CN115819093B - Ceramic aerogel prepared from polysilazane, preparation method and heat insulation coating thereof - Google Patents
Ceramic aerogel prepared from polysilazane, preparation method and heat insulation coating thereof Download PDFInfo
- Publication number
- CN115819093B CN115819093B CN202211268675.5A CN202211268675A CN115819093B CN 115819093 B CN115819093 B CN 115819093B CN 202211268675 A CN202211268675 A CN 202211268675A CN 115819093 B CN115819093 B CN 115819093B
- Authority
- CN
- China
- Prior art keywords
- polysilazane
- solution
- ceramic
- coating
- prepared
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001709 polysilazane Polymers 0.000 title claims abstract description 112
- 239000000919 ceramic Substances 0.000 title claims abstract description 84
- 238000000576 coating method Methods 0.000 title claims abstract description 76
- 239000011248 coating agent Substances 0.000 title claims abstract description 74
- 239000004964 aerogel Substances 0.000 title claims abstract description 53
- 238000009413 insulation Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 18
- 239000002518 antifoaming agent Substances 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 17
- 238000005507 spraying Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000010894 electron beam technology Methods 0.000 claims description 12
- 239000013008 thixotropic agent Substances 0.000 claims description 12
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 10
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 238000002468 ceramisation Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004321 preservation Methods 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 2
- 230000037380 skin damage Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 28
- 239000011347 resin Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 239000000126 substance Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 230000002378 acidificating effect Effects 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 239000004721 Polyphenylene oxide Substances 0.000 description 10
- 229910021485 fumed silica Inorganic materials 0.000 description 10
- 239000011858 nanopowder Substances 0.000 description 10
- 125000005375 organosiloxane group Chemical group 0.000 description 10
- 229920000570 polyether Polymers 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 8
- 229920000178 Acrylic resin Polymers 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000013530 defoamer Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920004482 WACKER® Polymers 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000003279 ceramming Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000012720 thermal barrier coating Substances 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 acrylic ester Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000000352 supercritical drying Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The application relates to the technical field of coatings, in particular to the field of IPC C08G77, and more particularly relates to ceramic aerogel prepared from polysilazane, a preparation method and a heat insulation coating thereof. The transparent heat-insulating coating prepared by the application is different from the traditional scheme of absorbing sunlight energy to achieve transparent heat preservation, avoids skin damage caused by overhigh temperature of a substrate itself due to light energy absorption of the substrate at room temperature, and simultaneously has higher high temperature resistance compared with the traditional aerogel transparent heat-insulating coating, and the obtained polysilazane coating with high molecular weight has higher high temperature resistance after electronic radiation ceramization, can work at higher temperature and achieves the effect of high temperature heat insulation.
Description
Technical Field
The application relates to the technical field of coatings, in particular to the field of IPC C08G77, and more particularly relates to ceramic aerogel prepared from polysilazane, a preparation method and a heat insulation coating thereof.
Background
Along with the development of science and technology, the living standard of people is improved, the production and manufacture and daily life are all in need of energy conservation and heat preservation, and because of some special scenes, transparent or high-temperature-resistant heat insulation coating is often required to be prepared. The traditional transparent heat insulation method is mainly realized by absorbing part of infrared rays, ultraviolet rays and visible light in sunlight through ATO/ITO/GTO and the like, but the method is easy to cause energy accumulation on the surface of a coating even when the method is used at room temperature, so that the surface temperature is too high, and the skin is slightly burnt after contacting.
The method disclosed in patent CN201710901815.0 has a transmittance of 60% or more in the visible light region (380-780 nm) of the coating, a near infrared blocking rate of 50% or more, and a large amount of solar energy is accumulated on the surface of the glass, which easily results in an excessively high temperature of the surface of the glass. In another method, the transparent heat-insulating coating is obtained by matching nano aerogel with resin, wherein the resin is an organic high polymer, and the coating prepared by the method cannot bear high temperature. Patent CN201610128805.3 provides a method for preparing transparent heat-insulating coating by utilizing the ground heat transfer efficiency of silica aerogel, and although the component of aerogel is silica, the resin adopts traditional organic resin, so that the heat-insulating requirement of high-temperature environment cannot be met.
Disclosure of Invention
In order to solve the above problems, the present application provides, in a first aspect, a ceramic aerogel prepared from polysilazane, comprising the steps of:
s1, adding first polysilazane into a solvent to obtain a first polysilazane solution;
s2, slowly dripping deionized water into the first polysilazane solution obtained in the step S1, stirring for 24 hours or more, then adjusting the pH value to 3-5, and continuously stirring for 24 hours or more to obtain a solution I;
s3, regulating the pH value of the solution I to 8-12, and stirring for 24 hours or more to obtain a solution II;
and S4, drying the solution II obtained in the step S3.
Preferably, in the first polysilazane solution in step S1, the content of the first polysilazane is 10-40wt%.
Preferably, the molecular weight of the first polysilazane is more than or equal to 10000.
Preferably, the first polysilazane is one or more of methyl polysilazane, vinyl polysilazane, polyborosilazane, polyaluminosilazane, polyiron silazane and polytitanium silazane; further preferably, the polymer is any one of methyl polysilazane and vinyl polysilazane.
The applicant has found that by selecting polysilazane with molecular weight more than 10000 as raw material of ceramic aerogel, stability of system in preparation process can be improved, thereby improving success rate of ceramic aerogel preparation. This is probably because the hydrolysis reaction of Si-N in polysilazane with molecular weight of 10000 or more becomes relatively mild due to the larger reaction steric hindrance, compared with that of polysilazane with low molecular weight, and the polysilazane with large molecular weight screened by the application is suitable for preparing ceramic aerogel by sol-gel method, and can be slowly hydrolyzed in water when adding a proper amount of deionized water, and is not easy to precipitate and gel, so that ceramic aerogel can be successfully prepared.
Preferably, the solvent is one or more of acetone, toluene, xylene, n-butyl ether and ethyl acetate; further preferably, acetone is used.
Preferably, the weight ratio of deionized water to first polysilazane in step S2 is (0.5-3): 1.
The manner of adjusting the pH in step S2 is not limited, and in some preferred embodiments, the pH is adjusted by adding an acidic substance, where the acidic substance is one or more of a hydrochloric acid solution, a hydrobromic acid solution, a nitric acid solution, a sulfuric acid solution, and an oxalic acid solution.
Preferably, the concentration of the acidic substance is 0.0001-0.01M; further preferably 0.001M.
The manner of adjusting the pH value of the first solution in the step S3 is not limited, and in some preferred embodiments, the pH value is adjusted by adding an alkaline substance, where the alkaline substance is one or more of ammonia, ethylenediamine and triethylamine; more preferably, ammonia is used.
Preferably, the concentration of the ammonia water is 15-25wt%; further preferably, 17wt%.
Preferably, the drying in step S4 is performed by CO 2 Any one of supercritical method drying, oven drying, freeze drying and spray drying; further preferably, is CO 2 Drying by supercritical method.
Preferably, the CO 2 The supercritical drying method comprises the specific steps of drying for 5-10h under the conditions that the temperature is 30-50 ℃ and the pressure is 8-15 MPa.
The second aspect of the application provides a heat-insulating coating prepared from ceramic aerogel prepared from polysilazane, which is prepared by the following steps: and adding the ceramic aerogel into a second polysilazane solution, simultaneously adding a dispersing agent, a thixotropic agent, a leveling agent and a defoaming agent, uniformly stirring, and filtering through filter paper to obtain the ceramic aerogel.
The applicant has found that, when the ceramic aerogel prepared by selecting specific polysilazane is applied to the heat insulation coating, the visible light transmittance of the prepared ceramic film can be maintained, and the high temperature resistance of the ceramic film can be improved. The ceramic aerogel prepared by the method has high porosity, can not block the passage of visible light when applied to a heat-insulating coating system, so that the prepared heat-insulating coating is very suitable for being applied to transparent glass in the field of buildings, and can reduce the heat conductivity coefficient of the prepared ceramic film, so that the ceramic film can not burn skin due to overhigh temperature of the substrate caused by accumulated heat of the absorbed solar energy, the high temperature resistance of the finally prepared ceramic film is improved, the hand feeling temperature is reduced, and the prepared heat-insulating coating can be applied to the fields of buildings, industry and the like.
Preferably, the specific process of stirring uniformly comprises the following steps: the rotating speed is 2000-4000r/min, and the shearing and dispersing are carried out for 1-5h.
Preferably, the filter paper mesh number of the filtration is 50-400 mesh.
Preferably, the second polysilazane solution is obtained by uniformly mixing second polysilazane in butyl acetate solution.
The second polysilazane is not particularly limited, and commercially available polysilazanes may be used.
Preferably, the weight ratio of the second polysilazane to the butyl acetate is 1 (0.5-2); further preferably, the ratio is 1:1.
Preferably, the weight ratio of the ceramic aerogel to the second polysilazane solution is 1 (3-8); further preferably, the ratio is 1:5.
The inventors creatively found that when the prepared ceramic aerogel and the second polysilazane are mixed together to prepare the heat-insulating coating, the hardness and the heat-resistant effect of the prepared ceramic film can be improved. This is probably due to the synergistic effect of the ceramic aerogel as a filler with the second polysilazane solution in the heat-insulating coating system of the present application, which reduces the volume shrinkage of the ceramic coating during curing, thereby improving the compactness and hardness of the finally prepared ceramic film, and also improving the high temperature stability thereof.
Preferably, the weight ratio of the dispersing agent, the thixotropic agent, the leveling agent and the defoaming agent is (1-3): (1-3): (0.5-2): 1.
preferably, the dispersant has an amine number of 5-20mg KOH/g and a density of 0.92-1.10g/ml; further preferably, the dispersant has an amine number of 10mg KOH/g and a density of 0.99g/ml.
In some preferred embodiments, the dispersant is purchased from Shanghai Hui research New Material company as dispersant HY-163.
Preferably, the thixotropic agent is one or more of fumed silica, kaolin, attapulgite, polyvinyl alcohol and bentonite; further preferred is fumed silica.
Preferably, the fumed silica has a specific surface area of 150 to 250m 2 /g, the filling density is 40-60g/l; further preferably, the fumed silica has a specific surface area of 200m 2 And/g, the packing density is 50g/l.
In some preferred embodiments, the fumed silica is purchased from fumed silica WACKER, manufactured by Wacker, germanyH20。
Preferably, the leveling agent is one or more of an organosilicon leveling agent and an acrylic ester leveling agent; further preferred is an organosilicon leveling agent.
Preferably, the organosilicon leveling agent is one or more of polyether modified organosiloxane leveling agents, polyester modified organosiloxane leveling agents, mo Ji modified organosiloxane leveling agents and end group modified organosilicon leveling agents; further preferred is a polyether modified organosiloxane leveling agent.
Preferably, the polyether modified organosiloxane leveling agent has a viscosity of 5-60s measured by a coating-4 cup method at 25 ℃ and an active matter content of 40-60wt%; further preferably, the polyether modified organosiloxane leveling agent has a viscosity of 10-50s at 25 ℃ measured by a coating-4 cup method, and an active matter content of 50wt%.
In some preferred embodiments, the polyether modified organosiloxane leveling agent is purchased from Anhui Jiazhi Xinnuo chemical Co., ltdWE-D5411R。
Preferably, the defoaming agent is one or more of polyether defoaming agent, mineral oil defoaming agent, organic silicon defoaming agent and fermentation defoaming agent; further preferred are silicone defoamers.
Preferably, the flash point of the organosilicon defoamer is 40-60 ℃ and the density is 0.72-0.88g/ml; further preferably, the silicone defoamer has a flash point of 47 ℃ and a density of 0.81g/ml.
In some preferred embodiments, the silicone defoamer is purchased from Pick byk066n, pick, germany.
The third aspect of the application provides a ceramic film prepared from the heat-insulating coating, which comprises the following preparation processes:
m1, spraying the heat insulation coating on the surface of a substrate, and baking at 150-250 ℃ for 0.5-3h to obtain a first coating;
and M2, ceramizing the coating by using an electron beam irradiation technology to prepare the ceramized film.
Preferably, the thickness of the spray coating in the step S1 is 5-30 μm.
Preferably, the substrate is any one of glass and stainless steel; further preferably, it is glass.
Preferably, the specific process of the electron beam irradiation technology is as follows: an electron beam with energy of 5-15MeV is generated by a linear accelerator to ceramic the coating in helium atmosphere, and the irradiation dose is 5-30MGy.
The inventor creatively discovers that after the resin film (coating one) is obtained by volatilizing the solvent in the heat-insulating coating under specific conditions, the resin film is subjected to ceramization by using a specific electron beam irradiation mode, so that the resin film can quickly form a ceramized film, the substrate damage caused by overhigh temperature of the substrate is avoided, and the high temperature resistance of the ceramized film is improved. And the absorption dosage of the coating is controlled by controlling the irradiation time in a fixed-point irradiation mode, so that the operation is simple and the efficiency is high.
The beneficial effects are that:
1. according to the application, polysilazane with molecular weight more than 10000 is selected as the raw material of the ceramic aerogel, so that the stability of the system in the preparation process can be improved, and the preparation success rate of the ceramic aerogel is improved.
2. The ceramic aerogel prepared by selecting the specific polysilazane is applied to the heat insulation coating, so that the visible light transmittance of the prepared ceramic film can be kept, and the high temperature resistance of the ceramic film can be improved.
3. According to the application, when the prepared ceramic aerogel and the second polysilazane are mixed together to prepare the heat-insulating coating, the hardness and the high temperature resistance of the prepared ceramic film can be improved.
4. According to the application, the resin film (the first coating) is obtained by volatilizing the solvent in the heat-insulating coating under specific conditions, and then the resin film is subjected to ceramization in a specific electron beam irradiation mode, so that the resin film can quickly form a ceramized film, and the high temperature resistance of the ceramized film is improved.
5. The transparent heat-insulating coating prepared by the application is different from the traditional scheme of absorbing sunlight energy to achieve transparent heat preservation, avoids skin damage caused by overhigh temperature of a substrate itself due to light energy absorption of the substrate at room temperature, and simultaneously has higher high temperature resistance compared with the traditional aerogel transparent heat-insulating coating, and the obtained polysilazane coating with high molecular weight has higher high temperature resistance after electronic radiation ceramization, can work at higher temperature and achieves the effect of high temperature heat insulation.
Detailed Description
Examples
Example 1
Example 1 provides a ceramic aerogel prepared from polysilazane comprising the steps of:
s1, adding first polysilazane into a solvent to obtain a first polysilazane solution;
s2, slowly dripping deionized water into the first polysilazane solution obtained in the step S1, stirring for 24 hours, then adjusting the pH value to 3, and continuing stirring for 24 hours to obtain a solution I;
s3, regulating the pH value of the solution I to 8, and stirring for 24 hours to obtain a solution II;
and S4, drying the solution II obtained in the step S3.
