CN105131741A - Bulk absorption type solar selective heat absorption paint and preparation method and application thereof - Google Patents
Bulk absorption type solar selective heat absorption paint and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of energy-saving paint and discloses bulk absorption type solar selective heat absorption paint and a preparation method and application thereof. The paint has sunlight selective absorption performance, and is high in photo-thermal conversion rate, good in protective performance and excellent in weather resistance. The paint is prepared from, by mass, 25%-33% of absorbent, 0%-5% of filler, 15%-20% of fluorocarbon resin, 2%-3% of dispersant, 3%-5% of crossk-linking agent, 0.1-0.3% of catalyst, 0.5%-1% of adhesion promoter, 0.2%-0.5% of defoamer, 0.2%-0.5% of flatting agent and 40%-50% of organic solvent. A coating obtained through the paint is a metal oxide-resin composite heat absorption coating, the solar absorption rate of the coating is larger than 93%, the radiance is smaller than 5%, and meanwhile excellent impact resistance, bending resistance, corrosion resistance, aging resistance and salt fog resistance are achieved; the paint can be applied to a solar heat collector.
Description
Technical field
The invention belongs to energy-saving coatings technical field, particularly a kind of body absorption-type solar selective heat-absorbing paint and preparation method thereof and application.This coating has sunlight Selective absorber, and photothermal conversion rate is high, barrier propterty good, weathering resistance is good.
Background technology
Along with the change of energy form, the reserves of conventional energy resources decline day by day, and replacing the fossil energy of high carbon content as much as possible with clear energy sources, is the principle that energy construction should be followed.China is coal production state maximum in the world and country of consumption, and coal accounts for 76% of commercial energy resource consumption structure, is the main source of China's topsoil.The technology that utilizes of Devoting Major Efforts To Developing new and renewable sources of energy will become the important measures reducing environmental pollution.
Solar selectively absorbing coating imagination is in the fifties proposition in last century.When sunlight incides coatingsurface time, coating to sunlight by generation reflect, absorb, transmission three kinds of phenomenons.In general, wavelength region contained by sunlight at visible region and near infrared region, if in coating the transition energy level of material just with the energy match corresponding to certain wavelength, in coating, material absorbs producing the light of respective wavelength.The principle of selective heat absorbing coating is: coating may be many for the ripple dampen out of sunlight medium-long wave band, simultaneously to the reflection of sunlight and transmission low as far as possible, the energy absorbed changes into heat energy, different application is become afterwards, as the thermoelectric material etc. in solar water heater, photovoltaic industry by suitable technical transform.
In order to improve the efficiency of selective heat absorbing coating, unique effective way is keeping reducing its convection current and radiation heat loss as far as possible while of gathering sun power to greatest extent.According to the difference of principle of absorption and structure, coating for selective absorption can be divided into following several: 1. interfere type absorber coatings: the film preparation adopting preparation multilayer to have different refractivity becomes composite membrane, form interference effect between film thus obtain selective absorbing; 2. surface tissue type absorber coatings: the surface roughness of structure micron-nanometer rank, forms selective absorbing to sunlight; 3. metal-semiconductor composite structure: semi-conductor has narrower energy gap, just can be formed sunlight and absorb; 4. body absorption-type coating: utilize nano metal/metal oxide-high molecular resin composite material to form selectively absorbing layers.
Chinese patent CN101284958A describes a kind of preparation method of solar energy heat absorbing coating being absorption agent with nickel or nickelalloy hollow ball.By selecting different-grain diameter and different types of nickelalloy, the heat absorbing coating that thermal absorptivity reaches 96% can be prepared, but thermal emissivity rate still maintains more than 10%.
US Patent No. 20150015960A1 discloses a kind of preparation method of double membrane structure solar energy heat absorbing coating.Adopt the mode of vacuum sputtering to prepare one deck nano-metal-oxide heat-sink shell, prepare solar energy heat absorbing coating with antireflective film compound.
US Patent No. 20140261390 describes a kind of preparation method of the selective heat absorbing coating based on multilayered structure composite membrane.Coating is made up of four tunics: protective membrane, antireflective film, metal matrix infrared reflection film and solar absorbing film.By the collocation of multiple different structure film, can prepare that thermal absorptivity reaches 96%, thermal emissivity rate reach 7% selective heat absorbing coating.
But, above-mentioned multiple existing technology or to there is thermal emissivity rate high, or there is sticking power deficiency, or there is the problems such as technical costs is high, therefore this area possesses high thermal absorptivity, low radiative thermal emissivity, economically viable selective heat absorbing coating in the urgent need to researching and developing one.
Summary of the invention
There is the high shortcoming of thermal emissivity rate with not enough to overcome above-mentioned existing selective heat absorbing coating, primary and foremost purpose of the present invention is to provide a kind of body absorption-type solar selective heat-absorbing paint.This coating has outstanding thermal absorptivity, lower thermal emissivity rate, thus ensure that high solar energy utilization ratio; Coating technology cost is far below methods such as vacuum sputterings; Coating itself has excellent shock-resistance, resistance to bend(ing), solidity to corrosion, ageing resistance and salt fog resistance, and solar absorptance is greater than 93%, and radiant ratio is less than 5%, can be used as the selective heat absorbing coating of solar energy collector heat sink.
Another object of the present invention is the preparation method providing a kind of above-mentioned body absorption-type solar selective heat-absorbing paint.
Still a further object of the present invention is to provide the application of above-mentioned body absorption-type solar selective heat-absorbing paint in solar energy collector.
Object of the present invention is realized by following proposal:
A kind of body absorption-type solar selective heat-absorbing paint, is made up of the component of following massfraction: absorption agent 25 ~ 33%; Filler 0 ~ 5%; Fluorocarbon resin 15 ~ 20%; Dispersion agent 2 ~ 3%; Linking agent 3 ~ 5%; Catalyzer 0.1 ~ 0.3%; Adhesion promoter 0.5 ~ 1%; Defoamer 0.2 ~ 0.5%; Flow agent 0.2 ~ 0.5%; Organic solvent 40 ~ 50%.
Described absorption agent comprises at least one in ferrimanganic mineral black, cupric oxide powder and carbon black.The absorption agent that the present invention selects has obvious absorption to sunlight.Described ferrimanganic mineral black is a kind of inorganic manganese iron black pigment with excellent tinting strength, has fabulous thermostability; Preferably its particle diameter≤100nm; Described cupric oxide powder preferable particle size is 300 ~ 400nm; Described carbon black is preferably at least one of Degussa degussa4# carbon black and Cabot 330R.
Described filler comprises at least one in titanium dioxide and flatting silica.Described flatting silica is preferably at least one of intelligent paddy chemistry RD304-C and Degussa OK520; Described titanium dioxide is preferably and at least one of alliance CR-57 and Du Pont R-902.
Described fluorocarbon resin is preferably the fluorocarbon resin with oh group, and hydroxyl value is 50 ~ 55mgKOH/g, and acid number is no more than 3mgKOH/g.Be more preferably at least one of DSM resin URACRONCR204CM40 and Huambo WF-J313.
Described dispersion agent is acrylate resin, and molecular weight is preferably 6000 ~ 8000, and described dispersion agent is more preferably BYK-161.
Described linking agent is aminoresin, is preferably the aminoresin of full methyl-etherified or the aminoresin of part methyl-etherified.
Described catalyzer is that an acidic catalyst is commonly used in this area, is preferably at least one in tosic acid, methanesulfonic and manganese naphthenate liquid.
Described adhesion promoter is preferably containing carboxy(l)polyester adhesion promoter, as modified polyester resin, preferably joins clean YX-909-B-72, moistens at least one of prosperous RHEPOL9999 and Changxing YX-909.
Described defoamer is silicone based defoamer, is preferably BYK-066N.
Described flow agent is preferably modified acroleic acid esters resin.Acrylic resin and most resin have good intermiscibility, have excellent effect to levelling, and effectively can prevent shrinkage cavity, have no effect to ply adhesion.Described flow agent is more preferably at least one in HENSICH-143 and BYK-340.
Described organic solvent is at least one in ester class and ketone; Preferably, described organic solvent is at least two kinds in ethyl acetate, vinyl acetic monomer, n-propyl acetate, n-butyl acetate, dimethyl succinate, Methyl glutarate, espeleton, mibk and pimelinketone.
The present invention also provides a kind of preparation method of above-mentioned body absorption-type solar selective heat-absorbing paint, specifically comprises the following steps:
Joined by dispersion agent in part organic solvent, stir and make it dissolve, then add absorption agent, grinding distribution 2 ~ 3h is less than 10 μm to coating fineness; Add fluorocarbon resin, linking agent, catalyzer, adhesion promoter and residue organic solvent, high speed dispersion 1 ~ 2h, add flow agent, defoamer, after high speed dispersion 0.5 ~ 1h, obtain coating.
Described dispersion agent adds preferred stirring after in organic solvent and adds absorption agent again after fully dissolving.
Described grinding distribution preferably uses sand mill to carry out.
The coating that coating of the present invention obtains is metal oxide-resin compound heat absorbing coating, and it has outstanding thermal absorptivity, lower thermal emissivity rate, thus ensure that high solar energy utilization ratio; There is excellent shock-resistance, resistance to bend(ing), solidity to corrosion, ageing resistance and salt fog resistance simultaneously, solar absorptance is greater than 93%, radiant ratio is less than 5%, can be used as the selective heat absorbing coating of solar energy collector heat sink, is applied in solar energy collector.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) absorption agent of the present invention adopts the mode of sand mill grinding to disperse in advance, thus prepare the slurry of high volumetric concentration, pigment particles major part is scattered in slurry with the form of primary particle, the wave reflection ability of coating to long-wave band is more weak, is conducive to the thermal emissivity rate reducing coating;
(2) heat-absorbing paint of the present invention has splendid weathering resistance, is applicable to long-term outdoor and uses;
(3) solar absorptance of heat absorbing coating of the present invention is greater than 93%, and thermal emissivity rate is less than 5%, can be applicable to solar energy collector heat sink.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1: the preparation of solar selective heat-absorbing paint
Basic recipe is as shown in table 1, and concrete preparation method is as follows:
Dispersant B YK-161 is joined in part n-propyl acetate and dimethyl succinate, stirs and make it dissolve.Join in above-mentioned mixing solutions by black for ferrimanganic powder, cupric oxide powder, Degussa 4# carbon black, after dispersed with stirring 2h, sand mill is ground to appointment fineness, prepares the black composite mortar of carbon black-ferrimanganic; Successively the aminoresin of DSM resin URACRONCR204CM40, full methyl-etherified, tosic acid, the clean YX-909-B-72 of connection, remaining n-propyl acetate and dimethyl succinate are joined in the black composite mortar of above-mentioned carbon black-ferrimanganic again, high speed dispersion 1h; Add flow agent BYK-340, defoamer BYK-066N afterwards, after high speed dispersion 0.5h, obtain coating.
The formula of table 1 solar selective heat-absorbing paint
Embodiment 2: the preparation of solar selective heat-absorbing paint
Basic recipe is as shown in table 2, and concrete preparation method is as follows:
Dispersant B YK-161 is joined in part methyl isobutyl ketone and vinyl acetic monomer, stirs and make it dissolve.Join in above-mentioned mixing solutions by black for ferrimanganic powder, cupric oxide powder, Cabot 330R, after dispersed with stirring 2h, sand mill is ground to appointment fineness, prepares the black composite mortar of carbon black-ferrimanganic; Successively DSM resin URACRONCR204CM40, the aminoresin of part methyl-etherified, tosic acid, the clean YX-909-B-72 of connection, remaining mibk and vinyl acetic monomer are joined in the black composite mortar of above-mentioned carbon black-ferrimanganic again, high speed dispersion 1h; Add flow agent BYK-340, defoamer BYK-066N afterwards, after high speed dispersion 0.5h, obtain coating.
The formula of table 2 solar selective heat-absorbing paint
Embodiment 3: the preparation of solar selective heat-absorbing paint
Basic recipe is as shown in table 3, and concrete preparation method is as follows:
Dispersant B YK-161 is joined in part vinyl acetic monomer and espeleton, stirs and make it dissolve.Join in above-mentioned mixing solutions by black for ferrimanganic powder, cupric oxide powder, Cabot 330R, after dispersed with stirring 2h, sand mill is ground to appointment fineness, prepares the black composite mortar of carbon black-ferrimanganic; Successively DSM resin URACRONCR204CM40, the aminoresin of part methyl-etherified, tosic acid, the clean YX-909-B-72 of connection, remaining vinyl acetic monomer and espeleton are joined in the black composite mortar of above-mentioned carbon black-ferrimanganic again, high speed dispersion 1h; Add flow agent HENSICH-143, defoamer BYK-066N afterwards, after high speed dispersion 0.5h, obtain coating.
The formula of table 3 solar selective heat-absorbing paint
Embodiment 4: the preparation of solar selective heat-absorbing paint
Basic recipe is as shown in table 4, and concrete preparation method is as follows:
The formula of table 4 solar selective heat-absorbing paint
Dispersant B YK-161 is joined in part vinyl acetic monomer and pimelinketone, stirs and make it dissolve.Join in above-mentioned mixing solutions by black for ferrimanganic powder, cupric oxide powder, Degussa 4# carbon black, after dispersed with stirring 2h, sand mill is ground to appointment fineness, prepares the black composite mortar of carbon black-ferrimanganic; Successively Huambo WF-J313, full methyl-etherified aminoresin, tosic acid, the clean YX-909-B-72 of connection, remaining vinyl acetic monomer and pimelinketone are joined in the black composite mortar of above-mentioned carbon black-ferrimanganic again, high speed dispersion 1h; Add flow agent HENSICH-143, defoamer BYK-066N afterwards, after high speed dispersion 0.5h, obtain coating.
Embodiment 5: the preparation of solar selective heat-absorbing paint
The formula of table 5 solar selective heat-absorbing paint
Basic recipe is as shown in table 5, and concrete preparation method is as follows:
Dispersant B YK-161 is joined in portion of ethyl acetate and dimethyl succinate, stirs and make it dissolve.Join in above-mentioned mixing solutions by black for ferrimanganic powder, cupric oxide powder, Degussa 4# carbon black, after dispersed with stirring 2h, sand mill is ground to appointment fineness, prepares the black composite mortar of carbon black-ferrimanganic; Successively Huambo WF-J313, full methyl-etherified aminoresin, tosic acid, the clean YX-909-B-72 of connection and alliance CR-57, remaining ethyl acetate and dimethyl succinate are joined in the black composite mortar of above-mentioned carbon black-ferrimanganic again, high speed dispersion 1h; Add flow agent BYK-340, defoamer BYK-066N afterwards, after high speed dispersion 0.5h, obtain coating.
Embodiment 6: the preparation of solar selective heat-absorbing paint
The formula of table 6 solar selective heat-absorbing paint
Basic recipe is as shown in table 6, and concrete preparation method is as follows:
Dispersant B YK-161 is joined in portion of ethyl acetate and dimethyl succinate, stirs and make it dissolve.Join in above-mentioned mixing solutions by black for ferrimanganic powder, cupric oxide powder, Cabot 330R, after dispersed with stirring 2h, sand mill is ground to appointment fineness, prepares the black composite mortar of carbon black-ferrimanganic; Successively Huambo WF-J313, full methyl-etherified aminoresin, tosic acid, the prosperous RHEPOL9999 of profit, Du Pont R-902, intelligent paddy chemistry RD304-C, remaining ethyl acetate and dimethyl succinate are joined in the black composite mortar of above-mentioned carbon black-ferrimanganic again, high speed dispersion 1h; Add flow agent HENSICH-143, defoamer BYK-066N afterwards, after high speed dispersion 0.5h, obtain coating.
Embodiment 7: comparative example 1-absorption agent consumption is less
Basic recipe is as shown in table 7, and concrete preparation method is as follows:
Dispersant B YK-161 is joined in portion of ethyl acetate and dimethyl succinate, stirs and make it dissolve.Join in above-mentioned mixing solutions by black for ferrimanganic powder, cupric oxide powder, Cabot 330R, after dispersed with stirring 2h, sand mill is ground to appointment fineness, prepares the black composite mortar of carbon black-ferrimanganic; Successively DSM resin URACRONCR204CM40, full methyl-etherified aminoresin, tosic acid, Changxing YX-909, Du Pont R-902, Degussa OK520, remaining ethyl acetate and dimethyl succinate are joined in the black composite mortar of above-mentioned carbon black-ferrimanganic again, high speed dispersion 1h; Add flow agent BYK-340, defoamer BYK-066N afterwards, after high speed dispersion 0.5h, obtain coating.
The formula of table 7 heat-absorbing paint
Embodiment 8: comparative example 2-fluorocarbon resin consumption is less
Basic recipe is as shown in table 8, and concrete preparation method is as follows:
Dispersant B YK-161 is joined in portion of ethyl acetate and dimethyl succinate, stirs and make it dissolve.Join in above-mentioned mixing solutions by black for ferrimanganic powder, cupric oxide powder, Degussa 4# carbon black, after dispersed with stirring 2h, sand mill is ground to appointment fineness, prepares the black composite mortar of carbon black-ferrimanganic; Successively Huambo WF-J313, full methyl-etherified aminoresin, tosic acid, Changxing YX-909 and alliance CR-57, Degussa OK520, remaining ethyl acetate and dimethyl succinate are joined in the black composite mortar of above-mentioned carbon black-ferrimanganic again, high speed dispersion 1h; Add flow agent BYK-340, defoamer BYK-066N afterwards, after high speed dispersion 0.5h, obtain coating.
The formula of table 8 heat-absorbing paint
Embodiment 9: comparative example 3-adhesion promoter consumption is less
Basic recipe is as shown in table 9, and concrete preparation method is as follows:
Dispersion agent (BYK-161) is joined in portion of ethyl acetate and dimethyl succinate, stirs and make it dissolve.Join in above-mentioned mixing solutions by black for ferrimanganic powder, cupric oxide powder, Degussa 4# carbon black, after dispersed with stirring 2h, sand mill is ground to appointment fineness, prepares the black composite mortar of carbon black-ferrimanganic; Successively DSM resin URACRONCR204CM40, full methyl-etherified aminoresin, tosic acid, Changxing YX-909, Du Pont R-902, intelligent paddy chemistry RD304-C, remaining ethyl acetate and dimethyl succinate are joined in the black composite mortar of above-mentioned carbon black-ferrimanganic again, high speed dispersion 1h; Add flow agent HENSICH-143, defoamer BYK-066N afterwards, after high speed dispersion 0.5h, obtain coating.
The formula of table 9 heat-absorbing paint
Technique effect
Adopt the method for line rod blade coating, by coatings on base material, form the uniform coating that thickness is about 10 μm after 250 DEG C of baking 60s, above-described embodiment and comparative example 1, comparative example 2 contrast.
According to thermal absorptivity, the thermal emissivity of GB/T2680-1994 standard testing coating;
According to the weather resistance of GB/T1766-2008 standard testing coating, adopt the weather resistance of QUV UV-light deterioration accelerator to coating to assess, coating is artificial circulation accelerated deterioration 3000h in ageing oven, and aging condition is as follows:
Ultraviolet lamp tube model: UVA-351
Intensity of illumination: 0.35W/m
2340nm
Cycling condition: 120min illumination/18min illumination+spray/6h is dark, 95 ± 4%RH
According to the glossiness of GB/T9754-2007 testing coating;
According to the sticking power of GB/T1720-1979 (1989) standard testing coating;
According to the solvent resistance (MEK) of GB/T23989-2009 standard testing coating;
The mode contrasting internal-external temperature difference after adopting infrared lamp to irradiate Baking out model tests the heat absorption efficiency of sample, and test condition is as follows:
Infrared lamp power: 250W;
Model and infrared lamp distance: 25cm;
Irradiation time: 60min;
Test environment: 25 DEG C;
Test result is as shown in table 10.
The performance index of table 10 coating
From table 10, solar selective heat-absorbing coating of the present invention has good thermal absorption efficiency, there is good sticking power to metal base simultaneously, coating possesses splendid solvent resistance, weathering resistance, but the consumption of the components such as absorption agent, fluorocarbon resin, adhesion promoter exceedes the decline that numerical range of the present invention all can cause properties of coating.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a body absorption-type solar selective heat-absorbing paint, is characterized in that being made up of the component of following massfraction: absorption agent 25 ~ 33%; Filler 0 ~ 5%; Fluorocarbon resin 15 ~ 20%; Dispersion agent 2 ~ 3%; Linking agent 3 ~ 5%; Catalyzer 0.1 ~ 0.3%; Adhesion promoter 0.5 ~ 1%; Defoamer 0.2 ~ 0.5%; Flow agent 0.2 ~ 0.5%; Organic solvent 40 ~ 50%.
2. body absorption-type solar selective heat-absorbing paint according to claim 1, is characterized in that: described absorption agent comprises at least one in ferrimanganic mineral black, cupric oxide powder and carbon black.
3. body absorption-type solar selective heat-absorbing paint according to claim 2, is characterized in that: the particle diameter≤100nm of described ferrimanganic mineral black; Described cupric oxide powder particle size is 300 ~ 400nm; Described carbon black is at least one of Degussa degussa4# carbon black and Cabot 330R.
4. body absorption-type solar selective heat-absorbing paint according to claim 1, is characterized in that: described filler comprises at least one in titanium dioxide and flatting silica.
5. body absorption-type solar selective heat-absorbing paint according to claim 1, is characterized in that: described fluorocarbon resin is the fluorocarbon resin with oh group, and hydroxyl value is 50 ~ 55mgKOH/g, and acid number is no more than 3mgKOH/g; Described adhesion promoter is for containing carboxy(l)polyester adhesion promoter.
6. body absorption-type solar selective heat-absorbing paint according to claim 1, is characterized in that: described fluorocarbon resin is at least one of DSM resin URACRONCR204CM40 and Huambo WF-J313; Described adhesion promoter is the clean YX-909-B-72 of connection, moistens at least one of prosperous RHEPOL9999 and Changxing YX-909.
7. body absorption-type solar selective heat-absorbing paint according to claim 1, is characterized in that: described dispersion agent is acrylate resin; Described linking agent is aminoresin; Described catalyzer is an acidic catalyst; Described defoamer is silicone based defoamer; Described flow agent is modified acroleic acid esters resin; Described organic solvent is at least one in ester class and ketone.
8. body absorption-type solar selective heat-absorbing paint according to claim 1, is characterized in that: described dispersion agent is BYK-161; Described linking agent is the aminoresin of full methyl-etherified or the aminoresin of part methyl-etherified; Described catalyzer is at least one in tosic acid, methanesulfonic and manganese naphthenate liquid; Described defoamer is BYK-066N; Described flow agent is at least one in HENSICH-143 and BYK-340; Described organic solvent is at least two kinds in ethyl acetate, vinyl acetic monomer, n-propyl acetate, n-butyl acetate, dimethyl succinate, Methyl glutarate, espeleton, mibk and pimelinketone.
9. a preparation method for the body absorption-type solar selective heat-absorbing paint according to any one of claim 1 ~ 8, is characterized in that specifically comprising the following steps:
Joined by dispersion agent in part organic solvent, stir and make it dissolve, then add absorption agent, grinding distribution 2 ~ 3h is less than 10 μm to coating fineness; Add fluorocarbon resin, linking agent, catalyzer, adhesion promoter and residue organic solvent, high speed dispersion 1 ~ 2h, add flow agent, defoamer, after high speed dispersion 0.5 ~ 1h, obtain coating.
10. the application of body absorption-type solar selective heat-absorbing paint in solar energy collector according to any one of claim 1 ~ 8.
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