CN105670344A - Preparation method of cuprous oxide/mica composite packing having antiseptic and antifouling functions - Google Patents
Preparation method of cuprous oxide/mica composite packing having antiseptic and antifouling functions Download PDFInfo
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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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
- C09D5/08—Anti-corrosive paints
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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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
Abstract
The invention relates to the field of anticorrosive coatings for metals and aims at providing a preparation method of a cuprous oxide/mica composite packing having antiseptic and antifouling functions. The preparation method comprises the steps that mica powder is subjected to ultrasonic treatment in an ethanol water solution and then is added into a concentrated sulfuric acid and hydrogen peroxide mixture to be treated so as to obtain activated mica powder; polyvinylpyrrolidone, a copper saline solution and hydrazine hydrate perform reaction, and the product further reacts with tetraethoxysilane and distilled water and then reacts with the activated mica powder to obtain the product. The problem that cuprous oxide nanoparticles easily agglomerate and are difficult to disperse in antifouling paints can be effectively solved by uniformly supporting the cuprous oxide nanoparticles on the surfaces of micron-grade mica sheets and converting nano dispersion of functional components into micron dispersion. In addition, the surface of the cuprous oxide is coated with a silicon dioxide layer having certain porosity, the cuprous ion release rate can be further adjusted, and accordingly the service life of antifouling coatings is prolonged.
Description
Technical field
The present invention relates to metal anti-corrosive paint field, it is specifically related to the preparation method of a kind of Red copper oxide/mica compounded mix with anticorrosion and antifouling function.
Background technology
China's economy and social development are played huge pushing effect by ocean, and national marine economy total output value in 2014 reaches 5.99 trillion yuan. But along with while marine economy development, hardware in ocean equipment, facility all faces serious marine corrosion problem, simultaneously for the facility of contact seawater part, component also can be brought destruction by the attachment of marine organisms, particularly boats and ships, will obviously increase surface resistance after a large amount of marine organisms of surface attachment, reduce the sensitivity of ship's speed and instrument, increase fuel consumption, blocking inlet and outlet pipe, corrosion hull. Therefore, development towards anticorrosion and antifouling (anti-halobios adhersion) coating of ocean environment is the focus that researchist pays close attention to always.
In marine anti-pollution, Red copper oxide is one of the longest anti-fouling material duration of service, has the advantages such as safe, inexpensive. Particularly along with the development of nanotechnology, nano cuprous oxide is applied widely in antifouling paint. But nano cuprous oxide is difficult to dispersion in antifouling paint, easily reunites, and cupric ion release is fast, is had a negative impact by long-term anti-fouling effect. Patent 200510043885.4 reports a kind of organic-polymer-coated nano cuprous oxide, it is characterized in that Red copper oxide grain diameter is 1～100nm, and its Surface coating organic polymer, by the coated problem solving nanoparticle and easily reuniting, improve resistance of oxidation, nano cuprous oxide and coating film forming matter have better bonding force simultaneously, make the mechanical property of coating better. Patent 200610014552.3 is reported for work and has utilized 10-60nm Red copper oxide to prepare marine antifouling coating as stain control agent, it is mixed with elastomeric propylene acid water miscible liquid, clorafin, red iron oxide, aerosil etc., and containing vibration resin solution in the paint shaker of granulated glass sphere at one, the uniform coating of acquisition has good anti-fouling effect.And in marine anticorrosion coating, mica has obtained widespread use as a kind of important functional filler. Flakey mica can combine with the molecular chain in resin the company of twining; it is in multilayer overlapping tile state, it is arranged in parallel with coating surface, form the resist chemical of a kind of densification and the protective layer of solar irradiation; stop air and moisture to be invaded, thus improve impermeability and the weathering resistance of paint film. In addition, owing to mica flake has elasticity, can slide between scale, thus prevent paint film stress to concentrate and chap, it is to increase the mechanical property of paint film, preservative property and weather resistance.
Summary of the invention
The technical problem to be solved in the present invention is, overcome nano cuprous oxide in prior art in antifouling paint, to be difficult to dispersion, easily reunite, and cupric ion discharges soon, is had a negative impact by long-term anti-fouling effect, it is provided that the preparation method of a kind of Red copper oxide/mica compounded mix with anticorrosion and antifouling function.
For solving the problems of the technologies described above, the solution of the present invention is:
The preparation method of a kind of Red copper oxide/mica compounded mix with anticorrosion and antifouling function is provided, comprises the following steps:
(1) mica powder being added in the aqueous ethanolic solution that mass percent concentration is 70%, mica powder and aqueous ethanolic solution quality are 1:1; Ultrasonication was filtered after 30 minutes, then joined filter the mica powder obtained in the ether with above-mentioned aqueous ethanolic solution homogenous quantities; Ultrasonication is filtered after 10 minutes, is dried;
(2) the above-mentioned mica powder processed being added to volume ratio is that in the vitriol oil of 3:1 and the mixture of hydrogen peroxide, the mass ratio of mica powder and this mixture is 1:9～1:2; Stir at 80 DEG C after 1～5 hour and filter, and with distilled water wash 3 times, after dry, obtain activation mica powder;
(3) polyvinylpyrrolidone being added in the copper salt solution that mass percent concentration is 10～30%, the mass percent concentration of polyvinylpyrrolidone in copper salt solution is 0.2～5%; Stirring after 30 minutes, add hydrazine hydrate, hydrazine hydrate and cupric ion mol ratio are 1:3～1:1; React and after 5 hours, obtain precipitation, after filtration first with distilled water wash 3 times again with absolute ethanol washing 3 times, obtained cuprous oxide nano particle after dry;
(4) cuprous oxide nano particle is distributed in the ethanol solution of polyvinylpyrrolidone that mass percent concentration is 0.2～2%, obtains the cuprous oxide nano particle dispersion liquid that solid content is 1～5%; Then adding the tetraethoxy that quality is cuprous oxide nano particle 1.5 times, add distilled water simultaneously, distilled water and tetraethoxy mol ratio are 1:4～1:10; At mixture ph being adjusted to 8,50 DEG C with ammoniacal liquor, stirring reaction filters after 4～8 hours, dries;
(5) activation mica powder being distributed in distilled water, forming solid content is the dispersion liquid of 1～10%; Then adding the product in step (4), this product is 1:100～1:10 with the mass ratio of activation mica powder; At 80 DEG C, stirring reaction is after 5 hours, filters, dries; The lower 500 DEG C of insulations of vacuum 1～5 hour, then cool, obtain having the Red copper oxide/mica compounded mix of anticorrosion and antifouling function.
In the present invention, in described step (1), the median size of described mica powder is 1～50 micron.
In the present invention, in described step (3), described mantoquita is any one in copper sulfate, cupric nitrate or neutralized verdigris.
In the present invention, in described step (5), by lower for vacuum 500 DEG C insulation 1～5 hour, change in a nitrogen atmosphere 500 DEG C insulation 1～5 hour.
Invention realizes principles illustrated:
The present invention as substrate, makes its rich surface hydroxyl by activation with micron-sized sheet mica; Utilize teos hydrolysis at the silicon dioxide layer of the certain porosity of cuprous oxide nano particle Surface coating simultaneously; It is bonded with mica sheet surface hydroxyl finally by silica sphere silicone hydroxyl, makes cuprous oxide nano particle load to mica sheet surface.
Compared with prior art, the useful effect of the present invention is:
The present invention is by being of a size of micron-sized mica sheet surface cuprous oxide nano particle uniform loading, the nano-dispersed of function ingredients is changed into micron dispersion, can effectively solve the problem that cuprous oxide nano particle is easily reunited in antifouling paint, difficulty is disperseed. In addition, by the silicon dioxide layer at the certain porosity of Red copper oxide Surface coating, the rate of release of cuprous ion can also be regulated, after 0.2g sample soaks 2 hours in distilled water, the maximum cuprous nano particle of pure zirconia that reduces to of cuprous ion precipitation concentration precipitates out the 24.3% of cuprous ion concentration, thus extends the work-ing life of antifouling coating.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph that the present invention prepares the Red copper oxide/mica compounded mix with anticorrosion and antifouling function.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment 1:
A preparation method with the Red copper oxide/mica compounded mix of anticorrosion and antifouling function, carries out following step successively:
(1) mica powder that median size is 1 micron is added in the aqueous ethanolic solution that mass percent concentration is 70%, mica powder and aqueous ethanolic solution quality are 1:1, ultrasonication was filtered after 30 minutes, then joining filter the mica powder obtained in the ether with above-mentioned aqueous ethanolic solution homogenous quantities, ultrasonication is filtered after 10 minutes, is dried.
(2) the above-mentioned mica powder processed is added the vitriol oil and hydrogen peroxide volume ratio be 3:1 mixture in, the mass ratio of mica powder and this mixture is 1:9, stir at 80 DEG C after 5 hours and filter, and with distilled water wash 3 times, after dry, obtain activation mica powder.
(3) polyvinylpyrrolidone is added in the copper nitrate aqueous solution that mass percent concentration is 15%, the mass percent concentration of polyvinylpyrrolidone in copper nitrate aqueous solution is 1%, stir after 30 minutes, adding with cupric ion mol ratio is the hydrazine hydrate of 1:2, react after 5 hours, obtain precipitation, wash 3 times respectively successively with distilled water and dehydrated alcohol after filtration, obtained cuprous oxide nano particle after dry.
(4) cuprous oxide nano particle is distributed in the ethanol solution that polyvinylpyrrolidone mass percent concentration is 0.2%, obtaining solid content is 3% cuprous oxide nano particle dispersion liquid, then the tetraethoxy that quality is cuprous oxide nano particle 1.5 times is added, add with tetraethoxy mol ratio is the distilled water of 1:6 simultaneously, and stirring reaction filters after 8 hours, dries at mixture ph being adjusted to 8,50 DEG C with ammoniacal liquor.
(5) activation mica powder being distributed in distilled water, forming solid content is the dispersion liquid of 1%; Then by being that the amount of 1:10 adds the product in step (4) with activation mica powder mass ratio, at 80 DEG C, stirring reaction filters after 5 hours, dries, the lower 500 DEG C of insulations of vacuum 5 hours, obtain having the Red copper oxide/mica compounded mix of anticorrosion and antifouling function after cooling.
After 0.2g sample is soaked 2 hours in distilled water, cuprous ion precipitates out the maximum cuprous nano particle of pure zirconia that reduces to of concentration and precipitates out the 24.3% of cuprous ion concentration
Embodiment 2:
A preparation method with the Red copper oxide/mica compounded mix of anticorrosion and antifouling function, carries out following step successively:
(1) mica powder that median size is 15 microns is added in the aqueous ethanolic solution that mass percent concentration is 70%, mica powder and aqueous ethanolic solution quality are 1:1, ultrasonication was filtered after 30 minutes, then joining filter the mica powder obtained in the ether with above-mentioned aqueous ethanolic solution homogenous quantities, ultrasonication is filtered after 10 minutes, is dried.
(2) the above-mentioned mica powder processed is added the vitriol oil and hydrogen peroxide volume ratio be 3:1 mixture in, the mass ratio of mica powder and this mixture is 1:2, stir at 80 DEG C after 1 hour and filter, and with distilled water wash 3 times, after dry, obtain activation mica powder.
(3) polyvinylpyrrolidone is added in the copper sulfate solution that mass percent concentration is 20%, the mass percent concentration of polyvinylpyrrolidone in copper sulfate solution is 5%, stir after 30 minutes, adding with cupric ion mol ratio is the hydrazine hydrate of 1:1, react after 5 hours, obtain precipitation, wash 3 times respectively successively with distilled water and dehydrated alcohol after filtration, obtained cuprous oxide nano particle after dry.
(4) cuprous oxide nano particle is distributed in the ethanol solution that polyvinylpyrrolidone mass percent concentration is 0.5%, obtaining solid content is 2% cuprous oxide nano particle dispersion liquid, then the tetraethoxy that quality is cuprous oxide nano particle 1.5 times is added, add with tetraethoxy mol ratio is the distilled water of 1:4 simultaneously, and stirring reaction filters after 6 hours, dries at mixture ph being adjusted to 8,50 DEG C with ammoniacal liquor.
(5) activation mica powder being distributed in distilled water, forming solid content is the dispersion liquid of 3%; Then by being that the amount of 1:100 adds the product in step (4) with activation mica powder mass ratio, at 80 DEG C, stirring reaction filters after 5 hours, dries, the lower 500 DEG C of insulations of vacuum 3 hours, obtain having the Red copper oxide/mica compounded mix of anticorrosion and antifouling function after cooling.
After 0.2g sample is soaked 2 hours in distilled water, cuprous ion precipitates out the maximum cuprous nano particle of pure zirconia that reduces to of concentration and precipitates out the 35.5% of cuprous ion concentration.
Embodiment 3:
A preparation method with the Red copper oxide/mica compounded mix of anticorrosion and antifouling function, carries out following step successively:
(1) mica powder that median size is 50 microns is added in the aqueous ethanolic solution that mass percent concentration is 70%, mica powder and aqueous ethanolic solution quality are 1:1, ultrasonication was filtered after 30 minutes, then joining filter the mica powder obtained in the ether with above-mentioned aqueous ethanolic solution homogenous quantities, ultrasonication is filtered after 10 minutes, is dried.
(2) the above-mentioned mica powder processed is added the vitriol oil and hydrogen peroxide volume ratio be 3:1 mixture in, the mass ratio of mica powder and this mixture is 1:4, stir at 80 DEG C after 2 hours and filter, and with distilled water wash 3 times, after dry, obtain activation mica powder.
(3) polyvinylpyrrolidone is added in the copper nitrate aqueous solution that mass percent concentration is 30%, the mass percent concentration of polyvinylpyrrolidone in copper nitrate aqueous solution is 0.2%, stir after 30 minutes, adding with cupric ion mol ratio is the hydrazine hydrate of 1:3, react after 5 hours, obtain precipitation, wash 3 times respectively successively with distilled water and dehydrated alcohol after filtration, obtained cuprous oxide nano particle after dry.
(4) cuprous oxide nano particle is distributed in the ethanol solution that polyvinylpyrrolidone mass percent concentration is 1%, obtaining solid content is 3% cuprous oxide nano particle dispersion liquid, then the tetraethoxy that quality is cuprous oxide nano particle 1.5 times is added, add with tetraethoxy mol ratio is the distilled water of 1:10 simultaneously, and stirring reaction filters after 4 hours, dries at mixture ph being adjusted to 8,50 DEG C with ammoniacal liquor.
(5) activation mica powder being distributed in distilled water, forming solid content is the dispersion liquid of 6%;Then by being that the amount of 1:20 adds the product in step (4) with activation mica powder mass ratio, at 80 DEG C, stirring reaction filters after 5 hours, dries, the lower 500 DEG C of insulations of nitrogen atmosphere 1 hour, obtain having the Red copper oxide/mica compounded mix of anticorrosion and antifouling function after cooling.
After 0.2g sample is soaked 2 hours in distilled water, cuprous ion precipitates out the maximum cuprous nano particle of pure zirconia that reduces to of concentration and precipitates out the 32.9% of cuprous ion concentration.
Embodiment 4:
A preparation method with the Red copper oxide/mica compounded mix of anticorrosion and antifouling function, carries out following step successively:
(1) mica powder that median size is 44 microns is added in the aqueous ethanolic solution that mass percent concentration is 70%, mica powder and aqueous ethanolic solution quality are 1:1, ultrasonication was filtered after 30 minutes, then joining filter the mica powder obtained in the ether with above-mentioned aqueous ethanolic solution homogenous quantities, ultrasonication is filtered after 10 minutes, is dried.
(2) the above-mentioned mica powder processed is added the vitriol oil and hydrogen peroxide volume ratio be 3:1 mixture in, the mass ratio of mica powder and this mixture is 1:8, stir at 80 DEG C after 4 hours and filter, and with distilled water wash 3 times, after dry, obtain activation mica powder.
(3) polyvinylpyrrolidone is added in the neutralized verdigris aqueous solution that mass percent concentration is 15%, the mass percent concentration of polyvinylpyrrolidone in the neutralized verdigris aqueous solution is 0.5%, stir after 30 minutes, adding with cupric ion mol ratio is the hydrazine hydrate of 1:2, react after 5 hours, obtain precipitation, wash 3 times respectively successively with distilled water and dehydrated alcohol after filtration, obtained cuprous oxide nano particle after dry.
(4) cuprous oxide nano particle is distributed in the ethanol solution that polyvinylpyrrolidone mass percent concentration is 2%, obtaining solid content is 1% cuprous oxide nano particle dispersion liquid, then the tetraethoxy that quality is cuprous oxide nano particle 1.5 times is added, add with tetraethoxy mol ratio is the distilled water of 1:4 simultaneously, and stirring reaction filters after 8 hours, dries at mixture ph being adjusted to 8,50 DEG C with ammoniacal liquor.
(5) activation mica powder being distributed in distilled water, forming solid content is the dispersion liquid of 10%; Then by being that the amount of 1:50 adds the product in step (4) with activation mica powder mass ratio, at 80 DEG C, stirring reaction filters after 5 hours, dries, the lower 500 DEG C of insulations of nitrogen atmosphere 5 hours, obtain having the Red copper oxide/mica compounded mix of anticorrosion and antifouling function after cooling.
After 0.2g sample is soaked 2 hours in distilled water, cuprous ion precipitates out the maximum cuprous nano particle of pure zirconia that reduces to of concentration and precipitates out the 41.5% of cuprous ion concentration.
Embodiment 5:
A preparation method with the Red copper oxide/mica compounded mix of anticorrosion and antifouling function, carries out following step successively:
(1) mica powder that median size is 33 microns is added in the aqueous ethanolic solution that mass percent concentration is 70%, mica powder and aqueous ethanolic solution quality are 1:1, ultrasonication was filtered after 30 minutes, then joining filter the mica powder obtained in the ether with above-mentioned aqueous ethanolic solution homogenous quantities, ultrasonication is filtered after 10 minutes, is dried.
(2) the above-mentioned mica powder processed is added the vitriol oil and hydrogen peroxide volume ratio be 3:1 mixture in, the mass ratio of mica powder and this mixture is 1:5, stir at 80 DEG C after 3 hours and filter, and with distilled water wash 3 times, after dry, obtain activation mica powder.
(3) polyvinylpyrrolidone is added in the copper nitrate aqueous solution that mass percent concentration is 10%, the mass percent concentration of polyvinylpyrrolidone in copper nitrate aqueous solution is 3%, stir after 30 minutes, adding with cupric ion mol ratio is the hydrazine hydrate of 1:2, react after 5 hours, obtain precipitation, wash 3 times respectively successively with distilled water and dehydrated alcohol after filtration, obtained cuprous oxide nano particle after dry.
(4) cuprous oxide nano particle is distributed in the ethanol solution that polyvinylpyrrolidone mass percent concentration is 1.5%, obtaining solid content is 5% cuprous oxide nano particle dispersion liquid, then the tetraethoxy that quality is cuprous oxide nano particle 1.5 times is added, add with tetraethoxy mol ratio is the distilled water of 1:8 simultaneously, and stirring reaction filters after 5 hours, dries at mixture ph being adjusted to 8,50 DEG C with ammoniacal liquor.
(5) activation mica powder being distributed in distilled water, forming solid content is the dispersion liquid of 8%; Then by being that the amount of 1:70 adds the product in step (4) with activation mica powder mass ratio, at 80 DEG C, stirring reaction filters after 5 hours, dries, the lower 500 DEG C of insulations of vacuum 1 hour, obtain having the Red copper oxide/mica compounded mix of anticorrosion and antifouling function after cooling.
After 0.2g sample is soaked 2 hours in distilled water, cuprous ion precipitates out the maximum cuprous nano particle of pure zirconia that reduces to of concentration and precipitates out the 53.7% of cuprous ion concentration.
Finally, in addition it is also necessary to it is to be noted that, what more than enumerate is only specific embodiments of the invention. Obviously, the invention is not restricted to above examples of implementation, it is also possible to have many distortion. All distortion that the those of ordinary skill of this area can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (4)
1. there is the preparation method of the Red copper oxide/mica compounded mix of anticorrosion and antifouling function, it is characterised in that, comprise the following steps:
(1) mica powder being added in the aqueous ethanolic solution that mass percent concentration is 70%, mica powder and aqueous ethanolic solution quality are 1:1; Ultrasonication was filtered after 30 minutes, then joined filter the mica powder obtained in the ether with above-mentioned aqueous ethanolic solution homogenous quantities; Ultrasonication is filtered after 10 minutes, is dried;
(2) the above-mentioned mica powder processed being added to volume ratio is that in the vitriol oil of 3:1 and the mixture of hydrogen peroxide, the mass ratio of mica powder and this mixture is 1:9～1:2; Stir at 80 DEG C after 1～5 hour and filter, and with distilled water wash 3 times, after dry, obtain activation mica powder;
(3) polyvinylpyrrolidone being added in the copper salt solution that mass percent concentration is 10～30%, the mass percent concentration of polyvinylpyrrolidone in copper salt solution is 0.2～5%; Stirring after 30 minutes, add hydrazine hydrate, hydrazine hydrate and cupric ion mol ratio are 1:3～1:1; React and after 5 hours, obtain precipitation, after filtration first with distilled water wash 3 times again with absolute ethanol washing 3 times, obtained cuprous oxide nano particle after dry;
(4) cuprous oxide nano particle is distributed in the ethanol solution of polyvinylpyrrolidone that mass percent concentration is 0.2～2%, obtains the cuprous oxide nano particle dispersion liquid that solid content is 1～5%; Then adding the tetraethoxy that quality is cuprous oxide nano particle 1.5 times, add distilled water simultaneously, distilled water and tetraethoxy mol ratio are 1:4～1:10;At mixture ph being adjusted to 8,50 DEG C with ammoniacal liquor, stirring reaction filters after 4～8 hours, dries;
(5) activation mica powder being distributed in distilled water, forming solid content is the dispersion liquid of 1～10%; Then adding the product in step (4), this product is 1:100～1:10 with the mass ratio of activation mica powder; At 80 DEG C, stirring reaction is after 5 hours, filters, dries; The lower 500 DEG C of insulations of vacuum 1～5 hour, then cool, obtain having the Red copper oxide/mica compounded mix of anticorrosion and antifouling function.
2. method according to claim 1, it is characterised in that, in described step (1), the median size of described mica powder is 1～50 micron.
3. method according to claim 1, it is characterised in that, in described step (3), described mantoquita is any one in copper sulfate, cupric nitrate or neutralized verdigris.
4. method according to claim 1, it is characterised in that, in described step (5), by lower for vacuum 500 DEG C insulation 1～5 hour, change in a nitrogen atmosphere 500 DEG C insulation 1～5 hour.
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| CN201610083018.1A CN105670344B (en) | 2016-02-06 | 2016-02-06 | The preparation method of cuprous oxide with anticorrosion and antifouling function/mica compounded mix |
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| CN107814390A (en) * | 2017-11-01 | 2018-03-20 | 山东圣泉新材料股份有限公司 | A kind of grapheme material combined mica, preparation method and purposes |
| CN112852246A (en) * | 2021-03-05 | 2021-05-28 | 中国海洋大学 | Preparation method of organic-inorganic three-phase composite antifouling paint with spirulina biochar as carrier |
| CN116836578A (en) * | 2023-07-07 | 2023-10-03 | 天津大学 | Composite material and paint for mica/zinc oxide and marine anti-corrosion and anti-fouling coating |
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| CN112852246A (en) * | 2021-03-05 | 2021-05-28 | 中国海洋大学 | Preparation method of organic-inorganic three-phase composite antifouling paint with spirulina biochar as carrier |
| 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 |
| CN116836578A (en) * | 2023-07-07 | 2023-10-03 | 天津大学 | Composite material and paint for mica/zinc oxide and marine anti-corrosion and anti-fouling coating |
| 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 |
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| CN105670344B (en) | 2017-10-27 |
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