CN105670344B - The preparation method of cuprous oxide with anticorrosion and antifouling function/mica compounded mix - Google Patents
The preparation method of cuprous oxide with anticorrosion and antifouling function/mica compounded mix Download PDFInfo
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The present invention relates to metal anti-corrosive paint field, it is desirable to provide a kind of preparation method of the cuprous oxide with anticorrosion and antifouling function/mica compounded mix.Including：Mica powder ultrasonication in ethanol water, then adds the concentrated sulfuric acid with being handled in dioxygen aqueous mixtures, obtains activation mica powder；Polyvinylpyrrolidone, copper salt solution, hydration hydrazine reaction, product further react with tetraethyl orthosilicate, distilled water, then obtain product with activation mica powder reaction again.The nano-dispersed of function ingredients is changed into micron and disperseed by the present invention by size being micron-sized mica sheet surface cuprous oxide nano particle uniform load, can effectively solve cuprous oxide nano particle easily reunite in antifouling paint, it is difficult the problem of disperse.In addition, by the silicon dioxide layer in the certain porosity of cuprous oxide Surface coating, the rate of release of cuprous ion can also be adjusted, so as to extend the service life of nonpolluting coating.
Description
Technical field
The present invention relates to metal anti-corrosive paint field, and in particular to a kind of cuprous oxide/cloud with anticorrosion and antifouling function
The preparation method of female compounded mix.
Background technology
Huge impetus, national marine economy total output value in 2014 are played to China's economy and social development in ocean
Reach 5.99 trillion yuans.While development however as marine economy, the hardware in marine settings, facility is all suffered from sternly
The marine corrosion problem of weight, simultaneously for the facility of contact seawater part, the attachment of marine organisms can also bring destruction to component,
To substantially increase skin resistance after particularly ship, a large amount of marine organisms of surface attachment, reduction ship's speed and instrument and meter it is sensitive
Degree, increases fuel consumption, blocks inlet and outlet pipe, corrodes hull.Therefore, the anticorrosion and antifouling towards marine environment is (anti-biological attached
) development of coating is always researcher's focus of attention.
In terms of marine anti-pollution, cuprous oxide is one of use time most long anti-fouling material, excellent with safety, inexpensive etc.
Point.In particular with the development of nanometer technology, nano cuprous oxide is applied widely in antifouling paint.But it is nano oxidized
It is cuprous to be difficult to disperse in antifouling paint, easily reunite, and copper ion release is fast, and unfavorable shadow is produced to long-term anti-fouling effect
Ring.Patent 200510043885.4 reports a kind of organic-polymer-coated nano cuprous oxide, it is characterized in that cuprous oxide
Grain diameter is 1~100nm, and its Surface coating organic polymer, passes through asking that cladding solves that nano-particle easily reunites
Topic, improves oxidation resistance, while nano cuprous oxide has more preferable adhesion with coating film forming matter, makes the mechanics of coating
Performance is more preferable.Reported for work in patent 200610014552.3 and prepared marine anti-pollution by the use of 10-60nm cuprous oxide as anti-fouling agent
Coating, it is mixed with elastomeric propylene sour water emulsion, chlorinated paraffin, iron oxide red, aerosil etc., and contains at one
Vibration resin solution in the paint shaker of bead, the uniform coating of acquisition has good anti-fouling effect.And in marine anticorrosion
In terms of coating, mica has obtained extensive use as a kind of important functional filler.Flakey mica can be with point in resin
Subchain is combined the company of twining, and in multiple-layer overlapped its flat presentation, with coating surface in arranged in parallel, forms a kind of fine and close anti-chemistry
Corrosion and the protective layer of solar irradiation, prevent air and moisture penetration, so as to improve the impermeability and weatherability of paint film.This
Outside, it because mica flake is flexible, can be slided between scale, so as to prevent paint film stress concentration and be cracked, improve paint
Mechanical property, anti-corrosive properties and the durability of film.
The content of the invention
The technical problem to be solved in the present invention be overcome in the prior art nano cuprous oxide be difficult in antifouling paint point
Dissipate, easily reunite, and copper ion release is fast, it is anti-with anti-corrosion there is provided one kind to have a negative impact to long-term anti-fouling effect
The preparation method of the cuprous oxide of dirty function/mica compounded mix.
In order to solve the above technical problems, the solution of the present invention is：
A kind of preparation method of the cuprous oxide with anticorrosion and antifouling function/mica compounded mix, including following step are provided
Suddenly：
(1) mica powder is added in the ethanol water that mass percent concentration is 70%, mica powder and ethanol water
Quality is 1:1；Ultrasonication is filtered after 30 minutes, and then the mica powder being filtrated to get is added to and above-mentioned ethanol water
In the ether of homogenous quantities；Ultrasonication is filtered after 10 minutes, dried；
(2) it is 3 above-mentioned treated mica powder to be added to volume ratio:In 1 concentrated sulfuric acid and the mixture of hydrogen peroxide, cloud
The mass ratio of female powder and the mixture is 1:9~1:2；Filtered after being stirred 1~5 hour at 80 DEG C, and with distilling water washing 3 times,
Activation mica powder is obtained after drying；
(3) polyvinylpyrrolidone is added in the copper salt solution for being 10~30% to mass percent concentration, poly- second
Mass percent concentration of the alkene pyrrolidone in copper salt solution is 0.2~5%；After stirring 30 minutes, hydrazine hydrate, water are added
It is 1 that hydrazine, which is closed, with copper ion mol ratio:3~1:1；Reaction is precipitated after 5 hours, is first used again for 3 times with distilling water washing after filtering
Absolute ethyl alcohol is washed 3 times, and cuprous oxide nano particle is made after drying；
(4) cuprous oxide nano particle is distributed to the polyvinylpyrrolidone that mass percent concentration is 0.2~2%
In ethanol solution, the cuprous oxide nano particle dispersion liquid that solid content is 1~5% is obtained；Then it is oxidation to add quality
The tetraethyl orthosilicate of cuprous 1.5 times of nano particle, while adding distilled water, distilled water is 1 with tetraethyl orthosilicate mol ratio:4~
1:10；Mixture ph is adjusted at 8,50 DEG C filtering, drying after stirring reaction 4~8 hours with ammoniacal liquor；
(5) activation mica powder is distributed in distilled water, forms the dispersion liquid that solid content is 1~10%；Then step is added
Suddenly the mass ratio of the product in (4), the product and activation mica powder is 1:100~1:10；Stirring reaction is after 5 hours at 80 DEG C,
Filtering, drying；Lower 500 DEG C of vacuum is incubated 1~5 hour, then cools down, obtains cuprous oxide/cloud with anticorrosion and antifouling function
Female compounded mix.
In the present invention, in the step (1), the average grain diameter of the mica powder is 1~50 micron.
In the present invention, in the step (3), the mantoquita is any one in copper sulphate, copper nitrate or copper acetate.
In the present invention, in the step (5), by vacuum, lower 500 DEG C are incubated 1~5 hour, are changed in a nitrogen atmosphere 500
DEG C insulation 1~5 hour.
Invention realization principle is described：
The present invention, as substrate, makes its surface be rich in hydroxyl with micron-sized mica sheet by activation；Positive silicon is utilized simultaneously
Silicon dioxide layer of the hydrolysis of ethyl acetate in the certain porosity of cuprous oxide nano particle Surface coating；Finally by silicon dioxide meter
Face silicone hydroxyl is bonded with mica sheet surface hydroxyl, cuprous oxide nano particle is loaded to mica sheet surface.
Compared with prior art, the beneficial effects of the present invention are：
The present invention by cuprous oxide nano particle uniform load size be micron-sized mica sheet surface, by function
The nano-dispersed of component be changed into micron disperse, can effectively solve cuprous oxide nano particle in antifouling paint easily reunite,
The problem of hardly possible is scattered.In addition, by the silicon dioxide layer in the certain porosity of cuprous oxide Surface coating, can also adjust cuprous
The rate of release of ion, 0.2g samples soak cuprous ion precipitation concentration maximum after 2 hours in distilled water and may decrease to pure oxygen
Change cuprous nano particle separates out cuprous ion concentration 24.3%, so as to extend the service life of nonpolluting coating.
Brief description of the drawings
Fig. 1 is the stereoscan photograph that the present invention prepares cuprous oxide/mica compounded mix with anticorrosion and antifouling function.
Embodiment
The present invention is described in further detail with reference to embodiment：
Embodiment 1：
A kind of preparation method of the cuprous oxide with anticorrosion and antifouling function/mica compounded mix, carries out following walk successively
Suddenly：
(1) mica powder that average grain diameter is 1 micron is added in the ethanol water that mass percent concentration is 70%, cloud
Female powder is 1 with ethanol water quality:1, ultrasonication is filtered after 30 minutes, and then the mica powder being filtrated to get is added to
In the ether of above-mentioned ethanol water homogenous quantities, ultrasonication is filtered after 10 minutes, dried.
(2) it is 3 above-mentioned treated mica powder to be added the concentrated sulfuric acid and dioxygen water volume ratio:In 1 mixture, mica powder
Mass ratio with the mixture is 1:Filter, and with water washing is distilled 3 times, lived after drying after being stirred 5 hours at 9,80 DEG C
Change mica powder.
(3) polyvinylpyrrolidone is added in the copper nitrate aqueous solution that mass percent concentration is 15%, polyethylene pyrrole
Mass percent concentration of the pyrrolidone in copper nitrate aqueous solution is 1%, after stirring 30 minutes, and addition is with copper ion mol ratio
1:2 hydrazine hydrate, after reacting 5 hours, is precipitated, and is washed 3 times, dried respectively successively with distilled water and absolute ethyl alcohol after filtering
Cuprous oxide nano particle is made afterwards.
(4) cuprous oxide nano particle be distributed to polyvinylpyrrolidone mass percent concentration for 0.2% it is anhydrous
In ethanol solution, acquisition solid content is 3% cuprous oxide nano particle dispersion liquid, and it is cuprous nano then to add quality
The tetraethyl orthosilicate of 1.5 times of grain, while it is 1 to add with tetraethyl orthosilicate mol ratio:6 distilled water, and with ammoniacal liquor mixture
PH value is adjusted to stirring reaction at 8,50 DEG C and filters, dries after 8 hours.
(5) activation mica powder is distributed in distilled water, forms the dispersion liquid that solid content is 1%；Then press and activation cloud
Female powder mass ratio is 1:The product that 10 amount is added in step (4), stirring reaction is filtered after 5 hours, dried at 80 DEG C, under vacuum
500 DEG C are incubated 5 hours, and the cuprous oxide with anticorrosion and antifouling function/mica compounded mix is obtained after cooling.
0.2g samples are soaked after 2 hours in distilled water, cuprous ion separates out concentration maximum and may decrease to pure zirconia Asia
Copper nano particles separate out the 24.3% of cuprous ion concentration
Embodiment 2：
A kind of preparation method of the cuprous oxide with anticorrosion and antifouling function/mica compounded mix, carries out following walk successively
Suddenly：
(1) mica powder that average grain diameter is 15 microns is added in the ethanol water that mass percent concentration is 70%,
Mica powder is 1 with ethanol water quality:1, ultrasonication is filtered after 30 minutes, and then the mica powder being filtrated to get is added
Into the ether with above-mentioned ethanol water homogenous quantities, ultrasonication is filtered after 10 minutes, dried.
(2) it is 3 above-mentioned treated mica powder to be added the concentrated sulfuric acid and dioxygen water volume ratio:In 1 mixture, mica powder
Mass ratio with the mixture is 1:Filter, and with water washing is distilled 3 times, lived after drying after being stirred 1 hour at 2,80 DEG C
Change mica powder.
(3) polyvinylpyrrolidone is added in the copper sulfate solution that mass percent concentration is 20%, polyethylene pyrrole
Mass percent concentration of the pyrrolidone in copper sulfate solution is 5%, after stirring 30 minutes, and addition is with copper ion mol ratio
1:1 hydrazine hydrate, after reacting 5 hours, is precipitated, and is washed 3 times, dried respectively successively with distilled water and absolute ethyl alcohol after filtering
Cuprous oxide nano particle is made afterwards.
(4) cuprous oxide nano particle be distributed to polyvinylpyrrolidone mass percent concentration for 0.5% it is anhydrous
In ethanol solution, acquisition solid content is 2% cuprous oxide nano particle dispersion liquid, and it is cuprous nano then to add quality
The tetraethyl orthosilicate of 1.5 times of grain, while it is 1 to add with tetraethyl orthosilicate mol ratio:4 distilled water, and with ammoniacal liquor mixture
PH value is adjusted to stirring reaction at 8,50 DEG C and filters, dries after 6 hours.
(5) activation mica powder is distributed in distilled water, forms the dispersion liquid that solid content is 3%；Then press and activation cloud
Female powder mass ratio is 1:The product that 100 amount is added in step (4), stirring reaction is filtered after 5 hours, dried, vacuum at 80 DEG C
Lower 500 DEG C are incubated 3 hours, and the cuprous oxide with anticorrosion and antifouling function/mica compounded mix is obtained after cooling.
0.2g samples are soaked after 2 hours in distilled water, cuprous ion separates out concentration maximum and may decrease to pure zirconia Asia
Copper nano particles separate out the 35.5% of cuprous ion concentration.
Embodiment 3：
A kind of preparation method of the cuprous oxide with anticorrosion and antifouling function/mica compounded mix, carries out following walk successively
Suddenly：
(1) mica powder that average grain diameter is 50 microns is added in the ethanol water that mass percent concentration is 70%,
Mica powder is 1 with ethanol water quality:1, ultrasonication is filtered after 30 minutes, and then the mica powder being filtrated to get is added
Into the ether with above-mentioned ethanol water homogenous quantities, ultrasonication is filtered after 10 minutes, dried.
(2) it is 3 above-mentioned treated mica powder to be added the concentrated sulfuric acid and dioxygen water volume ratio:In 1 mixture, mica powder
Mass ratio with the mixture is 1:Filter, and with water washing is distilled 3 times, lived after drying after being stirred 2 hours at 4,80 DEG C
Change mica powder.
(3) polyvinylpyrrolidone is added in the copper nitrate aqueous solution that mass percent concentration is 30%, polyethylene pyrrole
Mass percent concentration of the pyrrolidone in copper nitrate aqueous solution is 0.2%, after stirring 30 minutes, is added and copper ion mol ratio
For 1:3 hydrazine hydrate, after reacting 5 hours, is precipitated, and is washed 3 times, done respectively successively with distilled water and absolute ethyl alcohol after filtering
Obtained cuprous oxide nano particle after dry.
(4) cuprous oxide nano particle is distributed to the anhydrous second that polyvinylpyrrolidone mass percent concentration is 1%
In alcoholic solution, acquisition solid content is 3% cuprous oxide nano particle dispersion liquid, and it is cuprous oxide nano particle then to add quality
1.5 times of tetraethyl orthosilicate, while it is 1 to add with tetraethyl orthosilicate mol ratio:10 distilled water, and with ammoniacal liquor mixture pH
Value is adjusted to stirring reaction at 8,50 DEG C and filters, dries after 4 hours.
(5) activation mica powder is distributed in distilled water, forms the dispersion liquid that solid content is 6%；Then press and activation cloud
Female powder mass ratio is 1:The product that 20 amount is added in step (4), stirring reaction is filtered after 5 hours, dried, nitrogen gas at 80 DEG C
Lower 500 DEG C of atmosphere is incubated 1 hour, and the cuprous oxide with anticorrosion and antifouling function/mica compounded mix is obtained after cooling.
0.2g samples are soaked after 2 hours in distilled water, cuprous ion separates out concentration maximum and may decrease to pure zirconia Asia
Copper nano particles separate out the 32.9% of cuprous ion concentration.
Embodiment 4：
A kind of preparation method of the cuprous oxide with anticorrosion and antifouling function/mica compounded mix, carries out following walk successively
Suddenly：
(1) mica powder that average grain diameter is 44 microns is added in the ethanol water that mass percent concentration is 70%,
Mica powder is 1 with ethanol water quality:1, ultrasonication is filtered after 30 minutes, and then the mica powder being filtrated to get is added
Into the ether with above-mentioned ethanol water homogenous quantities, ultrasonication is filtered after 10 minutes, dried.
(2) it is 3 above-mentioned treated mica powder to be added the concentrated sulfuric acid and dioxygen water volume ratio:In 1 mixture, mica powder
Mass ratio with the mixture is 1:Filter, and with water washing is distilled 3 times, lived after drying after being stirred 4 hours at 8,80 DEG C
Change mica powder.
(3) polyvinylpyrrolidone is added in the acetic acid copper liquor that mass percent concentration is 15%, polyethylene pyrrole
Mass percent concentration of the pyrrolidone in acetic acid copper liquor is 0.5%, after stirring 30 minutes, is added and copper ion mol ratio
For 1:2 hydrazine hydrate, after reacting 5 hours, is precipitated, and is washed 3 times, done respectively successively with distilled water and absolute ethyl alcohol after filtering
Obtained cuprous oxide nano particle after dry.
(4) cuprous oxide nano particle is distributed to the anhydrous second that polyvinylpyrrolidone mass percent concentration is 2%
In alcoholic solution, acquisition solid content is 1% cuprous oxide nano particle dispersion liquid, and it is cuprous oxide nano particle then to add quality
1.5 times of tetraethyl orthosilicate, while it is 1 to add with tetraethyl orthosilicate mol ratio:4 distilled water, and with ammoniacal liquor mixture pH
Value is adjusted to stirring reaction at 8,50 DEG C and filters, dries after 8 hours.
(5) activation mica powder is distributed in distilled water, forms the dispersion liquid that solid content is 10%；Then press and activation cloud
Female powder mass ratio is 1:The product that 50 amount is added in step (4), stirring reaction is filtered after 5 hours, dried, nitrogen gas at 80 DEG C
Lower 500 DEG C of atmosphere is incubated 5 hours, and the cuprous oxide with anticorrosion and antifouling function/mica compounded mix is obtained after cooling.
0.2g samples are soaked after 2 hours in distilled water, cuprous ion separates out concentration maximum and may decrease to pure zirconia Asia
Copper nano particles separate out the 41.5% of cuprous ion concentration.
Embodiment 5：
A kind of preparation method of the cuprous oxide with anticorrosion and antifouling function/mica compounded mix, carries out following walk successively
Suddenly：
(1) mica powder that average grain diameter is 33 microns is added in the ethanol water that mass percent concentration is 70%,
Mica powder is 1 with ethanol water quality:1, ultrasonication is filtered after 30 minutes, and then the mica powder being filtrated to get is added
Into the ether with above-mentioned ethanol water homogenous quantities, ultrasonication is filtered after 10 minutes, dried.
(2) it is 3 above-mentioned treated mica powder to be added the concentrated sulfuric acid and dioxygen water volume ratio:In 1 mixture, mica powder
Mass ratio with the mixture is 1:Filter, and with water washing is distilled 3 times, lived after drying after being stirred 3 hours at 5,80 DEG C
Change mica powder.
(3) polyvinylpyrrolidone is added in the copper nitrate aqueous solution that mass percent concentration is 10%, polyethylene pyrrole
Mass percent concentration of the pyrrolidone in copper nitrate aqueous solution is 3%, after stirring 30 minutes, and addition is with copper ion mol ratio
1:2 hydrazine hydrate, after reacting 5 hours, is precipitated, and is washed 3 times, dried respectively successively with distilled water and absolute ethyl alcohol after filtering
Cuprous oxide nano particle is made afterwards.
(4) cuprous oxide nano particle be distributed to polyvinylpyrrolidone mass percent concentration for 1.5% it is anhydrous
In ethanol solution, acquisition solid content is 5% cuprous oxide nano particle dispersion liquid, and it is cuprous nano then to add quality
The tetraethyl orthosilicate of 1.5 times of grain, while it is 1 to add with tetraethyl orthosilicate mol ratio:8 distilled water, and with ammoniacal liquor mixture
PH value is adjusted to stirring reaction at 8,50 DEG C and filters, dries after 5 hours.
(5) activation mica powder is distributed in distilled water, forms the dispersion liquid that solid content is 8%；Then press and activation cloud
Female powder mass ratio is 1:The product that 70 amount is added in step (4), stirring reaction is filtered after 5 hours, dried at 80 DEG C, under vacuum
500 DEG C are incubated 1 hour, and the cuprous oxide with anticorrosion and antifouling function/mica compounded mix is obtained after cooling.
0.2g samples are soaked after 2 hours in distilled water, cuprous ion separates out concentration maximum and may decrease to pure zirconia Asia
Copper nano particles separate out the 53.7% of cuprous ion concentration.
Finally, in addition it is also necessary to it is noted that listed above is only specific embodiment of the invention.Obviously, the present invention not
It is limited to above embodiment, there can also be many deformations.One of ordinary skill in the art can be straight from present disclosure
Export or all deformations associated are connect, protection scope of the present invention is considered as.
Claims (3)
1. the preparation method of cuprous oxide/mica compounded mix with anticorrosion and antifouling function, it is characterised in that including following step
Suddenly：
(1) mica powder that average grain diameter is 1~50 micron is added in the ethanol water that mass percent concentration is 70%, cloud
Female powder is 1 with ethanol water quality:1；Ultrasonication is filtered after 30 minutes, and then the mica powder being filtrated to get is added to
With in the ether of above-mentioned ethanol water homogenous quantities；Ultrasonication is filtered after 10 minutes, dried；
(2) it is 3 above-mentioned treated mica powder to be added to volume ratio:In 1 concentrated sulfuric acid and the mixture of hydrogen peroxide, mica powder
Mass ratio with the mixture is 1:9~1:2；Filter, and with water washing is distilled 3 times, dry after being stirred 1~5 hour at 80 DEG C
Activation mica powder is obtained afterwards；
(3) polyvinylpyrrolidone is added in the copper salt solution for being 10~30% to mass percent concentration, polyethylene pyrrole
Mass percent concentration of the pyrrolidone in copper salt solution is 0.2~5%；After stirring 30 minutes, hydrazine hydrate, hydrazine hydrate are added
It is 1 with copper ion mol ratio:3~1:1；Reaction is precipitated after 5 hours, distillation water washing is first used after filtering 3 times again with anhydrous
Ethanol is washed 3 times, and cuprous oxide nano particle is made after drying；
(4) cuprous oxide nano particle is distributed to the anhydrous of the polyvinylpyrrolidone that mass percent concentration is 0.2~2%
In ethanol solution, the cuprous oxide nano particle dispersion liquid that solid content is 1~5% is obtained；Then it is cuprous oxide to add quality
The tetraethyl orthosilicate that 1.5 times of nano particle, while adding distilled water, distilled water is 1 with tetraethyl orthosilicate mol ratio:4~1:10；
Mixture ph is adjusted at 8,50 DEG C filtering, drying after stirring reaction 4~8 hours with ammoniacal liquor；
(5) activation mica powder is distributed in distilled water, forms the dispersion liquid that solid content is 1~10%；Then step (4) is added
In product, the product with activation mica powder mass ratio be 1:100~1:10；Stirring reaction is after 5 hours at 80 DEG C, filtering,
Drying；Lower 500 DEG C of vacuum is incubated 1~5 hour, then cools down, and obtains cuprous oxide/mica with anticorrosion and antifouling function and is combined
Filler.
2. according to the method described in claim 1, it is characterised in that in the step (3), the mantoquita is copper sulphate, nitric acid
Any one in copper or copper acetate.
3. according to the method described in claim 1, it is characterised in that in the step (5), by the lower 500 DEG C of insulations 1~5 of vacuum
Hour, be changed in a nitrogen atmosphere 500 DEG C be incubated 1~5 hour.
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| CN112852246B (en) * | 2021-03-05 | 2022-01-07 | 中国海洋大学 | Preparation method of organic-inorganic three-phase composite antifouling paint with spirulina biochar as carrier |
| CN116836578B (en) * | 2023-07-07 | 2023-12-15 | 天津大学 | Composite material and paint for mica/zinc oxide and marine anti-corrosion and anti-fouling coating |
| CN118637875A (en) * | 2024-08-14 | 2024-09-13 | 北京生态家园(乐亭)科技发展有限公司 | High-strength antibacterial mortar material and preparation method and application thereof |
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| EP1306412A1 (en) * | 2001-10-24 | 2003-05-02 | MERCK PATENT GmbH | Coloured interference pigments |
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| CN101096491A (en) * | 2006-06-30 | 2008-01-02 | 天津市振东涂料有限公司 | Method for preparing ocean anti-fouling paint |
| EP2230702A1 (en) * | 2009-03-19 | 2010-09-22 | Ecole Polytechnique Fédérale de Lausanne (EPFL) | Modified surface |
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