The first polysilazane solution in the step S1 has a content of 10wt%.
The molecular weight of the first polysilazane is 100000.
The first polysilazane is a vinyl polysilazane.
The first polysilazane was purchased from TC-P21, manufactured by Hangzhou clear porcelain New Material Co.
The solvent is acetone.
The weight ratio of deionized water to first polysilazane in step S2 is 0.5:1.
In the step S2, the pH value is adjusted by adding an acidic substance, wherein the acidic substance is an aqueous hydrochloric acid solution.
The concentration of the acidic substance was 0.001M.
In the step S3, the pH value is adjusted by adding an alkaline substance, wherein the alkaline substance is ammonia water.
The concentration of the aqueous ammonia was 17wt%.
The drying mode in the step S4 is CO 2 Drying by supercritical method.
The CO 2 The supercritical drying method comprises the specific steps of drying for 8 hours under the conditions that the temperature is 40 ℃ and the pressure is 12 MPa.
The second aspect of the embodiment provides the heat-insulating coating prepared from the ceramic aerogel prepared from polysilazane, which comprises the following preparation methods in parts by weight: and adding 40 parts of the ceramic aerogel obtained by the preparation method into 200 parts of the second polysilazane solution, simultaneously adding 2 parts of dispersing agent, 2.4 parts of thixotropic agent, 1.2 parts of leveling agent and 1.2 parts of defoaming agent, uniformly stirring, and filtering through filter paper to obtain the ceramic aerogel.
The specific process for stirring evenly comprises the following steps: the rotating speed is 3000r/min, and shearing and dispersing are carried out for 3h.
The filter paper mesh number of the filtration is 100 mesh.
The second polysilazane solution is obtained by uniformly mixing second polysilazane in a butyl acetate solution.
The second polysilazane was purchased from polysilazane HTT 1800, manufactured by Merck, germany.
The weight ratio of the second polysilazane to the butyl acetate is 1:1.
The amine value of the dispersant was 10mg KOH/g and the density was 0.99g/ml.
The dispersant is purchased from Shanghai Hui research New Material company, inc. of dispersant HY-163.
The thixotropic agent is fumed silica.
The specific surface area of the fumed silica is 200m 2 And/g, the packing density is 50g/l.
The fumed silica is purchased from fumed silica WACKER manufactured by Wacker, germanyH20。
The leveling agent is an organosilicon leveling agent.
The organosilicon leveling agent is polyether modified organosiloxane leveling agent.
The polyether modified organosiloxane leveling agent has viscosity of 10-50s and active matter content of 50wt% measured at 25 deg.c in a coating-4 cup process.
The polyether modified organosiloxane flatting agent is purchased from the polyether modified polysiloxane flatting agent Xinno produced by Anhui Jiazhi Xinno chemical industry Co., ltdWE-D5411R。
The defoaming agent is an organosilicon defoaming agent.
The silicone defoamer had a flash point of 47 ℃ and a density of 0.81g/ml.
The silicone defoamer was purchased from Pick byk066n, manufactured by Pick, germany.
The third aspect of the embodiment provides a ceramic film prepared from the heat-insulating coating, which is prepared by the following steps:
m1, spraying the heat insulation coating on the surface of a substrate, and baking for 1h at 200 ℃ to obtain a first coating;
and M2, ceramizing the coating by using an electron beam irradiation technology to prepare the ceramized film.
The thickness of the spray coating in the step S1 is 20 mu m.
The substrate is glass.
The specific process of the electron beam irradiation technology is as follows: an electron beam with an energy of 9MeV was generated by a linac to ceramic the coating in a helium atmosphere at an irradiation dose of 20MGy.
Example 2
Example 2 provides a ceramic aerogel prepared from polysilazane, and the embodiment is the same as example 1. The difference is that:
s1, adding first polysilazane into a solvent to obtain a first polysilazane solution;
s2, slowly dripping deionized water into the first polysilazane solution obtained in the step S1, stirring for 30 hours, then adjusting the pH value to 3, and continuing stirring for 30 hours to obtain a solution I;
s3, regulating the pH value of the solution I to 9, and stirring for 30 hours to obtain a solution II;
and S4, drying the solution II obtained in the step S3.
The first polysilazane solution in the step S1 has a content of 20wt%.
The molecular weight of the first polysilazane is 20000.
The first polysilazane is methyl polysilazane.
The first polysilazane was purchased from TC-P01, manufactured by Hangzhou clear porcelain New Material Co.
The weight ratio of deionized water to the first polysilazane in the step S2 is 1:1.
In the step S2, the pH value is adjusted by adding an acidic substance, wherein the acidic substance is oxalic acid.
The concentration of the acidic substance was 0.001M.
The CO 2 Supercritical processThe specific drying step is that the drying is carried out for 8 hours under the conditions that the temperature is 40 ℃ and the pressure is 10 MPa.
Example 3
Example 3 provides a ceramic aerogel prepared from polysilazane, and the embodiment is the same as example 1. The difference is that:
s1, adding first polysilazane into a solvent to obtain a first polysilazane solution;
s2, slowly dripping deionized water into the first polysilazane solution obtained in the step S1, stirring for 24 hours, then adjusting the pH value to 3, and continuing stirring for 24 hours to obtain a solution I;
s3, regulating the pH value of the solution I to be 10, and stirring for 24 hours to obtain a solution II;
and S4, drying the solution II obtained in the step S3.
The first polysilazane solution in the step S1 has a content of 30wt%.
The first polysilazane has a molecular weight of 190000.
The first polysilazane is a vinyl polysilazane.
The first polysilazane was purchased from TC-P11, manufactured by Hangzhou clear porcelain New Material Co.
The solvent is acetone.
The weight ratio of deionized water to the first polysilazane in the step S2 is 1:1.
In the step S2, the pH value is adjusted by adding an acidic substance, wherein the acidic substance is hydrobromic acid.
The second aspect of the embodiment provides the heat-insulating coating prepared from the ceramic aerogel prepared from polysilazane, which is prepared by the following steps: and adding 40 parts of the ceramic aerogel into 200 parts of a second polysilazane solution, simultaneously adding 2 parts of a dispersing agent, 2.4 parts of a thixotropic agent, 1.2 parts of a leveling agent and 1.2 parts of a defoaming agent, uniformly stirring, and filtering through filter paper to obtain the ceramic aerogel.
The second polysilazane was purchased from polysilazane OPZ 118 produced by north of the national institute of sciences.
Comparative example 1
Comparative example 1 provides a ceramic aerogel prepared from polysilazane, the specific embodiment being the same as example 1, except that:
the first polysilazane solution in the step S1 has a content of 30wt%.
The molecular weight of the first polysilazane is 2000-5000.
The first polysilazane is methyl polysilazane.
The first polysilazane was purchased from polysilazane 1500RC manufactured by merck, germany.
Comparative example 2
Comparative example 2 provides a ceramic aerogel prepared from polysilazane, the embodiment being the same as example 1, except that:
the first polysilazane solution in the step S1 has a content of 30wt%.
The first polysilazane has a molecular weight of 500-2000.
The first polysilazane was purchased from polysilazane NS3600 manufactured by the general technology, hangzhou.
Comparative example 3
Comparative example 3 provides a thermal barrier coating, and the embodiment is the same as example 1. The difference is that:
the preparation method comprises the following steps: adding 10 parts of ITO nano powder into 200 parts of second polysilazane solution, simultaneously adding 2 parts of dispersing agent, 2.4 parts of thixotropic agent, 1.2 parts of leveling agent and 1.2 parts of defoaming agent, uniformly stirring, and filtering through filter paper to obtain the ITO nano powder.
The particle size of the ITO nanometer powder is 20nm.
The ITO nanopowder was purchased from YY-ITO-20 manufactured by Suzhou friend research New Material practice Co.
The ceramic membrane prepared by the heat-insulating coating comprises the following preparation processes:
spraying the heat insulation coating on the surface of a substrate, and baking at 200 ℃ for 40min for curing to obtain the heat insulation coating.
The substrate is glass.
Comparative example 4
Comparative example 4 provides a thermal barrier coating, and the embodiment is the same as example 1. The difference is that:
the preparation method comprises the following steps: adding 10 parts of ATO nano powder into 200 parts of second polysilazane solution, simultaneously adding 2 parts of dispersing agent, 2.4 parts of thixotropic agent, 1.2 parts of leveling agent and 1.2 parts of defoaming agent, uniformly stirring, and filtering through filter paper to obtain the nano-powder.
The particle size of the ATO nano powder is 20nm.
The ATO nano powder is purchased from KR-ATO-1 manufactured by Anhui Hao electronic technologies Co.
The ceramic membrane prepared by the heat-insulating coating comprises the following preparation processes:
spraying the heat insulation coating on the surface of a substrate, and baking at 200 ℃ for 40min for curing to obtain the heat insulation coating.
The substrate is glass.
Comparative example 5
Comparative example 5 provides a ceramic aerogel prepared from polysilazane, and embodiments are the same as example 1. The difference is that:
the heat-insulating coating prepared from the ceramic aerogel prepared from polysilazane comprises the following preparation method: 10 parts of ceramic aerogel is added into 200 parts of resin solution, and simultaneously 2 parts of dispersing agent, 2.4 parts of thixotropic agent, 1.2 parts of leveling agent and 1.2 parts of defoaming agent are added, uniformly stirred and filtered through filter paper to obtain the ceramic aerogel.
The resin solution is obtained by uniformly mixing acrylic resin in butyl acetate solution.
The acrylic resin was purchased from thermoplastic acrylic resin B-44 manufactured by dow, usa.
The weight ratio of the acrylic resin to the butyl acetate is 1:1.
