CN106245088A - A kind of aluminium alloy anode oxide film is without nickel free-floride cold sealing agent - Google Patents
A kind of aluminium alloy anode oxide film is without nickel free-floride cold sealing agent Download PDFInfo
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- CN106245088A CN106245088A CN201610785277.9A CN201610785277A CN106245088A CN 106245088 A CN106245088 A CN 106245088A CN 201610785277 A CN201610785277 A CN 201610785277A CN 106245088 A CN106245088 A CN 106245088A
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- floride
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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
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Abstract
The present invention relates to a kind of aluminium alloy anode oxide film without nickel free-floride cold sealing agent, the raw material of described sealer is calculated as with 1L: slaine, 8 16g；Stabilizer, 0.5 3g；Corrosion inhibiter, 0.8 2.5g；Oxidant, 0.3 1g；Surfactant, 0.2 4g；PH buffer agent, 3.5 16g；Deionized water, addition is to add deionized water after remaining raw material mixes to be settled to the amount of 1L.It is an advantage of the current invention that: aluminium alloy anode oxide film of the present invention, without nickel free-floride cold sealing agent, has rapid osmotic function, it is possible to by micropore adequate closure, be effectively increased the etch resistant properties of metal surface；And sealer physics and chemical stability good, additive be not easily decomposed and can life-time service, saved production cost；After sealing of hole, surface of the work bright property is good, and wearability and hardness are greatly improved, and effectively prevent that the partial pore occurred because of sealing of hole poor effect is unclosed, surface of the work has the problem such as Refined Mercurous chloride and sealing of hole rear oxidation film difference against corrosion after sealing of hole.
Description
Technical field
The present invention relates to Aurum metallicum technical field of surface, floride-free without nickel particularly to a kind of aluminium alloy anode oxide film
Cold sealing agent.
Background technology
Aluminum and aluminium alloy generate oxide-film after anodic oxidation, and surface distributed the micropore of rule, and porosity is about 5%-
30%.These holes are that some dirts in environment enter film body and provide passage, the hardness of the film layer the most just aoxidized,
Wear-resisting poor with corrosion resistance.Therefore, oxide-film sealing of hole is the requisite operation of aluminum products industry.At present, the side of sealing pores
Method is a lot, mainly has: water and the method for closing, hydrolysis salt closing method, organic acid close method and nickel fluorine system cold sealing method etc..Water and
In closing method, the temperature of sealing of hole is high, and energy consumption is big, and time-consuming long and sealing of hole quality is difficult to ensure that.The principle of method closed by hydrolysis salt is gold
Belong in saline solution enters anodic oxidation membrane micropore and hydrolyzing, produce slaine hydroxide precipitation and micropore is closed, used
Slaine be mainly nickel salt.Organic acid close method, the surface of the work after closing have one layer of white oil film, affect outward appearance with
Use, easily sealer is washed from anode oxide film while subsequent handling removes oil film.Low temperature (room temperature) nickel fluorine gold
In genus salt closing method, processing speed is fast, energy consumption is low, sealing of hole is effective, but fluorinion concentration need to frequently adjust, to process stabilizing
Property bring greatly harm, due to nickel, the use of fluorine, it will environment to be caused bigger pollution.
Domestic prior art discloses some about aluminum and the research of aluminum alloy anodic oxide film sealant, patent
CN101665970A discloses aluminum and aluminium alloy anode oxide film normal-temperature sealer and enclosure method, with NiF2, triethanolamine, six
Methine tetramine, dodecyl sodium sulfate, Refined Mercurous chloride inhibitor are raw material, are prepared into sealer, and low cost, configuration are simple, operation
Easily, improve the contamination resistance of oxide-film, corrosion resisting property and electrical insulation capability good.
Patent CN103952743A discloses a kind of middle temperature aluminum oxidation post-treatment agent, is mainly composed of acetate, color changes
Good dose, dispersant, surface active agent etc., the sealing of hole speed of hole sealing agent is fast, bright property that sealing of hole film layer without Refined Mercurous chloride and has excellence,
The advantage such as planarization and corrosion resistance, but its acetate selected is nickel acetate.
Patent CN103590086A discloses a kind of aluminium alloy without nickel hole sealing agent and hole-sealing treatment process thereof, with fluotitanic acid,
Corrosion inhibiter and chelating agen are that raw material prepares hole sealing agent, and simple to operate, without nickel ion, waste water is disposable, it is easy to large-scale production.
The confining liquid of above-mentioned patent all contains Ni2+Or F-, Ni2+Serious environmental pollution can be caused, be detrimental to health,
Infringement human organ, and F-Respiratory system can be damaged, cause Acute Fluorine, and have environment pollution, more fluoride to make
Follow-up waste water treatmentntrol difficult, is unsatisfactory for national requirements for environmental protection.
Therefore, develop the most nickeliferous a kind of, fluorine etc. to human body and the element of bad environmental, safety and environmental protection, can quickly ooze again
Thoroughly, after stable performance, and sealing of hole, surface of the work bright property is good, wearability and the high aluminium alloy anode oxide sealer of corrosion resistance
It is particularly important.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of aluminium alloy anode oxide film without nickel free-floride cold sealing agent, logical
Crossing the component and proportioning changed in formula, the most nickeliferous in formula, fluorine etc. is to human body and the element of bad environmental so that be prepared into
Sealer safety and environmental protection, again can surface of the work bright property be good after rapid osmotic, stable performance, and sealing of hole, wearability and anticorrosive
Property high.
For solving above-mentioned technical problem, the technical scheme is that a kind of aluminium alloy anode oxide film is low without nickel free-floride
Temperature sealer, its innovative point is: the raw material of described sealer is calculated as with 1L: slaine, 8-16g；Stabilizer, 0.5-3g；Slow
Erosion agent, 0.8-2.5g；Oxidant, 0.3-1g；Surfactant, 0.2-4g；PH buffer agent, 3.5-16g；Deionized water, adds
Amount adds deionized water after mixing for remaining raw material and is settled to the amount of 1L.
Further, described slaine includes in acetic acid titanium, samaric nitrate, zinc acetate, cadmium nitrate, Yttrium chloride(Y2Cl6) and cerium chloride
At least one.
Further, described stabilizer is that the molecular structural formula of carboxylate derivatives is:
Wherein, R1、R4For the one in hydrogen atom, methyl and ethyl, R2、R3For hydroxyl, amino, phosphonate group, ethyl and hydroxyl
One in methyl.
Further, described corrosion inhibiter is organic carboxyl acid, and molecular structural formula is:
Wherein, R5For the one in hydrogen atom, methyl, carboxymethyl group, methylol, ethoxy and benzyl, R6For hydrogen atom,
One in hydroxyl, amino, methyl, methylol and ethoxy.
Further, described oxidant is potassium permanganate.
Further, described surfactant is AB type block macromolecular surfactant, and molecular structural formula is:
Wherein, R7For the one in hydrogen atom, carboxyl, isopropyl and carbomethoxy, R8For hydroxyl, benzyl, p-methylphenyl and
One in hydrogen atom.
Further, described pH buffer agent includes acetic acid, sodium acetate, ammonia, neck potassium hydrogen phthalate, potassium dihydrogen phosphate
With at least two in phosphoric acid.
It is an advantage of the current invention that: aluminium alloy anode oxide film of the present invention is without nickel free-floride cold sealing agent, with conventional formulation
Comparing, add corrosion inhibiter, surfactant and pH buffer agent, corrosion inhibiter is present in sealer with suitable concentration and form
Time, it is possible to prevent or slows down material and equipment corrosion；Surfactant can align on the surface of solution, and surface can be made to open
Power is remarkably decreased, and has emulsifying and wetting function；PH buffer agent can change the acidity of solution to 4.5～6.5, it is ensured that sealing of hole
The pH condition of reaction, and then make sealer have rapid osmotic function, it is possible to by micropore adequate closure, it is effectively increased metal watch
The etch resistant properties in face；And sealer physics and chemical stability good, additive be not easily decomposed and can life-time service, saved life
Produce cost；When use safeguarded by workpiece, it is not necessary to after adding other additives, and sealing of hole, surface of the work bright property is good, wear-resisting
Property and hardness are greatly improved, and effectively prevent that the partial pore occurred because of sealing of hole poor effect is unclosed, workpiece table after sealing of hole
There is the problem such as Refined Mercurous chloride and sealing of hole rear oxidation film difference against corrosion in face.
