CN105776317B - A kind of transparent hydrophobic nano-array and preparation method thereof - Google Patents
A kind of transparent hydrophobic nano-array and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of transparent hydrophobic nano-array and preparation method thereof.Spin coating or spraying process are used first, by zinc oxide crystal seed sol coating in substrate surface, obtain uniform nanosized seeds layer.Then, using the vertical Suspension Technique of cotton thread, suspension height is controlled and in KOH and Zn (NO3)2Position in the low concentration growth-promoting media of preparation, you can obtain transparent nano-zinc oxide array, excellent super-hydrophobicity can be also built after being fluorinated., can be in the two-sided all acquisitions transparent hydrophobic nano-array of substrate by substrate dual coating, sintering and growing technology.The drop of this surface condensation condensation is in spherical, size is small, easily merge spring, desorption rate is high, coverage rate is low, excellent Anti-dew effect is shown, has important application prospect in products such as external wall glass, solar cell and vehicle glasses, or the application such as dropwise condensation, frosting resistance, freezing provides thinking.
Description
Technical field
The present invention relates to a kind of transparent hydrophobic nano-array preparation method.
Background technology
ZnO has direct broad-band gap (3.37eV, 300K) compound semiconductor material of wurtzite structure as II-VI race
Material, because of its excellent physicochemical property, such as high modulus of elasticity, extremely low thermal coefficient of expansion, high heat endurance, big exciton
Binding energy and negative electron affinity energy etc., in sensor, UV transmittings, opto-electronic conversion, super-hydrophobic interface, photocatalysis and light-emitting diodes
The numerous areas such as pipe have potential application, in recent years, receive worldwide highest attention.At present, it is being prepared into
In numerous fine structure materials based on ZnO of work(, one-dimensional nano structure array material for example ZnO nanowire array, nanometer stick array,
Nano-tube array, nano needle arrays, nano-cone array etc., because with non-migratory, high transparency, fluorescence, piezoelectricity, absorption
With the special nature such as scatters ultraviolet ability, photocatalysis, amphipathic property, sterilization, and by the favor of researcher.
So far, the preparation method of ZnO one-dimensional nano structure materials mainly has：Template assisting growth method, metal are organic
Vapour phase epitaxy method (MOVPE), pulsed laser deposition (PLD), chemical vapour deposition technique (CVD), electrochemical vapor deposition and
Wet chemistry method etc..Wherein, it is necessary to expensive instrument and equipment and harshness the methods of template assisting growth method, MOVPE, PLD, CVD
Process conditions, it is difficult to carry out scale industrial production；Reaction temperature needed for wet chemistry method relatively low (compared with vapor phase method), operation letter
It is single, it is adapted to large-scale production.
Wet chemistry method generally comprises two steps, prepares zinc oxide crystal seed layer in substrate first, then will carry crystal seed
The substrate back-off of layer, which is put into the closed container filled in growth-promoting media, is incubated a period of time, and the key of the preparation process is exactly crystal seed
Layer prepares and growth-promoting media reaction, and it is spin coating method and magnetron sputtering method respectively that wherein crystal seed layer, which prepares method more conventional at present,
Above two preparation method is required to more than 200~300 DEG C reaction temperatures in crystal seed layer preparation process.Such as Application No.
200710119511.5 Chinese patent discloses " a kind of preparation method of large-area nano zinc oxide directional array ", this method
Using hot evaporation and the method for magnetron sputtering through 300~600 DEG C, sinter within 10~60 minutes, one layer of zinc oxide is prepared in substrate
Crystal seed layer, then using hydro-thermal method in 50~200 DEG C of synthesis of nano-zinc oxide arrays；In Application No. 201210536195.2
State's patent discloses a kind of " preparation method of growth of zinc oxide nano array ", the method that this method utilizes magnetron sputtering, through 300
~600 DEG C, annealing in 1~10 hour prepares one layer of zinc oxide crystal seed layer in substrate, then in the solution 60~90 DEG C, 10 minutes
Grow zinc oxide nano array.Although preparation technology is simple, cost is cheap, it can not meet that current large area prepares oxygen
Change the demand of zinc nano-array, especially for complex-shaped substrate.
To adapt to environment complicated and changeable, by the evolution of 1 years, reparation and perfect, many animals and plants surfaces form
Super wellability, directionality, which manipulates, to be realized with desorption to water drop motion, so as to existence.Surface of solids super-hydrophobicity (connects
Feeler>150 °, roll angle<10 °) be very common but the super infiltration phenomenon of very special one kind, affect more in nature
The vital movement of kind animals and plants, the water skipper leg of lotus leaf, super-hydrophobic high capacity such as super-hydrophobic automatic cleaning, the super-hydrophobic anti-mosquito hazed
Sub- eye etc..Research shows, the rule of the millions of multiple dimensioned organic micro/nano structure of every square millimeter of these organism surfaces
Property geometry arrangement, be considered as the formation to super-hydrophobicity and serve key effect.As inspiration, by bionical in material surface
Coarse structure is built, and carries out low-surface-energy material modification, or directly in low-surface-energy material surface construction coarse structure, you can
Obtain super-hydrophobicity.This surface has the characteristics such as the self-cleaning, anti-soil similar to lotus leaf etc., while is also found cocoa and delays to reveal
With the forming core of frost, and suppress to grow, i.e., with anti-dew and anti-fog characteristics.
The surfaces such as building glass exterior wall, windshield, solar battery panel are easily polluted, and condensation or frosting, are influenceed
The transparency and performance of base material.At present, although existing many methods can prepare transparent hydrophobic surface, for example, it is molten
Glue-gel method, coating spraying process, photoetching process, nano-imprint method etc., but not yet studies have reported that the condensation on this surface or frosting
How is characteristic, and this also limits application of the technology in above-mentioned transparent substrate surface.Research finds, super hydrophobic surface light water
For drop only at the top of wetting coarse structure (heat transfer efficiency is low), it is air (thermal resistance is big) that interface is most of, is contacted in Cassie compound states；
But under condensation or frosting condition, small yardstick (~10 μ m diameter) drop and hoar crystal are easily in relatively large sized micrometer structure gap
Forming core, growth, the Cassie states of thermodynamic instability is transformed into the lower Wenzel wetting states of energy, dramatically increase bionical super
The adhesiveness of hydrophobic surface, dew and frost are difficult to be desorbed.Therefore, Cassie state thermodynamic stabilities are improved, make super hydrophobic surface small
Yardstick drop is easy to be desorbed, and confrontation dew, the performance of anti-fog characteristics are most important.
Substantial amounts of research shows that compared with micrometer structure, nanostructured roughness is larger, and structure interval has limitation liquid
Growth is dripped, the array nanostructured super hydrophobic surface of reasonable size, drop Cassie states can be made more stable, dew drop or hoar crystal
Not only forming core is difficult, and is only slowly grown in structural top, adhesion is low, is easy to independently be desorbed.At present, chemical vapor deposition is passed through
The methods of product, reactive ion etching, chemical oxidation, obtainable compact nanometer array structure have CNT, silicon nanowires, oxygen
Change copper nanometer sheet, Nano bars of alumina, zinc oxide nano rod etc..Comparatively, the technology of preparing of zinc oxide nano array is more
It is easy.For example, this seminar uses nearly room-temperature water bath growing technology early stage, uniform oxidation is obtained on the copper sheet surface of back-off
Zinc nano-cone array【CrystEngComm,2014,16(24),5394】, after further pre-seed layer, obtain and vertically take
The more preferable nanometic zinc oxide rod array of tropism【Materials Letters,2014,131,178】, and can be in FTO glass surfaces
Growth【J.Phys.Chem.B,2014,118(41):12002】, but the transparency is bad, and can not substrate is two-sided again prepares simultaneously.
Recently, Gao etc. deposits layer of ZnO Seed Layer, then first by high vacuum physical gas phase deposition technology on ito glass surface
Under 90 DEG C of water bath conditions, using hydrothermal growth process, ZnO nano-rod array is prepared for, it is modified to obtain transparent hydrophobic
【ACS Applied Mater.Interfaces,2014,6,2219】.However, gas phase deposition technology prepares crystal seed layer and high temperature
Growth structure nano-array, not only cost is high, also increases the difficulty of scale application used time.
The content of the invention
What the present invention designed 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, methods described include following step
Suddenly：
It is prepared by the first step, crystal seed layer：ZnO crystal seeds colloidal sol is coated in by substrate surface using spin coating or spraying process, nitrogen is protected
It is heat-treated under the conditions of shield, i.e., obtains nano zine oxide crystal seed layer in substrate surface；Described ZnO crystal seeds collosol concentration be 0.1~
0.25M；
Second step, nano-array growth：Substrate corner is tied down with cotton thread, it is molten that vertical suspension is immersed in nano-array growth
In liquid, under the conditions of 35~90 DEG C of waters bath with thermostatic control, taken out after reacting fully, clean drying, it is saturating to obtain zinc oxide in seed layer surface
Bright nano-array, described growth solution are KOH and Zn (NO3)20.01~0.5M of concentration of preparation Zn (OH)4 2-The aqueous solution,
And the pH value of solution is controlled between 10~12；
3rd step, super-hydrophobicization：Dip the substrate into dilute silicon fluoride ethanol solution and be modified, after cleaning drying, solidification obtains
Transparent hydrophobic nano-array is obtained in substrate surface.
Described substrate passes through the clean substrate that pre-treatment obtains, and described pre-treatment is：By substrate successively with acetone, second
After alcohol and deionized water are cleaned by ultrasonic, then rinsed successively with watery hydrochloric acid, deionized water and absolute ethyl alcohol, cold wind dries up to obtain.
The substrate includes any one in copper, nickel, stainless steel, silicon chip, glass.
Described ZnO crystal seed colloidal sols are to be prepared by the following method：First by precursors Zinc diacetate dihydrate, stably
Agent monoethanolamine, surfactant polyethylene, deionized water are added separately in solvent ethylene glycol methyl ether, are first stirred
It is even then abundant in water-bath, it is still aging to obtain.
Spin-coating method concretely comprises the following steps in the first step：Using sol evenning machine, ZnO crystal seed colloidal sols are dropped into substrate surface, first with
900r/m speed spin coating 15s, then with 3000r/m speed spin coatings 20s.
Spraying process concretely comprises the following steps in the first step：By ZnO crystal seeds colloidal sol coated in be positioned over 50~80 DEG C of thermal station 1~
20min substrate surface, crystal seed colloidal sol dosage is 50~100mL/m during spraying2。
First step heat treatment temperature is 300~600 DEG C.
Described ZnO crystal seeds colloidal sol is one side or dual coating coated in substrate surface.
Described transparent hydrophobic nano-array, nanostructured are taper, a diameter of 60~100nm of nano-array, while arriving
Side 20~60nm of spacing, 500~1000nm of height, contact angle are 155 °~160 °, and roll angle is 1 °~4 °；Stable state condensation and dewfall
Under the conditions of, described transparent hydrophobic nano-array surface, drop is in spherical, during 5~20 μm of droplet coalescences, unnecessary surface from
By energy, promoting the drop spring after merging, self-powered spring characteristic occur, spring speed is 0.5~2m/s, 50~500 μm of height,
A diameter of 20~40 μm of the average dew drop on surface, the coverage rate on surface are 10~20%, and drop density is 4 × 108Individual/m2。
Beneficial effect：
(1) concentration of crystal seed colloidal sol and growth solution used in the present invention is all relatively low, and reaction is gentle, can effectively control zinc oxide
The speed of growth of nano-array, transparent nano-array is obtained, avoids high concentration from causing fast-growth, influences the transparency.
(2) the two-sided seed-solution spin coating of substrate or spraying technology, can all obtain crystal seed layer, hydrothermal growth on substrate two sides
Afterwards, transparent nano array can all be obtained on substrate two sides simultaneously.
(3) crystal seed colloidal sol spraying technology of preparing used in the present invention, not only uniform crystal seed layer can be obtained on flat surface surface,
After hydrothermal growth, uniform nano-array can be obtained, can also be in songs such as such as glass tube, glass bar, stainless steel tube, nickel alloy pipes
Uniform nano-array is obtained on face.
(4) cotton thread Suspension Technique, the vertical suspension height of control substrate and the position in growth solution are utilized, can be mitigated
Particles of solute in solution is even avoided to reunite in the sedimentation of substrate surface, so as to eliminate the growth of zinc oxide in large size particle,
Ensure the growth of array zinc oxide.
(5) a diameter of 60~100nm of nanometer zinc oxide array, edge to edge 20~60nm of spacing prepared by the present invention, height
500~1000nm.
(6) compared with untreated slide, the average visible photopic light transmitance of the slide after processing is 80~95%, due to nanometer
Structure is taper, has graded index, so in 650~800nm wave-length coverages, slide even anti-reflection phenomenon occurs.
(7) transparent nano array is modified through silicon fluoride, and contact angle is 155 °~160 °, and roll angle is 1 °~4 °, super thin
Water excellent performance.
(8) under the conditions of stable state condensation and dewfall, the transparent hydrophobic nano-array surface of the invention prepared, drop is still in ball
Shape, 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 occur
Spring characteristic, spring speed is 0.5~2m/s, 50~500 μm of height, so as to significantly increase the motion of surface drop, favorably
In desorption.Therefore, a diameter of 20~40 μm of the average dew drop on surface, the coverage rate on surface are 10~20%, drop density 4
×108Individual/m2。
(9) transparent hydrophobic nano-array prepared by the present invention can assign building glass exterior wall, windshield, the sun
The characteristics such as self-cleaning, waterproof, antifouling such as energy battery panel, to the surface such as dropwise condensation, Anti-dew, antifog, frosting resistance, freezing
Preparation can also provide new thinking.
Brief description of the drawings：
Fig. 1 is the copper sheet surface nanometer array SEM figures handled in example 1.
Fig. 2 is another surface nanometer array SEM figures of the copper sheet handled in example 1.
Fig. 3 is the glass surface nanostructured SEM figures handled in example 2.
Fig. 4 is another surface nano-structure SEM figures of the glass handled in example 2.
Fig. 5 is the light transmittance of the simple glass handled in example 2.
Fig. 6 is the simple glass substrate surface contact angle picture handled in example 2.
Fig. 7 is the copper sheet surface nanometer array SEM figures handled in example 3.
Fig. 8 is another surface nanometer array SEM figures of the copper sheet handled in example 3.
Fig. 9 is the glass surface nanostructured SEM figures handled in example 4.
Figure 10 is another surface nano-structure SEM figures of the glass handled in example 4.
Figure 11 is the glass surface actual transparency situation map handled in example 4.
The glass surface dropwise condensation condensation displaing micro picture that Figure 12 is handled using example 4.
High speed camera picture during the glass surface dew drop spring 0.75ms that Figure 13 is handled using example 4.
High speed camera picture during the glass surface dew drop spring 5.25ms that Figure 14 is handled using example 4.
Figure 15 is the glass surface nanostructured SEM figures handled in example 5.
Figure 16 is another surface nano-structure SEM figures of the glass handled in example 5.
Figure 17 is the glass surface actual transparency situation map handled in example 5.
Figure 18 is the copper pipe surface nano-array SEM figures handled in example 6.
Embodiment：
A kind of transparent hydrophobic nano-array preparation method, step are：
(1) prepared by crystal seed layer：Precursors Zinc diacetate dihydrate, stabilizer alcohol amine, surfactant are gathered first
Ethylene glycol, deionized water are added separately in solvent ethylene glycol methyl ether, first mix 20min in 800r/m speed magnetic agitation, then
After 60 DEG C of waters bath with thermostatic control, 1500r/m magnetic agitations 2h, still aging 24h, concentration 0.1~0.25M crystal seed colloidal sols are obtained, with
Sol evenning machine is used afterwards, crystal seed colloidal sol is dropped into substrate surface, first with 900r/m speed spin coating 15s, then with 3000r/m speed spin coatings
20s, then, substrate is put into vacuum tube furnace, 10min is handled under 350 DEG C of nitrogen protective conditions, you can obtained in substrate surface
Nano zine oxide crystal seed layer；
(2) nano-array grows：Substrate corner is tied down with cotton thread, vertical suspension is immersed in nano-array growth solution
In, it is highly 5~20cm to adjust between substrate and suspension fixing point, and adjustment substrate is located at 1/3rd position areas above growth-promoting media
Domain, under the conditions of 35~90 DEG C of waters bath with thermostatic control, take out after reacting 0.5~6h, rinsed with deionized water, cold wind drying can be in crystal seed
Layer surface obtains ZnO transparent nano-array, and described growth solution is KOH and Zn (NO3)20.01~0.5M of concentration of preparation
Zn (OH)4 2-The aqueous solution, and the pH value of solution is controlled between 10~12；
(3) super-hydrophobicization：30min in 1% silicon fluoride ethanol solution is dipped the substrate into, takes out and is rushed with deionized water, ethanol
After washing and drying up, solidify 15min in 60 DEG C of baking oven, you can obtain and obtain transparent hydrophobic nano-array in substrate surface.
Substrate removes surface impurity by pre-treatment, and specific method is：Substrate is used into acetone, ethanol and deionized water successively
It is each to be cleaned by ultrasonic 10min, 0.1M aqueous hydrochloric acid solution 30s are put into after taking-up, are rinsed followed in turn by deionized water and absolute ethyl alcohol, it is cold
Wind is done, standby, and the substrate includes copper, nickel, stainless steel, silicon chip, glass etc.；
Embodiment 1
Cu substrates grow ZnO nano array at 35 DEG C
Using the crystal seed colloid that concentration is 0.25M is prepared, by using desk-top sol evenning machine spin coating plated film, in clean Cu bases
Layer of ZnO colloid film is prepared on egative film；Through the lower 350 DEG C of annealing 10min of nitrogen atmosphere, i.e., form one layer uniformly in substrate surface
Fine and close nanoscale ZnO crystal seed film layers；By KOH and Zn (NO3)2The pH=12 of preparation 0.5M Zn (OH)4 2-Reaction system
In, there are the Cu pieces of crystal seed layer to prepare as substrate, obtained ZnO array films after 35 DEG C of water-bath growth 6h, two-sided pattern difference
As shown in Figure 1 and Figure 2.
Embodiment 2
Glass substrate grows ZnO nano array at 35 DEG C
Using prepare concentration be 0.1M colloid, by using the method plated film of spraying, in cleaned glass substrate sheet
Prepare layer of ZnO colloid film；Through the lower 350 DEG C of annealing 10min of nitrogen atmosphere, i.e., in substrate surface one layer of even compact of formation
Nanoscale ZnO crystal seed film layers；By KOH and Zn (NO3)2The pH=12 of preparation 0.09M Zn (OH)4 2-In reaction system, with
The sheet glass that preparing has crystal seed layer be substrate, is made ZnO arrays after 35 DEG C of water-baths growth 0.5-4h, two-sided pattern respectively such as Fig. 3,
Shown in Fig. 4, light transmittance is as shown in figure 5, contact corner shape is as shown in Figure 6.
Embodiment 3
Cu substrates grow ZnO nano array at 35 DEG C
Using the colloid that concentration is 0.15M is prepared, by using the desk-top sol evenning machine spin coating plated film of KW-4A types, in Cu bases
Layer of ZnO colloid film is prepared on egative film；Through the lower 350 DEG C of annealing 10min of nitrogen atmosphere, i.e., form one layer uniformly in substrate surface
Fine and close nanoscale ZnO crystal seed film layers；By KOH and Zn (NO3)2The pH=12 of preparation 0.5M Zn (OH)4 2-Reaction system
In, there are the Cu pieces of crystal seed layer to prepare as substrate, obtained ZnO array films after 35 DEG C of water-bath growth 4h, two-sided pattern difference
As shown in Figure 7, Figure 8.
Embodiment 4
Glass substrate grows ZnO nano array at 35 DEG C
Using the colloid that concentration is 0.1M is prepared, by using the method plated film of spraying, prepared on substrate of glass piece
Layer of ZnO colloid film；Through the lower 350 DEG C of annealing 10min of nitrogen atmosphere, the i.e. nanometer in substrate surface one layer of even compact of formation
Level ZnO crystal seed film layers；By KOH and Zn (NO3)2The pH=12 of preparation 0.01M Zn (OH)4 2-In reaction system, to prepare
The sheet glass for having crystal seed layer is substrate, and 35 DEG C of water-baths grow obtained ZnO array films after 2h, and two-sided pattern is respectively such as Fig. 9, figure
Shown in 10, transparent situation is as shown in figure 11.
Under the conditions of stable state condensation and dewfall, transparent hydrophobic nano-array surface prepared by the example, drop still in spherical,
A diameter of 20~40 μm of the average dew drop on surface, the coverage rate on surface are 10~20%, and drop density is 4 × 108Individual/m2, such 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, it is so-called to occur
Self-powered spring characteristic.Figure 13 is high speed camera picture of the dew drop since substrate during spring 0.75ms, illustrates that spring speed is
~2m/s, Figure 14 are then bound to high speed camera picture during peak for drop, and it is~330 μm to illustrate jumping height.
Embodiment 5
Glass substrate grows ZnO nano array at 35 DEG C
Using the colloid that concentration is 0.1M is prepared, by using the method plated film of spraying, prepared on substrate of glass piece
Layer of ZnO colloid film；Through the lower 350 DEG C of annealing 10min of nitrogen atmosphere, the i.e. nanometer in substrate surface one layer of even compact of formation
Level ZnO crystal seed film layers；By KOH and Zn (NO3)2The pH=12 of preparation 0.2M Zn (OH)4 2-In reaction system, to prepare
The sheet glass for having crystal seed layer is substrate, and 35 DEG C of water-baths grow obtained ZnO array films after 0.5h, and two-sided pattern is respectively as schemed
15th, shown in Figure 16, transparent situation is as shown in figure 17.
Embodiment 6
Copper pipe substrate grows ZnO nano array at 35 DEG C
Using the colloid that concentration is 0.1M is prepared, by using the method plated film of spraying, one is prepared on copper pipe substrate
Layer ZnO colloid film；Through the lower 350 DEG C of annealing 10min of nitrogen atmosphere, the i.e. nanoscale in substrate surface one layer of even compact of formation
ZnO crystal seed film layers；By KOH and Zn (NO3)2The pH=12 of preparation 0.05M Zn (OH)4 2-In reaction system, have to prepare
The copper pipe of crystal seed layer is substrate, and 35 DEG C of water-baths grow obtained ZnO array films after 3h, and surface topography is as shown in figure 18.
Claims (9)
1. a kind of transparent hydrophobic nano-array preparation method, it is characterised in that methods described comprises the following steps：
It is prepared by the first step, crystal seed layer：ZnO crystal seeds colloidal sol is coated in by substrate surface, nitrogen ceiling using spin coating or spraying process
It is heat-treated under part, i.e., obtains nano zine oxide crystal seed layer in substrate surface；Described ZnO crystal seeds collosol concentration be 0.1~
0.25M；
Second step, nano-array growth：Substrate corner is tied down with cotton thread, vertical suspension is immersed in nano-array growth solution
In, under the conditions of 35~90 DEG C of waters bath with thermostatic control, taken out after reacting fully, clean drying, ZnO transparent is obtained in seed layer surface
Nano-array, described growth solution are KOH and Zn (NO3)20.01~0.5M of concentration of preparation Zn (OH)4 2-The aqueous solution, and
The pH value of solution is controlled between 10~12；
3rd step, super-hydrophobicization：Dip the substrate into dilute silicon fluoride ethanol solution and be modified, after cleaning drying, solidification is obtained in base
Piece surface obtains transparent hydrophobic nano-array.
2. transparent hydrophobic nano-array preparation method as claimed in claim 1, it is characterised in that before described substrate passes through
Obtained clean substrate is handled, described pre-treatment is：After substrate is cleaned by ultrasonic with acetone, ethanol and deionized water successively,
Rinsed successively with watery hydrochloric acid, deionized water and absolute ethyl alcohol again, cold wind dries up to obtain.
3. transparent hydrophobic nano-array preparation method as claimed in claim 1, it is characterised in that the substrate include copper,
Any one in nickel, stainless steel, silicon chip, glass.
4. transparent hydrophobic nano-array preparation method as claimed in claim 1, it is characterised in that described ZnO crystal seeds are molten
Glue is to be prepared by the following method：First by precursors Zinc diacetate dihydrate, stabilizer alcohol amine, the poly- second of surfactant
Glycol, deionized water are added separately in solvent ethylene glycol methyl ether, are first uniformly mixed, then abundant in water-bath, are stood
Ageing obtains.
5. transparent hydrophobic nano-array preparation method as claimed in claim 1, it is characterised in that spin-coating method has in the first step
Body step is：Using sol evenning machine, ZnO crystal seed colloidal sols are dropped into substrate surface, first with 900r/m speed spin coating 15s, then with
3000r/m speed spin coatings 20s.
6. transparent hydrophobic nano-array preparation method as claimed in claim 1, it is characterised in that spraying process has in the first step
Body step is：ZnO crystal seeds colloidal sol is coated in and is positioned over 50~80 DEG C of 1~20min of thermal station substrate surface, crystal seed is molten during spraying
Glue dosage 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
For 300~600 DEG C.
8. transparent hydrophobic nano-array preparation method as claimed in claim 1, it is characterised in that described ZnO crystal seeds are molten
Glue is one side or dual coating coated in substrate surface.
9. the nano-array that any described transparent hydrophobic nano-array preparation method of claim 1~8 obtains, its feature exist
In, nanostructured be taper, a diameter of 60~100nm of nano-array, edge to edge 20~60nm of spacing, 500~1000nm of height,
Contact angle is 155 °~160 °, and roll angle is 1 °~4 °；Under the conditions of stable state condensation and dewfall, described transparent hydrophobic nano-array
Surface, drop is in spherical, during 5~20 μm of droplet coalescences, unnecessary surface free energy, promotes the drop spring after merging, occurs
Self-powered spring characteristic, spring speed is 0.5~2m/s, 50~500 μm of height, a diameter of 20~40 μm of the average dew drop on surface,
Coverage rate on surface is 10~20%, and drop density is 4 × 108Individual/m2。
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| WO2018053452A1 (en) | 2016-09-19 | 2018-03-22 | 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 |
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| 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 |
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| CN103523818B (en) * | 2013-10-31 | 2015-09-09 | 东南大学 | A kind of preparation method of height-oriented ZnO nano cone array structure materials |
| CN103603040B (en) * | 2013-10-31 | 2016-08-17 | 东南大学 | A kind of low temperature liquid phase growing method preparing ZnO nano cone array |
| CN104846369B (en) * | 2015-03-30 | 2017-08-25 | 陕西科技大学 | A kind of method for preparing super hydrophobe 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 |
| CN104888498B (en) * | 2015-06-12 | 2016-06-15 | 东南大学 | A kind of durability super-hydrophobic super-oleophylic foam copper preparation method for oil-water separation |
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