CN107116017A - It is a kind of can the lasting super-amphiphobic coating of freezing preparation method - Google Patents
It is a kind of can the lasting super-amphiphobic coating of freezing preparation method Download PDFInfo
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- CN107116017A CN107116017A CN201710263704.1A CN201710263704A CN107116017A CN 107116017 A CN107116017 A CN 107116017A CN 201710263704 A CN201710263704 A CN 201710263704A CN 107116017 A CN107116017 A CN 107116017A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/544—No clear coat specified the first layer is let to dry at least partially before applying the second layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2504/00—Epoxy polymers
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Abstract
The present invention relates to super-hydrophobic or super-amphiphobic coating preparation field, more particularly to it is a kind of can the lasting super-amphiphobic coating of freezing preparation method, specifically include：Step 1, substrate surface is cleaned and sandblasting roughening treatment；Step 2, epoxy resin, epoxy curing agent and the first solvent are blended after obtain epoxy resin solution；Step 3, submicron particle, nano-particle be scattered in the second solvent, add silicon fluoride, obtain particle composite suspension liquid；Step 4, the substrate surface for treating the epoxy resin solution spraying process 1 obtained by step 2, semi-solid preparation is carried out to epoxide-resin glue；Step 5, the substrate surface for spraying to the particle composite suspension liquid obtained by step 3 obtained by step 4, are fully cured；Step 6, obtain can lasting freezing super-amphiphobic coating.Beneficial effects of the present invention are：Preparing ground super-amphiphobic coating in each substrate surface has a good durability and fastness, and with can be lasting freezing performance.
Description
Technical field
The present invention relates to super-hydrophobic or super-amphiphobic coating preparation field, more particularly to it is a kind of can lasting freezing super-amphiphobic
The preparation method of coating.
Background technology
Surface wettability is one of key character of the surface of solids, and wetability can be weighed with the contact angle of water on surface
Amount；Super hydrophobic surface is because its contact angle to water is more than 150 °, roll angle is less than 10 °, and causes with self-cleaning characteristic
Academia and the great interest of industrial quarters.In nature, the leaf and petal of many plants, the wing of insect and birds
Feather etc. be natural super hydrophobic material.The self-cleaning function of super hydrophobic surface, i.e. surface contaminant such as dust etc. can be with
The water droplet tumbled is taken away without leaving any vestige.Automatic cleaning coating has the advantage such as water saving, energy-saving and environmental protection, increasingly by
It is one of focus of current material subject research to the extensive concern of people.
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
The different degrees of loss that evil is caused to transmission of electricity telecommunication circuit, aviation, navigation or high ferro transport, more makes people increase to super thin
Water or ice-covering-proof and freezing the research dynamics of super-double-hydrophobic surface.In actual environment, in such as high electric wire hung in the air, cloud layer
The aircraft wing of flight, wing of wind-driven generator etc., in the case where meeting with low temperature and big humidity, often surface is easily tied
Ice, so as to cause great economic loss.Therefore, strengthening can be in terms of freezing to the super-hydrophobic or ultra-amphosphobic of the surface of solids
Correlative study be just particularly important.
An important application of super-hydrophobic technology is exactly freezing frosting compared with traditional ice-melt and de-icing method, that is, is prolonged
Late, reduction even prevents frost in solids bulk completely, can preferably solve problem.Had shown that by substantial amounts of research, surface
Super-hydrophobicization reduce adhesion strength of the ice on surface.But nearest research shows again, prepared by major part super-hydrophobic
Or super-double-hydrophobic surface can not lasting freezing：Especially when super hydrophobic surface runs into, environment temperature is extremely low and the very big situation of humidity
When super hydrophobic surface freezing situation be not it is highly desirable, sometimes even its surface once freeze be more difficult to remove.
Based on above mentioned problem, the invention provides it is a kind of can the lasting super-amphiphobic coating of freezing preparation method, this hair
The bright super-amphiphobic coating prepared be able to can still transport under low temperature, big humidity environment, and realize super-amphiphobic coating can be persistently
Freezing performance.
The content of the invention
The invention provides it is a kind of can the lasting super-amphiphobic coating of freezing preparation method, by using subbing and
Investment precoat carries out super-amphiphobic coating preparation, and effectively increase under low temperature, the big humidity environment surface of solids can lasting resistive connection
Ice performance, while keeping the ultra-amphosphobic energy of the surface of solids.
The purpose of the present invention is mainly achieved through the following technical solutions：
It is a kind of can the lasting super-amphiphobic coating of freezing preparation method, specifically include following steps：
Step 1, substrate surface is cleaned and sandblasting roughening treatment, the base material handled well；
Step 2, epoxy resin, curing agent and the first solvent are blended after obtain epoxy resin solution；
Step 3, submicron particle, nano-particle be scattered in the second solvent, after ultrasound and stirring, add silicon fluoride, after
Continuous ultrasound and stirring, have obtained particle composite suspension liquid；
Step 4, the substrate surface for treating the epoxy resin solution spraying process 1 obtained by step 2, then the base material is done
It is dry, semi-solid preparation is carried out to epoxide-resin glue；
Step 5, the substrate surface for spraying to the particle composite suspension liquid obtained by step 3 obtained by step 4, then by the base
Material drying is fully cured；
Step 6, the substrate surface obtained by step 5 is rinsed, you can obtain can the super-amphiphobic of lasting freezing apply
Layer.
Further, in the step 1, the base material be plane, the silicon chip of curved surface or irregular shape, metal, glass,
Plastics, timber or stone material；Described to substrate surface progress cleaning is cleaned successively using acetone, deionized water, ethanol.
Preparation method in the present invention is not influenceed by the shape, size and species of base material, is also not limited to above-mentioned base material,
Meanwhile, metal base can be iron, aluminium or aluminium alloy, but be not limited only to that this is several, and glass baseplate can be quartz or common glass
Glass；Base material of the present invention can be cardboard, and cardboard only needs to scouring.
Further, in the step 1, the technological parameter of sandblasting roughening treatment is：0.5~1.0MPa of air pressure, spray
10 seconds~1 minute sand time, the mesh of sand blasting-used sand ball mesh number 40~200.
The present invention carries out matrix surface to sandblast roughening treatment, can increase the roughness of matrix surface, improve coating with
The bond strength of matrix, and then improve the fastness and durability on super-amphiphobic coating surface.
Further, in the step 2, the mass ratio of the epoxy resin, curing agent and the first solvent for (4~
10)：(2~10)：100.
Further, the epoxy resin is in bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy resin
One or more；The curing agent is alicyclic ring amine hardener；First solvent be toluene, dimethylbenzene, acetone, MEK,
Butanone, ethyl acetate, n-butyl acetate, one or more mixed solvents of tert-butyl acetate.
In order to construct super-hydrophobic or super-double-hydrophobic surface in smooth surface, conventional method is by inorganic nano-particle at present
It is blended with fluoropolymer or is fluorinated nano-particle, it is super so as to build that the nano-particle after fluorination then is coated onto into material surface
Hydrophobic or super-double-hydrophobic surface.It is difficult Nian Jie by chemical bond in these methods, between polymer and inorganic particulate and substrate
Together, only by physisorption, bonding force is not strong, so as to cause constructed super-hydrophobic or super-double-hydrophobic surface to exist
Insecure, rub resistance, washing fastness be not strong.The present invention carries out super-amphiphobic coating preparation using subbing and investment precoat, its
In, subbing uses bi-component epoxide-resin, and epoxy resin has the function of all-purpose adhesive, and on the one hand it can be strongly adhered to
Substrate surface, inorganic silicon dioxide particle is bonded with another aspect by it securely, plays adherent in the middle of one, is realized
The constructing of coarse structure needed for super-amphiphobic, so that constructed super-amphiphobic coating has good durability and firmly
Property, while having freezing performance that can be lasting.
Further, in the step 3, submicron particle, nano-particle are scattered in the second solvent, ultrasound and stirring 1
After~3 hours, silicon fluoride is added, continues ultrasound and stirs 1~3 hour, obtained particle composite suspension liquid；In the step 4
Base material is placed at 25~80 DEG C and dries 0.5~2h progress semi-solid preparations；In the step 5 by base material in the case where temperature is 25~80 DEG C
0.5~24h of drying is fully cured.
Further, the submicron particle is 200~500nm of particle diameter silicon dioxide granule；The nano-particle is
7~40nm of particle diameter hydrophilic aerosil particle, second solvent be acetone, ethanol, n-hexane, methyl acetate,
One or more mixed solvents of carbon tetrachloride.
The aerosil particle of the silica of 200~500nm sub-micros level and 7~40nm is scattered in the present invention
In surface layer solution, the coarse micro-nano structure of fine binary is formd in substrate surface and epoxy resin layer surface after spraying；Work as painting
When layer only has small particle-size silica, the external world is when external force puts on this coating, and small particle-size silica is easy to be rushed by external force
Dissipate, so as to lose ultra-amphosphobic energy；When the silica using only big particle diameter, coating surface, which does not reach, realizes the micro- of super-amphiphobic
Fine structure is received, so that the super-amphiphobic of substrate surface can not be realized；The present invention by the silicon dioxide granules of two kinds of particle diameters due to
Intersect and be bound to one piece, when the external world puts on this coating in external force, the silicon dioxide granule meeting of the sub-micro level of big particle diameter
The power that nano fumed silica to small particle is subject to has certain peptizaiton, therefore this structure can improve the resistance to of coating
Long property and firm performance, so as to extend the service life of coating.
Further, the mass ratio of the submicron particle, nano-particle, silicon fluoride and the second solvent is (1~3)：
(1~3)：(2~10)：100.
It is preferred that, the mass ratio of the nano-particle and submicron particle is (1~0.5)：(0.5~0.1).
The sub-micro grade silicon dioxide for be 7~40nm aerosils being 200~500nm with particle diameter by particle diameter in the present invention
Control be (1~0.5)：(0.5~0.1), prepared super-amphiphobic coating has spy that is super-hydrophobic, not sticking to water smoke
Property.When the water smoke after atomization continuously is sprayed on into sample surfaces with spray gun, in the case of this big humidity, water smoke to coating table
Small water droplet on face, which rapid can be rolled or bounced from coating, to be left, and will not be condensed into big drop, so as to realize coating surface
Antifog effect；It is placed on when that will apply in subzero 10 DEG C of low temperature environment, the water smoke after atomization is sprayed on coating by continuation with spray gun
During surface, the small water droplet on water smoke to coating surface remains to roll or bounce from coating rapidly to leave, and is not condensed into big liquid
Drop, after persistently spraying 200 minutes, there is not icing phenomenon in coating surface, and final coating has reached the effect and performance of freezing.
Further, the silicon fluoride is that carbon chain lengths are more than 4, and end group is the perfluor of methoxyl group, ethyoxyl or chloro
The one or more of silane.
It is preferred that, the silicon fluoride is perfluoro decyl trimethoxy silane, perfluoro decyl triethoxysilane, perfluoro decyl
Trichlorosilane, perfluoro capryl trimethoxy silane, perfluoro capryl triethoxysilane, one kind of perfluoro capryl trichlorosilane or many
Kind.
Further, in the step 3, total mass ratio of the silicon fluoride and two kinds of particle diameter silica is greater than 1：
1。
Ratio control of the present invention to silicon fluoride has total matter of strict requirements, silicon fluoride and two kinds of particle diameter silica
Amount ratio is greater than 1：1, under this ratio, silicon fluoride by silica surface except that can be grafted full chain hydrophobic lipophobic group completely
Group, can also be remaining a part of among solvent；When carrying out surface spraying to silicon dioxide granule composite suspension liquid, remained in solvent
Remaining silicon fluoride will carry out condensation reaction with the epoxy radicals of the epoxy resin layer of the semi-solid preparation sprayed before, so as to reduce
The surface of epoxy resin layer can be simultaneously, moreover it is possible to which the fluorin radical with silica particle surface is common in substrate surface one layer of fluorine of formation
Change film, and then further improve the persistence of the durability, fastness and freezing on super-amphiphobic coating surface.
Further, in the step 4 and step 5, 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 for sector, spray distance 10~20cm of the nozzle away from base material, nozzle with
Base material vertically in 90 ° of angles, is sprayed, 30~100psi of spray pressure, to base material successively with 2~5cm/s speed from left to right
Repeat spraying 2~5 times.
Further, ethanol or acetone rinsing are used in the step 6.
A kind of super-amphiphobic coating that can persistently prepared by the preparation method of the super-amphiphobic coating of freezing, raw material mainly includes
Epoxy resin solution and particle composite suspension liquid, the epoxy resin solution include 4~10 parts of epoxy resin, curing agent 2~10
Part, 100 parts of the first solvent；The particle composite suspension liquid includes 1~3 part of submicron particle, 1~3 part of nano-particle, silicon fluoride
2~10 parts, 100 parts of the second solvent.
The present invention has the beneficial effect that：
(1) super-amphiphobic coating that the present invention is prepared in each substrate surface, because of its connecing with water, glycerine, edible oil, crude oil etc.
Feeler is less than 10 ° more than 150 °, roll angle, so as to enable base material to have excellent super-hydrophobic and superoleophobic ultra-amphosphobic,
And good self-cleaning performance.
(2) present invention prepares ground super-amphiphobic coating in each substrate surface has good durability and fastness, and has
Freezing performance that can be lasting.
(3) prepared by the present invention can lasting freezing super-amphiphobic coating, it is ageing-resistant with acid-alkali-corrosive-resisting excellent performance, and
It is amenable to certain shock resistance；After being placed 1 year in natural environment, outward appearance, the color of coating change without obvious, and
Remain to protect excellent ultra-amphosphobic and freezing.
(4) present invention can flight in electric wire that persistently freezing super-amphiphobic coating can be hung in outdoor overhead, cloud layer
The overwhelming majority such as aircraft wing, the wing of wind-driven generator need to prevent that the surface frozen from being applied.
(5) technical grade reagent can be used in all reagents used in the present invention, the method operating procedure letter used
It is single, general commercial raw material are subjected to simple dilution and disperseed, is sprayed on base material, just can be directly obtained successively by spraying technology
Needed for coating, cost is low, environmental protection, without complicated process step, without expensive instrument and equipment, it is adaptable to phase
The preparation that substrate surface carries out high-volume super-amphiphobic coating is closed, the application prospect with heavy industrialization can be created great
Economic benefit.
Brief description of the drawings
Fig. 1 is the super-amphiphobic aluminum alloy surface of the embodiment of the present invention 1 to water and the super-hydrophobic superoleophobic macro-effect figure of oil.
Fig. 2 is the super-amphiphobic poplar plate surface of the embodiment of the present invention 2 to water and the super-hydrophobic superoleophobic macro-effect figure of oil.
Fig. 3 faces the super-hydrophobic superoleophobic macro-effect of water and oil for the super-amphiphobic corrugated cardboard sheet of the embodiment of the present invention 3
Figure.
Fig. 4 is the super-amphiphobic common brick surface of the embodiment of the present invention 4 to water and the super-hydrophobic superoleophobic macro-effect figure of oil.
Fig. 5 is the super-amphiphobic aluminum alloy surface coating of the embodiment of the present invention 1 and the contact angle test chart 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 chart of glycerine.
Fig. 7 tests schematic diagram to leak sand in 1-4 of embodiment of the present invention super-amphiphobic coating shock resistance detection.
In figure, 1- water, 2- soybean oils, 3- glycerine, 4- hydraulic oil, the 5- grains of sand fall to flowing, and 6- super-amphiphobic coatings, the 7- grains of sand are received
Storage, 8- grains of sand collector is highly 30cm away from super-amphiphobic coating.
Embodiment
The preferred embodiments of the present invention are specifically described below in conjunction with the accompanying drawings, wherein, accompanying drawing constitutes the application part, and
It is used for the principle for explaining the present invention together with embodiments of the present invention.
Embodiment 1
In present embodiment, the aluminium alloy plate that matrix material selection thickness is about 200*200*3mm, the aluminium alloy plate can be with
The type of Shanghai Zhi Xin Trade Co., Ltd.s -2014, can the aluminium alloy plate preparation method of the lasting super-amphiphobic of freezing be by as follows
What step was carried out：
(1) aluminium alloy plate is cleaned up as base material with water and clean cotton, afterwards using 80 mesh corundum sands to base
Body surface face carries out sandblasting roughening treatment, air pressure 0.5MPa, blast time 1 minute；Use acetone, ethanol and deionization again afterwards
Water cleans substrate surface successively, at room temperature dried for standby；
(2) by 5g epoxy resin (Xingchen Synthetic Matrials Co., Ltd., Nantong, Phoenix brand, epoxy resin (E-44)), 5g
Simultaneously stirring and dissolving is in 50mL acetone for alicyclic ring amine hardener ultrasound, and 30mL dimethylbenzene, the in the mixed solvent of 20mL tert-butyl acetates is made
It is standby to obtain epoxy resin adhesive liquid；
(3) the hydrophilic aerosil that 3g particle diameters are 7~40nm and the titanium dioxide that 3g average grain diameters are 200nm are weighed
Silicon, stirring and ultrasonic disperse are in 100mL acetone, ultrasound 1 hour；8g perfluoro decyl trichlorosilanes are added afterwards, continue to stir
Mix and ultrasound is after 1 hour, prepared particle composite solution；
(4) by the epoxy resin adhesive liquid prepared in (2) step by spray gun spraying in aluminium alloy plate substrate surface：Use
Nozzle diameter 0.5mm commercial spray gun, using compressed air as carrier, adjustment spray spot is sector, spray distance of the nozzle away from base material
15cm, nozzle is vertical with base material in 90 ° of angles, and spray pressure 30psi is constant, and from left to right base material is entered with 5cm/s speed
Row spraying；So it is repeated 2 times；Semi-solid preparation 1 hour under normal temperature, aluminium alloy plate base material obtains required semi-solid preparation epoxide-resin glue
Layer；
(5) use and spraying technology same in step (4), step is sprayed at by the particle composite solution in step (3)
(4) the epoxide-resin glue layer surface of semi-solid preparation, repeats spraying 3 times；Place and be fully cured under normal temperature afterwards for 5 hours；
(6) with the substrate surface obtained by ethanol or acetone rinsing step (5), you can obtain the super-amphiphobic of lasting freezing
Aluminium alloy plate.
Meanwhile, the present invention is detected to the performance of prepared super-amphiphobic aluminium alloy plate：
(1) super-hydrophobic and superoleophobic performance is detected：
At room temperature, the water and oil level that 5 μ L are measured with micro syringe are dripped in sample surfaces, are stood after 5s, using Shanghai
Middle morning digital technology equipment Co., Ltd JC2000C type contact angle measurements are measured, and read the contact angle numerical value of water and oil,
The roll angle of coating surface is measured using tilting plate method；Test result draws, the coating is to the contact angle of water up to 161 °, roll angle
3°；To the contact angle of glycerine up to 154 °, 5 ° of roll angle.
(2) freezing performance is detected：
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 into -10 DEG C, works as platform
Temperature reach this setting value and it is stable after, small water droplet (the about 0.5mm diameters) level after atomization is sprayed in ground by spray gun
Dissipate in sample coatings surface, persistently spray 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, and experimental data is shown in Table 1, and comparative example 1 is
The silica of two kinds of particle diameters in (3) step in the present embodiment 1 is changed to the hydrophilic gas phase that particle diameter 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 166 °, 2 ° of roll angle；158 ° of the contact angle of glycerine, 4 ° of roll angle, it was demonstrated that using only the aerosil of small particle,
Super-amphiphobic coating can also be realized；But this surface is subjected to freezing performance detection, the small water droplet after spraying atomization is (about
0.5mm diameters) when substrate surface, small water droplet can condense into about 2mm big water droplet first, can just be rolled afterwards in substrate surface
Fall, which substantially increases water droplet surface residence time；After lasting spray 20 minutes, aluminium alloy plate surface has just been formed thick
One layer of ice, illustrate aluminium alloy plate surface prepared by this comparative example 1 not freezing.
Comparative example 2 be the silica of two kinds of particle diameters in (3) step in the present embodiment 1 is changed to be using only particle diameter
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 154 °, 6 ° of roll angle；150 ° of the contact angle of glycerine, 8 ° of roll angle, it was demonstrated that using only the silica of 200nm particle diameters,
Super-amphiphobic coating can also be realized.Same that this surface is carried out into freezing performance detection, the small water droplet after spraying atomization is (about
0.5mm diameters) when substrate surface, small water droplet can condense into about 3mm big water droplet first, can just be rolled afterwards in substrate surface
Fall, this also increases water droplet surface residence time；After lasting spray 5 minutes, thickness has just been formed on aluminium alloy plate surface
One layer of thick ice, illustrates aluminium alloy plate surface prepared by this comparative example 2 equally not freezing.
And 3~comparative example of comparative example 5 is by changing 7~40nm hydrophilic aerosil and 200nm particle diameters
The mass ratio of silica is tested, and is specifically shown in Table 1.
The experimental data of freezing performance test in the embodiment 1 of table 1
(3) acid-alkali-corrosive-resisting performance detection：
By the super-amphiphobic aluminium alloy plate prepared by the present embodiment 1, this alloy sheets carries out positive and negative and all sprayed, and soaks respectively
In pH=1 sulfuric acid solution and pH=14 NaOH solution, soak 50 hours, the acid resistance and alkali resistance of testing coating.Leaching
Bubble is after 50 hours, it was observed that the unabroken sign of coating surface；And the water contact angle and oily contact angle of coating are measured, wherein acidproof
Water contact angle is up to 160 °, 4 ° of water roll angle, 152 ° of glycerine contact angle, 5 ° of roll angle after experiment；Water contact angle reaches after alkali resistance test
159 °, 4 ° of water roll angle, 152 ° of glycerine contact angle, 6 ° of roll angle；Illustrate the super-amphiphobic that embodiment 1 is prepared on aluminium alloy plate surface
Coating has good acid-alkali-corrosive-resisting.
(4) shock resistance is detected：
Embodiment 1 utilizes the mechanical property of the husky experimental verification aluminium alloy plate surface super-amphiphobic coating of leakage, the husky trystate of leakage
Figure is as shown in fig. 7, the super-amphiphobic aluminium alloy plate level angle at 45 ° prepared by embodiment 1 is placed, away from prepared by embodiment 1
Super-amphiphobic aluminium alloy plate center 30cm height at put sand of the 2kg particle diameter at 100~300 μm be placed with a container, container
Grain；The grains of sand are leaked down from container, touched with the super-amphiphobic coating on the super-amphiphobic aluminium alloy plate surface prepared by inclined embodiment 1
Hit, leakage husky speed about 1g/s, collision area about 1cm2；After the grains of sand have all leaked, aluminium alloy plate is gently washed out with deionized water
The sand on surface, the water contact angle for then measuring coating still can reach 158 °, and roll angle is up to 4 °；Also 151 ° of glycerine contact angle, rolling
Dynamic angle is up to 6 °, and illustrating the super-amphiphobic coating on aluminium alloy plate surface has good impact resistance；Meanwhile, the aluminium after husky experiment will be leaked
Alloy plate surface is placed in -10 DEG C of environment after atomized water spray and found, aluminium alloy plate surface is still without icing after persistently spraying 200 minutes
Phenomenon.
Meanwhile, after the leakage sand experiment that comparative example 1 and comparative example 2 are also carried out to condition same as Example 1, Qi Shui and oil
Contact angle all there occurs obvious reduction, and roll angle is also significantly raised, and specific experiment data are shown in Table 2.Meanwhile, by spraying mist
Water smoke after change carries out anti-fog performance detection and found, the coating surface of comparative example 1 and comparative example 2 after the husky experiment of leakage sprays in water smoke
Moment in surface, the flood for just beginning with condensation is oozed now, just can be from surface when big water droplet condenses into the 3~5mm globule
Tumble；Found after sample is placed in into atomized water spray in -10 DEG C of environment, only lasting atomized water spray 5 minutes, coating surface has just tied one
The obvious ice sheet of layer.
The present invention is prepared for comparative example 6 again, and the preparation method of comparative example 6 is not implement (2) step in the present embodiment 1 to spray
Epoxy glue layer, but the direct spraying compound particle solution on aluminium alloy plate, other steps are same as Example 1, to right
Aluminium alloy plate surface after ratio 6 solidifies is carried out and the identical anti-husky experiment of leakage of embodiment 1；After the completion of the husky experiment of leakage, hair
The compound particle coating on existing aluminium alloy plate surface is struck off completely, is exposed aluminium alloy, has been completely lost its ultra-amphosphobic, is had
Volume data is shown in Table 2.
The experimental data that shock resistance is tested in the embodiment 1 of table 2
Found from the detection of above comparative example 1,2,6 pairs of impact resistance of coating, epoxy glue layer on the one hand can jail
Admittedly be bonded in substrate surface, on the other hand inorganic silicon dioxide particle is bonded with by it securely, plays adherent in the middle of one
Effect, its durability, stability and sustainable freezing to super-amphiphobic coating plays the effect of key；In addition, two
The silicon dioxide granule for planting particle diameter is bound to one piece due to intersecting, when the external world puts on this coating in external force, big particle diameter
Sub-micro level silicon dioxide granule can have certain peptizaiton to the power that the nano fumed silica of small particle is subject to, this
The collective effect of the particle of two kinds of particle diameters, equally also to the durability of super-amphiphobic coating, stability and sustainable freezing
Play the effect of key.
By the experimental data of comparative example, further illustrate that the super-amphiphobic that the present embodiment 1 is prepared on aluminium alloy plate surface is applied
Layer has good impact resistance and can lasting freezing.
(5) resistance to ultrasonic performance detection：
Super-amphiphobic aluminium alloy plate prepared by the present embodiment 1 is immersed in absolute ethyl alcohol or acetone, because absolute ethyl alcohol
Or acetone has good wellability to coating, then using clean alliance JP-080S types supersonic wave cleaning machine, (the clean alliance's cleaning in Shenzhen is set
Standby Co., Ltd) ultrasound 200min, measure the water contact angle after ultrasound and still can reach 158 °, roll angle is up to 4 °；Glycerine contact angle
Also 151 °, roll angle illustrates that the super-amphiphobic coating that the present embodiment 1 is prepared on aluminium alloy plate surface has good resistance to ultrasound up to 6 °
Property.
(6) ageing-resistant performance is detected：
The ageing-resistant performance of super-amphiphobic coating prepared by the present invention is tested by xenon lamp aging instrument, by embodiment 1
Prepared super-amphiphobic coating aluminium alloy plate is placed in xenon lamp aging instrument, 38 DEG C, irradiation intensity 0.51W/m at 340nm2, irradiation
After 2000 hours, 2000 hours, coating is without significant change, and its water contact angle is up to 159 °, and roll angle is up to 4 °, glycerine contact angle
153 °, 6 ° of glycerine roll angle illustrates that super-amphiphobic coating that the present embodiment 1 prepared on aluminium alloy plate surface has ageing-resistant well
Performance.
Embodiment 2
In the present embodiment, matrix material selection thickness be about 200*200*15mm poplar plate, can persistently freezing surpass
Double thin poplar plate preparation methods are carried out as follows：
(1) poplar plate is cleaned up as base material with water and clean cotton, afterwards using 200 mesh corundum sands to base
Body surface face carries out sandblasting roughening treatment, air pressure 2.0MPa, blast time 30s；Use acetone, ethanol and deionized water again afterwards
Substrate surface is cleaned successively, at room temperature dried for standby；
(2) by 8g epoxy resin (Xingchen Synthetic Matrials Co., Ltd., Nantong, Phoenix brand, epoxy resin (E-51)), 5g
Simultaneously stirring and dissolving is in 50mL acetone for alicyclic ring amine hardener ultrasound, and 35mL toluene, the in the mixed solvent of 15mL ethyl acetate is prepared into
To epoxy resin adhesive liquid；
(3) 2.4g particle diameters are called the dioxy that 7~40nm hydrophilic aerosil and 1.6g average grain diameters are 500nm
SiClx, stirring and ultrasonic disperse are in 100mL absolute ethyl alcohol, ultrasound 1.5 hours；The epoxide silicon of 6g perfluoro decyls three is added afterwards
Alkane, continues to stir and ultrasound is after 1.5 hours, has prepared particle composite solution；
(4) by the epoxy resin adhesive liquid in step (2) by spray gun spraying in cottonwood plank stuff substrate surface：It is straight using nozzle
Footpath 0.5mm commercial spray gun, using compressed air as carrier, adjustment spray spot is sector, spray distance 20cm of the nozzle away from base material, spray
Mouth is vertical with base material in 90 ° of angles, and spray pressure 50psi is constant, and from left to right base material is sprayed with 5cm/s speed；
So it is repeated 3 times；Semi-solid preparation is after 2 hours under normal temperature, semi-solid preparation epoxy glue layer needed for poplar plate base material is obtained；
(5) use and spraying technology same in step (4), step is sprayed at by the particle composite solution in step (3)
(4) the epoxide-resin glue layer surface of semi-solid preparation, repeats spraying 5 times；Place and be fully cured under normal temperature afterwards for 5 hours；
(6) with the substrate surface obtained by ethanol or acetone rinsing step (5), you can obtain the super-amphiphobic of lasting freezing
Cottonwood plank stuff.
The present invention is detected to the performance of the cottonwood plank stuff prepared by embodiment 2, specific as follows：
(1) the super-hydrophobic and superoleophobic performance to cottonwood plank stuff is detected：
At room temperature, the water and oil level that 5 μ L are measured with micro syringe are dripped in sample surfaces, are stood after 5s, using Shanghai
Middle morning digital technology equipment Co., Ltd JC2000C type contact angle measurements are measured, and read the contact angle numerical value of water and oil,
The roll angle of coating surface is measured using tilting plate method；Test result draws, the coating is to the contact angle of water up to 166 °, roll angle
2°；To the contact angle of glycerine up to 156 degree, 4 ° of roll angle.
(2) the freezing performance to cottonwood plank stuff is detected：
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 into -10 DEG C, works as platform
Temperature reach this setting value and it is stable after, small water droplet (the about 0.5mm diameters) level after atomization is sprayed in ground by spray gun
Dissipate in sample coatings surface, persistently spray 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, and comparative example 7 is by two kinds of particle diameters in (3) step in the present embodiment 2
Silica be changed to that the hydrophilic aerosil that particle diameter is 7~40nm is used only, other steps are constant；Finally it is prepared into
To super-amphiphobic cottonwood plank stuff surface, surveyed by contact angle measurement and comparative example 7 is detected, obtained its contact angle to water and reach
167 °, 2 ° of roll angle；158 ° of the contact angle of glycerine, 3 ° of roll angle, it was demonstrated that, can also using only the aerosil of small particle
Realize super-amphiphobic coating.But this surface is subjected to freezing performance detection, (about 0.5mm is straight for the small water droplet after spraying atomization
Footpath) when poplar plate substrate surface, small water droplet can condense into about 2mm big water droplet first, afterwards just can be in poplar plate base material table
Face is tumbled, which substantially increases water droplet surface residence time；After lasting spray 20 minutes, cottonwood plank stuff surface is just formed
A thick layer of ice, illustrates cottonwood plank stuff surface prepared by this comparative example 7 not freezing.
Comparative example 8 be the silica of two kinds of particle diameters in (3) step in the present embodiment 2 is changed to be using only particle diameter
500nm silica, other steps are constant；Finally prepare super-amphiphobic cottonwood plank stuff surface.Pass through contact angle measurement
The contact angle of water is measured up to 152 °, 8 ° of roll angle；146 ° of the contact angle of glycerine, 10 ° of roll angle, it was demonstrated that using only 500nm particle diameters
Silica, although can realize super-hydrophobic, but not realize superoleophobic.Equally by the poplar plate prepared by comparative example 8
Substrate surface carries out freezing performance detection, and the small water droplet (about 0.5mm diameters) after spraying atomization is when substrate surface, small water droplet
About 2~5mm big water droplet can be condensed into first, can just be tumbled afterwards in substrate surface, this also increases water droplet on surface
Residence time；After lasting spray 5 minutes, a thick layer of ice has just been formed on cottonwood plank stuff surface, illustrates this contrast experiment institute
The cottonwood plank stuff surface of preparation equally not freezing.
(3) acid-alkali-corrosive-resisting performance detection：
By the super-amphiphobic cottonwood plank stuff sample prepared by the present embodiment 2, pH=1 sulfuric acid solution and pH=is soaked in respectively
In 14 NaOH solution, soak 50 hours, the acid resistance and alkali resistance of testing coating.After immersion 50 hours, it was observed that coating table
The unabroken sign in face；And the water contact angle to coating after immersion and oily contact angle are tested, wherein water connects after acid resistance test
Feeler is up to 164 °, 3 ° of water roll angle, 155 ° of glycerine contact angle, 6 ° of roll angle；Water contact angle is up to 163 ° after alkali resistance test, and water is rolled
3 ° of angle, 154 ° of glycerine contact angle, 6 ° of roll angle.Illustrate that the present embodiment 2 has in super-amphiphobic coating prepared by cottonwood plank stuff surface
Good acid-alkali-corrosive-resisting.
(4) shock resistance is detected：
By mechanical property of the present embodiment 2 using the husky experimental verification cottonwood plank stuff surface super-amphiphobic coating of leakage, Fig. 7 is seen：Will
Poplar plate base material level angle at 45 ° is placed, and is put in a container, container and is placed with the height away from poplar plate substrate center 30cm
The grains of sand of the 2kg particle diameter at 100~300 μm；The grains of sand are leaked down from container, the super-amphiphobic with inclined poplar plate substrate surface
Coating is collided, leakage husky speed about 1g/s, collision area about 1cm2；After the grains of sand have all leaked, poplar is gently washed out with deionized water
The sand on wood plank surface, the water contact angle for then measuring coating still can reach 160 °, and roll angle is up to 4 °；Glycerine contact angle reaches
152 °, roll angle is up to 6 °；Illustrate that the present embodiment 2 has good shock resistance in super-amphiphobic coating prepared by cottonwood plank stuff surface
Property；Meanwhile, the poplar plate surface leaked after husky experiment is placed in -10 DEG C of environment after atomized water spray and found, is persistently sprayed 200 minutes
Afterwards in sample surface still without obvious icing phenomenon.
(5) ageing-resistant detection performance：
The ageing-resistant performance of super-amphiphobic coating prepared by embodiment 2 is tested by xenon lamp aging instrument, and sample is put
In xenon lamp aging instrument, 38 DEG C, irradiation intensity 0.51W/m at 340nm2, after irradiating 2000 hours, 2000 hours, coating is without bright
Aobvious change, its water contact angle is up to 164 °, and roll angle is up to 3 °, 154 ° of glycerine contact angle, 5 ° of glycerine roll angle；Illustrate the present embodiment 2
The super-amphiphobic coating prepared on cottonwood plank stuff surface has good ageing-resistant performance.
Embodiment 3
In present embodiment, the corrugated board that matrix material selection thickness is about 200*200*5mm can lasting freezing
The corrugated board preparation method of super-amphiphobic is carried out as follows：
(1) corrugated board is stand-by with clean cotton wiped clean as base material；
(2) by 5g epoxy resin (Nanya Plastic Cement Industry Co., Ltd, epoxy resin (NPEL-128)), 2g alicyclic rings
Simultaneously stirring and dissolving is in 40mL acetone for amine hardener ultrasound, and 40mL dimethylbenzene, the in the mixed solvent of 20mL tert-butyl acetates is prepared into
To epoxy resin adhesive liquid；
(3) 1.1g particle diameters are called the dioxy that 7~40nm hydrophilic aerosil and 0.9g average grain diameters are 300nm
SiClx, stirring and ultrasonic disperse are in 100mL n-hexane, ultrasound 1.5 hours；4g perfluoro capryl trichlorosilanes are added afterwards,
Continue to stir and ultrasound is after 1.5 hours, prepared particle composite solution；
(4) by the epoxy resin adhesive liquid in step (2) by spray gun spraying in corrugated board substrate surface：It is straight using nozzle
Footpath 0.5mm commercial spray gun, using compressed air as carrier, adjustment spray spot is sector, spray distance 15cm of the nozzle away from base material, spray
Mouth is vertical with base material in 90 ° of angles, and spray pressure 30psi is constant, and from left to right base material is sprayed with 5cm/s speed；
So it is repeated 2 times；Semi-solid preparation is after 2 hours under normal temperature, semi-solid preparation epoxy glue layer needed for corrugated board base material is obtained；
(5) use and spraying technology same in step (4), step is sprayed at by the particle composite solution in step (3)
(4) the epoxide-resin glue layer surface of semi-solid preparation, repeats spraying 6 times；Placed afterwards under normal temperature after being fully cured within 5 hours；
(6) with the substrate surface obtained by ethanol or acetone rinsing step (5), you can obtain the super-amphiphobic of lasting freezing
Corrugated board.
The present invention is detected to the performance of the corrugated board of the super-amphiphobic prepared by embodiment 3, specific as follows：
(1) the super-hydrophobic and superoleophobic performance to the corrugated board of the super-amphiphobic prepared by embodiment 3 is detected：
At room temperature, the water and oil level that 5 μ L are measured with micro syringe are dripped in sample surfaces, are stood after 5s, using Shanghai
Middle morning digital technology equipment Co., Ltd JC2000C type contact angle measurements are measured, and read the contact angle numerical value of water and oil,
The roll angle of coating surface is measured using tilting plate method；Test result draws, the coating is to the contact angle of water up to 164 °, roll angle
3°；To the contact angle of glycerine up to 156 °, 5 ° of roll angle.
(2) the freezing performance to the corrugated board of the super-amphiphobic prepared by embodiment 3 is detected：
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 into -10 DEG C, works as platform
Temperature reach this setting value and it is stable after, small water droplet (the about 0.5mm diameters) level after atomization is sprayed in ground by spray gun
Dissipate in sample coatings surface, persistently spray 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, and comparative example 9 is by two kinds of particle diameters in (3) step in the present embodiment 3
Silica be changed to that the hydrophilic aerosil that particle diameter is 7~40nm is used only, other steps are constant；Finally it is prepared into
Super-amphiphobic corrugated board surface.The super-amphiphobic corrugated cardboard sheet prepared by comparative example 9 is measured by contact angle measurement and faces water
Contact angle up to 166 °, 2 ° of roll angle；157 ° of the contact angle of glycerine, 4 ° of roll angle, it was demonstrated that using only the gas phase dioxy of small particle
SiClx, can also realize super-amphiphobic coating；But this surface is subjected to freezing performance detection, the small water droplet after spraying atomization
(about 0.5mm diameters) when substrate surface, small water droplet can condense into about 2mm big water droplet first, afterwards just can be in substrate surface
Tumble, which substantially increases water droplet surface residence time；After lasting spray 20 minutes, thickness has just been formed on corrugated board surface
One layer of thick ice, illustrates corrugated board surface prepared by this comparative example 9 not freezing.
Comparative example 10 be the silica of two kinds of particle diameters in (3) step in the present embodiment is changed to be using only particle diameter
300nm silica, other steps are constant；Finally it is prepared into super-amphiphobic corrugated board surface；Surveyed by contact angle measurement
Water contact angle up to 153 °, 5 ° of roll angle；151 ° of the contact angle of glycerine, 7 ° of roll angle, it was demonstrated that using only the two of 300nm particle diameters
Silica, can also realize super-amphiphobic coating；It is same that this surface is subjected to freezing performance detection, the small water after spraying atomization
(about 0.5mm diameters) is dripped when substrate surface, and small water droplet can condense into about 3mm big water droplet first, afterwards just can be in base material table
Face is tumbled, this also increases water droplet surface residence time；After lasting spray 5 minutes, corrugated board surface is just formed
A thick layer of ice, illustrates corrugated board surface prepared by this comparative example 10 equally not freezing.
(3) shock resistance to the corrugated board of the super-amphiphobic prepared by embodiment 3 is detected：
The present embodiment 3 is shown in Fig. 7 using the mechanical property of the husky experimental verification corrugated board surface super-amphiphobic coating of leakage：Will be logical
Cross sample levels angle at 45 ° to place, the particle diameter that 2kg is placed with a container, container is put at the height away from sample center 30cm
In 100~300 μm of the grains of sand；The grains of sand are leaked down from container, collided with the super-amphiphobic coating of inclined sample surfaces, the husky speed of leakage
Spend about 1g/s, collision area about 1cm2.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 5 °；Also 152 ° of glycerine contact angle, roll angle is up to 7 °；
Illustrate that the present embodiment 3 has good impact resistance in super-amphiphobic coating prepared by corrugated board surface.Meanwhile, by the husky experiment of leakage
Corrugated board afterwards is placed in -10 DEG C of environment after atomized water spray and found, after persistently spraying 200 minutes in sample surface still without obvious
Icing phenomenon.
(4) ageing-resistant performance to the corrugated board of the super-amphiphobic prepared by embodiment 3 is detected：
Ageing-resistant performance to the super-amphiphobic coating prepared by the present embodiment 3 is tested by xenon lamp aging instrument, by sample
Product are placed in xenon lamp aging instrument, 38 DEG C, irradiation intensity 0.51W/m at 340nm2, after irradiating 2000 hours, 2000 hours, coating
Without significant change, its water contact angle is up to 161 °, and roll angle is up to 4 °, 153 ° of glycerine contact angle, 7 ° of glycerine roll angle；Illustrate this implementation
Example 3 has good ageing-resistant performance in super-amphiphobic coating prepared by corrugated board surface.
Embodiment 4
In the present embodiment, the common brick that matrix material selection thickness is about 200*100*50mm, can lasting freezing it is super double
Thin common brick preparation method is carried out as follows：
(1) common brick is cleaned up as base material with water and clean cotton, afterwards using 80 mesh corundum sands to matrix table
Face carries out sandblasting roughening treatment, air pressure 1.0MPa, blast time 1 minute；Afterwards again with acetone, ethanol and deionized water according to
Secondary cleaning substrate surface, at room temperature dried for standby；
(2) by 5g epoxy resin (Nanya Plastic Cement Industry Co., Ltd, epoxy resin (NPEF-170)), 5g alicyclic rings
Simultaneously stirring and dissolving is in 50mL acetone for amine hardener ultrasound, and 30mL dimethylbenzene, the in the mixed solvent of 20mL tert-butyl acetates is prepared into
To epoxy resin adhesive liquid；
(3) 2g particle diameters are called the titanium dioxide that 7~40nm hydrophilic aerosil and 2g average grain diameters are 200nm
Silicon, stirring and ultrasonic disperse are in 100mL acetone, ultrasound 1 hour；6g perfluoro capryl triethoxysilanes are added afterwards, after
Simultaneously ultrasound after 1 hour, has prepared particle composite solution for continuous stirring；
(4) by the epoxy resin adhesive liquid in step (2) by spray gun spraying in common brick substrate surface：Use nozzle diameter
0.5mm commercial spray gun, using compressed air as carrier, adjustment spray spot is sector, spray distance 15cm of the nozzle away from base material, nozzle
Vertical with base material is in 90 ° of angles, and spray pressure 30psi is constant, and from left to right base material is sprayed with 5cm/s speed；Such as
This is repeated 2 times；Semi-solid preparation 1 hour under normal temperature, common brick base material obtains required semi-solid preparation epoxy glue layer；
(5) use and spraying technology same in step (4), step is sprayed at by the particle composite solution in step (3)
(4) the epoxide-resin glue layer surface of semi-solid preparation, repeats spraying 5 times；Place and be fully cured under normal temperature afterwards for 5 hours；
(6) with the substrate surface obtained by ethanol or acetone rinsing step (5), you can obtain the super-amphiphobic of lasting freezing
Common brick sheet material preparation method.
The present invention is detected to the performance of the common brick sheet material of the super-amphiphobic prepared by embodiment 4, specific as follows：
(1) super-hydrophobic and superoleophobic performance detection is carried out to the common brick sheet material of the super-amphiphobic prepared by embodiment 4：
At room temperature, the water and oil level that 5 μ L are measured with micro syringe are dripped in sample surfaces, are stood after 5s, using Shanghai
Middle morning digital technology equipment Co., Ltd JC2000C type contact angle measurements are measured, and read the contact angle numerical value of water and oil,
The roll angle of coating surface is measured using tilting plate method；Test result draws, the coating is to the contact angle of water up to 165 °, roll angle
3°；To the contact angle of glycerine up to 158 degree, 4 ° of roll angle.
(2) freezing performance detection：
The freezing performance of super-amphiphobic coating passes through homemade apparatus measures：Marble slabs prepared by the present embodiment 4
Sample is placed on a platform, and platform is in 30 degree of angle horizontal rest, and platform surface temperature is cooled into -10 DEG C, when flat
The temperature of platform is reached after this setting value and stabilization, by spray gun by small water droplet (about 0.5mm diameters) level after atomization in ground
Send forth in sample coatings surface, persistently spray 200 minutes.Continue in spraying process it has been observed that when small water droplet is sprayed onto base material table
During face, moment is walked by bullet, and water droplet is extremely short in the substrate surface residence time；Sample surfaces are hung on its surface, 200 minutes without droplet
Do not occur icing phenomenon afterwards.
The present invention prepares comparative example 11 and comparative example 12, and comparative example 11 is by two kinds of grains in (3) step in the present embodiment 4
The silica in footpath is changed to that the hydrophilic aerosil that particle diameter is 7~40nm is used only, and other steps are constant；It is final to prepare
Obtain super-amphiphobic common brick surface；The contact angle of the reclaimed water of comparative example 11 is measured up to 166 °, 2 ° of roll angle by contact angle measurement；Glycerine
158 ° of contact angle, 4 ° of roll angle, it was demonstrated that using only the aerosil of small particle can also realize super-amphiphobic coating；But
It is that this surface is subjected to freezing performance detection, the small water droplet (about 0.5mm diameters) after spraying atomization is small when substrate surface
Water droplet can condense into about 2mm big water droplet first, can just be tumbled afterwards in substrate surface, which substantially increases water droplet on surface
Residence time；After lasting spray 20 minutes, common brick substrate surface has just formed a thick layer of ice, illustrates prepared by comparative example 11
Common brick substrate surface not freezing.
Comparative example 12 be the silica of two kinds of particle diameters in (3) step in the present embodiment 4 is changed to be using only particle diameter
200nm silica, other steps are constant；Finally it is prepared into super-amphiphobic common brick plate surface；Surveyed by contact angle measurement
Water contact angle up to 154 °, 6 ° of roll angle；150 ° of the contact angle of glycerine, 8 ° of roll angle, it was demonstrated that using only the two of 200nm particle diameters
Silica, can also realize the performance of super-amphiphobic coating；It is same that this surface is subjected to freezing performance detection, after spraying atomization
Small water droplet (about 0.5mm diameters) when substrate surface, small water droplet can condense into about 3mm big water droplet first, afterwards just can be
Substrate surface is tumbled, this also increases water droplet surface residence time；After lasting spray 5 minutes, common brick substrate surface
Just form a thick layer of ice, illustrate common brick substrate surface prepared by comparative example 12 equally not freezing.
(3) acid-alkali-corrosive-resisting performance detection：
The whole faces of super-amphiphobic common brick board samples prepared by the present embodiment 4 are all sprayed, pH=1 sulphur is soaked in respectively
In acid solution and pH=14 NaOH solution, soak 50 hours, the acid resistance and alkali resistance of testing coating；After immersion 50 hours,
It was observed that the unabroken sign of coating surface；And the water contact angle and oily contact angle of coating are measured, wherein water connects after acid resistance test
Feeler is up to 162 °, 5 ° of water roll angle, 156 ° of glycerine contact angle, 6 ° of roll angle；Water contact angle is up to 160 ° after alkali resistance test, and water is rolled
5 ° of angle, 155 ° of glycerine contact angle, 6 ° of roll angle；Illustrate that the present embodiment 4 has in super-amphiphobic coating prepared by common brick substrate surface
Good acid-alkali-corrosive-resisting.
(4) shock resistance is detected：
The present embodiment 4 is shown in Fig. 7 using the mechanical property of the husky experimental verification marble veneer surface super-amphiphobic coating of leakage：Will
Placed by sample levels angle at 45 °, the grain that 2kg is placed with a container, container is put at the height away from sample center 30cm
The grains of sand of the footpath at 100~300 μm；The grains of sand are leaked down from container, collided with the super-amphiphobic coating of inclined sample surfaces, leakage is husky
Speed about 1g/s, collision area about 1cm2；After the grains of sand have all leaked, marble veneer surface is gently washed out with deionized water
Sand, the water contact angle for then measuring coating still can reach 158 °, and roll angle is up to 5 °；Also 151 ° of glycerine contact angle, roll angle reaches
6°；Illustrate that the present embodiment 4 has good impact resistance in super-amphiphobic coating prepared by common brick substrate surface.Meanwhile, leakage is husky
Common brick after experiment is placed in -10 DEG C of environment after atomized water spray and found, after persistently spraying 200 minutes in sample surface still without obvious
Icing phenomenon.
(5) resistance to ultrasonic performance detection：
Super-amphiphobic common brick board samples prepared by the present embodiment 4 are immersed in absolute ethyl alcohol or acetone, because anhydrous
Ethanol or acetone have good wellability to coating, and then using clean alliance JP-080S types supersonic wave cleaning machine, (clean alliance of Shenzhen is clear
Wash equipment Co., Ltd) ultrasound 200min, measure the water contact angle after ultrasound and still can reach 159 °, roll angle is up to 4 °；Glycerine connects
Feeler is up to 154 °, and roll angle is up to 6 °；Illustrate that the super-amphiphobic coating that the present embodiment 4 is prepared on common brick surface has good resistance to ultrasound
Property.
(6) ageing-resistant performance is detected：
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 irradiating 2000 hours, 2000 hours, coating is without obvious
Change, its water contact angle is up to 163 °, and roll angle is up to 4 °, 156 ° of glycerine contact angle, 5 ° of glycerine roll angle；Illustrate that the present embodiment 4 exists
Super-amphiphobic coating prepared by common brick substrate surface has good ageing-resistant performance.
In summary, the invention provides it is a kind of can the lasting super-amphiphobic coating of freezing preparation method, energy of the present invention
Enough make different base materials that there is excellent super-hydrophobic and superoleophobic performance, and good self-cleaning performance；Meanwhile, institute of the present invention
The super-amphiphobic coating of preparation has antifog, freezing performance, and with good durability and fastness, with extensive work
The application prospect of industry, can create great economic benefit.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in,
It should all be included within the scope of the present invention.
Claims (10)
1. it is a kind of can the lasting super-amphiphobic coating of freezing preparation method, it is characterised in that specifically include following steps：
Step 1, substrate surface is cleaned and sandblasting roughening treatment, the base material handled well；
Step 2, epoxy resin, curing agent and the first solvent are blended after obtain epoxy resin solution；
Step 3, submicron particle, nano-particle be scattered in the second solvent, after ultrasound and stirring, add silicon fluoride, continue super
Sound and stirring, have obtained particle composite suspension liquid；
Step 4, the substrate surface for treating the epoxy resin solution spraying process 1 obtained by step 2, then the base material is dried,
Semi-solid preparation is carried out to epoxide-resin glue；
Step 5, the substrate surface for spraying to the particle composite suspension liquid obtained by step 3 obtained by step 4, then the base material is dried
It is dry to be fully cured；
Step 6, the substrate surface obtained by step 5 is rinsed, you can obtain can lasting freezing super-amphiphobic coating.
2. it is according to claim 1 it is a kind of can the lasting super-amphiphobic coating of freezing preparation method, it is characterised in that institute
State in step 1, described to substrate surface progress cleaning is cleaned successively using acetone, deionized water, ethanol.
3. it is according to claim 2 it is a kind of can the lasting super-amphiphobic coating of freezing preparation method, it is characterised in that institute
State in step 2, the epoxy resin is one kind in bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy resin
Or it is a variety of；The curing agent is alicyclic ring amine hardener；First solvent is toluene, dimethylbenzene, acetone, MEK, butanone, second
Acetoacetic ester, n-butyl acetate, one or more mixed solvents of tert-butyl acetate.
4. it is according to claim 1 it is a kind of can the lasting super-amphiphobic coating of freezing preparation method, it is characterised in that institute
State in step 2, the mass ratio of the epoxy resin, curing agent and the first solvent is (4~10)：(2~10)：100.
5. according to claim 1-4 it is a kind of can the lasting super-amphiphobic coating of freezing preparation method, it is characterised in that
In the step 3, sub-micron particles, nano-particle are scattered in the second solvent, after ultrasound and stirring 1~3 hour, fluorine silicon is added
Alkane, continues ultrasound and stirs 1~3 hour, obtained particle composite suspension liquid；Base material is placed in 25~80 DEG C in the step 4
0.5~2h of lower drying carries out semi-solid preparation；By base material, in the case where temperature is 25~80 DEG C, 0.5~24h of drying has been carried out in the step 5
All solidstate.
6. it is according to claim 5 it is a kind of can the lasting super-amphiphobic coating of freezing preparation method, it is characterised in that institute
State the silicon dioxide granule that sub-micron particles are 200~500nm of particle diameter；The nano-particle is 7~40nm of particle diameter hydrophilic
Aerosil particle, second solvent is acetone, ethanol, n-hexane, methyl acetate, the one or more of carbon tetrachloride
Mixed solvent.
7. it is according to claim 6 it is a kind of can the lasting super-amphiphobic coating of freezing preparation method, it is characterised in that institute
The mass ratio for stating submicron particle, nano-particle, silicon fluoride and the second solvent is (1~3)：(1~3)：(2~10)：100.
8. it is according to claim 7 it is a kind of can the lasting super-amphiphobic coating of freezing preparation method, it is characterised in that institute
State silicon fluoride and be more than 4 for carbon chain lengths, and end group is the one or more of the perfluor silane of methoxyl group, ethyoxyl or chloro.
9. it is according to claim 7 it is a kind of can the lasting super-amphiphobic coating of freezing preparation method, it is characterised in that institute
State in step 3, total mass ratio of the silicon fluoride and two kinds of particle diameter silica is greater than 1：1.
10. a kind of according to one of claim 1-9 can be persistently prepared by the preparation method of the super-amphiphobic coating of freezing
Super-amphiphobic coating, it is characterised in that raw material mainly include epoxy resin solution and particle composite suspension liquid, the epoxy resin
Solution includes 4~10 parts of epoxy resin, 2~10 parts of curing agent, 100 parts of the first solvent；The particle composite suspension liquid includes Asia
1~3 part of micro particles, 1~3 part of nano-particle, 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 |
| CN110180762A (en) * | 2019-05-31 | 2019-08-30 | 华为技术有限公司 | Appearance member with super-hydrophobic oleophobic coating and preparation method thereof and terminal |
| CN110204902A (en) * | 2019-05-31 | 2019-09-06 | 华南理工大学 | A kind of flexible bendable, active deicing super-hydrophobic ice-covering-proof composite material and preparation method and application |
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