CN104861868A - Preparation method of ultra-black coating - Google Patents

Preparation method of ultra-black coating Download PDF

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Publication number
CN104861868A
CN104861868A CN201510337460.8A CN201510337460A CN104861868A CN 104861868 A CN104861868 A CN 104861868A CN 201510337460 A CN201510337460 A CN 201510337460A CN 104861868 A CN104861868 A CN 104861868A
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silicon
carbon
coated
microballoon
dioxide
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CN104861868B (en
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潘磊
李垚
李娜
赵九蓬
孟庆强
王晶
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/10Encapsulated ingredients
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/70Additives characterised by shape, e.g. fibres, flakes or microspheres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

Abstract

The invention relates to a preparation method of an ultra-black coating, and aims to solve the problem of failure in meeting the reflectivity requirement in the optical field, strict limitation on the type and size of a substrate, or complex construction steps of the conventional black coating. The method has the following steps 1, preparation of silicon dioxide monodisperse microspheres; 2, preparation of carbon-coated silicon dioxide monodisperse microspheres; 3, preparation of ultra-black paint; 4, brushing or spraying, that is, forming of the ultra-black coating. The preparation method provided by the invention is used for forming of the ultra-black coating.

Description

A kind of preparation method of blacker-than-black coating
Technical field
The present invention relates to the preparation method of blacker-than-black coating.
Background technology
Black coating is all widely used in a lot of field such as building, furniture and optics, and the most common in black coating, use is exactly pitch-dark the most easily.In the optical system of survey of deep space, after the irradiate light that non-targeted celestial body sends to the surfaces such as lens barrel inside, because surface has certain reflectivity, light may enter into detector after repeatedly launching, and causes interference to the imaging of target celestial body.Because some celestial body to be observed is very remote, arrive the energy of detector very faint, therefore need the parts such as lens barrel apply high-absorbility, antiradar reflectivity with pitch-dark, absorb the stray light that non-targeted celestial body sends, to improve the precision of Optical devices.Stray light often needs could arrive detector after multiple reflections, and therefore the fine difference of reflectivity can obtain the amplification of exponential series after multiple reflections, and the difference in reflectivity of 1% will cause the impact of several order of magnitude on final stray light level.
The pitch-dark composition used both at home and abroad is at present mutually similar, main use carbon black absorbs light as black pigment, use resin as matrix or binding agent, use the powdered material such as white carbon black, talcum powder to reduce the specular reflection of paint film as matting agent, use various auxiliary agent to increase pitch-dark dispersion, workability.Although the concrete formula of the pitch-dark use of the variant trade mark has certain difference, because its principle is similar, reflectivity is also all close to each other, probably 3 ~ 5%.
For reducing the reflectivity on optical equipment surface further, except pitch-dark, each manufacturer additionally provides other technology of some surface-treateds or coating, such as various anodizing technology, black nickel coating and black silicon technology etc.The Main Means that these coatings reduce material surface reflectivity is exactly introduce orderly/accurate orderly two-dirnentional structure at material surface, coating technology as black in U.S. Martin (Martin Black) is exactly in the structure using corrosion technology to rise and fall in material surface preparation two dimension, in conjunction with the dyestuff added, form the effect falling into light, reduce the reflectivity of material, the people such as U.S. Sun are using the periodicity raised structures that ion etching is 360nm at silicon chip surface preparation size, significantly reduce the reflectivity of silicon chip, obtain " black silicon ".But these coatings or technology often have strict restriction to base type, size, construction procedure is complicated, and therefore application receives larger restriction, still needs use pitch-dark as high-selenium corn coating at a lot of occasion optical equipment.
Summary of the invention
The present invention will solve existing black coating or there is reflectivity and cannot meet optical field, or existence has strict restriction to base type, size, the problem of construction procedure complexity, and provides a kind of preparation method of blacker-than-black coating.
A preparation method for blacker-than-black coating, specifically carries out according to following steps:
One, the preparation of silicon-dioxide mono-dispersion microballoon: utilize sol-gel method to prepare silicon-dioxide mono-dispersion microballoon, obtain silicon-dioxide mono-dispersion microballoon;
The diameter standard deviations of same batch of described silicon-dioxide mono-dispersion microballoon is not more than 0.05, and the diameter of the described silicon-dioxide mono-dispersion microballoon of same batch is in 100 nanometer ~ 1000 nanometers;
Two, the preparation of the silicon-dioxide mono-dispersion microballoon that carbon is coated: so that the resin of carbon can be become to carry out coated for carbon source to silicon-dioxide mono-dispersion microballoon surface, obtain the silicon-dioxide mono-dispersion microballoon that carbon is coated;
The standard deviation of the silicon-dioxide mono-dispersion microballoon same batch of diameter that described carbon is coated is not more than 0.05, and in the coated silicon-dioxide mono-dispersion microballoon of the carbon of described same batch carbon coating layer thickness in 10 nanometer ~ 100 nanometers;
Three, the preparation of blacker-than-black paint: take the coated silicon-dioxide mono-dispersion microballoon of 3 parts ~ 6 parts caking agents, 7 parts ~ 14 parts thinners and 4 parts of carbon by mass fraction, then under ultrasonic or concussion condition, silicon-dioxide mono-dispersion microballoon coated to take 3 parts ~ 6 parts caking agents, 7 parts ~ 14 parts thinners and 4 parts of carbon is mixed, obtains blacker-than-black paint;
Four, brush or spray: utilize and brush or spraying, blacker-than-black paint is coated on matrix surface, and seasoning is also solidified, and obtains the blacker-than-black coating containing short distance order microballoon, namely completes a kind of preparation method of blacker-than-black coating.
The invention has the beneficial effects as follows: the monodisperse silica microspheres that the present invention uses carbon coated is pitch-dark as light absorber allotment, and add quantity of resin as binding agent, this pitch-dark can with spraying or brush mode construct, sequence structure is formed after construction, produce light trapping effect, make the coating reflectivity ratio obtained use carbon black as the pitch-dark obvious decline of tradition of light absorber, reflectivity can reach 1.4% ~ 2%, and be applicable to various base type and size, simple to operate.
The present invention is used for a kind of preparation method of blacker-than-black coating.
Accompanying drawing explanation
Fig. 1 is specular reflectance excluded comparison diagram; 1 is the blacker-than-black coating containing short distance order microballoon prepared by embodiment two; 2 mixed coatings prepared for contrast experiment;
Fig. 2 is the transmission electron microscope photo of the silicon-dioxide mono-dispersion microballoon that in embodiment two step 2, carbon is coated;
Fig. 3 is the blacker-than-black coating stereoscan photograph containing short distance order microballoon prepared by embodiment two;
Fig. 4 is carbon black transmission electron microscope picture;
Fig. 5 is traditional pitch-dark surface scan Electronic Speculum figure.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of a kind of blacker-than-black coating described in present embodiment, specifically carry out according to following steps:
One, the preparation of silicon-dioxide mono-dispersion microballoon: utilize sol-gel method to prepare silicon-dioxide mono-dispersion microballoon, obtain silicon-dioxide mono-dispersion microballoon;
The diameter standard deviations of same batch of described silicon-dioxide mono-dispersion microballoon is not more than 0.05, and the diameter of the described silicon-dioxide mono-dispersion microballoon of same batch is in 100 nanometer ~ 1000 nanometers;
Two, the preparation of the silicon-dioxide mono-dispersion microballoon that carbon is coated: so that the resin of carbon can be become to carry out coated for carbon source to silicon-dioxide mono-dispersion microballoon surface, obtain the silicon-dioxide mono-dispersion microballoon that carbon is coated;
The standard deviation of the silicon-dioxide mono-dispersion microballoon same batch of diameter that described carbon is coated is not more than 0.05, and in the coated silicon-dioxide mono-dispersion microballoon of the carbon of described same batch carbon coating layer thickness in 10 nanometer ~ 100 nanometers;
Three, the preparation of blacker-than-black paint: take the coated silicon-dioxide mono-dispersion microballoon of 3 parts ~ 6 parts caking agents, 7 parts ~ 14 parts thinners and 4 parts of carbon by mass fraction, then under ultrasonic or concussion condition, silicon-dioxide mono-dispersion microballoon coated to take 3 parts ~ 6 parts caking agents, 7 parts ~ 14 parts thinners and 4 parts of carbon is mixed, obtains blacker-than-black paint;
Four, brush or spray: utilize and brush or spraying, blacker-than-black paint is coated on matrix surface, and seasoning is also solidified, and obtains the blacker-than-black coating containing short distance order microballoon, namely completes a kind of preparation method of blacker-than-black coating.
Matrix described in step 4 is can anything of mopping, the light shield of such as camera lens.
The pitch-dark use carbon black of tradition is as light absorber, and Fig. 4 is carbon black transmission electron microscope picture; As seen from the figure, carbon black size less (tens nanometers), specific surface area is very big.Fig. 5 is traditional pitch-dark surface scan Electronic Speculum figure; As seen from the figure, use during carbon black and need to add a large amount of resin as binding agent, the paint liquid obtained just can be made to have certain mobility, so just cause the dry rear coatingsurface produced comparatively smooth, even if add a certain amount of matting agent, because carbon black pellet is less, to be distributed in the gap of matting agent, integrally formed film is more smooth densification still, light only occurs once to absorb just to be reflected pitch-dark coating at the upper surface of enamelled coating, and when light is incident, the part interface of contact is resin/Air Interface, and resin also can produce a small amount of reflection.
As used larger particles carbon black or the rear carbon black of reunion to prepare pitch-dark, the carbon light absorpting ability after particle increases can decline again, causes reflectivity to rise equally.
The resin-coated of carbon can be become in the present invention on the silicon dioxide microsphere surface of appropriate size, high temperature cabonization is carbon coating layer further again, carbon ratio prepared by this method is more loose, on the yardstick being shorter than visible wavelength, the short texture of (tens nanometers) can cause material effective refractive index to decline, and reduces the reflectivity of carbon; Carbon is coated on the silicon dioxide microsphere of the hundreds of nanometer close with optical wavelength simultaneously, can form optics black-hole effect, strengthens the absorption of light further, if select solid carbon ball herein, then reflectivity significantly rises to 4%; The coated microballoon of carbon of hundreds of nanometer will be reunited for the particle of short range order further, accumulation unordered is again got up, can produce during accumulation in larger (micron-sized space), the light entering space can by multiple reflections, add the number of times of absorption, therefore reduce further reflectivity, herein as selected the inhomogenous microballoon of size, then cannot form the agglomerating particles of short range order, therefore the space formed will be less, sunken light effect is also more weak, herein as selected minimicrosphere, also effectively cannot form space.
The beneficial effect of present embodiment is: the monodisperse silica microspheres that present embodiment uses carbon coated is pitch-dark as light absorber allotment, and add quantity of resin as binding agent, this pitch-dark can with spraying or brush mode construct, sequence structure is formed after construction, produce light trapping effect, make the coating reflectivity ratio obtained use carbon black as the pitch-dark obvious decline of tradition of light absorber, reflectivity can reach 1.4% ~ 2%, and be applicable to various base type and size, simple to operate.
Embodiment two: present embodiment and embodiment one unlike: the resin of the become carbon described in step 2 is resol, polyimide or poly-aryl ethane.Other is identical with embodiment one.
Embodiment three: present embodiment and one of embodiment one or two unlike: when the resin of described become carbon is resol, carry out coated to silicon-dioxide mono-dispersion microballoon surface so that the resin of carbon can be become for carbon source, specifically carry out according to the following steps: silicon-dioxide mono-dispersion microballoon is first used washing with alcohol 2 times, use deionized water wash again 1 time, obtain the silicon-dioxide mono-dispersion microballoon after cleaning, silicon-dioxide mono-dispersion microballoon after cleaning is placed in deionized water, obtain the microballoon emulsion that mass percent is 10%, then by water, mass percent is the microballoon emulsion of 10%, concentration to be the cetyl trimethylammonium bromide solution of 0.01mol/L and mass percent be 25% ammoniacal liquor mixing, stir 5min, obtain reaction system, then in reaction system, Resorcinol and formaldehyde is added, magnetic agitation 8h, obtain the silicon dioxide microsphere emulsion that resol is coated, the silicon dioxide microsphere emulsion that centrifugation resol is coated, and by washed with de-ionized water three times, obtain the silicon dioxide microsphere that resol is coated, finally under temperature is 800 DEG C and argon gas or nitrogen atmosphere, by silicon dioxide microsphere thermal treatment 2h coated for resol, obtain the silicon-dioxide mono-dispersion microballoon that carbon is coated,
Described mass percent is the microballoon emulsion of 10% and the volume ratio of water is 1:6; Described mass percent be 10% microballoon emulsion and concentration be the volume ratio of the cetyl trimethylammonium bromide solution of 0.01mol/L be 4:1; Described mass percent be 10% microballoon emulsion and mass percent be the volume ratio of the ammoniacal liquor of 25% be 8:0.1; Described mass percent is the volume of the microballoon emulsion of 10% and the mass ratio of Resorcinol is 8mL:0.1g; Described mass percent is the microballoon emulsion of 10% and the volume ratio of formaldehyde is 4:0.07.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: the caking agent described in step 3 is methyl silicon resin, polyacrylic resin or urethane; Thinner described in step 3 is the organic solvent of solubilized methyl silicon resin, polyacrylic resin or urethane.Other is identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: the diameter of the silicon-dioxide mono-dispersion microballoon described in step one is 100 nanometers, and described silicon-dioxide mono-dispersion microballoon diameter standard deviations is not more than 0.05; In the silicon-dioxide mono-dispersion microballoon that carbon described in step 2 is coated, carbon coating layer thickness is 10 nanometers, and the standard deviation of the coated silicon-dioxide mono-dispersion microballoon diameter of described carbon is not more than 0.05.Other is identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the diameter of the silicon-dioxide mono-dispersion microballoon described in step one is 360 nanometers, and described silicon-dioxide mono-dispersion microballoon diameter standard deviations is not more than 0.05; In the silicon-dioxide mono-dispersion microballoon that carbon described in step 2 is coated, carbon coating layer thickness is 40 nanometers, and the standard deviation of the coated silicon-dioxide mono-dispersion microballoon diameter of described carbon is not more than 0.05.Other is identical with embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: the diameter of the silicon-dioxide mono-dispersion microballoon described in step one is in 1000 nanometers, and described silicon-dioxide mono-dispersion microballoon diameter standard deviations is not more than 0.05; In the silicon-dioxide mono-dispersion microballoon that carbon described in step 2 is coated, carbon coating layer thickness is 100 nanometers, and the standard deviation of the coated silicon-dioxide mono-dispersion microballoon diameter of described carbon is not more than 0.05.Other is identical with embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: take the coated silicon-dioxide mono-dispersion microballoon of 3 parts of caking agents, 7 parts of thinners and 4 parts of carbon by mass fraction in step 3, then under ultrasonic or concussion condition, silicon-dioxide mono-dispersion microballoon coated to take 3 parts of caking agents, 7 parts of thinners and 4 parts of carbon is mixed, obtains blacker-than-black paint.Other is identical with embodiment one to seven.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one:
The preparation method of a kind of blacker-than-black coating described in the present embodiment, specifically carries out according to following steps:
One, the preparation of silicon-dioxide mono-dispersion microballoon: utilize sol-gel method to prepare silicon-dioxide mono-dispersion microballoon, obtain silicon-dioxide mono-dispersion microballoon;
Two, the preparation of the silicon-dioxide mono-dispersion microballoon that carbon is coated: so that the resin of carbon can be become to carry out coated for carbon source to silicon-dioxide mono-dispersion microballoon surface, obtain the silicon-dioxide mono-dispersion microballoon that carbon is coated;
The resin of described become carbon is resol, carry out coated to silicon-dioxide mono-dispersion microballoon surface so that the resin of carbon can be become for carbon source, specifically carry out according to the following steps: silicon-dioxide mono-dispersion microballoon is first used washing with alcohol 2 times, use deionized water wash again 1 time, obtain the silicon-dioxide mono-dispersion microballoon after cleaning, silicon-dioxide mono-dispersion microballoon after cleaning is placed in deionized water, obtain the microballoon emulsion that mass percent is 10%, then by 48mL water, 8mL mass percent is the microballoon emulsion of 10%, 2mL concentration to be the cetyl trimethylammonium bromide solution of 0.01mol/L and 0.1mL mass percent be 25% ammoniacal liquor mixing, stir 5min, obtain reaction system, then in reaction system, 0.1g Resorcinol and 0.14mL formaldehyde is added, magnetic agitation 8h, obtain the silicon dioxide microsphere emulsion that resol is coated, the silicon dioxide microsphere emulsion that centrifugation resol is coated, and by washed with de-ionized water three times, obtain the silicon dioxide microsphere that resol is coated, finally under temperature is 800 DEG C and argon gas or nitrogen atmosphere, by silicon dioxide microsphere thermal treatment 2h coated for resol, obtain the silicon-dioxide mono-dispersion microballoon that carbon is coated,
Three, the preparation of blacker-than-black paint: take methyl silicon resin solution and the coated silicon-dioxide mono-dispersion microballoon of 20g carbon that 50g mass percent is 30%, then under ultrasonic or concussion condition, by the 50g mass percent taken be 30% methyl silicon resin solution and the coated silicon-dioxide mono-dispersion microballoon of 20g carbon mix, obtain blacker-than-black paint;
Described mass percent be 30% methyl silicon resin solution be the mixing solutions of methyl silicon resin and Virahol; The quality of methyl silicon resin accounts for 30% of the mixing solutions total mass of methyl silicon resin and Virahol;
Four, utilize brushing, blacker-than-black paint is coated on surface of aluminum plate, seasoning is also at room temperature solidified, and obtains the blacker-than-black coating containing ordered arrangement microballoon, namely completes a kind of preparation method of blacker-than-black coating.
The diameter of the silicon-dioxide mono-dispersion microballoon described in step one is 100 nanometers, and described silicon-dioxide mono-dispersion microballoon diameter standard deviations is not more than 0.05;
In the silicon-dioxide mono-dispersion microballoon that carbon described in step 2 is coated, carbon coating layer thickness is 10 nanometers, and the standard deviation of the coated silicon-dioxide mono-dispersion microballoon diameter of described carbon is not more than 0.05.
Blacker-than-black coating average reflectance prepared by the present embodiment is 1.8%.
Embodiment two: the present embodiment and embodiment one unlike: the diameter of the silicon-dioxide mono-dispersion microballoon described in step one is 360 nanometers, and described silicon-dioxide mono-dispersion microballoon diameter standard deviations is not more than 0.05; In the silicon-dioxide mono-dispersion microballoon that carbon described in step 2 is coated, carbon coating layer thickness is 40 nanometers, and the standard deviation of the coated silicon-dioxide mono-dispersion microballoon diameter of described carbon is not more than 0.05.Other is identical with embodiment one.
Fig. 2 is the transmission electron microscope photo of the silicon-dioxide mono-dispersion microballoon that in embodiment two step 2, carbon is coated; As seen from the figure, the coated of silicon dioxide microsphere surface uniform has gone up one deck carbon shell, and thickness is about 40 nanometers.
Fig. 3 is the blacker-than-black coating stereoscan photograph containing short distance order microballoon prepared by embodiment two.As seen from the figure, less owing to adding amount of resin, microballoon is piled up with cluster-shaped, and the shape of microballoon own is high-visible, there is more space in coating.
Contrast experiment: this contrast experiment and embodiment two unlike: take methyl silicon resin solution, carbon black and 20g silicon-dioxide mono-dispersion microballoon that 50g mass percent is 30% in step 3, then under ultrasonic or concussion condition, be that the methyl silicon resin solution of 30%, carbon black and 20g silicon-dioxide mono-dispersion microballoon mix by the 50g mass percent taken, obtain tradition pitch-dark.Other is identical with embodiment two.
In the silicon-dioxide mono-dispersion microballoon that in the quality of described carbon black and embodiment two, carbon is coated, carbon coating layer is identical in quality.
Silicon-dioxide mono-dispersion microballoon coated for carbon is replaced into carbon black and the silica mixture of equivalent by contrast experiment; Fig. 1 is specular reflectance excluded comparison diagram; 1 is the blacker-than-black coating containing short distance order microballoon prepared by embodiment two; 2 mixed coatings prepared for contrast experiment; As seen from the figure, mixed coating average reflectance prepared by contrast experiment is about 2.9%, and the reflectivity of this and existing commercial pitch-dark coating is close, and blacker-than-black coating average reflectance prepared by the present embodiment then only has 1.4%.It can thus be appreciated that the present embodiment serves obvious effect to reduction coating reflectivity.
Embodiment three: the present embodiment and embodiment one unlike: the diameter of the silicon-dioxide mono-dispersion microballoon described in step one is in 1000 nanometers, and described silicon-dioxide mono-dispersion microballoon diameter standard deviations is not more than 0.05; In the silicon-dioxide mono-dispersion microballoon that carbon described in step 2 is coated, carbon coating layer thickness is 100 nanometers, and the standard deviation of the coated silicon-dioxide mono-dispersion microballoon diameter of described carbon is not more than 0.05.Other is identical with embodiment one.
Blacker-than-black coating average reflectance prepared by the present embodiment is 2.0%.

Claims (8)

1. a preparation method for blacker-than-black coating, is characterized in that a kind of preparation method of blacker-than-black coating carries out according to following steps:
One, the preparation of silicon-dioxide mono-dispersion microballoon: utilize sol-gel method to prepare silicon-dioxide mono-dispersion microballoon, obtain silicon-dioxide mono-dispersion microballoon;
The diameter standard deviations of same batch of described silicon-dioxide mono-dispersion microballoon is not more than 0.05, and the diameter of the described silicon-dioxide mono-dispersion microballoon of same batch is in 100 nanometer ~ 1000 nanometers;
Two, the preparation of the silicon-dioxide mono-dispersion microballoon that carbon is coated: so that the resin of carbon can be become to carry out coated for carbon source to silicon-dioxide mono-dispersion microballoon surface, obtain the silicon-dioxide mono-dispersion microballoon that carbon is coated;
The standard deviation of the silicon-dioxide mono-dispersion microballoon same batch of diameter that described carbon is coated is not more than 0.05, and in the coated silicon-dioxide mono-dispersion microballoon of the carbon of described same batch carbon coating layer thickness in 10 nanometer ~ 100 nanometers;
Three, the preparation of blacker-than-black paint: take the coated silicon-dioxide mono-dispersion microballoon of 3 parts ~ 6 parts caking agents, 7 parts ~ 14 parts thinners and 4 parts of carbon by mass fraction, then under ultrasonic or concussion condition, silicon-dioxide mono-dispersion microballoon coated to take 3 parts ~ 6 parts caking agents, 7 parts ~ 14 parts thinners and 4 parts of carbon is mixed, obtains blacker-than-black paint;
Four, brush or spray: utilize and brush or spraying, blacker-than-black paint is coated on matrix surface, and seasoning is also solidified, and obtains the blacker-than-black coating containing short distance order microballoon, namely completes a kind of preparation method of blacker-than-black coating.
2. the preparation method of a kind of blacker-than-black coating according to claim 1, is characterized in that the resin of the become carbon described in step 2 is resol, polyimide or poly-aryl ethane.
3. the preparation method of a kind of blacker-than-black coating according to claim 2, it is characterized in that when the resin of described become carbon is resol, carry out coated to silicon-dioxide mono-dispersion microballoon surface so that the resin of carbon can be become for carbon source, specifically carry out according to the following steps: silicon-dioxide mono-dispersion microballoon is first used washing with alcohol 2 times, use deionized water wash again 1 time, obtain the silicon-dioxide mono-dispersion microballoon after cleaning, silicon-dioxide mono-dispersion microballoon after cleaning is placed in deionized water, obtain the microballoon emulsion that mass percent is 10%, then by water, mass percent is the microballoon emulsion of 10%, concentration to be the cetyl trimethylammonium bromide solution of 0.01mol/L and mass percent be 25% ammoniacal liquor mixing, stir 5min, obtain reaction system, then in reaction system, Resorcinol and formaldehyde is added, magnetic agitation 8h, obtain the silicon dioxide microsphere emulsion that resol is coated, the silicon dioxide microsphere emulsion that centrifugation resol is coated, and by washed with de-ionized water three times, obtain the silicon dioxide microsphere that resol is coated, finally under temperature is 800 DEG C and argon gas or nitrogen atmosphere, by silicon dioxide microsphere thermal treatment 2h coated for resol, obtain the silicon-dioxide mono-dispersion microballoon that carbon is coated,
Described mass percent is the microballoon emulsion of 10% and the volume ratio of water is 1:6; Described mass percent be 10% microballoon emulsion and concentration be the volume ratio of the cetyl trimethylammonium bromide solution of 0.01mol/L be 4:1; Described mass percent be 10% microballoon emulsion and mass percent be the volume ratio of the ammoniacal liquor of 25% be 8:0.1; Described mass percent is the volume of the microballoon emulsion of 10% and the mass ratio of Resorcinol is 8mL:0.1g; Described mass percent is the microballoon emulsion of 10% and the volume ratio of formaldehyde is 4:0.07.
4. the preparation method of a kind of blacker-than-black coating according to claim 1, is characterized in that the caking agent described in step 3 is methyl silicon resin, polyacrylic resin or urethane; Thinner described in step 3 is the organic solvent of solubilized methyl silicon resin, polyacrylic resin or urethane.
5. the preparation method of a kind of blacker-than-black coating according to claim 1, is characterized in that the diameter of the silicon-dioxide mono-dispersion microballoon described in step one is 100 nanometers, and described silicon-dioxide mono-dispersion microballoon diameter standard deviations is not more than 0.05; In the silicon-dioxide mono-dispersion microballoon that carbon described in step 2 is coated, carbon coating layer thickness is 10 nanometers, and the standard deviation of the coated silicon-dioxide mono-dispersion microballoon diameter of described carbon is not more than 0.05.
6. the preparation method of a kind of blacker-than-black coating according to claim 1, is characterized in that the diameter of the silicon-dioxide mono-dispersion microballoon described in step one is 360 nanometers, and described silicon-dioxide mono-dispersion microballoon diameter standard deviations is not more than 0.05; In the silicon-dioxide mono-dispersion microballoon that carbon described in step 2 is coated, carbon coating layer thickness is 40 nanometers, and the standard deviation of the coated silicon-dioxide mono-dispersion microballoon diameter of described carbon is not more than 0.05.
7. the preparation method of a kind of blacker-than-black coating according to claim 1, it is characterized in that the diameter of the silicon-dioxide mono-dispersion microballoon described in step one is in 1000 nanometers, and described silicon-dioxide mono-dispersion microballoon diameter standard deviations is not more than 0.05; In the silicon-dioxide mono-dispersion microballoon that carbon described in step 2 is coated, carbon coating layer thickness is 100 nanometers, and the standard deviation of the coated silicon-dioxide mono-dispersion microballoon diameter of described carbon is not more than 0.05.
8. the preparation method of a kind of blacker-than-black coating according to claim 1, it is characterized in that taking the coated silicon-dioxide mono-dispersion microballoon of 3 parts of caking agents, 7 parts of thinners and 4 parts of carbon by mass fraction in step 3, then under ultrasonic or concussion condition, silicon-dioxide mono-dispersion microballoon coated to take 3 parts of caking agents, 7 parts of thinners and 4 parts of carbon is mixed, obtains blacker-than-black paint.
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