CN110042381A - A kind of preparation method of aluminum alloy surface film - Google Patents
A kind of preparation method of aluminum alloy surface film Download PDFInfo
- Publication number
- CN110042381A CN110042381A CN201910136972.6A CN201910136972A CN110042381A CN 110042381 A CN110042381 A CN 110042381A CN 201910136972 A CN201910136972 A CN 201910136972A CN 110042381 A CN110042381 A CN 110042381A
- Authority
- CN
- China
- Prior art keywords
- aluminium alloy
- parts
- aluminum alloy
- preparation
- surface film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1212—Zeolites, glasses
-
- 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Ceramic Engineering (AREA)
- Chemical Treatment Of Metals (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The present invention relates to a kind of preparation methods of aluminum alloy surface film, belong to surface technical field of membrane.The present invention passes through addition Ce elements; prepare aluminum alloy surface film; to effectively prevent or delay infiltration of the extraneous corrosive environment to the erosion and corrosive liquid of substrate material surface to conversion film, to protect alloy matrix aluminum from corrosion, the corrosion resistance of aluminium alloy is improved；The present invention is by preparing microporous silica membrane in aluminum alloy surface; improve the corrosion resistance of aluminium alloy; silica chemistry is stable, anti-etch ability is strong; it prepares that sol-gel method equipment used by microporous silica membrane is simple, sintering temperature is low, can coat big product, is reproducible; the size tunable of coating ingredients; it can also realize the dispersion of molecular level between component; aluminum alloy surface can be effectively coated in; energy effective protection alloy matrix aluminum is not corroded, to extend the use time of aluminium alloy.
Description
Technical field
The present invention relates to a kind of preparation methods of aluminum alloy surface film, belong to surface technical field of membrane.
Background technique
According to current correlative study, prevent metal material from corrosion occurs mainly by these mechanism:
(1) cathodic protection；
(2) anodic passivity；
(3) electrolysis inhibits；
(4) corrosion inhibiter.
Cathodic protection is to apply an impressed current to the metal material surface that is corroded, and becomes yin by protection metal material
Pole avoids or weakens the generation of corrosion so that the electron transfer that metal erosion occurs is inhibited.For a long time, zinc,
Al alloys andMg alloys are often used as anode, can form advantageous oxide layer in metal surface by means of electrochemical potential, are such as steel
The metal materials such as iron provide cathodic protection.Anodic passivity is by forming a passivating film in metal material surface, to weaken
The generation of metal material surface corrosion, this method is also a kind of method being in daily use, and oxidation film is collectively formed with passivating film
Sediment, or initially or on conversion coating, the adjacent layer of porous and finer and close oxide is produced, to have in anodic oxidation
Effect ground inhibits ion transmission.Electrolysis inhibits to be to add a low electric conductivity, diffusion barrier substrate between the anode and cathode, inhibits ion
Migration and electrolyte reach metal surface, to reach etch-proof purpose.Corrosion inhibiter processing includes the film layer when surface
Be damaged, protectiveness film can be rebuild at metal and environmental interface by it, this corrosion inhibition and " self-regeneration " this
A wider concept is different, this conception of species further includes introducing releasable material in the coating, even if without direct anti-corrosion
Protection, can also re-form polymer organic coating.On the basis of existing research, people are for preparation protectiveness film layer
The research of mechanism is never halted, and has more and more methods to can be applied to improve the corrosion resisting property of metal material.
The corrosion of metal material is a big problem, every year because corrode all can caused by a large amount of metal equipment or metal structure
Component is scrapped, and thus bring consequence is also unthinkable, because corrosion is frequently experienced in moment, can be brought and is difficult to estimate
Economy or security risk.The wide range of applications of aluminium and its alloy in life, because itself can produce oxidation film,
Protective effect can be generated to it, but in some specific environments, oxidation film can be destroyed, then its corrosion resistance poor
It needs to solve.
In practical applications, a distinct issues are that three proofings (preventing salt fog, damp and hot, mould) performance needs to be changed to aluminium alloy
Into.Especially in harsh marine corrosion environment, due to etch, pitting, the hard force cracking etc. by high humility and sea-salt fine particle
The service life of the collective effect of corrosion factor, alloy product greatly shortens.Since there is because of binding force for aluminum alloy surface coating
Bad and lead to the problem of underfilm corrosion, many Shipborne Electronic Equipments, radar and ocean weaponry etc. are served in marine climate ring
Alloy product under border, with surface electrochemistry conversion film as corrosion-resistant first choice, this oxidation electrolytically generated
Layer, can protect metallic substrates, prevents its corrosion and weathering, increases the flintiness and wear-resisting property on surface.
In numerous aluminium surfaces conversion membrane process, only the corrosion resistance of differential arc oxidation can be called outstanding (in resistance to
Property the salt spray test time up to 600h), still, due to differential arc oxidation film forming overtension, difficulty of processing is big, size changing amount is big
Etc. reasons, be restricted it in the application in electronics and each field of equipment.At present in the world, individually for the purpose of surface anticorrosion
Conversion Coatings on Aluminum Alloys, effect it is good be still using anode oxidation process.Aluminium anode oxide film is firmly combined with matrix, is hard resistance to
Mill, heat resistance is very prominent, but the resistance to neutral salt spray test time rarely exceeds 336h(14 period), this corrosion resisting property is generally being answered
It is substantially enough with environment, but problem is had become under marine environment.Generally praise highly in the world by improve oxidation filming quality come
Anti-corrosion capability is improved, process means are numerous, mainly have: improving film density, reduce its porosity；Increase oxidation
Film thickness；Change oxidation film itself current potential.
Summary of the invention
The technical problems to be solved by the invention: it for the problem that existing aluminum alloy surface film corrosion resistance is poor, provides
A kind of preparation method of aluminum alloy surface film.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
(1) aluminium alloy of rare earth Passivation Treatment is placed in ageing silica solution and impregnates 3~5min, then lift 15~20s of immersion, taken
It is placed at 75~80 DEG C dry 20~30min again after natural drying out, repeats lifting 5 times, obtain lifting sample；
(2) lifting sample is placed in chamber type electric resistance furnace in 450~500 DEG C of 0.5~1h of sintering, heat preservation 20 after sintering~
30min takes out, must cover the aluminium alloy of skin covering of the surface.
The aluminium alloy of rare earth Passivation Treatment described in step (1) and the mass ratio of ageing silica solution are 1: 5.
The specific preparation step of silica solution is aged described in step (1) are as follows:
(1) ethyl orthosilicate is added dehydrated alcohol, 10~15min is stirred with 100~150r/min revolving speed under room temperature, obtains positive silicon
Acetoacetic ester ethanol solution；
(2) by deionized water be added ethyl orthosilicate ethanol solution in, under room temperature with 500~600r/min revolving speed stirring 20~
30min obtains mixed liquor；
(3) hydrochloric acid is slowly added dropwise in mixed liquor, 5~10min of time for adding, with the stirring of 500~600r/min revolving speed under room temperature
Formamide is added after 10~15min and continues 10~15min of stirring, is aged 4~6h, obtains ageing silica solution.
The ethyl orthosilicate, ethyl alcohol, deionized water, hydrochloric acid, formamide parts by weight be 5~10 parts of positive silicic acid second
Ester, 20~30 parts of ethyl alcohol, 10~20 parts of deionized waters, 3~5 parts of mass fractions 10% hydrochloric acid, 3~5 parts of formamides.
The specific preparation step of the aluminium alloy of rare earth Passivation Treatment described in step (1) are as follows:
In mass ratio 1: 5 is placed in pretreated aluminium alloy in rare earth film process liquid, the Passivation Treatment 1 under 50~55 DEG C of water-baths
~1.5h takes out, and deionization is dried in vacuo 0.5~1h at washing 3~5 times, 50~60 DEG C, and the aluminium for obtaining rare earth Passivation Treatment closes
Gold.
The specific preparation step of rare earth film process liquid are as follows:
(1) citric acid is added in deionized water, 5~10min is stirred with 100~200r/min revolving speed under room temperature, obtains citric acid
Solution；
(2) cerous acetate, titanium sulfate and hydrogen peroxide are added in citric acid solution, with the stirring of 150~250r/min revolving speed under room temperature
15~20min obtains rare earth film process liquid.
The citric acid, cerous acetate, titanium sulfate, hydrogen peroxide, deionized water parts by weight be 3~5 parts of citric acids, 10~
12 parts of cerous acetates, 1.2~1.5 parts of titanium sulfates, 50~60 parts of hydrogen peroxide, 800~1000 parts of deionized waters.
The specific preparation step of the pretreated aluminium alloy are as follows:
(1) aluminium alloy after polishing is placed in acetone 3~5min of ultrasonic cleaning, then washed 3~5 times with dehydrated alcohol, go from
Sub- water rinses 3~5 times, the aluminium alloy after must cleaning；
(2) aluminium alloy after cleaning being placed in sodium hydroxide solution, heating water bath to 50~60 DEG C of etches handles 3~5min,
Obtain the aluminium alloy of etch processing；
(3) aluminium alloy that etch is handled is placed in 1~2min of soak at room temperature in nitric acid and carries out out light processing, obtain the aluminium of light processing
Alloy；
(4) by the aluminium alloy of light processing out first with dehydrated alcohol be cleaned by ultrasonic 3~5min, then with deionized water ultrasonic cleaning 3~
5min is placed in 0.5~1h of vacuum drying at 60~80 DEG C, obtains pretreated aluminium alloy.
After the parts by weight of aluminium alloy, acetone, sodium hydroxide solution, nitric acid after the polishing is 10~15 parts of polishings
Aluminium alloy, 40~50 parts of acetone, the sodium hydroxide solution of 40~50 parts of mass concentrations 1%, 40~50 parts of mass concentrations 30% nitre
Acid.
The specific preparation step of aluminium alloy after the polishing are as follows:
Taking a block specifications is 100mm × 50mm × 50mm aluminium alloy, is polishing to surface light with the silicon carbide paper of 600~2000 mesh
It is sliding, the aluminium alloy after must polishing.
