CN110042381B - Preparation method of aluminum alloy surface film - Google Patents
Preparation method of aluminum alloy surface film Download PDFInfo
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- CN110042381B CN110042381B CN201910136972.6A CN201910136972A CN110042381B CN 110042381 B CN110042381 B CN 110042381B CN 201910136972 A CN201910136972 A CN 201910136972A CN 110042381 B CN110042381 B CN 110042381B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/56—Treatment of aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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Abstract
The invention relates to a preparation method of an aluminum alloy surface film, and belongs to the technical field of surface films. According to the invention, the cerium element is added to prepare the aluminum alloy surface film, so that the corrosion of the external corrosive atmosphere on the surface of the base material and the penetration of corrosive liquid on the conversion film are effectively prevented or delayed, the aluminum alloy base is protected from being corroded, and the corrosion resistance of the aluminum alloy is improved; according to the invention, the silica ceramic membrane is prepared on the surface of the aluminum alloy, so that the corrosion resistance of the aluminum alloy is improved, the chemical property of the silica is stable, the etching resistance is strong, the sol-gel method for preparing the silica ceramic membrane is simple in equipment, the sintering temperature is low, a large part can be coated, the repeatability is good, the particle size of coating components is controllable, the dispersion of the components at the molecular level can be realized, the silica ceramic membrane can be effectively coated on the surface of the aluminum alloy, the aluminum alloy matrix can be effectively protected from corrosion, and the service life of the aluminum alloy is prolonged.
Description
Technical Field
The invention relates to a preparation method of an aluminum alloy surface film, and belongs to the technical field of surface films.
Background
According to the current research, the prevention of corrosion of metallic materials is mainly achieved by several mechanisms:
(1) cathodic protection;
(2) passivating the anode;
(3) electrolytic inhibition;
(4) and (4) corrosion inhibitor.
The cathodic protection is that an external current is applied to the surface of a corroded metal material, and the protected metal material becomes a cathode, so that the electron migration caused by metal corrosion is inhibited, and the corrosion is avoided or weakened. For a long time, zinc, aluminum and magnesium alloy are often used as anodes, and can form a favorable oxide layer on the surface of metal by means of electrochemical potential to provide cathodic protection for metal materials such as steel and the like. Anodic passivation is a method of reducing the occurrence of corrosion on the surface of a metal material by forming a passivation film on the surface of the metal material, and is also a method which is commonly used in which an oxide film forms a precipitate together with a passivation film, or an adjacent layer of a porous and denser oxide is generated on an anodic oxidation initiation or conversion coating, thereby effectively suppressing ion transport. The electrolytic inhibition is that a low-conductivity diffusion film substrate is added between an anode and a cathode to inhibit the migration of ions and the electrolyte reaches the surface of the metal, thereby achieving the purpose of corrosion prevention. Corrosion inhibitor treatment involves the reconstruction of a protective film at the metal-to-environment interface when the film layer on the surface is damaged, unlike the broader concept of "self-healing", which involves the incorporation of a release material into the coating to reform the polymeric organic coating even without direct corrosion protection. Based on the existing research, people have never studied the mechanism of preparing the protective film layer, and more methods can be applied to improve the corrosion resistance of the metal material.
The corrosion of metallic materials is a big problem, and the consequences caused by the corrosion are hard to imagine because the corrosion often happens in a moment and brings immeasurable economic or safety hazards. The application fields of aluminum and aluminum alloy in life are very wide, and the aluminum and aluminum alloy can generate an oxide film and can protect the aluminum and aluminum alloy, but in some specific environments, the oxide film can be damaged, so that the problem of poor corrosion resistance of the aluminum and aluminum alloy needs to be solved.
In practical applications of aluminum alloys, a significant problem is that the three-proofing (salt spray, damp heat, mold resistance) properties need to be improved. Especially in severe marine corrosive environment, the service life of the aluminum alloy product is greatly shortened due to the combined action of high humidity and corrosion factors such as sea salt particle erosion, pitting corrosion, hard force cracking and the like. Because the aluminum alloy surface coating has the problem of under-film corrosion caused by poor binding force, many aluminum alloy products serving in marine climate environments, such as ship-borne electronic equipment, radars, marine weaponry and the like, take a surface electrochemical conversion film as the first choice for corrosion prevention, and the oxide layer generated in an electrolytic way can protect a metal substrate, prevent the metal substrate from corrosion and weathering and increase the hardness and wear resistance of the surface.
