CN109402620A - Aluminum alloy surface Chrome-free is anti-corrosion chemical composition coating film forming solution and film layer preparation method - Google Patents
Aluminum alloy surface Chrome-free is anti-corrosion chemical composition coating film forming solution and film layer preparation method Download PDFInfo
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- 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
- C23C22/34—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 containing fluorides or complex fluorides
- C23C22/36—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 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—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 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
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- 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
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- 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
- C23C22/07—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 containing phosphates
- C23C22/08—Orthophosphates
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- 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
- C23C22/34—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 containing fluorides or complex fluorides
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- 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
- C23C22/34—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 containing fluorides or complex fluorides
- C23C22/36—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 containing fluorides or complex fluorides containing also phosphates
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- 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
- C23C22/78—Pretreatment of the material to be coated
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- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
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Abstract
The present invention relates to aluminium alloy surface anti-corrosion erosion processing technique, in particular to a kind of anti-corrosion chemical composition coating film forming solution of aluminum alloy surface Chrome-free and film layer preparation methods.The film forming solution is the mixed solution containing main salt, buffer, film forming accelerating, pH adjusting agent and water, and the pH of film forming solution is 2~5.The chemical conversion membrane preparation method includes four oil removing, alkali cleaning, acid-wash activation and film forming steps, without environmentally harmful ingredients such as chromium or chromate in entire treatment process, film forming procedure is simple, film forming solution constituent is cheap, gained chemical composition coating even compact, excellent corrosion-proof performance can significantly improve the binding force of organic coating and alloy matrix aluminum.
Description
Technical field
The present invention relates to aluminium alloy surface anti-corrosion erosion processing technique, in particular to a kind of anti-corrosion chemistry of aluminum alloy surface Chrome-free
Conversion film film forming solution and film layer preparation method.
Background technique
Aluminium alloy is widely used in aerospace, shipbuilding, communications and transportation and building because of its superior mechanical performance
Etc. industries, it has also become one of presently most important structural timber.Although aluminium alloy surface easy to form one in air
Layer oxide membranous layer, has certain protective effect to alloy, but be insufficient for industrial protection demand, in the ring of corrosivity harshness
Be easy to happen serious corrosion in border, therefore aluminium alloy needs to carry out before being put into use two-step pretreatment: surface modification treatment and
Spray organic coating.
Aluminum alloy surface modification treatment technology mainly has blasting treatment, differential arc oxidation, anodic oxidation and chemical conversion treatment
Etc. techniques, chemical conversion treatment technique because of the surface easy to operate, at low cost and applied widely for being preferentially elected to be aluminium alloy at
Science and engineering skill.Currently, chromate conversion treatments technique be aluminum alloy surface processing prevailing technology, have good corrosion resisting property and
Coating adhesion.But contain Cr in chromate6+, its toxic and carcinogenicity can cause huge harm to human body, especially
It is to threaten to the health of process operator, does not meet the requirement of environmental protection, is used by limitation.Therefore, work as business
Is suddenly to develop a kind of aluminum alloy chemically conversion treatment process with good corrosion resisting property and coating adhesion.
Chinese patent application (publication number CN103266315B, CN102212812B, CN101358341B, CN1683590A,
CN103305822A, CN104264144A) etc. a series of patents to disclose a variety of aluminium alloy non-chromium chemical composition coatings film forming in succession molten
Liquid and preparation method, but these conversion film film forming solutions and preparation method have the following problems: (1) it in film-forming technology process uses
The higher cobalt salt of cost price or toxic nitrite；(2) chemical composition coating preparation process is cumbersome, need to post-process sealing of hole or
Person needs higher reaction temperature；(3) some chemical composition coating corrosion resistances are bad, are unable to satisfy actual production and application
It needs.
Summary of the invention
The purpose of the present invention is to provide a kind of anti-corrosion chemical composition coating film forming solution of aluminum alloy surface Chrome-free and film layer systems
Preparation Method, to substitute containing Cr6+Chromate conversion treatments technique, solve existing chromiumfree conversion processing technique film-forming temperature
High, the problems such as corrosion resisting property is undesirable, at high cost, effectively improve corrosion resistance of the alloy matrix aluminum in harsh corrosive environment itself
Energy and the adhesive force with organic coating.
Technical scheme is as follows:
A kind of anti-corrosion chemical composition coating film forming solution of aluminum alloy surface Chrome-free, the film forming solution are containing main salt, delay
The mixed solution of electuary, film forming accelerating, pH adjusting agent and water, the pH of film forming solution are 2~5；Wherein:
Main salt is titanium sulfate, Titanium Nitrate, titanium sodium fluoride, potassium fluotitanate, ammonium titanium fluoride, zirconium carbonate ammonium, zirconium nitrate, fluorine zirconic acid
The mixtures of the one or more of potassium, sodium fluozirconate, ammonium fluozirconate, main salt concentration range are 0.1~20g/L；
Buffer is sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid, organic phospho acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide, phosphoric acid one
Hydrogen ammonium, ammonium dihydrogen phosphate, tertiary sodium phosphate, disodium-hydrogen, sodium dihydrogen phosphate, tripotassium phosphate, potassium phosphate,monobasic, biphosphate
One or more kinds of compoundings of potassium, sodium carbonate, sodium bicarbonate, potassium carbonate, saleratus, ammonium hydrogen carbonate, buffer concentration
For 1~30g/L；
Film forming accelerating is sodium fluoride, potassium fluoride, sodium bifluoride, potassium hydrogen fluoride, ammonium acid fluoride, sodium nitrate, potassium nitrate, nitre
The one or more of sour ammonium, film forming accelerating concentration are 1~15g/L.
The aluminum alloy surface Chrome-free is anti-corrosion chemical composition coating film forming solution, pH adjusting agent are sulfuric acid, nitric acid, hydrogen fluorine
Acid, phosphoric acid, organic phospho acid, citric acid, fluotitanic acid, fluorine zirconic acid, tartaric acid, acetic acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide one
Kind or two or more compoundings, pH adjusting agent content are 0.5~5mL/L.
The aluminum alloy surface Chrome-free is anti-corrosion chemical composition coating film forming solution, the concentration of preferred main salt is 0.5~
10g/L, the concentration of buffer are 5~20g/L, and the concentration of promotor is 5~10g/L.
A kind of film layer preparation method of the anti-corrosion chemical composition coating of aluminum alloy surface Chrome-free, this method includes oil removing, alkali cleaning, acid
Wash four steps of activation and film forming, in which:
(1) oil removing
Aluminium alloy is immersed in except being ultrasonically treated 2~15 minutes in oil solution, oil removing solution temperature is controlled at 15~40 DEG C
Between, it is rinsed 1~2 minute after oil removing with flowing water；
(2) alkali cleaning
Aluminium alloy after oil removing is immersed in soda-wash solution 10 seconds~5 minutes, soda-wash solution temperature is controlled 15~40
Between DEG C, rinsed 1~2 minute after alkali cleaning with flowing water；
(3) acid-wash activation
Aluminium alloy after alkali cleaning is immersed in acid-wash activation solution 0.5~10 minute, the control of acid-wash activation solution temperature
Between 15~40 DEG C, rinsed 1~2 minute after activation with flowing water；
(4) it forms a film
Aluminium alloy after acid-wash activation is immersed in film forming solution, is carried out film formation reaction 1~40 minute, film forming solution temperature
Degree control is cleaned 1~2 minute with flowing water after reaction between 15~50 DEG C, is placed in air, dries in the air naturally at room temperature
It is dry.
The film layer preparation method of the anti-corrosion chemical composition coating of aluminum alloy surface Chrome-free, solution used in oil removing are hydrogen-oxygen
Change the mixing water of one or more of sodium, potassium hydroxide, sodium carbonate, sodium phosphate, sodium metasilicate, neopelex
Solution, the concentration range of each ingredient are as follows: 10~50g/L of sodium hydroxide, 10~50g/L of potassium hydroxide, 5~20g/L of sodium carbonate, carbon
Sour 5~20g/L of potassium, 2~40g/L of sodium phosphate, 3~25g/L of sodium metasilicate, 1~10g/L of neopelex, surplus are water.
The film layer preparation method of the anti-corrosion chemical composition coating of aluminum alloy surface Chrome-free, solution used in alkali cleaning are hydrogen-oxygen
Change the mixed aqueous solution of one or more of sodium, potassium hydroxide, sodium carbonate, potassium carbonate, the concentration range of each ingredient are as follows:
10~50g/L of sodium hydroxide, 10~50g/L of potassium hydroxide, 5~20g/L of sodium carbonate, 5~20g/L of potassium carbonate, surplus are water.
