CN105776317A - Transparent super-hydrophobic nano-array and preparation method thereof - Google Patents
Transparent super-hydrophobic nano-array and preparation method thereof Download PDFInfo
- Publication number
- CN105776317A CN105776317A CN201610207076.0A CN201610207076A CN105776317A CN 105776317 A CN105776317 A CN 105776317A CN 201610207076 A CN201610207076 A CN 201610207076A CN 105776317 A CN105776317 A CN 105776317A
- Authority
- CN
- China
- Prior art keywords
- array
- nano
- substrate
- preparation
- crystal seed
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemically Coating (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention discloses a transparent super-hydrophobic nano-array and a preparation method thereof. The preparation method comprises the following steps: firstly coating the surface of a substrate with zinc oxide seed crystal sol by virtue of a spin coating method or a spray coating method, so as to obtain a uniform nano-seed crystal layer; then controlling the hanging altitude and the position in a low-concentration growth solution prepared from KOH and Zn(NO3)2 by virtue of a vertical cotton thread hanging technique, so as to obtain a transparent zinc oxide nano-array, and carrying out fluorination to construct excellent super-hydrophobicity; and carrying out double-surface coating, sintering and growth on the substrate, so as to obtain the transparent super-hydrophobic nano-array on two surfaces of the substrate. Liquid drops with condensed and frosted surfaces are of a sphere shape, small in sizes, extremely easy to combine and bounce, high in desorption rate and low in coverage rate, present excellent frosting resistance and have important application prospects in products of building exterior glass, solar cells, automotive glass and the like, and furthermore, concepts can be provided for application of dropwise condensation, frosting resisting, freezing resisting and the like.
Description
Technical field
The present invention relates to a kind of transparent hydrophobic nano-array preparation method.
Background technology
ZnO has the direct broad-band gap (3.37eV of wurtzite structure as II-VI race, 300K) compound semiconductor materials, physicochemical property because of its excellence, such as high elastic modelling quantity, extremely low thermal coefficient of expansion, high heat stability, big exciton bind energy and negative electron affinity energy etc., at numerous areas such as sensor, UV transmitting, opto-electronic conversion, super-hydrophobic interface, photocatalysis and light emitting diodes, there is potential application, in recent years, worldwide showing great attention to is received.At present, numerous in the fine structure material of ZnO what be successfully prepared, one-dimensional nano structure array material is ZnO nanowire array, nanometer stick array, nano-tube array, nano needle arrays, nano-cone array etc. such as, because having special natures such as non-migratory, high transparent, fluorescence, piezoelectricity, absorption and scatters ultraviolet ability, photocatalysis, amphipathic property, sterilization, and the favor of extremely researcher.
Up to now, the preparation method of ZnO one-dimensional nano structure material mainly has: template assisting growth method, metal organic vapor method (MOVPE), pulsed laser deposition (PLD), chemical vapour deposition technique (CVD), electrochemical vapor deposition and wet chemistry method etc..Wherein, the method such as template assisting growth method, MOVPE, PLD, CVD, it is necessary to expensive instrument and equipment and harsh process conditions, it is difficult to carry out large-scale industrial production；Wet chemistry method desired reaction temperature relatively low (compared with vapor phase method), simple to operate, it is suitable for large-scale production.
Wet chemistry method generally comprises two steps, first in substrate, prepare zinc oxide crystal seed layer, then the substrate back-off with crystal seed layer is put into insulation a period of time in the hermetic container filling in growth-promoting media, the key of this preparation process is exactly crystal seed layer preparation and growth-promoting media reaction, the method that wherein crystal seed layer preparation is comparatively conventional at present is spin coating method and magnetron sputtering method respectively, and above two preparation method all needs more than 200～300 DEG C reaction temperatures in crystal seed layer preparation process.Chinese patent if application number is 200710119511.5 discloses " preparation method of a kind of large-area nano zinc oxide directional array ", the method utilizes the method for heat evaporation and magnetron sputtering through 300～600 DEG C, 10～60 minutes sintering, substrate is prepared one layer of zinc oxide crystal seed layer, then utilizes hydro-thermal method at 50～200 DEG C of synthesis of nano-zinc oxide arrays；Application number be 201210536195.2 Chinese patent disclose one " preparation method of growth of zinc oxide nano array ", the method utilizes the method for magnetron sputtering, through 300～600 DEG C, one layer of zinc oxide crystal seed layer is prepared in annealing in 1～10 hour in substrate, then in the solution 60～90 DEG C, within 10 minutes, zinc oxide nano array is grown.Although, preparation technology is simple, with low cost, but cannot meet current large area and prepare the demand of zinc oxide nano array, especially for complex-shaped substrate.
For adapting to environment complicated and changeable, by the evolution of 1 years, reparation and perfect, many animals and plants surfaces define super wellability, water droplet motion and desorption can be realized directivity manipulation, in order to existence.Surface of solids super-hydrophobicity (contact angle>150 °, roll angle<10 °) it is a very common but very special super infiltration phenomenon of class, affect multiple vegeto-animal vital movement in nature, such as the Folium Nelumbinis of super-hydrophobic automatic cleaning, the water skipper lower limb of super-hydrophobic high capacity, the super-hydrophobic anti-mosquito eye etc. hazed.Research shows, the systematicness geometry arrangement of the multiple dimensioned organic micro/nano structure that these organism surfaces every square millimeter are millions of, it is believed that the formation of super-hydrophobicity is served pivotal role.As inspiration, by the bionical structure coarse structure of material surface, and carry out low-surface-energy material and modifiy, or directly at low-surface-energy material surface construction coarse structure, super-hydrophobicity can be obtained.This surface has the characteristics such as self-cleaning, the anti-soil similar to Folium Nelumbinis etc., is also found cocoa simultaneously and delays dew and the forming core of frost Developing restraint, namely has anti-dew and anti-fog characteristics.
The surfaces such as building glass exterior wall, windshield, solar battery panel are easily polluted, and condense or frosting, have impact on the transparency of base material and serviceability.At present, although existing many ways can prepare transparent hydrophobic surface, such as sol-gel process, spray painting method, photoetching process, nano-imprint method etc., but not yet studies have reported that how are the condensation on this surface or Frosting performance, and this also limits the application at above-mentioned transparent substrate surface of this technology.Research finds, super hydrophobic surface common water droplet moistening coarse structure top (heat transfer efficiency is low), and interface major part is air (thermal resistance is big), contacts in Cassie compound state；But under condensation or frosting condition, little yardstick (～10 μ m diameter) drop and hoar crystal are easily in relatively large sized micrometer structure gap forming core, growth, the Cassie state making thermodynamic instability is transformed into the less Wenzel moistening state of energy, dramatically increasing the adhesiveness of bionic super-hydrophobic surface, dew and frost are difficult to desorption.Therefore, improving Cassie state thermodynamic stability, make the little yardstick drop of super hydrophobic surface be prone to desorption, antagonism is revealed, the performance of anti-fog characteristics is most important.
Substantial amounts of research shows, compared with micrometer structure, nanostructured roughness is relatively big, and structure interval has restricting liquid drop growth, the array nanostructured super hydrophobic surface of reasonable size, drop Cassie state can be made more stable, dew drips or hoar crystal not only forming core is difficult, and only slowly grows in structural top, adhesion is low, it is easy to autonomous desorption.At present, by methods such as chemical vapour deposition (CVD), reactive ion etching, chemical oxidations, obtainable compact nanometer array structure has CNT, silicon nanowires, cupric oxide nano sheet, Nano bars of alumina, zinc oxide nano rod etc..Comparatively speaking, the technology of preparing of zinc oxide nano array is relatively simple.Such as, this seminar early stage adopts nearly room-temperature water bath growing technology, uniform zinc-oxide nano cone array [CrystEngComm is obtained on the copper sheet surface of back-off, 2014,16 (24), 5394], after further pre-seed layer, it is thus achieved that the better nanometic zinc oxide rod array [MaterialsLetters of vertical orientated property, 2014,131,178], and can FTO glass surface grow [J.Phys.Chem.B, 2014,118 (41): 12002], but the transparency is not good, and can not substrate is two-sided again prepares simultaneously.Recently, Gao etc. first pass through fine vacuum physical gas phase deposition technology, layer of ZnO Seed Layer is deposited on ito glass surface, subsequently under 90 DEG C of water bath condition, utilize hydrothermal growth process, be prepared for ZnO nano-rod array, modified obtain transparent hydrophobic [ACSAppliedMater.Interfaces, 2014,6,2219].But, gas phase deposition technology prepares crystal seed layer and high growth temperature builds nano-array, and not only cost is high, too increases difficulty during scale application.
Summary of the invention
Present invention design is a kind of transparent hydrophobic nano-array and preparation method thereof.
The technical scheme is that a kind of transparent hydrophobic nano-array preparation method, described method comprises the following steps:
The first step, prepared by crystal seed layer: adopt spin coating or spraying process that ZnO crystal seed colloidal sol is coated in substrate surface, and namely heat treatment when nitrogen protection obtains nano zine oxide crystal seed layer at substrate surface；Described ZnO crystal seed collosol concentration is 0.1～0.25M；
Second step, nano-array grows: tied down by substrate corner cotton thread, vertically hanging is immersed in nano-array growth solution, when 35～90 DEG C of waters bath with thermostatic control, take out after reaction fully, cleaning and dry up, obtain ZnO transparent nano-array at seed layer surface, described growth solution is KOH and Zn (NO3)2The Zn (OH) of the concentration 0.01～0.5M of preparation4 2-Aqueous solution, and control the pH value of solution between 10～12；
3rd step, super-hydrophobicization: dip the substrate in rare silicon fluoride alcoholic solution modified, clean after drying up, solidify and obtain at substrate surface acquisition transparent hydrophobic nano-array.
The clean substrate that described substrate obtains through pre-treatment, described pre-treatment is: after successively substrate is used acetone, ethanol and deionized water ultrasonic cleaning, then rinses with dilute hydrochloric acid, deionized water and dehydrated alcohol successively, and cold wind dries up and obtains.
Described substrate includes any one in copper, nickel, rustless steel, silicon chip, glass.
Described ZnO crystal seed colloidal sol is to prepare by the following method: be first added separately in solvent ethylene glycol methyl ether by precursors Zinc diacetate dihydrate, stabilizer alcohol amine, surfactant polyethylene, deionized water, first it is uniformly mixed, abundant at water-bath again, still aging obtain.
In the first step, spin-coating method concretely comprises the following steps: adopt sol evenning machine, and ZnO crystal seed colloidal sol drops to substrate surface, first with 900r/m speed spin coating 15s, then with 3000r/m speed spin coating 20s.
In the first step, spraying process concretely comprises the following steps: ZnO crystal seed colloidal sol is coated in the substrate surface being positioned over 50～80 DEG C of thermal station 1～20min, and during spraying, crystal seed colloidal sol consumption is 50～100mL/m2。
First step heat treatment temperature is 300～600 DEG C.
It is one side or dual coating that described ZnO crystal seed colloidal sol is coated in substrate surface.
Described transparent hydrophobic nano-array, nanostructured is taper, and nano-array diameter is 60～100nm, arrives while spacing 20～60nm, and height 500～1000nm, contact angle is 155 °～160 °, and roll angle is 1 °～4 °；When stable state condensation and dewfall, described transparent hydrophobic nano-array surface, drop is spherical, during 5～20 μm of droplet coalescences, unnecessary surface free energy, promoting the drop spring after merging, self-powered spring characteristic occur, spring speed is 0.5～2m/s, height 50～500 μm, it is 20～40 μm that the average dew on surface drips diameter, and the coverage rate on surface is 10～20%, and drop density is 4 × 108Individual/m2。
Beneficial effect:
(1) used by the present invention, the concentration of crystal seed colloidal sol and growth solution is all relatively low, reaction temperature and, can effectively control the speed of growth of zinc oxide nano array, it is thus achieved that transparent nano-array, it is to avoid high concentration causes fast-growth, the impact transparency.
(2) the two-sided seed-solution spin coating of substrate or spraying technology, can all obtain crystal seed layer on substrate two sides, after hydrothermal growth, can all obtain transparent nano array on substrate two sides simultaneously.
(3) crystal seed colloidal sol spraying technology of preparing used by the present invention, uniform crystal seed layer not only can be obtained on plane surface surface, after hydrothermal growth, uniform nano-array can be obtained, it is also possible on the curved surfaces such as such as glass tubing, Glass rod, stainless steel tube, nickel alloy pipe, obtain uniform nano-array.
(4) cotton thread Suspension Technique is utilized, control the vertical suspension height of substrate and the position in growth solution, alleviating and even avoid particles of solute in solution to reunite in the sedimentation of substrate surface, thus eliminating the growth of zinc oxide in large size granule, ensureing the growth of array zinc oxide.
(5) the nanometer zinc oxide array diameter that prepared by the present invention is 60～100nm, arrives while spacing 20～60nm, height 500～1000nm.
(6) compared with untreated slide, the average visible photopic light transmitance of the slide after process is 80～95%, owing to nanostructured is taper, has graded index, so in 650～800nm wave-length coverage, anti-reflection phenomenon even occurs in slide.
(7) transparent nano array is modified through silicon fluoride, and contact angle is 155 °～160 °, and roll angle is 1 °～4 °, and ultra-hydrophobicity is excellent.
(8) when stable state condensation and dewfall, transparent hydrophobic nano-array surface prepared by the present invention, drop is still in spherical, during 5～20 μm of droplet coalescences, and unnecessary surface free energy, the drop spring after merging can also be promoted, so-called self-powered spring characteristic occur, spring speed is 0.5～2m/s, height 50～500 μm, thus significantly increasing the motion of surface drop, be conducive to desorption.Therefore, it is 20～40 μm that the average dew on surface drips diameter, and the coverage rate on surface is 10～20%, and drop density is 4 × 108Individual/m2。
(9) the transparent hydrophobic nano-array that prepared by the present invention can give that building glass exterior wall, windshield, solar battery panel etc. are self-cleaning, waterproof, the characteristic such as antifouling, and the preparation on the surface such as dropwise condensation, Anti-dew, antifog, frosting resistance, freezing also can provide new thinking.
Accompanying drawing illustrates:
Fig. 1 is the copper sheet surface nanometer array SEM figure processed in example 1.
Fig. 2 is copper sheet another surface nanometer array SEM figure processed in example 1.
Fig. 3 is the glass surface nanostructured SEM figure processed in example 2.
Fig. 4 is glass another surface nano-structure SEM figure processed in example 2.
Fig. 5 is the light transmittance of the simple glass processed in example 2.
Fig. 6 is the simple glass substrate surface contact angle picture processed in example 2.
Fig. 7 is the copper sheet surface nanometer array SEM figure processed in example 3.
Fig. 8 is copper sheet another surface nanometer array SEM figure processed in example 3.
Fig. 9 is the glass surface nanostructured SEM figure processed in example 4.
Figure 10 is glass another surface nano-structure SEM figure processed in example 4.
Figure 11 is the glass surface actual transparency situation map processed in example 4.
Figure 12 utilizes the glass surface dropwise condensation condensation displaing micro picture that example 4 processes.
Figure 13 utilizes the glass surface dew that example 4 processes to drip high speed camera picture when bouncing 0.75ms.
Figure 14 utilizes the glass surface dew that example 4 processes to drip high speed camera picture when bouncing 5.25ms.
Figure 15 is the glass surface nanostructured SEM figure processed in example 5.
Figure 16 is glass another surface nano-structure SEM figure processed in example 5.
Figure 17 is the glass surface actual transparency situation map processed in example 5.
Figure 18 is the copper pipe surface nano-array SEM figure processed in example 6.
Detailed description of the invention:
A kind of transparent hydrophobic nano-array preparation method, step is:
(1) prepared by crystal seed layer: first by precursors Zinc diacetate dihydrate, stabilizer alcohol amine, surfactant polyethylene, deionized water is added separately in solvent ethylene glycol methyl ether, first mix 20min in 800r/m speed magnetic agitation, again 60 DEG C of waters bath with thermostatic control, 1500r/m magnetic agitation 2h, after still aging 24h, obtain concentration 0.1～0.25M crystal seed colloidal sol, adopt sol evenning machine subsequently, crystal seed colloidal sol is dropped to substrate surface, first with 900r/m speed spin coating 15s, again with 3000r/m speed spin coating 20s, subsequently, substrate is put into vacuum tube furnace, 10min is processed when 350 DEG C of nitrogen protections, nano zine oxide crystal seed layer can be obtained at substrate surface；
(2) nano-array growth: substrate corner cotton thread is tied down, vertically hanging is immersed in nano-array growth solution, adjusting between substrate and suspension fixing point is highly 5～20cm, adjust substrate and be positioned at 1/3rd band of position above growth-promoting media, when 35～90 DEG C of waters bath with thermostatic control, take out after reaction 0.5～6h, rinse with deionized water, cold wind dries up, and can obtain ZnO transparent nano-array at seed layer surface, and described growth solution is KOH and Zn (NO3)2The Zn (OH) of the concentration 0.01～0.5M of preparation4 2-Aqueous solution, and control the pH value of solution between 10～12；
(3) super-hydrophobicization: dip the substrate into 30min in 1% silicon fluoride alcoholic solution, taking-up deionized water, alcohol flushing after drying up, the baking oven of 60 DEG C solidifies 15min, can obtain and obtain transparent hydrophobic nano-array at substrate surface.
Substrate removes surface impurity through pre-treatment, method particularly includes: by substrate successively with acetone, ethanol and each ultrasonic cleaning 10min of deionized water, 0.1M aqueous hydrochloric acid solution 30s is put into after taking-up, rinse followed in turn by deionized water and dehydrated alcohol, cold wind dries up, standby, described substrate includes copper, nickel, rustless steel, silicon chip, glass etc.；
Embodiment 1
Cu substrate grows ZnO nano array at 35 DEG C
Utilize and prepare the crystal seed colloid that concentration is 0.25M, by using desk-top sol evenning machine spin coating plated film, preparation layer of ZnO colloid thin film in clean Cu substrate sheet；Through the lower 350 DEG C of annealing 10min of nitrogen atmosphere, namely form the nanoscale ZnO crystal seed rete of one layer of even compact at substrate surface；By KOH and Zn (NO3)2The Zn (OH) of the 0.5M of the pH=12 of preparation4 2-In reaction system, having the Cu sheet of crystal seed layer for substrate with preparation, the ZnO array film prepared after 35 DEG C of water-bath growth 6h, two-sided pattern is respectively as shown in Figure 1 and Figure 2.
Embodiment 2
Glass substrate grows ZnO nano array at 35 DEG C
Utilize and prepare the colloid that concentration is 0.1M, by using the method plated film of spraying, cleaned glass substrate sheet is prepared layer of ZnO colloid thin film；Through the lower 350 DEG C of annealing 10min of nitrogen atmosphere, namely form the nanoscale ZnO crystal seed rete of one layer of even compact at substrate surface；By KOH and Zn (NO3)2The Zn (OH) of the 0.09M of the pH=12 of preparation4 2-In reaction system, have the sheet glass of crystal seed layer for substrate with preparation, after 35 DEG C of water-baths growth 0.5-4h, prepare ZnO array, two-sided pattern respectively as shown in Figure 3, Figure 4, light transmittance as it is shown in figure 5, contact angle form as shown in Figure 6.
Embodiment 3
Cu substrate grows ZnO nano array at 35 DEG C
Utilize and prepare the colloid that concentration is 0.15M, by using the desk-top sol evenning machine spin coating plated film of KW-4A type, Cu substrate sheet is prepared layer of ZnO colloid thin film；Through the lower 350 DEG C of annealing 10min of nitrogen atmosphere, namely form the nanoscale ZnO crystal seed rete of one layer of even compact at substrate surface；By KOH and Zn (NO3)2The Zn (OH) of the 0.5M of the pH=12 of preparation4 2-In reaction system, having the Cu sheet of crystal seed layer for substrate with preparation, the ZnO array film prepared after 35 DEG C of water-bath growth 4h, two-sided pattern is respectively as shown in Figure 7, Figure 8.
Embodiment 4
Glass substrate grows ZnO nano array at 35 DEG C
Utilize and prepare the colloid that concentration is 0.1M, by using the method plated film of spraying, substrate of glass sheet is prepared layer of ZnO colloid thin film；Through the lower 350 DEG C of annealing 10min of nitrogen atmosphere, namely form the nanoscale ZnO crystal seed rete of one layer of even compact at substrate surface；By KOH and Zn (NO3)2The Zn (OH) of the 0.01M of the pH=12 of preparation4 2-In reaction system, having the sheet glass of crystal seed layer for substrate with preparation, the ZnO array film prepared after 35 DEG C of water-bath growth 2h, respectively as shown in Figure 9, Figure 10, transparent situation is as shown in figure 11 for two-sided pattern.
When stable state condensation and dewfall, transparent hydrophobic nano-array surface prepared by this example, drop is still in spherical, and it is 20～40 μm that the average dew on surface drips diameter, and the coverage rate on surface is 10～20%, and drop density is 4 × 108Individual/m2, as shown in figure 12.During 5～20 μm of droplet coalescences, unnecessary surface free energy, moreover it is possible to promote the drop spring after merging, so-called self-powered spring characteristic occurs.Figure 13 be dew drip from substrate start to bounce 0.75ms time high speed camera picture, the speed that illustrates to bounce is～2m/s, Figure 14 be then bound to high speed camera picture during peak for drop, illustrates that jumping height is～330 μm.
Embodiment 5
Glass substrate grows ZnO nano array at 35 DEG C
Utilize and prepare the colloid that concentration is 0.1M, by using the method plated film of spraying, substrate of glass sheet is prepared layer of ZnO colloid thin film；Through the lower 350 DEG C of annealing 10min of nitrogen atmosphere, namely form the nanoscale ZnO crystal seed rete of one layer of even compact at substrate surface；By KOH and Zn (NO3)2The Zn (OH) of the 0.2M of the pH=12 of preparation4 2-In reaction system, having the sheet glass of crystal seed layer for substrate with preparation, the ZnO array film prepared after 35 DEG C of water-bath growth 0.5h, two-sided pattern is respectively as shown in Figure 15, Figure 16, and transparent situation is as shown in figure 17.
Embodiment 6
Copper pipe substrate grows ZnO nano array at 35 DEG C
Utilize and prepare the colloid that concentration is 0.1M, by using the method plated film of spraying, copper pipe substrate is prepared layer of ZnO colloid thin film；Through the lower 350 DEG C of annealing 10min of nitrogen atmosphere, namely form the nanoscale ZnO crystal seed rete of one layer of even compact at substrate surface；By KOH and Zn (NO3)2The Zn (OH) of the 0.05M of the pH=12 of preparation4 2-In reaction system, having the copper pipe of crystal seed layer for substrate with preparation, the ZnO array film prepared after 35 DEG C of water-bath growth 3h, surface topography is as shown in figure 18.
Claims (9)
1. a transparent hydrophobic nano-array preparation method, it is characterised in that described method comprises the following steps:
The first step, prepared by crystal seed layer: adopt spin coating or spraying process that ZnO crystal seed colloidal sol is coated in substrate surface, and namely heat treatment when nitrogen protection obtains nano zine oxide crystal seed layer at substrate surface；Described ZnO crystal seed collosol concentration is 0.1～0.25M；
Second step, nano-array grows: tied down by substrate corner cotton thread, vertically hanging is immersed in nano-array growth solution, when 35～90 DEG C of waters bath with thermostatic control, take out after reaction fully, cleaning and dry up, obtain ZnO transparent nano-array at seed layer surface, described growth solution is KOH and Zn (NO3)2The Zn (OH) of the concentration 0.01～0.5M of preparation4 2-Aqueous solution, and control the pH value of solution between 10～12；
3rd step, super-hydrophobicization: dip the substrate in rare silicon fluoride alcoholic solution modified, clean after drying up, solidify and obtain at substrate surface acquisition transparent hydrophobic nano-array.
2. transparent hydrophobic nano-array preparation method as claimed in claim 1, it is characterized in that, the clean substrate that described substrate obtains through pre-treatment, described pre-treatment is: by substrate successively with after acetone, ethanol and deionized water ultrasonic cleaning, rinsing with dilute hydrochloric acid, deionized water and dehydrated alcohol successively, cold wind dries up and obtains again.
3. transparent hydrophobic nano-array preparation method as claimed in claim 1, it is characterised in that described substrate includes any one in copper, nickel, rustless steel, silicon chip, glass.
4. transparent hydrophobic nano-array preparation method as claimed in claim 1, it is characterized in that, described ZnO crystal seed colloidal sol is to prepare by the following method: be first added separately in solvent ethylene glycol methyl ether by precursors Zinc diacetate dihydrate, stabilizer alcohol amine, surfactant polyethylene, deionized water, first it is uniformly mixed, abundant at water-bath again, still aging obtain.
5. transparent hydrophobic nano-array preparation method as claimed in claim 1, it is characterized in that, in the first step, spin-coating method concretely comprises the following steps: adopt sol evenning machine, ZnO crystal seed colloidal sol is dropped to substrate surface, first with 900r/m speed spin coating 15s, then with 3000r/m speed spin coating 20s.
6. transparent hydrophobic nano-array preparation method as claimed in claim 1, it is characterized in that, in the first step, spraying process concretely comprises the following steps: ZnO crystal seed colloidal sol is coated in the substrate surface being positioned over 50～80 DEG C of thermal station 1～20min, and during spraying, crystal seed colloidal sol consumption is 50～100mL/m2。
7. transparent hydrophobic nano-array preparation method as claimed in claim 1, it is characterised in that first step heat treatment temperature is 300～600 DEG C.
8. transparent hydrophobic nano-array preparation method as claimed in claim 1, it is characterised in that it is one side or dual coating that described ZnO crystal seed colloidal sol is coated in substrate surface.
9. the nano-array that the arbitrary described transparent hydrophobic nano-array preparation method of claim 1～8 obtains, it is characterized in that, nanostructured is taper, nano-array diameter is 60～100nm, arrive while spacing 20～60nm, height 500～1000nm, contact angle is 155 °～160 °, and roll angle is 1 °～4 °；When stable state condensation and dewfall, described transparent hydrophobic nano-array surface, drop is spherical, during 5～20 μm of droplet coalescences, unnecessary surface free energy, promoting the drop spring after merging, self-powered spring characteristic occur, spring speed is 0.5～2m/s, height 50～500 μm, it is 20～40 μm that the average dew on surface drips diameter, and the coverage rate on surface is 10～20%, and drop density is 4 × 108Individual/m2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610207076.0A CN105776317B (en) | 2016-04-05 | 2016-04-05 | A kind of transparent hydrophobic nano-array and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610207076.0A CN105776317B (en) | 2016-04-05 | 2016-04-05 | A kind of transparent hydrophobic nano-array and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105776317A true CN105776317A (en) | 2016-07-20 |
| CN105776317B CN105776317B (en) | 2018-02-06 |
Family
ID=56395277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610207076.0A Active CN105776317B (en) | 2016-04-05 | 2016-04-05 | A kind of transparent hydrophobic nano-array and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105776317B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106835079A (en) * | 2017-01-17 | 2017-06-13 | 江苏理工学院 | A kind of preparation method of anti-fog micro-nano compound structure copper substrate superhydrophobic surface |
| CN108611625A (en) * | 2018-04-28 | 2018-10-02 | 北京航空航天大学 | A kind of compound super lubrication interfaces ZnO and the preparation method and application thereof |
| CN108940791A (en) * | 2018-08-22 | 2018-12-07 | 中国科学院海洋研究所 | A kind of zinc-base method for preparing super-hydrophobic surface for characteristic of bouncing certainly with condensing droplet |
| CN109715298A (en) * | 2016-09-19 | 2019-05-03 | 尼蓝宝股份有限公司 | Drop spray paint |
| CN109808398A (en) * | 2019-03-29 | 2019-05-28 | 湖北理工学院 | A kind of method that mechanical engraving method prepares very low power anisotropy superhydrophobic surface material |
| CN110331404A (en) * | 2019-08-07 | 2019-10-15 | 山东烯泰天工节能科技有限公司 | A kind of surface treatment method of heat exchanger |
| CN110440629A (en) * | 2019-08-07 | 2019-11-12 | 山东烯泰天工节能科技有限公司 | A kind of heat exchanger and air-conditioning with nano array structure surface |
| CN111362591A (en) * | 2020-03-19 | 2020-07-03 | 电子科技大学 | Method for spontaneously driving away condensed liquid drops in horizontal direction |
| CN111604018A (en) * | 2020-06-04 | 2020-09-01 | 深圳技术大学 | Thin film for triggering liquid to titrate to self bounce and preparation method and application thereof |
| CN112030355A (en) * | 2020-09-07 | 2020-12-04 | 渤海大学 | Preparation method of nano ZnO modified CMA/TP-PLA coaxial nanofiber membrane through in-situ synthesis |
| CN112657805A (en) * | 2020-12-01 | 2021-04-16 | 大连理工大学 | Nanowire-fluorocarbon composite coating and preparation method thereof |
| CN113024128A (en) * | 2021-03-31 | 2021-06-25 | 桂林理工大学 | Tin disulfide-C3N4Nano-sheet array photo-anode and preparation method thereof |
| CN113716876A (en) * | 2021-09-01 | 2021-11-30 | 电子科技大学 | Preparation method of intelligent glass with glass ambiguity regulation and control function |
| CN114289875A (en) * | 2021-12-03 | 2022-04-08 | 江苏大学 | Wetting gradient structure laser surface micro-nano machining device and machining process |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103523818A (en) * | 2013-10-31 | 2014-01-22 | 东南大学 | Preparation method of height-oriented ZnO nanocone array structure material |
| CN103603040A (en) * | 2013-10-31 | 2014-02-26 | 东南大学 | Low temperature liquid phase growing method for preparing ZnO nanocone array |
| CN104692671A (en) * | 2015-04-02 | 2015-06-10 | 天津城建大学 | Preparation method of super-hydrophobic self-cleaning glass based on ZnO nano array coating |
| CN104846369A (en) * | 2015-03-30 | 2015-08-19 | 陕西科技大学 | Method for preparing super-hydrophilic and hydrophobic composite nano array interface material |
| CN104888498A (en) * | 2015-06-12 | 2015-09-09 | 东南大学 | Preparation method of durable super-hydrophobic super-oleophylic foamy copper for oil and water separation |
-
2016
- 2016-04-05 CN CN201610207076.0A patent/CN105776317B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103523818A (en) * | 2013-10-31 | 2014-01-22 | 东南大学 | Preparation method of height-oriented ZnO nanocone array structure material |
| CN103603040A (en) * | 2013-10-31 | 2014-02-26 | 东南大学 | Low temperature liquid phase growing method for preparing ZnO nanocone array |
| CN104846369A (en) * | 2015-03-30 | 2015-08-19 | 陕西科技大学 | Method for preparing super-hydrophilic and hydrophobic composite nano array interface material |
| CN104692671A (en) * | 2015-04-02 | 2015-06-10 | 天津城建大学 | Preparation method of super-hydrophobic self-cleaning glass based on ZnO nano array coating |
| CN104888498A (en) * | 2015-06-12 | 2015-09-09 | 东南大学 | Preparation method of durable super-hydrophobic super-oleophylic foamy copper for oil and water separation |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109715298A (en) * | 2016-09-19 | 2019-05-03 | 尼蓝宝股份有限公司 | Drop spray paint |
| US11592246B2 (en) | 2016-09-19 | 2023-02-28 | Nelumbo Inc. | Nanostructure coating materials and methods of use thereof |
| US11255616B2 (en) | 2016-09-19 | 2022-02-22 | Nelumbo Inc. | Droplet ejecting coatings |
| CN106835079A (en) * | 2017-01-17 | 2017-06-13 | 江苏理工学院 | A kind of preparation method of anti-fog micro-nano compound structure copper substrate superhydrophobic surface |
| CN108611625A (en) * | 2018-04-28 | 2018-10-02 | 北京航空航天大学 | A kind of compound super lubrication interfaces ZnO and the preparation method and application thereof |
| CN108940791A (en) * | 2018-08-22 | 2018-12-07 | 中国科学院海洋研究所 | A kind of zinc-base method for preparing super-hydrophobic surface for characteristic of bouncing certainly with condensing droplet |
| CN109808398A (en) * | 2019-03-29 | 2019-05-28 | 湖北理工学院 | A kind of method that mechanical engraving method prepares very low power anisotropy superhydrophobic surface material |
| CN109808398B (en) * | 2019-03-29 | 2021-11-02 | 湖北理工学院 | Method for preparing micro-groove anisotropic super-hydrophobic surface material by mechanical engraving method |
| CN110440629A (en) * | 2019-08-07 | 2019-11-12 | 山东烯泰天工节能科技有限公司 | A kind of heat exchanger and air-conditioning with nano array structure surface |
| CN110331404A (en) * | 2019-08-07 | 2019-10-15 | 山东烯泰天工节能科技有限公司 | A kind of surface treatment method of heat exchanger |
| CN111362591A (en) * | 2020-03-19 | 2020-07-03 | 电子科技大学 | Method for spontaneously driving away condensed liquid drops in horizontal direction |
| CN111604018A (en) * | 2020-06-04 | 2020-09-01 | 深圳技术大学 | Thin film for triggering liquid to titrate to self bounce and preparation method and application thereof |
| CN112030355A (en) * | 2020-09-07 | 2020-12-04 | 渤海大学 | Preparation method of nano ZnO modified CMA/TP-PLA coaxial nanofiber membrane through in-situ synthesis |
| CN112030355B (en) * | 2020-09-07 | 2023-08-08 | 渤海大学 | Preparation method of in-situ synthesized nano ZnO modified CMA/TP-PLA coaxial nanofiber membrane |
| CN112657805A (en) * | 2020-12-01 | 2021-04-16 | 大连理工大学 | Nanowire-fluorocarbon composite coating and preparation method thereof |
| CN112657805B (en) * | 2020-12-01 | 2022-07-19 | 大连理工大学 | Nanowire-fluorocarbon composite coating and preparation method thereof |
| CN113024128A (en) * | 2021-03-31 | 2021-06-25 | 桂林理工大学 | Tin disulfide-C3N4Nano-sheet array photo-anode and preparation method thereof |
| CN113716876A (en) * | 2021-09-01 | 2021-11-30 | 电子科技大学 | Preparation method of intelligent glass with glass ambiguity regulation and control function |
| CN114289875A (en) * | 2021-12-03 | 2022-04-08 | 江苏大学 | Wetting gradient structure laser surface micro-nano machining device and machining process |
| CN114289875B (en) * | 2021-12-03 | 2024-03-19 | 江苏大学 | Micro-nano processing device and processing technology for laser surface with wetting gradient structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105776317B (en) | 2018-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105776317B (en) | A kind of transparent hydrophobic nano-array and preparation method thereof | |
| CN101560059B (en) | Aluminum-doped zinc oxide film coating and nano-rod array material as well as preparation method thereof | |
| CN102569508B (en) | Thin-film solar photovoltaic cell with nano wire array structure and preparation method for thin-film solar photovoltaic cell | |
| CN104846369B (en) | A kind of method for preparing super hydrophobe composite Nano array interface material | |
| CN101774537B (en) | Preparation method of micro-channel vertical-growth TiO2-clading ZnO nano rod array | |
| CN101794670A (en) | Preparation method of photo anode of dye-sensitized solar cell with optical gradient | |
| CN103586154B (en) | Electrospray device, electron spray is utilized to prepare method and the solar cell of solar cell anti-reflection layer | |
| CN104282847A (en) | Interruptible perovskite type organic halide thin-film solar cell photo-anode preparing method | |
| CN107983327A (en) | A kind of method for improving ZnO nano-rod array photocatalysis performance | |
| CN103296141B (en) | Method for producing dendritic heterojunction nanowire array structural materials | |
| CN105271362A (en) | Preparation method of ZnO nano-structure with petal effect | |
| CN103232172B (en) | Big area prepares the method for nano titania hollow ball order thin film | |
| CN101481135B (en) | Preparation of tin oxide nano tube | |
| CN108970612B (en) | Method for preparing Ag-loaded ZnO nanorod array | |
| CN104628262B (en) | Method for preparing matchstick-shaped TiO2 nanoparticle and nanorod composite array | |
| CN102013327B (en) | Fluorinion-doped zinc oxide porous prism array film, and preparation and application thereof | |
| CN105236472A (en) | Preparation method of SnO2 nano-wire array | |
| CN101439873A (en) | Method for titania film growth in fluorine-based aqueous solution | |
| CN111846193A (en) | Super-hydrophobic anti-icing aviation aluminum alloy surface and preparation method thereof | |
| CN111041451A (en) | Durable anti-icing surface modification material and preparation method thereof | |
| CN108456895B (en) | α -Fe2O3Au nano circular truncated array photoelectrode and preparation method and application thereof | |
| CN102795665B (en) | Preparation method of titanium dioxide nanotube (rod) array | |
| CN102225871B (en) | Preparation method of Ga doped ZnO nanowire catalyzed by Sn | |
| CN109518149A (en) | Along the preparation method of the antimony selenide optoelectronic film of<002>direction preferential growth | |
| CN105463564A (en) | ZnO nanorod and ZnO cluster composite structure and preparation method thereof |
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 |