In a plurality of aluminum surface conversion film processes, the corrosion resistance of micro-arc oxidation is only called as excellent (the neutral salt spray resistance test time can reach 600 h), but the micro-arc oxidation has limited application in various fields of electronics and equipment due to the reasons of overhigh film voltage, large processing difficulty, large size variation and the like. At present, the aluminum alloy conversion film which aims at surface corrosion prevention independently has good effect and still adopts the anodic oxidation process internationally. The aluminum anodic oxide film is firmly combined with a substrate, is hard and wear-resistant, and has outstanding heat resistance, but the neutral salt spray resistance test time rarely exceeds 336h (14 cycles), and the corrosion resistance is basically sufficient in common application environments, but becomes a difficult problem in marine environments. The international general advocates that the anticorrosion capability is improved by improving the quality of an oxidized film, and the process means are various and mainly comprise: the density of the oxide film is improved, and the porosity of the oxide film is reduced; increasing the thickness of the oxide film; the self potential of the oxide film is changed.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problem of poor corrosion resistance of the existing aluminum alloy surface film, the preparation method of the aluminum alloy surface film is provided.
In order to solve the technical problems, the invention adopts the technical scheme that:
(1) placing the aluminum alloy subjected to rare earth passivation treatment in aged silica sol to be soaked for 3-5 min, then pulling and soaking for 15-20 s, taking out the aluminum alloy to be naturally dried, then placing the aluminum alloy at 75-80 ℃ to be dried for 20-30 min, and repeatedly pulling for 5 times to obtain a pulling sample;
(2) and (3) placing the pulling sample in a box-type resistance furnace, sintering for 0.5-1 h at 450-500 ℃, preserving heat for 20-30 min after sintering, and taking out to obtain the aluminum alloy covering the surface film.
The mass ratio of the aluminum alloy subjected to rare earth passivation treatment in the step (1) to the aged silica sol is 1: 5.
The specific preparation steps of the aged silica sol in the step (1) are as follows:
(1) adding ethyl orthosilicate into absolute ethyl alcohol, and stirring at the normal temperature at the rotating speed of 100-150 r/min for 10-15 min to obtain an ethyl orthosilicate ethanol solution;
(2) adding deionized water into ethyl orthosilicate ethanol solution, and stirring at the rotating speed of 500-600 r/min for 20-30 min at normal temperature to obtain mixed solution;
(3) slowly adding hydrochloric acid dropwise into the mixed solution for 5-10 min, stirring at the normal temperature at the rotating speed of 500-600 r/min for 10-15 min, adding formamide, continuously stirring for 10-15 min, and aging for 4-6 h to obtain the aged silica sol.
The weight parts of the tetraethoxysilane, the ethanol, the deionized water, the hydrochloric acid and the formamide are 5-10 parts of tetraethoxysilane, 20-30 parts of ethanol, 10-20 parts of deionized water, 3-5 parts of hydrochloric acid with the mass fraction of 10% and 3-5 parts of formamide.
The specific preparation steps of the aluminum alloy subjected to rare earth passivation treatment in the step (1) are as follows:
placing the pretreated aluminum alloy into a rare earth film forming treatment liquid according to the mass ratio of 1: 5, passivating for 1-1.5 h in a water bath at 50-55 ℃, taking out, washing for 3-5 times with deionized water, and vacuum drying for 0.5-1 h at 50-60 ℃ to obtain the rare earth passivated aluminum alloy.
The rare earth film-forming treatment liquid comprises the following specific preparation steps:
(1) adding citric acid into deionized water, and stirring at the normal temperature at the rotating speed of 100-200 r/min for 5-10 min to obtain a citric acid solution;
(2) and adding cerium acetate, titanium sulfate and hydrogen peroxide into a citric acid solution, and stirring at the rotation speed of 150-250 r/min for 15-20 min at normal temperature to obtain the rare earth film forming treatment liquid.