The film layer preparation method of the anti-corrosion chemical composition coating of aluminum alloy surface Chrome-free, acid-wash activation solution be sulfuric acid,
The mixed aqueous solution of one or more of nitric acid, hydrofluoric acid, acetic acid, hydrochloric acid, the concentration range of each ingredient are as follows: sulfuric acid 10
~100mL/L, 30~300mL/L of nitric acid, 10~100mL/L of hydrofluoric acid, 5~50mL/L of acetic acid, 5~50mL/L of hydrochloric acid, surplus
For water.
The film layer preparation method of the anti-corrosion chemical composition coating of aluminum alloy surface Chrome-free, before oil removing, to aluminium alloy table
Face carries out polishing or blasting treatment, removes surface imperfection scratch and spot.
The film layer preparation method of the anti-corrosion chemical composition coating of aluminum alloy surface Chrome-free, the film layer of conversion film by nanometer and
Micron-sized spherical particle stacking forms, and even film layer is fine and close.
The film layer preparation method of the anti-corrosion chemical composition coating of aluminum alloy surface Chrome-free, the film layer of conversion film with a thickness of
0.5~2 μm.
The present invention is compared with existing Conversion Coating Technology, is had the advantages that
1, it is free of in the entire process flow of the present invention to the harmful chromate of environment and human body, and film forming procedure is simple, at
Coating solution constituent is cheap, the source chemicals without higher costs such as molybdate, vanadate and rare-earth salts.
2, after conversion film process of the invention, salt spray corrosion resistance has greatly improved aluminium alloy, such as Fig. 2 institute
Show, can achieve and corrosion resisting property similar in commercial chromate conversion coating.
Detailed description of the invention
Fig. 1 is the microscopic appearance photo of conversion film after 5083 aluminum alloy chemically conversion processings in present example
Fig. 2 is the photo in present example after 5083 aluminum alloy chemically conversion processings after 1500h salt spray test.
Specific embodiment
In the specific implementation process, film forming solution provided by the invention is to contain main salt, buffer, film forming accelerating, pH
The mixed solution of regulator and water, the pH of film forming solution are 2~5.Chemical conversion membrane preparation method provided by the invention includes removing
Four oil, alkali cleaning, acid-wash activation and film forming steps, in entire treatment process without chromium or chromate etc. it is environmentally harmful at
Point, film forming procedure is simple, and film forming solution constituent is cheap, gained chemical composition coating even compact, excellent corrosion-proof performance,
The binding force of organic coating and alloy matrix aluminum can be significantly improved.
Below just specific implementation method of the present invention citing detailed description, but protection scope of the present invention be not limited only to it is following
Embodiment.
Embodiment 1
In the present embodiment, aluminum alloy surface Chrome-free is anti-corrosion chemical conversion membrane preparation method is handled by following process flow:
(1) it polishes
It is polished with 1000 mesh sand paper and rolls 5083 aluminum alloy surface of state, aluminum alloy sample is hung for convenience, by aluminium alloy
The punching of sample upper center.
(2) oil removing
Aluminum alloy sample is ultrasonically treated 5 minutes in except oil solution, temperature is room temperature, rinses 1 with circulating water after oil removing
Minute.Wherein, the composition of electrochemical deoiling solution are as follows: 20g/L sodium hydroxide, 20g/L sodium carbonate, 5g/L sodium metasilicate, surplus are water.
(3) alkali cleaning
Aluminum alloy sample after oil removing is immersed in soda-wash solution 20 seconds, soda-wash solution temperature is room temperature, is used after alkali cleaning
Circulating water rinses 1 minute.Wherein, soda-wash solution are as follows: the sodium hydroxide of 50g/L, surplus are water.
(4) acid-wash activation
Aluminum alloy sample after alkali cleaning is immersed in immersion treatment 1 minute in acid-wash activation liquid, the aluminium alloy sample after activation
Product are rinsed 1 minute with circulating water, and acid-wash activation solution temperature is 20 DEG C.Wherein, acid-wash activation liquid form are as follows: 50mL/L nitric acid and
The mix acid liquor of 50mL/L hydrofluoric acid, surplus are water.
(5) it forms a film
It will be reacted 10 minutes in the film forming solution of 5083 aluminum alloy samples rinsed well suspension at room temperature, after film forming
After aluminum alloy sample cleans 1 minute with deionized water, naturally dry at room temperature.The composition of film forming solution are as follows: 10g/L di(2-ethylhexyl)phosphate
Hydrogen sodium, 1g/L disodium-hydrogen, 4g/L sodium fluoride, 1.5mL/L phosphoric acid, 1g/L potassium fluotitanate, 0.5g/L zirconium nitrate, surplus are
Water.
Performance test: after 5083 aluminum alloy samples after film forming place 12 hours at room temperature, the film layer of conversion film is by receiving
Rice and micron-sized spherical particle stacking form, and even film layer is fine and close.As shown in Figure 1, the thickness of the film layer of conversion film is about 1.3
μm.Salt spray test is carried out according to ASTM B-117, by the salt spray test of 1500h as shown in Fig. 2, observation aluminum alloy sample surface
Known to corrosion condition: slight erosion occurs for aluminum alloy sample surface, only observes that several places significantly corrode, therefore nothing of the invention
Chromaking conversion treatment process shows excellent corrosion resistance.
Table 1 is attached with epoxy coating after 5083 aluminum alloy chemically conversion processings in present example and mechanical blasting treatment
Put forth effort to compare.
Table 1
| Blasting treatment | Chemical conversion treatment | |
| Adhesive force (MPa) | 5.0 | 10.9 |
By the adhesive force test result of table 1 it is found that by chemical conversion treatment of the invention, alloy matrix aluminum and epoxy are applied
The more traditional mechanical blasting treatment of the adhesive force of layer improves 1 times.As it can be seen that the anti-corrosion chemistry of aluminum alloy surface Chrome-free provided by the invention
Conversion film film forming solution and film layer preparation method can not only greatly improve the corrosion resistance of alloy matrix aluminum, show simultaneously
Write the adhesive force of enhancing organic coating and alloy matrix aluminum.
Embodiment 2
In the present embodiment, aluminum alloy surface Chrome-free is anti-corrosion chemical conversion membrane preparation method is handled by following process flow:
(1) it polishes
It is polished with 1000 mesh sand paper and rolls 6061 aluminum alloy surface of state, aluminum alloy sample is hung for convenience, by aluminium alloy
The punching of sample upper center.
(2) oil removing
Aluminum alloy sample is ultrasonically treated 3 minutes in except oil solution, temperature is room temperature, is rinsed after oil removing with circulating water
1.5 minute.Wherein, the composition of electrochemical deoiling solution are as follows: 10g/L potassium hydroxide, 20g/L potassium carbonate, 3g/L sodium metasilicate, surplus are
Water.
(3) alkali cleaning
Aluminum alloy sample after oil removing is immersed in soda-wash solution 30 seconds, soda-wash solution temperature is room temperature, is used after alkali cleaning
Circulating water rinses 2 minutes.Wherein, soda-wash solution are as follows: the sodium hydroxide of 20g/L, the sodium carbonate of 20g/L, surplus are water.
(4) acid-wash activation
Aluminum alloy sample after alkali cleaning is immersed in immersion treatment 5 minutes in acid-wash activation liquid, the aluminium alloy sample after activation
Product are rinsed 2 minutes with circulating water, and acid-wash activation solution temperature is 40 DEG C.Wherein, acid-wash activation liquid forms are as follows: the nitre of 50mL/L
Acid, surplus are water.
(5) it forms a film
It will be reacted 20 minutes in the film forming solution of 6061 aluminum alloy samples rinsed well suspension at room temperature, after film forming
After aluminum alloy sample cleans 2 minutes with deionized water, naturally dry at room temperature.The composition of film forming solution are as follows: 15g/L di(2-ethylhexyl)phosphate
Hydrogen sodium, 1g/L disodium-hydrogen, 8g/L sodium fluoride, 1mL/L phosphoric acid, 0.5g/L potassium fluorozirconate, surplus are water.
Performance test: after 6061 aluminum alloy samples after film forming place 12 hours at room temperature, the film layer of conversion film is by receiving
Rice and micron-sized spherical particle stacking form, and even film layer is fine and close, the film layer of conversion film with a thickness of 1.2 μm.According to ASTM
B-117 carries out salt spray test, and by the salt spray test of 300h, slight erosion, therefore the present invention only occur for aluminum alloy sample surface
Chrome-free chemistry conversion treatment process show excellent corrosion resistance.
By chemical conversion treatment of the invention, the more traditional mechanical sandblasting of the adhesive force of alloy matrix aluminum and epoxy coating
Processing improves 1 times.As it can be seen that the anti-corrosion chemical composition coating film forming solution of aluminum alloy surface Chrome-free provided by the invention and film layer preparation side
Method can not only greatly improve the corrosion resistance of alloy matrix aluminum, while significantly increase organic coating and alloy matrix aluminum
Adhesive force.
