CN107022291B - A kind of preparation method of the super-amphiphobic coating of sprayable and lasting freezing - Google Patents
A kind of preparation method of the super-amphiphobic coating of sprayable and lasting freezing Download PDFInfo
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- CN107022291B CN107022291B CN201710263701.8A CN201710263701A CN107022291B CN 107022291 B CN107022291 B CN 107022291B CN 201710263701 A CN201710263701 A CN 201710263701A CN 107022291 B CN107022291 B CN 107022291B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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Abstract
The invention belongs to super-hydrophobic or super-amphiphobic coating preparation field, in particular to the preparation method of the super-amphiphobic coating of a kind of sprayable and lasting freezing specifically includes: step 1 carries out cleaning and sandblasting roughening treatment to substrate surface；Step 2 obtains polyurethane solutions after being blended using polyurethane with the first solvent；Sub-micron particles, nanoparticle are dispersed the second solvent by step 3, adds silicon fluoride, has obtained particle composite suspension liquid；Step 4, by the processed substrate surface of the resulting polyurethane solutions spraying process 1 of step 2, semi-solid preparation is carried out to polyurethane adhesive；Particle composite suspension liquid is sprayed to the obtained substrate surface of step 4 by step 5, is fully cured；Step 6, the super-amphiphobic coating for obtaining sprayable and lasting freezing.The invention has the benefit that the present invention, which prepares ground super-amphiphobic coating in each substrate surface by spraying technology, has good durability and fastness, and the freezing performance that having can be lasting.
Description
Technical field
The invention belongs to super-hydrophobic or super-amphiphobic coating preparation field, in particular to a kind of sprayable and lasting freezing
The preparation method of super-amphiphobic coating.
Background technique
Surface wettability is one of important feature of the surface of solids, and wetability can be weighed with the contact angle of water on surface
Amount；Super hydrophobic surface causes the contact angle of water greater than 150 °, roll angle because of it less than 10 °, and with self-cleaning characteristic
Academia and the great interest of industry.In nature, the leaf and petal of many plants, the wing of insect and bird
Feather of class etc. is natural super hydrophobic material.The self-cleaning function of super hydrophobic surface, i.e. surface contaminant such as dust etc. can
It is taken away with the water droplet tumbled without leaving any trace.Automatic cleaning coating has the advantages such as water-saving, energy-saving and environmental protection, increasingly
It gets more and more people's extensive concerning, is one of the hotspots in the research of material science.
As people are growing day by day to super-hydrophobic and super-double-hydrophobic surface research interest, especially sleet and snow ice calamity in recent years
Evil loss different degrees of caused by transporting to transmission of electricity telecommunication circuit, aviation, navigation or high-speed rail, increases people to super thin
Water or the ice-covering-proof research dynamics with freezing of super-double-hydrophobic surface.In actual environment, in the high electric wire hung in the air, cloud layer
Aircraft wing, wing of wind-driven generator of flight etc., in the case where meeting with low temperature and big humidity, often surface is easy knot
Ice, to result in significant economic losses.Therefore, reinforcing can be in terms of freezing to the super-hydrophobic or ultra-amphosphobic of the surface of solids
Correlative study be just particularly important.
The study found that an important application of super-hydrophobic technology is exactly freezing compared with traditional ice-melt and de-icing method
Frosting postpones, reduces or even prevent completely frost in solids bulk, can preferably solve the problems, such as.By largely studying
It proves, super-hydrophobicization on surface reduces ice in the adhesion strength on surface.But again prepared by surface, major part for nearest research
Super-hydrophobic or super-double-hydrophobic surface can not lasting freezing: especially when super hydrophobic surface encounters, environment temperature is extremely low and humidity
Very big situation when super hydrophobic surface freezing the case where be not it is highly desirable, sometimes even its surface once freeze be more difficult to remove.
The research of this respect at present is not very much, the patent of the relevant article delivered and authorization, in particular for this low temperature
The research influenced with many factors such as big humidity on super hydrophobic surface hydrophobic performance is even more fewer and fewer.
In addition, spraying technology is compared to etching method, template, solution infusion method and electrochemical process etc., preparation is super thin in the past
The method of water or super-amphiphobic coating, it has very big technical advantage.For substrate of various shapes, whether plane, facade be also
It is top surface, whether round, the complex object of spherical or other irregular shapes can directly be implemented to spray, not need
Expensive mold manufacturing expense；Also, spraying technology high production efficiency is particularly suitable for the processing of large area, Special-shaped object.
Therefore, this patent is intended to invent a kind of sprayable, and freezing that can be lasting under low temperature, big humidity environment is super
Double-hydrophobic surface.
Summary of the invention
In view of above-mentioned analysis, the present invention is intended to provide a kind of preparation of the super-amphiphobic coating of sprayable and lasting freezing
Method, solving in the case where low temperature and big humidity environment, the super-amphiphobic coating of the surface of solids is still able to maintain excellent super double
Dredge property and freezing.
The purpose of the present invention is mainly achieved through the following technical solutions:
A kind of preparation method of the super-amphiphobic coating of sprayable and lasting freezing, specifically includes the following steps:
Step 1 carries out cleaning and sandblasting roughening treatment, the substrate handled well to substrate surface；
Step 2 obtains polyurethane solutions after being blended using polyurethane resin with the first solvent；
Step 3 disperses submicron particle, nanoparticle in the second solvent, after ultrasonic and stirring, addition silicon fluoride, after
Continuous ultrasound and stirring, have obtained particle composite suspension liquid；
Step 4 is done by the processed substrate surface of the resulting polyurethane solutions spraying process 1 of step 2, then by the substrate
It is dry, semi-solid preparation is carried out to polyurethane adhesive；
The resulting particle composite suspension liquid of step 3 is sprayed to the obtained substrate surface of step 4 by step 5, then by the base
Material drying is fully cured；
Step 6 is rinsed the obtained substrate surface of step 5, and the super of sprayable and lasting freezing can be obtained
Double open coats.
Further, in the step 1, the substrate be plane, the silicon wafer of curved surface or irregular shape, metal, glass,
Plastics, timber or stone material.
Preparation method in the present invention is not influenced by the shape of substrate, size and type, is also not limited to above-mentioned substrate,
Meanwhile metal base can be iron, aluminium or aluminium alloy, but be not limited only to these types, glass baseplate can be quartz or common glass
Glass；Substrate of the present invention can be cardboard, and cardboard only needs cleaning.
Further, in the step 1, it is described to substrate surface carry out cleaning be using acetone, deionized water, ethyl alcohol according to
Secondary cleaning.
Further, in the step 1, the technological parameter of sandblasting roughening treatment are as follows: 0.5~1.0MPa of air pressure, spray
The sand time 10 seconds~1 minute, 40~200 mesh of sand blasting-used sand ball mesh number.
Matrix surface is carried out roughening treatment of sandblasting by the present invention, can increase the roughness of matrix surface, improve coating with
The bond strength of matrix, and then improve the fastness and durability on super-hydrophobic coat surface.
Further, in the step 2, polyurethane is one-part solvent type polyurethane；First solvent is toluene, two
Toluene, acetone, methyl ethyl ketone, butanone, ethyl acetate, n-butyl acetate, tert-butyl acetate one or more mixed solvents.
Further, the mass ratio of the polyurethane and the first solvent is (4~10): 100.
In order to construct super-hydrophobic or super-double-hydrophobic surface in smooth surface, currently used method is by inorganic nano-particle
It is blended with fluoropolymer or is fluorinated nanoparticle, the nanoparticle after fluorination is then coated onto material surface to which building is super
Hydrophobic or super-double-hydrophobic surface.It is difficult in these methods, between polymer and inorganic particulate and substrate Nian Jie by valence bond effect
Together, physisorption is only leaned on, bonding force is not strong, exists so as to cause constructed super-hydrophobic or super-double-hydrophobic surface
Insecure, rub resistance, washing fastness be not strong.
The present invention carries out super-amphiphobic coating preparation using bottom coating and investment precoat, wherein bottom coating uses poly- ammonia
Ester.Polyurethane adhesive has the function of all-purpose adhesive, it also has toughness adjustable and has splendid resistance to low temperature and excellent
Stability.In the present invention, on the one hand it can be strongly adhered to substrate surface, and on the other hand it is by inorganic silicon dioxide
Particle is bonded with securely, is played an intermediate adherent, constructing for coarse structure needed for super-amphiphobic is realized, to make
Obtaining constructed super-amphiphobic coating has good durability and fastness, has freezing performance that can be lasting.
Further, in the step 3, the second solvent, ultrasound and stirring 1 are dispersed by submicron particle, nanoparticle
After~3 hours, silicon fluoride is added, continues ultrasound and stirring 1~3 hour, has obtained particle composite suspension liquid；In the step 4
Substrate is placed at 25~80 DEG C dry 0.5~2h and carries out semi-solid preparation；In the step 5 by substrate in the case where temperature is 25~80 DEG C
Drying 0.5~be fully cured for 24 hours.
Further, the submicron particle is the silicon dioxide granule of 200~500nm of partial size；The nanoparticle
For the hydrophilic fumed silica particle of 7~40nm of partial size；Second solvent is acetone, ethyl alcohol, n-hexane, acetic acid first
One or more mixed solvents of ester, carbon tetrachloride.
The fumed silica particle of the silica of 200~500nm sub-micro grade and 7~40nm is dispersed in the present invention
In surface layer solution, the coarse micro-nano structure of fine binary is formd in substrate surface and layer of polyurethane surface after spraying；Work as coating
Only small particle-size silica when, the external world when external force is applied to this coating, small particle-size silica is easy to be broken up by external force,
To lose ultra-amphosphobic energy；When large-sized silica is used only, the micro-nano for realizing super-amphiphobic is not achieved in coating surface
Fine structure, to cannot achieve the super-amphiphobic of substrate surface；In the present invention, the silicon dioxide granule of two kinds of partial sizes is due to phase
Mutual cross bindings are in one piece, and when the external world is when external force is applied to this coating, the silicon dioxide granule of large-sized sub-micro grade can be right
The power that the nano fumed silica of small particle is subject to has certain peptizaiton, therefore the durable of coating can be improved in this structure
Property and secured performance, to extend the service life of coating.
Further, the mass ratio of the submicron particle, nanoparticle, silicon fluoride and the second solvent be (1~
3): (1~3): (2~10): 100.
Preferably, the control of the mass ratio of the nanoparticle and submicron particle is in (1~0.5): (0.5~0.1) range
It is interior.
In the present invention, partial size is the sub-micro grade silicon dioxide that 7~40nm fumed silica is 200~500nm with partial size
This appropriate ratio control be 1~0.5:0.5~0.1, pass through comparison sub-micro grade silicon dioxide and fumed silica be different
The experimental result of ratio, find under this particle ratio, prepared super-amphiphobic coating, to water mist have it is super-hydrophobic, do not stick
Characteristic.When the water mist after atomization is continuously sprayed on sample surfaces with spray gun, in the case where this big humidity, water mist to painting
Small water droplet in layer surface, which can be rolled or be bounced from coating rapidly, to be left, and will not be condensed into big drop, to realize coating
The antifog effect in surface；It is placed in subzero 10 DEG C of low temperature environment when that will apply, continues to be sprayed on the water mist after atomization with spray gun
When coating surface, the small water droplet on water mist to coating surface remains to roll or bounce from coating rapidly to leave, and is not condensed into
Big drop, after persistently spraying 200 minutes, there is not icing phenomenon in coating surface, final coating achieved the effect that freezing and
Performance.
Further, the silicon fluoride is that carbon chain lengths are greater than 4, and end group is the perfluor of methoxyl group, ethyoxyl or chloro
Silane it is one or more.
Preferably, the silicon fluoride is perfluoro decyl trimethoxy silane, perfluoro decyl triethoxysilane, perfluoro decyl
One kind or more of trichlorosilane, perfluoro capryl trimethoxy silane, perfluoro capryl triethoxysilane, perfluoro capryl trichlorosilane
Kind.
Further, in the step 3, total mass ratio of the silicon fluoride and submicron particle, nanoparticle is big
In 1:1.
The present invention of ratio control in to(for) silicon fluoride has a strict requirements, the particle of silicon fluoride and two kinds of partial sizes always
Mass ratio is greater than 1 ︰ 1.Under this ratio, silicon fluoride is in addition to that can be grafted full chain hydrophobic for the particle surface of two kinds of partial sizes completely
Oleophobic group, can also be remaining a part of in solvent；It is molten when carrying out surface spraying to silicon dioxide granule composite suspension liquid
Remaining silicon fluoride will carry out bonding reaction with the hydrogen bond isoreactivity group of the layer of polyurethane of the semi-solid preparation sprayed before in agent,
To while reducing layer of polyurethane surface energy, moreover it is possible to which the fluorin radical with silica particle surface is jointly in substrate surface
One layer of fluorinated film is formed, and then further improves holding for the durability on super-amphiphobic coating surface, fastness and freezing
Long property.
Further, it in the step 4 and step 5, is sprayed using spray gun, the spray gun is 0.5~2mm's of diameter
Commercial spray gun, using compressed air as carrier, adjustment spray spot be sector, spray distance 10~20cm of the nozzle away from substrate, nozzle with
Substrate is vertically in 90 ° of angles, is successively sprayed with the speed of 2~5cm/s from left to right, 30~100psi of spray pressure, to substrate
Repeat spraying 2~5 times.
Further, ethyl alcohol or acetone rinsing are used in the step 6.
Super-amphiphobic coating prepared by the preparation method of the super-amphiphobic coating of a kind of sprayable and lasting freezing, raw material master
It to include polyurethane solutions and particle composite suspension liquid, the polyurethane solutions include 4~10 parts of polyurethane, the first solvent 100
Part, the particle composite suspension liquid includes 1~3 part of submicron particle, 1~3 part of nanoparticle, 2~10 parts of silicon fluoride, second molten
100 parts of agent.
The present invention has the beneficial effect that:
(1) present invention the preparation of each substrate surface super-amphiphobic coating, because of its connecing with water, glycerol, edible oil, crude oil etc.
Feeler be greater than 150 °, roll angle less than 10 °, so as to make substrate have excellent super-hydrophobic and superoleophobic performance, and well
Self-cleaning performance.
(2) present invention, which prepares ground super-amphiphobic coating in each substrate surface by spraying technology, has good durability and jail
Solidity, and the freezing performance that having can be lasting.
(3) super-amphiphobic coating of the sprayable and lasting freezing prepared by the present invention, ageing-resistant and acid-alkali-corrosive-resisting
Can be excellent, and it is amenable to certain shock resistance；After placing 1 year in natural environment, appearance, the color nothing of coating are obvious
Variation, and remain to protect excellent ultra-amphosphobic and freezing.
(4) fly in the sprayable and durable super-amphiphobic coating of the present invention can be hung in outdoor overhead electric wire, cloud layer
The overwhelming majority such as capable wing of aircraft wing, wind-driven generator needs to prevent the surface to freeze from being applied.
(5) present invention prepares super-amphiphobic coating using spraying technology, and spraying technology is compared to etching method, template, solution
Infusion method and electrochemical process etc. prepare super-hydrophobic or super-amphiphobic coating method in the past, it has very big technical advantage.For
Substrate of various shapes, whether plane, facade or top surface, whether round, and spherical or other irregular shapes are answered
Sundries body can directly be implemented to spray, and not need expensive mold manufacturing expense；Spraying technology is easy to operate, speed of action
Fastly, the coating uniform of preparation is sprayed, property is stablized, and can spray repeatedly, can reach the effect of selfreparing to a certain extent；
In addition, spraying technology high production efficiency, is particularly suitable for the processing of large area, Special-shaped object.
(6) technical grade reagent, used method operating procedure letter can be used in all reagents used in the present invention
It is single, general commercial raw material are subjected to simple dilution dispersion, is successively sprayed on substrate, can directly be obtained by spraying technology
Coating needed for obtaining, processing step at low cost, environmentally protective, without complexity are suitable for without expensive instrument and equipment to phase
The preparation that substrate surface carries out high-volume super-hydrophobic coat is closed, the application prospect with heavy industrialization can be created great
Economic benefit.
Detailed description of the invention
Fig. 1 is super-hydrophobic superoleophobic macro-effect figure of the super-amphiphobic aluminum alloy surface to water and oil of the embodiment of the present invention 1.
Fig. 2 is super-hydrophobic superoleophobic macro-effect figure of the super-amphiphobic poplar plate surface to water and oil of the embodiment of the present invention 2.
Fig. 3 is super-hydrophobic superoleophobic macro-effect of the super-amphiphobic corrugated cardboard sheet in face of water and oil of the embodiment of the present invention 3
Figure.
Fig. 4 is super-hydrophobic superoleophobic macro-effect figure of the super-amphiphobic common brick surface to water and oil of the embodiment of the present invention 4.
Fig. 5 is the super-amphiphobic aluminum alloy surface coating of the embodiment of the present invention 1 and the contact angle test figure of water droplet.
Fig. 6 is the super-amphiphobic aluminum alloy surface coating of the embodiment of the present invention 1 and the contact angle test figure of glycerol.
The husky experiment schematic diagram of leakage in the super-amphiphobic coating shock resistance detection that Fig. 7 is 1-4 of the embodiment of the present invention.
In figure, 1- water, 2- soybean oil, 3- glycerol, 4- hydraulic oil, the 5- grains of sand, which fall, to flow, and 6- super-amphiphobic coating, the 7- grains of sand are received
Storage, 8- grains of sand collector are 30cm away from super-amphiphobic coating height.
Specific embodiment
Specifically describing the preferred embodiment of the present invention with reference to the accompanying drawing, wherein attached drawing constitutes the application a part, and
Together with embodiments of the present invention for illustrating the principle of the present invention.
Embodiment 1:
In present embodiment, basis material selects the aluminium alloy plate that thickness is about 200*200*3mm, which can be with
- 2014 type of Shanghai Zhi Xin Trade Co., Ltd., can the aluminium alloy plate preparation method of super-amphiphobic of lasting freezing be by as follows
What step carried out:
(1) aluminium alloy plate is cleaned up as substrate with water and clean cotton, later using 80 mesh corundum sands to base
The progress sandblasting roughening treatment of body surface face, air pressure 0.5MPa, blast time 1 minute；Use acetone, ethyl alcohol and deionization again later
Water successively cleans substrate surface, at room temperature dried for standby；
(2) by the monocomponent polyurethane adhesive of 10g, (717 one-component polyurethane adhesive of Great Wall board, Shanghai are finely cultural
Articles Co., Ltd) ultrasound and stirring and dissolving are in 50mL acetone, 30mL dimethylbenzene, the in the mixed solvent of 20mL tert-butyl acetate,
Polyurethane glue is prepared；
(3) 3g partial size is referred to as the hydrophilic fumed silica of 7~40nm and the titanium dioxide that 3g average grain diameter is 200nm
Silicon, stirring and ultrasonic disperse are in the acetone of 100mL, ultrasound 1 hour；8g perfluoro decyl trichlorosilane is added later, continues to stir
It mixes and ultrasound is after 1 hour, particle composite solution has been prepared；
(4) the polyurethane glue in (2) step is passed through into spray gun spraying in aluminium alloy plate substrate surface: uses nozzle diameter
The commercial spray gun of 0.5mm, using compressed air as carrier, adjustment spray spot is sector, spray distance 15cm of the nozzle away from substrate, nozzle
Vertical with substrate is in 90 ° of angles, and spray pressure 30psi is constant, is from left to right sprayed to substrate with the speed of 5cm/s；Such as
This is repeated 2 times；, semi-solid preparation 1 hour under room temperature, aluminium alloy plate substrate obtain needed for semi-solid preparation polyurethane glue-line；
(5) use and same spraying technology in step (4), are sprayed at step for the particle composite solution in step (3)
(4) the polyurethane adhesive layer surface of semi-solid preparation repeats spraying 3 times；It places 5 hours and is fully cured under room temperature later；
(6) ethyl alcohol or acetone rinsing step (5) obtained substrate surface are used, can be obtained the super-amphiphobic of lasting freezing
Aluminium alloy plate.
Meanwhile the present invention detects the performance of prepared sprayable and durable super-amphiphobic aluminium alloy plate:
(1) super-hydrophobic and superoleophobic performance:
At room temperature, the water and oil level drop for measuring 5 μ L with micro syringe are in sample surfaces, after standing 5s, using Shanghai
Middle morning digital technology equipment Co., Ltd JC2000C type contact angle measurement measures, and reads the contact angle numerical value of water and oil,
Using the roll angle of tilting plate method measurement coating surface；Test result obtains, the coating to the contact angle of water up to 160 °, roll angle
3°；To the contact angle of glycerol up to 156 degree, 4 ° of roll angle.
(2) freezing performance:
The freezing performance of super-amphiphobic coating passes through homemade apparatus measures: aluminium alloy plate sample prepared by the present embodiment 1
Product are placed on a platform, and platform is in 30 degree of angle horizontal rest, and platform surface temperature is cooled to -10 DEG C, works as platform
Temperature reach this setting value and stablize after, sprayed in ground by spray gun by the small water droplet (about 0.5mm diameter) after atomization is horizontal
It dissipates in sample coatings surface, persistently sprays 200 minutes.Continue in spraying process it has been observed that when small water droplet is sprayed onto substrate surface
When, moment is walked by bullet, and water droplet is extremely short in the substrate surface residence time；Sample surfaces are hung on its surface without droplet, after 200 minutes
Do not occur icing phenomenon.
The present invention prepares five comparative example aluminium alloy plate coatings, i.e. comparative example 1~5, experimental data is shown in Table 1, and comparative example 1 is
The silica of two kinds of partial sizes in (3) step in the present embodiment 1 is changed to the hydrophilic gas phase that partial size is 7~40nm is used only
Silica, other steps are constant；Finally it is prepared into super-amphiphobic aluminium alloy plate surface.Connecing for water is measured by contact angle measurement
Feeler is up to 165 °, 2 ° of roll angle；159 ° of the contact angle of glycerol, 3 ° of roll angle, it was demonstrated that using only the fumed silica of small particle,
Also super-amphiphobic coating may be implemented.But this surface is subjected to freezing performance detection, the small water droplet after spraying atomization is (about
0.5mm diameter) when substrate surface, small water droplet can condense into the big water droplet of about 2mm first, can just roll later in substrate surface
It falls, the residence time which substantially increases water droplet on surface；It is sprayed after twenty minutes when lasting, aluminium alloy plate surface has just been formed thick
One layer of ice, illustrate the not freezing of aluminium alloy plate surface prepared by this comparative example 1.
Comparative example 2 be the silica of two kinds of partial sizes in (3) step in the present embodiment 1 is changed to be using only partial size
200nm's, other steps are constant；Finally it is prepared into super-amphiphobic aluminium alloy plate surface.Connecing for water is measured by contact angle measurement
Feeler is up to 153 °, 5 ° of roll angle；151 ° of the contact angle of glycerol, 9 ° of roll angle, it was demonstrated that using only the silica of 200nm partial size,
Also super-amphiphobic coating may be implemented.This surface is equally subjected to freezing performance detection, the small water droplet after spraying atomization is (about
0.5mm diameter) when substrate surface, small water droplet can condense into the big water droplet of about 3mm first, can just roll later in substrate surface
It falls, the residence time this also increases water droplet on surface；It is sprayed after five minutes when lasting, thickness has just been formed on aluminium alloy plate surface
One layer of thick ice illustrates the equally not freezing of aluminium alloy plate surface prepared by this comparative example 2.
And 3~comparative example of comparative example 5 is the hydrophilic fumed silica and 200nm partial size by changing 7~40nm
The mass ratio of silica is tested, and is specifically shown in Table 1.
The experimental data of freezing performance test in 1 embodiment 1 of table
(3) acid-alkali-corrosive-resisting performance:
By super-amphiphobic aluminium alloy plate sample prepared by the present embodiment 1 (front and back sides all spray), it is soaked in pH=1 respectively
Sulfuric acid solution and pH=14 NaOH solution in, impregnate 50 hours, the acid resistance and alkali resistance of testing coating.It impregnates 50 hours
Afterwards, the unabroken sign of coating surface is observed；And the water contact angle and oily contact angle of coating are measured, wherein water after acid resistance test
Contact angle is up to 158 °, 4 ° of water roll angle, 154 ° of glycerol contact angle, 5 ° of roll angle；Up to 157 °, water rolls water contact angle after alkali resistance test
Dynamic 4 ° of angle, 152 ° of glycerol contact angle, 5 ° of roll angle.Illustrate the super-amphiphobic coating tool that the present embodiment 1 is prepared on aluminium alloy plate surface
There is good acid-alkali-corrosive-resisting.
(4) shock resistance
The present embodiment 1 is specifically shown in Fig. 7 using the mechanical property for leaking husky experimental verification aluminium alloy plate surface super-amphiphobic coating:
It will be placed by sample levels angle at 45 °, a container is put at the height away from sample center 30cm, is placed with 2kg's in container
The grains of sand of the partial size at 100~300 μm.The grains of sand are leaked down from container, are collided with the super-amphiphobic coating of inclined sample surfaces, leakage
Husky speed about 1g/s collides area about 1cm2.After the grains of sand have all leaked, aluminium alloy plate surface is gently washed out with deionized water
Sand, the water contact angle for then measuring coating still can reach 157 °, and roll angle is up to 4 °；Also 153 ° of glycerol contact angle, roll angle reaches
5 °, illustrate that the super-amphiphobic coating on aluminium alloy plate surface has good impact resistance；Meanwhile the aluminium alloy plate after testing leakage sand
Surface is placed in -10 DEG C of environment and finds after atomized water spray, after continuing spraying 200 minutes in sample surface still without icing phenomenon.
Meanwhile after comparative example 1 and comparative example 2 also to be carried out to the leakage sand experiment of condition same as Example 1, Qi Shui and oil
Apparent reduction all has occurred in contact angle, and roll angle also significantly increases, and specific experiment data are shown in Table 2.Meanwhile by spraying mist
Water mist after change carries out anti-fog performance detection discovery, and the coating after the husky experiment of leakage of comparative experiments 1 and 2 is sprayed on the wink on surface in water mist
Between, the flood for just beginning with condensation oozes now, and when big water droplet condenses into the droplet of 3~5mm, the surface Cai Huicong is tumbled；As general
Sample is placed in -10 DEG C of environment and finds after atomized water spray, and only persistently atomized water spray 5 minutes, coating surface have just tied one layer significantly
Ice sheet.
The present invention is prepared for comparative example 6 again, and the preparation method of comparative example 6 is will not implement (2) step in the present embodiment 1 to spray
Polyurethane glue-line is applied, the husky experiment of anti-leakage is carried out after the compound particle solution of aluminum alloy surface direct spraying (3) step, solidification.
After the completion of the husky experiment of leakage, it is found that the compound particle coating of aluminum alloy surface is struck off completely, expose aluminium alloy, lose completely
Its ultra-amphosphobic is lost, specific data are shown in Table 2.
The experimental data that shock resistance is tested in 2 embodiment 1 of table
It is found from the detection of 1,2,6 pair of impact resistance of coating of the above comparative example, on the one hand it can jail for polyurethane glue-line
Admittedly be bonded in substrate surface, on the other hand inorganic silicon dioxide particle is bonded with by it securely, plays an intermediate adherent
Effect, the durability of super-amphiphobic coating, stability and sustainable freezing are played a key role；In addition, two
The silicon dioxide granule of kind of partial size is bound to one piece due to intersecting, when the external world is when external force is applied to this coating, big partial size
The power that the nano fumed silica of small particle can be subject to of silicon dioxide granule of sub-micro grade have certain peptizaiton, this
The collective effect of the particle of two kinds of partial sizes, equally also to the durability of super-amphiphobic coating, stability and sustainable freezing
It plays a key role.
By comparative example, to further illustrate that the present embodiment 1 has in super-amphiphobic coating prepared by aluminium alloy plate surface
Good impact resistance and can lasting freezing.
(5) resistance to ultrasonic performance:
Super-amphiphobic aluminium alloy plate sample prepared by the present embodiment 1 is immersed in dehydrated alcohol or acetone, because anhydrous
Ethyl alcohol or acetone have good wellability to coating, and then using clean alliance JP-080S type supersonic wave cleaning machine, (clean alliance, Shenzhen is clear
Wash equipment Co., Ltd) ultrasound 200min, the water contact angle after measuring ultrasound still can reach 158 °, and roll angle is up to 5 °；Glycerol connects
Also 152 ° of feeler, roll angle is up to 6 °.It is resistance to well to illustrate that the present embodiment 1 has in super-amphiphobic coating prepared by aluminium alloy plate surface
Ultrasound.
(6) ageing-resistant performance:
The ageing-resistant performance of super-amphiphobic coating prepared by the present invention is tested by xenon lamp aging instrument, by the present embodiment
Super-amphiphobic coating aluminium alloy plate prepared by 1 is placed in xenon lamp aging instrument, and 38 DEG C, irradiation intensity 0.51W/m at 340nm2, irradiation
After 2000 hours, 2000 hours, coating is without significant change, and water contact angle is up to 159 °, and roll angle is up to 4 °, glycerol contact angle
153 °, 5 ° of glycerol roll angle.It is ageing-resistant well to illustrate that the present embodiment 1 has in super-amphiphobic coating prepared by aluminium alloy plate surface
Performance.
Embodiment 2:
In present embodiment, basis material selects the poplar plate that thickness is about 200*200*15mm, can lasting freezing
The poplar plate preparation method of super-amphiphobic carries out as follows:
(1) poplar plate is cleaned up as substrate with water and clean cotton, later using 200 mesh corundum sands to base
Body surface face carries out sandblasting roughening treatment, air pressure 2.0MPa, blast time 30s；Use acetone, ethyl alcohol and deionized water again later
Substrate surface is successively cleaned, at room temperature dried for standby；
(2) by the monocomponent polyurethane adhesive of 8g, (treasured monocomponent polyurethane adhesive, the new distant view science and technology in Dongguan have when conjunction
Limit company) in 50mL acetone, 35mL toluene, the in the mixed solvent of 15mL ethyl acetate is prepared poly- for ultrasound and stirring and dissolving
Urethane glue；
(3) 2.4g partial size is referred to as the hydrophilic fumed silica of 7~40nm and the dioxy that 1.6g average grain diameter is 500nm
SiClx, stirring and ultrasonic disperse are in the dehydrated alcohol of 100mL, ultrasound 1.5 hours；Three oxygroup silicon of 6g perfluoro decyl is added later
Alkane continues stirring and ultrasound after 1.5 hours, particle composite solution has been prepared；
(4) polyurethane glue will be passed through into spray gun spraying in cottonwood plank stuff substrate surface in (2) step: uses nozzle diameter
The commercial spray gun of 0.5mm, using compressed air as carrier, adjustment spray spot is sector, spray distance 20cm of the nozzle away from substrate, nozzle
Vertical with substrate is in 90 ° of angles, and spray pressure 50psi is constant, is from left to right sprayed to substrate with the speed of 5cm/s；Such as
This is repeated 3 times；Under room temperature after semi-solid preparation 2 hours, semi-solid preparation polyurethane glue-line needed for poplar plate substrate obtains；
(5) use and same spraying technology in step (4), are sprayed at step for the particle composite solution in step (3)
(4) the polyurethane adhesive layer surface of semi-solid preparation repeats spraying 5 times；It is placed 5 hours under room temperature after being fully cured later；
(6) ethyl alcohol or acetone rinsing step (5) obtained substrate surface are used, can be obtained the super-amphiphobic of lasting freezing
Cottonwood plank stuff preparation method.
The present invention detects the performance of cottonwood plank stuff prepared by embodiment 2, specific as follows:
(1) super-hydrophobic and superoleophobic performance:
At room temperature, the water and oil level drop for measuring 5 μ L with micro syringe are in sample surfaces, after standing 5s, using Shanghai
Middle morning digital technology equipment Co., Ltd JC2000C type contact angle measurement measures, and reads the contact angle numerical value of water and oil,
Using the roll angle of tilting plate method measurement coating surface；Test result obtains, the coating to the contact angle of water up to 164 °, roll angle
2°；To the contact angle of glycerol up to 155 degree, 5 ° of roll angle.
(2) freezing performance:
The freezing performance of super-amphiphobic coating passes through homemade apparatus measures: cottonwood plank stuff sample prepared by the present embodiment 2
Product are placed on a platform, and platform is in 30 degree of angle horizontal rest, and platform surface temperature is cooled to -10 DEG C, works as platform
Temperature reach this setting value and stablize after, sprayed in ground by spray gun by the small water droplet (about 0.5mm diameter) after atomization is horizontal
It dissipates in sample coatings surface, persistently sprays 200 minutes.Continue in spraying process it has been observed that when small water droplet is sprayed onto substrate surface
When, moment is walked by bullet, and water droplet is extremely short in the substrate surface residence time；Sample surfaces are hung on its surface without droplet, after 200 minutes
Do not occur icing phenomenon.
The present invention prepares comparative example 7 and comparative example 8, comparative example 7 are by two kinds of partial sizes in (3) step in the present embodiment 2
Silica be changed to that the hydrophilic fumed silica that partial size is 7~40nm is used only, other steps are constant；Finally it is prepared into
Super-amphiphobic cottonwood plank stuff surface.The contact angle of water is measured up to 166 °, 2 ° of roll angle by contact angle measurement；The contact angle of glycerol
156 °, 5 ° of roll angle, it was demonstrated that using only the fumed silica of small particle, super-amphiphobic coating also may be implemented.But by this
Surface carries out freezing performance detection, and for the small water droplet (about 0.5mm diameter) after spraying atomization when substrate surface, small water droplet is first
The big water droplet of about 2mm can be condensed into, can just be tumbled later in substrate surface, which substantially increases water droplets in the stop on surface
Between；It is sprayed after twenty minutes when lasting, a thick layer of ice has just been formed on cottonwood plank stuff surface, illustrates poplar prepared by this comparative example 7
Wood plank surface not freezing.
Comparative example 8 be the silica of two kinds of partial sizes in (3) step in the present embodiment 2 is changed to be using only partial size
500nm's, other steps are constant；Finally it is prepared into super-amphiphobic cottonwood plank stuff surface.Connecing for water is measured by contact angle measurement
Feeler is up to 154 °, 6 ° of roll angle；145 ° of the contact angle of glycerol, 11 ° of roll angle, it was demonstrated that using only the silica of 500nm partial size,
Although may be implemented super-hydrophobic, cannot be achieved superoleophobic.This surface is equally subjected to freezing performance detection, sprays mist
For small water droplet (about 0.5mm diameter) after change when substrate surface, small water droplet can condense into the big water droplet of about 2~5mm first, later
It can just be tumbled in substrate surface, the residence time this also increases water droplet on surface；It is sprayed after five minutes when lasting, poplar plate
A thick layer of ice has just been formed on material surface, illustrates the equally not freezing of cottonwood plank stuff surface prepared by this comparative example 8.
(3) acid-alkali-corrosive-resisting performance:
By super-amphiphobic cottonwood plank stuff sample prepared by the present embodiment 2, it is soaked in the sulfuric acid solution and pH=of pH=1 respectively
In 14 NaOH solution, impregnate 50 hours, the acid resistance and alkali resistance of testing coating.After impregnating 50 hours, coating table is observed
The unabroken sign in face；And the water contact angle and oily contact angle of coating are measured, wherein water contact angle is up to 161 ° after acid resistance test, water
3 ° of roll angle, 154 ° of glycerol contact angle, 6 ° of roll angle；Up to 160 °, 3 ° of water roll angle, glycerol contacts water contact angle after alkali resistance test
154 ° of angle, 6 ° of roll angle.Illustrate that the present embodiment 2 has good acid and alkali-resistance rotten in super-amphiphobic coating prepared by cottonwood plank stuff surface
Corrosion.
(4) shock resistance
The present embodiment 2 is shown in Fig. 7: will lead to using the mechanical property for leaking husky experimental verification cottonwood plank stuff surface super-amphiphobic coating
It crosses sample levels angle at 45 ° to place, a container is put at the height away from sample center 30cm, the partial size of 2kg is placed in container
In 100~300 μm of the grains of sand.The grains of sand are leaked down from container, are collided with the super-amphiphobic coating of inclined sample surfaces, husky speed is leaked
About 1g/s is spent, area about 1cm is collided2.After the grains of sand have all leaked, the sand on cottonwood plank stuff surface is gently washed out with deionized water
Son, the water contact angle for then measuring coating still can reach 159 °, and roll angle is up to 3 °；Also 151 ° of glycerol contact angle, roll angle is up to 6 °.
Illustrate that the present embodiment has good impact resistance in super-amphiphobic coating prepared by cottonwood plank stuff surface；Meanwhile leakage sand being tested
Poplar plate surface afterwards is placed in -10 DEG C of environment to be found after atomized water spray, after continuing spraying 200 minutes in sample surface still without bright
Aobvious icing phenomenon.
(5) ageing-resistant performance:
The ageing-resistant performance of super-amphiphobic coating prepared by the present embodiment 2 is tested by xenon lamp aging instrument, by sample
It is placed in xenon lamp aging instrument, 38 DEG C, irradiation intensity 0.51W/m at 340nm2, irradiation 2000 hours, 2000 hours after, coating without
Significant change, water contact angle is up to 162 °, and roll angle is up to 3 °, 152 ° of glycerol contact angle, 6 ° of glycerol roll angle.Illustrate the present embodiment
2 have good ageing-resistant performance in super-amphiphobic coating prepared by cottonwood plank stuff surface.
Embodiment 3
In present embodiment, basis material selects the corrugated board that thickness is about 200*200*5mm, can lasting freezing
The corrugated board preparation method of super-amphiphobic carries out as follows:
(1) corrugated board is as substrate, with clean cotton wiped clean, for use；
(2) by the monocomponent polyurethane adhesive of 5g, (718 one-component polyurethane adhesive of Great Wall board, Shanghai are finely cultural
Articles Co., Ltd) ultrasound and stirring and dissolving are in 40mL acetone, 40mL dimethylbenzene, the in the mixed solvent of 20mL tert-butyl acetate,
Polyurethane glue is prepared；
(3) 1.1g partial size is referred to as the hydrophilic fumed silica of 7~40nm and the dioxy that 0.9g average grain diameter is 300nm
SiClx, stirring and ultrasonic disperse are in the n-hexane of 100mL, ultrasound 1.5 hours；4g perfluoro capryl trichlorosilane is added later,
Continue stirring and ultrasound after 1.5 hours, particle composite solution has been prepared；
(4) polyurethane glue will be passed through into spray gun spraying in corrugated board substrate surface in (2) step: uses nozzle diameter
The commercial spray gun of 0.5mm, using compressed air as carrier, adjustment spray spot is sector, spray distance 15cm of the nozzle away from substrate, nozzle
Vertical with substrate is in 90 ° of angles, and spray pressure 30psi is constant, is from left to right sprayed to substrate with the speed of 5cm/s；Such as
This is repeated 2 times；Under room temperature after semi-solid preparation 2 hours, semi-solid preparation polyurethane glue-line needed for corrugated board substrate obtains；
(5) use and same spraying technology in step (4), are sprayed at step for the particle composite solution in step (3)
(4) the polyurethane adhesive layer surface of semi-solid preparation repeats spraying 6 times；It is placed 12 hours under room temperature after being fully cured later；
(6) ethyl alcohol or acetone rinsing step (5) obtained substrate surface are used, can be obtained the super-amphiphobic of lasting freezing
Corrugated board.
The present invention detects the performance of the corrugated board of super-amphiphobic prepared by embodiment 3, specific as follows:
(1) super-hydrophobic and superoleophobic performance:
At room temperature, the water and oil level drop for measuring 5 μ L with micro syringe are in sample surfaces, after standing 5s, using Shanghai
Middle morning digital technology equipment Co., Ltd JC2000C type contact angle measurement measures, and reads the contact angle numerical value of water and oil,
Using the roll angle of tilting plate method measurement coating surface；Test result obtains, the coating to the contact angle of water up to 163 °, roll angle
2°；To the contact angle of glycerol up to 156 degree, 4 ° of roll angle.
(2) freezing performance:
The freezing performance of super-amphiphobic coating passes through homemade apparatus measures: corrugated board sample prepared by the present embodiment 3
Product are placed on a platform, and platform is in 30 degree of angle horizontal rest, and platform surface temperature is cooled to -10 DEG C, works as platform
Temperature reach this setting value and stablize after, sprayed in ground by spray gun by the small water droplet (about 0.5mm diameter) after atomization is horizontal
It dissipates in sample coatings surface, persistently sprays 200 minutes.Continue in spraying process it has been observed that when small water droplet is sprayed onto substrate surface
When, moment is walked by bullet, and water droplet is extremely short in the substrate surface residence time；Sample surfaces are hung on its surface without droplet, after 200 minutes
Do not occur icing phenomenon.
The present invention prepares comparative example 9 and comparative example 10, comparative example 9 are by two kinds of partial sizes in (3) step in the present embodiment 3
Silica be changed to that the hydrophilic fumed silica that partial size is 7~40nm is used only, other steps are constant；Finally it is prepared into
Super-amphiphobic corrugated board surface.The contact angle of water is measured up to 164 °, 3 ° of roll angle by contact angle measurement；The contact angle of glycerol
156 °, 4 ° of roll angle, it was demonstrated that using only the fumed silica of small particle, super-amphiphobic coating also may be implemented.But by this
Surface carries out freezing performance detection, and for the small water droplet (about 0.5mm diameter) after spraying atomization when substrate surface, small water droplet is first
The big water droplet of about 2mm can be condensed into, can just be tumbled later in substrate surface, which substantially increases water droplets in the stop on surface
Between；When lasting spray after twenty minutes, a thick layer of ice has just been formed on corrugated board surface, is illustrated prepared by this comparative example 9 watt
Corrugated paper board surface not freezing.
Comparative example 10 be the silica of two kinds of partial sizes in (3) step in the present embodiment is changed to be using only partial size
300nm's, other steps are constant；Finally it is prepared into super-amphiphobic corrugated board surface.Connecing for water is measured by contact angle measurement
Feeler is up to 154 °, 7 ° of roll angle；150 ° of the contact angle of glycerol, 8 ° of roll angle, it was demonstrated that using only the silica of 300nm partial size,
Also super-amphiphobic coating may be implemented.This surface is equally subjected to freezing performance detection, the small water droplet after spraying atomization is (about
0.5mm diameter) when substrate surface, small water droplet can condense into the big water droplet of about 3mm first, can just roll later in substrate surface
It falls, the residence time this also increases water droplet on surface；It is sprayed after five minutes when lasting, thickness has just been formed on corrugated board surface
One layer of thick ice illustrates the equally not freezing of corrugated board surface prepared by this comparative example 10.
(3) shock resistance
The present embodiment 3 is shown in Fig. 7: will lead to using the mechanical property for leaking husky experimental verification corrugated board surface super-amphiphobic coating
It crosses sample levels angle at 45 ° to place, a container is put at the height away from sample center 30cm, the partial size of 2kg is placed in container
In 100~300 μm of the grains of sand.The grains of sand are leaked down from container, are collided with the super-amphiphobic coating of inclined sample surfaces, husky speed is leaked
About 1g/s is spent, area about 1cm is collided2.After the grains of sand have all leaked, the sand on corrugated board surface is gently washed out with deionized water
Son, the water contact angle for then measuring coating still can reach 159 °, and roll angle is up to 4 °；Also 152 ° of glycerol contact angle, roll angle is up to 5 °.
Illustrate that the present embodiment 3 has good impact resistance in the standby super-amphiphobic coating of corrugated cardboard sheet wheat flour.Meanwhile leakage sand being tested
Corrugated board afterwards is placed in -10 DEG C of environment and finds after atomized water spray, after continuing spraying 200 minutes in sample surface still without obviously
Icing phenomenon.
(4) ageing-resistant performance:
The ageing-resistant performance of super-amphiphobic coating prepared by the present embodiment 3 is tested by xenon lamp aging instrument, by sample
It is placed in xenon lamp aging instrument, 38 DEG C, irradiation intensity 0.51W/m at 340nm2, irradiation 2000 hours, 2000 hours after, coating without
Significant change, water contact angle is up to 161 °, and roll angle is up to 3 °, 154 ° of glycerol contact angle, 6 ° of glycerol roll angle.Illustrate the present embodiment
3 have good ageing-resistant performance in the standby super-amphiphobic coating of corrugated cardboard sheet wheat flour.
Embodiment 4
In present embodiment, basis material selects the common brick that thickness is about 2000*100*50mm, can lasting freezing it is super
Double thin common brick preparation methods carry out as follows:
(1) common brick is cleaned up as substrate with water and clean cotton, later using 80 mesh corundum sands to matrix table
Face progress sandblasting roughening treatment, air pressure 1.0MPa, blast time 1 minute；Later again with acetone, ethyl alcohol and deionized water according to
Secondary cleaning substrate surface, at room temperature dried for standby；
(2) by the monocomponent polyurethane adhesive of 5g (MPU-20 type one-component polyurethane adhesive, the bonding of Jingjiang City's special type
Agent Co., Ltd) ultrasound and stirring and dissolving are in 50mL acetone, 30mL dimethylbenzene, the in the mixed solvent of 20mL tert-butyl acetate, system
It is standby to obtain polyurethane glue；
(3) 2g partial size is referred to as the hydrophilic fumed silica of 7~40nm and the titanium dioxide that 2g average grain diameter is 200nm
Silicon, stirring and ultrasonic disperse are in the acetone of 100mL, ultrasound 1 hour；6g perfluoro capryl triethoxysilane is added later, after
Simultaneously particle composite solution has been prepared after 1 hour in ultrasound for continuous stirring；
(4) polyurethane glue will be passed through into spray gun spraying in common brick substrate surface in (2) step: uses nozzle diameter
The commercial spray gun of 0.5mm, using compressed air as carrier, adjustment spray spot is sector, spray distance 15cm of the nozzle away from substrate, nozzle
Vertical with substrate is in 90 ° of angles, and spray pressure 30psi is constant, is from left to right sprayed to substrate with the speed of 5cm/s；Such as
This is repeated 2 times；, semi-solid preparation 1 hour under room temperature, common brick substrate obtain needed for semi-solid preparation polyurethane glue-line；
(5) use and same spraying technology in step (4), are sprayed at step for the particle composite solution in step (3)
(4) the polyurethane adhesive layer surface of semi-solid preparation repeats spraying 5 times；It is placed 10 hours under room temperature after being fully cured later；
(6) ethyl alcohol or acetone rinsing step (5) obtained substrate surface are used, can be obtained the super-amphiphobic of lasting freezing
The preparation method of common brick plate.
The present invention examines the performance of the super-amphiphobic common brick plate of available lasting freezing prepared by embodiment 4
It surveys, specific as follows:
(1) super-hydrophobic and superoleophobic performance:
At room temperature, the water and oil level drop for measuring 5 μ L with micro syringe are in sample surfaces, after standing 5s, using Shanghai
Middle morning digital technology equipment Co., Ltd JC2000C type contact angle measurement measures, and reads the contact angle numerical value of water and oil,
Using the roll angle of tilting plate method measurement coating surface；Test result obtains, the coating to the contact angle of water up to 163 °, roll angle
4°；To the contact angle of glycerol up to 157 °, 4 ° of roll angle.
(2) freezing performance:
The freezing performance of super-amphiphobic coating passes through homemade apparatus measures: common brick sample quilt prepared by the present embodiment 4
It is placed on a platform, platform is in 30 degree of angle horizontal rest, platform surface temperature is cooled to -10 DEG C, when the temperature of platform
After degree reaches this setting value and stablizes, by spray gun by the small water droplet (about 0.5mm diameter) after atomization it is horizontal in ground send forth in
Sample coatings surface persistently sprays 200 minutes.In lasting spraying process it has been observed that when small water droplet is sprayed onto substrate surface, wink
Between walked by bullet, water droplet is extremely short in the substrate surface residence time；Sample surfaces are hung on its surface without droplet, do not go out after 200 minutes
Existing icing phenomenon.
The present invention prepares comparative example 11 and comparative example 12, comparative example 11 are by two kinds of grains in (3) step in the present embodiment 4
The silica of diameter is changed to that the hydrophilic fumed silica that partial size is 7~40nm is used only, and other steps are constant；Final preparation
Obtain super-amphiphobic common brick surface.The contact angle of water is measured up to 165 °, 2 ° of roll angle by contact angle measurement；The contact angle of glycerol
157 °, 4 ° of roll angle, it was demonstrated that using only the fumed silica of small particle, super-amphiphobic coating also may be implemented.But by this
Surface carries out freezing performance detection, and for the small water droplet (about 0.5mm diameter) after spraying atomization when substrate surface, small water droplet is first
The big water droplet of about 2mm can be condensed into, can just be tumbled later in substrate surface, which substantially increases water droplets in the stop on surface
Between；It is sprayed after twenty minutes when lasting, common brick substrate surface has just formed a thick layer of ice, illustrates common brick prepared by comparative example 11
Substrate surface not freezing.
Comparative example 12 be the silica of two kinds of partial sizes in (3) step in the present embodiment 4 is changed to be using only partial size
200nm's, other steps are constant；Finally it is prepared into super-amphiphobic common brick surface.The contact angle of water is measured by contact angle measurement
Up to 152 °, 6 ° of roll angle；150 ° of the contact angle of glycerol, 8 ° of roll angle, it was demonstrated that, can also using only the silica of 200nm partial size
To realize super-amphiphobic coating.This surface is equally subjected to freezing performance detection, small water droplet (the about 0.5mm after spraying atomization
Diameter) when substrate surface, small water droplet can condense into the big water droplet of about 3mm first, can just tumble later in substrate surface, in this way
Water droplet is also increased in the residence time on surface；It is sprayed after five minutes when lasting, common brick substrate surface has just been formed a thick layer of
Ice illustrates the equally not freezing of common brick substrate surface prepared by this comparative example 12.
(3) acid-alkali-corrosive-resisting performance:
By super-amphiphobic common brick board samples (whole faces all spray) prepared by the present embodiment 4, it is soaked in pH=1's respectively
In the NaOH solution of sulfuric acid solution and pH=14, impregnate 50 hours, the acid resistance and alkali resistance of testing coating.It impregnates 50 hours
Afterwards, the unabroken sign of coating surface is observed；And the water contact angle and oily contact angle of coating are measured, wherein water after acid resistance test
Contact angle is up to 162 °, 3 ° of water roll angle, 155 ° of glycerol contact angle, 5 ° of roll angle；Up to 161 °, water rolls water contact angle after alkali resistance test
Dynamic 4 ° of angle, 154 ° of glycerol contact angle, 5 ° of roll angle.Illustrate the super-amphiphobic coating tool that the present embodiment 4 is prepared in common brick substrate surface
There is good acid-alkali-corrosive-resisting.
(4) shock resistance
The present embodiment 4 is shown in Fig. 7: will lead to using the mechanical property for leaking husky experimental verification common brick plate surface super-amphiphobic coating
It crosses sample levels angle at 45 ° to place, a container is put at the height away from sample center 30cm, the partial size of 2kg is placed in container
In 100~300 μm of the grains of sand.The grains of sand are leaked down from container, are collided with the super-amphiphobic coating of inclined sample surfaces, husky speed is leaked
About 1g/s is spent, area about 1cm is collided2.After the grains of sand have all leaked, the sand on common brick surface is gently washed out with deionized water, so
The water contact angle for measuring coating afterwards still can reach 160 °, and roll angle is up to 5 °；Also 153 ° of glycerol contact angle, roll angle is up to 6 °.Explanation
The present embodiment 4 has good impact resistance in super-amphiphobic coating prepared by common brick substrate surface.Meanwhile it will be after the husky experiment of leakage
Common brick is placed in -10 DEG C of environment and finds after atomized water spray, and surface still shows without obvious freeze in sample after continuing spraying 200 minutes
As.
(5) resistance to ultrasonic performance:
Super-amphiphobic common brick sample prepared by the present embodiment 4 is immersed in dehydrated alcohol or acetone, because of dehydrated alcohol
Or acetone has good wellability to coating, then using clean alliance JP-080S type supersonic wave cleaning machine, (the clean alliance's cleaning in Shenzhen is set
Standby Co., Ltd) ultrasound 200min, the water contact angle after measuring ultrasound still can reach 160 °, and roll angle is up to 5 °；Glycerol contact angle
Also 153 °, roll angle is up to 6 °.Illustrate that the present embodiment 4 has good resistance to ultrasound in super-amphiphobic coating prepared by common brick surface.
(6) ageing-resistant performance:
The ageing-resistant performance of super-amphiphobic coating prepared by the present invention is tested by xenon lamp aging instrument, and sample is placed in
In xenon lamp aging instrument, 38 DEG C, irradiation intensity 0.51W/m at 340nm2, after irradiation 2000 hours, 2000 hours, coating is without obvious
Variation, water contact angle is up to 161 °, and roll angle is up to 4 °, 154 ° of glycerol contact angle, 5 ° of glycerol roll angle.Illustrate that the present embodiment 4 exists
The super-amphiphobic coating of common brick substrate surface preparation has good ageing-resistant performance.
In conclusion the present invention provides a kind of preparation method of the super-amphiphobic coating of sprayable and lasting freezing, this
The super-amphiphobic coating that invention is prepared in each substrate surface, because the contact angle of itself and water, glycerol, edible oil, crude oil etc. be greater than 150 °,
Roll angle is less than 10 °, so as to make substrate have excellent super-hydrophobic and superoleophobic performance and good self-cleaning performance；
The present invention, which prepares ground super-hydrophobic coat in each substrate surface, has good durability and fastness, and the resistive connection that having can be lasting
Ice performance；The super-amphiphobic coating of sprayable and lasting freezing prepared by the present invention, ageing-resistant and acid-alkali-corrosive-resisting performance are excellent
It is different, and it is amenable to certain shock resistance；After placing year in natural environment, appearance, the color of coating change without apparent,
And it remains to protect excellent ultra-amphosphobic and freezing；The sprayable and durable super-amphiphobic coating of the present invention can be in outdoor
The overwhelming majority such as the wing of the aircraft wing, wind-driven generator that fly in the high electric wire hung in the air, cloud layer need to prevent from freezing
Surface applied.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.
Claims (2)
1. a kind of preparation method of the super-amphiphobic coating of sprayable and lasting freezing, which is characterized in that specifically include following step
It is rapid:
Step 1 carries out cleaning and sandblasting roughening treatment, the substrate handled well to substrate surface；
Step 2 obtains polyurethane solutions after being blended using polyurethane with the first solvent；
Step 3 disperses submicron particle, nanoparticle in the second solvent, and after ultrasonic and stirring, addition silicon fluoride continues to surpass
Sound and stirring have obtained particle composite suspension liquid；
Step 4 is dried by the processed substrate surface of the resulting polyurethane solutions spraying process 1 of step 2, then by the substrate, right
Polyurethane adhesive carries out semi-solid preparation；
The resulting particle composite suspension liquid of step 3 is sprayed to the obtained substrate surface of step 4, then the substrate is dried by step 5
It is dry to be fully cured；
Step 6 is rinsed the obtained substrate surface of step 5, and the super-amphiphobic of sprayable and lasting freezing can be obtained
Coating；
In the step 1, described to carry out cleaning to substrate surface successively cleaned using acetone, deionized water, ethyl alcohol；The step
In rapid 1, the technological parameter of sandblasting roughening treatment are as follows: 0.5~1.0MPa of air pressure, blast time 10 seconds~1 minute, sandblasting was used
40~200 mesh of sand ball mesh number；
In the step 2, polyurethane is one-part solvent type polyurethane；First solvent is toluene, dimethylbenzene, acetone, first
Ethyl ketone, butanone, ethyl acetate, n-butyl acetate, tert-butyl acetate one or more mixed solvents, the polyurethane and first
The mass ratio of solvent is (4~10): 100；
In the step 3, the second solvent is dispersed by submicron particle, nanoparticle, and ultrasound and after stirring 1~3 hour is added
Silicon fluoride continues ultrasound and stirring 1~3 hour, has obtained particle composite suspension liquid；Substrate is placed in 25 in the step 4~
Dry 0.5~2h carries out semi-solid preparation at 80 DEG C；In the step 5 by substrate temperature be 25~80 DEG C at drying 0.5~for 24 hours into
Row is fully cured；
The submicron particle is the silicon dioxide granule of 200~500nm of partial size；The nanoparticle is 7~40nm of partial size
Hydrophilic fumed silica particle；Second solvent be acetone, ethyl alcohol, n-hexane, methyl acetate, carbon tetrachloride one
Kind or a variety of mixed solvents；
This for the sub-micro grade silicon dioxide that the fumed silica and partial size that the partial size is 7~40nm are 200~500nm is proper
When ratio control is 1~0.5:0.5~0.1；
The silicon fluoride is that carbon chain lengths are greater than 4, and end group is one kind or more of the perfluor silane of methoxyl group, ethyoxyl or chloro
Kind；In the step 3, total mass ratio of the silicon fluoride and submicron particle, nanoparticle is greater than 1:1；
It in the step 4 and step 5, is sprayed using spray gun, the spray gun is the commercial spray gun of 0.5~2mm of diameter, with pressure
Contracting air is carrier, and adjustment spray spot is sector, and spray distance 10~20cm of the nozzle away from substrate, nozzle and base material is vertically in 90 °
Angle is successively sprayed with the speed of 2~5cm/s from left to right, 30~100psi of spray pressure, repeats spraying 2~5 to substrate
It is secondary.
2. one kind according to claim 1 is sprayable and the preparation method of the super-amphiphobic coating of lasting freezing prepared by
Super-amphiphobic coating, which is characterized in that raw material mainly includes polyurethane solutions and particle composite suspension liquid, the polyurethane solutions packet
4~10 parts of polyurethane, 100 parts of the first solvent are included, the particle composite suspension liquid includes 1~3 part of submicron particle, nanoparticle
1~3 part, 2~10 parts of silicon fluoride, 100 parts of the second solvent.
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| CN108299880A (en) * | 2018-02-11 | 2018-07-20 | 东南大学 | A kind of aqueous super-amphiphobic coating and its preparation method and application |
| CN108504284B (en) * | 2018-04-18 | 2021-08-10 | 北京中科东亚纳米材料科技有限公司 | Preparation method of nano super-hydrophobic material |
| CN108912371B (en) * | 2018-05-23 | 2021-01-12 | 陕西科技大学 | Solvent-free hydrophobic self-repairing polyurethane coating and preparation method thereof |
| CN108676482B (en) * | 2018-05-25 | 2020-07-07 | 新冶高科技集团有限公司 | Self-repairing coating and preparation method thereof |
| CN109251345A (en) * | 2018-07-24 | 2019-01-22 | 华南理工大学 | A kind of super hydrophilic or super-hydrophobic frosting of durability and preparation method thereof |
| CN109370408B (en) * | 2018-10-11 | 2021-02-09 | 河北工业大学 | Method for preparing super-hydrophobic coating by compounding waterborne polyurethane and hydrophobic modified inorganic nanoparticles |
| CN111229565A (en) * | 2018-11-29 | 2020-06-05 | 南京理工大学 | Preparation method of magnetic super-hydrophobic surface |
| CN109746172A (en) * | 2019-01-29 | 2019-05-14 | 南京航空航天大学 | A kind of preparation method of the ice-covering-proof/anticorrosion integrated function super-hydrophobic coat of aviation |
| CN109929285B (en) * | 2019-03-13 | 2021-01-26 | 广东美的制冷设备有限公司 | Composite material and preparation method and application thereof |
| CN110144135A (en) * | 2019-05-22 | 2019-08-20 | 苏州清飙科技有限公司 | A kind of super-amphiphobic coating material and preparation method thereof and super-amphiphobic coating |
| CN112625591B (en) * | 2020-10-20 | 2022-02-11 | 兰州理工大学 | High-stability multifunctional conductive super-hydrophobic anticorrosive coating, preparation method and application |
| CN112812676A (en) * | 2021-02-04 | 2021-05-18 | 西北大学 | Super-amphiphobic acid-resistant coating 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 |
| CN116493217B (en) * | 2023-04-27 | 2024-01-26 | 南京工程学院 | Composite anti-icing coating and preparation method thereof |
| CN116426215A (en) * | 2023-04-28 | 2023-07-14 | 中国南方电网有限责任公司超高压输电公司大理局 | Composite coating, preparation method thereof, silicone rubber protective sleeve and insulator |
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