CN105820607A - Anticorrosive coating of titanium sol modified aluminum electrode and preparation method thereof - Google Patents
Anticorrosive coating of titanium sol modified aluminum electrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an anticorrosive coating of a titanium sol modified aluminum electrode. The anticorrosive coating is prepared from the following raw materials in parts by weight: 1 to 2 parts of tetrabutyl titanate, 0.1 to 0.3 part of diazolidinyl urea, 0.7 to 1 part of cetyl trimethyl ammonium bromide, 0.05 to 0.06 part of magnesium sulfate, 0.06 to 0.07 part of benzotriazole, 1.7 to 2 parts of octylphenol polyoxyethylene ether, 0.3 to 0.5 part of lauryl amine, 46 to 50 parts of tetraethyl orthosilicate, 0.3 to 0.4 part of trichloro(dodecyl)silane, 13 to 20 parts of zirconium n-propoxide, 7 to 10 parts of ethyl acetoacetate, 57 to 60 parts of isopropanol, 10 to 13 parts of silane coupling agents kh560, 0.4 to 0.7 part of calcium ricinoleate, 0.3 to 0.7 part of benzyl triethyl ammonium bromide, 0.1 to 0.2 part of aluminum sulfate, 0.2 to 0.3 part of epoxidized triglyceride and 0.6 to 1 part of deca-brominated diphenyl ether. The anticorrosive coating of the titanium sol modified aluminum electrode disclosed by the invention effectively improves the dispersion and surface resistance of the coating.
Description
Technical field
The present invention relates to electrode corrosion-resistant technical field, particularly relate to a kind of titanium sol-gel modified aluminum electrode corrosion-resistant coating and preparation method thereof.
Background technology
Metal coating anticorrosion is one of important method of anti-corrosion of metal; and coating itself only serves passive physical isolation effect; i.e. prevent metal surface from contacting, owing to coat inside there may be some defects (such as micropore), so metal can not be adequately protected with the direct of surrounding medium.In order to improve its Active Anticorrosion, in the way of direct or indirect, add inorganic or organic inhibitor.The corrosion inhibiter directly added may interact with coating, reduce the intensity of coating, also result in unnecessary waste simultaneously, and indirect mode mainly loads corrosion inhibiter by carrier material, prevent directly contacting of corrosion inhibiter and coating, also be able to if desired to discharge, preferable corrosion inhibiter carrier needs possess two big features, on the one hand, carrier material can not react with coating itself, and has the preferable compatibility with coating；On the other hand, corrosion inhibiter coating efficiency in the carrier should be higher, and when coating is stimulated by external environment, corrosion inhibiter can discharge at short notice, protects metal surface；
Recent study shows, can be by inorganic material as corrosion inhibition for metal agent carrier, such as kaolin nanotube, Ti02 and Si02 microsphere or nanotube the most mesoporous Si02 microsphere are widely used, and have high-specific surface area, high pore volume mainly due to it, chemical stability is good and easily carries out the advantages such as surface-functionalized modification；
And in terms of mesoporous Si02 microsphere is carried out functional modification, have the method that research uses LBL self-assembly, and forming multi-layer polyelectrolyte at mesoporous Si02 microsphere surface, polyelectrolyte layer has pH stimulating responsive, can reach the purpose of corrosion inhibiter controllable release；But owing to this method of modifying is more complicated, it is not easy to commercial production, so the exploitation simply method of the mesoporous Si02 microsphere surface of novelty modification, becomes the research direction of people.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of titanium sol-gel modified aluminum electrode corrosion-resistant coating and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of titanium sol-gel modified aluminum electrode corrosion-resistant coating, it is made up of the raw material of following weight parts:
Butyl titanate 1-2, double imidazolidinyl urea 0.1-0.3, cetyl trimethylammonium bromide 0.7-1, magnesium sulfate 0.05-0.06, BTA 0.06-0.07, OPEO 1.7-2, lauryl amine 0.3-0.5, tetraethyl orthosilicate 46-50, dodecyl trichlorosilane 0.3-0.4, zirconium-n-propylate 13-20, ethyl acetoacetate 7-10, isopropanol 57-60, silane coupler kh56010-13, calcium ricinoleate 0.4-0.7, benzyl triethyl ammonium bromide 0.3-0.7, aluminum sulfate 0.1-0.2, epoxidation triglyceride 0.2-0.3, decabromodiphenyl oxide 0.6-1.
The preparation method of a kind of described titanium sol-gel modified aluminum electrode corrosion-resistant coating, comprises the following steps:
(1) by above-mentioned cetyl trimethylammonium bromide, magnesium sulfate, BTA mixing, join in the deionized water of compound weight 20-30 times, ultrasonic disperse 1-2 minute, obtain aqueous phase premixed liquid；
(2) above-mentioned butyl titanate is taken, join in the deionized water of its weight 20-34 times, add aluminum sulfate, rise high-temperature and be 50-60 DEG C, insulated and stirred 10-20 minute, the sodium hydroxide solution of dropping 3-5mol/l, regulation pH is 10-13, mixes premixed liquid with above-mentioned aqueous phase and mixes, and rises high-temperature and is 70-80 DEG C, insulated and stirred 20-30 minute, obtains titanium colloidal sol aqueous phase mixed liquor；
(3) by above-mentioned OPEO, lauryl amine mixing, join in the kerosene of compound weight 10-14 times, ultrasonic 2-3 minute, obtain oil phase mixed liquor；
(4) by above-mentioned oil phase mixed liquor, the mixing of aqueous phase mixed liquor, 1600-2000 rev/min is stirred 16-20 minute, add the 3-5% of above-mentioned tetraethyl orthosilicate weight, stirring reaction 20-24 hour, adds the dehydrated alcohol of above-mentioned mixed system weight 1-2%, stirs 2-3 minute, centrifugal, by precipitation absolute ethanol washing 3-4 time, it is dried 20-25 hour at 46-50 DEG C, silicon microsphere must be loaded；
(5) above-mentioned pair of imidazolidinyl urea is joined in the dehydrated alcohol of its weight 6-8 times, stir, add epoxidation triglyceride, obtain alcohol ester solution；
(6) above-mentioned benzyl triethyl ammonium bromide is joined in the deionized water of its weight 10-14 times, stir, add calcium ricinoleate, insulated and stirred 4-7 minute at 60-70 DEG C, obtain calcium emulsion；
(7) above-mentioned dodecyl trichlorosilane is joined in the dehydrated alcohol of its weight 100-140 times, stir, add load silicon microsphere, at 80-86 DEG C ultrasonic 20-30 minute, centrifugal, precipitation is joined in above-mentioned calcium emulsion, at 70-80 DEG C, be heated to water do, obtain hydrophobically modified load silicon microsphere；
(8) by above-mentioned silane coupler kh560, remaining tetraethyl orthosilicate, isopropanol mixing, ultrasonic disperse 3-5 minute, add above-mentioned alcohol ester solution, magnetic agitation 20-30 minute, obtain Ludox；
(9) by above-mentioned zirconium-n-propylate, ethyl acetoacetate mixing, stir, mix with above-mentioned Ludox, stir, add hydrophobically modified load silicon microsphere, magnetic agitation 50-60 minute, add and remain each raw material, stir, at room temperature stand 20-25 hour, obtain described coating.
A kind of titanium sol-gel modified aluminum electrode corrosion-resistant coating and preparation method thereof, the using method of described coating is:
First by the sand paper of 8000 mesh, slowly it is polishing to become clear by the surface of aluminum electrode, is carried out with acetone, water the most respectively, respectively wash 3-4 time, natural drying, be soaked in 100-120s in the coating of the present invention, then slowly electrode is put forward, puts and be dried at room temperature,.
The invention have the advantage that the present invention is polymerized by water-in oil microemulsion, the hollow mesoporous Si02 microsphere of preparation cladding corrosion inhibiter BTA, and in aqueous phase, add magnesium ion, so in the mesoporous middle generation oxygen magnesium oxide inorganic salt precipitates of microsphere surface, this method is fairly simple, easily operate, it addition, microsphere surface is carried out hydrophobically modified, finally microsphere is mixed in inorganic coating, it is possible to increase the Corrosion Protection of inorganic coating；
nullFirst emulsifying agent and base catalyst lauryl amine are dissolved in kerosene by the present invention，To be added drop-wise in oil phase dissolved with the aqueous solution of cetyl trimethylammonium bromide and BTA，It is configured to water-in oil microemulsion，Then under the conditions of magnetic force stirs Chinese catalpa，Drip a certain amount of tetraethyl orthosilicate in oil phase，The hydrolysis of tetraethyl orthosilicate proceeds by，Owing to tetraethyl orthosilicate is oil-soluble molecule，Therefore in reverse micro emulsion,Its hydrolysis needs to be diffused into and carries out at oil-water interfaces，Tetraethyl orthosilicate molecule after hydrolysis is with partial negative charge，Can be with cationic emulsifier cetyl trimethylammonium bromide generation electrostatic adsorption，And be attracted on oil-water interfaces，Polycondensation reaction is there is in the tetraethyl orthosilicate molecule finally hydrolyzed in interface，Form the shell of Si02，Magnesium ion in aqueous phase and oxygen oxygen radical ion generation precipitation simultaneously，Generate oxygen magnesium oxide precipitation，Si02 is mesoporous or duct in blocking，And while generating hollow Si02 microsphere，BTA molecule is also covered by the inside of microsphere，The oxygen magnesium oxide precipitation generated hinders BTA oozing out from microsphere；
In electrochemical corrosion course, the change of Acidity of Aikalinity may can occur at regional area, stimulate the carrier of cladding corrosion inhibiter to respond；
When by alkali liquid corrosion, BTA dissolubility in alkali liquor is higher, constantly will discharge from micropore, plays the effect of inhibition；
When by acid liquid corrosion, the magnesium hydrate precipitate thing in the mesopore orbit of microsphere surface is dissolved by H+ in acid solution, and the BTA in duct can quickly discharge, and reaches antiseptical purpose；
The corrosion phenomenon of electrochemistry can occur in neutral etchant solution according to aluminum, the corrosion of metallic aluminium generation regional area, anode can generate aluminium ion freely, dissolve in the solution, generation oxygen aluminium oxide or precipitation of alumina can be reacted with other compositions (such as OH-) in solution, meanwhile, due to the consumption of OH-in anode region, hydrion and the formation of hydrogen ion in whole system can be promoted, solution is finally made to become acid, can be seen that from analysis above, under sour environment, magnesium hydrate precipitate thing in the mesopore orbit of microsphere surface is dissolved by H+ in acid solution, BTA in duct can quickly discharge, so can be in negative electrode or anode surface film forming, the further corrosion of suppression metal；The present invention, with butyl titanate as presoma, prepares titanium colloidal sol, effectively raises dispersibility and the surface resistive of coating.
Detailed description of the invention
A kind of titanium sol-gel modified aluminum electrode corrosion-resistant coating, it is made up of the raw material of following weight parts:
Butyl titanate 1, double imidazolidinyl urea 0.1, cetyl trimethylammonium bromide 0.7, magnesium sulfate 0.05, BTA 0.06, OPEO 1.7, lauryl amine 0.3, tetraethyl orthosilicate 46, dodecyl trichlorosilane 0.3, zirconium-n-propylate 13, ethyl acetoacetate 7, isopropanol 57, silane coupler kh56010, calcium ricinoleate 0.4, benzyl triethyl ammonium bromide 0.3, aluminum sulfate 0.1, epoxidation triglyceride 0.2, decabromodiphenyl oxide 0.6.
The preparation method of a kind of described titanium sol-gel modified aluminum electrode corrosion-resistant coating, comprises the following steps:
(1) by above-mentioned cetyl trimethylammonium bromide, magnesium sulfate, BTA mixing, join in the deionized water of compound weight 20 times, ultrasonic disperse 1 minute, obtain aqueous phase premixed liquid；
(2) above-mentioned butyl titanate is taken, join in the deionized water of its weight 20 times, adding aluminum sulfate, rising high-temperature is 50 DEG C, insulated and stirred 10 minutes, the sodium hydroxide solution of dropping 3mol/l, regulation pH is 10, mixes premixed liquid with above-mentioned aqueous phase and mixes, and rising high-temperature is 70 DEG C, insulated and stirred 20 minutes, obtains titanium colloidal sol aqueous phase mixed liquor；
(3) by above-mentioned OPEO, lauryl amine mixing, join in the kerosene of compound weight 10 times, ultrasonic 2 minutes, obtain oil phase mixed liquor；
(4) by above-mentioned oil phase mixed liquor, the mixing of aqueous phase mixed liquor, 1600 revs/min are stirred 16 minutes, add the 3% of above-mentioned tetraethyl orthosilicate weight, stirring reaction 20 hours, adds the dehydrated alcohol of above-mentioned mixed system weight 1%, stirs 2 minutes, centrifugal, by precipitation absolute ethanol washing 3 times, it is dried 20 hours at 46 DEG C, silicon microsphere must be loaded；
(5) above-mentioned pair of imidazolidinyl urea is joined in the dehydrated alcohol of its weight 6 times, stir, add epoxidation triglyceride, obtain alcohol ester solution；
(6) above-mentioned benzyl triethyl ammonium bromide is joined in the deionized water of its weight 10 times, stir, add calcium ricinoleate, insulated and stirred 4 minutes at 60 DEG C, obtain calcium emulsion；
(7) above-mentioned dodecyl trichlorosilane is joined in the dehydrated alcohol of its weight 100 times, stir, add load silicon microsphere, at 80 DEG C ultrasonic 20 minutes, centrifugal, precipitation is joined in above-mentioned calcium emulsion, at 70 DEG C, it is heated to water do, obtains hydrophobically modified load silicon microsphere；
(8) by above-mentioned silane coupler kh560, remaining tetraethyl orthosilicate, isopropanol mixing, ultrasonic disperse 3 minutes, add above-mentioned alcohol ester solution, magnetic agitation 20 minutes, obtain Ludox；
(9) by above-mentioned zirconium-n-propylate, ethyl acetoacetate mixing, stir, mix with above-mentioned Ludox, stir, add hydrophobically modified load silicon microsphere, magnetic agitation 50 minutes, add and remain each raw material, stir, at room temperature stand 20 hours, obtain described coating.
A kind of titanium sol-gel modified aluminum electrode corrosion-resistant coating and preparation method thereof, the using method of described coating is:
First by the sand paper of 8000 mesh, slowly it is polishing to become clear by the surface of aluminum electrode, is carried out with acetone, water the most respectively, respectively wash 3 times, natural drying, be soaked in 100s in the coating of the present invention, then slowly electrode put forward, put and be dried at room temperature,.
In the NaCl solution of 0.1 M, the inhibitor efficiency of aluminum is reached 98.97%.
Claims (3)
1. a titanium sol-gel modified aluminum electrode corrosion-resistant coating, it is characterised in that it is made up of the raw material of following weight parts:
Butyl titanate 1-2, double imidazolidinyl urea 0.1-0.3, cetyl trimethylammonium bromide 0.7-1, magnesium sulfate 0.05-0.06, BTA 0.06-0.07, OPEO 1.7-2, lauryl amine 0.3-0.5, tetraethyl orthosilicate 46-50, dodecyl trichlorosilane 0.3-0.4, zirconium-n-propylate 13-20, ethyl acetoacetate 7-10, isopropanol 57-60, silane coupler kh56010-13, calcium ricinoleate 0.4-0.7, benzyl triethyl ammonium bromide 0.3-0.7, aluminum sulfate 0.1-0.2, epoxidation triglyceride 0.2-0.3, decabromodiphenyl oxide 0.6-1.
2. the preparation method of a titanium as claimed in claim 1 sol-gel modified aluminum electrode corrosion-resistant coating, it is characterised in that comprise the following steps:
(1) by above-mentioned cetyl trimethylammonium bromide, magnesium sulfate, BTA mixing, join in the deionized water of compound weight 20-30 times, ultrasonic disperse 1-2 minute, obtain aqueous phase premixed liquid；
(2) above-mentioned butyl titanate is taken, join in the deionized water of its weight 20-34 times, add aluminum sulfate, rise high-temperature and be 50-60 DEG C, insulated and stirred 10-20 minute, the sodium hydroxide solution of dropping 3-5mol/l, regulation pH is 10-13, mixes premixed liquid with above-mentioned aqueous phase and mixes, and rises high-temperature and is 70-80 DEG C, insulated and stirred 20-30 minute, obtains titanium colloidal sol aqueous phase mixed liquor；
(3) by above-mentioned OPEO, lauryl amine mixing, join in the kerosene of compound weight 10-14 times, ultrasonic 2-3 minute, obtain oil phase mixed liquor；
(4) by above-mentioned oil phase mixed liquor, the mixing of aqueous phase mixed liquor, 1600-2000 rev/min is stirred 16-20 minute, add the 3-5% of above-mentioned tetraethyl orthosilicate weight, stirring reaction 20-24 hour, adds the dehydrated alcohol of above-mentioned mixed system weight 1-2%, stirs 2-3 minute, centrifugal, by precipitation absolute ethanol washing 3-4 time, it is dried 20-25 hour at 46-50 DEG C, silicon microsphere must be loaded；
(5) above-mentioned pair of imidazolidinyl urea is joined in the dehydrated alcohol of its weight 6-8 times, stir, add epoxidation triglyceride, obtain alcohol ester solution；
(6) above-mentioned benzyl triethyl ammonium bromide is joined in the deionized water of its weight 10-14 times, stir, add calcium ricinoleate, insulated and stirred 4-7 minute at 60-70 DEG C, obtain calcium emulsion；
(7) above-mentioned dodecyl trichlorosilane is joined in the dehydrated alcohol of its weight 100-140 times, stir, add load silicon microsphere, at 80-86 DEG C ultrasonic 20-30 minute, centrifugal, precipitation is joined in above-mentioned calcium emulsion, at 70-80 DEG C, be heated to water do, obtain hydrophobically modified load silicon microsphere；
(8) by above-mentioned silane coupler kh560, remaining tetraethyl orthosilicate, isopropanol mixing, ultrasonic disperse 3-5 minute, add above-mentioned alcohol ester solution, magnetic agitation 20-30 minute, obtain Ludox；
(9) by above-mentioned zirconium-n-propylate, ethyl acetoacetate mixing, stir, mix with above-mentioned Ludox, stir, add hydrophobically modified load silicon microsphere, magnetic agitation 50-60 minute, add and remain each raw material, stir, at room temperature stand 20-25 hour, obtain described coating.
3. according to a kind of titanium sol-gel modified aluminum electrode corrosion-resistant coating described in claim 1,2 and preparation method thereof, it is characterised in that the using method of described coating is:
First by the sand paper of 8000 mesh, slowly it is polishing to become clear by the surface of aluminum electrode, is carried out with acetone, water the most respectively, respectively wash 3-4 time, natural drying, be soaked in 100-120s in the coating of the present invention, then slowly electrode is put forward, puts and be dried at room temperature,.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111115854A (en) * | 2018-10-30 | 2020-05-08 | 芜湖美的厨卫电器制造有限公司 | Scale inhibitor coated mesoporous microsphere, preparation method thereof, water heater and liner |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105295722A (en) * | 2015-10-28 | 2016-02-03 | 天长市润达金属防锈助剂有限公司 | Corrosion-preventive lifting composite aluminum-titanium sol for aluminum alloy and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105295722A (en) * | 2015-10-28 | 2016-02-03 | 天长市润达金属防锈助剂有限公司 | Corrosion-preventive lifting composite aluminum-titanium sol for aluminum alloy and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 赵东: ""防腐蚀功能性微球的制备及其应用研究"", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111115854A (en) * | 2018-10-30 | 2020-05-08 | 芜湖美的厨卫电器制造有限公司 | Scale inhibitor coated mesoporous microsphere, preparation method thereof, water heater and liner |
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