Embodiment 3
In the present embodiment, aluminum alloy surface Chrome-free is anti-corrosion chemical conversion membrane preparation method is handled by following process flow:
(1) it polishes
It is polished with 1000 mesh sand paper and rolls 2024 aluminum alloy surface of state, aluminum alloy sample is hung for convenience, by aluminium alloy
The punching of sample upper center.
(2) oil removing
Aluminum alloy sample is ultrasonically treated 12 minutes in except oil solution, temperature is room temperature, rinses 2 with circulating water after oil removing
Minute.Wherein, the composition of electrochemical deoiling solution are as follows: 20g/L sodium carbonate, 10g/L sodium phosphate, 5g/L sodium metasilicate, 3g/L dodecane
Base benzene sulfonic acid sodium salt, surplus are water.
(3) alkali cleaning
Aluminum alloy sample after oil removing is immersed in soda-wash solution 60 seconds, soda-wash solution temperature is room temperature, is used after alkali cleaning
Circulating water rinses 1.5 minutes.Wherein, soda-wash solution are as follows: the potassium hydroxide of 30g/L, the sodium carbonate of 15g/L, surplus are water.
(4) acid-wash activation
Aluminum alloy sample after alkali cleaning is immersed in immersion treatment 3 minutes in acid-wash activation liquid, the aluminium alloy sample after activation
Product are rinsed 1.5 minutes with circulating water, and acid-wash activation solution temperature is 30 DEG C.Wherein, acid-wash activation liquid forms are as follows: 90mL/L nitre
The mix acid liquor of acid, 5mL/L acetic acid, surplus is water.
(5) it forms a film
It will be reacted 25 minutes in the film forming solution of 2024 aluminum alloy samples rinsed well suspension at room temperature, after film forming
After aluminum alloy sample cleans 1.5 minutes with deionized water, naturally dry at room temperature.The composition of film forming solution are as follows: 10g/L carbonic acid
Sodium dihydrogen, 4g/L ammonium dihydrogen phosphate, 3g/L sodium fluoride, 5g/L sodium nitrate, 2.5mL/L tartaric acid, 0.5g/L potassium fluotitanate,
0.5g/L zirconium carbonate ammonium, 0.5g/L zirconium nitrate, surplus are water.
Performance test: after 2024 aluminum alloy samples after film forming place 12 hours at room temperature, the film layer of conversion film is by receiving
Rice and micron-sized spherical particle stacking form, the film layer of conversion film with a thickness of 1 μm.Salt fog examination is carried out according to ASTM B-117
It tests, by the salt spray test of 200h, slight erosion, therefore Chrome-free chemical conversion treatment of the invention occur for aluminum alloy sample surface
Technical expression goes out excellent corrosion resistance.
By chemical conversion treatment of the invention, the more traditional mechanical sandblasting of the adhesive force of alloy matrix aluminum and epoxy coating
Processing improves 1 times.As it can be seen that the anti-corrosion chemical composition coating film forming solution of aluminum alloy surface Chrome-free provided by the invention and film layer preparation side
Method can not only greatly improve the corrosion resistance of alloy matrix aluminum, while significantly increase organic coating and alloy matrix aluminum
Adhesive force.
Claims (10)
1. a kind of anti-corrosion chemical composition coating film forming solution of aluminum alloy surface Chrome-free, which is characterized in that the film forming solution be containing
There is the mixed solution of main salt, buffer, film forming accelerating, pH adjusting agent and water, the pH of film forming solution is 2~5；Wherein:
Main salt be titanium sulfate, Titanium Nitrate, titanium sodium fluoride, potassium fluotitanate, ammonium titanium fluoride, zirconium carbonate ammonium, zirconium nitrate, potassium fluorozirconate,
One or more kinds of mixtures of sodium fluozirconate, ammonium fluozirconate, main salt concentration range are 0.1~20g/L；
Buffer be sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid, organic phospho acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide, monoammonium phosphate,
Ammonium dihydrogen phosphate, tertiary sodium phosphate, disodium-hydrogen, sodium dihydrogen phosphate, tripotassium phosphate, potassium phosphate,monobasic, potassium dihydrogen phosphate, carbonic acid
One or more kinds of compoundings of sodium, sodium bicarbonate, potassium carbonate, saleratus, ammonium hydrogen carbonate, buffer concentration is 1~
30g/L；
Film forming accelerating is sodium fluoride, potassium fluoride, sodium bifluoride, potassium hydrogen fluoride, ammonium acid fluoride, sodium nitrate, potassium nitrate, ammonium nitrate
One or more, film forming accelerating concentration be 1~15g/L.
2. the anti-corrosion chemical composition coating film forming solution of aluminum alloy surface Chrome-free according to claim 1, which is characterized in that pH value
Regulator is sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid, organic phospho acid, citric acid, fluotitanic acid, fluorine zirconic acid, tartaric acid, acetic acid, hydrogen-oxygen
Change one or more kinds of compoundings of sodium, potassium hydroxide, ammonium hydroxide, pH adjusting agent content is 0.5~5mL/L.
3. the anti-corrosion chemical composition coating film forming solution of aluminum alloy surface Chrome-free according to claim 1, which is characterized in that preferably
The concentration of main salt be 0.5~10g/L, the concentration of buffer is 5~20g/L, and the concentration of promotor is 5~10g/L.
4. a kind of film layer preparation side of the anti-corrosion chemical composition coating of aluminum alloy surface Chrome-free using film forming solution described in claim 1
Method, which is characterized in that this method includes four oil removing, alkali cleaning, acid-wash activation and film forming steps, in which:
(1) oil removing
Aluminium alloy is immersed in except being ultrasonically treated 2~15 minutes in oil solution, oil removing solution temperature controls between 15~40 DEG C,
It is rinsed 1~2 minute after oil removing with flowing water；
(2) alkali cleaning
Aluminium alloy after oil removing is immersed in soda-wash solution 10 seconds~5 minutes, soda-wash solution temperature control 15~40 DEG C it
Between, it is rinsed 1~2 minute after alkali cleaning with flowing water；
(3) acid-wash activation
Aluminium alloy after alkali cleaning is immersed in acid-wash activation solution 0.5~10 minute, acid-wash activation solution temperature is controlled 15
Between~40 DEG C, rinsed 1~2 minute after activation with flowing water；
(4) it forms a film
Aluminium alloy after acid-wash activation is immersed in film forming solution, is carried out film formation reaction 1~40 minute, film forming solution temperature control
System is cleaned 1~2 minute with flowing water after reaction, is placed in air, at room temperature naturally dry between 15~50 DEG C.
5. the film layer preparation method of the anti-corrosion chemical composition coating of aluminum alloy surface Chrome-free according to claim 4, feature exist
In solution used in oil removing is sodium hydroxide, in potassium hydroxide, sodium carbonate, sodium phosphate, sodium metasilicate, neopelex
One or more kinds of mixed aqueous solutions, the concentration range of each ingredient are as follows: 10~50g/L of sodium hydroxide, potassium hydroxide 10
~50g/L, 5~20g/L of sodium carbonate, 5~20g/L of potassium carbonate, 2~40g/L of sodium phosphate, 3~25g/L of sodium metasilicate, dodecyl
1~10g/L of benzene sulfonic acid sodium salt, surplus are water.
6. the film layer preparation method of the anti-corrosion chemical composition coating of aluminum alloy surface Chrome-free according to claim 4, feature exist
In solution used in alkali cleaning is the mixing water of one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate
Solution, the concentration range of each ingredient are as follows: 10~50g/L of sodium hydroxide, 10~50g/L of potassium hydroxide, 5~20g/L of sodium carbonate, carbon
Sour 5~20g/L of potassium, surplus are water.
7. the film layer preparation method of the anti-corrosion chemical composition coating of aluminum alloy surface Chrome-free according to claim 4, feature exist
In acid-wash activation solution is the mixed aqueous solution of one or more of sulfuric acid, nitric acid, hydrofluoric acid, acetic acid, hydrochloric acid, respectively
The concentration range of ingredient are as follows: 10~100mL/L of sulfuric acid, 30~300mL/L of nitric acid, 10~100mL/L of hydrofluoric acid, acetic acid 5~
50mL/L, 5~50mL/L of hydrochloric acid, surplus are water.
8. the film layer preparation method of the anti-corrosion chemical composition coating of aluminum alloy surface Chrome-free according to claim 4, feature exist
In carrying out polishing or blasting treatment to aluminum alloy surface, remove surface imperfection scratch and spot before oil removing.
9. the film layer preparation method of the anti-corrosion chemical composition coating of aluminum alloy surface Chrome-free according to claim 4, feature exist
In the film layer of conversion film is formed by nanometer and micron-sized spherical particle stacking, and even film layer is fine and close.
10. the film layer preparation method of the anti-corrosion chemical composition coating of aluminum alloy surface Chrome-free according to claim 4 or 9, special
Sign is, the film layer of conversion film with a thickness of 0.5~2 μm.
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