The citric acid, the cerium acetate, the titanium sulfate, the hydrogen peroxide and the deionized water are 3-5 parts by weight of citric acid, 10-12 parts by weight of cerium acetate, 1.2-1.5 parts by weight of titanium sulfate, 50-60 parts by weight of hydrogen peroxide and 800-1000 parts by weight of deionized water.
The specific preparation steps of the pretreated aluminum alloy are as follows:
(1) placing the polished aluminum alloy in acetone for ultrasonic cleaning for 3-5 min, then washing for 3-5 times by using absolute ethyl alcohol and washing for 3-5 times by using deionized water to obtain the cleaned aluminum alloy;
(2) placing the cleaned aluminum alloy into a sodium hydroxide solution, heating the aluminum alloy in a water bath to 50-60 ℃, and carrying out etching treatment for 3-5 min to obtain an etched aluminum alloy;
(3) soaking the etched aluminum alloy in nitric acid at normal temperature for 1-2 min to carry out light-emitting treatment to obtain the light-emitting treated aluminum alloy;
(4) and ultrasonically cleaning the aluminum alloy subjected to the light extraction treatment for 3-5 min by using absolute ethyl alcohol, ultrasonically cleaning for 3-5 min by using deionized water, and drying for 0.5-1 h in vacuum at the temperature of 60-80 ℃ to obtain the pretreated aluminum alloy.
The weight parts of the polished aluminum alloy, the acetone, the sodium hydroxide solution and the nitric acid are 10-15 parts of the polished aluminum alloy, 40-50 parts of the acetone, 40-50 parts of the sodium hydroxide solution with the mass concentration of 1% and 40-50 parts of the nitric acid with the mass concentration of 30%.
The concrete preparation steps of the polished aluminum alloy are as follows:
taking an aluminum alloy with the specification of 100mm multiplied by 50mm, and polishing the aluminum alloy with water-grinding abrasive paper of 600-2000 meshes until the surface is smooth to obtain the polished aluminum alloy.
Compared with other methods, the method has the beneficial technical effects that:
(1) the invention prepares the surface film of the aluminum alloy by adding the rare earth element cerium, after the surface passivation treatment is carried out on the aluminum alloy by adopting the rare earth element passivation technology, the rare earth passivation film with corrosion resistance can be obtained on the aluminum alloy, the corrosion resistance of the aluminum alloy can be obviously improved, the passivation film of the rare earth metal salt can effectively replace a chromate passivation film, the technology has simple process, the main film forming salt is the inorganic salt of lanthanide series metal, the inorganic salt is safe and nontoxic, the waste liquid can be directly discharged, the production operation is safe, the technology is a novel metal surface treatment technology which is environment-friendly, the rare earth element cerium can inhibit the cathode reaction and the anode reaction in the corrosion process while forming the rare earth conversion film on the surface of the aluminum alloy, the anode dissolution and the depolarization reaction of oxygen on the cathode are hindered, the corrosion of the surface of the aluminum alloy material by the external corrosion environment and the penetration of a corrosive liquid to the conversion film can be effectively prevented or delayed, thereby effectively protecting the aluminum alloy matrix from corrosion and improving the corrosion resistance of the aluminum alloy;
(2) according to the invention, the titanium sulfate is added to prepare the surface film of the aluminum alloy, the passive film containing the titanium element has good stability and self-repairing performance, the aluminum alloy matrix can be effectively protected, the titanium element can form a continuous, stable, firm-bonding and protective oxide film layer on the surface of the aluminum alloy, so that the corrosion resistance is good, and the titanium has high reaction activity and strong affinity with oxygen, so that when the surface of the aluminum alloy is exposed in humid air, the titanium can immediately form a protective film, and simultaneously, the titanium has strong affinity with oxygen, once the oxide film is damaged, the oxide film can be immediately generated after the titanium is contacted with the oxygen, and self-repairing is carried out, so that the corrosion resistance of the aluminum alloy is improved;
(3) the invention improves the corrosion resistance of the aluminum alloy by preparing the silica ceramic membrane on the surface of the aluminum alloy, coats a layer of compact and uniform silica ceramic protective membrane on the surface of the aluminum alloy, can effectively reduce the contact area of the aluminum alloy and water, can effectively prevent the membrane from being damaged by expansion and shrinkage stress difference, salt recrystallization and moisture evaporation generated by temperature change, has excellent high temperature resistance and freezing resistance, obviously improves the weather resistance, has stable chemical properties and strong etching resistance of the silica, adopts simple sol-gel method equipment for preparing the silica ceramic membrane, has low sintering temperature, can coat large workpieces, has good repeatability, can control the grain size of coating components, and can realize the dispersion of the molecular level among the components, can be effectively coated on the surface of the aluminum alloy, and can effectively protect the aluminum alloy matrix from being corroded, thereby prolonging the service life of the aluminum alloy.
Detailed Description
Taking an aluminum alloy with the specification of 100mm multiplied by 50mm, polishing the aluminum alloy with 600-2000 meshes of water-polishing abrasive paper until the surface is smooth to obtain the polished aluminum alloy, respectively weighing 10-15 parts of the polished aluminum alloy, 40-50 parts of acetone, 40-50 parts of 1% sodium hydroxide solution by mass concentration and 40-50 parts of 30% nitric acid by mass concentration according to parts by weight, placing the polished aluminum alloy in acetone for ultrasonic cleaning for 3-5 min, then washing for 3-5 times with absolute ethyl alcohol, washing for 3-5 times with deionized water to obtain the cleaned aluminum alloy, placing the cleaned aluminum alloy in the sodium hydroxide solution, heating in a water bath to 50-60 ℃ for etching treatment for 3-5 min to obtain the etched aluminum alloy, placing the etched aluminum alloy in the nitric acid for soaking at normal temperature for 1-2 min for light-emitting treatment to obtain the light-treated aluminum alloy, firstly ultrasonically cleaning the light-emitting aluminum alloy for 3-5 min with the absolute ethyl alcohol, ultrasonically cleaning the aluminum alloy with deionized water for 3-5 min, placing the aluminum alloy at 60-80 ℃ for vacuum drying for 0.5-1 h to obtain a pretreated aluminum alloy, weighing 3-5 parts by weight of citric acid, 10-12 parts by weight of cerium acetate, 1.2-1.5 parts by weight of titanium sulfate, 50-60 parts by weight of hydrogen peroxide and 800-1000 parts by weight of deionized water respectively, adding the citric acid into the deionized water, stirring at 100-200 r/min for 5-10 min at normal temperature to obtain a citric acid solution, adding the cerium acetate, the titanium sulfate and the hydrogen peroxide into the citric acid solution, stirring at 150-250 r/min for 15-20 min at normal temperature to obtain a rare earth film forming treatment solution, placing the pretreated aluminum alloy into the rare earth film forming treatment solution according to the mass ratio of 1: 5, passivating the aluminum alloy in a water bath at 50-55 ℃ for 1-1.5 h, taking out, washing with deionized water for 3-5 times, and vacuum drying at 50-60 ℃ for 0.5-1 h to obtain a rare earth passivated aluminum alloy, respectively weighing 5-10 parts by weight of tetraethoxysilane, 20-30 parts by weight of ethanol, 10-20 parts by weight of deionized water, 3-5 parts by weight of 10% hydrochloric acid and 3-5 parts by weight of formamide, adding tetraethoxysilane into absolute ethanol, stirring at the normal temperature at the rotating speed of 100-150 r/min for 10-15 min to obtain tetraethoxysilane ethanol solution, adding deionized water into the tetraethoxysilane ethanol solution, stirring at the rotating speed of 500-600 r/min for 20-30 min at normal temperature to obtain mixed solution, slowly dropwise adding hydrochloric acid into the mixed solution for 5-10 min, stirring at the rotating speed of 500-600 r/min for 10-15 min at normal temperature, adding formamide, continuously stirring for 10-15 min, aging for 4-6 h to obtain aged silica sol, placing the aluminum alloy subjected to rare earth passivation treatment into the aged silica sol according to the mass ratio of 1: 5, soaking for 3-5 min, lifting and soaking for 15-20 s, and taking out, naturally airing, drying at 75-80 ℃ for 20-30 min, repeatedly lifting for 5 times to obtain a lifting sample, sintering the lifting sample in a box-type resistance furnace at 450-500 ℃ for 0.5-1 h, preserving heat for 20-30 min after sintering is finished, and taking out to obtain the aluminum alloy covering the surface film.
Taking an aluminum alloy with the specification of 100mm multiplied by 50mm, polishing the aluminum alloy with 600 meshes of water-mill abrasive paper until the surface is smooth to obtain the polished aluminum alloy, respectively weighing 10 parts of the polished aluminum alloy, 40 parts of acetone, 40 parts of sodium hydroxide solution with the mass concentration of 1% and 40 parts of nitric acid with the mass concentration of 30% according to parts by weight, placing the polished aluminum alloy in acetone for ultrasonic cleaning for 3min, then washing for 3 times with absolute ethyl alcohol and washing for 3 times with deionized water to obtain the cleaned aluminum alloy, placing the cleaned aluminum alloy in the sodium hydroxide solution, heating in a water bath to 50 ℃ for etching treatment for 3min to obtain the etched aluminum alloy, placing the etched aluminum alloy in the nitric acid for soaking for 1min at normal temperature for light extraction treatment to obtain the light-treated aluminum alloy, firstly using the absolute ethyl alcohol for ultrasonic cleaning for 3min and then using the deionized water for ultrasonic cleaning for 3min, placing the aluminum alloy into a vacuum drying furnace at 60 ℃ for vacuum drying for 0.5h to obtain a pretreated aluminum alloy, respectively weighing 3 parts by weight of citric acid, 10 parts by weight of cerium acetate, 1.2 parts by weight of titanium sulfate, 50 parts by weight of hydrogen peroxide and 800 parts by weight of deionized water, adding the citric acid into the deionized water, stirring at the normal temperature of 100r/min for 5min to obtain a citric acid solution, adding the cerium acetate, the titanium sulfate and the hydrogen peroxide into the citric acid solution, stirring at the normal temperature of 150r/min for 15min to obtain a rare earth film forming treatment solution, placing the pretreated aluminum alloy into the rare earth film forming treatment solution according to the mass ratio of 1: 5, passivating for 1h in a 50 ℃ water bath, taking out, washing for 3 times by using the deionized water, vacuum drying at 50 ℃ for 0.5h to obtain a rare earth passivated aluminum alloy, and respectively weighing 5 parts by weight of ethyl orthosilicate, 20 parts by weight of ethanol, 10 parts by weight of deionized water, 3 parts by weight of hydrochloric acid with the mass fraction of 10%, 3 portions of formamide, adding tetraethoxysilane into absolute ethyl alcohol, stirring for 10min at the normal temperature at the rotating speed of 100r/min to obtain tetraethoxysilane ethanol solution, adding deionized water into the tetraethoxysilane ethanol solution, stirring at the rotation speed of 500r/min for 20min at normal temperature to obtain a mixed solution, slowly dripping hydrochloric acid into the mixed solution, dropwise adding for 5min, stirring at the normal temperature at the rotating speed of 500r/min for 10min, adding formamide, continuously stirring for 10min, aging for 4h to obtain aged silica sol, soaking the aluminum alloy subjected to rare earth passivation treatment in the aged silica sol for 3min according to the mass ratio of 1: 5, then pulling and soaking for 15s, taking out, naturally drying, then drying at 75 ℃ for 20min, repeatedly pulling for 5 times to obtain a pulled sample, sintering the pulled sample at 450 ℃ for 0.5h in a box-type resistance furnace, preserving heat for 20min after sintering is finished, and taking out to obtain the aluminum alloy covered with the surface film.
Taking an aluminum alloy with the specification of 100mm multiplied by 50mm, polishing the aluminum alloy with 1300 meshes of water-polishing abrasive paper until the surface is smooth to obtain the polished aluminum alloy, respectively weighing 12 parts of the polished aluminum alloy, 45 parts of acetone, 45 parts of sodium hydroxide solution with the mass concentration of 1% and 45 parts of nitric acid with the mass concentration of 30% according to parts by weight, placing the polished aluminum alloy in acetone for ultrasonic cleaning for 4min, then washing with absolute ethyl alcohol for 4 times and washing with deionized water for 4 times to obtain the cleaned aluminum alloy, placing the cleaned aluminum alloy in the sodium hydroxide solution, heating in a water bath to 55 ℃ for etching treatment for 4min to obtain the etched aluminum alloy, placing the etched aluminum alloy in the nitric acid for soaking at normal temperature for 1min for light-emitting treatment to obtain the light-treated aluminum alloy, firstly using the absolute ethyl alcohol for ultrasonic cleaning for 4min and then using the deionized water for ultrasonic cleaning for 4min, placing the aluminum alloy into a vacuum drying furnace at 70 ℃ for vacuum drying for 0.8h to obtain a pretreated aluminum alloy, respectively weighing 4 parts by weight of citric acid, 11 parts by weight of cerium acetate, 1.3 parts by weight of titanium sulfate, 55 parts by weight of hydrogen peroxide and 900 parts by weight of deionized water, adding the citric acid into the deionized water, stirring at the normal temperature and the rotating speed of 150r/min for 8min to obtain a citric acid solution, adding the cerium acetate, the titanium sulfate and the hydrogen peroxide into the citric acid solution, stirring at the normal temperature and the rotating speed of 200r/min for 18min to obtain a rare earth film forming treatment solution, placing the pretreated aluminum alloy into the rare earth film forming treatment solution according to the mass ratio of 1: 5, passivating for 1.2h in a 52 ℃ water bath, taking out, washing for 4 times by weight of deionized water, vacuum drying at the temperature of 55 ℃ for 0.8h to obtain the rare earth passivated aluminum alloy, and respectively weighing 8 parts by weight of ethyl orthosilicate, 25 parts by weight of ethanol, 15 parts by weight of deionized water, 4 parts by weight of hydrochloric acid with the mass fraction of 10%, and the weight fraction of citric acid, 4 portions of formamide, adding tetraethoxysilane into absolute ethyl alcohol, stirring for 12min at the normal temperature at the rotating speed of 125r/min to obtain tetraethoxysilane ethanol solution, adding deionized water into the tetraethoxysilane ethanol solution, stirring at 550r/min for 25min at normal temperature to obtain mixed solution, slowly dripping hydrochloric acid into the mixed solution, dripping for 8min, stirring at the normal temperature at the rotating speed of 550r/min for 12min, adding formamide, continuously stirring for 12min, aging for 5h to obtain aged silica sol, soaking the aluminum alloy subjected to rare earth passivation treatment in the aged silica sol for 4min according to the mass ratio of 1: 5, then pulling and soaking for 18s, taking out, naturally drying, then drying at 78 ℃ for 25min, repeatedly pulling for 5 times to obtain a pulled sample, sintering the pulled sample in a box-type resistance furnace at 475 ℃ for 0.8h, preserving heat for 25min after sintering is finished, and taking out to obtain the aluminum alloy covering the surface film.
Taking an aluminum alloy with the specification of 100mm multiplied by 50mm, polishing the aluminum alloy with 2000 meshes of water-mill abrasive paper until the surface is smooth to obtain the polished aluminum alloy, respectively weighing 15 parts of the polished aluminum alloy, 50 parts of acetone, 50 parts of sodium hydroxide solution with the mass concentration of 1% and 50 parts of nitric acid with the mass concentration of 30% according to parts by weight, placing the polished aluminum alloy in acetone for ultrasonic cleaning for 5min, then washing for 5 times by absolute ethyl alcohol and washing for 5 times by deionized water to obtain the cleaned aluminum alloy, placing the cleaned aluminum alloy in the sodium hydroxide solution, heating in a water bath to 60 ℃ for etching treatment for 5min to obtain the etched aluminum alloy, placing the etched aluminum alloy in the nitric acid for soaking at normal temperature for 2min for light-emitting treatment to obtain the light-treated aluminum alloy, firstly using the absolute ethyl alcohol for ultrasonic cleaning for 5min and then using the deionized water for ultrasonic cleaning for 5min, placing the aluminum alloy into a vacuum drying machine at 80 ℃ for 1 hour to obtain pretreated aluminum alloy, respectively weighing 5 parts by weight of citric acid, 12 parts by weight of cerium acetate, 1.5 parts by weight of titanium sulfate, 60 parts by weight of hydrogen peroxide and 1000 parts by weight of deionized water, adding the citric acid into the deionized water, stirring for 10min at the normal temperature at the rotating speed of 200r/min to obtain a citric acid solution, adding the cerium acetate, the titanium sulfate and the hydrogen peroxide into the citric acid solution, stirring for 20min at the normal temperature at the rotating speed of 250r/min to obtain a rare earth film forming treatment solution, placing the pretreated aluminum alloy into the rare earth film forming treatment solution according to the mass ratio of 1: 5, performing passivation treatment for 1.5 hours in a water bath at 55 ℃, taking out, washing for 5 times by using the deionized water, performing vacuum drying for 1 hour at 60 ℃ to obtain rare earth passivated aluminum alloy, and respectively weighing 10 parts by weight of ethyl orthosilicate, 30 parts by weight of ethanol, 20 parts by weight of deionized water, 5 parts by weight of hydrochloric acid with the mass fraction of 10 percent, 5 parts of formamide, adding tetraethoxysilane into absolute ethyl alcohol, stirring at the normal temperature at the rotating speed of 150r/min for 15min to obtain tetraethoxysilane ethanol solution, adding deionized water into the tetraethoxysilane ethanol solution, stirring at the rotation speed of 600r/min for 30min at normal temperature to obtain a mixed solution, slowly dripping hydrochloric acid into the mixed solution, dripping for 10min, stirring at the normal temperature at the rotating speed of 600r/min for 15min, adding formamide, continuously stirring for 15min, aging for 6h to obtain aged silica sol, soaking the aluminum alloy subjected to rare earth passivation treatment in the aged silica sol for 5min according to the mass ratio of 1: 5, then pulling and soaking for 20s, taking out, naturally drying, then drying at 80 ℃ for 30min, repeatedly pulling for 5 times to obtain a pulled sample, sintering the pulled sample at 500 ℃ for 1h in a box-type resistance furnace, preserving heat for 30min after sintering is finished, and taking out to obtain the aluminum alloy covered with the surface film.
Experiments show that: by electrochemical testingThe sample is tested in strong acid test solution 0.5MH2SO4The corrosion resistance in +2ppm HF showed that the corrosion potential (vs. SCE) of the pyrolytic film was shifted by 241mV compared with-794 mV for the blank aluminum alloy sample, and the corrosion current density of the pyrolytic film was 7.461X 10-8A·cm-2Compared with a blank aluminum alloy, the alloy is 1.247 multiplied by 10- 4A·cm-2The method is reduced by 4 orders of magnitude, the protection efficiency is up to 99.940%, and the corrosion resistance is very good, which indicates that the method is very efficient. The samples were subsequently investigated in a strongly acidic test solution 0.5MH2SO4Research on different soaking times in +2ppm HF shows that after the pyrolytic film is soaked in the solution for 14400s, the corrosion current density can still reach 3.206 multiplied by 10-6A·cm-2。
Claims (5)
1. The preparation method of the aluminum alloy surface film is characterized by comprising the following specific preparation steps:
(1) placing the aluminum alloy subjected to rare earth passivation treatment in aged silica sol to be soaked for 3-5 min, then pulling and soaking for 15-20 s, taking out the aluminum alloy to be naturally dried, then placing the aluminum alloy at 75-80 ℃ to be dried for 20-30 min, and repeatedly pulling for 5 times to obtain a pulling sample;
the specific preparation steps of the aluminum alloy subjected to rare earth passivation treatment are as follows:
placing the pretreated aluminum alloy into a rare earth film forming treatment liquid according to the mass ratio of 1: 5, passivating for 1-1.5 h in a water bath at 50-55 ℃, taking out, washing for 3-5 times with deionized water, and vacuum drying for 0.5-1 h at 50-60 ℃ to obtain a rare earth passivated aluminum alloy;
the specific preparation steps of the pretreated aluminum alloy are as follows:
placing the polished aluminum alloy in acetone for ultrasonic cleaning for 3-5 min, then washing for 3-5 times by using absolute ethyl alcohol and washing for 3-5 times by using deionized water to obtain the cleaned aluminum alloy; the concrete preparation steps of the polished aluminum alloy are as follows: taking an aluminum alloy with the specification of 100mm multiplied by 50mm, and polishing the aluminum alloy with water-grinding abrasive paper of 600-2000 meshes until the surface is smooth to obtain the polished aluminum alloy;
secondly, placing the cleaned aluminum alloy into a sodium hydroxide solution, heating the aluminum alloy in a water bath to 50-60 ℃, and carrying out etching treatment for 3-5 min to obtain an etched aluminum alloy;
thirdly, soaking the etched aluminum alloy in nitric acid at normal temperature for 1-2 min to carry out light-emitting treatment to obtain the light-emitting treated aluminum alloy;
ultrasonically cleaning the aluminum alloy subjected to the light extraction treatment for 3-5 min by using absolute ethyl alcohol, ultrasonically cleaning for 3-5 min by using deionized water, and drying in vacuum at the temperature of 60-80 ℃ for 0.5-1 h to obtain a pretreated aluminum alloy;
the rare earth film-forming treatment liquid comprises the following specific preparation steps:
adding citric acid into deionized water, and stirring at the normal temperature at the rotating speed of 100-200 r/min for 5-10 min to obtain a citric acid solution;
secondly, adding cerium acetate, titanium sulfate and hydrogen peroxide into a citric acid solution, and stirring at the normal temperature at the rotating speed of 150-250 r/min for 15-20 min to obtain a rare earth film forming treatment solution;
the specific preparation steps of the aged silica sol are as follows:
adding ethyl orthosilicate into absolute ethyl alcohol, and stirring at the normal temperature at the rotating speed of 100-150 r/min for 10-15 min to obtain an ethyl orthosilicate ethanol solution;
adding deionized water into ethyl orthosilicate ethanol solution, and stirring at the rotating speed of 500-600 r/min for 20-30 min at normal temperature to obtain mixed solution;
thirdly, slowly dripping hydrochloric acid into the mixed solution for 5-10 min, stirring at the normal temperature at the rotating speed of 500-600 r/min for 10-15 min, then adding formamide, continuously stirring for 10-15 min, and aging for 4-6 h to obtain aged silica sol;
(2) and (3) placing the pulling sample in a box-type resistance furnace, sintering for 0.5-1 h at 450-500 ℃, preserving heat for 20-30 min after sintering, and taking out to obtain the aluminum alloy covering the surface film.
2. The method for preparing the surface film of the aluminum alloy as recited in claim 1, wherein the mass ratio of the rare earth passivated aluminum alloy and the aged silica sol in the step (1) is 1: 5.
3. The method for preparing the aluminum alloy surface film according to claim 1, wherein the weight parts of the ethyl orthosilicate, the ethanol, the deionized water, the hydrochloric acid and the formamide are 5-10 parts of ethyl orthosilicate, 20-30 parts of ethanol, 10-20 parts of deionized water, 3-5 parts of hydrochloric acid with the mass fraction of 10% and 3-5 parts of formamide.
4. The method for preparing the aluminum alloy surface film according to claim 1, wherein the citric acid, the cerium acetate, the titanium sulfate, the hydrogen peroxide and the deionized water are 3-5 parts by weight of citric acid, 10-12 parts by weight of cerium acetate, 1.2-1.5 parts by weight of titanium sulfate, 50-60 parts by weight of hydrogen peroxide and 800-1000 parts by weight of deionized water.
5. The method for preparing the aluminum alloy surface film according to claim 1, wherein the polished aluminum alloy, the acetone, the sodium hydroxide solution and the nitric acid are 10-15 parts by weight of the polished aluminum alloy, 40-50 parts by weight of the acetone, 40-50 parts by weight of the 1% sodium hydroxide solution and 40-50 parts by weight of the 30% nitric acid.
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