Detailed description of the invention
Aluminium alloy anode oxide film of the present invention is without nickel free-floride cold sealing agent, and the raw material of this sealer is calculated as with 1L: metal
Salt, 8-16g；Stabilizer, 0.5-3g；Corrosion inhibiter, 0.8-2.5g；Oxidant, 0.3-1g；Surfactant, 0.2-4g；PH buffers
Agent, 3.5-16g；Deionized water, addition is to add deionized water after remaining raw material mixes to be settled to the amount of 1L.
Specifically, at least during slaine includes acetic acid titanium, samaric nitrate, zinc acetate, cadmium nitrate, Yttrium chloride(Y2Cl6) and cerium chloride
Kind；Stabilizer is that the molecular structural formula of carboxylate derivatives is:
Wherein, R1、R4For the one in hydrogen atom, methyl and ethyl, R2、R3For hydroxyl, amino, phosphonate group, ethyl and hydroxyl
One in methyl；Corrosion inhibiter is organic carboxyl acid, and molecular structural formula is:
Wherein, R5For the one in hydrogen atom, methyl, carboxymethyl group, methylol, ethoxy and benzyl, R6For hydrogen atom,
One in hydroxyl, amino, methyl, methylol and ethoxy；Oxidant is potassium permanganate；Surfactant is that AB type block is high
Molecular surface active agent, molecular structural formula is:
Wherein, R7For the one in hydrogen atom, carboxyl, isopropyl and carbomethoxy, R8For hydroxyl, benzyl, p-methylphenyl and
One in hydrogen atom；PH buffer agent includes in acetic acid, sodium acetate, ammonia, neck potassium hydrogen phthalate, potassium dihydrogen phosphate and phosphoric acid
At least two.
Embodiment 1
The present embodiment aluminium alloy anode oxide film is without nickel free-floride cold sealing agent, and the raw material of this sealer is calculated as with 1L: gold
Belong to salt, 8g；Stabilizer, 3g；Corrosion inhibiter, 2.5g；Oxidant, 1g；Surfactant, 4g；PH buffer agent, 16g；Deionized water,
Addition is to add deionized water after remaining raw material mixes to be settled to the amount of 1L.
In the present embodiment, slaine includes 5g acetic acid titanium and 3g Yttrium chloride(Y2Cl6), and stabilizer is carboxylate derivatives, molecular structure
Formula is:
Wherein, R1For hydrogen atom, R2For amino, R3For amino, R4For methyl；Corrosion inhibiter is organic carboxyl acid, molecular structural formula
For:
Wherein, R5For hydrogen atom, R6For methyl；Surfactant is AB type block macromolecular surfactant, molecular structure
Formula is:
Wherein, R7For isopropyl, R8For benzyl；PH buffer agent includes 8g acetic acid and 8g sodium acetate.
Embodiment 2
Without nickel free-floride cold sealing agent compared with Example 1, each component is constant for the present embodiment aluminium alloy anode oxide film, only
Change the proportioning of each component.
The raw material of the present embodiment sealer is calculated as with 1L: slaine, 16g；Stabilizer, 0.5g；Corrosion inhibiter, 0.8g；Oxidation
Agent, 0.3g；Surfactant, 0.2g；PH buffer agent, 3.5g；Deionized water, addition is to add deionization after remaining raw material mixes
Water is settled to the amount of 1L.
In the present embodiment, slaine includes 10g acetic acid titanium and 8g Yttrium chloride(Y2Cl6), and stabilizer is carboxylate derivatives, molecular structure
Formula is:
Wherein, R1For hydrogen atom, R2For amino, R3For amino, R4For methyl；Corrosion inhibiter is organic carboxyl acid, molecular structural formula
For:
Wherein, R5For hydrogen atom, R6For methyl；Surfactant is AB type block macromolecular surfactant, molecular structure
Formula is:
Wherein, R7For isopropyl, R8For benzyl；PH buffer agent includes 2g acetic acid and 1.5g sodium acetate.
Embodiment 3
Without nickel free-floride cold sealing agent compared with Example 1, each component is constant for the present embodiment aluminium alloy anode oxide film, only
Change the proportioning of each component.
The raw material of the present embodiment sealer is calculated as with 1L: slaine, 12g；Stabilizer, 1.75g；Corrosion inhibiter, 1.65g；Oxygen
Agent, 0.65g；Surfactant, 3.1g；PH buffer agent, 9.75g；Deionized water, addition is to add after remaining raw material mixes
Ionized water is settled to the amount of 1L.
In the present embodiment, slaine includes 8g acetic acid titanium and 4g Yttrium chloride(Y2Cl6), and stabilizer is carboxylate derivatives, molecular structure
Formula is:
Wherein, R1For hydrogen atom, R2For amino, R3For amino, R4For methyl；Corrosion inhibiter is organic carboxyl acid, molecular structural formula
For:
Wherein, R5For hydrogen atom, R6For methyl；Surfactant is AB type block macromolecular surfactant, molecular structure
Formula is:
Wherein, R7For isopropyl, R8For benzyl；PH buffer agent includes 5g acetic acid and 4.75g sodium acetate.
The aluminium alloy anode oxide film that the present invention provides is without the performance ratio of nickel free-floride cold sealing agent with commercially available sealer
More as shown in the table:
As can be seen from the above table, the cold sealing agent of free-floride without nickel prepared by the present invention is mainly used in aluminum alloy anode oxygen
Change the micropore Guan Bi in film；Sealer high-efficiency environment friendly, the most nickeliferous, fluorine etc. is to human body and the element of bad environmental；And present invention envelope
Close the cold sealing agent of free-floride without nickel prepared by agent for aluminum component is carried out sealing of hole maintenance, it is not necessary to add the interpolation of other components
Agent；There is rapid osmotic function, it is possible to by micropore adequate closure, be effectively increased the etch resistant properties of metal surface；Sealer thing
Reason and chemical stability are good, and additive is not easily decomposed and energy life-time service, has saved production cost；Surface of the work light after sealing of hole
Bright property is good, and wearability and hardness are greatly improved.Effectively prevent the partial pore occurred because of sealing of hole poor effect unclosed, envelope
Behind hole, surface of the work has the problem such as Refined Mercurous chloride and sealing of hole rear oxidation film difference against corrosion.
The ultimate principle of the present invention and principal character and advantages of the present invention have more than been shown and described.The skill of the industry
The art personnel simply explanation it should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and description
The principle of the present invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these
Changes and improvements both fall within scope of the claimed invention.Claimed scope by appending claims and
Its equivalent defines.
Claims (7)
1. an aluminium alloy anode oxide film is without nickel free-floride cold sealing agent, it is characterised in that: the raw material of described sealer is with 1L
It is calculated as: slaine, 8-16g；Stabilizer, 0.5-3g；Corrosion inhibiter, 0.8-2.5g；Oxidant, 0.3-1g；Surfactant, 0.2-
4g；PH buffer agent, 3.5-16g；Deionized water, addition is to add deionized water after remaining raw material mixes to be settled to the amount of 1L.
Aluminium alloy anode oxide film the most according to claim 1 is without nickel free-floride cold sealing agent, it is characterised in that: described
Slaine includes at least one in acetic acid titanium, samaric nitrate, zinc acetate, cadmium nitrate, Yttrium chloride(Y2Cl6) and cerium chloride.
Aluminium alloy anode oxide film the most according to claim 1 is without nickel free-floride cold sealing agent, it is characterised in that: described
Stabilizer is that the molecular structural formula of carboxylate derivatives is:
Wherein, R1、R4For the one in hydrogen atom, methyl and ethyl, R2、R3For hydroxyl, amino, phosphonate group, ethyl and methylol
In one.
Aluminium alloy anode oxide film the most according to claim 1 is without nickel free-floride cold sealing agent, it is characterised in that: described
Corrosion inhibiter is organic carboxyl acid, and molecular structural formula is:
Wherein, R5For the one in hydrogen atom, methyl, carboxymethyl group, methylol, ethoxy and benzyl, R6For hydrogen atom, hydroxyl,
One in amino, methyl, methylol and ethoxy.
Aluminium alloy anode oxide film the most according to claim 1 is without nickel free-floride cold sealing agent, it is characterised in that: described
Oxidant is potassium permanganate.
Aluminium alloy anode oxide film the most according to claim 1 is without nickel free-floride cold sealing agent, it is characterised in that: described
Surfactant is AB type block macromolecular surfactant, and molecular structural formula is:
Wherein, R7For the one in hydrogen atom, carboxyl, isopropyl and carbomethoxy, R8Former for hydroxyl, benzyl, p-methylphenyl and hydrogen
One in son.
Aluminium alloy anode oxide film the most according to claim 1 is without nickel free-floride cold sealing agent, it is characterised in that: described
PH buffer agent includes at least two in acetic acid, sodium acetate, ammonia, neck potassium hydrogen phthalate, potassium dihydrogen phosphate and phosphoric acid.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107604414A (en) * | 2017-08-22 | 2018-01-19 | 珠海市奥美伦精细化工有限公司 | A kind of aluminium and aluminium alloy anode oxide high temperature is without nickel sealer |
| CN108221026A (en) * | 2018-01-18 | 2018-06-29 | 江苏飞拓界面工程科技有限公司 | A kind of high gloss retention mid-temperature sealing agent of aluminaization and preparation method thereof |
| CN109056028A (en) * | 2018-07-20 | 2018-12-21 | 江苏飞拓界面工程科技有限公司 | A kind of aluminium and aluminium alloy anode oxide aftertreatment fluid and preparation method thereof |
| CN109440162A (en) * | 2018-12-28 | 2019-03-08 | 江苏飞拓界面工程科技有限公司 | A kind of aluminium alloy anode oxide film is without nickel hole sealing agent and preparation method |
| CN111893488A (en) * | 2020-08-04 | 2020-11-06 | 深圳市乾行达科技有限公司 | Etching solution and preparation method thereof |
| 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 |
| CN115726016A (en) * | 2022-12-05 | 2023-03-03 | 仙桃市伟方新材料科技有限公司 | Nickel-free fluorine-free medium-temperature sealing agent containing rare earth components and preparation method thereof |
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| CN107604414A (en) * | 2017-08-22 | 2018-01-19 | 珠海市奥美伦精细化工有限公司 | A kind of aluminium and aluminium alloy anode oxide high temperature is without nickel sealer |
| CN107604414B (en) * | 2017-08-22 | 2020-03-24 | 珠海市奥美伦精细化工有限公司 | Aluminum and aluminum alloy anodic oxidation high-temperature nickel-free sealing agent |
| CN108221026A (en) * | 2018-01-18 | 2018-06-29 | 江苏飞拓界面工程科技有限公司 | A kind of high gloss retention mid-temperature sealing agent of aluminaization and preparation method thereof |
| CN109056028A (en) * | 2018-07-20 | 2018-12-21 | 江苏飞拓界面工程科技有限公司 | A kind of aluminium and aluminium alloy anode oxide aftertreatment fluid and preparation method thereof |
| CN109056028B (en) * | 2018-07-20 | 2021-04-06 | 江苏飞拓界面工程科技有限公司 | Aluminum and aluminum alloy anodic oxidation post-treatment fluid and preparation method thereof |
| CN109440162A (en) * | 2018-12-28 | 2019-03-08 | 江苏飞拓界面工程科技有限公司 | A kind of aluminium alloy anode oxide film is without nickel hole sealing agent and preparation method |
| CN111893488A (en) * | 2020-08-04 | 2020-11-06 | 深圳市乾行达科技有限公司 | Etching solution and preparation method thereof |
| 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 |
| CN115726016A (en) * | 2022-12-05 | 2023-03-03 | 仙桃市伟方新材料科技有限公司 | Nickel-free fluorine-free medium-temperature sealing agent containing rare earth components and preparation method thereof |
| CN115726016B (en) * | 2022-12-05 | 2023-08-11 | 仙桃市伟方新材料科技有限公司 | Nickel-free fluoride-free medium-temperature sealing agent containing rare earth component and preparation method thereof |
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