The present invention is compared with other methods, and advantageous effects are:
(1) present invention prepares aluminum alloy surface film, using rare earth element passivating technique to aluminium alloy by addition rare-earth element cerium
After carrying out surface passivating treatment, the rare-earth salt passive film with corrosion resisting property can be obtained on aluminium alloy, be remarkably improved aluminium conjunction
The resistance to corrosion of gold, the passivating film of rare earth metal salt can effectively substitute chromate passivation film, the simple process of the technology, at
Film main salt is the inorganic salts of lanthanide series metal, these inorganic salts are safe and non-toxic, waste liquid can direct emission, production operation safety, be one
The environment amenable new metal surface treatment technology of item, rare-earth element cerium is while aluminum alloy surface forms rare-earth conversion coatings
The cathode reaction and anode reaction being able to suppress in corrosion process hinder the depolarising reaction of oxygen on anodic solution and cathode, energy
It is enough effectively to prevent or delay infiltration of the extraneous corrosive environment to the erosion and corrosive liquid of aluminum alloy material surface to conversion film, from
And effective protection alloy matrix aluminum improves the corrosion resistance of aluminium alloy from corrosion；
(2) present invention prepares aluminum alloy surface film by addition titanium sulfate, and the passivating film containing titanium elements has good stability
With the performance of self-regeneration, continuous-stable and knot can be formed in aluminum alloy surface with effective protection alloy matrix aluminum, titanium elements
Resultant force securely and has protective oxidation film layer, so tool has good corrosion resistance, since the reactivity of titanium is high and
There is extremely strong affinity with oxygen, so titanium can form protective film immediately when aluminum alloy surface is exposed in wet air,
Being also due to titanium and oxygen simultaneously has extremely strong affinity, once oxidation film is damaged, oxidation film energy after titanium is contacted with oxygen
It is immediately generated, self-regeneration is carried out, to improve the corrosion resistance of aluminium alloy；
(3) present invention improves the corrosion resistance of aluminium alloy, aluminium alloy table by preparing microporous silica membrane in aluminum alloy surface
Face coats the SiO 2-ceramic protective film of one layer of dense uniform, and the contact area of aluminium alloy and water can be effectively reduced, and has and hates
The microporous silica membrane of water function can effectively prevent due to temperature change generate dilation stress difference, salt knot again
Brilliant and moisture evaporates the destruction to film, and SiO 2-ceramic protective film has excellent high temperature resistant and freeze-resistant performance time, resistance to
It waits performance to be also obviously improved, silica chemistry is stable, anti-etch ability is strong, prepares microporous silica membrane
Used sol-gel method equipment is simple, sintering temperature is low, can coat big product, is reproducible, and the partial size of coating ingredients can
Control, can also realize the dispersion of molecular level between component, can effectively be coated in aluminum alloy surface, can effective protection alloy matrix aluminum
Do not corroded, to extend the use time of aluminium alloy.
Specific embodiment
Taking a block specifications is 100mm × 50mm × 50mm aluminium alloy, is polishing to table with the silicon carbide paper of 600~2000 mesh
Face is smooth, the aluminium alloy after must polishing, according to parts by weight, respectively weigh 10~15 parts polishing after aluminium alloy, 40~50 parts
Acetone, the sodium hydroxide solution of 40~50 parts of mass concentrations 1%, 40~50 parts of mass concentrations 30% nitric acid, by the aluminium after polishing
Alloy is placed in 3~5min of ultrasonic cleaning in acetone, then washs 3~5 times, deionized water flushing 3~5 times with dehydrated alcohol, obtains clearly
Aluminium alloy after cleaning is placed in sodium hydroxide solution by the aluminium alloy after washing, and heating water bath to 50~60 DEG C of etch processing 3~
5min obtains the aluminium alloy of etch processing, and the aluminium alloy that etch is handled is placed in 1~2min of soak at room temperature in nitric acid and is carried out out at light
Reason, obtain the aluminium alloy of light processing, by the aluminium alloy of light processing out first with dehydrated alcohol be cleaned by ultrasonic 3~5min, then spend from
Sub- water is cleaned by ultrasonic 3~5min, is placed in 0.5~1h of vacuum drying at 60~80 DEG C, obtains pretreated aluminium alloy, then by weight
Number meter, weighs 3~5 parts of citric acids, 10~12 parts of cerous acetates, 1.2~1.5 parts of titanium sulfates, 50~60 parts of hydrogen peroxide, 800 respectively
~1000 parts of deionized waters, by citric acid be added deionized water in, under room temperature with 100~200r/min revolving speed stirring 5~
10min obtains citric acid solution, cerous acetate, titanium sulfate and hydrogen peroxide is added in citric acid solution, with 150~250r/ under room temperature
Min revolving speed stirs 15~20min, obtains rare earth film process liquid, and pretreated aluminium alloy is placed in rare earth film forming by mass ratio 1: 5
In treatment fluid, 1~1.5h of Passivation Treatment under 50~55 DEG C of water-baths is taken out, vacuum at deionization is washed 3~5 times, 50~60 DEG C
Dry 0.5~1h, obtains the aluminium alloy of rare earth Passivation Treatment, then according to parts by weight, weigh respectively 5~10 parts of ethyl orthosilicates,
20~30 parts of ethyl alcohol, 10~20 parts of deionized waters, 3~5 parts of mass fractions 10% hydrochloric acid, 3~5 parts of formamides, by positive silicic acid second
Dehydrated alcohol is added in ester, stirs 10~15min with 100~150r/min revolving speed under room temperature, obtains ethyl orthosilicate ethanol solution, will
Deionized water is added in ethyl orthosilicate ethanol solution, stirs 20~30min under room temperature with 500~600r/min revolving speed, obtains mixed
Liquid is closed, hydrochloric acid is slowly added dropwise in mixed liquor, 5~10min of time for adding, with 500~600r/min revolving speed stirring 10 under room temperature
Formamide is added after~15min and continues 10~15min of stirring, is aged 4~6h, obtains ageing silica solution, in mass ratio 1: 5 will be dilute
The aluminium alloy of native Passivation Treatment, which is placed in ageing silica solution, impregnates 3~5min, then lifts 15~20s of immersion, takes out naturally dry
It is placed at 75~80 DEG C dry 20~30min again afterwards, repeats lifting 5 times, obtain lifting sample, lifting sample is placed in box resistance
In 450~500 DEG C of 0.5~1h of sintering in furnace, 20~30min is kept the temperature after sintering, is taken out, and the aluminium that must cover skin covering of the surface closes
Gold.
Taking a block specifications is 100mm × 50mm × 50mm aluminium alloy, is polishing to surface light with the silicon carbide paper of 600 mesh
It is sliding, the aluminium alloy after must polishing, according to parts by weight, aluminium alloy, 40 parts of acetone, 40 parts of quality after weighing 10 parts of polishings respectively
The nitric acid of the sodium hydroxide solution of concentration 1%, 40 parts of mass concentrations 30%, the aluminium alloy after polishing is placed in acetone and is cleaned by ultrasonic
3min, then 3 times, deionized water flushing 3 times are washed with dehydrated alcohol, the aluminium alloy after must cleaning sets the aluminium alloy after cleaning
In sodium hydroxide solution, heating water bath to 50 DEG C of etches handles 3min, obtains the aluminium alloy of etch processing, the aluminium that etch is handled
Alloy is placed in soak at room temperature 1min in nitric acid and carries out out light processing, obtains the aluminium alloy of light processing, by the aluminium alloy of light processing out
First it is cleaned by ultrasonic 3min with dehydrated alcohol, then is cleaned by ultrasonic 3min with deionized water, is placed at 60 DEG C and is dried in vacuo 0.5h, obtain pre-
The aluminium alloy of processing, then according to parts by weight, 3 parts of citric acids, 10 parts of cerous acetates, 1.2 parts of titanium sulfates, 50 parts of dioxygens are weighed respectively
Citric acid is added in deionized water for water, 800 parts of deionized waters, stirs 5min under room temperature with 100r/min revolving speed, obtains citric acid
Cerous acetate, titanium sulfate and hydrogen peroxide are added in citric acid solution solution, stir 15min under room temperature with 150r/min revolving speed, obtain
Rare earth film process liquid, in mass ratio 1: 5 is placed in pretreated aluminium alloy in rare earth film process liquid, blunt under 50 DEG C of water-baths
Change processing 1h, take out, deionization is dried in vacuo 0.5h at washing 3 times, 50 DEG C, obtains the aluminium alloy of rare earth Passivation Treatment, then by weight
Number meter is measured, weighs 5 parts of ethyl orthosilicates, 20 parts of ethyl alcohol, 10 parts of deionized waters, the hydrochloric acid of 3 parts of mass fractions 10%, 3 parts respectively
Ethyl orthosilicate is added dehydrated alcohol, stirs 10min under room temperature with 100r/min revolving speed, obtain ethyl orthosilicate second by formamide
Deionized water is added in ethyl orthosilicate ethanol solution alcoholic solution, stirs 20min under room temperature with 500r/min revolving speed, obtains mixed
Liquid is closed, hydrochloric acid is slowly added dropwise in mixed liquor, time for adding 5min, is added after stirring 10min under room temperature with 500r/min revolving speed
Formamide simultaneously continues to stir 10min, is aged 4h, obtains ageing silica solution, in mass ratio 1: 5 sets the aluminium alloy of rare earth Passivation Treatment
3min is impregnated in ageing silica solution, then lifts and impregnates 15s, taking-up is placed at 75 DEG C dry 20min again after natural drying, repeats
Lifting 5 times, obtains lifting sample, and lifting sample is placed in chamber type electric resistance furnace in 450 DEG C of sintering 0.5h, is kept the temperature after sintering
20min takes out, must cover the aluminium alloy of skin covering of the surface.
Taking a block specifications is 100mm × 50mm × 50mm aluminium alloy, is polishing to surface light with the silicon carbide paper of 1300 mesh
It is sliding, the aluminium alloy after must polishing, according to parts by weight, aluminium alloy, 45 parts of acetone, 45 parts of quality after weighing 12 parts of polishings respectively
The nitric acid of the sodium hydroxide solution of concentration 1%, 45 parts of mass concentrations 30%, the aluminium alloy after polishing is placed in acetone and is cleaned by ultrasonic
4min, then 4 times, deionized water flushing 4 times are washed with dehydrated alcohol, the aluminium alloy after must cleaning sets the aluminium alloy after cleaning
In sodium hydroxide solution, heating water bath to 55 DEG C of etches handles 4min, obtains the aluminium alloy of etch processing, the aluminium that etch is handled
Alloy is placed in soak at room temperature 1min in nitric acid and carries out out light processing, obtains the aluminium alloy of light processing, by the aluminium alloy of light processing out
First it is cleaned by ultrasonic 4min with dehydrated alcohol, then is cleaned by ultrasonic 4min with deionized water, is placed at 70 DEG C and is dried in vacuo 0.8h, obtain pre-
The aluminium alloy of processing, then according to parts by weight, 4 parts of citric acids, 11 parts of cerous acetates, 1.3 parts of titanium sulfates, 55 parts of dioxygens are weighed respectively
Citric acid is added in deionized water for water, 900 parts of deionized waters, stirs 8min under room temperature with 150r/min revolving speed, obtains citric acid
Cerous acetate, titanium sulfate and hydrogen peroxide are added in citric acid solution solution, stir 18min under room temperature with 200r/min revolving speed, obtain
Rare earth film process liquid, in mass ratio 1: 5 is placed in pretreated aluminium alloy in rare earth film process liquid, blunt under 52 DEG C of water-baths
Change processing 1.2h, take out, deionization is dried in vacuo 0.8h at washing 4 times, 55 DEG C, obtains the aluminium alloy of rare earth Passivation Treatment, then press
Parts by weight meter weighs 8 parts of ethyl orthosilicates, 25 parts of ethyl alcohol, 15 parts of deionized waters, the hydrochloric acid of 4 parts of mass fractions 10%, 4 respectively
Ethyl orthosilicate is added dehydrated alcohol, stirs 12min under room temperature with 125r/min revolving speed, obtain ethyl orthosilicate by part formamide
Deionized water is added in ethyl orthosilicate ethanol solution ethanol solution, stirs 25min under room temperature with 550r/min revolving speed, obtains
Hydrochloric acid is slowly added dropwise in mixed liquor mixed liquor, time for adding 8min, adds after stirring 12min under room temperature with 550r/min revolving speed
Enter formamide and continue to stir 12min, be aged 5h, obtain ageing silica solution, in mass ratio 1: 5 by the aluminium alloy of rare earth Passivation Treatment
It is placed in ageing silica solution and impregnates 4min, then lift and impregnate 18s, taking-up is placed at 78 DEG C dry 25min, weight again after natural drying
It lifts 5 times again, obtains lifting sample, lifting sample is placed in chamber type electric resistance furnace in 475 DEG C of sintering 0.8h, is kept the temperature after sintering
25min takes out, must cover the aluminium alloy of skin covering of the surface.
Taking a block specifications is 100mm × 50mm × 50mm aluminium alloy, is polishing to surface light with the silicon carbide paper of 2000 mesh
It is sliding, the aluminium alloy after must polishing, according to parts by weight, aluminium alloy, 50 parts of acetone, 50 parts of quality after weighing 15 parts of polishings respectively
The nitric acid of the sodium hydroxide solution of concentration 1%, 50 parts of mass concentrations 30%, the aluminium alloy after polishing is placed in acetone and is cleaned by ultrasonic
5min, then 5 times, deionized water flushing 5 times are washed with dehydrated alcohol, the aluminium alloy after must cleaning sets the aluminium alloy after cleaning
In sodium hydroxide solution, heating water bath to 60 DEG C of etches handles 5min, obtains the aluminium alloy of etch processing, the aluminium that etch is handled
Alloy is placed in soak at room temperature 2min in nitric acid and carries out out light processing, obtains the aluminium alloy of light processing, by the aluminium alloy of light processing out
First it is cleaned by ultrasonic 5min with dehydrated alcohol, then is cleaned by ultrasonic 5min with deionized water, is placed at 80 DEG C and is dried in vacuo 1h, obtain pre- place
The aluminium alloy of reason, then according to parts by weight, 5 parts of citric acids, 12 parts of cerous acetates, 1.5 parts of titanium sulfates, 60 parts of dioxygens are weighed respectively
Citric acid is added in deionized water for water, 1000 parts of deionized waters, stirs 10min under room temperature with 200r/min revolving speed, obtains lemon
Cerous acetate, titanium sulfate and hydrogen peroxide are added in citric acid solution acid solution, stir 20min under room temperature with 250r/min revolving speed,
Rare earth film process liquid is obtained, in mass ratio 1: 5 is placed in pretreated aluminium alloy in rare earth film process liquid, under 55 DEG C of water-baths
Passivation Treatment 1.5h takes out, and deionization is dried in vacuo 1h at washing 5 times, 60 DEG C, obtains the aluminium alloy of rare earth Passivation Treatment, then press
Parts by weight meter, weigh respectively 10 parts of ethyl orthosilicates, 30 parts of ethyl alcohol, 20 parts of deionized waters, 5 parts of mass fractions 10% hydrochloric acid,
Ethyl orthosilicate is added dehydrated alcohol, stirs 15min under room temperature with 150r/min revolving speed, obtain ethyl orthosilicate by 5 parts of formamides
Deionized water is added in ethyl orthosilicate ethanol solution ethanol solution, stirs 30min under room temperature with 600r/min revolving speed, obtains
Hydrochloric acid is slowly added dropwise in mixed liquor mixed liquor, time for adding 10min, adds after stirring 15min under room temperature with 600r/min revolving speed
Enter formamide and continue to stir 15min, be aged 6h, obtain ageing silica solution, in mass ratio 1: 5 by the aluminium alloy of rare earth Passivation Treatment
It is placed in ageing silica solution and impregnates 5min, then lift and impregnate 20s, taking-up is placed at 80 DEG C dry 30min, weight again after natural drying
It lifts 5 times again, obtains lifting sample, lifting sample is placed in chamber type electric resistance furnace in 500 DEG C of sintering 1h, is kept the temperature after sintering
30min takes out, must cover the aluminium alloy of skin covering of the surface.
Experiment shows: having studied sample by electro-chemical test and tests solution 0.5MH in highly acid2SO4In+2ppmHF
Corrosion resisting property, the results showed that, be pyrolyzed corrosion potential (vs.SCE) 553mV of film compared with blank aluminum alloy specimen 794mV just
241mV is moved, the corrosion electric current density 7.461 × 10 of the pyrolysis film-8A·cm-2Compared with the 1.247 × 10 of blank aluminium alloy- 4A·cm-24 orders of magnitude are had dropped, protection efficiency is up to 99.940%, and corrosion resisting property is very good, illustrates that this method is very
Efficiently.Sample is then had studied again tests solution 0.5MH in highly acid2SO4The research that different time is impregnated in+2ppmHF,
Pyrolysis film was immersed in the solution after the 14400s time, and corrosion electric current density remains to reach 3.206 × 10-6A·cm-2。
Claims (10)
1. a kind of preparation method of aluminum alloy surface film, which is characterized in that specific preparation step are as follows:
(1) aluminium alloy of rare earth Passivation Treatment is placed in ageing silica solution and impregnates 3~5min, then lift 15~20s of immersion, taken
It is placed at 75~80 DEG C dry 20~30min again after natural drying out, repeats lifting 5 times, obtain lifting sample；
(2) lifting sample is placed in chamber type electric resistance furnace in 450~500 DEG C of 0.5~1h of sintering, heat preservation 20 after sintering~
30min takes out, must cover the aluminium alloy of skin covering of the surface.
2. a kind of preparation method of aluminum alloy surface film according to claim 1, which is characterized in that described in step (1)
The aluminium alloy of rare earth Passivation Treatment and the mass ratio of ageing silica solution are 1: 5.
3. a kind of preparation method of aluminum alloy surface film according to claim 1, which is characterized in that described in step (1)
It is aged the specific preparation step of silica solution are as follows:
(1) ethyl orthosilicate is added dehydrated alcohol, 10~15min is stirred with 100~150r/min revolving speed under room temperature, obtains positive silicon
Acetoacetic ester ethanol solution；
(2) by deionized water be added ethyl orthosilicate ethanol solution in, under room temperature with 500~600r/min revolving speed stirring 20~
30min obtains mixed liquor；
(3) hydrochloric acid is slowly added dropwise in mixed liquor, 5~10min of time for adding, with the stirring of 500~600r/min revolving speed under room temperature
Formamide is added after 10~15min and continues 10~15min of stirring, is aged 4~6h, obtains ageing silica solution.
4. a kind of preparation method of aluminum alloy surface film according to claim 3, which is characterized in that the positive silicic acid second
Ester, ethyl alcohol, deionized water, hydrochloric acid, formamide parts by weight be 5~10 parts of ethyl orthosilicates, 20~30 parts of ethyl alcohol, 10~20 parts
Hydrochloric acid, 3~5 parts of formamides of deionized water, 3~5 parts of mass fractions 10%.
5. a kind of preparation method of aluminum alloy surface film according to claim 1, which is characterized in that described in step (1)
The specific preparation step of the aluminium alloy of rare earth Passivation Treatment are as follows:
In mass ratio 1: 5 is placed in pretreated aluminium alloy in rare earth film process liquid, the Passivation Treatment 1 under 50~55 DEG C of water-baths
~1.5h takes out, and deionization is dried in vacuo 0.5~1h at washing 3~5 times, 50~60 DEG C, and the aluminium for obtaining rare earth Passivation Treatment closes
Gold.
6. a kind of preparation method of aluminum alloy surface film according to claim 5, which is characterized in that the rare earth film forming
The specific preparation step for the treatment of fluid are as follows:
(1) citric acid is added in deionized water, 5~10min is stirred with 100~200r/min revolving speed under room temperature, obtains citric acid
Solution；
(2) cerous acetate, titanium sulfate and hydrogen peroxide are added in citric acid solution, with the stirring of 150~250r/min revolving speed under room temperature
15~20min obtains rare earth film process liquid.
7. a kind of preparation method of aluminum alloy surface film according to claim 6, which is characterized in that the citric acid,
Cerous acetate, titanium sulfate, hydrogen peroxide, deionized water parts by weight be 3~5 parts of citric acids, 10~12 parts of cerous acetates, 1.2~1.5 parts
Titanium sulfate, 50~60 parts of hydrogen peroxide, 800~1000 parts of deionized waters.
8. a kind of preparation method of aluminum alloy surface film according to claim 5, which is characterized in that described is pretreated
The specific preparation step of aluminium alloy are as follows:
(1) aluminium alloy after polishing is placed in acetone 3~5min of ultrasonic cleaning, then washed 3~5 times with dehydrated alcohol, go from
Sub- water rinses 3~5 times, the aluminium alloy after must cleaning；
(2) aluminium alloy after cleaning being placed in sodium hydroxide solution, heating water bath to 50~60 DEG C of etches handles 3~5min,
Obtain the aluminium alloy of etch processing；
(3) aluminium alloy that etch is handled is placed in 1~2min of soak at room temperature in nitric acid and carries out out light processing, obtain the aluminium of light processing
Alloy；
(4) by the aluminium alloy of light processing out first with dehydrated alcohol be cleaned by ultrasonic 3~5min, then with deionized water ultrasonic cleaning 3~
5min is placed in 0.5~1h of vacuum drying at 60~80 DEG C, obtains pretreated aluminium alloy.
9. a kind of preparation method of aluminum alloy surface film according to claim 8, which is characterized in that after the polishing
Aluminium alloy, acetone, sodium hydroxide solution, nitric acid parts by weight be 10~15 parts polishing after aluminium alloy, 40~50 parts of acetone, 40
The nitric acid of the sodium hydroxide solution of~50 parts of mass concentrations 1%, 40~50 parts of mass concentrations 30%.
10. a kind of preparation method of aluminum alloy surface film according to claim 9, which is characterized in that after the polishing
Aluminium alloy specific preparation step are as follows:
Taking a block specifications is 100mm × 50mm × 50mm aluminium alloy, is polishing to surface light with the silicon carbide paper of 600~2000 mesh
It is sliding, the aluminium alloy after must polishing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910136972.6A CN110042381B (en) | 2019-02-25 | 2019-02-25 | Preparation method of aluminum alloy surface film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910136972.6A CN110042381B (en) | 2019-02-25 | 2019-02-25 | Preparation method of aluminum alloy surface film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110042381A true CN110042381A (en) | 2019-07-23 |
| CN110042381B CN110042381B (en) | 2021-12-07 |
Family
ID=67274309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910136972.6A Active CN110042381B (en) | 2019-02-25 | 2019-02-25 | Preparation method of aluminum alloy surface film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110042381B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110219031A (en) * | 2019-06-06 | 2019-09-10 | 北京航空航天大学 | Anodic oxidation electrolyte and method, the aluminum or aluminum alloy with anode oxide film |
| CN111304652A (en) * | 2020-03-22 | 2020-06-19 | 浙江宇达新材料有限公司 | Process method for replacing phosphorization by coating ceramic membrane |
| CN113293389A (en) * | 2021-05-21 | 2021-08-24 | 重庆沛轩精密电子有限公司 | Electrochemical surface treatment process applied to aluminum alloy |
| CN114657581A (en) * | 2022-04-27 | 2022-06-24 | 深圳市格瑞珂林水电解技术开发有限公司 | Preparation method of special anti-rust functional water for ultrahigh-pressure water derusting construction of large ships |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1147842B (en) * | 1981-04-16 | 1986-11-26 | Hooker Chemicals Plastics Corp | WATER SOLUTION AND PROCEDURE TO APPLY A FILM WITH METALLIC SUBSTRATES WITH THE APPEARANCE OF CHROME PASSIVATE |
| CN101892477A (en) * | 2010-06-21 | 2010-11-24 | 华南理工大学 | Treatment solution for preparing aluminum alloy surface amorphous composite passivation film, preparation method and application |
| CN107587009A (en) * | 2017-07-28 | 2018-01-16 | 宁波华源精特金属制品有限公司 | A kind of engine foundation |
| CN107604216A (en) * | 2017-07-28 | 2018-01-19 | 宁波华源精特金属制品有限公司 | A kind of motor cabinet cover plate |
-
2019
- 2019-02-25 CN CN201910136972.6A patent/CN110042381B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1147842B (en) * | 1981-04-16 | 1986-11-26 | Hooker Chemicals Plastics Corp | WATER SOLUTION AND PROCEDURE TO APPLY A FILM WITH METALLIC SUBSTRATES WITH THE APPEARANCE OF CHROME PASSIVATE |
| CN101892477A (en) * | 2010-06-21 | 2010-11-24 | 华南理工大学 | Treatment solution for preparing aluminum alloy surface amorphous composite passivation film, preparation method and application |
| CN107587009A (en) * | 2017-07-28 | 2018-01-16 | 宁波华源精特金属制品有限公司 | A kind of engine foundation |
| CN107604216A (en) * | 2017-07-28 | 2018-01-19 | 宁波华源精特金属制品有限公司 | A kind of motor cabinet cover plate |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110219031A (en) * | 2019-06-06 | 2019-09-10 | 北京航空航天大学 | Anodic oxidation electrolyte and method, the aluminum or aluminum alloy with anode oxide film |
| CN110219031B (en) * | 2019-06-06 | 2020-12-08 | 北京航空航天大学 | Anodic oxidation electrolyte and method, and aluminum or aluminum alloy with anodic oxidation film |
| CN111304652A (en) * | 2020-03-22 | 2020-06-19 | 浙江宇达新材料有限公司 | Process method for replacing phosphorization by coating ceramic membrane |
| CN113293389A (en) * | 2021-05-21 | 2021-08-24 | 重庆沛轩精密电子有限公司 | Electrochemical surface treatment process applied to aluminum alloy |
| CN114657581A (en) * | 2022-04-27 | 2022-06-24 | 深圳市格瑞珂林水电解技术开发有限公司 | Preparation method of special anti-rust functional water for ultrahigh-pressure water derusting construction of large ships |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110042381B (en) | 2021-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110042381A (en) | A kind of preparation method of aluminum alloy surface film | |
| CN102154673B (en) | Method for preparing environment-friendly micro-arc oxidation black ceramic film on aluminum alloy surface | |
| CN103173836B (en) | Magnesium alloy differential arc oxidation low energy consumption black ceramic membrane and preparation method | |
| Ranjbar-Nouri et al. | Applying the protective CuMn2O4 spinel coating on AISI-430 ferritic stainless steel used as solid oxide fuel cell interconnects | |
| Song et al. | Advanced microcapsules for self-healing conversion coating on magnesium alloy in Ce (NO3) 3 solution with microcapsules containing La (NO3) 3 | |
| Zhang et al. | Preparation and corrosion performance of PEO coating with low porosity on magnesium alloy AZ91D in acidic KF system | |
| Li et al. | Effect of intermetallic phases on the anodic oxidation and corrosion of 5A06 aluminum alloy | |
| Veeraraghavan et al. | Synthesis and characterization of a novel non-chrome electrolytic surface treatment process to protect zinc coatings | |
| CN101914765B (en) | Method for preparing dark-colored ceramic membranes by chemical conversion-micro-arc oxidation of magnesium alloys | |
| CN1211500C (en) | Metal surface anti-corrosion method based on surface nanometer construct | |
| CN102234800A (en) | Aluminum alloy rare earth passivating liquid taking chlorine salt as accelerator and use method thereof | |
| CN105908204A (en) | Surface anti-corrosion treatment technology for aluminum fuel tanks | |
| CN108018591A (en) | A kind of aluminium and aluminium alloy anode oxide film are without nickel free-floride sealer | |
| Wang et al. | Corrosion resistance enhancement of micro-arc oxidation ceramic layer by Mg-Al-Co layered double hydroxide coating | |
| CN105350049A (en) | Preparing method for graphene oxide composite coating on surface of magnesium alloy | |
| CN100462483C (en) | Preparing process of anticorrosive coating on surface of aluminium base composite material | |
| WO2024056109A1 (en) | "brick-mortar" layered structure corrosion-resistant phosphate composite coating, and preparation method and use therefor | |
| CN100564608C (en) | Two-step electrochemical prepares the method for aluminum base composite material surface protection coating | |
| CN1858306A (en) | Process for cathode electrolytic deposition of rare-earth conversion film | |
| CN102465286A (en) | Composition for anti-corrosion treatment, corrosion-resistant material and preparation method of the corrosion-resistant material | |
| CN103147112B (en) | A kind of electrolytic solution and for the preparation of the purposes of nuclear fuel rod zirconium alloy cladding micro-arc oxidation films and method | |
| Yao et al. | Effects of ceramic coating by micro-plasma oxidation on the corrosion resistance of Ti–6Al–4V alloy | |
| Huanhuan et al. | Study of corrosion protection of the composite films on A356 aluminum alloy | |
| CN105880136A (en) | Preparation method of copper-based super-hydrophobic corrosion and scale preventing film for chloride ion corrosion and calcium carbonate scale | |
| CN101435081B (en) | No-voltage chemical membrane preparing and low voltage electrochemical membrane preparing combined process for magnesium alloy surface |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210508 Address after: No.13, roadside villager group, Xinzhuang village, Pengtang Township, Hengyang City, Hunan Province Applicant after: Tang Fusheng Address before: 213000 No.24, Xiaoyuan group, Weimin village, Yonghong street, Zhonglou District, Changzhou City, Jiangsu Province Applicant before: CHANGZHOU WANBO METAL COMPONENT FACTORY |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20211118 Address after: 222000 No. 23, Liuyuan Road, Mashan Industrial Park, Chaoyang Street, economic and Technological Development Zone, Lianyungang City, Jiangsu Province Applicant after: Ruishangxing communication signal equipment (Lianyungang) Co.,Ltd. Address before: No.13, roadside villager group, Xinzhuang village, Pengtang Township, Hengyang City, Hunan Province Applicant before: Tang Fusheng |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |