by weight:
(1) mixing 1-3 parts of chitosan oligosaccharide and 80-120 parts of water to obtain a chitosan oligosaccharide aqueous solution, adjusting the pH value of the chitosan oligosaccharide aqueous solution to 7.5-8.5 by using a sodium hydroxide aqueous solution with the mass fraction of 10%, then adding 1-2 parts of salicylic acid, and stirring at the temperature of 60-70 ℃ at 100-300 r/m for 80-120 minutes to obtain a reaction product;
(2) setting the rotation speed of a rotary evaporator to be 100 rpm, and carrying out rotary evaporation on a reaction product at the vacuum degree of 0.05-0.2MPa and the temperature of 60-70 ℃ until no moisture exists to obtain a solid;
(3) mixing the solid and ethanol according to a mass ratio of 1: (80-100), stirring for 10-20 minutes at 15-25 ℃ at 100-300 r/min, centrifuging for 8-12 minutes at 3000-5000 r/min, and drying the obtained precipitate at 60-70 ℃ to constant weight to obtain modified salicylic acid;
the polyol is pentaerythritol.
2. Use of the aluminum alloy hard anodizing electrolyte of claim 1 in a corrosion resistant aluminum alloy.
3. The use of an aluminum alloy hard anodizing electrolyte according to claim 2 in a corrosion resistant aluminum alloy comprising the steps of:
(1) oil removal: immersing the aluminum alloy matrix in a sulfuric acid solution with the concentration of 120g/L at the temperature of 18 ℃ for 4 minutes, taking out the aluminum alloy matrix, and washing the aluminum alloy matrix with water;
(2) alkaline etching: immersing the aluminum alloy matrix treated in the step (1) in a sodium hydroxide solution with the temperature of 40 ℃ and the concentration of 40g/L for 4 minutes, taking out, and washing with water;
(3) neutralizing: dipping the aluminum alloy matrix treated in the step (2) in a sulfuric acid solution with the temperature of 18 ℃ and the concentration of 120g/L for 3 minutes, taking out, and washing with water;
(4) anodic oxidation: anodizing the aluminum alloy substrate treated in the step (3) in electrolyte, wherein the aluminum alloy is used as an anode, the aluminum plate is used as a cathode, the oxidation voltage is 18V, and the current density is 1.5A/dm2The temperature of the electrolyte is 18 ℃, and the oxidation time is 30 minutes;
(5) hole sealing: dipping the aluminum alloy matrix treated in the step (4) in hole sealing liquid at 90 ℃ for 20 minutes, taking out and draining surface moisture, and drying at 85 ℃ for 3 hours to obtain a corrosion-resistant aluminum alloy section;
the electrolyte is prepared by the following method, wherein the parts are all by weight: adding 15 parts of sulfuric acid, 3 parts of organic acid and 0.2 part of polyalcohol into 100 parts of water, stirring for 8 minutes at 200 revolutions per minute, adding 0.1 part of boron nitride, and stirring for 25 minutes at 200 revolutions per minute to obtain electrolyte;
the hole sealing liquid is prepared by the following method, wherein the parts are all by weight: mixing 1.5 parts of cerium nitrate and 100 parts of water, and stirring for 15 minutes at 200 revolutions per minute to obtain hole sealing liquid;
the organic acid is a mixture of modified salicylic acid and gallic acid, and the mass ratio of the modified salicylic acid to the gallic acid is 1: 4;
the polyhydric alcohol is pentaerythritol;
the modified salicylic acid is prepared by the following method, wherein the parts are all by weight:
(1) mixing 2 parts of chitosan oligosaccharide and 100 parts of water to obtain a chitosan oligosaccharide aqueous solution, adjusting the pH value of the chitosan oligosaccharide aqueous solution to 8.0 by using a sodium hydroxide aqueous solution with the mass fraction of 10%, then adding 1.5 parts of salicylic acid, and stirring at 65 ℃ at 200 rpm for 100 minutes to obtain a reaction product;
(2) setting the rotating speed of a rotary evaporator to be 100 rpm, and carrying out rotary evaporation on a reaction product at the vacuum degree of 0.1MPa and the temperature of 65 ℃ until no moisture exists to obtain a solid;
(3) mixing the solid and ethanol according to a mass ratio of 1: 90, stirring at 20 ℃ for 15 minutes at 200 rpm, centrifuging at 4000 rpm for 10 minutes, and drying the obtained precipitate at 65 ℃ to constant weight to obtain the modified salicylic acid.
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