CN109208056B - Nickel-free sealing agent, preparation method thereof and aluminum alloy hole sealing method - Google Patents
Nickel-free sealing agent, preparation method thereof and aluminum alloy hole sealing method Download PDFInfo
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- CN109208056B CN109208056B CN201710523296.9A CN201710523296A CN109208056B CN 109208056 B CN109208056 B CN 109208056B CN 201710523296 A CN201710523296 A CN 201710523296A CN 109208056 B CN109208056 B CN 109208056B
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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 relates to a nickel-free sealing agent which is an aqueous solution containing cobalt acetate, silicate, benzene sulfonate, polyoxypropylene ether, a surfactant and a complexing agent. The sealing agent can achieve good hole sealing effect without adding nickel and fluorine, and does not affect human health. The invention also relates to a preparation method of the nickel-free sealing agent and a hole sealing method of aluminum and aluminum alloy.
Description
Technical Field
The invention relates to a nickel-free sealing agent, a preparation method thereof and a hole sealing method for aluminum and aluminum alloy, belonging to the technical field of material surface treatment.
Background
The aluminum alloy has the advantages of light weight, strong corrosion resistance, good heat and electricity conduction and the like, and is widely applied to the aviation, aerospace, automobile, mechanical manufacturing and civil industries. The surface treatment of the aluminum alloy is mainly carried out by anodic oxidation, but an oxide film layer is porous and has strong chemical activity, if hole sealing treatment is not carried out or hole sealing quality is poor, pollutants in the environment can be adsorbed by micropores and cause corrosion of a base material, and finally, the service life of the aluminum material is reduced in the period. And the aluminum alloy after anodic oxidation is subjected to hole sealing, so that the corrosion resistance of the aluminum alloy can be effectively improved.
The sealing quality directly determines the corrosion resistance of the aluminum alloy, and Ni-F sealing agents with Ni2+ and F-as basic components are generally used at home and abroad. The sealing agent consumes more nickel and fluorine, has influence on human health and is difficult to pass ROSH test. The existing nickel-free sealing agent is difficult to meet the quality requirement on production and cannot be popularized and applied on a large scale. Therefore, it is an urgent problem to develop a nickel-free sealant with good sealing effect.
Disclosure of Invention
In order to solve the problems, the invention provides a nickel-free sealant, and the sealant is an aqueous solution containing cobalt acetate, silicate, a surfactant, benzene sulfonate and polyoxypropylene ether. According to the invention, the problem of dye falling in high-temperature sealing can be prevented by adding the benzene sulfonate into the sealing agent; by adding the polyoxypropylene ether, the sealing film layer can be more compact and uniform. Under the synergistic effect of the two materials, the surface color of the aluminum alloy can be maintained unchanged, and the corrosion resistance is improved. Meanwhile, the sealing agent can achieve a good hole sealing effect without adding nickel and fluorine, and does not affect human health.
The invention also provides a preparation method of the nickel-free sealing agent, which comprises the following steps: adding cobalt acetate, silicate, benzene sulfonate, polyoxypropylene ether, surfactant and complexing agent into water, and stirring until the cobalt acetate, the silicate, the benzene sulfonate, the polyoxypropylene ether, the surfactant and the complexing agent are dissolved.
The invention also provides a hole sealing method for aluminum and aluminum alloy, which comprises the following steps: immersing the dyed aluminum or aluminum alloy material into the sealant; the hole sealing time is 15-30min, and the temperature is 80-95 ℃.
The sealant provided by the invention is simple in formula and convenient to prepare, and has good hole sealing effect and corrosion resistance under the synergistic effect of the components.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The technical scheme of the invention relates to a nickel-free sealing agent, which is an aqueous solution containing cobalt acetate, silicate, benzene sulfonate, polyoxypropylene ether, a surfactant and a complexing agent. The sealing agent can prevent the problem of dye falling in high-temperature sealing by adding benzene sulfonate and polyoxypropylene ether, and can further enable a sealing film layer to be more compact and uniform. Under the synergistic effect of the two materials, the surface color of the aluminum alloy can be maintained unchanged, and the corrosion resistance is improved.
According to the nickel-free sealing agent provided by the invention, the pH value of the sealing agent is preferably 5-11.
According to the nickel-free blocking agent provided by the invention, at least one terminal group of the polyoxypropylene ether is preferably a hydroxyl group. Specifically, the solvent may be one or more of 1,1' - (2- (N-2-hydroxyethyl-2-hydroxypropyl amino) ethyl imine) dipropyl-2-ol, trihydroxy polyoxypropylene ether and dihydroxyl polyoxypropylene ether. More preferably, the polyoxypropylene ether has an average molecular weight of 200-500. More preferably, the polyoxypropylene ether is contained in an amount of 0.1 to 10 g/L.
According to the nickel-free sealing agent provided by the invention, preferably, the content of the benzene sulfonate is 0.01-5 g/L; more preferably, the benzene sulfonate is one or more of sodium alkyl benzene sulfonate, sodium nitrobenzene sulfonate and potassium alkyl benzene sulfonate. The benzene sulfonate can effectively prevent the problem of dye fading in the high-temperature sealing process.
According to the nickel-free sealing agent provided by the invention, preferably, in order to improve the surface glossiness of the aluminum and aluminum alloy materials after sealing, the mass ratio of the benzene sulfonate to the polyoxypropylene ether is 1: 10-100.
According to the nickel-free sealing agent provided by the invention, preferably, the content of the cobalt acetate is 0.1-7 g/L. Cobalt acetate can form hydroxide to close the pores of the aluminum alloy at high temperature.
According to the nickel-free sealing agent provided by the invention, silicate can be adsorbed to the surface of the aluminum alloy oxidation layer to play a corrosion inhibition role. The silicate is a silicate product commonly used in the field, and specifically can be one or more of sodium silicate, potassium silicate, lithium silicate, magnesium silicate and aluminum silicate. Preferably, the silicate is present in an amount of 0.01 to 1 g/L.
According to the nickel-free sealing agent provided by the invention, the surfactant can be matched with other components to reduce the porosity of the sealing film. The surfactant is a surfactant commonly used in the field, and specifically can be one or more of alkylphenol ethoxylates, octylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether sodium sulfate (AES), triethanolamine and triethanolamine salt. Preferably, the surfactant is present in an amount of 0.001 to 0.01 g/L.
According to the nickel-free sealant provided by the invention, the complexing agent is a complexing agent commonly used in the field, and specifically can be one or more of tartaric acid, potassium sodium tartrate, potassium tartrate, sodium acetate, citric acid, ammonium citrate, sodium citrate, potassium citrate, ethylene diamine tetraacetic acid disodium, ethylene diamine tetraacetic acid tetrasodium, gluconic acid, sodium gluconate, succinic acid, glycine, glycolic acid and acetic acid. Preferably, the content of the complexing agent is 0.5-5 g/L.
The invention also provides a preparation method of the nickel-free sealing agent, which comprises the following steps: adding cobalt acetate, silicate, benzene sulfonate, polyoxypropylene ether, surfactant and complexing agent into water, and stirring until the cobalt acetate, the silicate, the benzene sulfonate, the polyoxypropylene ether, the surfactant and the complexing agent are dissolved.
According to the preparation method of the nickel-free sealing agent provided by the invention, preferably, the cobalt acetate and the complexing agent are sequentially added into water and stirred to be dissolved, and then the silicate, the benzene sulfonate, the polyoxypropylene ether and the surfactant are added and stirred to be dissolved.
According to the preparation method of the nickel-free sealing agent provided by the invention, preferably, the content of the cobalt acetate is 0.1-7g/L, the content of the silicate is 0.01-1g/L, the content of the benzene sulfonate is 0.01-5g/L, the content of the polyoxypropylene ether is 0.1-10g/L, the content of the surfactant is 0.001-0.1, and the content of the complexing agent is 0.5-5 g/L.
The invention also provides an aluminum and aluminum alloy hole sealing method, which comprises the step of immersing the dyed aluminum or aluminum alloy material into the sealant.
According to the aluminum alloy hole sealing method provided by the invention, under the preferable condition, the aluminum alloy hole sealing time is 15-30min, and the temperature is 80-95 ℃.
The present invention will be described in further detail with reference to examples, but is not limited thereto.
All the raw materials in the examples of the present invention are commercially available products unless otherwise specified.
Example 1
Preparing a nickel-free sealant: dissolving cobalt acetate in water, adding a complexing agent, stirring for dissolving, finally adding sodium silicate, sodium benzenesulfonate, 1' - (2- (N-2-hydroxyethyl-2-hydroxypropyl amino) ethyl imine) dipropyl-2-alcohol and alkylphenol polyoxyethylene ether, and stirring until dissolving. Wherein the content of the cobalt acetate is 4g/L, the content of the potassium sodium tartrate is 3g/L, the content of the sodium silicate is 0.05g/L, the content of the sodium benzenesulfonate is 0.5g/L, the content of the 1,1' - (2- (N-2-hydroxyethyl-2-hydroxypropyl amino) ethyl imine) dipropyl-2-ol is 6g/L, and the content of the alkylphenol polyoxyethylene ether-10 (OP-10) is 0.005 g/L.
Example 2
Preparing a nickel-free sealant: dissolving cobalt acetate in water, adding a complexing agent, stirring for dissolving, finally adding sodium silicate, sodium benzenesulfonate, 1' - (2- (N-2-hydroxyethyl-2-hydroxypropyl amino) ethyl imine) dipropyl-2-alcohol and alkylphenol polyoxyethylene ether (OP-10), and stirring until dissolving. Wherein the content of cobalt acetate is 7g/L, the content of potassium sodium tartrate is 5g/L, the content of sodium silicate is 1g/L, the content of sodium benzenesulfonate is 5g/L, the content of 1,1' - (2- (N-2-hydroxyethyl-2-hydroxypropyl amino) ethylenimine) dipropyl-2-ol is 10g/L, and the content of alkylphenol polyoxyethylene ether (OP-10) is 0.01 g/L.
Example 3
Preparing a nickel-free sealant: dissolving cobalt acetate in water, adding a complexing agent, stirring for dissolving, finally adding sodium silicate, sodium benzenesulfonate, 1' - (2- (N-2-hydroxyethyl-2-hydroxypropyl amino) ethyl imine) dipropyl-2-alcohol and alkylphenol polyoxyethylene ether (OP-10), and stirring until dissolving. Wherein the content of cobalt acetate is 0.1g/L, the content of potassium sodium tartrate is 0.5g/L, the content of sodium silicate is 0.01g/L, the content of sodium benzenesulfonate is 0.01g/L, the content of 1,1' - (2- (N-2-hydroxyethyl-2-hydroxypropyl amino) ethylenimine) dipropyl-2-ol is 0.1g/L, and the content of alkylphenol polyoxyethylene ether (OP-10) is 0.01 g/L.
Example 4
Preparing a nickel-free sealant: dissolving cobalt acetate in water, adding a complexing agent, stirring for dissolving, finally adding sodium silicate, sodium benzenesulfonate, 1' - (2- (N-2-hydroxyethyl-2-hydroxypropyl amino) ethyl imine) dipropyl-2-alcohol and alkylphenol polyoxyethylene ether (OP-10), and stirring until dissolving. Wherein the content of the cobalt acetate is 3g/L, the content of the sodium acetate is 1g/L, the content of the sodium silicate is 0.02g/L, the content of the sodium benzenesulfonate is 0.1g/L, the content of the 1,1' - (2- (N-2-hydroxyethyl-2-hydroxypropyl amino) ethyl imine) dipropyl-2-alcohol is 5g/L, and the content of the alkylphenol polyoxyethylene ether (OP-10) is 0.003 g/L.
Comparative example 1
Example 1 blocking agent used in patent application No. CN 201510235716.
Comparative example 2
Commercial nickel-containing blocking agents: australian DX-500 of Japan.
Comparative example 3
The same amount of sodium benzenesulfonate was used instead of 1,1' - (2- (N-2-hydroxyethyl-2-hydroxypropylamino) ethylenimine) diprop-2-ol, and the other components and contents were the same as in example 1.
And (3) performance testing:
1. test sample preparation
Anodic oxidation: cleaning and pretreating a 5cm by 5cm aluminum alloy sample, and then soaking the sample into an anodic oxidation solution for oxidation, wherein the voltage is 15V, the solution temperature is 15 ℃, and the oxidation time is 30 min;
dyeing: immersing the anodized aluminum alloy sample wafer into a dyeing solution for dyeing, wherein the dye is yellow YW310, the concentration is 2g/L, the temperature is 50 ℃, and the time is 2 min;
hole sealing treatment: and (3) washing the dyed aluminum alloy sample wafer with clean water, and then soaking the aluminum alloy sample wafer into a sealing agent, wherein the hole sealing time is 25min, and the temperature is 92 ℃. And after hole sealing, testing after washing and drying.
2. Appearance: and observing the phenomena of color uniformity, decoloration and the like of the surface of the aluminum alloy sample piece after hole sealing treatment.
3. And (3) salt spray testing: carrying out salt spray test on the aluminum alloy sample wafer subjected to hole sealing treatment, adopting a (macrography science and technology limited, H-SST-90) salt spray box, using (5 +/-0.1)% NaCl solution, controlling the pH value between 6.5 and 7.2, and settling amount of salt spray: 1-2 ml/80 cm2H, temperature: performing salt spray test at 35 +/-2 ℃; and (3) placing the hole-sealed aluminum alloy sample into a salt spray box, observing the time of corrosion spots or discoloration on the surface of the sample, and recording once every 12 h.
The test results are given in the following table:
according to the test results, the aluminum alloy sample wafer treated by the sealant provided by the invention has uniform color and no problems of decoloration and the like; meanwhile, the sealant does not contain nickel, so that the sealant cannot cause damage to human bodies.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. It is not necessary or necessary to exhaustively enumerate all embodiments herein, and obvious variations or modifications can be introduced thereby while remaining within the scope of the invention as claimed.
Claims (9)
1. The nickel-free blocking agent is characterized in that the blocking agent is an aqueous solution containing cobalt acetate, silicate, benzene sulfonate, 1' - (2- (N-2-hydroxyethyl-2-hydroxypropyl amino) ethyl imine) dipropyl-2-alcohol, a surfactant and a complexing agent, the content of the cobalt acetate is 0.1-7g/L, the content of the silicate is 0.01-1g/L, the content of the benzene sulfonate is 0.01-5g/L, the content of 1,1' - (2- (N-2-hydroxyethyl-2-hydroxypropyl amino) ethyl imine) dipropyl-2-alcohol is 0.1-10g/L, the content of the surfactant is 0.001-0.1g/L, and the content of the complexing agent is 0.5-5 g/L.
2. The nickel-free blocking agent according to claim 1, wherein the nickel-free blocking agent has a pH of 5 to 11.
3. The nickel-free blocking agent of claim 1, wherein the weight ratio of the benzenesulfonate salt to 1,1' - (2- (N-2-hydroxyethyl-2-hydroxypropylamino) ethylenimine) diprop-2-ol is 1: 10-1000.
4. The nickel-free sealing agent as claimed in claim 3, wherein the benzene sulfonate is one or more of sodium alkyl benzene sulfonate, sodium nitrobenzene sulfonate and potassium alkyl benzene sulfonate.
5. The nickel-free sealant according to claim 1, wherein the surfactant is one or more of alkylphenol ethoxylates, octylphenol polyoxyethylene ether, sodium fatty alcohol-polyoxyethylene ether sulfate, triethanolamine, and triethanolamine salts.
6. The nickel-free sealant according to claim 1, wherein the complexing agent is one or more of tartaric acid, potassium sodium tartrate, potassium tartrate, sodium acetate, citric acid, ammonium citrate, sodium citrate, potassium citrate, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, gluconic acid, sodium gluconate, succinic acid, glycine, glycolic acid, and acetic acid.
7. A method for preparing a nickel-free sealant is characterized by comprising the following steps: adding cobalt acetate, silicate, benzene sulfonate, 1,1'- (2- (N-2-hydroxyethyl-2-hydroxypropyl amino) ethyl imine) dipropyl-2-alcohol, a surfactant and a complexing agent into water, and stirring until the cobalt acetate, the silicate and the benzene sulfonate are dissolved, wherein the cobalt acetate is 0.1-7g/L, the silicate is 0.01-1g/L, the benzene sulfonate is 0.01-5g/L, the 1,1' - (2- (N-2-hydroxyethyl-2-hydroxypropyl amino) ethyl imine) dipropyl-2-alcohol is 0.1-10g/L, the surfactant is 0.001-0.1g/L, and the complexing agent is 0.5-5 g/L.
8. The method for preparing the nickel-free sealing agent as claimed in claim 7, wherein the method comprises the steps of sequentially adding cobalt acetate and the complexing agent into water, stirring and dissolving, then adding the silicate, the benzenesulfonate, the 1,1' - (2- (N-2-hydroxyethyl-2-hydroxypropyl amino) ethylenimine) dipropyl-2-ol and the surfactant, and stirring until the mixture is dissolved.
9. A hole sealing method for aluminum and aluminum alloy is characterized by comprising the following steps: immersing the dyed aluminum or aluminum alloy material in the nickel-free sealant of any one of claims 1-6; the hole sealing time is 15-30min, and the temperature is 80-95 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105040067A (en) * | 2015-09-09 | 2015-11-11 | 佛山市海化表面处理科技有限公司 | Environment-friendly nickel-free fluoride-free intermediate-temperate sealing agent and sealing method |
| CN105200482A (en) * | 2015-09-24 | 2015-12-30 | 马鞍山杰创塑胶科技有限公司 | Nickel-free hole sealing agent for improving abrasion resistance of aluminum alloy anode oxide film and preparation method of nickel-free hole sealing agent |
| CN106191959A (en) * | 2015-05-08 | 2016-12-07 | 广州市汉科建材科技有限公司 | A kind of environment-friendly type aluminium alloy sealing agent |
| CN106400085A (en) * | 2016-06-21 | 2017-02-15 | 武汉风帆电化科技股份有限公司 | Hole sealing agent and method for aluminum and aluminum alloy anode oxide film aftertreatment |
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- 2017-06-30 CN CN201710523296.9A patent/CN109208056B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106191959A (en) * | 2015-05-08 | 2016-12-07 | 广州市汉科建材科技有限公司 | A kind of environment-friendly type aluminium alloy sealing agent |
| CN105040067A (en) * | 2015-09-09 | 2015-11-11 | 佛山市海化表面处理科技有限公司 | Environment-friendly nickel-free fluoride-free intermediate-temperate sealing agent and sealing method |
| CN105200482A (en) * | 2015-09-24 | 2015-12-30 | 马鞍山杰创塑胶科技有限公司 | Nickel-free hole sealing agent for improving abrasion resistance of aluminum alloy anode oxide film and preparation method of nickel-free hole sealing agent |
| CN106400085A (en) * | 2016-06-21 | 2017-02-15 | 武汉风帆电化科技股份有限公司 | Hole sealing agent and method for aluminum and aluminum alloy anode oxide film aftertreatment |
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