The ceramic membrane prepared by the heat-insulating coating comprises the following preparation processes:
and spraying the heat-insulating coating on the surface of a substrate, and self-drying for 2 hours at 25 ℃ to obtain the heat-insulating coating.
The substrate is glass.
Comparative example 6
Comparative example 6 provides a ceramic aerogel prepared from polysilazane, and embodiments are the same as example 1. The difference is that:
the heat-insulating coating prepared from the ceramic aerogel prepared from polysilazane comprises the following preparation method: 10 parts of ceramic aerogel is added into 200 parts of resin solution, and simultaneously 2 parts of dispersing agent, 2.4 parts of thixotropic agent, 1.2 parts of leveling agent and 1.2 parts of defoaming agent are added, uniformly stirred and filtered through filter paper to obtain the ceramic aerogel.
The resin solution was a methylphenyl silicone resin having a solids content of 50wt%.
The resin solution was purchased from SH-9601, manufactured by Hubei New Sihai chemical Co., ltd.
The ceramic membrane prepared by the heat-insulating coating comprises the following preparation processes:
spraying the heat insulation coating on the surface of a substrate, and baking at 200 ℃ for 40min to obtain the heat insulation coating.
The substrate is glass.
Comparative example 7
Comparative example 7 provides a thermal barrier coating, and the embodiment is the same as comparative example 4. The difference is that:
the preparation method comprises the following steps: adding 10 parts of ATO nano powder into 200 parts of resin solution, simultaneously adding 2 parts of dispersing agent, 2.4 parts of thixotropic agent, 1.2 parts of leveling agent and 1.2 parts of defoaming agent, uniformly stirring, and filtering through filter paper to obtain the nano ATO powder.
The particle size of the ATO nano powder is 20nm.
The ATO nano powder is purchased from KR-ATO-1 manufactured by Anhui Hao electronic technologies Co.
The resin solution is obtained by uniformly mixing acrylic resin in butyl acetate solution.
The acrylic resin was purchased from thermoplastic acrylic resin B-44 manufactured by dow, usa.
The weight ratio of the acrylic resin to the butyl acetate is 1:1.
The ceramic membrane prepared by the heat-insulating coating comprises the following preparation processes:
and spraying the heat-insulating coating on the surface of a substrate, and self-drying for 2 hours at 25 ℃ to obtain the heat-insulating coating.
The substrate is glass.
Comparative example 8
Comparative example 8 provides a ceramic aerogel prepared from polysilazane, and embodiments are the same as example 1. The difference is that:
the preparation process of the ceramic membrane comprises the following steps: spraying the heat insulation coating on the surface of a substrate, and baking at 200 ℃ for 40min for curing to obtain the heat insulation coating.
Comparative example 9
Comparative example 9 provides a ceramic aerogel prepared from polysilazane, and embodiments are the same as example 2. The difference is that:
the preparation process of the ceramic membrane comprises the following steps: spraying the heat insulation coating on the surface of a substrate, and baking at 200 ℃ for 40min for curing to obtain the heat insulation coating.
Performance testing
1. Visible light transmittance test
The visible light transmittance of the coating film at 380-760nm wavelength was measured by using the Shenzhen precision instruments Co., ltd. NS13A optical transmittance tester test method for the ceramic films prepared in examples 1-3 and comparative examples 1-9, and the results are reported in Table 1.
2. Temperature of touch
The ceramic films prepared in examples 1 to 3 and comparative examples 1 to 9 were placed outdoors for 2 hours with direct solar irradiation for a period of time of 12:00 to 14:00, and the outdoor temperature was 30 to 35 ℃ (experimental time was 6 months), and the film surface temperature after 2 hours was measured with a thermometer, and the results are reported in table 1.
3. Thermal insulation coefficient (Heat transfer coefficient/heat conductivity)
The ceramic films prepared in examples 1 to 3 and comparative examples 1 to 9 were measured for heat insulation coefficient by referring to the method described in the method for measuring the steady-state thermal resistance and the related characteristics of the heat insulating material of GB/T10294-2008 and the results are reported in Table 1.
4. Heat resistance
The ceramic films prepared in examples 1 to 3 and comparative examples 1 to 9 were vertically sprayed on the coating layer with a gas flame of 1200℃for 30 minutes, and the surface conditions of the films were observed after the spraying was completed, and the results are shown in Table 1.
5. Hardness of
The ceramic films prepared in examples 1 to 3 and comparative examples 1 to 9 were measured for film hardness by the test method for measuring film hardness by GBT6739-2006 paint and varnish pencil method, and the results are reported in Table 1.
TABLE 1
In the table "-" indicates that the ceramic film could not be produced by the method of this example. In both comparative examples 1 and 2, the ceramic film could not be prepared, and in the experimental process, it was found that when deionized water was slowly dropped, the system precipitated, which indicates that polysilazane with a low molecular weight had poor stability in the system, and thus the success rate of preparing the ceramic aerogel and the ceramic film was affected. As can be seen from comparative examples 3, 4 and 7, the clear coating, which insulates against heat in the form of absorbing sunlight, is liable to overheat on the surface of the substrate and is unsuitable for skin contact. As can be seen from comparative examples 5 and 6, the ceramic aerogel prepared by filling the non-ceramic polysilazane resin into the ceramic film was poor in high temperature resistance and hardness. As can be seen from comparative examples 8 and 9, the high temperature resistance of the coating prepared in a non-ceramming manner is significantly reduced, indicating that the ceramming manner of electron beam irradiation can improve the high temperature resistance of the ceramming film.
Claims (4)
1. A thermal insulation coating prepared from ceramic aerogel, characterized in that the thermal insulation coating is prepared by the following method: adding the ceramic aerogel into the second polysilazane solution, simultaneously adding a dispersing agent, a thixotropic agent, a leveling agent and a defoaming agent, uniformly stirring, and filtering to obtain the ceramic aerogel;
the second polysilazane solution is obtained by uniformly mixing second polysilazane in butyl acetate solution, and the weight ratio of the second polysilazane to the butyl acetate is 1 (0.5-2);
the weight ratio of the ceramic aerogel to the second polysilazane solution is 1 (3-8);
the method for preparing the ceramic aerogel comprises the following steps:
s1, adding first polysilazane into a solvent to obtain a first polysilazane solution;
s2, slowly dripping deionized water into the first polysilazane solution obtained in the step S1, stirring for more than 24 hours, then adjusting the pH value to 3-5, and continuously stirring for 24 hours and more to obtain a solution I;
s3, regulating the pH value of the solution I to 8-12, and stirring for 24 hours or more to obtain a solution II;
s4, drying the solution II obtained in the step S3 to obtain the product;
in the first polysilazane solution in the step S1, the content of the first polysilazane is 10-40wt%;
the molecular weight of the first polysilazane is more than or equal to 10000;
the weight ratio of deionized water to first polysilazane in the step S2 is (0.5-3): 1.
2. The heat-insulating coating according to claim 1, wherein the drying in step S4 is performed by CO 2 Any one of supercritical method drying, oven drying, freeze drying and spray drying.
3. A ceramic film prepared from the heat-insulating coating according to claim 1 or 2, wherein the preparation process of the ceramic film comprises the following steps:
m1, spraying the heat insulation coating on the surface of a substrate, and baking at 150-250 ℃ for 0.5-3h to obtain a first coating;
and M2, ceramizing the coating by using an electron beam irradiation technology to prepare the ceramized film.
4. A ceramic film according to claim 3, wherein the electron beam irradiation technique comprises the following specific processes: an electron beam with energy of 5-15MeV is generated by a linear accelerator to ceramic the coating in helium atmosphere, and the irradiation dose is 5-30MGy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211268675.5A CN115819093B (en) | 2022-10-17 | 2022-10-17 | Ceramic aerogel prepared from polysilazane, preparation method and heat insulation coating thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211268675.5A CN115819093B (en) | 2022-10-17 | 2022-10-17 | Ceramic aerogel prepared from polysilazane, preparation method and heat insulation coating thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115819093A CN115819093A (en) | 2023-03-21 |
| CN115819093B true CN115819093B (en) | 2023-10-24 |
Family
ID=85524838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211268675.5A Active CN115819093B (en) | 2022-10-17 | 2022-10-17 | Ceramic aerogel prepared from polysilazane, preparation method and heat insulation coating thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115819093B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5209979A (en) * | 1990-01-17 | 1993-05-11 | Ethyl Corporation | Silicon carbide coated article with ceramic topcoat |
| JPH0647862A (en) * | 1990-12-20 | 1994-02-22 | Tonen Corp | Steel sheet and steel sheet molding material having coating of ceramic or its precursor, and their manufacture |
| CN105601317A (en) * | 2015-12-18 | 2016-05-25 | 厦门纳美特新材料科技有限公司 | SiCN aerogel and preparation method thereof |
| CN107266996A (en) * | 2016-04-08 | 2017-10-20 | 南京唯才新能源科技有限公司 | A kind of transparent heat-insulated thermal insulation coatings of silicon oxide-containing aeroge and preparation method thereof |
| CN107778875A (en) * | 2016-08-29 | 2018-03-09 | 天津城建大学 | Polysilazane zirconium dioxide aerogel composite and its preparation method and application |
| CN110373108A (en) * | 2018-04-13 | 2019-10-25 | 中国科学院化学研究所 | A kind of high-temperature insulation coating and its preparation method and application |
| CN110479564A (en) * | 2019-08-20 | 2019-11-22 | 海洋化工研究院有限公司 | A kind of preparation and technique of in-situ ceramic high temperature resistant heat insulation coating |
| CN112063300A (en) * | 2020-09-26 | 2020-12-11 | 库贝化学（上海）有限公司 | Polysilazane high-temperature resistant coating and preparation method thereof |
| CN113716966A (en) * | 2021-09-09 | 2021-11-30 | 航天特种材料及工艺技术研究所 | SiCN ceramic aerogel and preparation method and application thereof |
| CN113717639A (en) * | 2021-09-15 | 2021-11-30 | 库贝化学（上海）有限公司 | Polysilazane high-temperature resistant paint for carbon fiber composite material and preparation method thereof |
| CN113979773A (en) * | 2021-12-03 | 2022-01-28 | 南京工业大学 | Method for preparing polymer-converted ceramic aerogel |
-
2022
- 2022-10-17 CN CN202211268675.5A patent/CN115819093B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5209979A (en) * | 1990-01-17 | 1993-05-11 | Ethyl Corporation | Silicon carbide coated article with ceramic topcoat |
| JPH0647862A (en) * | 1990-12-20 | 1994-02-22 | Tonen Corp | Steel sheet and steel sheet molding material having coating of ceramic or its precursor, and their manufacture |
| CN105601317A (en) * | 2015-12-18 | 2016-05-25 | 厦门纳美特新材料科技有限公司 | SiCN aerogel and preparation method thereof |
| CN107266996A (en) * | 2016-04-08 | 2017-10-20 | 南京唯才新能源科技有限公司 | A kind of transparent heat-insulated thermal insulation coatings of silicon oxide-containing aeroge and preparation method thereof |
| CN107778875A (en) * | 2016-08-29 | 2018-03-09 | 天津城建大学 | Polysilazane zirconium dioxide aerogel composite and its preparation method and application |
| CN110373108A (en) * | 2018-04-13 | 2019-10-25 | 中国科学院化学研究所 | A kind of high-temperature insulation coating and its preparation method and application |
| CN110479564A (en) * | 2019-08-20 | 2019-11-22 | 海洋化工研究院有限公司 | A kind of preparation and technique of in-situ ceramic high temperature resistant heat insulation coating |
| CN112063300A (en) * | 2020-09-26 | 2020-12-11 | 库贝化学（上海）有限公司 | Polysilazane high-temperature resistant coating and preparation method thereof |
| CN113716966A (en) * | 2021-09-09 | 2021-11-30 | 航天特种材料及工艺技术研究所 | SiCN ceramic aerogel and preparation method and application thereof |
| CN113717639A (en) * | 2021-09-15 | 2021-11-30 | 库贝化学（上海）有限公司 | Polysilazane high-temperature resistant paint for carbon fiber composite material and preparation method thereof |
| CN113979773A (en) * | 2021-12-03 | 2022-01-28 | 南京工业大学 | Method for preparing polymer-converted ceramic aerogel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115819093A (en) | 2023-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1702012B1 (en) | Metallic substrates comprising a deformable glass-type coating | |
| CN109294394B (en) | Super-hydrophilic self-cleaning epoxy coating and preparation method and application thereof | |
| CN102046699B (en) | Method of making porous materials and porous materials prepared thereof | |
| CN103524049B (en) | A kind of monolayer SiO2the preparation method of anti-reflection film | |
| CN111303763A (en) | High-temperature-resistant high-power-density graphene heating coating and preparation method thereof | |
| CN111592805B (en) | Coating and preparation method and application thereof | |
| CN1872753A (en) | Ceramic material of microcrystalline glass, and preparation method | |
| JPH021778A (en) | Coating liquid for forming oxide coating film and production of oxide coating film | |
| KR101401754B1 (en) | Superhydrophobic coating solution composition and method for producing the coating composition | |
| CN103304149B (en) | A kind of method and coated substance of constructing hydrophobic coating at glass surface | |
| CN105036143B (en) | Preparation method of nano silicon dioxide aerogel | |
| CN109096853B (en) | Heat-insulation exterior wall coating | |
| CN105543798A (en) | Method for improving high-temperature oxidization resistance of titanium-based alloy | |
| CN115819093B (en) | Ceramic aerogel prepared from polysilazane, preparation method and heat insulation coating thereof | |
| KR101894453B1 (en) | Volatile organic compound elimination coatings containing graphin, platinum, and titanium dioxide and methods for producing the same | |
| CN103508484B (en) | Infrared low-emissivity nanocrystalline thin-film material SnO2 and preparation method thereof | |
| CN111099596A (en) | Simple method for coating high-hydrophobicity boron nitride nanosheet thin layer on surface of silicon dioxide aerogel particle | |
| CN110606736A (en) | Solvent-free synthesized ceramic microsphere and preparation method and application thereof | |
| CN102463130A (en) | Method for preparing modified TiO2 coatings by sol-gel method | |
| CN111233498A (en) | Environmental barrier coating and preparation method and application thereof | |
| JP2010538099A5 (en) | ||
| CN110724428A (en) | Special primer for heat insulation and preparation method thereof | |
| TW201117412A (en) | Manufacturing method for solar cell Cux ZnSnSy (CZTS) this film | |
| KR101111662B1 (en) | Method for Preparing Large-area Silica Aerogel Coatings by Using DCCA | |
| CN110240816B (en) | Transparent self-cleaning anti-dust deposition coating material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |