CN106277839B - Composite film with super-amphiphobic self-cleaning, anti-reflection and permeability-increasing performances and preparation method thereof - Google Patents
Composite film with super-amphiphobic self-cleaning, anti-reflection and permeability-increasing performances and preparation method thereof Download PDFInfo
- Publication number
- CN106277839B CN106277839B CN201510249599.7A CN201510249599A CN106277839B CN 106277839 B CN106277839 B CN 106277839B CN 201510249599 A CN201510249599 A CN 201510249599A CN 106277839 B CN106277839 B CN 106277839B
- Authority
- CN
- China
- Prior art keywords
- laminated film
- super
- silicon dioxide
- amphiphobic
- silica
- 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
- 238000004140 cleaning Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 226
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 109
- 239000002077 nanosphere Substances 0.000 claims abstract description 54
- 239000000758 substrate Substances 0.000 claims abstract description 48
- 239000011521 glass Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 40
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 30
- 238000005507 spraying Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 42
- 239000011248 coating agent Substances 0.000 claims description 35
- 238000000576 coating method Methods 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 239000000908 ammonium hydroxide Substances 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002604 ultrasonography Methods 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 235000013339 cereals Nutrition 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical group F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 4
- -1 perfluoro Chemical group 0.000 claims description 3
- 241000446313 Lamella Species 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005052 trichlorosilane Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 6
- 238000002834 transmittance Methods 0.000 abstract description 5
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical group [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000002135 nanosheet Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 28
- 230000003075 superhydrophobic effect Effects 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000004576 sand Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 239000008236 heating water Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention discloses a composite film with super-amphiphobic self-cleaning, anti-reflection and permeability-increasing performances and a preparation method thereof. The composite film comprises a silicon dioxide solid nano-sphere layer, a silicon dioxide hollow nano-sphere layer paved on the silicon dioxide solid nano-sphere layer and a silicon dioxide nano-sheet layer paved on the silicon dioxide hollow nano-sphere layer; the particle size of the solid silicon dioxide nanospheres is 20-50 nanometers; the particle size of the silicon dioxide hollow nanospheres is 40-100 nanometers; the thickness of the composite film is 0.5-1.5 micrometers; the surface of the composite film is modified with fluorosilane groups. The composite film which is constructed on the glass substrate and has the advantages of simple preparation method, good mechanical property, super-amphiphobic self-cleaning property, anti-reflection property and permeability-increasing property is prepared by taking the glass substrate as a substrate and then adopting a pulling method and a spraying method. The composite film has the advantages of simple preparation process, low cost, good light transmittance, excellent mechanical strength, good durability, wide application range and the like.
Description
Technical field
The present invention relates to technical field of nanometer material preparation.There is super-amphiphobic automatically cleaning more particularly, to one kind and subtract
The laminated film and preparation method thereof of anti-anti-reflection performance.
Background technology
Growing with population in the world, fossil resources are petered out, and finding emerging resource becomes today's society
The most important thing.Solar energy has obtained the extensive concern of society as a kind of inexhaustible resource.Solar-electricity
Therefore pond industry has also obtained significant progress.Although solar energy power generating is the generation technology of a cleanliness without any pollution,
Due to higher cost and lower photoelectric conversion efficiency, can not also be competed now with thermal power generation.If the sun can be improved
The light utilization efficiency of energy battery, then can improve the generated energy of solar cell module and can reduce cost.It is covered in solar energy
The cover-plate glass of battery component upper surface typically uses the ultra-clear glasses of tempering, in crystal silicon solar energy battery spectral response
Wave-length coverage in the average transmittance of (380 nanometers~1100 nanometers) be about 90%~92%, still there is about 8%~9% to carry
High spatial.Thus, a kind of method that can improve light utilization efficiency as effective low cost using antireflection film.
Simultaneously as sun-drenched desert area is more suitable for solar panel power generation, the sand on solar panel is cleaned
Dirt needs to expend a large amount of manpower and materials, therefore structure automatic cleaning coating becomes focus of people's attention on solar panel.It is super
The one kind of hydrophobic coating as automatic cleaning coating, can well solve this problem.Super-hydrophobic coat has larger surface
Roughness and low surface energy result in contact angle of the water on its surface and are more than 150 degree, and roll angle is less than 10 degree.
In practical applications, super-hydrophobic coat inevitably touches low-surface-energy organic reagent, to pollute coating
Surface makes it lose super-hydrophobic performance.It can be well solved with not only super-hydrophobic but also superoleophobic super-double-hydrophobic surface coating
This problem.Super-amphiphobic coating needs the surface roughness of bigger, it will usually prodigious light scattering is generated, to reduce coating
Light transmission.In addition, the micron-nanometer double-layer structure that super-amphiphobic coating has is easy to be destroyed by external force, lost so as to cause it
The performance of super-amphiphobic is gone.Accordingly, it is desirable to provide a kind of not only with super-amphiphobic self-cleaning performance but also with anti-reflection performance
Laminated film.
Invention content
It is an object of the present invention to provide a kind of laminated films with super-amphiphobic automatically cleaning and anti-reflection performance.
The THIN COMPOSITE with super-amphiphobic automatically cleaning and anti-reflection performance that it is another object of the present invention to provide a kind of
The preparation method of film.
The present invention uses three kinds of different Nano particles of silicon dioxide solution, is the titanium dioxide of 20~50 nanometers of grain size respectively
Silicon solid nanospheres colloidal sol, grain size be 40~100 nanometers silicon dioxide hollow nanosphere colloidal sol and with a certain amount of tetraethoxy
The silica nanometer piece solution of silane and mixed in hydrochloric acid, then prepares film using czochralski method and spray coating method.System of the present invention
Preparation Method is simple, of low cost, the laminated film good strength prepared, performance and super-amphiphobic automatically cleaning with anti-reflection
Performance, be well suited for outdoor large-scale application.
To reach above-mentioned first purpose, the present invention uses following technical proposals：
A kind of laminated film with super-amphiphobic automatically cleaning and anti-reflection performance, the laminated film includes silica
Solid nanospheres layer, the silicon dioxide hollow nanometer layers of balls being laid on silica solid nanospheres layer and it is laid in dioxy
Silica nanometer lamella in SiClx hollow Nano layers of balls；The grain size of the silica solid nanospheres is received for 20~50
Rice；The grain size of the silicon dioxide hollow nanosphere is 40~100 nanometers；The thickness of the laminated film is 0.5~1.5 micro-
Rice；The surface modification of the laminated film has silicon fluoride group.
To reach above-mentioned second purpose, the present invention uses following technical proposals：
A kind of preparation method of the laminated film with super-amphiphobic automatically cleaning and anti-reflection performance, which is characterized in that packet
Include following steps：
1) silica solid nanospheres colloidal sol is prepared；
2) silicon dioxide hollow nanosphere colloidal sol is prepared；
3) silica nanometer piece is prepared；
4) the silica nanometer piece obtained by step 3) is scattered in ethyl alcohol, tetraethoxysilane (99 is then added
+ %) and concentrated hydrochloric acid (36~38wt%), ultrasound is carried out, silica nanometer piece solution is obtained；
5) glass substrate cleaned is immersed in the silica solid nanospheres colloidal sol that step 1) obtains, is lifted out
Glass substrate spontaneously dries in air, this step of repetition is multiple, obtains silica solid nanospheres coating；Followed by
Spray coating method by the silicon dioxide hollow nanosphere colloidal sol that step 2) obtains and silica nanometer piece solution that step 4) obtains according to
It is secondary to spray to silica solid nanospheres coating surface, obtain composite coating；Then obtained composite coating is placed on horse
Not calcined in stove；Finally utilizing Simplified chemical vapor deposition method, (hydrophobization is repaiied to composite coating surface modification silicon fluoride group
Decorations), you can obtain laminated film of the final products with super-amphiphobic automatically cleaning and anti-reflection performance.
Preferably, real using stober legal systems prepared silicon dioxide using tetraethoxysilane and ammonium hydroxide as raw material in step 1)
Heart nanosphere colloidal sol.
Preferably, in step 2), the method for preparing silicon dioxide hollow nanosphere colloidal sol is：By 0.3~0.9 gram of polypropylene
Acid is dissolved in 3~6 milliliters of ammonium hydroxide, ultrasonic disperse 5~20 minutes；Then it is added dropwise in 50~150 milliliters of absolute ethyl alcohols,
Stirring obtains mixed liquor in 10~50 minutes；1~4 milliliter of tetraethoxysilane is added dropwise with 20~70 microlitres of speed per minute
Into mixed liquor；After completion of dropwise addition, acquired solution is stirred at room temperature 5~15 hours, and it is molten to obtain silicon dioxide hollow nanosphere
Glue.
Preferably, in step 3), the method for preparing silica nanometer piece is：The method for preparing silica nanometer piece
For：0.2~0.8 gram of cetyl trimethylammonium bromide is dissolved in 50~100 milliliters of water, 0.6~1 milliliter of ammonium hydroxide and 10~30 millis
In the mixed solution for rising ether, after stirring 10~50 minutes, 1~5 milliliter of tetraethoxysilane is rapidly joined, is stirred at room temperature 2~6
After hour, white precipitate is obtained；Through detaching, washing, dry, white precipitate is calcined 4~6 hours under 500~600 degree, you can
Silica nanometer piece is made.
Preferably, in step 4), it is scattered in a concentration of 0.5~1.5 grams per liter of the silica nanometer piece in ethyl alcohol；Institute
The ratio of the addition and silica nanometer piece overall solution volume of stating tetraethoxysilane is 0~1：10；The concentrated hydrochloric acid adds
The ratio for entering amount and silica nanometer piece overall solution volume is 0~1：75；The time of the ultrasound is 5~15 minutes.
Preferably, in step 5), the glass substrate cleaned, cleaning method is that glass substrate is first carried out ultrasound
Washing 10~30 minutes, is then dried up with inert gas, then is cleaned 5~10 minutes by oxygen plasma, and cleaning is with voltage
600 volts, the flow of oxygen is 800~1000 ml/mins.
Preferably, in step 5), the time that glass substrate immerses in silica solid nanospheres colloidal sol is 10~50 seconds；
The speed of the lifting is 100~200 mm/mins；The time that the glass substrate lifted out spontaneously dries in air be 1~
3 minutes；Preferably, lifting drying steps are repeated 3 times.
Preferably, in step 5), the composite coating is calcined 2~4 hours in 500~600 degrees Celsius of Muffle furnace.
Preferably, in step 5), the method for the Simplified chemical vapor deposition is that the composite coating after calcining is placed in appearance
In device, 30~70 microlitres of perfluoro capryl trichlorosilane is added dropwise in container bottom, sealing heats 2~6 under 100~150 degree
Hour；Then container is opened, 1~3 hour is heated under 100~200 degree.
The present invention constructs simple, satisfactory mechanical property, super-amphiphobic automatically cleaning with preparation method and subtracts on the glass substrate
Anti- antireflective laminated film.Surface coats the glass substrate of laminated film of the present invention in a length of 300~2500 nanometers of the area of light wave
The highest light transmittance in domain is increased to 96.3% by the 91.4% of blank glass substrate, wherein in 400~800 nanometers of visible light wave
The average transmittance in long region is increased to 95.4% by the 90.8% of blank glass substrate, visible close at 400~2500 nanometers
The average transmittance of infrared wavelength region is increased to 93.4% by the 90.2% of blank glass substrate.
Contact angle (WCA) of the water on the glass substrate that there is laminated film of the present invention on surface is 169~171 degree, ethylene glycol
Contact angle (OCA) on laminated film of the present invention is 150~152 degree.
Surface has the glass substrate of laminated film of the present invention being subjected to 2H, 3H, 4H, and 5H Pencil scratch test rear film is not
There is breakage, only particle therein deformation, it is possible thereby to illustrate that the film has good adhesion property.
Surface has the glass substrate of the laminated film of the present invention coating after being subjected to the test of ASTM D3359-93 tape methods not have
Damage, coating adhesion are 5A ranks.
There is the glass substrate of laminated film of the present invention on surface primary with 3M scotch tape adhesions, ten times, 20 times, and 30
Secondary, the contact angle of water is 169 degree, 161 degree, 155 degree, 155 degree and 155 degree after 40 times, all has super-hydrophobic performance.
Surface has the glass substrate of laminated film of the present invention being subjected to 30 grams of sea sands from water after one meter of eminence impact test
Contact angle is 157 degree, is still super-hydrophobic coat.Surface has the glass substrate of laminated film of the present invention to be subjected in two minutes
4500 contact angles for dripping and (often dripping about 22 microlitres) after 50 centimetres of eminence impact experiments water are 160 degree, are still super thin
Water coating.
Surface has the glass substrate of laminated film of the present invention being subjected to one week, two weeks, one month, two months and four months families
The contact angle of water after outer test, respectively 167 degree, 166 degree, 164 degree, 163 degree and 163 degree, be still super-hydrophobic coat.
Simple, satisfactory mechanical property, super-amphiphobic automatically cleaning are constructed with preparation method on the above test specification glass substrate
And the laminated film of the present invention of anti-reflection has good mechanical strength, is suitable for outdoor application.
Beneficial effects of the present invention are as follows：
The present invention prepares the tool constructed on glass substrate using glass substrate as substrate, then by czochralski method and spray coating method
Have that preparation method is simple, laminated film of satisfactory mechanical property, super-amphiphobic automatically cleaning and anti-reflection performance.On the glass substrate
The laminated film of simple, satisfactory mechanical property, super-amphiphobic automatically cleaning and anti-reflection with preparation method constructed is with system
The advantages that standby simple for process, at low cost, light transmission is good, mechanical strength is superior, durability is good, applied widely.
Description of the drawings
Specific embodiments of the present invention will be described in further detail below in conjunction with the accompanying drawings.
Fig. 1 shows the transmission electron microscope picture of the silicon dioxide hollow nanosphere colloidal sol prepared in the embodiment of the present invention 1.
Fig. 2 shows the transmission electron microscope pictures of the silica nanometer piece solution prepared in the embodiment of the present invention 1.
Fig. 3 shows the laminated film with super-amphiphobic automatically cleaning and anti-reflection performance prepared in the embodiment of the present invention 1
Scanning electron microscope (SEM) photograph under low power number (a) and high magnification numbe (b).
Glass substrate coated with laminated film that Fig. 4 shows to prepare in the embodiment of the present invention 1 and blank glass substrate
Integrating sphere penetrates spectrogram.
Fig. 5 shows the water contact angle (a) and second of the glass substrate coated with laminated film prepared in the embodiment of the present invention 3
The digital pictures of glycol contact angle (b).
Fig. 6 shows that prepared laminated film is being subjected to 2H, 3H, 4H in the embodiment of the present invention 4, after the test of 5H Pencil scratch
Scanning electron microscope (SEM) photograph under low power number (a) and high magnification numbe (b).
Fig. 7 shows that laminated film prepared in the embodiment of the present invention 5 is low after being subjected to tape adhesion test
Scanning electron microscope (SEM) photograph under multiple (a) and high magnification numbe (b).
Fig. 8 shows that prepared laminated film is being subjected to 1 time (a) in the embodiment of the present invention 6,10 times (b), 20 times (c), 30 times
(d) the contact angle digital photograph of the water and after 40 (e) viscose glue tests.
Fig. 9 shows the contact of prepared laminated film (a) and rear (b) before being subjected to sand surfing test in the embodiment of the present invention 7
Angle digital photograph.
Figure 10 shows (a) and the contact of (b) afterwards before the test that is subjected to dripping of prepared laminated film in the embodiment of the present invention 8
Angle digital photograph.
Figure 11 shows that prepared laminated film is before through tested person (a) in the embodiment of the present invention 9, is subjected to one week (b), two
All (c), one month (d), the contact corner brace photo of two month (e) and water after four months (f) outdoor test.
Specific implementation mode
In order to illustrate more clearly of the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.Similar component is indicated with identical reference numeral in attached drawing.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
1) silica solid nanospheres colloidal sol is prepared；
2) silicon dioxide hollow nanosphere colloidal sol is prepared；
3) silica nanometer piece is prepared；
Embodiment 1
1) silica solid nanospheres colloidal sol is prepared：
5 milliliters of ammonium hydroxide is placed in 100 milliliters of ethanol solutions, 3 milliliters of four ethoxies are added to after 60 degree in heating water bath
Base silane keeps isothermal reaction 10 hours.The grain size of prepared silica solid nanospheres is 20~50 nanometers.
2) silicon dioxide hollow nanosphere colloidal sol is prepared：
The polyacrylic acid of certain mass is dissolved in 4.5 milliliters of ammonium hydroxide respectively, ultrasonic disperse 10 minutes；Then add dropwise
Enter to being mounted in the container of 90 milliliters of absolute ethyl alcohols, stirring obtains mixed liquor in 15 minutes；By the four of 1.5 milliliters~2.5 milliliters
Ethoxysilane is added drop-wise to 45 microlitres of speed per minute in the mixed liquor；After completion of dropwise addition, acquired solution at room temperature (25
DEG C) be stirred 10 hours, obtain the sol solutions containing hollow silica ball nano-particle.
When the quality of polyacrylic acid is respectively 0.3 gram, 0.6 gram and 0.9 gram, prepared hollow silica ball nanometer
The average grain diameter of hollow silica ball nano-particle in the sol solutions of particle is respectively 42 nanometers, 60 nanometers and 93 nanometers.
Fig. 1 is the transmission electron microscope picture of the silicon dioxide hollow nanosphere colloidal sol prepared by the present invention.
3) silica nanometer piece is prepared：
0.2~0.8 gram of cetyl trimethylammonium bromide (CTAB) is dissolved in 70 milliliters of water, 0.8 milliliter of ammonium hydroxide and 20 millis
In the mixed solution for rising ether.After solution stirs 30 minutes, 1~5 milliliter of tetraethoxysilane is rapidly joined.Solution is stirred at room temperature
After 4 hours, white precipitate is obtained.By detaching, washing, dry, white precipitate calcined under 550 degree 5 hours it is extra to remove
Cetyl trimethylammonium bromide, you can silica nanometer piece is made.
4) silica nanometer piece solution is prepared：
Nanometer sheet obtained by step 3) is scattered in ethyl alcohol, a concentration of 1g/L then will be total with silica nanometer piece
Liquor capacity ratio is 0~1：10 tetraethoxysilane (99+%) and 0~1：75 concentrated hydrochloric acid (36~38wt%), ultrasound are molten
Liquid 10 minutes.
Fig. 2 is the transmission electron microscope picture of the silica nanometer piece solution containing crosslinking agent prepared by the present invention.
5) the functional laminated film with super-amphiphobic automatically cleaning and anti-reflection performance of processing machinery：
Multi-function membrane is prepared using czochralski method and spray coating method：The sheet glass cleaned is immersed in silica is solid to be received
In rice ball sol solutions, (time being generally immersed in is 30 seconds or so), lifting out glass substrate, (speed of lifting is 100 millis m/min
The mm/min of clock~200), it spontaneously dries in air (generally the dry time is 2 minutes or so).Repeat this step 3 time；
Followed by spray coating method by the silicon dioxide hollow nanosphere colloidal sol that step 2) obtains and the silica nanometer that step 4) obtains
The solution that piece solution obtains, which is sprayed onto, have been obtained on coating.Then it is small obtained coating to be placed on 550 DEG C of calcinings 3 in Muffle furnace
When.Coating is finally subjected to hydrophobization modification using Simplified chemical vapor deposition method.
The glass substrate cleaned up, the method for cleaning can be carries out ultrasonic washing (generally by glass substrate
The time of ultrasound washing is 10~30 minutes), then inert gas (such as nitrogen) is used to dry up, then cleaned by oxygen plasma
(time of the oxygen gas plasma cleaning is generally 5~10 minutes, and the voltage of cleaning is 600V or so, the stream of oxygen
Amount is 800~1000mL/min).
It is 150 mm/mins that Fig. 3, which is pull rate, and tetraethoxysilane volume ratio is 1 in solution：20, concentrated hydrochloric acid volume
Than being 1:The scanning electron microscope (SEM) photograph of the glass substrate of laminated film prepared by 150.
Fig. 4 is coated with the glass substrate of laminated film and the integrating sphere of blank glass substrate through spectrogram prepared by being.
Fig. 5 is that pull rate is 150 mm/mins, the water contact angle (a) and second of the glass substrate of prepared laminated film
The digital pictures of glycol contact angle (b).The contact angle (WCA) of THIN COMPOSITE film water is 173.2 degree, the contact angle (OCA) of ethylene glycol
It it is 150.7 degree, film has the performance of super-amphiphobic.
Embodiment 2
Pencil scratch test is carried out to the laminated film prepared by embodiment 1.Fig. 6 is that tetraethoxysilane volume ratio is 1/
20 laminated film is being subjected to 2H, 3H, 4H, the low power number (a) after the test of 5H Pencil scratch and the scanning electron microscope under high magnification numbe (b)
Figure.By observation it can be found that after Pencil scratch, film is not damaged, only particle therein deformation,
It is possible thereby to illustrate that film has good adhesion property.
Embodiment 3
Tape adhesion test (standard is ASTM D3359-93) is carried out to the laminated film prepared by embodiment 1.Fig. 7
For the scanning electron microscope (SEM) photograph under the low power number (a) of test end rear film and high magnification numbe (b).It can be seen that by testing rear film
There is no any damage in cut both sides, 5A test grades can be reached, film adhesion force is very strong.
Embodiment 4
Viscose glue test is carried out to the laminated film prepared by embodiment 1, is pasted using 3M adhesive tapes.Fig. 8 is prepared
Film is being subjected to 1 time (a), 10 times (b), 20 times (c), and the contact angle number of the water after 30 times (d) and 40 (e) viscose glue tests shines
Piece, it can be found that film still has super-hydrophobic performance.Thus prove that film has good adhesion strength and mechanical performance.
Embodiment 5
Sand surfing test is carried out to the laminated film prepared by embodiment 1.The sea sand for being 100~300 microns by 40 gram particle diameters
It is placed on apart from 1 meter of eminence of film, sand is impacted in two minutes on film.Fig. 9 is that prepared film is being subjected to rushing
The contact angle of (a) and rear (b) variation before sand test.It can be found that be 157 degree by the contact angle of the water of sand surfing test rear film,
Still there is super-hydrophobic performance.Thus prove that film has good mechanical performance.
Embodiment 6
Test of dripping is carried out to the silica laminated film prepared by embodiment 1.It drips in test, by 100 milliliters of water
60 centimetres of eminences of scrapping off film are placed in, are impacted on film with fast speed.All tests are dripped off with water in two minutes.Figure 10
The contact angle of (a) and rear (b) variation before the test that is subjected to dripping for prepared film.It can be found that thin after test of dripping
The contact angle of the water of film is 160 degree, still has super-hydrophobic performance.Thus prove that film has good mechanical performance.
Embodiment 7
Outdoor test is carried out to the silica laminated film prepared by embodiment 1.Figure 11 is that prepared film is passing through
Before tested person (a), through tested person one week (b), two weeks (c), one month (d), two month (e) and four months (f) outdoor test
The contact angle of water afterwards, respectively 174 degree, 167 degree, 166 degree, 164 degree, 163 degree and 163 degree, be still super-hydrophobic coat.Explanation
Coating has preferable application prospect outdoors.
Embodiment 8
1) silica solid nanospheres colloidal sol is prepared：
4 milliliters of ammonium hydroxide is placed in 50 milliliters of ethanol solutions, 2 milliliters of four ethoxies are added to after 50 degree in heating water bath
Base silane keeps isothermal reaction 6 hours.The grain size of prepared silica solid nanospheres is 20~50 nanometers.
2) silicon dioxide hollow nanosphere colloidal sol is prepared：
The method for preparing silicon dioxide hollow nanosphere colloidal sol is：0.3 gram of polyacrylic acid is dissolved in 3 milliliters of ammonium hydroxide,
Ultrasonic disperse 5 minutes；Then it is added dropwise in 50 milliliters of absolute ethyl alcohols, stirring obtains mixed liquor in 10 minutes；By the four of 1 milliliter
Ethoxysilane is added drop-wise to 20 microlitres of speed per minute in mixed liquor；After completion of dropwise addition, acquired solution is stirred at room temperature 5
Hour, obtain silicon dioxide hollow nanosphere colloidal sol.
3) silica nanometer piece is prepared：
The method for preparing silica nanometer piece is：0.2 gram of cetyl trimethylammonium bromide is dissolved in 50 milliliters of water,
In the mixed solution of 0.6 milliliter of ammonium hydroxide and 10 milliliters of ether, stirring after ten minutes, rapidly joins 1 milliliter of tetraethoxysilane, room
After temperature stirring 2 hours, white precipitate is obtained；Through detaching, washing, dry, white precipitate is calcined 4 hours under 500 degree, you can system
Obtain silica nanometer piece.
4) silica nanometer piece solution is prepared：
Nanometer sheet obtained by step 3) is scattered in ethyl alcohol, a concentration of 0.5g/L then will be with silica nanometer piece
Total solution volume ratio is 0~1：10 tetraethoxysilane (99+%) and 0~1：75 concentrated hydrochloric acid (36~38wt%), ultrasound
Solution 5 minutes.
5) the functional laminated film with super-amphiphobic automatically cleaning and anti-reflection performance of processing machinery：
Multi-function membrane is prepared using czochralski method and spray coating method：The sheet glass cleaned is immersed in silica is solid to be received
In rice ball sol solutions, (time being generally immersed in is 30 seconds or so), lifting out glass substrate, (speed of lifting is 100 millis m/min
The mm/min of clock~200), it spontaneously dries in air (generally the dry time is 2 minutes or so).Repeat this step 2 time；
Followed by spray coating method by the silicon dioxide hollow nanosphere colloidal sol that step 2) obtains and the silica nanometer that step 4) obtains
The solution that piece solution obtains, which is sprayed onto, have been obtained on coating.Then obtained coating is placed on 500 calcining 2 hours in Muffle furnace.
Coating is finally subjected to hydrophobization modification using Simplified chemical vapor deposition method.
The glass substrate cleaned up, the method for cleaning can be carries out ultrasonic washing (generally by glass substrate
The time of ultrasound washing is 10~30 minutes), then inert gas (such as nitrogen) is used to dry up, then cleaned by oxygen plasma
(time of the oxygen gas plasma cleaning is generally 5~10 minutes, and the voltage of cleaning is 600V or so, the stream of oxygen
Amount is 800~1000mL/min).
The various performance test effects of gained laminated film of the invention are similar to Example 1.
Embodiment 9
1) silica solid nanospheres colloidal sol is prepared：
6 milliliters of ammonium hydroxide is placed in 150 milliliters of ethanol solutions, 4 milliliters of four ethoxies are added to after 70 degree in heating water bath
Base silane keeps isothermal reaction 18 hours.The grain size of prepared silica solid nanospheres is 20~50 nanometers.
2) silicon dioxide hollow nanosphere colloidal sol is prepared：
The method for preparing silicon dioxide hollow nanosphere colloidal sol is：0.9 gram of polyacrylic acid is dissolved in 6 milliliters of ammonium hydroxide,
Ultrasonic disperse 20 minutes；Then it is added dropwise in 150 milliliters of absolute ethyl alcohols, stirring obtains mixed liquor in 50 minutes；By 4 milliliters
Tetraethoxysilane is added drop-wise to 70 microlitres of speed per minute in mixed liquor；After completion of dropwise addition, acquired solution is stirred at room temperature
It mixes 15 hours, obtains silicon dioxide hollow nanosphere colloidal sol.
3) silica nanometer piece is prepared：
The method for preparing silica nanometer piece is：0.8 gram of cetyl trimethylammonium bromide is dissolved in 100 milliliters of water, 1
In the mixed solution of milliliter ammonium hydroxide and 30 milliliters of ether, after stirring 50 minutes, 5 milliliters of tetraethoxysilanes, room temperature are rapidly joined
After stirring 6 hours, white precipitate is obtained；Through detaching, washing, dry, white precipitate is calcined 6 hours under 600 degree, you can is made
Silica nanometer piece.
4) silica nanometer piece solution is prepared：
Nanometer sheet obtained by step 3) is scattered in ethyl alcohol, a concentration of 1.5g/L then will be with silica nanometer piece
Total solution volume ratio is 0~1：10 tetraethoxysilane (99+%) and 0~1：75 concentrated hydrochloric acid (36~38wt%), ultrasound
Solution 15 minutes.
5) the functional laminated film with super-amphiphobic automatically cleaning and anti-reflection performance of processing machinery：
Multi-function membrane is prepared using czochralski method and spray coating method：The sheet glass cleaned is immersed in silica is solid to be received
In rice ball sol solutions, (time being generally immersed in is 30 seconds or so), lifting out glass substrate, (speed of lifting is 100 millis m/min
The mm/min of clock~200), it spontaneously dries in air (generally the dry time is 2 minutes or so).Repeat this step 4 time；
Followed by spray coating method by the silicon dioxide hollow nanosphere colloidal sol that step 2) obtains and the silica nanometer that step 4) obtains
The solution that piece solution obtains, which is sprayed onto, have been obtained on coating.Then obtained coating is placed on 600 calcining 4 hours in Muffle furnace.
Coating is finally subjected to hydrophobization modification using Simplified chemical vapor deposition method.
The glass substrate cleaned up, the method for cleaning can be carries out ultrasonic washing (generally by glass substrate
The time of ultrasound washing is 10~30 minutes), then inert gas (such as nitrogen) is used to dry up, then cleaned by oxygen plasma
(time of the oxygen gas plasma cleaning is generally 5~10 minutes, and the voltage of cleaning is 600V or so, the stream of oxygen
Amount is 800~1000mL/min).
The various performance test effects of gained laminated film of the invention are similar to Example 1.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is every to belong to this hair
Row of the obvious changes or variations that bright technical solution is extended out still in protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the laminated film with super-amphiphobic automatically cleaning and anti-reflection performance, it is characterised in that：It is described
The silicon dioxide hollow that laminated film includes silica solid nanospheres layer, is laid on silica solid nanospheres layer is received
Rice layers of balls and the silica nanometer lamella being laid in silicon dioxide hollow nanometer layers of balls；The solid nanometer of silica
The grain size of ball is 20~50 nanometers；The grain size of the silicon dioxide hollow nanosphere is 40~100 nanometers；The laminated film
Thickness is 0.5~1.5 micron；The surface modification of the laminated film has silicon fluoride group；
The preparation of the laminated film includes the following steps：
1）Prepare silica solid nanospheres colloidal sol；
2）Prepare silicon dioxide hollow nanosphere colloidal sol；
3）Prepare silica nanometer piece；
4）By step 3）The silica nanometer piece of gained is scattered in ethyl alcohol, and tetraethoxysilane and concentrated hydrochloric acid is then added,
Ultrasound is carried out, silica nanometer piece solution is obtained；
5）The glass substrate cleaned is immersed in step 1）In obtained silica solid nanospheres colloidal sol, glass is lifted out
Substrate spontaneously dries in air, this step of repetition is multiple, obtains silica solid nanospheres coating；Followed by spraying
Method is by step 2）Obtained silicon dioxide hollow nanosphere colloidal sol and step 4）Obtained silica nanometer piece solution sprays successively
It is coated onto silica solid nanospheres coating surface, obtains composite coating；Then obtained composite coating is placed on Muffle furnace
Middle calcining；Finally utilize Simplified chemical vapor deposition method to composite coating surface modification silicon fluoride group, you can to obtain final
Product has super-amphiphobic automatically cleaning and the laminated film of anti-reflection performance.
2. a kind of preparation side of laminated film with super-amphiphobic automatically cleaning and anti-reflection performance according to claim 1
Method, it is characterised in that：Step 1）In, it is real using stober legal systems prepared silicon dioxide using tetraethoxysilane and ammonium hydroxide as raw material
Heart nanosphere colloidal sol.
3. a kind of preparation side of laminated film with super-amphiphobic automatically cleaning and anti-reflection performance according to claim 1
Method, which is characterized in that step 2）In, the method for preparing silicon dioxide hollow nanosphere colloidal sol is：By 0.3 ~ 0.9 gram of polyacrylic acid
It is dissolved in 3~6 milliliters of ammonium hydroxide, ultrasonic disperse 5~20 minutes；Then it is added dropwise in 50~150 milliliters of absolute ethyl alcohols, stirs
It mixes 10~50 minutes and obtains mixed liquor；1 ~ 4 milliliter of tetraethoxysilane is added drop-wise to 20~70 microlitres of speed per minute
In mixed liquor；After completion of dropwise addition, acquired solution is stirred at room temperature 5~15 hours, obtains silicon dioxide hollow nanosphere colloidal sol.
4. a kind of preparation side of laminated film with super-amphiphobic automatically cleaning and anti-reflection performance according to claim 1
Method, which is characterized in that step 3）In, the method for preparing silica nanometer piece is：By 0.2~0.8 gram of cetyl trimethyl
Ammonium bromide is dissolved in 50~100 milliliters of water, in the mixed solution of 0.6~1 milliliter of ammonium hydroxide and 10~30 milliliters of ether, stirring 10~50
After minute, rapidly joins 1~5 milliliter of tetraethoxysilane and obtain white precipitate after being stirred at room temperature 2~6 hours；Through detaching, washing
It washs, dry, white precipitate is calcined 4~6 hours under 500~600 degrees Celsius, you can silica nanometer piece is made.
5. a kind of preparation side of laminated film with super-amphiphobic automatically cleaning and anti-reflection performance according to claim 1
Method, which is characterized in that step 4）In, it is scattered in a concentration of 0.5~1.5 grams per liter of the silica nanometer piece in ethyl alcohol；It is described
The addition of tetraethoxysilane and the ratio of silica nanometer piece overall solution volume are 0 ~ 1：10；The addition of the concentrated hydrochloric acid
And the ratio of silica nanometer piece overall solution volume is 0 ~ 1：75；The time of the ultrasound is 5~15 minutes.
6. a kind of preparation side of laminated film with super-amphiphobic automatically cleaning and anti-reflection performance according to claim 1
Method, which is characterized in that step 5）In, the glass substrate cleaned, cleaning method is that glass substrate is first carried out ultrasound
Washing 10 ~ 30 minutes, is then dried up with inert gas, then is cleaned 5 ~ 10 minutes by oxygen plasma, and cleaning voltage is 600
The flow of volt, oxygen is 800 ~ 1000 ml/mins.
7. a kind of preparation side of laminated film with super-amphiphobic automatically cleaning and anti-reflection performance according to claim 1
Method, which is characterized in that step 5）In, the time that glass substrate immerses in silica solid nanospheres colloidal sol is 10~50 seconds；
The speed of the lifting is 100 ~ 200 mm/mins；The time that the glass substrate lifted out spontaneously dries in air is 1~3
Minute.
8. a kind of preparation side of laminated film with super-amphiphobic automatically cleaning and anti-reflection performance according to claim 7
Method, which is characterized in that step 5）In, it repeats to lift drying steps 3 times.
9. a kind of preparation side of laminated film with super-amphiphobic automatically cleaning and anti-reflection performance according to claim 1
Method, which is characterized in that step 5）In, the composite coating is calcined 2~4 hours in 500~600 degrees Celsius of Muffle furnace.
10. a kind of preparation of laminated film with super-amphiphobic automatically cleaning and anti-reflection performance according to claim 1
Method, which is characterized in that step 5）In, the method for the Simplified chemical vapor deposition is that the composite coating after calcining is placed in appearance
In device, 30 ~ 70 microlitres of perfluoro capryl trichlorosilane is added dropwise in container bottom, sealing heats 2 ~ 6 under 100 ~ 150 degrees Celsius
A hour；Then container is opened, 1 ~ 3 hour is heated under 100 ~ 200 degrees Celsius.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510249599.7A CN106277839B (en) | 2015-05-15 | 2015-05-15 | Composite film with super-amphiphobic self-cleaning, anti-reflection and permeability-increasing performances and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510249599.7A CN106277839B (en) | 2015-05-15 | 2015-05-15 | Composite film with super-amphiphobic self-cleaning, anti-reflection and permeability-increasing performances and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106277839A CN106277839A (en) | 2017-01-04 |
| CN106277839B true CN106277839B (en) | 2018-10-30 |
Family
ID=57632078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510249599.7A Active CN106277839B (en) | 2015-05-15 | 2015-05-15 | Composite film with super-amphiphobic self-cleaning, anti-reflection and permeability-increasing performances and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106277839B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107555811A (en) * | 2017-09-15 | 2018-01-09 | 重庆市中光电显示技术有限公司 | A kind of anti-scratch anti-reflection protective glass for touch-screen and preparation method thereof |
| CN113731772B (en) * | 2021-08-24 | 2022-11-04 | 哈尔滨工业大学 | Self-cleaning anti-reflection film for protecting lunar dust and preparation method thereof |
| CN115572406B (en) * | 2022-11-07 | 2023-06-20 | 常州大学 | Double-layer micro-nano structure super-amphiphobic polyamide-imide composite film and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391776B (en) * | 2007-09-21 | 2011-01-12 | 中国科学院理化技术研究所 | Preparation method of porous silicon dioxide nanosphere with special structure on surface and porous silicon dioxide nanosphere |
| JP5154971B2 (en) * | 2008-02-18 | 2013-02-27 | ペンタックスリコーイメージング株式会社 | Antireflection film, optical component having the same, interchangeable lens, and imaging device |
| WO2011044519A2 (en) * | 2009-10-09 | 2011-04-14 | Yazaki Corporation | Durable anti-reflection coatings |
| JP2012035411A (en) * | 2010-08-03 | 2012-02-23 | Nsk Ltd | Surface modified structure |
| JP2016001200A (en) * | 2012-10-15 | 2016-01-07 | 旭硝子株式会社 | Antifouling antireflection film, article and production method thereof |
-
2015
- 2015-05-15 CN CN201510249599.7A patent/CN106277839B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106277839A (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sarkın et al. | A review of anti-reflection and self-cleaning coatings on photovoltaic panels | |
| CN102849962B (en) | Preparation method of SiO2 super-hydrophobic film and super-hydrophobic material | |
| CN108299869B (en) | High-strength super-hydrophobic self-cleaning coating, high-strength anti-reflection super-hydrophobic self-cleaning coating and preparation methods thereof | |
| CN102617045B (en) | SiO2 antireflection thin film and preparation method thereof | |
| CN105565678B (en) | A kind of super-hydrophobic automatic cleaning SiO of anti-reflection2Nano coating | |
| CN105731821B (en) | Method for constructing super-hydrophilic, anti-reflection and moisture-proof composite film on glass substrate | |
| Li et al. | A facile two-step dipping process based on two silica systems for a superhydrophobic surface | |
| Ren et al. | A versatile route to polymer-reinforced, broadband antireflective and superhydrophobic thin films without high-temperature treatment | |
| CN102061111A (en) | Preparation method of self-cleaning ceramic nanometer glass antireflective coating material and preparation method of reflection deducting coating | |
| CN103097918A (en) | Optical coating comprising porous silica nanoparticles | |
| CN101519278A (en) | Method for preparing transparent super-hydrophobic automatic cleaning coating | |
| CN103771728B (en) | Preparation method of coating with anti-reflection property in visible light and near infrared light regions and super-hydrophobic coating | |
| CN108623185A (en) | A kind of two-layer compound SiO2The preparation method of antireflective coating | |
| Zhang et al. | Transparent dust removal coatings for solar cell on mars and its Anti-dust mechanism | |
| CN105399340A (en) | Super-hydrophobic high-transmittance SiO2 anti-reflecting thin film and preparation method thereof | |
| CN106277839B (en) | Composite film with super-amphiphobic self-cleaning, anti-reflection and permeability-increasing performances and preparation method thereof | |
| CN103881419B (en) | Hydrophobic hollow SiO2Spherical nano-particles and preparation method and application thereof | |
| CN102951848A (en) | Preparation method of anti-reflection coating | |
| CN108912754A (en) | A kind of super-hydrophobic SiO2The preparation method and application of nano functional liquid | |
| CN102064204B (en) | Broadband antireflection nano structure and preparation method thereof | |
| CN113731772B (en) | Self-cleaning anti-reflection film for protecting lunar dust and preparation method thereof | |
| CN100540153C (en) | The hydrophobic structure of substrate surface and method for making thereof | |
| CN103592701B (en) | Antireflection coating on surface of Fresnel lens and preparation method thereof | |
| CN108948802A (en) | A kind of automatic cleaning coating of translucency enhancing | |
| Pinto et al. | Random subwavelength structures on glass to improve photovoltaic module performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |