CN108018591A - A kind of aluminium and aluminium alloy anode oxide film are without nickel free-floride sealer - Google Patents
A kind of aluminium and aluminium alloy anode oxide film are without nickel free-floride sealer Download PDFInfo
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- CN108018591A CN108018591A CN201711235426.5A CN201711235426A CN108018591A CN 108018591 A CN108018591 A CN 108018591A CN 201711235426 A CN201711235426 A CN 201711235426A CN 108018591 A CN108018591 A CN 108018591A
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- aluminium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/246—Chemical after-treatment for sealing layers
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Abstract
The invention discloses a kind of aluminium and aluminium alloy anode oxide film without nickel free-floride sealer, it is made of following component：1 15g/L hydration accelerators, 0.1 5g/L pH buffers, the grey agent L of 0.01 1g/ suppressions, 0.1 0.5g/L wetting agents, surplus is deionized water.Inventive closure agent not only can be to avoid the heavy metal pollution in wastewater treatment, it can also obtain the good oxide-film of corrosion resistance, meet 8753.1 2005 phosphorus chromic acid requirement of experiment of GB/T, even film layer is smooth, resistance to dye speck performance is good, can meet true qualities anode oxide film at the same time, dye the sealing of hole of anode oxide film.The present invention is concentrated type formula, and preparation method is simple, easy to operate.
Description
Technical field
The present invention relates to aluminium and aluminium alloy anode oxide post-processing technology field, and in particular to a kind of aluminium and aluminum alloy anode
Oxide-film is without nickel free-floride sealer.
Background technology
Aluminium and its alloy material have a series of excellent physical and chemical performances, can meet building decoration, cosmetics with
And the different requirements that the industry such as electronic information proposes aluminum and aluminum alloy mateial.But some of aluminium and aluminium alloy performances
Such as the defects of wearability and corrosion resistance cannot be met the requirements, and process for treating surface can effectively make up this aspect.Industrially
Main process for treating surface to be used is anodic oxidation, and aluminium and aluminium alloy generate the controllable porous knot of thickness after anodic oxidation
The anode oxide film of structure, has bond strength, hardness, wearability and the consistency of higher, has greatly widened aluminium and aluminium closes
The use scope of gold, but anode oxide film is loose structure, be easily corroded erosion medium resistance, and corrosion resistance declines.
In practical applications, it is necessary to carry out sealing pores for oxide-film, the adsorptivity of oxide-film is reduced with this, is improved
Its surface anti-pollution ability, corrosion resistance and electrical insulating property.However, the closing skill of existing aluminium and aluminium alloy anode oxide film
Art is sealer host agent usually using metal salt, mostly containing fluorine, nickel, not only results in cost for wastewater treatment height, pollutes environment,
Human body is damaged at the same time larger.Therefore exploitation is without nickel fluorine-free and environment-friendly sealer, has a vast market prospect and significant
Social benefit.
The content of the invention
It is an object of the present invention to provide a kind of aluminium and aluminium alloy anode oxide film without nickel free-floride sealer, to solve the prior art
Deficiency.
The present invention uses following technical scheme：
A kind of aluminium and aluminium alloy anode oxide film are made of without nickel free-floride sealer following component：
Further, one or more of the hydration accelerator in sorbose, trehalose, mannitol.
Further, one or more of the pH buffer in ammonium acetate, sodium acetate, boric acid.
Further, one or more of the grey agent in benzene sulfonic acid sodium salt, neopelex are pressed down.
Further, wetting agent is sodium 2-ethylhexyl sulfate.
The above-mentioned preparation method of aluminium and aluminium alloy anode oxide film without nickel free-floride sealer, includes the following steps：Will formula
The hydration accelerator of amount, pH buffer, the grey agent of suppression, wetting agent are added in deionized water, are uniformly mixed, are obtained the sealer.
The application method of the aluminium and aluminium alloy anode oxide film of above-mentioned preparation without nickel free-floride sealer, includes the following steps：
Sealer is diluted to 3-20ml/L with deionized water, and adjusts pH to 5.5-6.5 and obtains working solution, at 75-95 DEG C, will be treated
Closed work piece, which is immersed in working solution, to be closed, and speed in a closed circuit is 1.0-2.0min/ μm.
Further, pH to 5.8-6.2 is adjusted.
Further, pH is adjusted with acetic acid and sodium acetate.
Further, at 85-90 DEG C, workpiece to be closed is immersed in working solution and is closed.
Beneficial effects of the present invention：
Inventive closure agent not only it is good can also to obtain corrosion resistance to avoid the heavy metal pollution in wastewater treatment
Oxide-film, meet GB/T 8753.1-2005 phosphorus chromic acid requirement of experiment, even film layer is smooth, and resistance to dye speck performance is good, energy
Meet true qualities anode oxide film at the same time, dye the sealing of hole of anode oxide film.The present invention is concentrated type formula, and preparation method is simple,
It is easy to operate.
Embodiment
The present invention is done with reference to embodiment and is further explained.The following example is merely to illustrate the present invention, but
It is not used to limit the practical range of the present invention.
A kind of aluminium and aluminium alloy anode oxide film are made of without nickel free-floride sealer following component：
Wherein, one or more of the hydration accelerator in sorbose, trehalose, mannitol；PH buffer is selected from
One or more in ammonium acetate, sodium acetate, boric acid；The one kind of the grey agent of suppression in benzene sulfonic acid sodium salt, neopelex
It is or several；Wetting agent is sodium 2-ethylhexyl sulfate.
The above-mentioned preparation method of aluminium and aluminium alloy anode oxide film without nickel free-floride sealer, includes the following steps：Will formula
The hydration accelerator of amount, pH buffer, the grey agent of suppression, wetting agent are added in deionized water, are uniformly mixed, are obtained the sealer.
The application method of the aluminium and aluminium alloy anode oxide film of above-mentioned preparation without nickel free-floride sealer, includes the following steps：
Sealer is diluted to 3-20ml/L with deionized water, and pH to 5.5-6.5 is adjusted with acetic acid and sodium acetate, preferably adjusts pH
To 5.8-6.2, working solution is obtained, at 75-95 DEG C, preferably at 85-90 DEG C, workpiece to be closed is immersed in working solution and is carried out
Closing, speed in a closed circuit are 1.0-2.0min/ μm.
Following embodiments and comparative example test detection oxide-film seal quality according to GB/T 8753.1-2005 phosphorus chromic acid, molten
Liquid is prepared and experimental method is as follows：
Phosphorus chromic acid solution：20g chromium trioxides and 35ml85% phosphoric acid (ρ=1.7g/ml) are weighed in 500ml pure water, it is molten
Solution is completely rear to move into 1000ml volumetric flasks, is diluted to scale with pure water, mixes；
Experimental method：First sample is dried and is weighed, then sample is erectly completely immersed in and is previously heated to 38 ± 1 DEG C
Phosphorus chromic acid solution in, take out sample after soaking 15min, rinse well, then be dried, weigh, calculate every square decimeter of oxygen
Change the mass loss of film；Criterion：Recommended standard GB/T 8013.1-2007, test result are less than 30mg/dm2 for qualification.
Following embodiments and comparative example judge anode oxide film sealing of hole presentation quality using ocular estimate, close dried sun
Pole oxide-film is qualification without obvious lime, discoloration, water stain, evidence of corrosion etc., checks oxidation film surface dusting.
Following embodiments and comparative example are according to the dye speck method evaluation oxide-film after GB/T8753.4-2005 acid treatments
Anti-pollution energy：
Solution is formulated as follows:
Acid solution A：25ml98% sulfuric acid is pipetted, 10g potassium fluorides is weighed in 1000ml volumetric flasks, is slowly diluted with water to
Scale；
Dye solution B：5g aluminium indigo plant 2LW solution (national standard color code is 69 blue dyeing agent) is pipetted in 1000ml capacity
In bottle, solution ph is adjusted to 5.0 ± 0.5 (temperature is about 23 DEG C) with 5% sulfuric acid of mass fraction or 5% sodium hydroxide；
Laboratory operating procedures：
1st, dropped in 1 drop acid solution A on the surface of workpiece for measurement, and accurately (experimental solutions temperature is 23 to holding 1min
℃)；
2nd, acid drop is removed, by the cleaning, drying of workpiece for measurement surface；
3rd, dropped in 1 drop dye solution B on the spot with acid-treated workpiece for measurement surface, and treating solution
Survey workpiece surface and accurately keep 1min；
4th, dyestuff drop is cleaned, and it is dry；
5th, grade with the contrast of dye speck experimental result evaluation form.
Following embodiments and comparative example carry out effect experiment and comprise the following steps that：
First, aluminium alloy anode oxide film is prepared
1st, 1060 Al alloy parts of model are immersed in degreasing agent ODM ALCLEAN 10 and carries out ungrease treatment, time
5min, 55 DEG C of temperature, it is intended to remove the greasy dirt and other inorganic pollutions of workpiece surface, then rinsed with tap water；
2nd, then workpiece is continued to immerse and microetch processing, time 1min, temperature 55 is carried out in micro-etching agent ODM ALETCH M
DEG C, it is intended to the natural oxide film of workpiece surface is removed, exposes aluminum alloy material matrix, tap water rinses；
3rd, workpiece is immersed in stain remover ODM DESMUT GE and carried out except stain is handled, time 1min, 30 DEG C of temperature, it is intended to
Neutralize the acid on microetch processing surface and carry out ash disposal processing, tap water rinses；
4th, will workpiece immerse the oxidation trough containing sulfuric acid in carry out anodic oxidation, be put into content for 98% sulfuric acid of 180g/L,
Aluminium ion 5g/L is (with Al3+Meter) in electrolyte sulfuric acid solution, DC anodizing is determined at a temperature of 20 ± 2 DEG C 40 minutes, electric current
Density is 1A/dm2, film thickness 10-12um；Tap water is washed after workpiece is taken out in power-off, deionization washing；To be dyed or closing
Processing.
2nd, aluminium alloy anode oxide film dyes
Workpiece will be aoxidized to be immersed in dyestuff ODM DYE BLACK (BK945) solution, concentration 10g/L, 55 DEG C of temperature,
10 minutes time, processing to be closed after deionized water cleaning.
3rd, the dyeing workpiece Jing Guo above-mentioned steps one, two is immersed in following examples and comparative example confining liquid and carried out
Sealing of hole, is cleaned after closing with deionized water, and the presentation quality of film is observed after dry.
4th, the workpiece Jing Guo above-mentioned steps one is immersed in following examples and comparative example confining liquid and carries out sealing of hole,
Cleaned after closing with deionized water, the chromic acid of the resistance to phosphorus test of film is observed after dry, it is real according to GB/T 8753.1-2005 phosphorus chromic acid
Test detection oxide-film seal quality.
5th, the workpiece Jing Guo above-mentioned steps one is immersed in following examples and comparative example confining liquid and carries out sealing of hole,
Cleaned after closing with deionized water, the resistance to stain test of film is observed after dry, after GB/T8753.4-2005 acid treatments
Dye speck method evaluates the anti-pollution energy of oxide-film.
Embodiment 1：
After following combinatorial weighing, deionized water is added, the solution of 10L is configured to, 90 DEG C is heated to, at sealing of hole
Reason：
Comparative example 1
After following combinatorial weighing, deionized water is added, the solution of 10L is configured to, 90 DEG C is heated to, at sealing of hole
Reason：
Ammonium acetate 20g
Neopelex 8g
Sodium 2-ethylhexyl sulfate 2g
Deionized water：Surplus
Process conditions：PH6.0 (is adjusted) with acetic acid and sodium acetate；Closure temperature：90℃；Off-period：20min.Effect
Experimental result is as shown in table 1：
Table 1
The hydration facilitation effect that trehalose in sealer has had for the phosphorus chromic acid experiment test of closing, can significantly drop
The weightlessness of low-phosphorous chromic acid and the anti-pollution power of lifting stain.
Embodiment 2：
After following combinatorial weighing, deionized water is added, the solution of 10L is configured to, 90 DEG C is heated to, at sealing of hole
Reason：
Comparative example 2
After following combinatorial weighing, deionized water is added, the solution of 10L is configured to, 90 DEG C is heated to, at sealing of hole
Reason：
Sorbierite 50g
Ammonium acetate 20g
Sodium 2-ethylhexyl sulfate 2g
Deionized water：Surplus
Process conditions：PH6.0 (is adjusted) with acetic acid and sodium acetate；Closure temperature：90℃；Off-period：20min.Effect
Experimental result is as shown in table 2：
Table 2
The inhibition that neopelex in sealer has had for the presentation quality test of closing, can be preferably
Ground suppresses film surface dusting.
Embodiment 3：
After following combinatorial weighing, deionized water is added, the solution of 10L is configured to, 90 DEG C is heated to, at sealing of hole
Reason：
Comparative example 3
After following combinatorial weighing, deionized water is added, the solution of 10L is configured to, 90 DEG C is heated to, at sealing of hole
Reason：
Trehalose 50g
Sodium acetate 15g
Benzene sulfonic acid sodium salt 8g
Deionized water：Surplus
Process conditions：PH6.0 (is adjusted) with acetic acid and sodium acetate；Closure temperature：90℃；Off-period：20min.Effect
Experimental result is as shown in table 3：
Table 3
The antifouling effect that sodium 2-ethylhexyl sulfate in sealer has had for the dye speck test of closing, can be preferably
Ground reduces dye speck pollution.
Claims (10)
1. a kind of aluminium and aluminium alloy anode oxide film are without nickel free-floride sealer, it is characterised in that are made of following component：
Surplus is deionized water.
2. aluminium according to claim 1 and aluminium alloy anode oxide film are without nickel free-floride sealer, it is characterised in that hydration promotees
Into one or more of the agent in sorbose, trehalose, mannitol.
3. aluminium according to claim 1 and aluminium alloy anode oxide film are without nickel free-floride sealer, it is characterised in that pH is buffered
One or more of the agent in ammonium acetate, sodium acetate, boric acid.
4. aluminium according to claim 1 and aluminium alloy anode oxide film are without nickel free-floride sealer, it is characterised in that the grey agent of suppression
One or more in benzene sulfonic acid sodium salt, neopelex.
5. aluminium according to claim 1 and aluminium alloy anode oxide film are without nickel free-floride sealer, it is characterised in that wetting agent
For sodium 2-ethylhexyl sulfate.
6. the preparation side of aluminium and aluminium alloy anode oxide film without nickel free-floride sealer described in claim 1-5 any claims
Method, it is characterised in that include the following steps：The hydration accelerator of formula ratio, pH buffer, the grey agent of suppression, wetting agent are added to
In ionized water, it is uniformly mixed, obtains the sealer.
7. the application method of aluminium and aluminium alloy anode oxide film without nickel free-floride sealer prepared by claim 6, it is characterised in that
Include the following steps：Sealer is diluted to 3-20ml/L with deionized water, and adjusts pH to 5.5-6.5 and obtains working solution,
At 75-95 DEG C, workpiece to be closed is immersed in working solution and is closed, speed in a closed circuit is 1.0-2.0min/ μm.
8. the application method of aluminium according to claim 7 and aluminium alloy anode oxide film without nickel free-floride sealer, its feature
It is, adjusts pH to 5.8-6.2.
9. the application method of aluminium according to claim 7 and aluminium alloy anode oxide film without nickel free-floride sealer, its feature
It is, pH is adjusted with acetic acid and sodium acetate.
10. the application method of aluminium according to claim 7 and aluminium alloy anode oxide film without nickel free-floride sealer, its feature
It is, at 85-90 DEG C, workpiece to be closed is immersed in working solution and is closed.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711235426.5A CN108018591A (en) | 2017-11-30 | 2017-11-30 | A kind of aluminium and aluminium alloy anode oxide film are without nickel free-floride sealer |
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| CN201711235426.5A CN108018591A (en) | 2017-11-30 | 2017-11-30 | A kind of aluminium and aluminium alloy anode oxide film are without nickel free-floride sealer |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108950645A (en) * | 2018-09-28 | 2018-12-07 | 上海铝通化学科技有限公司 | A kind of aluminium and aluminium alloy anode oxide are without nickel sealer |
| CN110029389A (en) * | 2019-04-17 | 2019-07-19 | 安徽华淮新材料有限公司 | Remove the solution of aluminium alloy anode oxide film sealing of hole ash |
| CN110241449A (en) * | 2019-06-24 | 2019-09-17 | 辽宁忠旺集团有限公司 | A kind of method of 6 line aluminium alloy surface insulation oxidation |
| CN111793817A (en) * | 2019-04-09 | 2020-10-20 | 平顶山市美伊金属制品有限公司 | Preparation method of aluminum alloy anodic oxide film |
| CN113026074A (en) * | 2021-03-01 | 2021-06-25 | 佛山市广成铝业有限公司 | Preparation method of wear-resistant anodic aluminum oxide profile |
| CN113279035A (en) * | 2021-05-15 | 2021-08-20 | 江门市优博科技有限公司 | Novel sealing agent for aluminum and aluminum alloy anodic oxide film and preparation method thereof |
| CN114855240A (en) * | 2022-05-17 | 2022-08-05 | 山东南山铝业股份有限公司 | Medium-temperature hole sealing hydration experiment process |
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| CN101864589A (en) * | 2010-06-11 | 2010-10-20 | 武汉材料保护研究所 | Metal salt-free sealing agent for aluminum alloy anodic oxide film |
| CN103668387A (en) * | 2012-09-03 | 2014-03-26 | 台山市科美金属表面处理技术有限公司 | Practical nickel-free sealing agent for aluminum alloy anodic oxidation |
| CN107130278A (en) * | 2017-05-22 | 2017-09-05 | 深圳市梦之坊通信产品有限公司 | The method for dyeing current mark suppressant additive and aluminum alloy anode dyeing |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101864589A (en) * | 2010-06-11 | 2010-10-20 | 武汉材料保护研究所 | Metal salt-free sealing agent for aluminum alloy anodic oxide film |
| CN103668387A (en) * | 2012-09-03 | 2014-03-26 | 台山市科美金属表面处理技术有限公司 | Practical nickel-free sealing agent for aluminum alloy anodic oxidation |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108950645A (en) * | 2018-09-28 | 2018-12-07 | 上海铝通化学科技有限公司 | A kind of aluminium and aluminium alloy anode oxide are without nickel sealer |
| CN111793817A (en) * | 2019-04-09 | 2020-10-20 | 平顶山市美伊金属制品有限公司 | Preparation method of aluminum alloy anodic oxide film |
| CN110029389A (en) * | 2019-04-17 | 2019-07-19 | 安徽华淮新材料有限公司 | Remove the solution of aluminium alloy anode oxide film sealing of hole ash |
| CN110029389B (en) * | 2019-04-17 | 2020-10-16 | 安徽华淮新材料有限公司 | Solution for removing hole sealing ash of aluminum alloy anodic oxide film |
| CN110241449A (en) * | 2019-06-24 | 2019-09-17 | 辽宁忠旺集团有限公司 | A kind of method of 6 line aluminium alloy surface insulation oxidation |
| CN113026074A (en) * | 2021-03-01 | 2021-06-25 | 佛山市广成铝业有限公司 | Preparation method of wear-resistant anodic aluminum oxide profile |
| CN113279035A (en) * | 2021-05-15 | 2021-08-20 | 江门市优博科技有限公司 | Novel sealing agent for aluminum and aluminum alloy anodic oxide film and preparation method thereof |
| CN114855240A (en) * | 2022-05-17 | 2022-08-05 | 山东南山铝业股份有限公司 | Medium-temperature hole sealing hydration experiment process |
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